A Study of the Reactions of Ketene Monomer, Dimer and Polymers

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PUBDUE UNIVERSITY

TH IS IS TO CERTIFT THAT THE T H E SIS P R E P A R E D U N D E R MT SU P E R V IS IO N

BY

Luther Lansing B olstad

ENTITLED

& Study of th e R eactions of Ketene Monomer, Dimer and Polymers

COM PLIES WITH TH E UNIVERSITY REG U LA TIO N S O N G RADUATION T H E SE S

A N D IS APPRO VED BY ME A S FULFILLIN G TH IS PART O F TH E REQ UIREM ENTS

F O R TH E D EG R EE O F

Doctor of Philosophy

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TO THE LIBRARIAN;IS ■Yvo't' TH IS T H E SIS J f id S a r TO B E REG ARDED A S CONFIDEN'

GRAD, SCHOOIf FORM9— 3.49— lM

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A STUDY OF THE REACTIONS OF KETENE MONCMER, DIMER AND POLYMERS A Thesis Suhmitted to th e F a c u lty of Purdue U n iv e rsity by L uther Lansing B olstad In P a r t i a l F u lfillm e n t of th e Requirements f o r th e Degree of Doctor of Philosophy August, 1949

ProQuest Number: 27712191

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uest ProQuest 27712191 Published by ProQuest LLO (2019). C opyright of the Dissertation is held by the Author. All rights reserved. This work is protected against unauthorized copying under Title 17, United States C o d e M icroform Edition © ProQuest LLO. ProQuest LLO. 789 East Eisenhower Parkway P.Q. Box 1346 Ann Arbor, Ml 4 8 1 0 6 - 1346

ACKNCILEDGMENT During h is s ta y a t Purdue U n iv e rsity , th e au th o r has enjoyed th e generous f a c i l i t i e s th e U n iv e rsity provides fo r in te lle c t u a l and c u ltu r a l development.

He i s indebted

to the s t a f f of not only th e Chemistry Department, but other departm ents a s •well, vhose cooperation and t a l e n t s have co n trib u te d g re a tly to t h i s work.

The au th o r i s

p a r tic u la r ly indebted to Dr, Ed, F, Degering as d ir e c to r o f t h i s re se a rc h . The author acknowledges th e fin a n c ia l a id provided by th e Tennessee Eastman C orporation and Purdue Research Foundation,

imûDUCTION The academic and commercial in te r e s t in ketene and derived compounds i s re fle c te d by th e ever in c re asin g number of p u b lic a tio n s and p a te n ts concerned w ith k eten e.

The g re a t and v a rie d a c t i v i t y of

these compounds and th e u sefu ln ess of t h e i r d e riv a tiv e s in s u re con­ tin u e d in te r e s t in t h i s f i e l d ,

ülie p re sen t work on ketene was f i ­

nanced jo in tly by th e Tennessee Eastman C orporation and th e Purdue Research Foundation, This th e s is has been prepared w ith th e in te n t of (1) introducing the read er to th e chem istry o f k e ten e , (2) a ffo rd in g a comprehensive annotated bibliography on k eten es in g e n eral, and ( 3 ) d escrib in g and d iscu ssin g th e la b o ra to ry experim ents performed by th e au th o r. There are th re e major d iv is io n s corresponding re s p e c tiv e ly to th e monomer, dimer, and h ig h er polymers o f k eten e.

TABLE OF CONTENTS

ABSTRACT...................... PART I ,

Page i

KETENE MONCMER

INTMÜCTION........................................................................

1

D iscovery and p re p a ra tio n ............................................... P h y sical p r o p e r t i e s .......................................................... Chemical p ro p e rtie s ...............................................

1 2 3

A cétylation with ketene ....................... «.......... 3 b e ta-Lactones .........................................................................................

CH3 *GH - 0

> 1 I CH3*àip;CH- GO GH3*GH*CH*C0*CH3 + OO2 , In the case of d ik e te n e, th e b e ta -la cto n e formed i s u n stab le and lo s e s GO2 re a d ily . In t h i s work, th e p a ra lle lis m between re a c tio n s of ketene and diketene has been extended to include th e d iketene analogs of enol a c e ta te s .

In ste ad of th e expected enol a c e to a c e ta te s however,

a c y c lic isomer i s obtained* GH3*C0«CH3 + HaC-GsO-* GH3G0-0«G(CH3)=CHa /O , / H 3 GH3*G0*CH3 + C E 3.C 0.C H = C = 0 -*■ CE 3 .G

c

II

i'gHj HG^ ^0 GO

The s im ila r ity of these two re a c tio n s i s more evident on co n sid eratio n o f a D iels Alder type mechanism* CH3-G

GO

J

+

HgC

0 GH 3.C‘^ 1 CH ^G C

GH3*G 0

GH2

OH2 CH3

,CH3 +

CO

II

G^ (I CH3 0

I

yO. ,CH3 CH3 G ^

C^ I GH3 HC^ ^0 GO

II

iii

Favorable co n d itio n s fo r th e two re a c tio n s are s im ila r, a c id c a ta ly s ts and moderate tem peratures C50 to lOCF'C.) being s u ita b le . A search of th e a v a ila b le l i t e r a t u r e d isclo se d onere a c tio n of d iketene of t h i s ty p e ,

Naylor found dik eten e to re a c t w ith acetone

in th e presence of ZnGla to form a compound la te d to be th e enol a c e to a c e ta te of aceto n e. 2.

which he postuNaylor’ s compound and

N aylor, J . Ghem. S oc,, 1945 . 244,

th e corresponding analogs of chloroacetone, triflu o ro a c e to n e , a c e ta l­ dehyde and c h lo ra l have been prepared in t h i s la b o ra to ry .

The enol

a c e ta te s tru c tu re was found untenable and th e c y c lic s tru c tu re pro­ posed on th e b a s is of th e follow ing c o n sid é râ tionst Cl)

The b o ilin g p o in ts of th e diketene a d d itio n products

with aldehydes and ketones a re higher th a n would be p re d ic te d fo r th e enol a ce to a c e ta te s tru c tu re .

The enol a c e ta te o f acetaldehyde Cvinyl

a c e ta te ) b o ils lower than i t s hydrogenation product, e th y l a c e ta te (74®G. and 78®C,, re s p e c tiv e ly ).

On t h i s b a s is , th e enol a ce to a ce ta te

of acetaldehyde would be expected to b o il a t a tem perature below th a t of e th y l a ce to a c e ta te (32 to 40 ^G, a t 2 mm, p re ssu re , depending on en o l-k eto com position).

However th e re a c tio n product o f d ik eten e and

acetaldehyde b o ils much higher (70,8®C, a t 3.5 mm,), (2)

The re a c tio n products of d ik eten e with aldehydes and

ketones r e s i s t c a ta ly tic hydrogenation.

Experience in t h i s la b o ra to ry

in d ic a te s th a t enols in general hydrogenate re a d ily . 3.

3

Fuhman, Ph,D, T hesis, Purdue U n iv e rsity , June 1948,

IV

The u n sa tu ra tio n in th e c y c lic s tru c tu re , however, i s very s im ila r to th a t in dehydroacetic acid* C H 3C

G R 1R 2

C H 3C

It

\ \ \ HC

HC^

^ 0 CO

CO

( /G A c GO

The o le f in band in the l a t t e r compound i s hydrogenated with rin g ru p tu re only under extreme conditions* 4*

4,5

Adkins, Connor and Cramer, J . Am, Ghem. S oc.. 52. 5192 (l93C ),

5, Malachowski and Wanezura, B u ll, in te r n , acad. polonaise c lasse §c±, ma-t^. n a t ., 1933A. 547. I3)

C hloral does not have an alpha p o s itio n halogen, and

consequently cannot form an enol d e riv a tiv e .

Diketene condenses

re a d ily with c h lo ra l and th e product has p ro p e rtie s sim ila r to th e other diketene a d d itio n products with aldehydes and k eto n es, (4 )

In fra re d spectrograms of dehydroacetic a cid and th e

diketene d e riv a tiv e s of acetone and d ilo r a l were o b tain ed ,*

The

* Samuel P, S a d tle r and Son, I n c , , P h ila d e lp h ia , Pa, sig n ific a n c e of a few bands common to each o f th ese compounds can be s ta te d with considerable c e r ta in ty . presence of a G=G bond.

The 6 ,1 micron band in d ic a te s th e

The band between 5 ,6 and 5.8 microns i s prob­

ably a ttr ib u ta b le to th e C-0 group.

The presence of ab so rp tio n maxima

a t 240 m illim icrons i s in harmony with th e conjugated linkage G=G*G=0, The a b so rp tio n band near 11 microns i s c h a r a c te r is tic o f a l l s ix membered rin g s containing oxygen, co rroborating th e c y c lic s tru c tu re .

(5) Bromination of th e enol a c e to a c e ta te

o f acetone diould

give a d e riv a tiv e containing bromine in th e acetone m olecule.

p o rtio n of th e

However, brom ination of th e d ik e te n e-a c et one re a c tio n

product evolves HBr and gives an a lo h a -brom oaoetoacetic a cid d eriv a­ tiv e ,

The p o s itio n of th e bromine was e sta b lish e d by re a c tin g th e

bromo compound w ith phenylhydrazine to o b ta in a product m elting a t 156-157®C,

alTha-Bromoacetic a c id d e riv a tiv e s give 3-m ethyl-l-phenyl-

4 -ihenyhydrazono-5-pyrazolone (m elting p o in t 157®C,) w ith phenylhydra6

z in e.

The re a c tio n is* CH3G

G fl rCH) BrC 0 '^GO

6 , Blomquist

+ GgH^NHNEa

OC N 1 II G ^ g .N H M r— G-CHj

and Baldwin, J . Amer. Ghem. Soc. . 70 . 29 ( 1949 ) ,

( 6 ) A cetoacetates u su a lly give deep red c o lo rs w ith s o lu tio n ,

FeGlg

TOien p ure, th e d iketene a d d itio n products of aldehydes and

ketones give no c o lo r with FeGls, Experim ental R eaction of diketen e with aldehydes and k eto n es. -

Hie gen­

e r a l procedure fo r re a c tin g diketene with carbonyl compounds i s to add dropwise an equimolar m ixture of th e two re a c ta n ts to an in e r t solvent containing th e c a ta ly s t, a t tem peratures u su a lly below 100®C, re a c tio n s were u su a lly conducted on a 0 ,1 mole b a sis . th a t s t i r r i n g th e re a c tio n mixture i s unnecessary.

The

I t m s found

The re a c tio n

m ixture i s d i s t i l l e d a t dim inidied p ressu re and th e product fu rth e r p u rif ie d

low tem perature r e c r y s ta lliz a tio n from e th y l e th e r .

The

Vi

The reaction between diketene and chloroacetone i s cited as an example} Three drops o f su lfu ric acid Isp .g . 1*84) ure d issolved in 10 ml* purified dioxan in a 125 ml* Erlenmeyer fla sk fit t e d with a reflu x condenser*

The fla sk i s placed on a steaoqalate and a mixture

of 7 .7 ml. diketene (O .l mole) and 8 .0 ml. chloroacetone (O .l mole) i s added from a dropping funnel over a period o f about 15 minutes. After heating 15 to 30 minutes more, the reaction product i s d is tille d at dim ini^ed pressure, yield in g about 11 g. b oilin g between 79 and 99^0. at 1 mm* (61^ y ie ld as C7H9O3C I).

On redi at illa tio n , the bulk

d is t ills between 84 and 89*0. a t 1 mm* Further p u rification i s ob­ tained by recry sta lliza tio n from ether. equal volume of eth y l ether. a dry ice cooled bath.

D issolve the product in an

Cool slowly while stir r in g to - 4 CPG. in

F ilte r in a precooled Buckner funnel, wash

once with precooled ether and place the funnel and contents in a vacuum desiccator*

The product i s allowed to melt under a pressure

of about 2 mm* The melt i s collected by standing the funnel in a beaker*

After two recry sta lliza tio n s, the product melted a t 2^29*0.

Elemental analysis: C

H

G1

Theoiy

47*6^

5*1^

20.5^

Found

4 7 .1

5.29

V lll

ble m a te ria l was a lso obtained corresponding to th e e m p irical formula G^HgOa,

I t m elts a t 29.5 to 30.5®C, and slowly forms a 2 ,4 - d in itr o -

phenylhydrazone m elting a t 92 to 93®C, The carbonyl compound-diketene a d d itio n products r e s i s t hydrogenation.

The acetone analog was recovered unchanged a f t e r

shaking a dioxan s o lu tio n with Raney n ic k e l and 50 p . s . i , hydrogen f o r two days a t room tem perature. R eaction of diketene with N^Oa. dropwise to liq u id by flam es.

When d ik eten e i s added

an explosive re a c tio n ta k e s p la ce accompanied

The spontaneous detonation immediately upon c o n ta c t, and

th e violence of th e re a c tio n , suggest i t s use f o r rocket p ro p u lsio n . The energy and gas volume per gram o f re a c ta n ts produced by th is re a c tio n i s comparable w ith t h a t of perhydrol 180^ HgO^) and hydrazine hydrate (57^ in methanol with potassium cyanocuprate ), and about one7 h a lf th a t of the re a c tio n of liq u id hydrogen with liq u id oxygen. 7,

V ic to r, Rev. Aluminium. 2^, 69 (l9 4 7 ).

The diketene

combination probably meets th e requirem ents of a

rocket fu e l in so f a r a s ( l ) h eat of combustion, l2 ) r a p id ity of combustion, (3 ) autom atic s ta r tin g , ( 4 ) sm all s p e c ific volume, and ( 5 ) ease of manufacture are concerned.

However diketene f a i l s to meet

safety requirem ents in storage and tra n s p o rt.

At p resen t no in h ib ito r

i s known th a t w ill prevent cdketene from polym erizing v io le n tly on long standing. Reaction of ketene and ch lo ral -

No d e s c rip tio n of th e b eta

lacto n e from the condensation of ketene w ith c h lo ra l could be found in

XX

the a v a ila b le l i t e r a t u r e .

The compound was prepared in t h i s la b o ra ­

to ry . D issolve 3 ml, of boron tr i f lu o r id e - e th e r complex in 42 ml, (0,43 mole) fre s h ly d i s t i l l e d c h lo ra l, ab le re a c tio n v e ss e l.

A la rg e t e s t tube i s a s u it­

While cooling in an ic e b a th , bubble in 22 ml,

(0,43 mole) of ketene over a p erio d of s ix hours.

The product i s

steam d i s t i l l e d , giving about 48 g, of th e b e ta -lacto n e ( 59 % y ie ld ) , (Caution*

One batch polymerized v io le n tly a t th e s t a r t o f steam d is ­

tilla tio n , )

The product i s r e d i s t i l l e d under dim inished p ressu re 25 (b ,p , 75^0 , a t 2 ,5 mm, p re ssu re ; n^ 1,4863). Elemental Analysis* C

H

Cl

Found

25,40%

1.55%

56,2%

Theory fo r G4H3CI3

25.32

1.60

56,1

Reflu x in g th e product with d ilu te HCl gives 4 ,4 » 4 -tric h lo ro 3-hydro 3Qrbutyric a cid (m,p. 118-119*0. ),

The rep o rted m elting p oint

fo r t h i s compound i s 118-119*0. ( B e ils te in , GI3C.CH 0 + HgO H2G

H'*' -

3rd supplement, 22),

C1C.CH(Œ)Œ2C02H

CO

Acknowledgment . -

The autho rs a re indebted to the Tennessee Eastman

C orporation and th e Purdue Research Foundation idio financed t h i s work.

X

Summary The d iketene analog of enol a c e ta te has be@a prepared from ,

sev e ra l aldehydes and ketones.

S u ita b le re a c tio n co n d itio n s and ■' S .. •, ' c a ta ly s ts are about th e same a s those employed in th e p re p a ratio n of enol a c e ta te s from ketene and carbonyl compounds,

A study o f th e .

d ik eten e analogs showed them to have a c y c lic s tru c tu re ra th e r th an the expected enol a c e to a c e ta te s tru c tu re . Diketene was found to re a c t v io le n tly with

The s u it­

a b i l i t y of t h i s re a c tio n fo r j e t p ropulsion i s d iscu ssed . The re a c tio n of ketene w iih anhydrous c h lo ra l in th e pre­ sence of BF3 forms 4 .4 .4 -tric h lo ro b u ty ro -b e ta -lacto n e in good y ie ld .

PARTI

:!r

KETBNE MC3NGMER

‘

,•

> *

'.

INTRODUCTION

*-

D iscoveiy and P re p a ra tio n

.

_'

Ketene was f i r s t prepared by Wilsmore in 1907 by pyrolyzing a c e tic anhydride. m a te ria ls.

Since th e n ketene h as been prepared from nomerous

Most methods of p re p a ra tio n involve th e therm al decon^osi-

tio n of compounds containin g th e -OHgCO- group, such as aldehydes, ketones, a c id s , e s te r s , a cid anhydrides and dim eric ketene.

The

scores of p u b lic a tio n s on t h i s su b jec t are not e n tir e ly c o n siste n t among

them selves; ap p aren tly in some in sta n c e s th e therm al decomposi­

tio n i s d e f in ite ly aided by th e presence o f c a ta ly s ts . S everal o th er methods of p rep arin g ketene have been re ­ p o rted ,

The re a c tio n o f GO w ith

a t hig h tem peratures and p res­

sures in th e presence of su ita b le c a ta ly s ts i s rep o rted to give ketene (8 6 ),

Ketene and ketene analogs can be formed from th e a c tio n

o f 00 on a lip h a tic a lco h o ls in th e presence o f su ita b le c a ta ly s ts (ÇD), The p y ro ly sis o f v in y l e s te r s give ketene (8 3 ),

The dehalogenation o f

c e r ta in alnha-halo a c id h a lid e s with zinc forms ketene and ketene analogs (288), The most g e n erally used la b o ra to ry method f o r preparing k e t t l e i s th e p y ro ly sis of acetone or ketene dimer.

The l a t t e r ,

though not g en erally a v a ila b le due t o 1 ,0 ,0 , re g u la tio n s fo rb id d in g i t s shipment, has th e advantage of giving only ketene a s a p y ro ly sis product,

A veiy convenient h o t-fila m en t ap p aratu s has been devised

fo r th e la b o ra to ry p re p a ra tio n o f k eten e (2 2 4 ), tem peratures f o r acetone are 695-705®C,

S u ita b le p y ro ly sie

At th e se tem peratures th e

r a te of decomposition of ketene i s g re a te r th an i t s r a te o f formaticai ( 97)1 th e re fo re a ^ o r t co n tact tim e i s d e s ira b le .

The y ie ld

of k etene approaches 100% as th e f r a c tio n o f acetone decomposed p er pass approaches zero (245), Commercially, ketene i s prepared in la r g e s t q u a n titie s from a c e tic a cid ( l2 7 ) .

Spent a c e tic a c id from th e a c é ty la tio n o f c e llu ­

lo se i s reacted w ith k etene to reg en erate a c e tic anhydride.

The

ketene i s very lik e ly made ty pyrolyzing a p o rtio n o f th e a c e tic a c id . P h y sical P ro p e rtie s The o lder l i t e r a t u r e i s in good agreement on -56® and -134®C, a s th e b o ilin g and fre e z in g p o in ts , re s p e c tiv e ly , o f k e ten e .

Rice and

Greenburg, Wbo took g re a t p ain s to prepare pure k e ten e , re p o rt -41® and "134®G,, re s p e c tiv e ly ( 245 ) ,

I n view of th e f a c t th a t th e c h ie f con­

taminant o f k etene i s ethylene ( b ,p , - 104®Gj m,p, -169,4®0, ) vhich i s d i f f i c u l t to remove from k e ten e , i t i s l i k e ly th a t th e l a t t e r values are th e more c o rre c t. 0 ,9 ,

The d e n sity of liq u id ketene a t -75®C, i s about

I t i s c o lo rle ss in both th e liq u id and gaseous s t a t e s ,

Ketene

has an odor som e^at ak in to a c e tic anhydride, but more pow erful. i s a poison, resem bling phosgene in i t s p h y sio lo g ical a c tio n .

It

I n con­

fin e d t e s t anim als, th e a lv e o la r s tru c tu re and e s p e c ia lly th e c a p il­ l a r i e s were a tta c k e d , causing pulmonary edema and c a p illa ry conges­ tio n

(53),

In t h i s la b o ra to ry no i l l e f f e c t s from accidental exposure

to ketene have been observed; ap p aren tly th e discom fort dosage i s well enough below th e to x ic dosage to cause th e v ic tim to seek b e tte r a i r .

Dry soda lim e in gas masks a ffo rd s p ro te c tio n a g a in st k eten e (5 3 ), Chemical P ro p e rtie s A cétylation w ith ketene. -

In th e v a st m a jo rity o f i t s reac­

tio n s , ketene e f f e c ts th e in tro d u c tio n o f an a c e ty l groiç>.

Most com­

pounds w ith l a b ile hydrogen a t m s a re a c e ty la te d re a d ily , many reac­ tio n s re q u irin g no c a ta ly s t.

Thus a lc o h o ls , phenols, t h i o l s , en o ls of

ketones and aldehydes, a c id s , prim ary and secondary amines are in gen­ e r a l a c e ty la te d .

Some s p e c ific examples o f in te r e s t are;

(GH3)30ai + H2G=G*0- (CH3)3C0Ac (79,163) + H2C=C*0 - GgRjOAc (163) RzS + 2 H2C=C=0

AC'S*Ac 158 )

acetone + EgGC^O

-» CH2*C(0Ac)CH3 ( 123 ) ,

The enol a c e ta te of acetone, isopropenyl a c e ta te (IPA ), i s a compound of growing commercial impoirtance.

I t copolymerizes with

m aleates and o th er monomers to form p l a s t ic s resem bling p o ly a c ry la te s in p h y sica l p ro p e rtie s , but cheaper to manufacture ( l7 9 ) .

As a chemi­

c a l in te rm e d ia te, i t i s one o f th e b e st and most v e r æ t i l e a c e ty la tin g agents a v a ila b le (l27A ). E-COCH + H2G=C=e

R*GG»OAc (228),

Mixed anhydrides can in general be made by t h i s method.

D is­

p ro p o rtio n atio n ta k e s p lace a t d i s t i l l a t i o n te i^ e r a tu r e s , a ffo rd in g a good method of making symmetrical anhydrides (l5 3 ) . Many in o rg an ic a cid s may a lso be a c e ty la te d w ith ketene as; HjPO^ + H2G=C=0 -i' ACOPO3H2 (18) HCN + HaG^QaO

CH2=G(CH)CN g c^C^CT GH2=0(OAc)CN (174,239).

The a c e ty l group can be in tro d u ced in to some compounds by th e use o f F rie d e l c r a f t c a ta ly s ts (226,323),

Ketene combines w ith anhy­

drous AIOI3 to form a yellow complex, s ta b le only a t low tem p eratu res. This condenses with th e arom atic compounds to form methyl a r y l ketones upon h y d ro ly sis: H20*C«0 + AICI3 - fAlCli OHg'GO'Oj ^«^^^{^GlgGHg'GO'GgPj + HGl CH3*G0*G

CH3 *C(0 Ac)iC(Bz)*C 02E t + A c^m m 'G gH ^

Without knowing th e re a c tio n sequence, i t i s im possible to s ta te which of the two p o ssib le isom ers th e enol a c e ta te i s . Ethyl b enzoylacetate was re a cte d w ith ketene using o ther c a ta ly s ts .

The follow ing ta b le summarizes th e re su lts*

Table I ,

A cétylation Products of E thyl B enzoylacetate

C ataly st

C -a ce ty la te d product

tr i - n - b u ty l amine

4% (+ 31%)

p e rc h lo ric a cid (70%)

7

p -toluene su lfo n ic acid

0 (+ 20%)

0 -a c e ty la te d products of EBA* o f EBAA** 0%

31%

76

0

0

20

* EBA = e th y l benzoylacetate ** EBAÂ = e th y l benzoylaceto acetate The enol a c e ta te o f e th y l ben zo y lacetate Ce th y l-b e te -a c e t oxycinnamate) was id e n tif ie d by i t s reacticai w ith two e q u iv alen ts o f phenylhydrazine to form Ph*EHEH«Ac and l,3 -d ip h en y lp y razo lo n e-5 .

The l a t t e r i s rep o rted

to m elt a t 137®C. ( B e ils te in , 24 , 149)$ observed v a lu e , 134-136®C, There i s an e rro r in the l i t e r a t u r e concerning th e m elting p o in t of e th y l-b e ta -acetoxycinnam ate_ Bernhard (Ann, Chem, (L eib ig ’ s ) ,

13

282, 164) re p o rts i t to m elt a t 27-28®G,

He prepared th e compound by-

re a c tin g th e copper s a lt o f e th y l b enzoylacetate w ith a c e ty l c h lo rid e . R epeating h is p re p a ra tio n in t h i s la b o ra to ry gave a product m elting a t 41,5-42®G, id e n tic a l w ith th a t obtained from e th y l benzoylacetate and ketene in the presence of BGIO^, R eaction of e th y l le v u lln a te w ith k eten e. -

In th e absence

o f a c a ta J y s t, th e re i s no re a c tio n between ketene and e th y l le-vulinate a t 120>C.

I n th e presence o f s u lf u r ic , p -to lu en e su lfo n ic and

mixed su lfo n ic a c id s , th e same product described independently bySpence (2 7 l) and Hurd Cl56) i s obtain ed ,

Hurd concluded two products

to be formed in about equal proportions* OHa'GO^GHgGH^GOgEt + H2G=G=0

Cl) GH2=iGCOAc)CH20H2G02 Et and

( 2 ) CH3GC0 Ac)=CHGH2G02Bt He based h is conclusion on th e f a c t t h a t ozonolysis of one mole o f th e product gave 0 ,4 2 mole succinic a c id and 1,16 moles of a c e tic a c id . The other expected products o f o zo n o ly sis, 0,5 mole o f CH^O and 0,5 mole of malonic a c id , were not found. In t h is la b o ra to ry , i t was found th a t th e re a c tio n product o f ketene and e th y l le v u lin a te d id not behave towards phenylhydrazine in th e same manner as o th e r enol a c e ta te s .

That i s , th e phenylhydra­

zone of th e o rig in a l k e to e s te r was not obtained.

The 2 ,4 - d in itr o -

phenylhydrazine of e th y l le v u lin a te i s yellow and m elts a t 100- 101®0 , The re a c tio n product of ketene w ith e th y l le v u lin a te ap p aren tly forms a m ixture of 2 , 4 -d in itro p h e iy lh y d ra zo n e s 5 a compound m elting a t 14 O141®C, was obtained a f t e r s ix r e c r y s t a lliz a tio n s from a b so lu te

e th an o l.

Furtherm ore, a l l o th e r enol a c e ta te s prepared in t h i s

u

work a re in so lu b le in cold 10% NaOH and are f a i r l y s ta b le tow ards t h i s reagent in th e cold.

The re a c tio n product o f e th y l le v u lin a te and

ketene however d is so lv e s ra p id ly in 10% NaOH w ith th e e v o lu tio n of h e a t.

More evidence should be accumulated towards e s ta b lis h in g th e

s tru c tu re of th e supposed enol a c e ta te o f e th y l le v u lin a te . A céty latio n of 2 -a c e tv l thionhene. 2-A cetyl thiophene Gone, H^SO^ Ketene

77 g, (0 ,6 1 mole) ,8 4 g#

27 ml, (0 ,5 8 mole)

The 2 -a c e ty l thiophene and c a ta ly s t were p laced in a 200 ml, re a c to r f i t t e d w ith s t i r r e r , gas in l e t and re flu x condenser.

Main­

ta in in g th e tenç)erature between 70 and 80®G,, ketene was passed in over a period of two hours.

The re a c tio n was somewhat exothermic and

th e ab so rption of k etene f a i r l y com plete.

The product was black,

weighed97,5 g, and had a b itin g odor lik e AcgO.

A fter shakjjig w ith

th re e 25 ml, p o rtio n s of 10% NaOH and washing w ith th re e 25 ml, por­ tio n s of d i s t i l l e d w ater, th e product was d i s t i l l e d a t dim inished p re ssu re , b o ilin g between 68 to 100®G, a t 1,5 mm.

The d i s t i l l a t e was

r e d i s t i l l e d through a 26” Podbdelniak type column.

An 18 g, fra c tio n

(b ,p , 70 to 74®G, a t 1 ,5 ram,) was obtained (n^

1,5472 to 1,5455),

The y ie ld of enol a c e ta te i s 18% based on 2 -a c e ty l thiophene.

The

combined products from sev e ra l ru n s were r e d i s t i l l e d , giving a p u rif ie d 25 product (b ,p , 68-7CPG, a t 1 ,3 mm,^ 1,5469), The product gave ty p ic a l re a c tio n s o f enol a c e ta te s , reducing 2% KMnO^, Br2/()G1 ^ and re a c tin g w ith phenylhydrazine to form th e phenylhydrazone of 2- a c e ty l thiophene and symmetrical a c e ty l phei%rlhydrazine*

15

S ^-G = 0 H2

+ G

"*

___ O-GO-CHa

\-G -G H c Il + GgP^mm.GO'GH) MCfiHg

I

II

Coaçonents I and I I are e a s ily separated because I I i s so lu b le in hot w ater.

A fter r e c r y s ta lliz a tio n o f th e phenylhydrazone from a w ater-

ethanol m ixture, i t m elted a t 94^ 95®G, I i s 96®G, (B e ils te in , 1%, 287),

The rep o rted m eltin g p o in t of

Gr y s ta l l i z a t i o n of th e h o t w ater

soluble p o rtio n gave a product m elting a t 127®C,

The re p o rte d value

fo r I I i s 127-128®C, (B e ils te in , 11, 241 ) , Although c o lo rle s s and p r a c tic a lly o d o rless when fre s h ly d i s t i l l e d under a n itro g e n atmosphere, th e enol a c e ta te becomes yellow on standing, even in w ell closed c o n ta in e rs .

A fter a day o r two, th e

odor o f formaldehyde i s d e te c ta b le and a p o s itiv e t e s t w ith Fuchsin aldehyde reagent i s obtained.

A fter bubbling oxygen through a p o rtio n

of th e enol a c e ta te f o r sev e ra l days c r y s ta ls formed, which a f t e r re ­ c r y s ta lliz a tio n from w ater melted a t 125-126®C, odor resembling benzoic a c id ,

The product had an

2 - Thiophene carboxylic a c id i s re p o rte d

as m elting a t 126,2®G, (B e ils te in , 8 , 289),

The re a c tio n of th e enol

a c e ta te w ith oxygen i s apparently; OAc

Ü

-GO* OAc + Og -» CH gO +

Attempted a c é ty la tio n of triflu o ro a c e to n e . to prepare the conpound GHg=G(0 Ac)GP3 were made.

S everal attem p ts

I t was d e sired to

coaçare t h i s compound w ith i t s acetone analog CHg=G(0 Ac)GH3 from th e

16

standpoint of p o ly m e riz a b ility . Run 1.

triflu o ro a c e to n e

7 g, (0,064 mole)

iso p ro p e iy l a c e ta te

22 ml, ( 0 ,2 mole)

p -to lu en e su lfo n ic a c id

0 ,1 g,

copper a c e ta te

tra c e

These reag en ts were sealed in a C arius tube and heated f o r 19 hours a t 65®C,

The product was separated from th e c a ta ly s t by d i s t i l l i n g in to

a dry ice tra p a t room tem perature under diminished p re ssu re ,

Cta re ­

d i s t i l l a t i o n a t atm ospheric p re ssu re , th e re a c ta n ts were recovered. Run 2 .

triflu o ro a c e to n e

17,6 g, (0 ,1 6 mole)

ketene

23 ml, (0,51 mole)

p -to lu en e su lfo n ic acid

0 ,4 g.

The triflu o ro a c e to n e contain in g th e c a ta ly s t was placed in a small re a c to r f i t t e d w ith a s t i r r e r , gas i n l e t , and a dry ic e cooled re flu x condenser,

Ketene was passed in slowly over a p erio d of th re e hours.

The r# flu x tem perature grad u ally decreased, in d ic a tin g accuaailation of unreacted ketene,

A fter re flu x in g fo r 7 hours, th e re a c ta n ts were

allowed to d i s t i l l in to a dry ic e tr a p .

On warming to room tempera­

tu re th e r e a c t a i t s had d i s t i l l e d com pletely, in d ic a tin g no re a c tio n . From th e acetone a n alo g s, i t was estim ated th a t th e enol a c e ta te of triflu o ro a c e to n e should b o il above 50®C, Run 3.

triflu o ro a c e to n e

17,6 g. (0 ,1 6 mole)

ketene

2 3 ,0 g, (0.54 mole)

The re a c ta n ts were sealed in a C arius tube and allowed to re a c t f o r one month a t room tem perature.

The tube was cooled, opened and th e prod­

u c ts d i s t i l l e d in to a dry ic e tra p under dim inished p re ssu re .

Redis-

17

t i l l a t i o n a t atmospheric p ressu re y ie ld e d a 68% recovery o f t r i f l u o r o ­ a ce t one d i s t i l l i n g between 22,8 to 38®C, and 76% of th e k eten e as i t s dimer b o ilin g 120-127®0, d is tille d ,

A small amount ( 4 ,5 g. ) of t a r remained un­

No dehydroacetic was observed. Apparently triflu o ro a c e to n e i s p e cu la rly r e s i s t a n t to acéty­

la tio n , a c e ta l,

However i t d id re a c t w ith d ik eten e to form th e c y c lic e s t e r^ 0 ,. GH3 *C

II

CF3

which suggests th a t triflu o ro a c e to n e may

f CH3

GH .0 ■'CiO form a d ie s te r more r e a d ily th an an enol a c e ta te .

The re a c tio n of

triflu o ro a c e to n e w ith a c e tic anhydride follow ed by s p l i t t i n g out a c e tic a cid may give th e d e sired enol a c e ta te ; CF3 *00 *CH3 + Ac2Û

GF3 *C(0Ac)2CH3 P yrolysiq^ AcOH + CH2=0 (OAc)CF3 ,

T his procedure p a r a lle l s th e p re p a ra tio n of v in y l a c e ta te from acetyLdehyde and a c e tic anhydride,

and would be w ell worth in v e s tig a tin g .

R eaction of ketene w ith th jo n v l c h lo rid e . -

F o rty -e ig h t ml,

( 1 ,0 mole) of ketene (measured as a liq u id ) was bubbled in to 50 ml, o f p u rifie d SIGI2 (0,67 mole) under re flu x .

An exothermic re a c tio n took

place and th e ketene was completely absorbed.

The product was d is ­

t i l l e d , y ie ld in g 40 ml, b o ilin g 54-57,5®C, a t 745 mm. fumes were evolved.

S u lfu r dioxide

Towards th e end of the d i s t i l l a t i o n th e resid u e

decomposed suddenly, forming a porous in fu s ib le charred m a te ria l.

The

d i s t i l l a t e was r e c t i f i e d through a 18 in ch g la ss packed column, y ie ld ­ in g 1 6 ,2 g, a c e ty l c h lo rid e ( 21 % based on k e te n e ), b o ilin g 49 ® to 50,8®C, a t 752 mm. p o in t of SCCI2 ,

The tem perature th en ro se to 76®C,, th e b o ilin g

T his corresponds t o a recovery of about 25 ml, or

18

50 % o f th e thloB yl c h lo rid e .

On th e b a sis of th e re a c ta n ts n o t recovered and th e a c e ty l c h lo rid e formed; SOCI2 + H2C*G=0 -* CH3 *G0 *G1 ,3 4 mole

1 mole

,21 mole

i t appears th a t two e q u iv alen ts o f ketene have been condensed w ith one of SOCI2 to y ie ld one eq u iv alen t of HGl, which re a cte d w ith more ketene to form a c e ty l c h lo rid e . Condensation of c h lo ra l w ith k e ten e . -

A d e s c rip tio n o f th e

b e ta -la c to n e formed by th e a d d itio n of k eten e to c h lo ra l has not y e t appeared in th e l i t e r a t u r e , so i t was prepared in t h i s laboratory* C hloral (fre s h ly d i s t i l l e d )

42 ml, (0,43 mole)

BP3 *Et20 coD^lex

3 ml,

Ketene

22 ml, (0,43 m ole).

The c h lo ra l and c a ta ly s t were placed in a 100 ml, graduate f i t t e d w ith a gas i n l e t tube.

While cooling in an ic e b a th , k eten e ira.s bubbled in

over a period of 6 hours, giving 59 ml, of product.

On steam d i s t i l l a ­

tio n , 48 g, of the b eta-la c to n e was obtained (59% y ie ld ) ,

The product

was r e d i s t i l l e d under dim inished p re ssu re , d i s t i l l i n g m ostly a t 75®G, and 2 ,5 mm, p re ssu re , n^

1,4863,

Elemental analysis*

Found

Theory f o r G^H302Cl 3

C

25 , 40 %

25,32%

H

1,55

1,60

G1

56,2

56.1

The product has p ro p e rtie s ty p ic a l of b e ta -la c to n e s .

On th e

a d d itio n of a tra c e of s u lfu ric a c id , i t polym erizes exotherm ically to

19

a b r i t t l e s o lid p o ly e s te r.

Eefluxing w ith d ilu te HCl and e x tra c tin g

w ith e th y l a c e ta te gives 4$4> 4^trichloro-3-hydroxybatyric a c id , GGl3*GH- 0 I \ + H2O + GH2-G«0

/ V c c i 3GhCoh)ch2C02H

A fter r e c r y s ta lliz in g from hot benzene, th e product m elts a t 118-U9®G, The re p o rte d value fo r 4 ,4 ,4 -tr i o h lo r o - 3 -hydroxybutyric a c id i s 118119®G. (B e ils te in , 2» 3rd supplement, p . 22), Elemental a n a ly s is o f hydroxy acid ; Found

Theory f o r C4H5O3GI3

C

23,25%

23,18%

H

2 .4 7

2,43

01

50,8

51,3

Because of t h i s g reat and v a rie d a c ti v ity o f b e ta -la c to n e s , b e ta -trich lo ro m eth v l-b e ta -pro p io lacto n e should be considered as a p o ssib le interm ediate when th e trich lo ro m eth y l group i s d e sire d , A word of p recau tio n concerning th e p re p a ra tio n o f b etat r ic h lo r omethyl- b e ta- p r o p io lact one ;

I n one run an exotherm ic poly­

m erization re a c tio n took place a t th e beginning of th e steam d i s t i l l a ­ tio n ste p , r e s u ltin g in th e d ep o sitio n o f a stic k y r e s in on th e c e il­ ing,

In a subsequent ru n , enough NaHG€3 was added to n e u tra liz e th e

BF3 c a ta ly s t p rio r t o steam d i s t i l l a t i o n .

No b e ta -lacto n e was ob­

tained^ only th e h y d ro ly sis product 4 $4$4 -tr i c h l o r o-3-hydr oxybutyric acid .

I t would be w ell to work w ith sm all q u a n titie s (about 0 ,1 mole)

u n til reproducible re a c tio n co n d itio n s are e s ta b ilis e d . Phosgene and k e t ^ e . -

Boese re p o rte d phosgene to re a c t w ith

ketene to form malonyl c h lo rid e (3 9 ),

However, in a p riv a te coramunica-

20

c a tio n to Degerlng August 21, 1949 he s t a t e s th a t poor y ie ld s were ob­ tained*

"Our work was c a rrie d out a t a tem perature below -6C®C,, em­

ploying liq u id ketene and liq u id phosgene in th e absence o f a so lv e n t. Under thqse conditions th e re a c ta n ts condensed to give d a rk , viscous liq u id s from which by h y d ro ly sis we were a b le to is o la te malonic a c id in y ie ld s no g re a te r th a n fiv e per cen t.

We were unable to fin d

solv en ts or c a ta ly s ts t h a t would advantageously a f f e c t the course o f th e condensation.

No products o f sig n ific a n c e were obtained from th e

vapor phase re a c tio n s e iik e r in th e presence or absence o f c a ta ly s ts ," A number of in v e s tig a to rs (Tonçikins C309 ) , Spence (2 7 0 ), DeHoff (80A) ) in t h i s la b o ra to ry have conducted numerous experim ents attem p tin g to condense ketene w ith phosgene.

A ll r e s u l t s have been n e g a tiv e .

Thermodynamic co n sid eratio n s w ith a v a ila b le d a ta in d ic a te th a t th e re a c tio n QH2*G0 + C1«C0-C1

G1*C0*GH2*G0*C1

i s thermodynamically f e a s ib le .

The enç>irical methods o f Anderson,

Beyer and Watson (N atio n al Petroleum News,

R476 (1944)) were used

to obtain th e follow ing thermodynamic v alu es on th e reaction* HO

8®

a

b(xlO^)

C(xlO^)

Ketene

-1 5 .9

60,4

6,54

2,91

7,03

Phosgene

-4 8 ,0

70,8

10,74

6,00

2 6 .3 2

Malonyl ch lo rid e

rêQjJk 96,5

30.71

- 4 .3 2

For in d ic a te d re a c tio n

- 25,5 -3 4 ,7

21,80

-37,67

Units*

1.55

H® = kilogram calo rieq /g ,-m o le fo r the id e a l gaseous s ta te a t 25®G, S® = calories/(g,-m ole)(® K ) in th e id e a l gaseous s ta te a t 2$®G,

21

a , b and c are con stan ts fo r c a lc u la tin g th e h e at in c a l o r i e ^ g.-m ole req u ired to warm one mole in th e id e a l gaseous s ta te from one te n ç e ra tu re to another according to th e equation* , -3 -6 2. (a + 10 bT + 10 cT )dT

- Haçg = I

The equilibrium co nstant i s given by th e re la tio n sh ip s

-R*lnK -

=-| + (

a-Ig)-

a*lnT - |

M! - | oT*

I n the id ea l gaseous sta te at 25®G, for the above reaction Iji =“25,500 calories/g ,-m o le Ig = -34*7 calorie s/C g,-mole )(®K) a = 1,55 b = 21,80 X 10”^ c = -37,67 X 10 ^ T » 298®K G® » standard fr e e energy change a t T®K R = gas law constant = 1,987 cal,/m ole-degree G® 25.500 -R IhK = T « " 298 + 1,55-1-34*7) - 1,55 In 298 - “

X

,0218 x 298 -

^ ( 298 )^

= -85,5 + 36,25 - 8,84 - 3.24 + 1,67 = -59,66 "

^ ” 2,303^x^^987 “ ^ K = 10^^ and G® = -5 9.6 6 x 298 = -17,800 c a l.

These co n sid e ra tio n s in d ic a te th a t th e re a c tio n should go to completeness i f i t can be made to ta k e p la c e .

22

An estim ate as to th e r e l i a b i l i t y o f th ese thermodynamic v a lu es i s afforded ty comparing th e c a lc u la te d and re p o rte d values where possibles H eats of form ation in c a l,/g ,-m o le C alcu lated

Reported

Ketene

-1 5 .9

-14.68 C244)

Phosgene

-4 8 ,0

-5 3 .3

Thus i t appears th a t the fo rm a tim of malonyl c h lo rid e from ketene and phosgene i s not thermodynamicaliy im possible, Ketene p lu s phosgene. AlCl-a c a ta ly s t. -

S ix grams ( 0 ,45 mole)

of fre s h ly sublimed AICI3 were placed i n a sm all re a c to r f i t t e d w ith a s t i r r e r , dry ic e cooled r e flu x condenser and gas i n l e t ,

IVhile s t i r r i n g ,

15 g, ( 0,15 mole) phosgene was d i s t i l l e d in , using P2O5 d rie d % a s a c a r r ie r gas.

The AIOI3 dissolved forming a yellow s o lu tio n .

About

0 ,1 mole ketene was then passed in , producing a two phased system.

The in c re ase in r e f lu x ra te in d ic a te d an exothermic re a c tio n .

P a rt of

the phosgene was then allowed to d i s t i l l , leav in g a viscous mass.

De­

composing the product w ith ( l ) ethanol and ( 2 ) w ater gave no d e te c ta b le e th y l malonate or malonic a c id , re s p e c tiv e ly .

The l a t t e r n&s te s te d f o r

by evaporating a drop o f the w ater e x tra c t on a microscope s lid e and examining th e c ry s ta ls under a pétrographie microscope w ith p o larized lig h t.

Only is o tro p ic c ry s ta ls were p re s e n t,

Malonic acid i s aniso­

tr o p ic . Repeating th e experiment using CCI4 in s te a d o f phosgene gave sim ila r r e s u l t s , in d ic a tin g th a t phosgene was not In corporated in th e products formed,

Ketene reacted w ith AICI3 to form a yellow s o lid a t

23

ic e teaç}eratures,

Hurd has a lso observed t h i s a d d itio n product 1146),

Ketene p lu s phosgene. SO3 so lv e n t. SO2 so lu tio n of phosgene.

Ketene was added to a

A fter re flu x in g a sh o rt p e rio d , th e reac­

ta n ts were allowed to warm to room tem perature, fo u l sm elling t a r remained.

A sm all amount of

No c h lo rid e io n was found in w ater b o iled

f i r s t w ith the t a r and then a c id ifie d w ith HNO3 , ta in e d from th e re a c tio n o f ^ 2 w ith k eten e.

The same t a r was ob­

24

PART I I KETENE DIMEE INTRODUCTION Discovery__and Preparaticai Ketene d in e r was discovered by Chick and Wilsmore s h o rtly a f te r t h e i r discovery o f th e monomer (5 9 ).

They prepared i t by se a l­

ing ketene in a tube and allow ing i t to warm to room tem perature. A ll p re p a ratio n s of diketene involve d im erizatio n o f th e monomer.

Many in e r t so lv en ts and some c a ta ly s ts have been u sed , but

no p rep aratio n i s more simple or d ire c t than d isso lv in g th e monomer in th e dimer while removing th e heat o f d im erizatio n ( l2 7 ) .

Acetone

i s recommended as a solvent ^ e n d ik eten e i s not a v a ila b le . P hysical P ro p e rtie s and S tru c tu re Freshly d i s t i l l e d d ik eten e b o ils a t 127,4®C, a t 760 mm, o r 43®C, a t 28 mm. and m elts a t -6.5®C.t u l l 1,0897,

1,4379 ( 52,59).

I t i s c o lo rle ss when f i r s t d i s t i l l e d , but becomes yellow to red in color on standing a short time a t room tem perature.

The pow erful odor

and lachrom atory e f f e c ts o f diketene makes exposure to i t even more unbearable th a n k e te n e , and because o f i t s lower vapor p re ssu re , an a c c id e n ta l s p i l l ren d ers a p lace u n in h a b ita b le fo r a lo n g er p erio d , A s p i l l on one’ s person re q u ire s f a s t a c tio n fo r th e discom fort quickly reduces one to fre n z ie d , disorganized a c ti v i ty .

The vapors ren d er one

b lin d with an extreme burning sen satio n in th e eyes and chokes o ff breath in g .

Remove contam inated c lo th in g immediately and wash o ff con­

tam inated skin a re a s w ith an abundance o f w ater and d ilu te ammonium hydroxide so lu tio n .

For going in to contam inated a re a s , a t i g h t f i t t i n g

25

gas mask with soda lime canister affords protection.

No la s tin g e ffe c t

from accidental exposure to diketene has been observed in t h is labors^ tory, but i t has in f lic te d moments of extreme discom fort. The structure o f diketene has been a point o f contention ever since i t s discovery (6 ,1 4 ,1 6 ,2 8 ,5 2 ,2 4 6 ,3 0 7 ,3 1 9 ).

Of the proposed struc­

tu res, the most seriou sly considered are* CH3*C0 *CH*=C*0

H2C-GO OG-GH2

H2CKI-O 1 1 HaC-GO

cyclobutandione

v i i y l acet o- beta- la c t one

I

a cety l ketene I

{

II

III

GHj^G = CH I » o-co beta- crot onçüact one IV Chemical evidence for structural proof i s not r e lia b le because of th e extreme a c t iv it y of diketene and the lack of knowledge concerning reaction sequences.

Unknown intermediates of transient existen ce may

give r is e to products giving l i t t l e clue as to the structure of the origin al reactant. Recent electron d iffra ctio n studies e sta b lii^ unequivocally the beta-lactone structure as being present ( 14)$ however i t does not f i x the p osition of the double bond as I I I or IV,

Furthermore, th ese

data do not preclude the presence of other isomeric structures.

M iller

and Kook determined the infrared absorption of diketene vapor at vari­ ous temperatures (204),

They observed changes which they f e e l are too

26

marked to be a ttr ib u te d e n tir e ly to changes in th e p(|nilation o f v ib ra ­ t io n a l and r o ta tio n a l le v e ls and th a t th e r e s u lt s in d ic a te an e q u ili­ brium between two or more forms a t room tem perature#

Thus th e com­

p le te understanding of th e s tru c tu re of d ik eten e remains a problem f o r the fu tu re to so lv e, w ith v in y l a ce t o-b e ta -la c t one being th e most favored a ssig m e n t a t th e p re se n t. Chemical P ro p e rtie s A cetoacetylation w ith d ik eten e. -

Regarding d ik eten e a s

a c e ty l ketene, i t s re a c tio n s la rg e ly p a r a lle l those of k eten e ( 39 ) . Thus confounds acetylated with ketene are usually acetoacetylated with diketene.

Alcohols react to give acetoacetates (34)*

CH3*G0*CH=G=0 + ROH -* CH3*C0*CH2*C0*0R This re a c tio n has placed e th y l a c e to a c e ta te among th e commercially im portant chemicals and completely outmodes th e a ld o l condensation method of p re p a ra tio n . Ammonia and amines react with diketene to y ie ld acetoacetamides (195).

A cetoacetanilide fin d s extensive use in the dye industry

for preparing Hansa yellow s (3 9 ). CH3 " 0 O.GH=C=O + CgPsKHj

ca 3 .GO.GH2 .GO.rn.C 6R5

Many a ce to a ce ty l compounds can be cy clize d by v ir tu e of th e e n o liz ab le beta carbonyl group.

Thus a c e to a c e ta n ilid e may be dehydrated w ith

s u lfu ric a cid to form 4 ^ m e th y lc a ro sty ril ( 39 )% . m X \/^ G O

/ CH, HO

27

In an analogous m nner tiie a ce t o acetate s of u re a s , hydrazines and phenols may be dehydrated to 4-m e th y lu ra o ils, methyl pyrazolones, and 4 -m ethyl hydroxy coumerins re s p e c tiv e ly (3 9 ).

The arom atic

nucleus may be a c e to a c e ty la te d in th e presence of F rie d e l-C ra ft c a ta ly s ts to form arom atic l,3 -d ik e to n e s .

With hydrogen h a lid e s ,

a ce to a c e ty l h a lid e s a re formed (44*159)» GH3.G0«CH*G=0 + HZ

GH3 .CO.CH2 -CO.Gl.

alo h a. beta-U nsaturated k eto n es. -

Diketene condenses w ith

aldehydes and ketones to form a lp h a . b e ta -u n satu rated ketones (3 1 ). This re a c tio n apparently p a r a lle l s th e form ation of b e ta -la c to n e s between ketene and carboqyl compounds: GH3.G0.GH=G=0 + HiRgC^O ^

GH3.CO.OH-GO

CH3.C0.GH*CRiR2 + GO2

R1R2G - O a b e ta -la c t one I n no case has th e in term ed iate b e ta -lacto n e been iso la ted ^ ap p aren tly i t decarboxylates too re a d ily , forming th e a lp h a , b e ta -u n satu rated ketone. 6-Methyl-1 .3 - dioxa-5-cyclohexene-4- one d eriv a tiv es. -

Di­

ketene adds to Carbonyl compounds in the presence of acid ca ta ly sts to form a c y c lic h a lf e ste r , h a lf a c e ta l.

The reaction may be related to

the D iels-Alder type reactions as illu s tr a te d by the equation: CH3*C

+

I GH

■^00

GR1R2

II 0

GH3.G

U HC

GR1R2

I ^0 CO

This i s a h ith e r to unreported re a c tio n .

Much of t h i s t h e s i s

i s concerned w ith th e p re p a ratio n and s tr u c tu r a l determ ination of

28

compounds of t h i s ty p e having v ario u s

and Ra groups.

M iscellaneous re a c tio n o f d ik eten e. -

D iketene r e a c ts w ith

halogens to form gamma-h a lo a c e ty l h a lid e s I 149 ): GH3.C0*CH=G=0 + Cla

ClGHa-GO.CHg.GO.Gl

Hydrogenation y ie ld s b e ta-h u ty ro lacto n e as w ell as b u ty ric a c id Cl72), CHjjC-C t 1 + Ha RaC - C O

CHj-GH^O I 1

CH3CH2CH2C0aH

HaC — GO

Bromination with ît-bromosuccinimide ( Z ieg le r* s re a g en t) a tta c k s th e a lth a p o sitio n (2 8 )s H aC -G O

I ^ N B r + H aC -G O

CHa:G - 0

I

C H a -.C -O

I

H a G -C O

1 )

H aC -G O

+

Br*CH*CO

I ' i m H a G -G O

The alp h a-bromo d e riv a tiv e was not is o la te d as such, but re a cte d with ethanol to give e th y l- ( a lp h a-brom oaoetoacetate).

This re a c tio n con­

s t i t u t e s chemical evidence fo r the v in y l a c e to -b eta la cto n e s tru c tu re of diketene as Ziegler* s reagent i s s p e c ific in brom inating th e a l l y l i c p o s itio n .

MPEmiEHTAL P rep a ra tio n of diketene and general experim ental procedures. • The re sid u es l e f t a f t e r th e d i s t i l l a t i o n of ketene monomer were accu­ m ulated, and worked up fo r th e recovery of aceto n e, diketene and de­ h y d ro acetic a cid as follow s:

D i s ti lla t io n a t atmospheric p ressu re

29

through a 15 inch V igreux column using steam h eat g iv es a 63^ recovery o f acetone.

D i s t i l l a t i o n i s continued a t 20 to 30 mm. p re ssu re w ith a

w ater a s p ir a to r , y ie ld in g 23^ crude d ik eten e and about 4 ^ more acetone in th e dry ic e tr a p . dehydroacetic a c id . tio n s ,

The resid u e (about 7^) i s saved f o r recovery o f No CO^ ev o lu tio n was d e tec te d in th e se d i s t i l l a ­

T his observation in d ic a te s th a t e ith e r ( l ) acetone d o e sn 't form

a re a d ily decarboxylated b eta-la c to n e on long standing w ith diketene (a s aldehydes do), or ( 2 ) th e b e ta -la c t one i s s ta b le tow ards decarboxy­ la tio n under th e co n d itio n s employed. The crude diketen e i s r e c tif i e d through a fiv e -f o o t g la s s packed column, y ie ld in g a t o t a l o f about 16^ (o f o rig in a l re sid u e) of p u rif ie d d ik eten e, b o ilin g in th e v ic in ity of 43 ®0 , a t 28 mm, p res­ sure,

Thus a re p re se n ta tiv e batch d i s t i l l e d between 42 ®C, a t 33 mm.

and 43 . 2^G. a t 29 mm,,

1,4333 to 1,4357,

Most of th e d ik eten e used

i n t h i s work was obtained in t h i s manner, the tra c e im p u ritie s probably being a c e tic a c id and a c e tic anhydride. P urer diketene was made fo r some experim ents by dim erizing p u rifie d ketene monomer.

The monomer i s allowed to v o l a t i l i z e ^o w ly

and passed in to about 100 ml, o f d ik eten e through a f r i t t e d g la ss d isp e rsio n d isk .

The slow v o la tiliz a tio n o f ketene i s obtained ty

p lacin g th e ketene re c e p ta c le (a twelve inch t e s t tube w ith a 19/38 in te r jo in t) in a s ilv e re d one-quart Dewar f la s k . g a s - t i ^ t and h e ld to g e th e r w ith sp rin g s. be dimerizW overnight i n t h i s manner,

The jo i n t s must be

About ICXD ml, o f k eten e can

Ketene i s re a d ily absorbed,

and th e mixture warms s lig h tly from th e evolved heat o f d im e riz a tio n . The re a c tio n m ixture ta k e s on a deep wine c o lo r, in d ic a tin g sid e re a c -

30

tic a is,

D i s tilla tio n of the product from a C laisen f la s k a t about 28 mm,

p ressu re gives s u b s ta n tia lly pure d ik eten e in 75 to 80^ y ie ld .

In a

ty p ic a l ru n , a 77^ y ie ld o f diketene was obtained d i s t i l l i n g between 25 37®C, a t 23 mm. and 38®C, a t 22 mm.j n^ 1,4348* The re s id u a l t a r was saved fo r recovery of dehydroacetic a c id . The general procedure used f o r re a c tin g diketene w ith car­ bonyl compounds was to add dropwise an equimolar m ixture o f th e two re a c ta n ts to an in e r t solvent co n tain in g th e c a ta ly s t, a t tem peratures u su a lly below 1(XPG,

In e a rly experim ents a s t i r r e r was u sed , but i t

was found th a t an Erlenmeyer fla s k f i t t e d with a re flu x condenser sur­ mounted by a dropping fu n n e l, and heated on a steam plate gave eq u ally good r e s u lts in most in s ta n c e s.

D eviations from t h i s g en eral procedure

are given in th e in d iv id u a l exasples c ite d . The re a c tio n products were u su a lly d i s t i l l e d a t dim inished p ressu re from a small C la ise n , using th e same procedures and apparatus described in P a rt I , R eaction of diketene and a ceto n e.-

In many o f i t s re a c tio n s

diketene behaves as a s u b s titu te d ketene^ where ketene gives a c e ta te s , diketene y ie ld s a c e to a c e ta te s,

Ry analogy, diketene should form enol

a c e to a c e ta te 8 w ith th e aldehydes and ketones th a t form enol a c e ta te s w ith ketene,

A search of th e l i t e r a t u r e d isclo se d only one such com­

pound reported (215):

In attem pting to re a c t ketene w ith o le fin s in

the presence of ZnClg, Naylor is o la te d a product 25

a t ,03 mm,, nj)

1,4604,

b ,p , 4 ^ C ,

He e sta b lish e d th a t th e compound was a reac­

tio n product of diketene and acetone (from th e g en erato r) and postu­ la te d i t to be the enol a c e to a ce ta te o f acetone:

31

OH3 *CO*CH»C»0 + CH3 .CO.CH3 -» GH3 "C0 -CH2 -CO.0C(GH3)=CH% In t h i s la b o ra to ry co n d itio n s were e sta b lis h e d fo r prep arin g th e diketene-acetone a d d itio n product in good y ie ld s : Acetone

15 ml.

Diketene

7 ,7 ml, ( 0 ,1 mole)

p-Toluene su lfo n ic a c id

0 ,1 g.

The acetone and c a ta ly s t a re heated to re flu x i n a 125 ml. Erlenmeyer f la s k f i t t e d w ith a re flu x condenser.

The d ik eten e i s th en

added dropwise over a perio d of te n minutes and re flu x in g continued fo r fo u r hours.

The product i s th en d i s t i l l e d tmder dim inished p ressu re

frcma a small C laisen f la s k , giving a 90^ y ie ld o f crude product b o il­ ing between 52® and 72®G, a t 1.5 mm.

F u rth e r p u r if ic a tio n of th e prod­

u c t by d i s t i l l a t i o n may be obtain ed , but th e method i s lim ite d Ty appreciable decomposition of th e product in to dehydroacetic a cid and acetone a t high re f lu x r a ti o s .

The decom position i s a p p aren tly c ata ­

lyzed by an unknown fa c to r because th e amount o f decomposition on re ­ d i s t i l l i n g d if f e r e n t batches v a rie d from 1 €X^ in one in sta n ce to very l i t t l e in o th e rs.

T his aspect was not in v e stig a te d e x te n siv e ly , but i t

was found th a t th e compound was s ta b le in th e presence o f sodium a c e ta te and tr i - n - b u ty l amine in re flu x in g acetone. F u rth er p u r if ic a tio n i s b e st obtained by rep eated p a r t i a l r e c r y s ta lliz a tio n o f th e product or r e c r y s ta lliz a tio n from e th y l e th e r. By th e l a t t e r method, the product i s d isso lv ed in an equal volume o f e th y l e th e r.

While s t i r r i n g , th e s o lu tio n i s cooled g rad u ally to

-40®C, by dropping sm all p o rtio n s o f dry ic e in to a surrounding acetone bath.

C ry sta ls sep a ra te on cooling.

These are f i l t e r e d o ff with

32

su ctio n in a p re-cooled Buchner fu n n el.

A fter washing once w ith cold

e th e r (cooled to about -ACPC,) and sucked d ry , th e funnel and c o n ten ts a re placed in vacuum d e sic c a to r.

The product i s allowed to m elt under

a p ressu re of 2 mm, and c o lle c te d in a beaker in which th e funnel i s placed.

The y ie ld per r e c r y s t a lliz a tio n i s about 67^,

so lu tio n i s acounrulated fo r rep ro cessin g .

The e th e r

The m elting p o in t of th e

product may be used as a c r i t e r i a of p u rity .

The b est product ob­

ta in e d by repeated r e c r y s ta lliz a tio n (th re e tim es) to constant m elting p o in t, melted a t 9 *4®C, Elemental analyses* C

H

T h eo retical fo r

59,1/^

7,04^

Found

59.3

7,02

A number of c a ta ly s ts were found e ffe c tiv e to varying d e ^ e e s in th e re a c tio n of acetone w ith d ik eten e.

All th e a c id s t r i e d , in clu d ­

ing Lewis acids as AICI3 , BF3 , ZïÙlz aud SnGl^ gave p o s itiv e r e s u lt s . Some basic c a ta ly s ts were a lso e ffe c tiv e s quinoline and 2 ,6 - lu tid in e ,

p y rid in e , q u in o lin e , iso ­

Stronger b a s is a s m e ta llic sodium, sodium

a c e ta te and tri-n -p ro p y l amine however gave only dehydroacetic a c id , Tribenzylamine produced no re a c tio n . R eaction of diketene w ith chloroacetone. D iketene

7 ,7 ml. ( 0 ,1 mole)

Ohloroacetone

8 ,0 ml, ( 0 ,1 mole)

Dioman

10 ml.

Cone,

3 drops The dioxan and s u lfu ric a c id are placed in a 125 ml,

Erlenmeyer f la s k f i t t e d w ith a re flu x condenser.

While h eatin g on a

33

steam plate, th e equimolar mixture of d ik eten e and ketone i s added over a p erio d of about 15 m inutes.

A fter h e a tin g 15 minutes more, th e re ­

a c tio n product i s d i s t i l l e d a t dim inished p ressu re y ie ld in g 1 0 ,8 g. o f crude product b o ilin g between 79-99^0, a t 1 mm, p re ssu re ; y ie ld 61^ as C7 H9O3C I, 21®G,

The product s o l id if i e s on co o lin g , rem elting a t about

On r e d i s t i l l a t i o n , the bulk d i s t i l l s between 84-89®C. a t 1 mm.

F u rth er p u rif ic a tio n by re c r y s ta lliz in g from e th e r y ie ld s a product m elting 28 to 29®G, a f t e r two r e c r y s ta lliz a tio n s , follow ing th e pro­ cedure described under th e acetone analog, Elemental analysis* C

H

Cl 20,2%

Theory fo r O7H9Û3GI

4 7.6^

5.1^

Found

47 ,1

5.29

R eaction of diketen e w ith trlflu o ro a c e to n e . Diketene

17,5 g, ( 0 ,2 1 mole)

T rifluoroacetone

1 2 ,0 g, ( 0 ,1 1 mole)

p-Toluene su lfo n ic a c id

0 ,2 g,

Dioxan

5 ,0 ml.

The re a c ta n ts are introduced in to a cooled C arius tube in order*

( l ) th e dioxan so lu tio n of p -to lu en e su lfo n ic a c id , ( 2 ) th e

mixture of diketene and triflu o ro a c e to n e .

The tube i s s e a le d , th e

re a c ta n ts mixed and h eated to 75®G, fo r e ig h t hours.

A fter co o lin g ,

th e tube i s opened and th e contents d i s t i l l e d under dim inished p res­ sure,

About 17 g, o f product i s obtained (b ,p , 42-52®C, a t 2 mm,,

8€^ based on triflu o ro a c e to n e ).

The product was r e d i s t i l l e d and th e

middle p o rtio n (m ,p, 22,5 to 23®C,) subm itted fo r a n a ly s is .

34

Elem ental a n a ly sis: G

H

Theory fo r G7H7 Û3F3

42.9%

3.5%

Found

4 3 .2

3.77

R eaction of diketen e and acetaldehyde. -

F 29.1%

In prep arin g th e

d ik e te ne-aoetaldehyde re a c tio n p ro d u ct, i t was found advantageous to use paraldehyde.

The same product was obtained using monomeric

acetaldehyde, but in lower y ie ld s . Paraldehyde

5.2 g, (0.118 mole)

D iketene

10 g, ( 0 . I I 9

Dioxan

4 ml*

Concentrated H^SO^

3 drops.

The s u lfu ric acid i s d isso lv ed

mole)

in th e dioxan.

While main­

ta in in g t h i s so lu tio n a t about 8CPC,, th e equimolar mixture of p a ra l­ dehyde and diketene i s added from a dropping funnel over a p erio d of about one-half hour.

The tem perature i s m aintained f o r about te n

hours or u n t i l th e odor of diketene and p arald eiy d e cannot be d etec te d . D is tilla tio n a t dim inished pressu re y ie ld s about 8,5 g. ( 56 % as C^HgO^) d i s t i l l i n g between 64^ 0 . and 75*^G, a t 2 ,5 mm. pressu re (n^

1,4627 to

1 . 4645 ) .

R e c tific a tio n through a 24 inch ro ta ry co n cen tric tube column y ield ed a product d i s t i l l i n g between 70,8®C, to 71,3®C, a t 3 mm, pressure (n^

1.4659).

Elemental a n a ly sis: G

H

T h e o re tic al f o r

56,22%

6 , 30 %

Found

56,77

6,30

35

R eaction o f diketen e w ith c h lo ra l, C hloral

29.5 g, Co,2 mole)

D iketene

1 6 ,8

g, Co,2 mole)

Dioxan

5 ml.

Cone, H^SO^

6 drops

Dioxan containing th e c a ta ly s t i s placed in a sm all re a c to r f i t t e d with a s t i r r e r , w ater cooled condenser and a dropping ftinnel, While m aintaining th e tem perature o f the re a c tio n fla s k between 94^ 98®C, with an o i l b a th , th e equimolar m ixture of fre s h ly d i s t i l l e d

c h lo ra l and diketene i s added over a p erio d o f about two h o u rs. ing i s continued f o r about one hour more.

Heat­

D is til la ti o n a t dim inished

pressure y ie ld s about 27 g, (58% a s C5H5Û3CI3 ) b o ilin g in th e v ic in i ty of 127®G, a t 4 mm, p re ssu re .

The d i s t i l l a t e s o l id if ie s .

R e c ry s ta lli­

z a tio n from 60-70°G, petroleum e th er g iv es g ran u lar white c ry s ta ls m elting 96-97*^0,

A fter being siblim ed th re e tim es a t one to two mm,

p re ssu re , i t m elts a t 97.5-98®C, Elemental analysis* 0

H

Cl 46,00%

Theory fo r C6H5O3GI3

31,10%

2,16%

Found

31.05

2,22

Other carbonyl compounds re a cte d w ith diketene. -

A number

of other aldehydes and ketones were re a c te d w ith d ik e te n e, but the re a c tio n products have not been p u rif ie d as in th e above in s ta n c e s. Following i s a ta b u la tio n o f the r e s u lts obtained*

36

Table H ,

M iscellaneous Carbonyl

Compounds Reacted w ith Diketene B o ilin g range of main product

C a ta ly s t

Confound

Methyl e th y l ketone

HaSO^

Y ield

around 97,2^0, a t 7 mm.

33^(as O4H12O3 )

82-84®C, a t 2 mm.

16^(as CioHijOj 27 ^tas CaHi^Oj)

Methyl isobutylketone Propionaldéhyde

HaSO^

72-8C®C, a t 4 mm.

Phenylacet aldehyde

H2 SO4

124-13PC , a t 3 mm.

69% ( l )

In gen eral, th ese products had p ro p e rtie s s im ila r to those o f the carbonyl compound-diketene a d d itio n products discu ssed in more d e ta il.

With pheryl a c e t aldehyde however th e re a c tio n ta k e s a d if ­

fe re n t course.

The re a c tio n was accoBç>anied by a copious ev o lu tio n

of CO2 , suggesting th e form ation o f an alp h a, b eta un sa tu ra te d ketones CH3*G0*CH*C*0 + GgH5*CH2*CH0

GaH^'GE^.CH-'O

I ! GH3 .GO. GH-CO -* GgHjg'GE^*GE*CH.GOeCHa + GO^ 5-p h en y l- 3- penten- 2- one

I % e product d i s t i l l e d a t 124-13P C , a t 3 mm, p ressu re I t s sendcarbazone m elts a t 241®G,

1,5117),

No d e sc rip tio n o f t h i s compound

could be found in th e a v a ila b le l i t e r a t u r e .

I t was e s ta b lis h e d how­

ever th a t th e compound had not isom erized to 5- phenyl- 4 -p e n te n - 2 -one which b o ils a t 150^0, a t 15 mm., and whose semicarbazone m elts a t 160»C. ( J . Chgm. S o s., 1 ^ , 2735 ).

37

In a ZiClz catalyzed re a c tio n o f d ik eten e and butyraldéhyde, two re a c tio n s were observed to tak e p lace sim ultaneously, y ie ld in g 45% of th e alp h a, b eta u n satu rated ketone b o ilin g 27 to 39^C, a t 3 mm, and 14% of th e d ik e te n e-butyraldéhyde a d d itio n compound b o ilin g 75-81^0, a t 3 mm.

The former was id e n tif ie d as tr a n s - b u ty lid en e acetone whose

semicarbazone m elts a t 124®C, ( J . Chem. Soc, . 1930. ^ 5 ) , L i t t l e , i f a iy , re a c tio n was obtained between d ik eten e and th e follow ing confounds in the presence o f c a ta ly tic q u a n titie s o f Cl) e th y l form ate, (2 ) d ie th y l carbonate, and (3 ) p ro p io n itrile . Reactions and s tr u c tu r a l p roof of diketene a d d itio n products of aldehydes and ketones. -

The a cid cata ly z ed carbonyl compound-

diketene a d d itio n compounds in g en eral have th e follow ing chemical p ro p e rtie s: Acid hydro ly sis On a cid h y d ro ly sis acetone, GOg and th e o rig in a l carbonyl compound i s formed.

This re a c tio n was studied most ex ten siv e ly in th e

case of th e acetaldehyde d e riv a tiv e using 50% H^SO^, per cent of the th e o r e tic a l GOg was obtained.

N inety-eight

Assuming th e c y c lic

h a lf e s te r h a lf a c e ta l s tru c tu re , th e h y d ro ly sis re a c tio n i s GEjf/ ^GH*GH3 + H^O n 1

CH3*C0*CH2*G0*Π+ GH3.GHO.

A cetoacetic a cid decarboxylate s re a d ily to acetone and CO^,

A cetalde­

hyde was id e n tifie d q u a lita tiv e ly in th e presence o f acetone by n»ans of th e methone I 5,5 -d im e th y l-l,3 -cyclohexandione) d e riv a tiv e , e th y li-

38

dene dimethone, m elting a t 177-178**G,

T his conç>oimd i s rep o rted a s

m elting a t 174®C, ( B e ils te in , 17, 509, o f. a lso Walker, '*Formaldehyde,” pp. 263-266),

Making an a u th e n tic sample according to th e reported

procedure gave a product m elting 177-178*’C ,, id e n tic a l w ith the above compound. A lkaline h y d ro ly sis A lkaline h y d ro ly sis ap p aren tly forms the same i n i t i a l prod­ u c ts a s a cid h y d ro ly sis, but gives r is e to secondary a l k a l i catalyzed condensation products in th e case o f th e aldehyde d e riv a tiv e s .

On

acid ific atic a a CO^ i s evolved, Bromination Bromine i s ra p id ly absorbed by these compounds w ith th e e v o lu tio n of HBr,

The monobromo d e riv a tiv e of th e acetone-diketene

compound was prepared in th e follow ing manner* P yridine

8 ml. 10 ,1 mole)

Bromine

5*5 ml, (0 ,1 mole)

Chloroform

10 ml,

Acetone-diketene ccaqjound

14*2 g. (,0,1 mole)

P yridine i s disso lv ed in th e chloroform and bromine added slowly to th e m ixture.

P yridine and bromine re a c t exotherraically to

form a red s a l t which i s soluble in chloroform .

The acetone-diketene

coHç>ound i s then added slow ly, r e s u ltin g in a second exothermic reac­ tio n and th e p r e c ip ita tio n o f a s a l t , presumably p y rid in e hydrobromide. The re a c tio n product i s washed with sev e ra l p o rtio n s o f w ater, which d isso lv e s the s a l t , le av in g a chloroform so lu tio n o f th e p roduct.

On

d i s t i l l i n g under dim inished p re ssu re , 16,3 g. of product was obtained b o ilin g 83,5 to 93®C, a t 1,5 mm,, corresponding to a 74% y ie ld of

39

The d i s t i l l a t e s o lid if ie s on cooling and may be r e c r y s ta l­ liz e d from a w ater-ethanol m ixture, but th e b e st p ro d u ct, obtained by subliming a t 2 mm, p re ssu re , melted a t 44 to 45 , 2®C, C l), Elemental a n a ly s is : C

H

Br

Theory f o r G^H^OjBr

38.0%

4.10%

36,8%

Found

38,2

4 .1 2

36,5

The bromine in t h i s compound i s not very re a c tiv e , suggesting the p o s s ib ility of th e v in y l s tru c tu re (C:C*Br),

Thus re flu x in g w ith

a lco h o lic s ilv e r n i t r a t e gives no p r e c ip ita te of s ilv e r bromide. Continued re flu x in g a f t e r th e a d d itio n o f a tra c e o f s u lf u r ic acid a lso gives no p r e c ip ita te ,

Basic substances however d is ru p t th e

molecule giving r i s e to th e bromide io n .

The compound d isso lv e s in

5% NaCH on h eatin g .

A c id ific a tio n w ith n i t r i c a cid causes th e evolu­

tio n of a gas ICOg),

A ddition of A^Oj now gives a copious p re c ip i­

ta te of AgBr,

R efluxing the bromine compound with d ilu te s u lf u r ic

a cid produces a v i l e lachrom ator Cbromoacetone) ,

The follow ing s tru c ­

tu re s and re a c tio n s agree w ith th e above observations* GH3 C C. CH3 C 0 II I CH3 + Py + Brz -* u ^ 0^3 + PyHBr CH yO BrC^ ^0 ^00 GO /Ox ,GH3 CE3 C II I CH3 + EgC BlOx . 0 GO

GH3 .GO.CE2 .Br + CH3 .C 0 -GH3 + GO2

I CH3 .C0 *CE2Br + "OH

Br" + GH3 *C0 *CH2CH

40

The l a t t e r compound, a c e to l, i s u n stab le and forms colored condensa­ tio n products,

Ohloroacetone was found to give th e same colored cont-

pounds on tr e a tin g w ith 5% NaCH, aluha-Bromoacetoacetic a cid e s te r s re a c t w ith pheiylhydrazine to form 3-m ethyl-1-phenyl-4-phenylhydrazono-5-pyrazolone (Blomquist and Baldwin, J , Affi# Ghem. S o c .. 70y 29 11948)), was added to an excess of pher^rlhydrazine. ta k e s p la ce .

Compound I

An exothermic re a c tio n

The product was added to a c e tic a c id , p re c ip ita tin g th e

p r a c tic a lly pure pyrazolone Cm,p, 156-157**C, ),

R e c ry s ta lliz a tio n of

th e ccanpound from AdDH d id n o t change th e m elting p o in t.

The reported

m elting p o in t fo r 3-m ethyl-l-phenyl-4-phei^lhydrazono-5-pyrazolone i s 157**G, (B e ils te in , 24 , 319),

Thus we have chemical evidence th a t I i s

an alpha- bromoacet oacet Ic a cid d e riv a tiv e , th e re a c tio n being* A /GH3 CH3C C II I GH3 BrG^ ^0 CO

. 0^5 + G^Hg.HH.HHa ->

0*0 N I II G6H5 .NH.NiC - G.GH3

O xidation Potassium permanganate (2%) i s very ra p id ly reduced in la rg e q u a n titie s hST th e carbonyl compound-diketene a d d itio n p ro d u cts.

No

attem pt was made to is o la te any of th e re a c tio n pro d u cts.

These compounds give p o s itiv e t e s t s fo r th e e s te r linkage ( . 00 . 0 *0 . ) in th e hydroxamic a cid t e s t fo r e s te r s , Fuchsin aldehyde reagent The aldehyde-diketene compounds slow ly gave a p o s itiv e t e s t with fu ch sin aldehyde re a g en t, in d ic a tin g th e form ation of aldehyde on h y d ro ly sis.

41

E s te r interchange E s te r interchange ta k es p lace w ith ethanol forming e th y l a c e to a c e ta te and re g e n era tin g was stu d ied in some

th e carbonyl ccmçjound.

d e ta i l in th e case o f th e

This re a c tio n

acetone d e riv a tiv e .

The

compound was d isso lv ed in excess e th a n o l, a small q u a n tity o f p -to lu en e su lfo n ic a cid added a s c a ta ly s t and acetone d i s t i l l e d slow ly.

Acetone

in th e d i s t i l l a t e was id e n tif ie d by i t s 2 , 4 -dinitropherylhydrazone d e riv a tiv e , m elting a t 124®G,

E thyl a c e to a c e ta te in th e pot was sep­

a ra te d by d i s t i l l a t i o n a t dim inished p re ssu re and id e n tifie d a s i t s copper d e riv a tiv e , m elting a t 191,5 to 192®G,

The rep o rted m e ltii^

p o in t of CCH3 .C 0 .CH.C0 . 0E t) 2Gu i s 192 to 193®C. ( B e ils te in , The y ie ld was about 15% of th e o r e tic a l.

6 5 l).

An u n id e n tifie d h ig h er b o il­

in g a l k a l i in so lu b le m a te ria l was a lso formed, which s o li d i f ie s on cooling.

Subliming a t 10 mm, p ressu re gave a product m elting 29,5»

30.5®G, Elemental analysis* 0

59.4^

H

8 .5 ^

0

32.1^ (tor d iffe re n c e )

The a n a ly s is corresponds approxim ately to th e formula G^EgOg,

The

compound i s u n sa tu ra te d , reducing 2 % KMnO^ ra p id ly , and d eco lo rizin g bromine in CGl^ im m ediately, with th e e v o lu tio n of HBr,

I t i s not

e ffe c te d by b o ilin g 5% NaCH, but d isso lv e s slowly i n hot 5% HCl, N e u tra lizin g th e HGl does not cause r e p r e c ip ita tio n , in d ic a tin g th a t hyd ro ly sis has taken p la c e .

I t slowly re a c ts w ith 2 ,4 -d in itro p h e n y l-

hydrazlne to form a d e riv a tiv e m elting a t 92-93®C, (.from e th a n o l).

42

Hydrogenation The a d d itio n compounds of d ik eten e w ith aldehydes and ketones are not re a d ily hydrogenated.

Several unsuccessful attem p ts were made

to hydrogenate th e acetaldehyde and acetone d e riv a tiv e s .

Thus th e

l a t t e r was recovered unchanged a f t e r shaking a dioxan so lu tio n w ith Raney n ic k e l and 50 p, s , i , hydrogen fo r two days a t room tem perature. Fresh c a ta ly s t was added from tim e to tim e to compensate f o r p o ssib le poisoning. The re s is ta n c e o f th ese compounds towards hydrogenation i s somewhat s u rp ris in g in view of t h e i r u n sa tu ra tio n .

However th e double

bond in dehydroacetic a cid i s a lso r e s i s t a n t to hydrogenation.

In th e

presence of Adams c a ta ly s t (PtO^) th e a c e ty l group i s reduced without a ffe c tin g th e double bond (202): QH3G GO (( I ^ HC^ ^CH.G0 .CH3 + E2 M O 2 CO

A CH3G 00 li f HG, CO

More vigorous hydrogenating conditions d is ru p t th e rin g ( J . An, Ghem. S o c .. 52. 5192 ( 1930 ) ) ,

Thus th e re s ista n c e towards hydrogenation

corro b o rates th e s im ila r ity of s tru c tu re between the carbonyl compounddiketene a d d itio n compounds ( l ) and dehydroacetic a cid ( l l ) :

A

CH3 C ORiRa II t EC. ^0 GO I

CH3 C GO I) I HC^ ^CHAc CO II

Naylor ( 215 ), who f i r s t prepared the acetone-diketene addi­ tio n product, proposed th e enol a c e to a ce ta te s tru c tu re ( i l l ) .

I n th e

43

p re sen t work t h i s s tru c tu re i s found untenable and th e c y c lic s tru c tu re IV i s proposed as general fo r th e a c id cataly zed a d d itio n products of aldehydes and ketones w ith diketene: GH3*C0«CH2.C0.0.C(GH3)*CH2

/O CH) C GRj^Rg II \

“Vo" III

IV

This ccaaclusion i s made on th e b a s is of th e follow ing co n sid eratio n s: (l)

The b o ilin g p o in ts of th ese compounds are higher th an

would be p red icted f o r th e enol a c e to a ce ta te s tru c tu re .

Thus th e enol

a c e ta te of acetaldehyde (v in y l a c e ta te ) b o ils lower th an i t s hydro­ genated product e th y l a c e ta te , 74**G. and 78**C,, re s p e c tiv e ly .

On t h i s

b a s is , th e enol a c e to a c e ta te o f acetaldehyde would be expected to b o il a t a tem perature below th a t of e th y l a c e to a ce ta te (33 to depending on enol-keto com position).

a t Z mm,,

However th e acetaldehyde-diketene

a d d itio n product b o ils much higher (70,8®C, a t 3,5 mm, ), Cs)

The re s is ta n c e o f th e se compounds to hydrogenation i s

n o t in accord with th e enol s tru c tu re ,

Enols g e n erally hydrogenate

re a d ily a t room tem perature w ith 50 p . s . i , hydrogen in th e presence of Raney n ic k e l, ( 3)

C hloral does not have an alpha- po s i t ion hydrogen, and

consequently cannot form an enol d e riv a tiv e ,

Diketene condenses

re a d ily w ith c h lo ra l and th e product has p ro p e rtie s s im ila r t o the o th er diketene a d d itio n products with aldehydes and ketones, (4 )

The in fr a r e d spectrograms of dehydroacetic a c id and th e

diketene d e riv a tiv e s o f acetone and c h lo ra l were obtained from Samuel

44

P, S a d tle r and Son, In c , o f P h ila d e lp h ia ,

Although t h i s evidence i s

only of a co rrobative n a tu re , i t i s in agreement w ith th e c y c lic stru c ­ tu r e s proposed.

With our p resen t knowledge of in fra re d s p e c tra , th e

sig n ific a n c e o f a few bands can be s ta te d w ith considerable c e r ta in ty . The 6 ,1 micron band e s ta b lis h e s th e C=C lin k ag e in each o f th e com­ pounds,

The band between 5 .6 and 5.8 microns i s probably a ttr ib u ta b le

to th e 0=0 group.

The presence of ab so rp tio n maxima a t 240 m illim i­

crons (not shown in spectrogram) i s in harmony with th e conjugated lin k ag e C*C*GjO,

The ab so rp tio n band near 11 microns i s ch aracter­

i s t i c of six-membered rin g s co n tain in g oxygen, favoring th e cy clic s tru c tu re , ( 5)

The brom ination of th e acetone d e riv a tiv e to incor­

p o rate th e bromine in th e a c e to a c e tic a c id p a rt of th e molecule in ­ stead o f th e acetone p o rtio n d isfa v o rs th e enol s tru c tu re I I I , and fa v o rs IV, Other evidence o f s tru c tu ra l sig n ific a n c e was s o u ^ t ,

Ihen

an unsymmetrical carbonyl compound i s used, an assym etric cen ter (*) i s formed in th e c y c lic s tru c tu re , as with chloral* CH3 G t C , II I H EG 0 CO In sta n c e s of spontaneous re s o lu tio n on c r y s ta lliz a tio n a re known (a s w ith KNa t a r t r a t e ) ; so th e c r y s ta ls o f th e c h lo ra l product were examined under a microscope. cerned,

No c r y s ta llin e assymetry could be d is ­

Sometimes o p tic a lly a c tiv e c a ta ly s ts fav o r the form ation of

one enantiomorph above th a t o f an o th er.

However th e use of d-campho-

OVERSIZED IMAGES OVERSIZED IMAGES OVERSIZED IMAGES

46

su lfo n ic a c id as c a ta ly s t gave r i s e to an o p tic a lly in a c tiv e product. The attem pted h y d ro ly sis o f th e trich lo ro m eth y l group to th e carboxyl group, by means of which th e compound could be resolved w ith an o p tic a lly a c tiv e base, re s u lte d in extensive decom position.

Saponi­

f ic a tio n e q u iv alen ts and ch lo rid e io n determ inations showed th a t the re a c tio n approached:

C^H^O^Cl) + 7NaCH -* 3NaCl + ZNagCO), on t r e a t ­

ment w ith sodium hydroxide under mild c o n d itio n s.

The form ation of

d ia sterio iso m e rs by th e re a c tio n o f d ik eten e w ith an o p tic a lly a c tiv e carbonyl conçound would in d ic a te th e form ation of another cen ter o f assymetry.

No supporting evidence was obtained here e ith e r ; d-camphor

f a ile d to re a c t w ith d ik eten e. In conclusion, th e c y c lic s tru c tu re i s p re fe rre d to th e enol a ce to acetate s tru c tu re fo r th e d ik ^ e n e a d d itio n products w ith ald e­ hydes and ketones.

T his does not exclude th e p o s s ib ility o f o ther

s tru c tu re s , but no o th e r fe a s ib le s tru c tu re has been conceived. Reaction of diketene w ith liq u id N ?0/.-

Wien diketene i s

added dropwise to liq u id NgO^, an explosive re a c tio n tak es p lace ac­ companied by flam es.

This observation le d to a c o n sid e ra tio n of th e

s u i t a b i l i t y of th ese re a c ta n ts as a ro ck et f u e l. According to V ic to r (Rev, Aluminum,

69-74 (1947);

C,A, 4 1 , 5700 ( 1947 )) rock et fu e ls a re chosen on th e b a sis o f th e follow ing considerations* 1,

I t must have a high h e at o f combustion,

2,

Oombustion must be ra p id , alm ost in stan tan eo u s,

3,

High d e n sity o r small s p e c ific volume,

4,

Automatic s ta r tin g .

47

5*

Safety in storage, tra n s p o rt and m anipulation,

6.

Easy manufacture from c o n s titu e n ts .

In reg ard to 1 diketene and

compares q u ite fav o rab ly with

liq u id hydrogen and liq u id oxygen as shown by th e follow ing calcu­ latio n s* C ^ O j ( l , 2 CP)+4 DjCg,2 0 »>HCC2 Cg,2 0 )+2 H2 0 ( g , 2 0 »)

2iH=l47.1 k g .o a V l6 )

2N2 0 4 l..lg»>» 2 K2 ( g . l 8° > 4X)2 ( g .ie » )_____________

(a ) C.jH*0 s+2Hj04^

0 j+ 2H*O 2Kj

+2 ^ . 2 k g .o a l/* aH= -422,7 k g .o a l/ mole

A ctually th e re would be a small c o rre c tio n here due to th e d iffe re n t tem peratures a t which th e above thermodynamic d ata were re p o rte d , Hj(g,18®G) + i OaCgjlS®) - HjO(g,18®)

*H= -5 7 .8 kg c a l.

Ha (1 , -255®C) -H jC g , -255®)

+.216

H2 (g , -255®) - H4g,18®)

H= +

(29^-18)

iOj l l , .183») - iOi (g , -183®) z z

■»H. + 1 ^ 2

iO , Ig , -183®) - iO j I g , 18») f ________________ *

'»H= + .22x32 ( 293. 90 ) 2 x1000^ '

lb ) H % ll,. 255®C)+ ^ 2 ll,-183)-HjOlg,18®C)

H- -5 4 .2 kg. c a l.

Coi^ariiig re a c tio n s l a ) and lb ) on a n e i ^ t b a sis : la ) C^H^02 + HjO^i

100 g. y ie ld s 3 .0 moles volumes + 158 kg. c a l.

lb) llq . H% + l l q . Ojt 100 g. y ie ld s 5 .6 moles volumes + 3 0 0 kg. c a l.

* Bichowi^y and R o ssin i, "Thermochemistry of Chemical Substances," Reinhold Cl936),

48

The s p e c ific impulse of perhydrol (80% H^Og) and hydrazine hydrate (^ % i n methanol w ith potassium cyanocuprate) i s about o n e -h a lf th a t of liq u id Hg and liq u id 0^, expect diketene and

Judging from th e above d a ta , one would

to r a te about w ith perhydrol and hydrazine

hydrate as a rocket f u e l. In regards to 2, and 4 . , q u a lita tiv e o b serv atio n s a re q u ite convincing th a t diketene and dropped in to liq u id

are s u ita b le .

When d ik eten e i s

th e re a c tio n i s immediate and v io le n t,

Diketene and liq u id %0^ meet requirem ent 3, s a t i s f a c t o r i l y . As to sa fe ty in tra n s p o rt and storage ( 5 . ) , diketene does not meet q u a lific a tio n s a t the p re se n t. on standing.

I t sometimes polym erizes v io le n tly

I f th e n atu re of t h i s re a c tio n were known, i t i s q u ite

probable th a t in h ib ito r s could be developed which would make storage of diketene fo r in d e f in ite p erio d s p o s s ib le , as has so su c c e ssfu lly been done in the case of monomeric sty re n e. In regards to 6, diketene could be manufactured a t only a s l i ^ t l y g re a te r cost than k eten e, which i s a r e la tiv e ly cheap internmediate in In d u s tria l chem istry and ra p id ly becoming a chemical of fundamental importance.

49

PART n i

HIGHER POLYMERS OF KETENE INTRQDUGTION Ketene monomer and dimer r e a d ily polymerize to dehydro­ a c e tic acid and higher u n id e n tifie d re sin o u s m a te ria ls.

The form ation

of th ese m a te ria ls accompanies most re a c tio n s of ketene monomer and dimer as co ssetin g side re a c tio n s , and indeed, a t tim es c o n s titu te s the major re a c tio n ,

 knowledge of th e se m a te ria ls i s th e re fo re

d e sira b le in th e u t i l i z a t i o n of ketene monomer and dimer as chemical in term ed iates.

I n f a c t , th e r e a c tiv i ty and p o te n tia l a v a ila b ility of

dehydroacetic a c id makes i t a v alu ab le in term ed iate in i t s own r i ^ i t (35). Besides being formed from ketene monomer and dimer, ddaydroa c e tic a cid may be prepared by the dehydration of a c e tic anhydride, the dehydrohalogenation of a c e ty l c h lo rid e , or by th e C laisen condensa­ tio n of e th y l a c e to a c e ta te CS),

Pure dehydroacetic a cid i s a white

c ry s ta llin e s o lid m elting a t 108,5 to 109®C, and b o ilin g a t 269.9^0. ( B e ils te in , 17, 559).

I t i s q u ite in so lu b le in cold water but very

soluble in ho t water ishich makes w ater a s u ita b le solvent fo r r e ­ c r y s ta lliz a tio n ,

A product of high p u rity i s obtained by r e c r y s ta l­

liz a tio n from a w ater-eth an o l m ixture, followed by sublim ation under diminiËied p re ssu re , Dehydroacetic a cid i s a weak a c id forming s a l t s w ith metals* 2 CgHgO^ + Cu( 0Ae)2 -* On(CgH,0*)j + 2 AoŒ. With m ineral a c id s dehydroacetic a cid forms pyrone d eriv a­ tives*

50

CH3 -C II HC

/O x

CH3 *C n HO

CH3 *C It HO

GjO I .CWAc CO

conc. H C lA o il

CH3C CCH3 II H + CO2 HC^ ^CH GO

85% HaSO,^ -

CH3O GO II I HC^ ^CHCOCH CO

90% H280yU5('G,

CH3G II HC

GjO I

^GHAo ^00

GiO I

,CHAc ''CO

-*

GO » , GH2 ^ CO

In g e n eral, th e pyrone d e riv a tiv e s can be converted in to corresponding pyridine d e riv a tiv e s by tr e a tin g w ith ammonia or prim ary amines.

Thus 6-methylpyrone gives l , 6-dim ethyl- 4.-hydroxy-2 -pyridine

with aqueous Œ 3NH2 a t 30®G, (lO ), CH3 CH3G II HC

GO I ^GH2 ''GO

+ CH3NH2 -*

GH3*C II HC

go

I CH

+ H2 O

''Œ On tr e a tin g dehydroacetic a cid with m ineral b ases, extensive deconçjositio n ta k e s p la c e , forming CO2 , acetone, AcOH and malonic a c id .

With

concentrated NaCH a t 150®C,, th e form ation o f o rcin o l i s re p o rte d ( 68 ) , Amines and hydrazones condense w ith th e a c e ty l group forming imines and hydrazones.

With ammonia, fo r example:

51

GH3C II HC

GO I ^ CHGOCH3 '' CO

+ NH3/ I 2O-»

CH3C CO II I HC^ / CHCCcH3 )îNH, CO

The hydrogenation of dehydroacetic a c id has a lre ad y been discussed as being d i f f i c u l t , rin g ru p tu re occurring before th e rin g CtC bond i s hydrogenated ClA,202),

I t i s in te re s tin g to note th a t th e

attem pted hydrogenation of dehydroacetic a cid with Raney n ic k e l in ethanol solvent a t 190®C, r e s u lt s in 70 % conversion to e th y l aceto­ a c e ta te C ia), Some of th e observed re a c tio n s of dehydroacetic a c id have not been completely e lu c id a te d y e t.

Thus with hydroaylamine under

d if f e r e n t co nditions two compounds CgH^O^N a re obtained, one m elting a t 171®C. th e o th er 149.5 to 15CPC. ( B e ils te in , 17, 559 (2 8 3 )), Concerning higher polymers of k e ta ie , no formal treatm ent in the l i t e r a t u r e has appeared. ta r s and apparently d iscard ed .

They are re fe rre d to a s unmanageable Work done on th ese m a te ria ls 3n t h i s

la b o ra to ry w ill be presented and discussed in th e experim ental p a rt of th i s se c tio n .

52

EXPERIMENTAL P rep a ra tio n of dehvdroaoetlo a d d . -

D ehydroacetic a c id was

obtained from th e resin o u s m a te ria ls l e f t a f te r th e d i s t i l l a t i o n of dik eten e.

The t a r from an o rig in a l two g allo n s of re sid u es accumulated

from th e p re p a ra tio n of ketene i s melted and poured in to a 500 ml, round bottom f la s k .

The fla s k i s f i t t e d w ith a G laisen head having

a la rg e siz e o u tle t to the condenser,

(Conventional side arms on

G laisen fla s k s a re too re a d ily clogged w ith th e h i ^ m elting d i s t i l ­ la te , )

A long Pyrex tube 1 l / 2 by 30 inches i s jo in ed to th e G laisen

head by means of a 24 / 4 O i n te r j o in t.

The la rg e tube fu n c tio n s as a

combined a i r cooled condenser and re c e iv e r.

The fa r end of th e re ­

ceiver i s a ttach ed to a vacuum system w ith a sm all water cooled con­ denser in terp o sed to prevent th e sublim ation of dehydroacetic a cid in to the vacuum lin e ,

A c a p illa ry e b u lla to r tube leading in to the

d i s t i l l a t i o n fla s k provides smooth d i s t i l l a t i o n . The d i s t i l l a t i o n i s accompanied by considerable decomposi­ tio n forming an uncondensible gas (probably CO^) which makes i t im possible to o b tain very low p re ssu re s.

In a ty p ic a l d i s t i l l a t i o n ,

about 100 g, of dehydroacetic acid was obtained b o ilin g between 140®C, a t 11,5 mm, to 169®C, a t 49 mm.

Towards the end of th e d i s t i l l a t i o n ,

extensive therm al decomposition tak es place y ield in g a very yellow liq u id condensate.

The decoijç>osition sometimes becomes v io le n t; on

one occasion, th e g la ss jo in ts were fo rced ap art and a cloud o f dense white fumes was produced.

On cooling, th e residue in th e fla s k so lid ­

i f i e s to a b r i t t l e porous ch ariy m a te ria l which i s re a d ily removed from th e f la s k .

53

The crude product i s r e c iy s ta lliz e d from eth an o l and sub­ limed a t dim inished p re ssu re .

The t r i p l e sublimed m a te ria l submitted

fo r an in fr a - re d spectrum m elted a t 110,5-111®G, a s compared to th e rep o rted value 108.5 to 109®G, D ehydroacetic a cid in th e S treck er amino a c id sy n th esis. I t was attem pted to prepare an a lo h a-amino a cid by su b jec tin g dehydro­ a c e tic a cid to th e S treck er % m thesis.

The procedure followed was

e s s e n tia lly th a t given in "Organic S y n th esis," 2^, 9 Cl944), tr e a tin g th e carbonyl compound w ith NaCN, NH^Cl and aqueous ammonia.

Only

dehydroacetic a cid monoimide was obtained, m elting a t 209- 210 ®0 , I t was id e n tif ie d by comparing w ith an a u th en tic sample prepared according to B e ils te in , 7 , 564* P rep a ra tio n of ketene oolvmer. -

The dry ic e tr a p condensate

from the ketene generator forms a w hite so lid on standing a t -75®C, On warming to room tem perature to d i s t i l l th e ketene monomer, the polymer d isso lv e s and forms colored products—f i r s t yellow , tu rn in g to a deep wine color on standing.

Cooling the residue a f te r th e

ketene has d i s t i l l e d forms a g e l. I f the p r e c ip ita te i s sep arated a t -75**G, however, a white s ta rc h -lik e powder i s obtained.

The b est product was obtained by th e

follow ing procedure; Allow th e condensate from th e ketene generator to stand a t -75**G, fo r sev eral days, or u n t i l i t i s sem i-solid w ith polymer. an equal volume of e th y l e th e r and shake to crush th e lumps.

Add

The e th e r

f u r th e r in s o lu b iliz e s th e polymer ren d erin g f i l t r a t i o n e a s ie r . the polymer o ff in a 4 inch f r i t t e d g la s s Pyrex funnel (médium

F ilte r

54

p o ro s ity ).

The fum iel i s f i t t e d w ith a la rg e one hole stopper which

i s clamped down t i g h tly w ith a s u ita b ly co n stru cted clamp.

N itrogen

or carbon dioxide from a c y lin d er i s passed in , fo rcin g th e liq u id th r o u ^ a funnel.

O rdinary su ctio n f i l t r a t i o n i s in e ffe c tiv e because

of th e high vapor p ressu re o f th e m ixture,

(Work in a hoodi)

A p res­

sure of 10 p , s , i , may be safely ap p lied to a funnel of good construc­ tio n ,

Twenty p . s . i . was ap p lied w ithout mishap, but perhaps i s not

advisable in view o f th e g re a t fo rc e s involved (over 200 pounds on the a rea of th e f r i t t e d d is k ). Remove the polymer cake from th e funnel and s t i r with e th y l e th e r, breaking th e lu n p s.

F i l t e r , sucking th e powder a s dry a s pos­

s ib le udiile working w ith a sp a tu la .

Repeat th e treatm ent with fresh

e th e r u n t i l th e odor of ketene i s gone ( s i x to seven tim e s).

The

polymer may be d isso lv ed in a sm all amount of dioxan and re p re c ip i­ ta te d with e th e r.

T his gives a fin e product but r e s u lts in consider­

able lo s s . P ro p e rtie s and re a c tio n s of th e oolvmer, -

Subjecting th e

polymer to about 2 mm, p ressu re in a vacuum d e ssic a to r removes th e re s id u a l e th e r (about 35% by w e i ^ t ) , leav in g a i ^ i t e , o d o rless, ta s t e le s s product having th e appearance o f sta rc h . prepared polymer m elts a t 63 to 65®C,

The fre s h ly

I t i s soluble in dioxan,

acetone, a c e tic a c id , a c e tic anhydride, a c e ty l c h lo rid e , chloroform , p y rid in e, concentrated s u lfu ric a c id , liq u id ammonia, 5% NaCH; s lig h tly soluble in e th y l alco h o l; in so lu b le in w ater, 5% HCl and e th y l e th e r. The polymer i s u n stab le a t room tem perature.

On standing o v e m i ^ t ,

i t becomes cream colored and i s no longer so lu b le; i t decomposes

55

before m elting, and has an a c rid odor.

Carbon and hydrogen a n a ly s is

on a fre s h and old sample o f th e polymer are as follow s: C %

H %

Fresh

56,6

4.82

Old

53,6

4 .8 0

Theory fo r (0;Hg0)g

57.1

4.7 6

The m olecular weight of th e fre s h polymer was determined cry oscopically in dioxan.

Three d if f e r e n t batches of polymer gave

values 1290 , 1234 , and 1327, re s p e c tiv e ly , corresponding t o a degree of polym erization o f about 30, The sa p o n ific a tio n e q u iv alen t of th e polymer was determined by d isso lv in g a weighed q u a n tily in excess standard NaCH so lu tio n and back t i t r a t i n g with standard HOI so lu tio n .

The end p o in t obtained

with methyl orange in d ic a to r was tw ice t h a t obtained w ith phenolp h th a le in in d ic a tin g th a t Na^GO) had been formed on sa p o n ific a tio n . The follow ing v alu es were obtained w ith phenolphthalein in d ic a to r: Fresh sample

8 -day old sample

90,5

90,6

9 0 ,0

9 2 ,0

The value 84 corresponds to th e form ation of one CO2 p er dimer u n it CCzHaO)^, The polymer i s a lso hydrolyzed by acid s to form CO2 ,

The

follow ing q u a n tita tiv e r e s u lts were obtained using 50 % s u lf u r ic a c id . Fresh polymer

8 day old

weeks old

47 . 7 %

40.7%

25 , 4 %

4 6 ,7

4 1 .6

27,6

56

The th e o r e tic a l v alu e fo r one GOg per k eten e dimer u n it i s 52 , 4 %,

The o ld er samples were not c o n p le te ly so lu b le , leav in g a

charred re s id u e .

The o th er product of h y d ro ly sis i s a ceto n e, iflfoich

was recovered as i t s 2,4-dinitrophenylhydrazone in 64% and 50 % y ie ld s by a cid and a lk a lin e h y d ro ly sis re s p e c tiv e ly .

The h y d ro ly sis was

conducted by slowly d i s t i l l i n g a w ater-alco h o l m ixture c o n tain in g the polymer and c a ta ly s t. The iodine number o f th e polymer was obtained by adding excess brom inating reag en t C jyridine s u lfa te dibromide in a c e tic a c id so lu tio n ) and determ ining th e unused

bromine by adding excess KI

s o lu tio n and t i t r a t i n g w ith standard Na^SaOj s o lu tio n , u sin g sta rc h in d ic a to r.

The end p o in t was tr a n s ie n t.

On continued t i t r a t i o n 97%

of the o rig in a l bromine was accounted f o r before a permanent end p o in t was obtained.

The f i r s t tra n s ie n t end p o in t on two samples c o rre s­

ponded to iodine valu es of 275 and 250 re s p e c tiv e ly .

The th e o r e tic a l

value fo r one Br^ per ketene dimer u n it i s 303, P y ro ly sis of ketene polymer gave about 40% dehydroacetic a c id , 20% acetone, an unmeasured q u a n tity o f GOg, leav in g about 27% Carbonaceous re sid u e .

Other u n id e n tifie d substances were a lso evolved

as in d ic a te d by th e yellow color and u n fam iliar odor. Acidic substances were found to have a s ta b iliz in g e ffe c t on the polymer.

Thus d isso lv in g the polymer in a c e tic a c id and re -

p re c ip ita tin g with eth er gave a product sim ila r to th e s ta r tin g m a te ria l in a l l re s p e c ts except th a t i t did not decompose on stan d in g .

R epreci-

p ita tin g th e polymer from dioxan co n tain in g dry HCl gas in so lu tio n gave a s im ila r sta b le p ro d u ct, ^ i c h does not co n tain c h lo rin e .

57

The polymer r e a c ts exotherm ically -with liq u id ammonia. Evaporation of th e excess ammonia le av e s a ta n , t a f f y - lik e m a te ria l. A fter su b jectin g to 2 mm. p ressu re t o remove l a s t tra c e s o f ammonia, th e follow ing was obtained* 49,7^ G, 6,56^ H and about 13^ N. The th e o r e tic a l value fo r the a d d itio n o f one MH3 to one ketene dimer u n it i s 47 , 5 ^ C, 6.9fo H, and 13,86^ W, When dropped in to liq u id NO2 in small p o rtio n s, th e polymer re a c ts e x p lo siv ely , producing a flame in m ch th e same manner as d iketene. E sta b lish in g the s tru c tu re o f th e polymer from chemical evidence probably involves th e same in h eren t d i f f i c u l t i e s a s in th e case of dik eten e.

However, th e follow ing observations may be of

value* The dimer u n it seems to be im portant in i t s chemical reac­ tio n s ,

Thus about one GO^ per ketene dimer u n it was produced in both

acid and a lk a lin e h y d ro ly sis, p er dimer u n it.

Bromination seems to involve one Br^

The re a c tio n w ith ammonia involves one NH3 per dimer

u n it. Since ketene dim erizes to form a beta^la c to n e . i t i s pro­ posed th a t th e polymer i s formed by th e continued a d d itio n of ketene u n its to form a n o lv -b e ta -lactone* H^C— C^O

H^C^C—0 / / H2C-C=0 H2G=G- 0 1 I H2C— G—0 \ 1 H 2 G -C -O

\

I

H2C-G-O 1 I H2G-G=0

58

H ydrolysis of th i s compound could fe a s ib ly give r i s e to acetone and GOg, th e products obtained experim entally:

r 1 H a G- C- O I I H g G -G -O I I H g C -G O

+ H2O

-CH 2«CÛ *CH 2*CO *G H 200*Œ

HaO -

.(Ha*CO*CH + GH3*G0*CH2*C0*CH

GHg'GO.CH^ + GO2

Exhaustive h y d ro ly sis o f th e polymer would give r is e to one GO2 and one acetone molecule p er ketene dimer u n it. Hydrogenation of th e proposed s tru c tu re should give r i s e to polyvinyl alco h o l,

A dioxane so lu tio n o f th e polymer was subjected

to 50 p . s , i , hydrogen in th e presence of Adams c a ta ly s t a t room tem perature.

Wo hydrogen was absorbed.

More vigorous hydrogenation

conditions and other reducing agents should be t r i e d , Acetaldehyde i s known to form a po ly eth er a t low tempera­ tu re s (N ature, 157. 267 (1 9 4 6 )), having th e s tru c tu re : CH3

CH3

CH3

CH3

t i l l • • -C H -G u G H -0 * C H * 0 * C H * a . • • I t i s p o ssib le th a t k etene may fcrm an analogous polymer a t low tem­ p e ra tu re s: GH2 CH2

GH2

tl

II

II

• • -C «O-C • 0 * C * 0 - • •

However i f such were th e c a se , one would expect th e trim e r o f ketene to e x is t comparable to paraldehyde, th e trim er o f a ce t aldehyde:

59

y GH>CH O H -C H j I l ^0 GH ^ CH,

^\ C H a ïC C sC H a 1 1 0^ 0 C ;C H 2

That no such trim er of ketene i s known makes th e po ly eth er s tru c tu re appear improbable. In fu r th e r illu c id a tin g th e s tru c tu re of th e polymer, th e use of in fra re d spectrum a n a ly sis i s reconaaended.

The fr e s h ly pre­

pared polymer probably has a com paratively simple repeated s tru c tu ra l u n it fh ic h would give r i s e to re a d ily in te rp re ta b le sp ectra bands. Comparison with th e s p e c tra of d ik eten e and b eta propiolactone would quickly e s ta b lis h whether or not th e polymer had th e b e ta -lacto n e s tru c tu re a s proposed.

60

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64

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Chick and Wilsmore, Proc. Ghea. S e e .. 2A, 77 (1908)» G.A. 2 , 1823* (1908). R eaction of liq u id ketene with HCl, and HGN,

3622 (1938).

59. Chick and Wilsmore, Proc. Chem. Soc. . 24. 100 (1908): J , Chem. Soc. . 22, 946 (1908)» G.A. 2 , 2224, 2673 (1908). P rep a ra tio n and re a c tio n s o f d ik eten e. Ib id . . Proc. Ghea. S o c.. 2^, 217 (l910)« J . Ghea. S o c.. ^ 9 1 0 7 T £ . A . 2 , 4805 (1911). R eactions of dik eten e,

22,

1978

60.

Choh, Simpson, and Evans, J . B iol. Chenu. 131. 259 (l9 3 9 ): G,A. 54 , 147 ( 1940 ): Science.140 (1939): G.A, 35, 8269^ (1939). Action of ketene on hormones.

61.

Choh, S cience. 22, 143 (1939): G,A, 55, 7521^ (l9 3 9 . Ketene gen erato r of Hurd lamp ty p e,

62. Claborn and Smith, J , Chem. Soc. . 61. 2727 (1939): C.A, 54, 377® (1940). A cétylation of alnha-hydroxv e s te rs with ketene, 63.

Clarke and Waring, U.S. P aten t 1,723,724 (Aug, 6 , 1929): G.A, 25 , 4485 (1929)& B r itis h P aten t 309,577 (A p ril 13, 1928): C.A, 2 4 , 6308 (l9 3 0 )j German P atent 556,367 (March 27, 1929)* C.A. 26, 5579 ( 1932 ), Manufacture of ketene.

64 .

Coenen, German P a te n t 729,849 (Dec, 3 , 1942): C.A, 58, 550^ (1944). H eterocyclic ketones from k eten e,

65.

Cohn, Ghem. 2 t g . , J 7 , 1469 ( l9 4 l) i G.A. S , 1098 (1914). Review of a ce to a c e tic e s te r ,

66 .

Coleman and C an^bell, J , Jfea, Ghem. Soc. . 50, 2754 (l9 2 8 ): C.A, 4459 (1928). R eaction of diphenyl ketene with n itro g en tr i c h lo r id e .

65

67.

Colegan and P e te rso n , Proc. Iowa Aoad. S cl. . 42. 1223 (l9 3 5 ): 5 .1 . iO , 8156* (1 9 3 6 7 T j. M . Ghem. S o c .. 5 8 , 1874 tl936)« 0 .1 . 25, 8155® (1936). “ R eactions of N-halo amines with k eten es.

68.

C o llie , J , Chem. S o c .. 52. 179 (l8 9 l)« J . Chem. S o c.. 52, 607 (1891)I Proc. Chem. S o c.. 22, 230 (1907), C .i. 2 , 798 ( 19 O8 ) . R eactions and s tru c tu re of dehydroacetic a c id .

69.

C o llie and H ild itc h , J . Chem. S oc.. 21, 789 (1907): G.A. 1, 2362 (1907)J Proc. Chem. S o c.. 22, 92 ( 1907 ): 0 .1 . 1 , 1560 (Î9C7). Isom eric change of dehydroacetic a c id .

70.

C o llie and R e illy , J . Ghem. S oc.. p i , 1984 Cl922). D iacetyl acetone and dim ethyl pyrone form dehydroacetic acid .

71.

Consortium fu r elektrochem ische In d u s trie , G.m.b,H,, B ritis h P aten t 435,219 (S ep t. 17, 1935), C.A. 22, 1072* (1936): French P a te n t 777,483 (Feb. 21, 1935): C.A. 22, 40298 (1935). Manufacture of keten e.

72.

Ib id . . B r itis h P aten t 498,280 (Ja n . 5, 1939): 0 .1 . 55 , 3820^ (l939)> French P a te n t 835,162 (Dec. 14, 1938): C.A. 4274 (l9 3 9 ). Manufacture of d ik eten e.

73.

I b i d . . French P a te n t 46,965 (Nov. 23, 1936): C.A. j l , 7893^ (l9 3 7 ). P u r ific a tio n of keten e,

74 .

Ib id . . German P aten t 515,307 (March 11, 1927): C.A, 25, 1537 Ketene from v i i y l e s te r s .

75.

Ib id . . German P a te n t 734,349 (March 18, 1943): O.A. Manufacture of ketene from a c e tic a c id ,

76.

Ib id . . French P aten t 777,483 (Feb, 21, 1935): C.A, 25 , 4029^ (l9 3 5 ). Manufacture of ketene from a c e tic a c id ,

77.

Cook and Jones, J . Chem. Soc.. 1941. 184» C.A. 5 5 , 4765 ( l9 4 l) . R eactions of diphenylketene w ith cis-azo compounds.

6

(l93L).

1250^ (l9 4 4 ).

78A. Dashkevich, R ussian P aten t 51,926 (Nov. 30, 1937): C.A. 21, 2862 ( 1 9 ^ : J . Got. Chem. (U .S .S .R .), 8, 779 (l9 3 8 ): G.A. 22, 1293® ( 1939)5 J . Gen. Ghem. (tJ.S .S .R .), 205 (1948): C.A. 12, 7244 (1948). R eaction of ketene with Grignard re a g en t, 78B, Dashkevich, Sbornik Trudov Leningrad Tekh. I n s t . VSPK 1940. ( 3 ) 12: G.A. 2Z, 4363* (1943)1 Khim. R e fe ra i. Zhyr. . 1 , (3) 3 0 (1 9 4 1 ). C h lo rin a tio n and brom ination o f ketene, 780, Dashkevich, J . Gm. Chem. (U .S .S .R .), 16, 739 (l9 4 6 ). Ketene in F rie d e l-G ra fts re a c tio n .

66

7

79A. D avis, J . Pbys. Chem.. 25, 330 (1932)s C.A. 2^, 922 Ketene from brush discharge in aceto n e.

(1932).

79B. Davis and Murray, In d . Eng. Chem. . IS , S46 Cl926), A céty latio n and t e r t i a r y butanol w ith k eten e, 80.

Deakin and Wilsmore, Proc. Ghem. Soc. . 2^, 216 11910); J . Chem. 80Ç ,, 27, 1968 C l9 1 ô y r ç .i. 480® C19I I ) . R eaction of ketene with HGN , GH3I, NOGl,

80A, DeHoff, Ph,D, T h esis, Purdue U n iv e rsity , August 1949. 81.

Deshapande and Kaweeshwar, J , In d ian Chem. Soc. . 19. 153 Cl942): Ç.A. 2S., 3176 ( 1944 ). Parachor of dehydroacetic a c id ,

82.

D esneulle and Roverv, Compt. re n d .. 224. 235 I 1947): C,A. 4 I , 3142® (1947). Action of ketene on p ro te in t h i o l groups,

83.

Deutsch and Heumann, German P aten t 515,307 (la rc h 11, 1927): Ç.A. 2 5 , 1537 (1931). Ketene from v in y l e s te r s .

84 .

Deutsche Hydrierwerke A,G,, B r itis h P atent 522,033 (June 6, I 940 ): Ç.A. 26, 781® ( 1942 ). H i ^ m olecular w e i^ t ketenes by dehalogenation of a cid h a lid e s ,

85.

Drayton and Thompson, J , Chem. S oc,, 1948. 1416: C.A,42> 1657^ (1949). In fra re d sp e c tra o f ketene and in te r p r e ta tio n th e re o f,

86.

Dreyfus, B ritis h P aten t 262,364 (June 13, 1925): C,A, 21, 3626 ( 1927 ) ; U.S, P a te n t 1,773,970 (Aug. 26, 1939): C.A, 24 , 5046% ( 1930 ), Ketene from hydrogen and carbon monoxide.

87.

Ib id . . B r itis h P aten t 273,622 (June 26, 1925): G.A, 1981 “ U 928); U.S. P a te n t 1,870,104 (Aug. 2, 1932): G.A, 26, 5315 (1932). Ketene from acetaldehyde.

88.

I b i d . . U.S. P a te n t 2,176,419 (D ot. 17, 1939): C.A. 24» 1D37* U 940). Ketene from acetone,

89.

I b i d . . B ritis h P a te n t 478,213 (Ja n . 14, 1938): B r itis h P aten t 478,325 (Ja n , 14, 1938): B ritis h P aten t 478,326 (J a n , 17, 1938): G.A, 32, 4610® (1938); B ritis h P a te n t 509,777 (J u ly 2fi, 1939): C.A. 34, 4080® (1940); B r i t i ^ P a te n t 503,962 (A p ril 18, 1939):

67

89 C oontlm ed) « Ç.A. 21» 7319 (1939)» French P a te n t 845,655 (Aug. 30, 1939)» C.A. 35, 1070* (1941). Manufacture of ketene and homologues from a lip h a tic a c id s, 90.

I b id ..

B r itis h P a te n t 537,480 (June 24, 1941)» C.A. 2&, 1336

n i9 4 2 ). Ketenes from carbonmonoxide and a lip h a tic a lc o h o ls, 91.

Dreyfus and Fallow s, U.S. P a te n t 2,202,046 (May 28, 1940): C.A, 6656® (1940). Ketenes from a lip h a tic a c id s ,

92,

du Pont de Nemours and C o., U.S. P a te n t 2,007,968 (J u ly 16, 1935): Ç.A. 22, 5857 (1935). A céty latio n o f alco h o ls and phenols,

93.

I b i d .. D.S. P aten t 2,135,709 (Nov. 8 , 1939)» 0 ,^ . 22. 134? (1939). Mixed anhydrides from re a c tio n of ketene with a c id s ,

94.

I b i d .. B ritis h P a te n t 504,626 (A p ril 27, 1939)» C.A. 33, 7818 ^ 9 3 9 ). Ketenes from therm al decom position of e s te r s ,

95.

Eschenbach, German P a te n t 598,953 (June 22, 1934)» C.A. 28, 7268° ( 1934)4 U.S. P a te n t 2,080,562 (May 18, 1937)» C.a7 21, 4994* (1937). Ketene from acetone, z I b i d .. German P aten t 638,441 (Nov, 16, 1936): C.A, 1042 1 ^ 9 3 7 ). Acetyl h a lid e s from ketene and hydrogen h a lid e s ,

96,

97,

Falkovski and Kagan, J . Phys. Chem. (U .S .S .R .), 22 , 445 (1948): Ç.A. èà, 7146® (1948). K in e tic s of th e homogenous deconçjosition of acetone in th e presence o f HgO vapor,

98,

Fallows and M ellers, U.S. P a te n t 2,295,644 (S ep t. 15, 1942): G.A, 22, 1133* ( 1943)4 B ritis h P aten t 509,778 (J u ly 20, 1939)» Ç .2. 21, 4080® ( 1940 ) . Manufacture o f ketene ty therm al dehydration of a c e tic acid ,

99,

Farbenfabriken vorm. F, Bayer and G o,, B ritis h P aten t 19,088 (Aug, 19, 1909 ) ; German P aten t 222,551 (Ja n , 8, 1909). Ketenes from h eatin g hydroxy ketones with dehydrating ag en ts.

100,

Farmer and Farooq, Chemistry and In d u s try . 1937. 1079» G.A, 1257 * (1938). R eaction of diphenylketene w ith o le fin s .

68

101,

P ie s t, Aaa., 152, 2 5 3 (I 8 9 0 ). S tru c tu re of dehydroacetic a c id ,

102 ,

F itz p a tr ic k , J . t o . Chem. S o c.. gg, 2236 Cl947)> C.A. 42, 115 (1948). Aliéné from p y ro ly sis of d ik e te n e ,

103,

F r e r i and Maximoff, Gazz, chim. i t a l . . 836 (1940)« G.A, 26* 1024^ (1942), F rie d e l-C ra fts re a c tio n between ketene and s u b stitu te d benzenes,

104,

Fuhrman, Ph,D, T h e sis, Purdue U n iv e rsity , June 1948, Enol a c e ta te s of aldehydes,

105,

Fybelson and Johnson, J , Am, Chem. S o c.. 306 (1942): C,A, 26* 1905* ( 1942 ). R eaction of ketene w ith 5 ,5-dibrom ohydroxyhydrouracil,

106,

Gershinowitz and W ilson, J , Chem. Phys. . 2* 500 (1937): C.A, 21* 4901« ( 1937 ). The in fr a - re d ab so rp tio n o f ^ s e o u s keten e,

107 ,

Gilamn and Adams, Rec. tr a y , chim. . 2 9 5 0 (1929). D i-p -to ly l ketene manufactured,

108,

Gilman and H eckert, J , Am, Chem. S o c.. 4 2 , 1010 (1920): C.A, 1 4 , 1831 (1920). Mechanism of Grignard re a c tio n with k eten es,

109 ,

Gilman, K irty and Kinney, J , ^ Chem. S o c.. 21* 2252 (l9 2 9 ). Mechanism of ketene re a c tio n s ,

110,

Gilman, Wobley and W r i^ t, J , Ghem. Soc. . 26* 2609 (1933): C.A. 3471® ( 1933 ). Reaction of ketene with organic m ercu rials,

111,

Gleason, U.S, P a te n t 2,174,239 (S ep t. 26, 1939): C.A, 2A, 450^ ( 1940 ), R eaction of diketen e with u re a , hydroxylamine and analogs,

112,

Gleason, U.S. P a te n t 2,178,752 (Nov. 7 , 1939): G.A. 2 à , 1335* ( 1940 ). Mixed anhydrides from ketene and organic carboxylic a c id s,

113,

Gleason, U.S, P a te n t 2,180,953 (Nov, 21, 1939): C.A, 24, 1685^ ( 1940 ). Phenol w ith ketene and d ik e te n e.

464 (l9 2 9 ): G,A, 22,

69

114, G oldie, Compt. rend, soc. b lo l. . 126, 974 Cl947)« C.A, 22* 2604 ' Cl938); Goldie and Sandor, Compt. rend, soc. b io l. . 126. 291 (1937); C,A, 22, 986^ (1938% The e f f e c t o f ketene on d ip h th e ria to x in and antiserum , 115, Goldschmidt and O rthner, Z, angew. Chem. . 42 * 40 (1929)* C,A, 2094 ( 1929 ). Apparatus f o r m anufacturing ketene, 116,

Gonzalez, Anales soc. espan. f i s , aulm. . 17, 130 ( 1919 ); C.A, 14 , 34C7 ( l ^ O J T The r e a c tiv i ty of diphenyl ketene w ith th e n i t r i l e group,

117, Graves, D.S. P a te n t 2,007,968 (J u ly 16, 1935)» C.A. 2g, 5857 (1935). A cétylation of polyhydroxy compounds w ith k eten e, 118, Ib id . . D.S. P a te n t 2,135,709 (Nov. 8 , 1938)» C .4. 5 5 , 1347 ^ 939 ). Mixed anhydrides by a c tio n o f ketene on a c id s , 119 , I b i d .. D.S. P aten t 2,069,043 (Feb. 2 , 1937)» C.A. J l , 1826° ^ 9 3 7 ). Manufacture of ketene from acetone and o th er compounds,

120, Greenewalt, U S, P aten t 2,053,286 (S ep t. 8 , 1936); C.A, 22* 71277 (1936); B ritis h P aten t 472,988 (O ct. 4 , 1937)7 C.A, 2&* 1278 (1938), Manufacture of ketene from acetone, 121, Gresham, Jansen, and Shaver, C ontributions from th e Re sear L ab o rato ries o f th e B, F, Goodrich Company, To be published, b e ta -P ro p jo lacto n e, polym erization re a c tio n s , " " re a c tio n s with s a lt s o f organic a c id s , " " re a c tio n s w ith s a lt s o f dithiocarbam ic acid s, " " re a c tio n s with s a lt s of carboxylic a c id s , 122,

Gresham and Shaver, U.S. P aten t 2,411,875 (Dec, 3 , 1946); C.A, Q ., 2431 (1947). R eactions of b e ta -lacto n es with th io ^ y l c h lo r id e ,.

123,

Gwynn and Degering, J , Ghem. Soc,, 64 * 2216 (l9 4 2 ); G.A. 26* 6498® ( 1942)4 D.S. P aten t 2,383,965 (1945)» C.A. 4 0 , 346(1946). Enol a c e ta te s by re a c tio n o f ketene w ith ketone,

124 ,

I b i d . . D.S. P a te n t 2,418,708 (A p ril 8 , 1947)» C.A. 4 I , 4507^ (l9 4 ) . P rep a ra tio n of 2 -a c e toxy-4-meth y l-1 , 3-pentadiene,

125,

Gwynn, Ph.D. T h e sis, Purdue U n iv e rsity , June 1942, Condensation products of ketene w ith k eto n es.

70

126.

Hagemeyer, U.8. P a te n t 2,417,748 (March 18, 1947); C.A, 4 I , 3478 11947). Methyl a c ry la te from ketene and methyl l a c t a te ,

127.

Hagemeyer, In d . Eng. Chem. . 41, 765 (l9 3 9 ). R eaction of k eten e-en o l a c e ta te s and bet a -l a c t one s.

127A, Hagemeyer, C o n trib u tio n from th e Research L a b o ra to rie s of th e Tennessee Eastman C orporation ( to be p u b lish ed ), R eacticns of isopropenyl a c e ta te , 127B, Hagemeyer, U.S, P aten t 2,450,131 (S ep t, 28, 1948): U.S. P aten t 2,450,132 (S ep t, 28, 1948): U.S, P aten t 2,450,133 (S e p t. 28, 1948): U.S. P a te n t 2,450,134 (S e p t. 28, 1948): G.A, 42, 1056 a ,b ,c ( 1949 ); U.S. P a te n t 2,456,503 (Dec, 14, 1948): C.A. 42, 2635 (1949); U.S. P aten t 2,466,420 (A p ril 5, 1949): G.A. A2, 5 0 3 7 ( 1 9 4 9 ). bet a-Lact ones from ketene and carbonyl compounds. 128.

Hagemeyer, U.S. P a te n t 2,458,373 (Ja n . 4 , 1949): G.A, 42, 38360 tl% 9 ) . N itr ile s by dehydration of amides or ammonium s a l t s with ketene, a c e tic anhydride, e tc ,

129 .

H ale, N ature. U P . 1017 (I9 4 7 )t Ç .4. Ketene from acetone.

130.

H ale, J , ^m. Qiem. S o c ,, 22, 1119 (l91l). C o n stitu tio n of dehydroacetic a c id ,

131.

H alverson and Van Zandt, J , Ghem. Phys. . 12, 552 (l9 4 7 ): G.A, 41* 7259 (1947). In fra re d spectrum of k eten e.

132.

Hamalainen and R eid, In d . Eng, Ghem,, 41, 1018 (l9 4 9 )i P a r ti a l a c é ty la tio n of co tto n c e llu lo se by ketene,

133.

Hanford and Homes, U.S. Patent 2,284,896 (June 2 , 1942): C.A, 26, 6706^ (1942). Reaction of X:G:Y compounds, in clu d in g ketene w ith c e llu lo se ,

134.

Hannay and Smith, J . Am. Chem. Soc. . 68. 1357 (1946). The d i e l e c t r i c co n stan t and d ip o le moment o f gaseous keten e.

2085

(1938).

135. Harp and Rasmussen, J , Chem. Phys. . 15, 778 (1947): C.A. 4* 825 (1948), The in fra re d spectrum of k e ten e . 136. fiartough and Kosak, U.S. P aten t 2,460.822 (Feb, 8 , 1949): C.A, 4»!, 3465 (1949); U.S, Patent 2,460,823 (Feb, 8 , 1949): G.A, 42, 3464h (1949;; A bstract of papers presented a t Am. Chem, Soc, m eeting, A tla n tic C ity , A pril 1946, p. 64M, Fur an and s u g s titu te d fu r ans a c e ty la te d w ith k e ten e .

71

137.

H a r r io tt, J . G^g. P h y g io l.. G enerator f o r k eten e,

69 (1934): Ç.A. 28, 7075

(1934).

138.

H esse, J . U . Cbem.. 22, 390 ( 19O8 ) : C .i. 2 , 2547 (1908). D ehydroacetic a cid formed from e th y l a c e to a c e ta te ,

139 .

H ill and g e n te r, J . *8. Chto. S o o .. 21, 364 (1949): Ç .4. 4 2 , 29646 (1949). Dehydrohalogenation of a cid h a lid e s to form k eten e,

140 .

H ochster Farbwerke, German P a te n ts 96,761 (J u ly 2 , 1697), 101,917 (Aug. 6, 1897), 158,148 (Feb. 4 , 1904). % oetoacetanilde from a n ilin e used jpor making Hansa yellow s,

141.

Hopff and Rapp, D .S. P a te n t 2,265,163 (Deo, 9, 1941): C.A. 2 é , 1614® (1942). Reaction of v in y l ketones with ketene,

142.

Hopkinson, D.S. P a te n t 2,258,985 (O o V U , 1 9 4 l): C.A. 2É, 497® (1942). Ketene from acetone,

143.

H ueter, U.S. P aten t 2,383,663 Cl945)s C.A. 4 0 , 351* (1946). High m olecular weight ketenes by a ctio n of t e r t i a r y amines on organic a cid h a lid e s .

144 .

H u ll, D.S. P a te n t 2,232,705 (Feb. 25, 1 9 4 l): C .i. 21, 3651 (1941). Acetone pyrolyzed to ketene in sp e c ia l chamber.

145.

H nu and A gett, D .S. P aten t 2,422,679 (June 24, 1947): C .i. ü , 6895 (1947). Enol a c e ta te s from aldehydes and ketones.

146.

Hurd, J . i a . Chem. Soc.. 47, 2777 (1925): C .i. 12, 1853, 2187 (1925). Ketene from acetone and re a c tio n s of k eten e. Organic S y n th esis, C oll. Vol. I , 326 (l9 3 2 ): C o ll. Vol. I , 330 (1941). L aboratory p re p a ratio n of ketene.

147.

Hurd, J . M . Chem. Soc.. Ü , 3095 (1923): C.A. 18, 1982 (l9 2 4 ). Ketene from methyl e th y l ketone.

148.

Hurd, J . &S. Chem. Soc.. 291 (l9 2 6 ): C.A. 20, 590 (1926). R eaction of ketene with diphenyl amine,

149.

Hurd and Abernathy, J , Chem. Soc., fô , 1147 (l9 4 0 ): C.A. 6222® (194). C h lo rin a tio n of diketene and s tru c tu ra l c o n sid e ra tio n .

7

72

150.

Hurd and Cochran, J , M , Chem. S o c .. 515 (1923)* C.A. 1%* 1427 (1923). Hydroxamic a c id from ketene and hydroxylamine.

151.

Hurd, Cantor, and Roe, J , Chem. Soc. . 61. 426 (l939)* C .J. 2 2 , 2109 ® ( 1939 ). A céty latio n of carbohydrates by ketene,

152 .

Hurd, Cashion and P e r le tz , J . Org. Chem. . 8, 367 (1943)* G.A, 22, 5945® C1943 ) . . D ehalogenation of alo h a-h alo ao id h a lid e s,

153 .

Hvu-d and D u ll, J . f e . Chem. S o c.. 24, 3428 ll9 3 2 ): C.A. 26, 4794 (1932). Mixed anhydrides from ketene with a c id s.

154.

Hurd and D u ll, J . i®. Chem. S o c.. 24, 2432 (193:& C.A. 26. 3788* ( 1 9 3 2 ) . Diketene from acetylphthalim ide and N -acetyl carbazole.

155.

Hurd, D ull aM W illiam s, J . Âm, Ghem. Soc.. j 7 , 774 (1935)* P y ro ly sis products o f acety lp h th alim id e,

156.

Hurd, Edwards and Roach, J . M . Ghem. Soc.. 66. 2013 (1944). R eaction of ketene w ith k eto e s te r s and d ik eto n es.

157.

Hurd and G laas, J . M . CHem. S o c.. 21, 3490 (1939)» C .i. 24, 986 (1940). Ketene from therm al decomposition of d ig ly c o lic anhydride,

158.

Hurd, Jones and Blunck, J , Am. Chem. Soc.. 57 . 2033 (1935) Ç.A. 2 0 , 82 (1936). Reaction of ketenes with G irgnard reag en ts.

159.

Hurd and K elso, J . Ghem. Soc. , tô , 1548 (l940)« C.A, 24* 6222^ (1940). “ A cetoacetyl ch lo rid e from diketene and dry HGl,

160.

Hurd and Kocour, J , Aja. Ghem. S oc,, 45.» 2167 (l9 2 3 ): C,|L, 17, 3479 ( 1923 ) , K etenic decomposition of methyl eth y l ketone.

161.

Hurd, Malcolm, and W illiam s, J . Aa. Ghem. Soo., f7 , 774 (l935)* G.A, 22, 3667^ (l9 3 5 ). P y ro ly sis of acety lp h th alim id e,

162.

Hurd and M artin, J , Ghem. S oc., 339® (1930). Ketene from a c e tic a c id .

3614 (l929)« G.A,

73 2

163.

Hurd and Roe, J , Chem. S oc.. 3355 (1939)* C.A. 1615 (1940). R eactions of ketene w ith a lc o h o ls, phenols, and aldehydes.

164 .

Hurd, Sweet and Thomas, J , Jig, Chem. Soc., 2 1 , 955® I 1933 ) . R eactions of ketene.

165.

Hurd and l a lly n , J . t o . Chem. Soo.. 4%, 1427 ll9 2 5 ): O.A. 12, 1853 (1925). Apparatus and optimum o p eratin g conditions fo r ketene from acetone,

166.

Hurd and T allyn, J . Am, Ghem. Soc.. 4 7 , 1779 (l925)* G.A. 1^, 2167 ( 1925 ) . K etenic decomposition of a cety la c e tone, d ia c e ty l, and pinacolone.

335 (l9 3 3 ): G.A.

167. Hurd and Thomas, J . Am. Ghem. S o c.. 275 (l933)* C,A, 27, 970 (1933). R eactions of ketene with a ry l aldehydes and a c id s , 168 .

Hurd and W illiam s, J . Jg . Chem. S o c.. gg, 962 (1936): C.A. JO, 5182® (1936). R eactions of ketene monomer and dimer,

169. H urdis and Snyth, J , Am, Chem. S oc.. 89 (1943)* C,A, j 7 , 1309* (1943). D ie le c tric constan t of diketene vapor, 170.

Jackson and C a h ill, J . B io l. Chem. . 126. 37 (1938): G.A. J J , 1317 (1939). A cétylation of 1-tryptophan and l-*phenylalamine,

171.

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172. Johnson and G ross, Paper presented a t the New York meeting of the American Chemical Society, A pril 1935. Hydrogenation of diketene to n -b u ty ric a cid and anhydride, 173.

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174. Johnston and Newton, U.S, P aten t 2,395,930 (March 5, 1946)* C.A. 429, 4078^ (1946). R eaction of HGN with ketene. 175. Kagan and F a lk o v sk ii, Compt. re n d , acad. s c i, (U .S .S .R .), 127 (1947)* C .i* 41, 7376 (1947). Heterogenous c a ta ly tic decomposition of acetone.

74

176.

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177.

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178.

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179.

Kodak, Lim ited, B ritis h P a te n t 581,473 (O ct. 14, 1946): C.A. 4 I , 2C73b ( 1947 ). Copolym erization of isopropenyl a c e ta te w ith m aleic and fum aric e s te r s ,

160.

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181.

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(1937).

182.

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(1945).

183.

2441

4 Kung, Canadian P a te n t 422,362 (to g . 29, 1944): Ç.A. J g , 6301 (l9 4 4 ): D.S. P a te n t 2,352,641 (J u ly 4 , 1944): Ç . ^ J g , 5507® (1944): " " « 2,376,704 (May 22, 1945): C.A. &0, 18681 (1946): 2,352,641 (J u ly 4 , 1944): Ç.A. J g , 55C7® (1944). R eactions of b e ta -la c to n e s.

164.

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185.

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186.

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187.

186,

2746

Law, German P a te n t 604,910 (Nov. 2 , 1934): U.S. P aten t 1,982,675 (Deo. 4, 1934): C.A. 2g, 482* (1935). R eaction of diketen e with ammonia and amines.

75

189.

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190 .

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191 .

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192 .

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193 .

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194 .

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195.

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196.

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197.

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C.A. j l ,

776

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198.

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199 .

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200.

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201.

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X 4692 7

6134

76

202. Malachowski and Wanizura, B u ll, in te r n , acad. p o lo n a ise , c la sse s c i. math, n a t . . 1933A. 547* C,A. 28, 4421^ 11934). Hydrogenation of dehydroacetic a cid using PtOg, 203.

Mellon I n s t i t u t e , Chem. Eng. Negs, 1522 (l9 4 S ), R eaction of diketene with th io u re a ,

204.

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205. M itch ell and R eid, J . M . Chem. S o c.. 912 (1931), K etenic decomposition of ketones.

330 (l9 3 l)* G.A. 2j^,

206.

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207.

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208. Mugdan and Sdxt, U.S. P aten t 2,249,543 (Ju ly 15, 1941): C.A. 21, 6604® (1941). Ketene from a c e tic acid , 209 .

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210. M uller and P e y tra l, Compt. re n d .. 196. 279 (l933)* G.^. (1933). Thermal decomposition of ketene. 211.

1864

Murty, C urrent S c i.. i , 424 (l9 3 7 ): C.A. 4644^ (l9 3 7 ). P a ra lle lis m between ketene and diazomethane,

212. Magnanl and McElvain, J . Am, Ghem. Soc. . 60, 2210 (l938)* C,4. 8360^ (1938). Bromoketene d ie th y l a c e ta l, 213.

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214.

Namethin and Fedosewa, Sintezy Dushistykh Veshchestv. Shornik S t a t e i . 1939. 199* Khim. R eferai, ghur... 1940 I 4 ) . 116: C.A, J 6 , 3783%11942), Ketene from acetone and a c é ty la tio n of alco h o ls.

77

215.

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216. New, R.G.A,, and Im perial Ghem, Ind. L td ,, B ritis h P a te n t 550,486 (Ja n . 11, 1943)1 Ç.A. 2à, 1534® (1944). D iketene used to convert a n ilin e to a c e to a c e ta n ilid e , 217. N i^ tin g a le , Canadian P a te n t 257,831 (Feb. 2 , 1926): C.A, 20, 2333 (1926), A cetic anhydride from k eten e, 218.

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219. N orrish, Crane, Saltm arsh, J . Chem. Soc.. 1933. 1533» G.A, 28, 1603® (1934). A bsorption sp e c tra and p h o to ly sis of ketene, 220.

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221.

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222. N.V. de B ataafsche Petroleum Naatschappy, French P a te n t 851,816 (Ja n . 16, 1940): G.A. 2 è , 1944® (1942). Ketene from alpha- b eta-u n sa tu ra te d k eto n es, 223.

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224. Oliveri-M andala and Ckilderaro, Gazz. chim. i t a l . 41, I» 538: G.A. 7, 3755 (1913). R eaction of ketenes with hydrazoic a c id . 225. O tt., Ann., AÇ1, 159 (1914)» C.A. 8 , 333 (1914). P rep a ra tio n of methyl bromo k eten e. 226. O t t ., I s E ., AZ, 2393 (l914)» G.A. 8, 3442 ( l 9 U ) . Carbon suboxide from d la c e ty l t a r t a r i c anhydride, 227. O t t ., S c h ra te r, and Packendorff, J , prakt chem., 130, 177 (l9 3 l): C.A. 25, 4221^ (1931). Ketene from acetone.

78

228.

Packendorff, Z e lin s k ii and Leder-Packendorff, B e r,, 66B, 1069 (1933)i Ç.A. 27, 4786 (1933). Ketene in th e F rie d e l-C ra fts re a c tio n ,

229.

Pappenhelmer, J . B lo l. Chem.. 125. 20 (1938): G.A. j 2 , 7954 (1938). E ffe c t o f ketene on d ip th e ria to x in ,

230.

Pearson. P u rc e ll and S a i ^ , J , Chem. S o c.. 1938. 409» C,A. (1938). Ketene from acetone,

231.

Perez and Candor, B u ll, soc. chim. b io l. . 2kt 5826® (1940). A céty latio n of cy stein e with ketene.

232.

P e y tra l, B u ll, soc. chim. ( 4 ) , 31, 122 (1922). Ketene from acetone,

233 .

P e y tra l, Comet, rend. . 193. 1119 (l9 3 l)» C.g. Ketene from a c e tic anhydride,

234 .

P e y tra l, French P aten t 722,477 (S ep t. 4 , 1931 ); C.A. 2^, 4063^ (1932), Manufacture of ketene.

235 .

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236.

P ïS tz ana D ie tl, German P aten t 736,194 (A p ril 29, 1943): O.A. 68, 2967® (1944). Action o f ketene with alp h a-b et a alkylene im ines,

237.

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238 .

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239.

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240 .

Reid, U.S. P a te n t 1,975,663 (O ct. 2 , 1934): G.A. 7268 (1934): B ritis h P aten t 413,709 (J u ly 20, 1934): G.to 22, 482® ( 1935 ): Canadian P aten t 355,617 (Ja n . 28, 1936): G.A. 62, 2578* (1936). Ketene generating apparatus.

149 (l940)» O.A,

1897^ (1932),

7

(1946),

79

241.

R ice, U.S. P aten t 1,879,497 (S ep t. 27, 1933): G .A . 27, 313* (1933), Ketene from acetone.

242.

R ice, U.S. P aten t 1,898,687 (Feb. 21, 1933): G.A. 27, 2694^ (1933), A cétylation with k eten e,

243 .

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244 .

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245 .

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246 . Rice and R obert, J . M . Ghem. Soc. . 65. 1677 (l943)» G.A. 6643® ( 1943 ). S tru c tu re o f dik eten e. 247 . Rice and V o lla rth , Proc. n a t. acad. s c i . . 15 . 702 ( 1929)» B ritis h dhem. a e r t . A, 1425 11929)» G.A. 2^, 5401 (1929), P y ro ly sis of acetone to k eten e. 248 . R oberts, Armstrong, Trimble, and Burg, J , A©. Chem. Soc. . 71, 843 ( 1949)1 G .a. 42, 4220e (1949). Use of 0** in the determ ination of th e s tru c tu re of aldoketene dim ers. 249 .

Roe and McGe^ee, J . Chem. Soc. . 70. 1662 (1948). R eaction of ketene with 2 n itro -4 -o h lo ro p h en y lsu lfen y l c h lo rid e and o ther organic halogen compounds,

250. Hosa, Rev. b r a s i l . chim .. 2 , 312 ( l9 3 l) i G.A. 21, 4523 P re p a ra tio n , p ro p e rtie s and re a c tio n s of k eten e.

( l9 3 l ) .

251. Rosenblum, J . Jn , Ghem. Soc. . 63. 3322 (l9 4 l)» G.A, 2^, 968 (1942). P h o to ly sis of ketene in presence of hydrogen and methane. 252 .

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1112-15 (l934)»

253 .

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80

254.

Sauer, D. S. P a te n t 2,238,826 (A p ril 15, l % l ) : C.A. J l , 4970 , ( 19141)1 U.S. P a te n t 2,268,169 (Deo. 30, 1 9 4 l)i G.4. 21, 2737 ( 1942 ) . Dehydrohalogenation of a cid c h lo rid e s to k eten es,

255 .

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256.

S o h e ib le r, B g r., 428 (l9 3 3 )i C .g. Z7 , 3195 (1933). P rep a ra tio n of th e d ie th y l a c e ta l o f ketene,

257.

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258 .

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259 .

Schonberg and S ina, J . Ghem. Soa, X9èlt 175; G.A. 4%, 5123c ( 1947 ). C o n stitu tio n of dim eric permanganate-colored diphenylketene.

260.

S ch ro eter, German P aten t 220,852 (S ep t. 16, 1908): G.A. 4 » 2188 ( 1910 ) . Ketenes and esocyanates from acid azides and diazoketones.

261.

Shilov, J . Chem. In d .. 7, 110 (l9 3 0 ): G.A. 2^, 4524 ( l9 3 l) . D ehydroacetic a c id a by-product of re a c tio n of methyl c h lo rid e and CO,

262.

Sixb and Mugdan, G .m ,b.h., U.S. 2 9 6 r (1938): 66 O4 ) ( 1941 ): 5988® ( 1943 ): 40299 ( 1935 ), Manufacture

488 C19I I ) ,

Ho Consortium fu r Electrochemische In d u s trie , P aten t 2,108,829 (Feb 22, 1938): G.A. J2 , U.S. P aten t 2,249,543 (Ju ly 15, 1941): G.A. 35. German P aten t 687,065 (Dec. 28, 1939): C.A. French P aten t 777,483 (Feb. 24 , 1935): C.A. 2^, of ketene from a c e tic a c id .

263 .

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264 .

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265.

Smith and Hoehn, J . Chem. S oc., §2, 1175 (1941): C.A. 2i» 43725 ( 1941 ). R eaction of diphenylketene with a s u b stitu te d a ce ty le n e.

7

81

266,

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267.

Snyder, Ph.D. T h esis, Purdue U n iv e rsity , June 1949, V inyl a c e ta te from acetalddhyde and k eten e,

268,

Soc. Kodak Polke, French P a te n t 673,051 (A p ril 13, 1929): G.A. 2 4 , 24.7 4 * ( 1930 ). Ketene from acetone.

269.

Sommelet, fiey. ggn. 62, 465 (1921): 0 .4 . 23, 58 (1922). A review of k eten es.

270 ,

Spence, M a ste r's T h esis, Purdue U n iv e rs ity , February 1944; Ph.D. T h esis, Purdue U n iv e rsity , February 1946. A cétylation of carbonyl compounds with keten e,

271,

Spence and D egering, B ritis h P aten t 605,471, U.S. P aten t 2.407.301 (S ep t. 10 , 1946): G.A. 41, 478b,d (1947); U.S. P aten t 2.407.302 (S ep t. 10, 1946); B r itis h P aten t 605,471 (J u ly 23, 1948): O.A. 42» 1436b (1949); U.S. P aten t 2,417,381 (March 11, 1947): C.A. 41, 4169b (l9 4 7 ): J . Am. Chem. S oc., ^ 6 , 1624 (1944): C.A. 4975 ( 1945 ), Condensation of ketenes with k eto e s te r s or diketones.

272 .

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273 ,

Standard O il Development Company, French P aten t 742,985 (Mardi 2 1 , 1933)1 Ç.E. 27, 3722* ( 1933 ). Manufacture of ketene.

274,

Standard Oil Development Company, U.S. P a t e n t 1 , 998,404 (A p ril 16, 1935)1 2 2 , 3689 ( 1935 ). Manufacture of diketene and u t i l i z a t i o n in c e llu lo se e s te r s .

275 .

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276.

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277.

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82

278.

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279.

S taudinger, Helv. c h ia , a c t a ., 7 , 3 Cl924)* G.A. Ig , 1284 Cl924). S tru ctu re of dim eric k eten es,

280,

Staudinger e t . a l . , H elv. ohlm. a c ta . . 6, 287 (1923)î G,A, 37, 1952 11923)» B ez., 6É, 3539 tl9 1 3 ) . " Ketenes prepared from h e atin g malonic anhydrides.

281.

S taudinger, D yckerhoff, K lever, and Ruzicka, B e r., ( 1925 ): Ç.A. 12, 2658 ( 1925 ). Peroxides from s u b s titu te d k eten es,

282,

Staudinger e t . a l . , Helv. ohlm. a c ta . . 8, 314, 322 ( 1925)4 C.Â. 1 2 , 2189 I 1925 ) . R eactions of dimethyl ketene with iso cy an ate.

283,

S taudinger, (jôhring, and ScH dller, B e r.. 4 7 , 40 ( I 9I 4 ); C.A. 8, 1112 ( 1914 ). R eactions of diphenyl ketene w ith acid c h lo rid e s,

284 .

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1079

285. Staudinger and J e la g in , B e r,, 44, 365 (l9 U )* C.A, Action of diphenyl ketene on n itro so compounds,

1746 (1 9 H ),

286. Staudinger and K lev er, B e r., 4 0 , 1149 ( W ) s R eactions of dim ethyl ketene,

1562 (1907).

Ç.A, I ,

287,

Sta.udinger and K lever, B ^ . , 4 I , 594 (19% ): C.A, 2 , 1552 (1908). P rep a ra tio n and re a c tio n s of keten e,

288,

Staudinger and K lever, B e r,, 906 (1908): C.A. 2, 1693 ( 19 O8 ). P rep a ra tio n of ketenes ty dehalogenation of alnha-h alo a cid h a lid e s ,

289. Staudinger and K lever, Ber. , 41. 1516 ( 19O8 ): C.A. 2 , 2224 ( 19 O8 ), P r io r ity i s adm itted to Wilsmore and Stewart concerning discovery of ketene. 290 ,

Staudinger, K lever, and Kober, Ann. . 374. 1 (l9 1 0 ): C.A, 4 , 2304 ( 1910 ). R eaction of dimethyl ketene with beta-n ap th aq u jn o lin e.

291 ,

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83

292.

Staudinger and Kubinsky, B e r., 4 2 , 4213 11909): C.A. 4 , 450 C19IO ). Ketene from dehalogenation of h a lo -a c e ty l h a lid e s .

293 .

Staudinger and O tt., B e r., 4 I , 2208 ( I 9OS): C.A, 2 , 2808 (1 9 % ). D ialkylm alonic anhydrides y ie ld k etenes on h e a tin g .

294 .

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295 .

Staudinger, Schneider, Schatz and Strong, Helv. chim. a c ta . . 6, 291 ( 1923)1 G,A. a , 1953 ( 1923 ). S u b stitu te d keten es from s u b s titu te d malonic a c id s,

2625

296 .

Staudinger and Schneider, Helv. chim. a c ta . . 6 , 304 (l9 2 3 )i C.A. U ., 1953 (1923). Amino, halogen, and hydro%y s u b s titu te d k e ten e s,

297 .

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298 . Staudinger and Tuerck, B r itis h P aten t 539,163 (Aug. 29, 194l)s £ . 4 . 2â, 35095 ( 1942)1 U.S. P a te n t 2,316,465 (A p ril 13, 1943): G.A. J 2 . 5734* (1943). Reaction of ketene w ith alpha h alo e th e rs.

299.

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7413a a

300. S te ik , U .S. P aten t 2,086,582 (J u ly 13, 1937): C.A. 21, 6260 (1937). Ketenes from aldehydes and alco h o ls, 301. S te ik and Gleason, U.S. P aten t 2,099,909 (Hew. 23, 1938): C.A. 22, 195^ (1938). Mixed anhydrides from ketene and naphthenic a c id s, 6 302. S te ik , U.S. P aten t 2,184,963 (Deo. 26, 1939): G.A. 2à, 2866 (1940). Manufacture of ketene, 303.

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4687

304 .

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84 5

305.

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2635

11936).

306 .

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307.

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308.

Thompson and L in n e tt, J , Chem. Soc. , 1937. 1384: G.A, 31, 7754 (1937). C a lcu la tio n of force c o n sta n ts from v ib ra tio n freq u en cies of ketene,

309 .

Tompkins, M aster’ s T hesis, Purdue U n iv e rsity , June 1945. alp h a. b e ta-U nsaturated a c id s from ketene and carbonyl coEpounds,

310.

Tsukervanik and Ermolehko, B u ll, un lv . Asie. Cen tr a le . 22, 215 (1938), Ethyl a ce to a c e ta te from d ik eten e and a lco h o l.

e

311. van Alphen, Rec. tr a v . chim .. 41, 823 ( I 924 ): G ,|. 3 ^, 1253 (1925). ^ t i o n of d is u b s titu te d k eten es on hydrazine d e riv a tiv e s, 312. van Alphen, Re^. tr a v . chim. . 4 4 , 838 (l9 2 5 ): G.A. I g , 3483 (l925)< R eaction of ketene w ith hydroxybenzoic acids and e s te r s , 313.

Vollman. S c h lo ffer and Ostrawski, German P aten t 736,504: C.A, 18, 2970 ( 1944 ). R eaction of ketene with HCN,

314 .

von E uler and Ahlstrom, Arkiv. Eemj Min. Geol. , 11 ( 2 ), 1 (1932): c .a . 2 2 , 950 ( 1933 ). R eaction of ketene with quinone and isoprene,

315.

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316.

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317.

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85

318.

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319 .

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320.

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321.

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322.

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323.

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324.

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325.

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326.

W illiams and Osborn, J . Ghem. S ag ., 2 à , 1004 (1940). F rie d e l-G ra fts c a ta ly s ts with k eten e,

327.

W illiams and Sadie, J . ghem. S o c., 62, 2801 ( 194 O): C.A. 2A, 7878 ( 1940 ) . R eaction of ketene with ortho and p ara-hydroxybenzald^ydes.

328.

Wil3.iams, Yancey, D ickert and K rynitsky, J . Chem. S oc,, 61, 2510 (19a) » G .J. 21, 7379* ( l9 4 l ) . Mixed a c e tic anhydrides from ketene and organic a c id s,

329 .

Williamson, J . Am. Ghem. S oc., 16, 2216 (l943)» G.A. 729 ( 1935 ). Polym erization and therm al decomposition of k eten e.

4

2510

3438 (l939)» G.A.

6

86

330.

Wilsmore, J . Ghem. S oc.. 91. 1938 (19Û7): fro o . Chem. S oc., 21, 229* N a to e . $10, C.A. 2 , 798 (1908). D iscovery of ketene.

331.

Wilsmore and S tew art, B e r., 41, 1025 (l908): C.A. 2, 1961 (1 9 % ). P r io r ity claim s on k eten e discovery.

332.

W ollenberg, B e r., 1675-9 (1934): G.A. 22, 471 Condensation of ketene w ith p y rid in e .

333.

Wood and Ross, J . B io l. Chem.. 146. 59-62 (l9 4 2 )t G.A. 27, 1 4 ^ ^ (1943). A cétylation of p arath y ro id hormone with k eten e.

334.

Young and R eid, U.S. P a te n t 1,926,642 (S ep t. 12, 1933), G.A. 27, 5753 (1933): B r itis h P a te n t 377,574 (Ju ly 28, 1932), G.A. 27, 3946 (1933)* French P a te n t 730,797 (Feb. 1, 1932): G .Ï. 27, 306 (1933)* Canadian P a te n t 338,162 (Dec. 26, 1933): C.A. 2^, 1718 (1934). U tiliz a tio n of ketene fo r a c é ty la tio n s .

335.

Young, U.S. P aten t 2,461,016 (Feb. 8 , 1949)* C.A. 42, 3838h (1949). Enol a c e ta te s from ketene and k etones.

(1935).

87

APPE1DI2 Reagents American Gyanamid Company Cyanuric ch lo rid e 25 Glyooni^brile, 50^ aqueous s o lu tio n , b. 70-72^0, a t 4 mm.) n^

1.4085

L a c to n itrile J . T. Baker Chemical Company A cetic a c id , C .P ., g la c ia l P e rc h lo ric a c id , G .P ., 7Cl ?2^ Phosphoric a c id , C .P ., 85^ S u lfu ric a c id , C .P ., sp, g r. 1.84 The B a rre tt D ivision Benzene Cthiophene fre e ) Carbide and Carbon Chemicals Corporation A cetic anhydride Acetone 99'"100 ^ 25 B utanal, b. 74.5-75®C. a t 754 mm.) n^ 1.3782 Butanone Dioxan, b. 99.8®C. 25 Ethyl a c e to a c e ta te , b. 33-4%G. a t 2 mm.) n^ 1.4172 Methyl e th y l k etone, b . 78.5^C. a t 746 mm.) n^^ 1.3767 Methyl iso b u ty l k eto n e, b . 114.5^0., n^^ 1.3940 2.4-Pentanedione, b. 38,8-39^C. a t 21 ram.) n^^ 1.4452 C ity Chemical C orporation 1-Menthol Dow Chemical Company Carbon te tr a c h lo r id e , b. 75®C. Eastman Kodak Company Chloroacetone P647, b. 117.5 to 119®C. Ethyl benzoylacetate 2371, b, 104®C. a t ,5 mm.) n_ 1.5268 2.4-D initrophenylhydrazine, 1866 25 Isopropenyl a c e ta te , b. 97.9®G. a t 751 mm.) n^ 1.3986 P r o p io n itrile P528, b. 96.8^0. a t 740 mm.

88

du Pont de Nemours and Company. In c . Trioxan Ammonia, liq u id T ric h lo re th y le n e , b. 85*7®C. a t 741 mm. T etrahydrofuran, b. 65®C. a t 740 mm. F o rest Products Company