The Synthesis of Rocket Propellants

Citation preview

/ P ,5 5 7 PU R D U E UNIVERSITY

T H IS I S TO C E R T IF Y TH A T T H E T H E S IS P R E P A R E D U N D E R MY S U P E R V IS IO N

BY

Wayne May

e n title d

THE SYNTHESIS OF ROCKET PROPELLANTS

C O M P L IE S W ITH T H E U N IV E R S IT Y R E G U L A T IO N S O N G R A D U A T IO N T H E S E S

A N D IS A P P R O V E D B Y M E A S F U L F IL L IN G T H IS P A R T O F T H E R E Q U IR E M E N T S

FO R THE D E G R E E O F

Doctor o f Philosophy

P

-H

r o f e s s o r in

ead

of

S

Charge

chool or

19

TO T H E L IB R A R IA N :---T H IS T H E S IS I S N O T TO B E R E G A R D E D A S C O N F ID E N T IA L ,

G R A D . SC H O O L FO RM

9 —3 . 4 9 —1 M

D

of

Th

e s is

epartm ent

THE SYNTHESIS OF ROCKET PROPELLANTS

A Thesis Submitted to the Faculty of Purdue U niversity

by

Wayne May

In P a r tia l F u lfillm en t o f the Requirements fo r the Degree

of

Doctor o f Philosophy

August, 19!>Q

ProQuest Number: 27714181

All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is d e p e n d e n t upon the quality of the copy subm itted. In the unlikely e v e n t that the a u thor did not send a c o m p le te m anuscript and there are missing pages, these will be noted. Also, if m aterial had to be rem oved, a n o te will ind ica te the deletion.

uest ProQuest 27714181 Published by ProQuest LLC (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 LLC. ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106 - 1346

ACKNOWLEDGMENT

The author wishes to express h is sin cere ap p reciatio n to Dr. Henry Feuer f o r h is guidance and help and to Dr. G. B. Bachman and Dr. H. B. Hass fo r th e i r many valuable suggestions during the course o f t h i s resea rch . The author a lso wishes to thank the A erojet Engineering Corpor­ a tio n , the O ffice of Naval Research and the Purdue Research Foundation fo r g ranting the funds necessary fo r th is rese a rc h .

TABLE OF CONTENTS Page ABSTRACT PART 1. THE MANNICH REACTION OF CERTAIN DINITRÛ ALCOHOLS iETH GLYCINE AND BTHANOLAMENB................................................

i

PART 2. THE PREPARATION OF 2-METHYL-2-NITRO-1,3DIBRŒ&OPROPANE............................................................................

x lx

INTRODUCTION....................................................................................................

1

PART I . THE MANNICH REACTION OF CERTAIN DINITRÛ ALCOHOLS DETH GLYCINE AND ETHANOLAMINE In tro d u ctio n .

...................................................................................

D i s c u s s i o n .................................................

h b

Experimental 1. Reaction of 2 ,2 - D in itr o -l,3-propanediol n ith Ethyl G l y c i n e .....................................................................

22

2. P reparation o f l-Carbethoxymethyl-3,3> 5 - t e t r a n i t r o p i p e r i d i n e ................................................................

23

3. P reparation o f l-Carboxym ethyl-3,3 , 5 - te tr a n i t r o p i p e r i d i n e ................................................................

23

Reaction of 2 ,2 -D in itro -l,3 -p ro p an ed io l with Glycine H y d r o c h lo r id e ....................................................

2h

*>. P reparation o f l-C arbethoxym ethyl-3,3 , 5 - te tr a n itro p ip e rid in e and l-Carboxym ethyl-3,3 * 5t e t ran i tro p ip e rid in e from 2 ,2 -D in itro -l, 3propanediol and Ethyl Glycine Hydrochloride . • •

21*

6. Hydrolysis o f l-Carbethoxymethyl-3^3 ,5 ,S - te tr a n i t r o p i p e r i d i n e ................................................................

25

7. E s té rif ic a tio n o f l-Carboxymethyl-3,3> 5 » 5te tr a n i t r o p i p e r i d i n e ........................................................

25

8.

25

P reparation o f Sodium Dini t r o e t h a n o l .........................

Page 9.

Reaction o f Glycine Hydrochloii de with Sodium D i n i t r o e t h a n o l ....................................................

25

10.

P reparation of Ethyl 5> 5 -D in itro -3 -azav alerate

. .

26

11.

P reparation of Ethyl 3> 5> 5 -T rin itro -3 -a z a v a le ra te .

26

12.

P rep aratio n of Ethyl 5-Bromo-3> 5>5 - t r i n i t r o 3 - a z a v a l e r a t e ...................................................................

27

Attempted Reaction o f Ethyl 3 ,5 > 5-T rinitro3 -azav alerate, Formaldehyde, and Ethyl Glycine H y d r o c h lo r id e ....................................................................

28

Attempted Reaction of Ethyl 3> 5>5 -T rin itro 3-azaval era te , Formaldehyde, and Glycine H y d r o c h lo r id e ....................................................................

28

Attempted Reaction o f Ethyl 3 ,5 ,5 -T rin itro 3 -az av a lera te , Formaldehyde,and G ly c in e ...................

28

Attempted Reaction o f the Sodium S a lt o f Ethyl 3 ,5 ,5 -T rin itro -3 -a z a v a le ra te , Formaldehyde, and Ethyl Glycine H y d r o c h lo r id e ................................

29

Attempted Addition of Formaldehyde to Ethyl 3 ;5 ;5 -T rin itro -3 -azav al e ra te .......................................

29

18.

P reparation of 5; 5 -D in itro -3 -aza-l-p en tan o l . . . .

29

19.

Reaction of 2 ,2 -D in itro -l,3 -p ro p an ed io l with Ethanolamine Hydrochloride .......................................

30

Reaction o f Sodium D in itroethanol with Ethanolamine ....................................................................

31

Reaction o f 5> 5 -D in itro -3 -aza-l-p en tan o l with Acetyl C h l o r i d e ......................... .......................................

31

Attempted Addition of Formaldehyde to 5 ,5 D in itro -3 -a za -l-p e n ta n o l ................................................

31

13*

11*.

15• 16.

17.

20. 21. 22. PART H .

ATTEMPTED SYNTHESES OF POLYNITRO CARBOXYL!C ACIDS

In tro d u ctio n D iscussion

...................

33

............................................................................................

31*

P reparation of 2-M ethyl-2-nitro-1,3-dibrom op r o p a n e ................................................................................

1*0

Experimental 23*

Page 21*. 2f>. 26. 27. 28. 29 • 30. 31. 32. 33. PART H I .

Attempted V ictor Meyer Reaction on 2-Methyl2-ni tro -1,3-dibrom opropane...........................

1*1

P reparation o f 2 ,2 -D in itro -l, 3-dibromo­ propane ............................................................................

1*2

Reaction of 2 ,2 -D in itro -l,3 -p ro p an ed io l with Chromic Trioxide and Acetic A n h y d r id e ................

1*2

Attempted Oxidation o f 2,2-D in itro -1 ,3 propanediol w ith Fuming N itric A c i d .....................

1*3

Attempted Reaction o f Potassium Dinitromethane with Ethyl C hloroacetate .......................

1*3

Attempted Reaction o f Potassium Dinitromethane ............................ with Ethyl lo d o acetate

1*1*

Attempted Reaction of Potassium Dinitromethane w ith Ethyl - i o d o p r o p io n a te ................................

1*1*

Reaction o f Sodium Mai onate with Dibromo........................................... d in i tromethane

1*5

Attempted Reaction o f 2-M eth y l-2 -n itro -1 ,3dibromopropane with G l y c i n e .......................................

1*5

Attempted Reaction of Dibromodinitromethane w ith Glycine ................................................................

1*6

AN ATTEMPTED SYNTHESES OF 2 ,2-DINITRO-l, 3-PR3PANEDEOL

I n t r o d u c t i o n ........................................................................................

1*7

D i s c u s s i o n ...................

1*7

Experimental 31*. 35» 36. 37•

P reparation o f the Sodium S a lt of 2-N itro1 ,3-propanediol ............................................................

50

P reparation of 2-B rom o-2-nitro-l,3p r o p a n e d i o l ...................................................................

50

P reparation o f th e D iacetate of 2-Bromo-2n itro - 1 , 3-propanediol ................................................

51

Attempted P reparation o f the D iacetate o f 2 ,2 -D in itro -l,3 -p ro p an ed io l by the V ictor Meyer Reaction

51

Page 38.

P reparation o f 2 ,2 -D in itro -l, 3-propanediol by the Method of Shechter andK a p la n ......................

£1

PART IV . THE ATTEMPTED REACTION OF NITRO PARAFFINS WITH ISOCYANATES I n t r o d u c t i o n ........................................................................................

53

D i s c u s s i o n ............................................................................................

Sk

Experimental 39»

Attempted Reaction o f Nitromethane with Phenyl I s o c y a n a t e ........................................................

55

1*0.

Attempted Reaction o f Nitromethane with Naphthyl I s o c y a n a t e .....................................................

56

Attempted Reaction of Ethyl Isocyanate and Potassium Nitroform .........................................

56

Reaction of Nitroform

57

1*1. 1*2.

. .

.................................................................................................

58

................................................................................................................

60

BIBLIOGRAPHY VITA

w ith PhegylIsocyanate

LIST OF TABLES Table I

II

III

IV

V

Page E ffe ct o f pH on the Reaction o f Ethyl Glycine Hydro­ chloride w ith 2 ,2 -D in itro -l,3 -p ro p an ed io l .........................

8

E ffe c t of Temperature o f th e Reaction o f Ethyl Glycine Hydrochloride with 2 ,2 - D in itr o -l,3propanediol . . .................................................................

9

E ffe ct o f Mole Ratio on th e Reaction o f Ethyl Glycine Hydrochloride w ith 2 ,2 -D in itro -l,3 -p ro p an e d io l . . . .

10

E ffe ct o f Mole Ratio on th e Reaction of Glycine with 2 ,2 -D in itro -l, 3 -p ro p a n e d io l...........................................

12

. •

Attempted P reparation of 2-Meth y l-2 -n itr o - 1 ,$ p e n ta n e d in itrile ........................................................

36

Department of Chemistry and Purdue Research Foundation, Purdue U niversity, L afay ette, Indiana THE MANNICH REACTION OF CERTAIN DINITRO ALCOHOLS WITH GLYCINE AND ETHANOLAMINE1

1.

A bstracted from a th e s is by Wayne May, subm itted to the fa c u lty of Purdue U niversity, in p a r tia l fu lfillm e n t o f the requirem ents for the degree o f Doctor of Philosophy, August, 1950.

By H. Feuer, G. B. Bachman and W. May AN ABSTRACT The Mannich re a c tio n s o f d in itro alcohols itith glycine and ethanol­ amine were in v e stig a te d as a means of obtaining nitromonomers which would be u sefu l in the prep aratio n o f n itr o p la s tic s .

I t was expected

th a t 2 ,2 -d in itro -l,3 -p ro p a n e d io l (I) would condense w ith 2 molecules of glycine ( I I ) to form S,S -dinitro-3,7-diazanonanedioic acid . no2

H no2 H HOCH2-C-CH2OH + 2H2N-CHg-C02H ------> HOgC-CHg-N-CHg-C-CHg-N-CHg-COgH no2 no2 I

II

However, when I was reacted with glycine ( I I ) , glycine hydro­ ch lo ride ( I I I ) , and ethyl glycine hydrochloride* (IV) re sp e c tiv e ly , the expected nonanedioic acid d e riv a tiv e s were not obtained; in ste a d c y c lizatio n occurred with the form ation of l-carbethoxym ethyl-3,3 ,5 ,5 - te tr a n itro p ip e rid in e (V) and l-carboxym ethyl-3,3 ,5 ,5 -te tra n itro p ip e rid in e (V I).

a.

Ethyl glycine can not be used because i t polymerizes re a d ily .

il

These re a ctio n s are summarized in the follow ing equations: o2n j ° 2 no2

/ _CH\

c T H,N+-CH5-C0,Et 4- HOCH,-C-CH,OH ■ H2°—>■ H-CI 3 2 2 2 NO 2 70° 2

N-CH2-C02Bt 4* 71

CH^ 17 BtOH H+

HC1 A

A

II h2m- ch2- co2h

09N NO, 2 \/ 2 C— CHa.

or Cl H,N -CHj-COgH

/

\

H,C 2X

4-

n- ch2- co2h

70

in

C— CHg OgN NOg /\

The re a c tio n procedure consisted of h eatin g an aqueous so lu tio n o f I and th e glycine d e riv a tiv e to 70° and recovering the p re c ip ita te d pro­ duct by f i l t r a t i o n .

Removal o f th e p r e c ip ita te as i t formed during the

re a c tio n o f I w ith 17 gave the e s te r (7) as the only product.

However,

i f th e p r e c ip ita te was allowed to remain in the a c id ic re a c tio n mixture fo r sev eral hours, p a rt o f e s te r (7) was hydrolyzed to acid (7 1 ).

The

acid (71) was separated by r e c r y s ta lliz a tio n from $0% alcohol, while the e s te r (7) was recovered from the alcohol in so lu b le resid u e by r e c r y s t a l l i ­ zatio n from carbon te tr a c h lo rid e .

The e s te r (7 ), a l i g h t yellow c r y s ta llin e

compound, melted a t 126-127°5 the a cid (71) was a white s o lid m elting a t 1U5-1U60 . The in flu en ce o f tem perature, pH, and mole r a tio on the re a c tio n of th e d io l ( I) w ith th e e s te r hydrochloride (17) i s shown in Tables I , I I , and I I I .

An aqueous m ixture o f the two re a c ta n ts had a pH o f U

ill

Table I E ffe c t o f pH on the Reaction o f Ethyl Glycine Hydrochloride w ith 2 ,2 -D in itro -l, 3-propanediol.

Run

Solvent

Temperature

pH o f Reaction

Reaction Time

1

Water

70°

7a

8 hours

Tar form ation

2

Water

30°

7a

8 hours

Tar form ation

3

Water

30°

U

8 hours

5% y ie ld of Ib

a.

Reaction m ixture was n e u tra liz e d w ith sodium carbonate.

b.

I

= l-Carbethoxymethyl-3> 3# 5> 5 -te tra n itr o p ip e r id in e .

Remarks

Table I I E ffe c t o f Temperature on the Reaction of Ethyl Glycine Hydrochloride w ith 2 ,2 -D in itro -l,3 -p ro p a n e d io l.

Run

Solvent

Temperature

pH o f Reaction

Reaction Time

h

Water

35°

k

8 hours

656 y ie ld of I b

5

Water

70°

h

8 hours^

2056 y ie ld o f I b>e

6

Water

70°

k

8 hours

656 y ie ld of I b 9% y ie ld o f I I e»f

7

Water

70°

h

18 hours

356 y ie ld of I b 1556 y ie ld o f I I e»8

8

Water

90°

U

2 hours

Tar form ation

Remarks

b. c.

I = l-Carbethoxym ethyl-3,3, 5 -te tra n i tro p ip e rid in e • I I = l-Carboxymethyl-3, 3,5 >5 -te tr a n i tro p ip e rid in e .

d.

Product was f i l t e r e d from so lu tio n as i t formed.

e.

Recovered 1$% o f th e d io l, 26% o f ethyl glycine hydrochloride and t a r

f.

Recovered 1756 o f the d io l, 23% o f eth y l glycine hydrochloride and t a r

g.

Recovered 9% of th e d io l, 1256 o f e th y l glycine hydrochloride and t a r .

Y

Table I B E ffe c t o f Mole R atio on th e Reaction of Ethyl Glycine Hydrochloride w ith 2 ,2 -D in itro -l,3 -p ro p an e d io l.

M illim oles o f Diol

M illim oles o f Ethyl Glycine HC1

Temperature

Reaction Time

9

20

hO

70°

8 hours**

20% y ie ld of Ib

10

20

20

70°

8 hours**

956 y ie ld of Ib

11

ko

20

70°

8 hours^

T% y ie ld of Ib

Run

b.

I

s

l-C ^b eth o x y m eth y l-3 > 3 ,5 > 5 -tetran itro p ip erid in e.

d.

Product was f i l t e r e d from so lu tio n as i t formed.

Remarks

▼i

(Hydrion B paper) and any attem pt to n e u tra liz e th e so lu tio n caused t a r form ation.

The optimum re a c tio n tem perature was about 70°; higher

tem peratures gave a t a r as th e only product while lower tem peratures decreased the y ie ld s .

A r a tio o f 2 moles o f IV to 1 mole o f I gave a

b e tte r y ie ld than e ith e r a 1 to 1 r a t i o o r a 1 to 2 r a t i o o f th e re ­ a c ta n ts .

The h ig h est y ie ld o f V obtained was 20$ and even though the

recovery o f some s ta r tin g m aterial a f t e r 18 hours in d ic a te d th a t the re a c tio n was incomplete# a longer re a c tio n tim e le d to an in crease in th e amount o f t a r in ste a d o f the d esired product. Glycine ( I I ) rea cte d with th e d io l (I) to give a $2% y ie ld o f acid (V I).

However, the use o f glycine hydrochloride ( I I I ) in p lace o f I I

lowered th e pH of the re a c tio n m ixture below h (Hydrion B paper) and gave only an 18$ y ie ld o f VI.

The a c id (VI) could be e s te r if ie d to the

same e s te r (V) as obtained from the d io l ( I) and the e s te r hydro­ ch lo rid e (IV ). Sodium d in itro e th a n o l (VII) gave a 25$ y ie ld of the c y c lic a d d (VI) when reacted with glycine hydrochloride ( I I I ) . ( I I ) did not r e a c t w ith VII a t a pH o f 7»

However, glycine

When the pH was lowered from

7 to k (Hydrion B paper) a re a c tio n appeared to occur because the solu­ tio n turned red and the tem perature rose from 27° to 3h° * However, no compound could be is o la te d . 2 Urbanski rep o rted th a t 1-nitropropane, formaldehyde, and ammonia

2.

Urbanski, e t a l . , J . Chem. Soc. , 921* (191*7) •

rea cte d to give a c y clic product (V III).

Heating V III in hydrochloric

v il

HC1 v

wnnw

NOg âi c. Et

v

0„NZ VEt 2

Cl N09 H |i i | *t -n-n» _mm«p.h OH -j- CH^O Bt

VIII

a d d re s u lte d in rin g opening, thus showing t h a t an e th e r linkage was p re se n t.

The fa c t t h a t the acid (VI) was not changed a f t e r heating

f o r 12 hours with concentrated hydrochloric acid i s evidence th a t a carbon-carbon bond was formed in t h is compound. The presence of a t e r t i a r y nitro g en was in d ic a te d by the f a ilu r e o f sev eral attem pts to n i tr a te e ith e r V o r VI as w ell as the f a ilu r e to prepare a p-toluenesulfonam ide d e riv a tiv e . I n c o n tra s t to t h e ir s t a b i l i t y to acid, compounds V and VI de­ composed in basic media.

Attempts to is o la te a decomposition product

by treatm ent o f V with base were u n successful. The e s te r (V) was t i t r a t e d po ten tio m etid eally to give a value o f 3U5 fo r the m olecular weight (ca lcd . 351) > but attem pts to t i t r a t e th e acid (VI) gave no sharp end p o in t. Experimental evidence i s not a v aila b le to show the manner in which th ese c y c lic products (V and VI) were formed but some analagous re a c tio n s are rep o rted in th e l i t e r a t u r e .

The follow ing sequence o f re a ctio n s i s

proposed only as one o f the ways in which the re a c tio n s might have occurred.

i.

hoch2- c- ch2oh

I

^

t

HOCH2-CH 4 - CHgO

viil

2.

CHgO

+ H2N-CH2-C02H

^ H0CH2-N-CH2-C02H

II

?

3.

HOCH2-N-CH2-C02H

1*.

N°2 HOCH2-CH

{

c

~ >

H+

7.

+ ? CH2-N-CH2-C02H

N02 HOCH2-C ®

N02

5.

»

+

4 - H20

H+

no2

? °2 , 4 ? HOCHg-C (S) _j_ CH2-N-CH2-C02H

HOg N02 H HOCH2- C ^ ^GHg-C-CHg-N-CHg-COgH NO,

0oN NOp 2 xy c CHgOH

/

h2c

\

» C— CH^- N—CH^—COjH °2N »°2 X

NO.

0«N NOp 8.

X

/ x-> HgC

c\

N-CH2-C02H H

The various ste p s can be compared to analagous re a c tio n s reported i n th e l i t e r a t u r e .

The equilibrium o f re a c tio n 1 i s in agreement w ith

ix

th e experim ental evidence o f Senkus^ and was f a rth e r strengthened by

3»

Senkus, J . Am* Chem. Soc., 68, 10 (19^6).

th is in v e s tig a tio n .

The f a c t th a t the d io l (I) and d in itro e th a n o l (VII)

gave the same product when rea cte d w ith glycine ( I I ) shows th a t formalde­ hyde was s p l i t from the n itr o alcohol during the re a c tio n .

The form ation

o f a methylol d e riv a tiv e of th e amine as the f i r s t interm ediate (re a c tio n 2) i s supported by th e work o f Alexander and U nderhill^ which showed th a t

I*.

Alexander and U nderhill, J . Am. Chem. S o c., 71» UOlU (19U9) •

the same r a te constant was obtained when the N -methyl o l amine was used i n place o f th e amine and formaldehyde in the Mannich re a c tio n .

Re­

a ctio n s 3, L, and 9 lead to th e expected Mannich product (IX) according to the mechanism proposed by Liebermarm and Wagner.** Compound IX then

5»

Liebermarm and Wagner, J . Org. Chem.» lit, 1001 (191*9)•

re a c ts with another molecule o f d in itro e th a n o l (re a c tio n s 6 and 7) to form the u n stab le interm ediate (X) which cy cliz es immediately to the f in a l product (re a c tio n 8 ).

The in term ed iate (X) has the s tru c tu re of

a d e lt a - amino alcohol and such compounds are known to cy clize very re a d ily to p ip e rid in e d e riv a tiv e s .^

6.

Lipp and TEdmann, Ann. 1*091 79 (1912).

X

In th e case o f the re a c tio n of sodium d in itro e th a n o l (VII) with eth y l glycine hydrochloride (IV) c y c lis a tio n d id not occur, in ste a d e th y l 5>, f> -dinitro-3-azavalerate (XI) was formed in a &$% y ie ld .

A

fa c to r which might account fo r th is was the higher pH (5-6) o f the re a c tio n m ixture as compared w ith the pH o f U in the rea ctio n s which le d to c y c lis a tio n .

The product (XI) was obtained as yellow p la te - lik e c ry s ta ls which m elted a t 102-103° with decomposition.

This e s te r (XI) decomposed

when allowed to stand a t 25° fo r two o r th ree days. The presence o f a secondary nitro g en was in d ic a te d by the f a c t th a t e s te r (XI) was n itr a te d with a m ixture of concentrated s u lfu ric and fuming n i t r i c acids to give eth y l 3 ,5> 5 -trin itro -3 -a z a v a le ra te (XII) as a white s o lid which melted a t 1*1 - 142° .

XI

NOg N02 H— C— CHg—N— CHg— COgEt

In c o n tra st to the u n n itra te d e s te r (X I), XII did not decompose on stan d in g . The presence o f a hydrogen on the carbon containing th e two n itr o groups was e sta b lish e d by tr e a tin g e s te r (XII) with sodium methoxide to give a q u a n tita tiv e y ie ld of the sodium s a l t (X III) which decomposed a t

xi

87-88° •

By re a c tin g XIII w ith bromine, a white s o lid , e th y l 5-bromo-

3,5»5 - t r i n i tro -3 -a z a v a le ra te (XIV), was obtained which melted a t $7-58°* N i O20 N09 i CHC1. '3

NOg NOg Br-C-CHA-N-CHo-C0oBt . ‘2 ^ 2 2^ N0o XIV

A t t e s t s to hydrolyze the e s te r (XU) to the corresponding acid by reflu x in g with concentrated hydrochloric acid gave only decomposition w ith ev olution o f n itro g en dioxide. Ethyl 3 ,5 ,5 - t r i n i t r o-3-azavale ra te (XII) would not undergo a fu rth e r Mannich condensation w ith formaldehyde and glycine ( I I ) , glycine hydro­ c h lo rid e ( I I I ) , o r e th y l glycine hydrochloride (IV ).

In each case some

t a r form ation occurred and glycine o r the hydrochlorides were recovered. The use o f the sodium s a l t (X III) i n place o f the e s te r (XU) i t s e l f in a re a c tio n w ith formaldehyde and e th y l glycine hydrochloride (IV) gave a ta r.

An attem pt to add formaldehyde to the e s te r (XII) re s u lte d in a

dark gummy residue which could not be c ry s ta lliz e d . Ethanolamine (XV) was found to re a c t w ith 2 ,2 - d i n it r o - l,3-propane­ d io l ( I) to give an 82% y ie ld o f $ ,5 -d in itro -3 -a z a -l-p e n ta n o l (XVI) as

xii

b rig h t yellow c ry s ta ls which melted a t 115-116° with decomposition. The pH o f t h is re a c tio n was 6-7*

The same product (XVI) could be ob­

ta in e d from the d io l (I) and ethanolamine hydrochloride i f th e pH o f th e aqueous so lu tio n was ra is e d from 3 to 6 by the ad d itio n o f base. When sodium d in itro e th a n o l (VII) was reacted with ethanolamine (XV) i t was necessary to lower th e pH from 11 to 7-8 before th e pentanol (XVI) would form in a 69% y ie ld . The pentanol (XVI) reacted with a c e ty l ch lo rid e to give N -acetylg -aminoethyl alcohol, m.p. 62-63° ( l i t . value^ 63-65°)*

7.

An au th en tic

Frankel and C ornelius, Her., 51» 1651; (1918).

sample was prepared from ethanolamine and a c e ty l chloride and a mixed m elting p o in t gave no low ering.

In t h is re a c tio n th e Mannich condensa­

tio n was reversed to give ethanolamine which then reacted with a ce ty l c h lo rid e . An attem pt to add formaldehyde to 5 ,5 -d in itr o -3 -a z a - l-pentanol (XVI) was unsuccessful and the s ta r tin g m ateria l was recovered. Experimental 1-Carbethoxymethyl-3, 3» 5» 5 - te tr a n itro p ip e r id in e .

Ethyl glycine

hydrochloride was prepared from glycine according to the procedure of o H a rris. A m ixture o f 6 g. (0.036 mole) o f 2 ,2 -d in itro -l,3 -p ro p a n e d io l,

8.

H arris and Hfeiss, Ann., 327, 365 (1903)•

xLii

10.2 g. (0.073 mole) o f eth y l glycine hydrochloride and 20 ml. o f w ater was heated to 65-70° w ith s t i r r i n g .

A fter about 15 minutes a p re c ip i­

t a te formed in th e so lu tio n and was removed by f i l t r a t i o n .

While main­

ta in in g the tem perature a t 65-70°, any a d d itio n a l s o lid was f i l t e r e d a t approxim ately 30 minute in te rv a ls u n t i l no fu rth e r p re c ip ita tio n occurred (8 h o u rs).

The product, l-carbethoxym ethyl-3,3 ,5 ,5 -te tra n itro p ip e rd in e ,

r e c r y s ta lliz e d from carbon te tra c h lo rid e to give 1.3 g. (20%) o f l i g h t yellow c r y s ta ls , m.p. 126-127°• Anal.

Mol. w t.

Calcd.fo r C ^ ^ O ^ :

C, 30.77; N, 19.9k; H, 3.70.

Found:

C, 31.00; N, 19.78; H, 3.75.

Calcd: 351

Found: 3L5 (potenti© m etric t i t r a t i o n ) .

l-Carboxym ethyl-3.3 .5 ,5 - te tra n itro p ip e rid in e .

To 3.6 g . (O.OliB

mole) o f glycine dissolved in 30 ml. o f w ater was added k g . (0.021; mole) o f 2 ,2 - d in itr o - l, 3-propanediol.

While s t i r r i n g , the m ixture was

heated to 65-70° and held a t th a t tem perature fo r 5 hours.

At the end

o f th a t time th e s o lid which had p re c ip ita te d from th e so lu tio n was f i l t e r e d and r e c r y s ta lliz e d from $0% alcohol to give 2.0 g. ($2%) o f l-carboxym ethyl-3,3,5»5 -te tra n itro p ip e rid in e as w hite c ry s ta ls , m.p. lU5-Ui6°. Anal.

Calcd. f o r

C, 26.00;

N, 21.67;

H, 2.78.

Found: C, 26.1(0;

N, 21.78;

H, 3.18.

Reaction o f 2»2 -D in itro -l,3 -p ro p an ed io l w ith Glycine Hydrochloride. Glycine hydrochloride was prepared by b o ilin g a hydrochloric acid solu­ tio n o f glycine to dzyness and cooling to recover the s o lid product. To 1.35 g. (0.012 mole) o f glycine hydrochloride in 10 ml. of w ater was

x iv

added 1 g. (0*006 mole) of 2 ,2 - d in itr o - l, 3-propanediol.

While s t i r r i n g ,

the mixture was heated to 65-70° and held a t th a t tem perature fo r 16 ho u rs.

The s o lid which p re c ip ita te d from th e so lu tio n was f i l t e r e d .

Upon r e c r y s ta lliz a tio n from 50% alcohol, 0.18 g. (18%) o f 1-carboxymethyl3>3,5* 5 -te tra n itro p ip e rid in e was obtained.

A mixed m elting p o in t w ith an

au th en tic sample gave no low ering. Sodium D in itro e th a n o l* A so lu tio n o f 5 g* (0.03 mole) o f 2 ,2 d in itro -1 ,3 -p ro p an e d io l in 25 ml. o f absolute methanol was cooled in an ic e bath to 5°*

While s t i r r i n g , sodium methoxide (0.75 g- sodium in 10

ml. absolute methanol) was added slow ly.

The yellow p re c ip ita te of

sodium d in itro e th a n o l which formed during the addition o f base, was f i l t e r e d , washed w ith a small amount of methanol and d ried under vacuum. The yellow s o lid , sodium d in itro e th a n o l, melted a t 132° and exploded when heated to 135-136°. Reaction of Glycine Hydrochloride w ith Sodium D in itro e th a n o l.

To

a so lu tio n o f 5 g* (0.032 mole) of sodium d in itro e th a n o l i n 30 ml. o f w ater was added 3 .5 g. (0.03b mole) of glycine hydrochloride.

A fter

s t i r r in g fo r about 10 minutes a t 25°, the so lu tio n darkened, a la rg e number o f bubbles appeared and the tem perature tended to r i s e bu t was kept a t 30° or below by in te r a d tta n t cooling w ith an ic e b a th .

This

i n i t i a l re a c tio n soon subsided and over a period o f se v e ra l hours a s o lid g rad u ally p re c ip ita te d from the s o lu tio n .

This p r e c ip ita te was

f i l t e r e d and re c ry s ta lliz e d from $0% alcohol to give 1.3 g. (25%) of l-carboxym ethyl-3,3 ,5 ,5 -te tra n itro p ip e rid in e , m.p. 11*7°• m elting p o in t w ith an au th en tic sample gave no low ering.

A mixed

XV

Hydrolysis of l-C arbetho^cym ethyl-3,3,5>,5~tetranitropiperdine.

To a

so lu tio n of 0.5 ml* of concentrated hydrochloric acid (36*5%) in $ ml* of w ater was added 0*5> g. o f l-carbethoxym ethyl-3,3 , $ - te tr a n itr o ­ p ip e rid in e and the m ixture heated for 18 hours a t 70°.

The white s o lid

was f i l t e r e d , re c z y s ta lliz e d from $0# alcohol and id e n tif ie d as 1carboxymethyl-3,3 ,5 ,5 -te tra n itro p ip e rid in e by means o f a mixed m elting p o in t (lU5>°) • E s té rific a tio n o f l-C arboxym ethyl-3»3,5»$-tetranitropiperidine.

A

m ixture o f U ml. of absolute eth an o l, 0.2 ml. o f concentrated s u lfu ric acid ( 96^) and 0.2 g. o f l-carboxym ethyl-3,3 ,5 ,5 -te tra n itro p ip e rid in e was heated fo r 8 hours a t 70°. so lu tio n .

On cooling, a p r e c ip ita te formed in the

This s o lid was f i l t e r e d , r e c ry s ta lliz e d from carbon t e t r a ­

ch lo rid e and id e n tifie d as l-carbethoxym ethyl-3,3 ,5 ,5“te tra n itro p ip e rid in e by means o f a mixed m elting p o in t (125°) • Ethyl 5 ,5-Pin itro -3 -a z av alera t e .

In a 100 ml. round-bottom fla s k

equipped with a s t i r r e r and a thermometer, $ g. (0.032 mole) of sodium d in itro e th a n o l was added

to 5 g. (0.035 mole) of eth y l glycine hydro­

ch lo rid e dissolved in 50ml. o f w ater.

A fter s t i r r i n g

fo r about 30

minutes a t 25°, a la rg e amount o f s o lid formed in th e so lu tio n and was filte re d .

A s o lid continued to fo ra in the re a c tio n m ixture and was

f i l t e r e d a t frequent in te r v a ls u n t i l the p r e c ip ita tio n ceased (2 h o u rs). R e c ry sta lliz a tio n from e th y l a c e ta te gave 1*.5 g« (65%) o f eth y l 5 ,5 d in itro -3 -a z a v a le ra te as yellow p la te - lik e c r y s ta ls , m.p. 102-103° with decomposition. Anal.

Calcd. fo r C^H^N^O^î Found:

Mol. w t.

Calcd: 221

C, 32.6; C, 33.0;

N, 19.0; H, U.98 . N, 19.26; H, 5.19.

Found: 229 (p otentiom etric t i t r a t i o n ) .

Ethyl 3»5 ,$ -T iïn itro -3 -a z a v a le ra te .

To a m ixture of 7 ml. o f fuming

n i t r i c acid (sp. g r. about 1 .5) and 7 ml. o f concentrated s u lfu ric acid (96%) cooled i n an ic e bath was slowly added 5 g. (0.023 mole) o f eth y l 5> 5 -d in itro -3 -a z a v a le ra te .

The so lu tio n was slowly warmed to 55-60° and

held a t th a t tem perature fo r 5 m inutes.

A fter allow ing i t to cool slowly

to 30°, th e m ixture was poured in to a beaker o f chipped ic e .

The white

o il which p re c ip ita te d from the aqueous so lu tio n became a s o lid a f te r about te n minutes o f s t i r r in g .

The product was f i l t e r e d and re c r y s ta lliz e d

from carbon te tra c h lo rid e to give 3*7 g* ( 60 %) o f eth y l 3 ,5 > 5 -trin itro -3 a za v alera te , m.p. i|l-ii20. Anal.

Calcd. fo r

Mol. wt.

C, 27*07;

N, 21.05;

H,

3*76.

Founds C, 26.98;

N, 21.00;

H, 3*78.

Calcd: 266 Found: 257 (p otentiom etric t i t r a t i o n ) .

Ethyl 5-Bromo-3,5»5 - t r i n i tro -3 -a z a v a le r a te .

To a s lu r ry o f 1 g.

(0.0037 mole) o f eth y l 3> 5> 5-trinitro -3 -a z a v a le ra te i n 5 ml. o f eth e r a t 5° was added slowly sodium methoxide (0.1 g. sodium in 3 ml. of m ethanol).

The l ig h t yellow sodium s a lt which formed was f i l t e r e d ,

washed w ith a l i t t l e methanol aid d rie d ; i t decomposed a t 87-88°. Tlhile cooling in an ic e b ath , 0.11* g. (0.0017 mole) o f bromine dissolved in 5 ml. o f

chloroform was added slowly to 0 .5

g*(0.0017

mole) o f the sodium s a l t o f eth y l 3 ,5 ,5 - t r i n i tro -3 -a z a v a le ra te suspended i n 10 ml. of e th e r.

The m ixture was allowed to stand fo r 15 minutes and

then f i l t e r e d to remove th e inorganic s a l t .

The e th e r f i l t r a t e was

evaporated under vacuum to give a yellow-white s o lid .

R e c ry sta lliz a tio n

from carbon te tra c h lo rid e gave 0.1*9 g* (80#) o f eth y l 5-bromo-3>5»5t r i n i tro -3 -a z a v a le ra te as a white s o lid , m.p. 57-58°.

x v ii

Anal.

Calcd. fo r C^N^OgBr:

C, 20.37;

N, 16.20;

H, 2.61.

Founds

C, 21.00;

N, 15.61;

H, 3.12.

5»5~~Dinitro-3~aza-l-pentanol.

To a so lu tio n of 1.85 g* (0.03

mole) of ethanolamiae i n 25 ml. of w ater was added 5 g* (0.03 mole) of 2 ,2 -d in itro -l,3 -p ro p a n e d io l.

The tem perature rose from 28° to 35°

and the p re c ip ita te which formed almost immediately was f i l t e r e d .

The

re a c tio n was allowed to continue fo r th ree more hours but only a small amount o f a d d itio n a l product formed.

The s o lid was re c ry s ta lliz e d

from w ater to give I*.2 g. (82#) of l i g h t yellow c ry s ta ls o f 5 ,5 -d in itro 3 -az a-l-p en tan o l, m.p. 115-116° ( decomposition with the evolution of a g as). Anal.

Calcd. fo r C^H^N^O^s. Found:

Mol. wt.

Calcd: 179

C, 26.81;

N, 23*1*6;

H, 5*03.

C, 26.95;

N, 23-1*1;

H, 5*1*5*

Found: 172 (potentiom etric t i t r a t i o n ) .

Reaction o f 5»5 -D in itro -3 -aza-l-p en tan o l with Acetyl C hloride.

A

mixture of 1 g. (0.0056 mole) of 5>5- d in itro -3 -a z a -l-p e n tan o l and 5 g* ( 0.06 mole) of a ce ty l chloride was allowed to stand a t 25° fo r 12 hours with occasional sw irling of the m ixture.

At the end o f th is tim e, the

white so lid was f i lt e r e d , dissolved in water and n e u tra liz e d with d ilu te sodium hydroxide.

The aqueous so lu tio n was d i s t i l l e d under vacuum to

give a white s o lid resid u e, th e organic p o rtio n of which re c ry s ta lliz e d frem acetone to give N -acetyl- § -am inoethyl alcohol as white needles, m.p. 62-63° ( l i t . value^ 63-65°).

An au th en tic sample was prepared from

ethanolamine and a ce ty l chloride and a mixed m elting p o in t gave no lower­ in g .

xviii

Summary 1.

The Mannich re a c tio n s o f 2 ,2 -d in itro -l,3 -p ro p a n e d io l with

g lycine, glycine hydrochloride, o r eth y l glycine hydrochloride gave th e c y c lic products, l-carbethoxym ethyl-3,3 ,5 ,5 -te tra n itro p ip e rid in e and 1-carboxymethyl-3,3 , 5 ,5 -te tra n itro p ip e rid in e .

The l a t t e r compound

was a lso formed when sodium d in itro e th a n o l was rea cte d with glycine hydrochloride. 2.

Sodium d in itro e th a n o l rea cte d with eth y l glycine hydrochloride

to give eth y l 5> 5 -d in itro -3 -a z a v a le ra te •

This compound was n itr a te d

to the corresponding N -nitro d e riv a tiv e , which i n tu rn was brominated to e th y l 5-bromo-3, 5 , 5 - t r i n i tro -3 -a z a v a le r a te . 3*

The re a c tio n o f ethanolamine with 2 ,2 -d in itro -l,3 -p ro p a n e d io l

o r sodium d in itro e th a n o l gave 5>5 -d in itro -3 -a z a -l-p e n tan o l.

Department o f Chemistry and Purdue Research Foundation, Purdue U n iversity, L afay ette, Indiana THE PREPARATION OF 2-MSTHÏL-2-NITRO - 1 ,3-DIBROMOPROPANE1

1.

A bstracted from a th e s is by Wayne May, subm itted to th e fa c u lty o f Purdue U n iv ersity , in p a r t i a l fu lfillm e n t o f th e requirem ents fo r th e degree o f Doctor o f Philosophy, August, 1950.

By H. Feuer, G. B. Bachman and W. May AN ABSTRACT The compound, 2-m ethyl-2-nitro-l,3-dibrom opropane ( I ) was prepared by th e a c tio n o f phosphorus tribrom ide on 2 -m ethyl-2-m .tro-l, 3-propane­ d io l ( I I ) .

When I I and phosphorus tribrom ide were heated to 150°, a 1*0#

y ie ld o f I was obtained.

The dibromide ( I ) was a c le a r liq u id with a

camphor-like odor d i s t i l l i n g a t 76-77° a t 1.5 mm. Hg. The aim o f t h is work was to convert 2-m ethyl-2- n itro-1,3-dibrom o­ propane

( I) to the corresponding d i n i t r i l e followed by hydrolysis to

o b tain a n itr o d e riv a tiv e o f g lu ta ric a c id . go f u r th e r re a c tio n .

However, I would n o t under­

Reactions o f I w ith e ith e r sodium cyanide o r

cuprous cyanide were unsuccessful and the s ta r tin g m a teria ls were r e ­ covered.

The dibromide (I) a lso f a ile d to undergo a V icto r Meyer r e ­

a ctio n w ith s i l v e r n i t r i t e in an e f f o r t to replace th e bromine atoms w ith n itr o groups.

I t i s known th a t neopentyl h a lid e s are unusually i n e r t

2.

p

and a

Whitmore, "Organic Chemistry”, p . 73> New York, D. Van Nostrand Co., 1937.

p o ssib le explanation fo r th e u n re a c tiv ity o f I w ith cyanides and s ilv e r n i t r i t e may be i t s s im ila r ity in s tru c tu re to t h a t o f a neopentyl h a lid e . Experimental 2-Methyl-2 -n i tro -1 »3-dibromopropane.

Twenty-five grams (0.185

mole) o f 2 -m eth y l-2 -n itro -l,3 -p ro p an ed io l was placed i n a 200 ml. roundbottom fla s k supplied with an a i r condenser and a thermometer.

The d io l

was heated by means o f an o i l bath to 70° and 50 g. (0.185 mole) o f phosphorus tribrom ide was added dropwise w hile m aintaining the tempera­ tu re o f th e re a c tio n m ixture below 100°.

A fter the phosphorus tribrom ide

was added the tem perature o f th e o i l bath was slowly ra is e d to 150-160° over a p erio d o f 3-U hours.

Once the bath tem perature reached 130°, the

tem perature o f the re a c tio n m ixture tended to r i s e above th a t o f the b ath ; th ere fo re i t was necessary from time to time to remove the r e ­ a c tio n fla s k from the o i l bath in o rder to keep the re a c tio n under c o n tro l.

A fter th e tem perature of th e re a c tio n m ixture no longer tended

to r i s e above th a t of the bath, i t was held between 150-160° fo r 5 hours and then allowed to cool slowly to 25°.

About 200 ml. o f w ater was

added to th e gummy mass and allowed to stand u n t il th e e n tire so lu tio n could be poured from the f la s k .

The organic la y e r was separated from

the w ater and was d i s t i l l e d under vacuum.

There was obtained 19»7 g.

( W ) of 2-methyl-2 -nitro-1,3-dibrom opropane, d i s t i l l i n g a t 76-77° a t 20 m

Anal.

Calcd. f o r C ^N C ^B r^

C, 18.39;

N, 5.36;

H, 2.68.

Foundï

C, 18.30;

N, 5.39;

H, 2.53.

Mol. w t.

Calcd: 261 Found: 256 (cryoscopic method).

Summary 1.

2-Methyl-2-n i tro - 1 , 3-dibromopropane was prepared by the

actio n o f phosphorus tribrom ide on 2 -m eth y l-2-nitro-1,3-propanediol.

THE SYNTHESIS OF ROCKET PROPELLANTS INTRODUCTION The work presented in th is th e s is i s a p a rt of th e Rocket Fuel Program sponsored by the O ffice of Naval Research.

This research

program has as i t s u ltim ate goal the p rep a ratio n o f n itr o polymers to be used as s o lid rocket p ro p e lla n ts . The s o lid rocket p ro p ellan ts in use a t the p resen t time are g en erally e ith e r o f th e double-base or composite type.

The former type

c o n sists p rim arily of m ixtures of c e llu lo se n i tr a te and gly cery l t r i ­ n i tr a te while the l a t t e r u t i l i z e s a sp h alt, rubber, o r sy n th e tic re s in s as a fu e l mixed w ith o x id izers such as ammonium o r potassium p er­ ch lo ra te or th e resp e c tiv e n i t r a t e s .

Such p ro p e lla n ts have been found

to have c e rta in disadvantages, two o f which are th e production o f smoke 22 and flu c tu a tio n s in the burning r a t e . These lim ita tio n s made i t d e sira b le to seek new types of m ateria ls to be used as rocket fu e ls . In order to o btain a new p ro p e lla n t which w ill be su p erio r to those now in use, c e rta in requirem ents have been e sta b lish e d .

The f i r s t re ­

quirement i s th a t s u f fic ie n t oxygen be p resen t to bum a l l the carbon to carbon monoxide and o n e-th ird of th e hydrogen to steam.

To th is re ­

quirement has re c e n tly been added the concept o f sp e c ific im pulse,^ a term designating fo o t pound seconds of th r u s t per pound o f p ro p e lla n t. The p resen t requirement i s a sp e c ific impulse g re a te r than 200 lb . s e c ./lb . Since the sp e c ific impulse o f th e p ro p e lla n t i s in v ersely propor­ tio n a l to the square ro o t o f the molecular weight of th e combustion gases, i t i s necessary th a t the gaseous products o f combustion be of a low

2

molecular w eight.

Such low m olecular weight gases would be produced by

a p ro p e lla n t composed o f th e chemical elements carbon, hydrogen, n itr o ­ gen, and oxygen.

The sp e c ific impulse i s also a ffe c te d g re a tly by the

type o f chemical bonds p resen t in the p ro p e lla n t.

A nitrogen-oxygen

bond c o n trib u tes more to the sp e c ific inpulse than e ith e r a carbonoxygen or a hydrogen-oxygen bond, thus a tte n tio n was turned to s tru c ­ tu re s containing n itro s o , n i t r i t e , n i tr a te and n itr o groups. Another requirement e sta b lish e d fo r a s o lid p ro p e lla n t was th a t o f s t a b i l i t y to both heat and shock which would be encountered i n the handling and use o f the m a te ria l.

A s o lid p ro p e lla n t must have s u f f i ­

c ie n t stre n g th to w ithstand th e high p ressu res to which i t i s subjected i n a rocket motor, and thus i t i s necessary th a t i t be a polymeric m a te ria l.

The range o f thermal s t a b i l i t y was sp e c ifie d as -5U° to 71° C.

S tru c tu re s containing n itro s o , n i t r i t e , or n i tr a te groups were elim i­ nated from fu rth e r consideration because they f a i l to s a tis f y th is s t a b i l i t y requirem ent.

This narrowed the problem to one of preparing

polymers containing e ith e r n itr o or nitram ino groups. In o rder to synthesize n itr o polymers, th re e general methods may be used: 1.

Polym erization of n itr o monomers by a d d itio n or condensation re a c tio n s .

2.

The in tro d u c tio n o f n itro groups in to polymers by p o st­ n itr a tio n .

3»

The re a c tio n of polymers containing fu n ctio n al groups with n itr o compounds.

The f i r s t of these general methods seems to o ffe r the b e st means o f

3

preparing the d esired polymers and has th e re fo re been emphasized more than th e o th er two methods. Before polym erization re a c tio n s can be c a rrie d out, i t i s neces­ sary to have a v a ila b le p o ly n itro compounds containing fu n ctio n al groups which are capable of fa rth e r re a c tio n .

Only very few such compounds

were known previous to th e i n i t i a t i o n o f th e rocket p ro p e lla n t program and a g re a t deal o f e f f o r t has been spent in synthesizing p o ly n itro compounds which might be u se fu l as monomers. syntheses of such n itr o monomers.

This work i s a study of

PART I .

THE MANNICH REACTION OF CERTAIN DIMETRO ALCOHOLS WITH GLYCINE AND ETHANOLAMINE In tro d u ctio n

The f a c t th a t n itr o alcohols undergo a Mannich re a c tio n with am in es^ suggested th a t a sim ila r re a c tio n would occur between poly­ n itr o alcohols and amino acids or amino a lco h o ls.

The products of such

re a ctio n s would be p o ly n itro compounds containing acid o r alcohol groups capable o f fu rth e r re a c tio n to form condensation polymers. I t has been shown th a t the Mannich re a c tio n o f tr in itr o e th a n o l with the e s te rs of glycine, a s p a rtic , and glutam ic acids i s an ex ce llen t 18 method o f introducing th ree n itr o groups in to these m olecules. In view o f t h is , the re a c tio n of d in itr o alcohols with amino acids o r amino alcohols appeared to be a good method of preparing compounds which would contain two n itr o groups and a lso have fu n ctio n al groups p resen t fo r fu rth e r re a c tio n .

Therefore, th e Mannich condensation o f glycine and

i t s e s te r with the d in itro alcohols, 2, 2- d i n i t r o - l , 3-propanediol and d in itro e th a n o l, was in v e s tig a te d . a lso rea cte d w ith ethanolamine.

These same d in itro alcohols were

The r e s u lts of t h i s work are presented

i n the follow ing discu ssio n . Discussion The Mannich Reaction o f C ertain D in itro Alcohols w ith Glycine. N itro alcohols re a c t w ith amines to give the same Mannich re a c tio n pro­ ducts as those obtained from amines, formaldehyde, and th e corresponding

5

n itr o p a ra ffin .

Senkus

and Johnson

found th a t 2-m ethyl-2-nitro

1 , 3 -propanediol would re a c t with both primary and secondary amines to

give products o f the follow ing general s tru c tu re in which R i s alk y l and R^ i s alk y l or Hs

In an analogous manner, 2 ,2 -d in itro -l,3 -p ro p a n e d io l might be expected to re a c t w ith two molecules o f glycine to form 5 , 5- d in itr o 3 >7-diazanonanedioic acid:

HOCHg-C-CHgOH _j_ 2H2N-CH2-C 0 2H

* H02G-CH2-N-CH2 -C-CH 2 -N-CH2-C 0 2H

F urther n itr a tio n o f the two amino nitrogens to nitram ine groups would give an acid i n good oxygen balance. In an attem pt to prepare the e th y l e s te r o f 5 > 5 -d in itro -3 ,7 -d iaz a ­ nonanedioic acid , eth y l glycine was rea cte d with 2, 2- d i n i t r o - l , 3 -pro­ p anediol.

The product o f th is re a c tio n was a black t a r .

This r e s u lt

might have been expected since i t i s known th a t eth y l glycine poly­ m erizes to a polypeptide e s te r even on standing fo r a day a t 25° . ^ In order to prevent polym erization, the hydrochloride of eth y l glycine was used i n subsequent re a c tio n s . I n a s e rie s o f experiments 2 ,2 - d in itr o - l, 3-propanediol was rea cte d w ith eth y l glycine hydrochloride, glycine hydrochloride, and glycine re s p e c tiv e ly .

The expected nonanedioic a cid d e riv a tiv e s were not ob­

ta in e d ; in ste a d c y c liz a tio n occurred w ith the form ation o f two new

6

compounds, l-carbethoxym ethyl- 3 >3 , 5- te tr a n itr o p ip e r id in e ( I) and 1-carboxym ethyl-3,3 , 5 -te tra n itro p ip e rid in e ( I I ) .

These re a c tio n s

are summarized in the follow ing equations $ 02N W 2 C — CH,

NO, Cl H3N+-CH2-C0 2E t 4 - HOCH2-C-CH2QH

NOm

HdO 700

B -C H .-C O jB t +

h2 c

II

o 2n n o 2

HCl

A

h 2n-ch 2-co2h or

EtOH

A

o2n s ° 2

c -o * z

NO, H2C

Cl H3N't-CH2-C02H -(- HOCH2-C-CH2OH

N0a

\ N-CH2-C02H

70 II o 2n n o 2

The re a c tio n procedure con sisted o f heating an aqueous so lu tio n o f th e d io l and glycine d e riv a tiv e to 70° and recovering the p re c ip ita te d product by f i l t r a t i o n .

Removal of th e p re c ip ita te as i t formed during

the re a c tio n o f the d io l and eth y l glycine hydrochloride gave the e s te r ( I ) as th e only product.

However, i f the p r e c ip ita te was allowed to

remain i n the a c id ic re a c tio n mixture fo r sev eral hours, both the e s te r ( I ) and the acid ( I I) were is o la te d .

The acid ( H ) was separated by

r e c r y s ta lliz a tio n from $0% alcohol, w hile the e s te r ( I ) was recovered from th e alcohol in so lu b le residue by r e c r y s ta lliz a tio n from carbon t e t r a ­ c h lo rid e .

The e s te r ( I ) was a lig h t yellow c ry s ta llin e compound which

melted a t 126- 127° and was soluble in acetone, benzene, e th e r, and carbon

7

te tra c h lo rid e but in so lu b le in water and alco h o l.

The acid ( I I ) , a

w hite c r y s ta llin e so lid m elting a t lU 5-Oi*6 °, was soluble in acetone, alcohol, and e th e r b u t in so lu b le in w ater, carbon te tra c h lo rid e , and benzene. Numerous experiments between eth y l glycine hydrochloride and 2 ,2 -d in itro -l,3 -p ro p a n e d io l showed th a t tem perature, pH, and mole r a tio have a pronounced e ffe c t en t h is re a c tio n .

An aqueous mixture

of the two re a c ta n ts had a pH of U (Hydrion B paper) and any attem pt to n e u tra liz e the so lu tio n caused t a r form ation.

The optimum re a ctio n

tem perature was about 70°5 higher tem peratures gave a t a r as the only product while lower tem peratures decreased the y ie ld s .

A r a tio o f two

moles o f the e s te r hydrochloride to one mole o f th e d io l gave a b e tte r y ie ld than e ith e r a 1 to 1 r a t i o or a 1 to 2 r a tio o f th e re a c ta n ts . The in flu en ce o f these fa c to rs on the re a c tio n i s shown in Tables I , I I , and I I I .

The use of absolute ethanol as a solvent in place o f

w ater reduced the y ie ld by 60%.

As shown in Table I I , th e h ig h est

y ie ld obtained was 20% and even though th e recovery of some s ta r tin g m aterial a f te r 18 hours in d ic a te d th a t the re a c tio n was incom plete, a longer re a ctio n time le d to an in crease in the amount o f t a r in stea d o f th e d esired product. The compound, 1-carboxyme th y l- 3 ,3 ,5 > ,5 -tetran itro p ip erid in e ( I I ) , was also found to be the product o f the re a c tio n o f glycine or glycine hydrochloride with 2 ,2 -d in itro -l,3 -p ro p a n e d io l.

As in the case with

eth y l glycine hydrochloride, the re a ctio n was c a rrie d out by heating an aqueous m ixture o f the d io l and glycine to 70° and f i l t e r i n g the

8

Table I E ffect o f pH on the Reaction o f Ethyl Glycine Hydrochloride w ith 2 ,2 -D in itro -l,3 -p ro p a n e d io l.

pH of Reaction

Reaction Time

70°

7a

8 hours

Tar form ation

Water

30°

7®

8 hours

Tar form ation

Water

30°

h

8 hours

5% y ie ld of Ib

Run

Solvent

1

Water

2

3

Temperature

a.

Reaction m ixture was n e u tra liz e d with sodium carbonate.

b.

I

z

l-Carbethoxym ethyl- 3 , 3, 5>>5 -te tra n itr o p ip e r id in e .

Remarks

9

Table I I E ffect o f Temperature on th e Reaction o f Ethyl Glycine

Run

Solvent

Temperature

pH of Reaction

U

Water

35°

u

8 hours

6 $ y ie ld of Ib

5

Water

70°

u

8 hours**

20 # y ie ld o f I b’e

6

Water

70°

It

8 hours

6% y ie ld of I b 9# y ie ld o f H c>f

7

Water

O ©

Hydrochloride with 2, 2-D in itro - 1 , 3-propanediol.

it

18 hours

3% y ie ld of I b IS# y ie ld o f I I C’ 8

8

Water

90°

it

2 hours

Tar form ation

Reaction Time

Remarks

b.

I

= l-Carbethoxymethyl-3,3>

5 -te tra n itro p ip e rid in e »

c.

II

s

d.

Product was f i lt e r e d from so lu tio n as i t formed.

e.

Recovered 15% of the d io l, 26% o f the eth y l glycine hydrochloride and t a r .

f.

Recovered 17% o f th e d io l, 23% of eth y l glycine hydrochloride *and t a r .

g.

Recovered 9# of the d io l, 12% o f eth y l glycine hydrochloride and t a r .

l-Carboxym ethyl-3,3,5? 5 - te tra n itr o p ip e rid in e .

10

Table H I E ffe c t o f Mole Ratio on th e Reaction o f Ethyl Glycine Hydrochloride with 2 , 2-D ini t r o - 1 ,3 -p ro p an ed io l.

M illim oles o f Diol

Run

M illim oles o f Ethyl Glycine HCl

Temperature

Reaction Time

Remarks

9

20

UO

70°

8 hours**

20$ y ie ld of Ib

10

20

20

70°

8 hours**

9$ y ie ld of Ib

11

1*0

20

70°

8 hours**

7$ y ie ld of Ib

b.

I

as l-Carbethoxym ethyl-3,3,

5 - te tr a n i tro p ip e rid in e .

d.

Product was f i l t e r e d from so lu tio n as i t formed.

11

product which p re c ip ita te d .

This re a c tio n gave a much higher y ie ld o f

acid ( I I ) than th a t between the d io l and eth y l glycine hydrochloride. The mole r a tio o f 2 , 2- d i n it r o - l, 3-propanediol and glycine was found to a ffe c t g re a tly th e amount o f product as shown in Table IV, with a 2 to 1 r a tio o f glycine to d io l giving th e highest y ie ld . The use o f glycine hydrochloride in place of glycine lowered the pH o f the re a c tio n mixture below It ( Hydrion B pa> e r) and gave only an 18% y ie ld o f I I .

Acid ( I I ) could be e s te r if ie d to th e same e s te r ( I)

as obtained from 2 , 2- d i n i t r o - l , 3-propanediol and eth y l glycine hydro­ ch lo rid e. The same cy clic compound, 1-carboxyme thyl-3,3>

5 -te tr a n i tr o ­

p ip e ri dine ( I I ) , was formed in 2%% y ie ld when sodium d in itro eth a n o l was reacted with glycine hydrochloride.

When these two re a c ta n ts were

mixed in water (pH o f k) a t 25° and s t i r r e d fo r 10 minutes, an exo­ thermic re a ctio n occurred causing a 10° r is e in tem perature.

This

i n i t i a l re a c tio n soon subsided and a p re c ip ita te of H g rad u ally formed in th e so lu tio n over a period of se v era l hours.

An e th e r e x tra c tio n o f

the remaining f i l t r a t e gave a yellow o i l which would not c ry s ta lliz e and which decomposed when d i s t i l l e d under vacuum.

Evaporation of the

remaining aqueous so lu tio n gave a t a r . CELycine i t s e l f did not r e a c t with sodium d in itro e th a n o l a t a pH o f 7.

When the pH was lowered from 7 to I4. (Hydrion B psp e r) a re a c tio n

appeared to occur because the so lu tio n turned red and the tem perature rose from 27° to 3U°.

However, no compound could be is o la te d .

Evapor­

atio n of the re a c tio n mixture gave a dark viscous o i l which decomposed upon d i s t i l l i n g under vacuum.

12

Table IV E ffe ct o f Mole Ratio on the Reaction of Glycine n ith 2 ,2 -D in itro -1 , 3-propanediol.

Run

M illim oles o f Diol

M illim oles o f Glycine

1

2U

1*8

70°

8 hours

52% y ie ld o f n c ,h

2

18

18

70°

8 hours

3156 y ie ld of I I e

3

12

6

70°

8 hours

2756 y ie ld o f IXe

Temperature

c.

II

h-

Recovered no d io l, 20^ o f glycine and tar*

Reaction Time

= 1-Carboxymethyl-3> 3> 5> 5 -te tra n itro p ip e rid in e .

Remarks

13

The form ation o f p ip e rid in e d e riv a tiv e s in the Mannich re a c tio n i s not uncommon e sp e c ia lly Wien ammonia o r a primary amine and formaldehyde are reacted with a methyl ketone o r compounds having re a c tiv e hydrogen p in the 1 , 3-p o s itio n s . HO

X [ |

,

CH --C-CH

s? 2C H ,-C -C H 3 - f

CH-

3

2CH20 +

C H J r a -jC l

>

CH2

CHg CHg

N I CH3 However, only one example was found i n which c y c liz a tio n occurred when a n itr o p a ra ffin was used.

U rb an sk i^ reported th a t 1 -nitropropane,

formaldehyde, and ammonia reacted to give a c y clic product ( I I I ) .

Z ° \ CH,

CH,-CHo-CH,N0, 4- CH,0 4- NH, ------ > 3 2 2 2 2 -r 3

H,C 2| HOH,C-N 2 , H,C

I 2,B t CX | HO, CH, t

2\

/

/

\

02N

2

Et

XII

Ring closure in such a re a c tio n could occur e ith e r by form ation o f an e th e r linkage (C-O-C) or a carbon-carbon lin k ag e.

Heating I I I i n

hydrochloric acid re s u lte d in rin g opening and form ation of compound IV, thus showing th a t an e th e r linkage was p re s e n t.

lit

HCl

HOH2

»2 >

f 2

HOCH2-C-CH2-C-CH2-NH-CH2OH - f - CHgO

Ét

Et

+ IV

ch 2o

ON

Cl H

/ x Bt n i

The f a c t t h a t l-carboxym ethyl-3,3,

5> -tetran i tro p ip e ri dine ( I I ) was

not changed a f t e r heating fo r 12 hours w ith concentrated hydrochloric acid i s evidence th a t a carbon-carbon bond was formed in the re a c tio n between glycine and 2, 2- d i n i t r o - l , 3 -propanediol• The presence of a t e r t i a r y n itrogen was in d ic a te d by the f a ilu r e o f sev eral attem pts to n itr a te e ith e r compound I o r I I .

The use of

e ith e r mixed acid or an a c e tic a n h y d rid e -n itric acid m ixture re s u lte d only in the recovery of the s ta r tin g m a te ria l.

Attempts to prepare a

p-toluenesulfonam ide d e riv a tiv e were also unsuccessful. I n c o n tra st to th e ir s t a b i l i t y to acid, compounds I and I I decomposed in basic media.

l-Carbetho:*ymethyl-3> 3*5» 5 -te tr a n i tro p ip e rid in e (I) was

tre a te d with base in an attem pt to s p l i t the rin g and p o ssib ly is o la te a d e riv a tiv e which could be id e n tifie d .

A re a c tio n with potassium

meth­

oxide did give a red so lid but i t was so un stab le th a t i t could no t be p u rifie d . The e s te r (I) was t i t r a t e d p o ten tio m e tric a lly to give a value of 3ii5 fo r the m olecular weight (ca lcd . 351), but attem pts to t i t r a t e the acid ( I I ) gave an in d e fin ite end p o in t.

15

Experimental evidence i s not a v aila b le to show the manner i n which th ese cy clic products were formed but some analogous rea ctio n s were found i n the l i t e r a t u r e .

The follow ing sequence o f re a ctio n s i s pro­

posed only as one of the ways in which the re a c tio n s might have occurred.

HOCH2-C -C H 2OH NOo

£

î

no2 HOCILÇH N02

H H0CH2 -N -C H 2-C 0 2H

2.

CH20 4 -

3.

H H0CH2-N-GH2-C02H

i

k.

N02 HOCH2 -GH vno2

m2 HocH.-c® 2 no2

5.

f_2 H0CH2 -C e :4 NO,

4

H"

>

H CH2-6-CH2-C02H

»

H 1CH2 -]i-C H 2 -C 0 29

H

6.

4-

HgO

?°2 H -> H0CH2 -C -C H 2 -6 -C H 2-C 0 2 H NO. ^ V +

P 2 H ch -c-c h 2-n-ch 2-co2h no2

+

HgO

o2N æ 2 c- ch2oh

NO2 H / HQCH2- C ^ -f- +CH2-Ç-CH2-à-CH2-G02H ----- > H2C \ NO, N02 NO,

7-

h 2n-ch 2-co2h

ch2o

H C-CH -N-CH -CO H

/\

o 2 n no 2

2

2

VI

2

The various steps can be compared to analogous re a c tio n s reported i n the l i t e r a t u r e .

The equilibrium o f re a ctio n 1 i s in agreement with

the experim ental evidence o f Senkus^ and was fu rth e r v e rifie d by th is in v e s tig a tio n .

The f a c t th a t 2, 2-d in itro -l,3 -p ro p a n e d io l and d in itro ­

ethanol gave the same product when reacted with glycine shows th a t foimaldehyde was s p l i t from the n itr o alcohol during th e re a c tio n .

The

form ation of a methylol d e riv a tiv e of the amine a s the f i r s t i n t e r ­ mediate (re a c tio n 2) i s supported by the work of Alexander and U nderhill^ which showed th a t the same ra te constant was obtained when the N-methylolamine was used in place of the amine and formaldehyde in the Mannich re ­ a c tio n .

Reactions 3, U, and $ lead to th e expected Mannich product (V)

between 1 molecule o f glycine and 1 molecule of 2, 2- d i n i t r o - l , 3-propane­ d io l according to the mechanism proposed by Liebermann and W agner.^ Compound V then re a c ts with another molecule of d in itro e th a n o l (rea ctio n s 6 and 7) to form the unstable interm ediate (VI) which cy cliz es immediate­

ly to th e f in a l product (rea c tio n 8) .

This interm ediate (VI) has the

s tru c tu re o f a d e lta -amino alcohol and such compounds are known to c y clize very re a d ily to p ip erid in e d e riv a tiv e s.

20

In the case o f the re a c tio n of sodium d in itro e th a n o l w ith ethyl glycine hydrochloride c y c liz a tio n did not occur.

A fa c to r which might

account fo r th is was the higher pH (5-6) o f the re a c tio n mixture as

17

compared with the pH o f U i n the reactio n s which le d to cy cliz atio n , The product formed was eth y l 5>5-dinitro -3 -a z a v a le ra te (V II). N0 2Na C-CHpOH + )

2

T

Cl H_N^-CHg-C0g2t 3

2 2

- H2-^ -»

no2

30

N02 h HC-CH.-LcH^-CO^Et 1

2

2

2

m2 VII

On mixing sodium d in itro eth a n o l and e th y l glycine hydrochloride in w ater (pH -

5-6) and allowing to s t i r fo r 30 m inutes, a yellow p re c ip i­

ta te formed.

A fter f i l t r a t i o n , the so lid was r e c r y s ta lü z e d from ethyl

a c e ta te to give a 65 # y ie ld of yellow p la te - lik e c ry s ta ls which melted a t 102-103° with decomposition. in g re a c tio n m ixture.

On standing, a t a r formed in the remain­

This e s te r (VII) was soluble in acetone, alcohol,

and eth y l a c e ta te but in so lu b le in w ater, e th e r, chloroform, carbon te tra c h lo rid e , and benzene. th re e days, i t decomposed.

When allowed to stand a t 25

©

fo r two or

The e s te r was t i t r a t e d p o te n tiometr ic a lly

to give a value of 229 fo r the m olecular weight (ca lcd . 221) . The presence of a secondary nitrogen was in d ic a te d by the f a c t th a t th is e s te r (VII) was n itr a te d with a m ixture o f fuming n i t r i c acid and concentrated su lfu ric acid to give ethyl 3 , 5 >5- t r i n i t r o - 3-az av a lera te (V III). y°2 h H-C-CHg-N-CHg-COgBt NO,

—

3..+ H2S0U 60°

N02 “°2 H-C-CHg-N-CH.-CC^Et NO, VUI

This re a c tio n was c a rrie d out by d issolving the u n n itra te d e s te r (VII) in a mixture o f concentrated s u lfu ric acid and fuming n i t r i c acid

18

and heating to 60° fo r 5 m inutes.

Upon pouring the so lu tio n in to ic e ,

th e product (V III) c ry s ta lliz e d as a white s o lid .

In order to obtain

th e n itr a te d product as a c ry s ta llin e s o lid , i t was necessary to use p u rifie d eth y l £ ,5 -d in itro -3 -a z a v a le ra te (VII) i n the re a c tio n .

The

n itr a te d e s te r (V III) was r e c i y s t a l l i zed from carbon te tra c h lo rid e and melted a t U1 -U20 .

À potentiom etric t i t r a t i o n gave a value o f 257 f o r

th e molecular weight (calcd . 266).

I n c o n tra st to th e u n n itra te d e s te r

(V II), eth y l 3 ,5 ,5 - t r i n i tro -3 -a z a v a le ra te (V III) did not decompose on stan d in g . The proposed s tru c tu re o f e s te r (VIII) shows a hydrogen on the carbon containing the two n itr o groups and th is was e sta b lish e d by conversion of VIII to a sodium s a l t .

Treatment o f eth y l 3»5 ,5 - t r i n i t r o -

3 -az a v a le ra te w ith sodium methoxide gave a q u a n tita tiv e y ie ld of a lig h t

yellow s a l t (IX) which decomposed a t 87-88°.

This s a l t was reacted with

bromine to form e th y l 5-b ro m o -3 ,5 > 5 -trin itro -3 -azav alerate (X), a white so lid , m.p. 57-58°. N°2 f °2 H-C-CH2-N-CH2 -C02Et NOp

IX

NaOMe >

Br? -------=—) chci3

*j°2Na ? ° 2 C-CHg-N-CHg-COgEt NO, d H

no2 no2 Br-Ç-CHg-N-CHg-COgEt

io2

Attempts to hydrolyze eth y l 3 ,5>5 -trin itro -3 ~ a z a v a le ra te (V III) to the corresponding acid , 3 , 5 »5- t r i n i t r o - 3 -a z a v a le ric a c id , were

19

unsuccessful.

VRien the e s te r (V U I) was reflu x ed with concentrated

hydrochloric acid, decomposition with the evolution o f n itro g en dioxide was observed and no product could be is o la te d from the so lu tio n when d i s t i l l e d under vacuum. In an e f f o r t to prepare th e e s te r o f 3,5*5 -trin itro -3 > 7 -d ia z a ­ nonanedioic acid, a Mannich re a c tio n was attem pted between eth y l 3 ,5 ,5 tr in itr o - 3 - a z a v a le ra te (V III), formaldehyde and eth y l glycine hydro­ ch lo rid e .

Ihen eth y l glycine hydrochloride f a ile d to give the desired re a c tio n , i t was repeated using glycine hydrochloride and glycine, re sp e c tiv e ly . In each case a re a c tio n a t 70° gave a t a r , however upon evaporation o f th e aqueous so lu tio n a q u a n tita tiv e recovery o f glycine or th e hydro­ ch lo rid e was obtained.

Upon re a c tin g the sodium s a l t o f eth y l 3 ,5 ,5 -

trin itr o -3 - a z a v a le r a te (IX) with formaldehyde and eth y l glycine hydro­ ch lo rid e a t 30°, t a r formed ra p id ly .

No o th er product was is o la te d .

As a stepw ise method o f obtaining t h is Mannich product, the v a le ra te e s te r (VUI) was rea cte d with formaldehyde in an attem pt to form a methylol compound, which in tu rn could condense with eth y l glycine hydrochloride to give the f in a l product. such a m ethylol d e riv a tiv e were unsuccessful.

Attempts to prepare

When an aqueous so lu tio n

20

of the sodium s a l t of eth y l 3 ,5 > 5 -trin itro ~ 3 wa zav alerate (IX) and formaldehyde was slowly a c id ifie d with a c e tic acid, an o i l formed in th e so lu tio n .

When placed under vacuum, most o f the o i l evaporated

leaving a dark gummy residue which could not be c r y s ta lliz e d .

A small

amount o f sodium a c e ta te was is o la te d from the remaining aqueous solu­ tio n . The Mannich Reaction o f C ertain D in itro Alcohols with Ethanolamine. Sim ultaneously w ith the stucfcr o f the Mannich re a c tio n s between glycine and d in itr o alcohols, sim ila r re a c tio n s between ethanolamine and d in itro alcohols were in v e s tig a te d .

One molecule o f 2 , 2-d in itro -l,3 -p ro p a n e d io l

would be expected to re a c t w ith 2 molecules o f ethanolamine to form 3>, S - d in itr o -3 , 7- d ia z a - l, 9-nonanediol. no2 hoch2-c-ch 2oh

+

2H2nch2-ch2oh

^ hoch2-ch 2-h-ch 2-c-c h 2-h-ch 2-ch2oh no2

F urther n itr a tio n o f the amino nitrogens to nitram ine groups would give a long-chain d io l in good oxygen balance.

However, in ste a d o f the ex­

pected nonanediol, 5 > 5 -d in itro -3 -aza-l-p en tan o l (XI) was the product which formed in the re a c tio n .

n On mixing 2 ,2 -d in itro -l,3 -p ro p a n e d io l and ethanolamine in water (pH s

6 -7 ), a p re c ip ita te formed immediately accompanied by a 10° r is e

21

in tem perature.

The so lid was f i lt e r e d and re c ry s ta lliz e d from water to

give 5 ,5 -d in itro -3 -a z a -l-p e n ta n o l as b rig h t yellow c ry s ta ls in 82% y ie ld . I t m elted a t 115-116° w ith decomposition.

A potentiom etric t i t ra tio n

gave a value o f 172 fo r the molecular weight (ca lcd . 179)•

The same

product was obtained from ethanolamine hydrochloride and 2 ,2 -d in itro 1 ,3-propanediol i f th e pH o f th e aqueous so lu tio n was ra is e d to about 5 by the addition of sodium carbonate. The pentanol (XI) was also formed when ethanolamine was reacted with sodium d in itro e th a n o l.

No re a c tio n took place when th e two re ­

a ctan ts were mixed in w ater (pH = 11).

However, by lowering the pH of

the so lu tio n to about 7 or 8 by the a d d itio n of hydrochloric acid , the 5 ,5 -d in itr o -3 -a z a -l-pentanol could be obtained in a 69% y ie ld . In an e f f o r t to prepare a d e riv a tiv e , 5> 5 -d in itro -3 -a z a -l-p e n ta n o l (XI) was reacted with a c e ty l c h lo rid e.

On allowing a mixture of th e two

re a c ta n ts to stand a t 30°, a white s o lid formed and was recovered by f iltra tio n . io n .

The product was q u ite acid ic and gave a t e s t fo r chloride

Therefore, the s o lid was dissolved in w ater, c a re fu lly n e u tra liz e d

with sodium hydroxide and then recovered by evaporating th e w ater under vacuum.

The organic p o rtio n o f th is residue was re c ry s ta lliz e d from

acetone to give N -acetyl- (j&-aminoethyl alcohol, m.p. 62-63° ( l i t . value^ 63-65°).

An a u th en tic sample was prepared from ethanolamine and acety l

c h lo rid e and a mixture melted a t 62°. The presence o f ethanolamine must have been due to a re v e rsa l of the Mannich condensation.

Acetyl chloride then reacted w ith ethanol­

amine to give N -acetyl- 0 -aminoethyl alcohol.

22

HpO H-C-CH2-N-CH2-CH2OH no2

?°2 H-C-CH^OH no2

f

4 - H2N-CH2-CH2OH

XL 0 H2N-CH2 -CH2OH 4 -

> CH3 -C-ii-CH2-CH2OH 4 - HC1

C H j-G -C l

An unsuccessful attem pt was also made to re a c t 5> 5-*dinitro -3 -a z a 1-pentanol (XI) with formaldehyde.

No re a c tio n occurred and the

pentanol (XI) was recovered in 67% y ie ld . Experimental Experiment 1 - R eaction of 2,2-D in itro -1 , 3-propanediol with Ethyl G lycine.

The e th y l glycine used in t h is experiment was prepared by

the method of Fischer^ (b .p . 51-52° a t 10 mm. Hg). While cooling the fla s k in an i c e - s a l t bath (0 °), 1 .6 g. (0.01 mole) of 2 , 2- d i n i t r o - l , 3-propanediol was added slowly to 2 g. ( 0.02 mole) o f ethyl g ly cin e.

The mixture was wanned c au tio u sly to 35°

during which time the yellow paste became a liq u id and then s ta r te d to darken ra p id ly .

When the so lu tio n became a deep red co lo r, i t was

dissolved immediately in e th e r.

A fter evaporation o f th e e th e r, the

re sid u a l liq u id was d i s t i l l e d under vacuum.

Soon a f t e r applying h eat

to the d i s t i l l i n g fla s k , the liq u id began to b o il vigorously and sudden­ l y polymerized to a t a r . P rep aration o f Ethyl Glycine H ydrochloride.

The eth y l glycine

hydrochloride used in the follow ing experiments was prepared according to the procedure o f H a r r is ^ by reflu x in g glycine with absolute ethanol

23

which was sa tu ra te d with dry hydrogen c h lo rid e . Experiment 2 - P rep aratio n of l-Garbethoxymethyl-3,3>5» 5 - te tr a n itro p ip e rid in e ♦ In a 100 ml. round-bottom f la s k provided w ith a s t i r r e r and thermometer, a mixture o f 6 g. ( 0.036 mole) of 2 , 2 - d in itr o 1 , 3 -propanediol, 10.2 g. ( 0.073 mole) of eth y l glycine hydrochloride

and 20 ml. of water was heated to 65-70°•

A fter about 15 minutes a

p r e c ip ita te formed in the so lu tio n and was removed by f i l t r a t i o n .

While

m aintaining the tem perature a t 65 - 70°, any a d d itio n al s o lid was f i l t e r e d a t approximately 30 minute in te rv a ls u n t i l n® fu rth e r p r e c ip ita tio n occurred (8 h o u rs).

The p ro d ic t, l-carbethoxym ethyl-3,3>5 > 5 -te tra n itro ­

p ip e rid in e , re c ry s ta lliz e d from carbon te tra c h lo rid e to give 1 .3 g. ( 20#) o f lig h t yellow c ry s ta ls , m.p. 126 - 127®• Anal.

Calcd. fo r Found:

Mol. w t.

Calcd: 351.

C, 30.77;

N, 19.9k; H, 3.70.

C, 31.00;

N, 19.78; H, 3.75.

Found: 3k5 (p o te n ti om etric t i t r a t i o n ) .

Experiment 3 - P reparation of l-Carboxym ethyl-3,3,5# 5 - te tr a n itr o ­ p ip e rid in e .

To 3*6 g. (0.0U8 mole) o f glycine d issolved in 30 ml. o f

w ater was added U g. (0.02k mole) o f 2 ,2 -d in itro -l,3 -p ro p a n e d io l.

While

s t i r r i n g , the mixture was heated to 65 - 70° and held a t th a t tem perature f o r 5 hours.

At the end o f th a t time th e s o lid which had p re c ip ita te d

from the so lu tio n was f i l t e r e d and re c r y s ta lliz e d from 50# alcohol to give 2.0 g. (52#) o f l-carboxym ethyl-3,3 ,5 ,5 -te tra n itro p ip e rid in e as white c iy s ta ls , m.p. Ik 5-lk 6 ° . Anal.

Calcd. fo r C7H9N^°10: C, 26.00;

N, 21.67; H, 2.78.

Found: C, 26.1*0;

N, 21.78; H, 3.18.

21*

P rep aratio n of Glycine H ydrochloride.

A mixture o f £ g* o f g lycine,

6 ml. of concentrated hydrochloric acid ( 36 . 5^) and 5 ml. o f w ater was

b o iled to dryness on a hot p l a t e .

The white so lid which foraed on cool­

ing th e m ixture was f i lt e r e d , washed with absolute alcohol and d ried under vacuum.

The product, glycine hydrochloride, melted a t 183°

( l i t . value 18 £ °). Experiment 1* - Reaction o f 2 ,2 -D in itro - 1 ,3-propanediol w ith Glycine Hydrochloride.

To 1.35 g* (0.012 mole) o f glycine hydrochloride in 10

ml. o f w ater was added 1 g. ( 0.006 mole) o f 2 , 2- d i n i t r o - l , 3 -propanediol. While s t i r r i n g , the m ixture was heated to 65-70° and held a t th a t tem­ p eratu re fo r 16 h ours. was f i l t e r e d .

The s o lid which p re c ip ita te d from the so lu tio n

Upon r e c r y s ta lliz a tio n from 50% alcohol, 0.18 g. (18#) o f

l-carboxym ethyl-3,3 ,5 ,5 - te tra n i tro p ip e rid in e was obtained.

A mixed

m elting p o in t with an authentic sample gave no low ering. Experiment 5 - P reparation of l-Carbethoxym ethyl-3,3 ,5 * 5^-tetran itro p ip e iid in e and l-Carboxym ethyl-3.3* 5>5-te t ra n itro p ip e rid in e from 2 , 2-D in itro - 1 , 3-propanediol and Ethyl Glycine Hydrochloride.

To 10.2 g.

(0.073 mole) o f e th y l glycine hydrochloride i n 25 ml. o f w ater was added 6 g. (0.036 mole) o f 2 ,2 -d in itro -l,3 -p ro p a n e d io l.

While s t i r r i n g , th e

m ixture was heated to 65- 70° and held a t th a t tem perature fo r 18 hours• The s o lid which p re c ip ita te d out o f so lu tio n was f i l t e r e d .

Most of th is

crude product was re c ry s ta lliz e d from 50# alcohol to give 0 .9 g* ( 15#) of l-carboxym ethyl-3,3 ,5> 5 -te tra n i tro p ip e rid in e (m.p. 11*1*°).

The

a lco h o l-in so lu b le p o rtio n was r e c ry s ta lliz e d from carbon te tra c h lo rid e to give 0 .2 g. (3#) o f l-carbethoxym ethyl-3,3 ,5 ,5 -te tra n itro p ip e rid in e (m.p. 125° ) .

25

Experiment 6 - Hydrolysis of l-C arbethoxym ethyl-3,3*5,5 ~ te tra n itro ­ p ip erid in e « To a so lu tio n of 0.5 ml. o f concentrated hydrochloric acid (36.5$) in 5 ml. of w ater was added 0.5 g. o f l-carbethoxym ethyl-3,3>5»5te tra n itro p ip e rid in e and the mixture heated fo r 18 hours a t 70*.

The

white so lid was f i l t e r e d , re c ry s ta lliz e d from $0% alcohol and id e n tifie d as l-carboxym ethyl-3,3,5* 5 -te tra n i tro p ip e rid in e by means o f a mixed m elt­ ing p o in t (11*5°) • Experiment 7 ~ E s té rific a tio n of l-Carboxym ethyl-3,3 ,5 ,5 - te tr a ­ n i tro p ip e rid in e .

To a mixture o f 1* ml. o f absolute ethanol and 0.2 ml.

o f concentrated s u lfb ric acid {96%) was added 0.2 g. o f 1-carboxymethyl3 ,3 ,5 ,5 -te tra n itro p ip e rid in e and the m ixture heated fo r 8 hours a t 70°. On codling, a p re c ip ita te formed i n so lu tio n .

This s o lid was f i l t e r e d ,

re c r y s ta lliz e d from carbon te tra c h lo rid e and id e n tifie d as l-carbethoxy­ methyl-3 ,3 ,5 ,5 -te tra n itro p ip e rid in e by means of a mixed m elting point (125°). Experiment 8 - P reparation o f Sodium D in itro e th a n o l.

A so lu tio n of

5 g. (0.03 mole) of 2 ,2 -d in itro -l,3 -p ro p a n e d io l i n 25 ml. o f absolute methanol was cooled in an ic e bath to 5 °.

Hhile s t i r r in g , sodium

methoxide (0.75 g. sodium in 10 ml. absolute methanol) was added slowly. The yellow p re c ip ita te o f sodium d in itro eth a n o l which formed during the a d d itio n o f base, was f i l t e r e d , washed with a sm all amount o f methanol and d ried under vacuum.

The yellow s o lid , sodium d in itro e th a n o l, melted

a t 132° and exploded when heated to 135-136°. Experiment 9 - Reaction o f Glycine Hydrochloride w ith Sodium D in itro e th a n o l.

In a 50 ml. round bottom fla s k equipped w ith a s t i r r e r

and thermometer, 5 g* (0.032 mole) of sodium d in itro e th a n o l was added to

26

3*5 g* ( 0.0314 mole) of glycine hydrochloride d issolved in 30 ml. of w ater.

A fter s t i r r i n g fo r about 10 minutes a t 25°> the so lu tio n

darkened, a la rg e number of bubbles appeared and the tem perature tended to l i s e b u t was kept at 30° o r below by in te n d .tta n t cooling with an ic e b a th .

This i n i t i a l re a c tio n soon subsided and over a period of

sev eral hours a so lid gradually p re c ip ita te d from the so lu tio n .

This

p re c ip ita te was f i l t e r e d and re c r y s ta lliz e d from 5>0$ alcohol to give 1.3 g. {2$%) of l-carboxymethyl-3,3> 5» 5 -te tra n i tro p ip e ri dine, m.p. ll*?0 A mixed m elting point with an authentic sample gave no low ering. Experiment 10 - P reparation o f Ethyl 5* $ -D in itro -3 -a z a v a le ra te . I n a 100

ml. round

m eter, 5 g«

bottom

fla sk equipped with a

s t i r r e r and a thermo­

(0.032 mole)of sodium d in itro e th a n o l was added to 5 g.

(0.035 mole) of ethyl glycine hydrochloride dissolved in 50 ml. of w ater.

A fter s t i r r in g fo r about 30 minutes a t 25°> a la rg e amount of

so lid formed in the so lu tio n and was f i l t e r e d .

A so lid continued to

form in th e re a c tio n mixture and was f i l t e r e d a t frequent in te rv a ls u n t il th is p re c ip ita tio n ceased (2 h o u rs).

R e c ry sta lliz a tio n from ethyl

a c e ta te gave I*.5 g. (65%) o f e th y l 5 ,5 -d in itro -3 -a z avale ra te as yellow p la te - lik e c ry s ta ls , m.p. 102-103° with decomposition. Anal.

Calcd. fo r

C, 32.6; Found: C, 33.0;

Mol. w t.

Calcd: 221

N, 19.0;

H, I4. 98 .

N, 19.26;

H, $.19.

Found: 229 (potentiom etric t i t r a t i o n ) .

Experiment 11 - P reparation o f Ethyl 3 ,5 j 5 -T rin itro -3 -a z a v a le ra te . To a m ixture of 7 ml. of fuming n i t r i c acid (sp. g r. about 1.5) and 7 ml. of concentrated s u lfu ric acid (96%) cooled in an ic e bath was slowly added 5 g. (0.023 mole) o f eth y l 5 > 5 -d in itro -3 -a za v alera te.

The

27

so lu tio n was slowly warmed to 55- 60 ° and h eld a t th a t tem perature fo r 5 m inutes.

A fter allowing i t to cool slowly to 30°, the m ixture was

poured in to a beaker o f chipped ic e .

The white o il which p re c ip ita te d

from the aqueous so lu tio n became a s o lid a f te r about te n minutes o f s tirrin g .

The product was f i l t e r e d and re c ry s ta lliz e d from carbon t e t r a ­

ch lo rid e to give 3«7 g. ( 60%) of ethyl 3 ,5 ,5 -trin itro -3 -a z a v à le ra te , m.p. i*l-ii2°. Anal.

Mol. wt.

Calcd. fo r C ^ qN^Oqï C, 27.07;

N, 21.05;

H, 3.76.

Found: C, 26.98;

N, 21.00;

H, 3.78.

Calcd: 266

Found: 257 (potentiom etric t i t r a t i o n ) .

Experiment 12 - Preparation of Ethyl 5-Bromo-3,5* 5 - t r in i t r o - 3 a z a v a le ra te .

To a s lu rry of 1 g. (0.0037 mole) of eth y l 3 ,5 ,5 - t r in i t r o -

3 -azav alerate in 5 ml. o f e th e r a t 5° was added slowly sodium meth­ oxide (0.1 g. sodium in 3 ml. of m ethanol).

The l i g h t yellow sodium

s a l t which formed was f i l t e r e d , washed w ith a l i t t l e methanol and d ried ; i t decomposed a t 87-88°♦ While

cooling in an ic e b ath , 0.11* g. (0.0017 mole) o f bromine

dissolved in 5 ml.

of

chloroform was added slowly to 0 .5 g. (0.0017 mole)

o f the sodium s a l t o f eth y l 3 > 5 > 5 -trin itro -3 -azav alerate suspended in 10 ml. of e th e r.

The mixture was allowed to stand fo r 15 minutes aid

then f i l t e r e d to remove the inorganic s a l t .

The e th e r f i l t r a t e was

evaporated under vacuum to give a yellow-white s o lid .

R e c ry sta lliz a tio n

from carbon te tra c h lo rid e gave 0.1*6 g. (80%) o f eth y l 5-bromo-3,5 ,5 - t r i n itro -3 -a z a v a le ra te as a white s o lid , m.p. 57-58°. Anal.

Calcd. fo r C ^ N O^Brs

C, 20.87;

N, 16.20;

H, 2 . 61 .

Found:

C, 21.00;

N, 15.61;

H, 3.12.

28

Experiment 13 - Attempted Reaction o f Ethyl 3 ,5 ,S-T rin itro -3 a za v alera te . Formaldehyde, and Ethyl glycine Hydrochloride.

A mixture

of 2 g. (7*^2 m illim ole) of e th y l 3,5>5 -tzd .n itro -3 -azav alerate, 0.616 g. (7*52 m illim ole) of 37^ form alin, 1.0U g. (7.52 m illim ole) of eth y l o glycine hydrochloride and 20 ml. of w ater was heated to 70 fo r a p erio d of 5 hours.

A sm all amount o f dark brown t a r had formed in the

m ixture and was removed by d écan tatio n .

The re a c tio n so lu tio n was

ex tra cted with e th e r and the e th e r evaporated but no product was is o la te d .

Upon concentrating the remaining aqueous so lu tio n under

vacuum, eth y l glycine hydrochloride was recovered q u a n tita tiv e ly . Experiment 1U - Attempted Reaction o f Ethyl 3 ,5 ,5 -T rin itro -3 az aval e ra te . Formaldehyde, and Glycine Hydro c h lo rid e .

A m ixture o f 2 g.

(7.52 m illim ole) o f eth y l 3,5»5 - t r i n i tro-3-azavaL erate, 0.616 g. (7.52 m illim ole) o f 37# form alin, 0.85 g. (7.52 m illim ole) o f glycine hydro­ ch lo rid e and 20 ml. o f w ater was heated to 70° fo r a p erio d o f 5 hours. The brown t a r which formed in the mixture was removed by d écantation. The re a c tio n so lu tio n was e x tra cted with e th e r and the e th e r evaporated but no product was is o la te d .

Upon concentrating the remaining aqueous

so lu tio n under vacuum, glycine hydrochloride was recovered unreacted. Experiment 15 - Attempted Reaction of Ethyl 3 ,5 ,5~ T rinitro-3~ az aval era te . Formaldehyde and Glycine.

A m ixture of 2 g. (7.52 m illim ole)

o f eth y l 3 ,5 ,5 - t r i n i tro-3-azavaLe ra te , 0.616 g. (7.52 m illim ole) of 37% form alin, 0.6 g. (7.52 m illim ole) of glycine and 20 ml. o f w ater was heated to 70° f o r a period o f 5 hours. and was removed by d écantation. o f the so lu tio n w ith e th e r .

A t a r formed in the m ixture

No product was is o la te d upon e x tra c tio n

Evaporation o f the remaining aqueous solu­

tio n under vacuum gave a q u a n tita tiv e recovery o f g ly cin e.

29

Experiment 16 - Attempted Reaction o f the Sodium S a lt o f Ethyl 3 ,5 ,5 -T rin itro -3 -a z a v a lc ra te , Formaldehyde, and Ethyl Glycine Hydro­ c h lo rid e .

Two grams (6.94 m illim ole) o f th e sodium s a l t o f eth y l 3,5>>5-

tr in itr o -3 - a z a v a le r a te , 0.57 g« (6.94 m illim ole) o f 37% form alin, and 0.96 g . (6.94 m illim ole) o f eth y l glycine hydrochloride were mixed in 20 ml. o f w ater.

A dark brown t a r formed almost imm ediately.

A fter

standing fo r one hour a t 30° the aqueous so lu tio n was decanted from the t a r and concentrated under vacuum to give a very small amount of a ta r r y re sid u e . Experiment 17 ~ Attempted Addition o f Formaldehyde to Ethyl 3 ,5 ,5 T rin itro -3 -a z a v a le r a t e .

A mixture of 2 g. (6.94 m illim ole) o f the

sodium s a l t of e th y l 3 , 5 - t r i n i tro -3 -a z a v à le ra te and 0 .6 g . (7.0 m illi­ moles) o f 37% form alin in 20 ml. o f water was cooled to 5° in an ic e b a th .

A so lu tio n of 0.4 g. of a c e tic acid in 1 ml. of w ater was added

dropwise and the mixture allowed to stand fo r one hour while m aintain­ in g the tem perature under 20°.

The o il which formed in the so lu tio n

was separated by d écan tatio n .

Ihen placed under vacuum, most o f the

o i l evaporated leaving a dark gummy resid u e which could not be cry­ s ta lliz e d .

Evaporation o f the w ater so lu tio n gave a sm all amount o f

resid u e which melted a t 317° (sodium a c e ta te m elts a t 324°). Experiment 18 - P reparation o f 5>,5-Din itro - 3 -a z a -l-p en ta n o l.

To

5 g. (0.03 mole) o f 2 ,2 -d in itro -l,3 -p ro p a n e d io l in a 100 ml. round bottom f la s k provided with a s t i r r e r and a thermometer was added a so lu tio n o f 1.85 g. (0.03 mole) o f ethanolamine in 25 ml. o f w ater. The tem perature rose from 28° to 35° and the p r e c ip ita te which formed almost immediately was f i l t e r e d .

The re a c tio n was allowed to continue

30

fo r th re e more hours but only a small anount o f a d d itio n a l product formed.

The s o lid was re c r y s ta lliz e d from w ater to give U*2 g." (82%)

o f l ig h t yellow c ry s ta ls of 5> ,5-dinitro-3-aza-l-pentanol, m.p. 115116° ( i t decomposed w ith th e evolution o f a g a s ). Anal.

Calcd. fo r C jH ^O ^:

C, 26.81$

N, 23.1*6$

H, 5.03.

Found:

C, 26.95$

N, 23.l*l$

H, 5.U5»

Mol. w t.

Calcd: 179 Found: 172 (potentiom etric t i t r a t i o n ) .

P rep aration of Ethanolamine H ydrochloride.

While cooling in an

ic e bath, 5 g. (0.08 mole) o f ethanolamine was added to a so lu tio n o f 7 ml. concentrated hydrochloric acid (36.5%) in 7 ml. of w ater. so lu tio n was then b o ile d to dryness on a hot p la te . ic e bath , a white s o lid formed. propanol and d ried under vacuum.

The

On cooling in an

I t was f i l t e r e d , washed with 1 The product, ethanolamine hydro­

c h lo rid e, melted a t 96° ( l i t . value 100°). Baperiment 19 - Reaction of 2 ,2-D initro-1,3-propanediol w ith Ethanolamine Hydrochloride.

On mixing 0.58 g. (0.006 mole) ethanol­

amine hydrochloride, 1 g. ( 0.006 mole) 2 ,2 -d in itro -l,3 -p ro p a n e d io l and 5 ml. o f w ater, no re a c tio n occurred. 3-1* (Hydrion B p a p er).

The pH o f th is so lu tio n was

To th is so lu tio n was added dropwise a 5%

aqueous so lu tio n o f sodium carbonate u n t il a p re c ip ita te began to form (pH o f so lu tio n was 5 -6 ).

The p r e c ip ita te was f i lt e r e d from th e solu­

tio n as i t formed and the pH was gradually ra is e d to 7, a t which p o in t no more product farmed.

This s o lid (0.1* g .) was r e c ry s ta lliz e d from

w ater and id e n tifie d as 5»5 -d in itro -3 -a z a -l-p e n ta n o l by means o f a mixed m elting p o in t (115°)•

31

Experiment 20 - Reaction of Sodium D initroethanol w ith Ethanol­ amine.

To a so lu tio n of 0.38 g. (.0063 mole) o f ethanolamine in 15 ml.

of w ater was added 1 g. ( .0063 mole) o f sodium d in itro e th a n o l. pH of th is so lu tio n was 11.

The

Ihen the so lu tio n was n e u tra liz e d slowly

to a pH o f 7-8 with concentrated hydrochloric a c id , a p r e c ip ita te formed in the s o lu tio n .

This p re c ip ita te was f i l t e r e d and re c ry s ta lliz e d from

w ater to give 0.?6 g. (69%) o f 5>5-dinitr o -3 -a z a - l-pentanol, m.p. 117°• A mixed m elting point with an au th en tic sample melted a t 116°. Experiment 21 - Reaction of 5>5>-Pinitro-3-aza-l-pentanol with Acetyl C hloride.

A mixture of 1 g. (0.9056 mole) o f 5>5 -d in itro -3 -

aza-1-pentanol and 5 g. (0.06 mole) of a cety l ch lo rid e was allowed to stand a t 25° fo r 12 hours with occasional sw irlin g of the m ixture.

At

th e end o f th is tim e, the white s o lid was f i lt e r e d , dissolved in w ater and n e u tra liz e d with d ilu te sodium hydroxide.

The aqueous so lu tio n

was d i s t i l l e d under vacuum to give a white s o lid resid u e, the organic p o rtio n o f which re c ry s ta lliz e d from acetone to give N -acetyl - 0 aminoethyl alcohol as white needles, m.p. 62-63° ( l i t . value^ 63-65°)• An au th en tic sample was prepared from ethanolamine and a c e ty l chloride and a mixed m elting p o in t gave no low ering. Experiment 22 - Attempted Addition o f Formaldehyde to 5 ,5-D initro3 -a z a -l-p e n ta n o l.

A mixture o f 1 g. (5*58 m illim ole) of 5 ,5 -d in itro -3 -

aza-1-pentanol, 0.i|8 g. (6.0 m illim ole) of 31% form alin, 5 ml. of 1 N sodium hydroxide, and 10 ml. o f w ater was cooled to 15°*

A fter standing

fo r 15 minutes, th e mixture was slowly a c id ifie d by th e dropwise ad d itio n o f a so lu tio n o f 0.33 g. of a c e tic acid in 3 ml. o f w ater.

When no

n o ticeab le re a c tio n had occurred a t the end o f 1 hour, the so lu tio n was

32

heated to 60 ° fo r 30 minutes and then concentrated under vacuum to give 3 ml. o f a yellow o i l . o il.

On standing, a s o lid c ry s ta lliz e d from the

R e c ry sta lliz a tio n o f the s o lid from w ater gave a 6?$ recovery of

5 >5> -dinitro-3-aza-l-pentanol.

PART I I .

ATTEMPTED SYNTHESES OP POUNITRO CARBOXYL!C ACIDS In tro d u ctio n

P olynitro carboxyl!c acids are valuable as n itr o p la s tic i n t e r ­ mediates because they can be used as monomers to form p o ly este rs aid polyamides o r can be converted to other monomers such as acid c h lo rid e s, amines o r iso c y an a te s. Two methods o f preparing p o ly n itro acids have been used with consi­ derable success on th is program.

One of these involves the ad d itio n of

p o ly n itro p a ra ffin s , such as nitroform o r dinitrom ethane, to unsaturated acid s.

Dinitromethane re a c ts with methyl a c ry la te and nitroform w ith

a c ry lic , m ethacrylic and ita c o n ic a c id s.

However, attem pts to add

nitroform to c ro to n ic, fu ro ic , muconic, maleic or fumaric acids were unsuccessful.

Apparently the addition of nitroform does not occur

i f resonance energy i s l o s t on form ation o f the new compound.

The

second method i s th e Mannich condensation o f polynitro alcohols with c e rta in amino acids, such as described in P art I of th is th e s is . The work presented here discusses attem pts to prepare poly n itro ac id s’ by two general methods.

The f i r s t method consisted o f converting

fu n ctio n al groups presen t in p o ly n itro compounds to carboxyl groups. The second method was to re a c t p o ly n itro compounds with molecules con­ ta in in g carboxyl groups. N either o f these two methods le d to new polynitro acid s, however two new in term ed iates, 2-methyl-2- n itro-1,3-dibrom opropane and 2 ,2 dinitro-1,3-dibrom opropane, were prepared and th e ir syntheses are re ­ ported here.

3k

D iscussion Attempted P reparation o f 3 ,3 -D in itro g lu ta ric Acid.

A p o ly n itro

acid "which has received considerable a tte n tio n on the n itr o polymer program i s 3 ,3 -d in itro g lu ta ric a cid .

and t r i e d but so f a r none have been

t h is compound have been proposed su c ce ssfu l.

A number o f methods fo r preparing

This in v e s tig a to r attem pted to synthesize the acid accord­

ing to the follow ing sequence o f re a c tio n s: no2

1.

3H0CHo-C-CH_0H

4- 2PBr

f

3BrCH2-C-CH2Br

4 - 2P(0H)3

ho2

2.

N°2 BrCH0-C-CH Br 2 i 2 N°2

3.

“°2 NC-CH2-C-CH2-CN -f- UHgO

4- 2NaCN

NC— CHg— Ç— CHg— ON -j— 2NaBr

H >

H02C-CH2-C-CH;[2-C02H no2 ‘

4 - 2NH

S ta rtin g w ith 2 ,2 -d in itro -l,3 -p ro p a n e d io l, i t was proposed to re a c t i t with phosphorus tribrom ide to give the corresponding 1 ,3-dibromo­ propane .

The dibromide was to be converted to the 1 ,5 -pentanedL nitrile

by the re a c tio n with sodium cyanide and the d i n i t r i l e then hydrolyzed to the g lu ta ric a cid . This s e rie s o f reactio n s was f i r s t stu d ied by using 2-methyl-2 n itr o - 1 , 3-propanediol as the s ta r tin g m ateria l because of i t s ready a v a ila b ility .

Once the re a c tio n conditions were determined, the re ­

actio n s were repeated using 2 ,2 -d in itro -l,3 -p ro p a n e d io l.

35

Of th is s e rie s of re a c tio n s only the f i r s t one was su ccessfu lly c a rrie d o u t, re s u ltin g in th e p rep aratio n o f both 2 -m ethyl-2-nitro1 .3-dibromopropane a id 2 ,2-dinitro-l,3-dibrom opropane from the re ­ sp ectiv e d io ls . Using the general procedure of S hriner and Young,^ a re a c tio n of 2-m ethyl-2-nitro-1,3-propanediol with phosphorus tribrom ide a t -5° using tetrahydrofuran as a solvent re s u lte d only in brom ination o f the so lv en t to give 1, li-dibromobutane.

In a re a c tio n a t 0° w ithout so lv en t,

the s ta r tin g m ateria ls were recovered. On the assumption th a t 2-methyl-2 - n itro -1 ,3 -p ro p an ed io l, because of i t s somewhat analogous s tru c tu re to p e n ta e ry th rit o i, would re a c t sim ila rly , the procedure fo r the re a c tio n o f p e n ta e ry th rito l with phosphorus trib ro m id e ^ was used.

"While heating 2 -m ethyl-2-nitro-

1 .3-propanediol a t 60-80°, phosphorus tribrom ide was added dropwise. The re a c tio n tem perature was then ra ise d very slowly to 15O-16O0 and held th e re f o r 5 hours.

The ra te o f heating had to be c a rrie d out

slowly otherw ise the re a c tio n mixture decomposed.

By t h is method a

h0% y ie ld of 2-m ethyl-2- n itro-1,3-dibrom opropane was obtained.

I t is

a c le a r liq u id with a camphor-like odor, d i s t i l l i n g a t 76-77° a t 1.5 mm. Hg. In the second step o f th is proposed sy n th e sis, several unsuccess­ f u l attem pts were made to re a c t 2-meth y l-2 -n itro-1,3-dibrom opropane with both sodium cyanide o r cuprous cyanide. experiments are summarized in Table V.

The d e ta ils o f these

36

Table V Attempted P reparations of 2-Meth y l-2 -n itr o - 1 ,5 -p e n ta n e d in itrile .

Reaction Time

Remarks

80°

16 hours

No re a c tio n

95# alcohol

85®

Wi hours

No re a c tio n

NaCN

e th y l cello so lv e

135®

20 hours

No re a c tio n

U

NaCN

none

70°

6 hours

No re a c tio n

5

NaCN

none

150°

20 hours

No re a c tio n

6

Cn2(CN)2

none

150°

2i* hours

No re a c tio n

Ban

Reactant

Solvent

1

NaGN

95^ alcohol

2

NaCN

3

Temperature

37

A p o ssib le explanation fo r th e i n a b i l it y to obtain a re a c tio n with 2-methyl-2- n i tro - 1 , 3-dibromopropane may be i t s s im ila r ity in stru c tu re to th a t of a neopentyl halide* I t i s known th a t neopentyl h a lid es are 32 unusually i n e r t , and the f a ilu re fo r th e dibromide to re a c t may be a ttr ib u te d to i t s "neopentylw structure* Another example o f th is in e rtn e ss was demonstrated when an attem pt was made to replace the bromine atoms with n itro groups by means o f a V icto r Meyer re a c tio n .

2 -M eth y l-2 -n itro -l, 3-dibromopropane was added

to an e th e r s lu rry of s i l v e r n i t r i t e and allowed to re flu x fo r 2U hours. I f su ccessfu l, th e product o f th e re a c tio n should have been e ith e r 1bromo-2-methyl-2, 3-dinitropropane or 2 -m e th y l-l,2 ,3 -trin itro p ro p a n e ; however only the s ta r tin g m aterial was recovered. When i t was found th a t 2-methyl-2 - n itro -1 ,3 -p ro p an ed io l would re a c t with phosphorus tribrom ide, experiments were i n i t i a t e d between 2 ,2 -d in itro -l,3 -p ro p a n e d io l and phosphorus tribrom ide.

I t was soon

evident th a t 2 ,2 -d in itro -l,3 -p ro p a n e d io l was even more se n s itiv e to h eat than 2 -m ethyl-2-nitro-1,3-propanediol.

Phosphorus tribrom ide

and 2 ,2 -d in itro -l,3 -p ro p a n e d io l did not re a c t u n t il heated to 11*0°, a t which tem perature fumes were evolved and only one ml. o f product was recovered.

I t was very d i f f i c u l t to re p e a t th is p rep aratio n because

decomposition always occurred. The product was assumed to be 2 ,2-dinitro-l,3-dibrom opropane even though only enough was a v a ila b le fo r a nitro g en a n aly sis, which checked reasonably w e ll.

I t was a c le a r liq u id w ith a camphor-like odor, sim i­

l a r to 2-methyl-2 -nitro-1,3-dibrom opropane, and d i s t i l l e d a t 60° a t 5 mm. Hg.

38

F urther work on 2 ,2 - d in itr o - l, 3-dibromopropane was discontinued because of the d if f ic u lty o f p rep aratio n . Attempted Oxidation of 2 ,2-D initro-1,3-propanediol.

The oxidation

o f 2 ,2 -d in itro -l,3 -p ro p a n e d io l was attempted in an e ff o r t to prepare e ith e r th e corresponding dialdehyde or dibasic a c id .

A re a c tio n between

the d io l and chromic trio x id e in the presence of a c e tic anhydride and s u lfu ric acid a t 10° re su lte d in the form ation of th e d ia c e ta te o f the d io l.

No oxidation had occurred; in stea d the d io l had reacted with

a c e tic anhydride. Fuming n i t r i c acid has been used to oxidize primary alcohols to a c id s .^

However, attem pts to re a c t 2 ,2 -d in itro -l,3 -p ro p a n e d io l with

fbming n i t r i c acid , e ith e r a t 25° or a t 60-70° gave a q u a n tita tiv e recovery of the d io l.

F urther work on th is re a c tio n was discontinued.

Attempted Reaction of Halogen Acid E sters with Potassium D in itro ­ methane.

As another p ossible approach to the synthesis of p o ly n itro

d ib asic a cid s, i t was proposed to re a c t potassium dinitrom ethane with two moles o f an e s te r of a h a lo su b stitu ted a c e tic acid to give the d ie s te r of 3 ,3 -d in itro g lu ta ric acid . ÜÛ2K HC + I no2

2 XCH2-C02C2H5

---------»

»°2 H5C202C-CH2-C-CH2-C02C2H5 no2

This e s te r could then be hydrolyzed to 3 ,3 -d in itro g lu ta ric a cid . The f i r s t attem pt was made with the e s te r of ch lo ro acetic acid . Ihen a mixture of eth y l chloroacetate and potassium dinitrom ethane was heated a t 70° fo r sev eral hours, no rea ctio n occurred.

A fter th is

f a ilu r e , eth y l io doacetate was prepared and reacted with potassium

39

dinitrom ethane.

As in the previous case only the s ta r tin g m ateria ls

were recovered. In order to determine whether a halogen atom on th e b e ta carbon atom would re a c t, eth y l

Ç -iodopropionate was prepared and a lso reacted

with potassium dinitrom ethane.

This experiment a lso f a ile d to give a

re a c tio n . Reaction o f Sodium Mai onate with Dibromodini trome thane.

I t had been

rep o rted th a t some h a lo n itro p a ra ffin s would re a c t with malonic e s t e r , ^ th e re fo re i t was thought th a t dibromodinitromethane might re a c t with the sodium s a l t o f eth y l malonate to give 2 ,2 -d in itro p ro p an etetracarb o x y lic e s te r .

2Na [CH(C02C2H^)2J "

+

Br-C-Br

Hydrolysis and decarboxylation o f th is compound would then y ie ld the d esired 3 > 3 -d in itro g lu ta ric acid . A re a c tio n d id occur upon the ad d itio n o f dibromodinitromethane to an alco h o lic so lu tio n o f sodium malonic e s te r .

The yellow p r e c ip ita te

which formed was found to be sodium dinitrom ethane while an e th e r ex­ tr a c tio n o f the re a c tio n mixture a f t e r d ilu tio n w ith w ater y ield ed a white s o lid which was id e n tifie d as eth an etetracarb o x y lic e s te r . These products could have formed by the follow ing re a c tio n s: EtOH »

BrCH(CCLC9Hc) 0 +

NCUNa II * ÇH

ho

Na+[CH(C02C2H5) 2] " 4 - B rC H -iCO ^H j2------ » (

)g-CH-CH-fCOgCgHg)^

Attempted Reaction o f H alonitro P a ra ffin s vdth G l y c in e » Since attem pts to form carbon-carbon bonds were unsuccessful, experiments were c a rrie d out which involved the form ation o f a carbon-nitrogen bond. Using the p rev io u sly prepared 2-methyl-2 - n i tro-1,3-dibrom opropane, i t was thought th a t i t might re a c t with glycine in the follow ing manners

Such a compound, 5-m ethyl-5-nitro-3,7-diazanonanedioic acid , would contain two amino n itrogens which might be fu rth e r n itr a te d to give nitram ine groups. As in the previous c ase s, 2-m eth y l-2 -n itro -1 , 3-dibromoprepane f a ile d to r e a c t.

When mixed with glycine and heated in the presence o f

acid o r base, w ith o r w ithout a solvent, no re a c tio n occurred and the s ta r tin g m ate ria ls were recovered. Another a v a ila b le h a lo n itro p a ra ffin which was rea cte d w ith glycine was dibromodini trom ethane.

Heating the re a c ta n ts alone or i n the

presence o f base a t 70° gave no re a c tio n .

With the f a ilu r e o f these

experim ents, the irork on a re a c tio n o f t h is type was discontinued. Experimental Experiment 23 - P reparation o f 2 -M e th y l-2 -n itro -l, 3-dibromopropane. Twenty-five grams (0.185 mole) o f 2-meth y l-2 -n itro - 1 , 3-propanediol was placed i n a 200 ml. round-bottom fla s k supplied with an a i r condenser

iil

and a thermometer.

The d io l was heated by means o f an o i l bath to 70e

and 50 g. (0.185 mole) o f phosphorus tribrom ide was added dropwise while m aintaining the tem perature o f the re a c tio n mixture below 100°.

A fter

the phosphorus tribrom ide was added the tem perature of th e o i l bath was slowly ra is e d to 150-160° over a period of 3-ii hours.

Once the bath

tem perature reached 130°, th e tem perature o f the re a c tio n m ixture tended to r is e

above th a t o f the bath; th ere fo re i t was necessary from time to

time to remove the re a c tio n fla s k from th e o i l re a c tio n under c o n tro l.

bath in order to keep the

A fter the tem perature of the re a c tio n mixture

no longer tended to r is e above th a t o f the bath, i t was held between 150-160° fo r 5 hours and then allowed to cool slowly to 25°•

About

200 ml. o f w ater was added to the gummy mass and allowed to stand u n t il th e e n tire so lu tio n could be poured from th e f la s k .

The organic la y e r

was separated from the w ater and was d i s t i l l e d under vacuum.

There was

obtained 19«7 g. (1*0%) o f 2-m ethyl-2-nitro-1,3-dibrom opropane, d i s t i l l in g a t 76-77° a t 1 .5 mm. Hg; n*° 1.525. Anal.

Calcd. f o r C jfyrc^B iy

C, 18.39;

N, 5.36;

H, 2.68.

Found!

C, 18.30;

N, 5.39;

H, 2.53.

Mol. w t.

Calcd: 26l

Found: 256 (cryoscopie method).

Experiment 2k - Attempted V ictor Meyer Reaction on 2-Methyl-2n itr o - 1 , 3-dibromopropane.

To a s lu rry o f 8.8 g. (0.058 mole) o f s ilv e r

n i t r i t e i n 20 ml. of e th e r a t 18° was added slowly 6 g. (0.023 mole) o f 2-meth y l-2 -n itro-1,3-dibrom opropane.

The tem perature was in creased to

35-37° and s t i r r in g continued f o r 2k hours. and the so lid residue washed with e th e r.

The mixture was f i l t e r e d

The e th e r f i l t r a t e a id washings

h2

were combined and d i s t i l l e d under vacuum.

Over a 70% recovery of the

2-methyl-2 - n itr o - 1 , 3-dibromopropane was obtained. Experiment 25 - P reparation o f 2,2-D initro-1,3-dibrom opropane. Two grains (0.012 mole) o f 2 ,2 - d in itr o - l, 3-propanediol was placed in a 100 ml. round-bottom fla s k supplied with an a i r condenser and a th e r­ mometer.

Four grams (O.Olli mole) o f phosphorus tribrom ide was added

slowly and then the m ixture was heated to 75° i n an o i l b a th .

A fter

16 hours a t 7f>°j th e tem perature was slowly ra is e d to lii0° over a period o f four hours, removing th e fla s k from the o i l bath as neces­ sary in order to c o n tro l the re a c tio n .

At l!t0° the m ixture began to @ give o ff brown fumes so i t was cooled quickly to 25 • A fter the ad d itio n o f 100 ml. o f w ater, th e mixture was allowed to stand fo r sev eral hours.

The organic la y e r which formed was separated and the

remaining aqueous la y e r e x tra c te d with e th e r.

The e th e r e x tra c t was

added to the organic la y e r and the combined so lu tio n d i s t i l l e d under vacuum.

One ml. of 2 ,2-dinitro-l,3-dibrom opropane was obtained which

d i s t i l l e d a t 60° a t 5 mm. Hg.

A residue o f t a r remained in the d i s t i l l ­

in g fla s k . L ater attem pts to rep e at th is experiment re s u lte d in decomposition o f the rea ctio n m ixture. Anal.

Calcd. fo r C3H|iN2°UBr2:

9-59.

Found:

N, 9.12.

Experiment 26 - Reaction o f 2 ,2-D initro-1,3-propanediol with Chromic Trioxide and Acetic Anhydride.

A m ixture o f 5 g. (0.03 mole) of

2 ,2 - d in itr o - l, 3-propanediol aid 30 g. (0.03 mole) o f a c e tic anhydride was cooled to 20° and 6 g. o f concentrated s u lfu ric acid added slow ly.

U3

The mixture was then cooled to 5° i n an ic e bath and 1.1 g. (0.011 mole) o f chromic trio x id e added slowly.

A fter s t i r r in g fo r an a d d itio n al 2^

hours a t 10-15°> the so lu tio n was poured in to cracked ic e and then ex­ tra c te d w ith e th e r.

Die e th e r was evaporated and the remaining organic

liq u id was washed repeatedly with w ater to remove the l a s t tra c e s o f s u lfu ric a cid .

Vacuum d i s t i l l a t i o n o f the organic e x tra c t gave 2.3 g.

o f a c le a r liq u id b o ilin g a t 113-115° a t 1 mm. Hg.

This liq u id was

id e n tif ie d as the d ia c e ta te of 2 ,2 -d in itro -l,3 -p ro p a n e d io l. Anal.

Calcd. f o r Found:

C, 33.6;

N, 11.2;

H, U.O.

C, 33.55;

N, 10.8k; H, k.02.

Acid hydrolysis of the d ia c e ta te gave a c e tic acid and the o rig in a l 2 .2 - d in itr o - l, 3-propanediol. Experiment 27 - Attempted Oxidation of 2 ,2-D initro-1,3-propanediol with Fuming

N itric Acid.

A mixture of 3 g. (0.018 mole) of 2 ,2 -d in itro -

1 . 3-propanediol and 7 g. (0.1 mole) of fuming n i t r i c acid (sp . g r . about 1.5) was heated slowly to 60-70° on a steam bath and held a t th a t tem­ p era tu re fo r 5 hours.

A fter cooling to 28°, the so lu tio n was e x tra cted

with e th e r and the e th e r e x tra c t evaporated under vacuum to give 2.1* g« of a mushy white s o lid .

A fter r e c r y s ta lliz a tio n from benzene, t h i s

white s o lid was id e n tifie d as the o rig in a l d io l by means o f a mixed m elting p o in t. Experiment 28 - Attempted Reaction o f Potassium Dinitromethane with Ethyl C hloroacetate.

To 0.5 g. (O.OOl* mole) of e th y l ch lo ro acetate

was slowly added 0.3 g. (0.002 mole) o f potassium dinitrom ethane and the mixture heated on a steam bath fo r two hours.

No re a c tio n occurred and

th e so lid potassium dinitrom ethane was recovered q u a n tita tiv e ly by f i l ­ tr a tio n .

kh

Experiment 29 - Attempted Reaction, o f Potassium Dinitromethane with Ethyl Io d o a c e ta te .

lo doacetic acid was prepared from ch lo ro acetic acid

follow ing the procedure of Abderhalden and Guggenheim."*" This acid was then e s te r if ie d with ethanol and sulfU ric acid (b .p . 68-70° a t 10 mm. Hg). A mixture o f 10 g. (0.02*6 mole) o f e th y l iodoacetate and 3*3 g* (0.023 mole) o f potassium dinitrom ethane was heated a t 70° on a steam bath fo r a period o f 38 hours.

The re d mixture was dissolved in e th e r

and the in so lu b le residue f i l t e r e d from the so lu tio n .

This s o lid

rep resen ted a q u a n tita tiv e recovery o f potassium dinitrom ethane.

The

red so lu tio n remaining a f t e r evaporation o f the e th e r was decolorized by sodium th io s u lfa te so lu tio n and was d i s t i l l e d under vacuum to give the o rig in a l e s te r (b .p . 67-68° a t 9 mm. Hg).

There was 0 .5 ml. o f a

red liq u id resid u e which, could not be d i s t i l l e d a t 2 mm. Hg p ressu re . Experiment 30 - Attempted Reaction o f Potassium Dinitromethane with E thyl @ -iodopropionate.

Using the procedure o f Gresham e t a l,^ *

iodopropionic a cid was prepared from

-p ro p io la cto n e .

£ -

This acid was

then e s te r if ie d with ethanol and su lfu ric acid to e th y l g -iodopropionate. (b .p . 70-71° a t 13 mm. Hg)• In a 50 ml. round-bottom fla s k provided w ith a thermometer and a s t i r r e r , was placed 1 g. (0.007 mole) o f potassium dinitrom ethane and 3.2 g. (0.012* mole) o f e th y l

g -iodopropionate.

While s t i r r i n g , the

mixture was heated over a steam bath (80°) fo r 1*8 hours.

The red

re a c tio n m ixture was e x tra cted with e th e r and th e potassium d in itr o ­ methane recovered q u a n tita tiv e ly by f i l t r a t i o n .

The e th e r f i l t r a t e was

decolorized w ith sodium th io s u lfa te aid upon evaporation o f the e th e r, th e o rig in a l e s te r was recovered.

U5

Experiment 31 - Reaction o f Sodium Malonate with Dibrom odinitromethane.

The dibromodinitromethane used in th is re a c tio n was obtained

from Dr. G illila n d o f th is lab o ra to ry ,

(b .p . 76-77°) •

In a small beaker 0.175 g* (0.0076 atom) of sodium was dissolved in 5 ml. o f absolute ethanol and 1.25 g* ( 0.0078 mole) o f e th y l malonate was added to the s o lu tio n .

A fter allowing the m ixture to coel to 25°,

1 g. (0.0038 mole) of dibromodinitromethane was slowly added. tio n turned yellow and a p re c ip ita te farmed immediately. fo r 3 hours, the s o lid was f i l t e r e d .

The so lu ­

A fter standing

This l ig h t yellow s o lid was id e n ti­

fie d as sodium dinitrom ethane ( exploded a t 215°) by conversion to a potassium dinitrom ethane. Water was added to the f i l t r a t e of the re ­ a ctio n mixture and then the aqueous so lu tio n was e x tra c te d with e th e r. The e th e r e x tra c t, upon standing, y ield ed a white c ry s ta llin e s o lid which was f i l t e r e d . 68- 69 ° .

This so lid did n o t co ntain nitro g en and melted a t

I t was id e n tifie d as ethanet e tracarb o x y lic e s te r (m.p. 72°).

Basic h y drolysis yielded ethanet e tracarb o x y lic acid (m.p. 167-168°). The w ater la y e r remaining from the e th e r e x tra c tio n y ield ed inorganic m aterial upon evaporation. Experiment 32 - Attempted Reaction o f 2 -M e th y l-2 -n itro -l,3 dibromopropane w ith Glycine.

A mixture of 3 g. (O.OU mole) o f glycine

and I4..2 g. ( 0.016 mole) o f 2-iaethyl- 2- n i tr o - 1 , 3-dibromopropane was heated a t 70° on a steam bath fo r two hours.

Having observed no re­

a c tio n a t the end o f th is tim e, 10 ml. o f water was added and the

a.

Sodium dinitrom ethane was placed in a w ater-eth er mixture and while cooling in ic e the so lu tio n was c a re fu lly n e u tra liz e d with hydro­ c h lo ric a cid . The e th e r la y e r was separated and tre a te d with potassium methoxide to give a red d ish -ta n p r e c ip ita te of potassium dinitrom ethane (exploded a t 20U°)•

k.6

so lu tio n a c id ifie d to a pH of b with hydrochloric a cid .

Since two more

hours o f heating gave no re a c tio n , sodium hydroxide was added to ra is e the pH to 9»

A fter sev eral more hours o f h e atin g , the re a c tio n was

discontinued and the s ta r tin g m aterials recovered. Experiment 33 - Attempted Reaction o f Dibromodinitromethane with G lycine.

A m ixture o f 1.2 g. (0.016 mole) o f glycine and 2 g. (0.007

mole) of dibromodinitromethane was heated a t 70° fo r 2 days.

IShen no

change occurred a f te r th is period o f tim e, a so lu tio n of 0.7U2 g. (0.007 mole) of sodium carbonate in 10 ml. o f w ater was added but h e at­ ing f o r one more day f a ile d to give a re a c tio n . were recovered.

The s ta r tin g m aterials

PART I I I .

AN ATTEMPTED SYNTHESIS OF 2,2-DINITRO- 1 ,3-PROPANEDIOL In tro d u ctio n

Another c la ss of compounds which has received considerable a tte n ­ tio n on th e n itr o polymer program are poljm itro alco h o ls. im portant alcohol has been 2 ,2 -d in itro -1 ,3 -p ro p a n e d io l.

One very Because o f i t s

good oxygen balance and the presence o f two fu n ctio n al groups f o r f u rth e r re a c tio n i t has proved a valuable monomer in the p rep aratio n o f n itr o p la s tic s . I t was found th a t 2 ,2 -d in i tro -1 ,3 -p ro p an ed io l could be prepared by the re a c tio n of potassium dinitrom ethane with two moles of f or mal dehyde. 17

Because o f the low y ie ld s in the p rep aratio n of potassium d i­

nitrom ethane, a lte rn a te methods of sy n th esis fo r t h is d io l were sought. The work on an attem pted sy n th esis i s described in the follow ing d is ­ cussion. D iscussion Attempted P reparation of 2 ,2 -D in itro -1 ,3 -p ro p an ed io l.

The method

proposed fo r preparing the im portant 2,2-dLn it r o - 1 ,3-propanediol i s shown i n th e follow ing s e rie s o f reactio n s s ta r tin g with th e commercially a v a ila b le t r i s (hydroxymethyl)ni tromethane:

no2

1.

HOCH2 -C -C H 2 OH + NaOMe CHgOH

NOpNa ii ^ > HOCH2-C-CH2OH -h MeOH + CHgO I

ue

2.

NOgNa e th e r HOCH2-C-CH2OH -f Br2 ------- >

^2 ér

3.

+

HOCHg-C-CHgOH

NaBr

n

N0o 0 0 NO. 0 I 2 h if I ^ II HGCH2-C-CH2OH 4- 2CH3-C-C1 -----> CH3-C-OCH2-C-CH2CM3-CH3 4* 2HC1 Br Br III

0 N°2 0 CH3-C-OCH2-C-CH20-C-CH3 4 - AgNOg

e th e r o r

9

f°2

Br

enZene

NO. IV

%•

o no2 o CH .-C-O CH 0-C -C H .O -C -C H , 3 2 m 2 2 3

h2o

■ —} h+

9

'b en zen ~ > C ^-C -O C ^C -C H gO -C -C ^

no2 HOCH.~C—CH.OH no2 2

+ AgBr

CH -CO H 3 2

V The f i r s t two re a ctio n s of th is s e r ie s were c a rrie d out according to a procedure o u tlin e d by Dr. Boy of th e General T ire and Rubber Co* His attem pts to form 2 ,2 -d in itro -1 ,3 -p ro p an ed io l d ir e c tly by the r e ­ a c tio n o f s i l v e r n i t r i t e on 2-bromo-2- n itro -1 ,3 -p ro p an ed io l ( I I ) in a V icto r Meyer re a c tio n were unsuccessful.

In order to p ro te c t the

alcohol groups and prevent p o ssib le com plications in the re a c tio n , i t was proposed to e s t e r i f y 2-bromo-2-nitro -1 ,3 -p ro p an ed io l ( I I ) to the d ia c e ta te e s te r (re a c tio n 3) and then attem pt a V ictor Meyer re a c tio n (re a c tio n it) .

The d ia c e ta te e s te r could then be hydrolyzed to give

2 ,2 -d in itro -1 ,3 -p ro p an ed io l (re a c tio n £ ).

h9

The p rep aratio n of the sodium s a l t o f 2 -n itro -1 ,3 -p ro p an ed io l ( I ) was q u a n tita tiv e , however, i t s conversion to the 2-bromo-2-n it r o - 1 , 3p ro p an ed io l(II) gave y ie ld s of $0%.

Acetyl chloride reacted w ith 2-

bromo-2-nitro -1 , 3-propm edi ol ( I I ) to give an 8U% y ie ld of the diace­ t a t e e s te r ( I I I ) . A ll attem pts to o btain a re a c tio n between th is e s te r and s ilv e r n i t r i t e (re a c tio n I4.) were u n su ccessfu l.

Reactions using so lv en ts such

as e th e r and benzene and a tem perature range o f 15° to U0 ® gave a t le a s t 70% recovery o f the o rig in a l e s te r ( I I I ) . At t h is tim e a new re a c tio n discovered by Shechter and K aplan^ a t Ohio S ta te U n iv ersity gave a good method fo r the p rep aratio n of 2 .2 -d in itro -l,3 -p ro p a n e d io l.

Because o f the importance o f the d io l

to th is work, the Ohio S ta te procedure i s included h ere. This synthesis also s t a r t s with the commercially a v a ila b le t r i s (hydroxymethyl) n i tromethane but req u ires only two step s to obtain 2 . 2- d i n i t r o - l , 3-propanediol.

1.

2.

HOCH.-C-CHgOH no2

NaOMe ------ > HOCHg-C-CHgOH 4 - MeOH - f CH.O

NOgNa HOCH2 -ê-CH2OH 4- 2AgNO^ +

NaNO^

* HOCH2-C-CH2OH 4- 2Ag 4- 2NaN0^

Shechter and Kaplan found th a t i n general gem d in itro compounds could be prepared by tr e a tin g the s a l t o f a mononitro p a ra ffin with 1 mole of sodium n i t r i t e and 2 moles of s ilv e r n i t r a t e .

The re a c tio n was almost

5o

instantaneous and a f te r f i l t e r i n g the s ilv e r re sid u e , the product was removed by e th e r e x tra c tio n of the aqueous so lu tio n .

Based upon t r i s -

(hydroxymethyl)n itromethane, an o v e ra ll y ie ld o f 50# o f the p u rifie d d io l can be obtained by t h is p ro cess. Experimental Experiment 3U - P reparation o f SocS-um S a lt o f 2-Nit r o - 1 ,3propanediol.

In a 2 1. beaker a so lu tio n o f 90 g. (0.66 mole) of 2-

m ethyl-2-nitro -1,3-propanediol in 900 ml. of absolute methanol was cooled in an ic e bath to 7°«

While s t i r r in g , sodium methoxide (15-75 g»

(0.68 atom) sodium dissolved in 180 ml. absolute methanol) was added over a p eriod o f 15 minutes in order to keep the tem perature below 10°. A fter standing fo r 15 minutes longer, the n h ite s a l t was f i l t e r e d , washed with a sm all amount of methanol and d ried under vacuum to give a q u a n tita tiv e y ie ld o f th e product, m.p. 85-86°. Experiment 35 - P reparation o f 2-Brom o-2-nitro-1, 3-propanediel. A suspension o f 26 g. (0.19 mole) o f the sodium s a l t o f 2 - n i tr o - l ,3 propanediol in 200 ml. of e th e r was cooled to 10° i n a ic e b ath . While s t i r r i n g , a so lu tio n o f 15*5 g. (0.19 atom) of bromine dissolved in 20 ml. o f chloroform was added slow ly.

The mixture was then allowed

to stand i n the ic e bath fo r 3-b hours before f i l t e r i n g .

A fter f i l t r a ­

tio n , th e e th e r so lu tio n was evaporated to give a yellow-white s o lid . This s o lid was dissolved in hot 1 -c h lo ro -l-n itro e th a n e and poured in to 3 volumes o f carbon te tra c h lo rid e to p r e c ip ita te the 2-bromo-2 - n i tr o 1,3-propanediol.

The product was f i l t e r e d and d ried under vacuum,

m.p. 127-128° ( l i t . v a lu .23 125*), y ie ld 13.3 g. (50%).

51

Experiment 36 - P reparation of the D iacetate of 2-Bromo-2-nitro1 .3 -propanediol.

Ten grams (0.05 mole) of 2-brom o-2-nitro-l,3-propane­

d io l was added to 12.7 g. (0.16 mole) of a c e ty l chloride and th e mix­ tu re warmed s u f f ic ie n tly to m aintain a gentle r e f lu x .

A fter reflux!ng

fo r two hours, the excess a cety l chloride was d i s t i l l e d a t atmospheric p ressu re .

Uoon d i s t i l l i n g th e remaining so lu tio n under vacuum, 12 g.

(81$) o f the e s te r was obtained as a c le a r, dense liq u id , b o ilin g a t 112-111*° a t 3 mm. Hg. Anal.

Calcd. fo r CyH^NO^Brs

N, 1**93.

Founds

N, 1**98.

Acid hydrolysis o f the e s te r gave a c e t i c acid and 2-brom o-2-nitro1 . 3-propanediol• Experiment 37 - Attempted P reparation of the D iacetate of 2 ,2 D in itro -1 , 3-propanediol by the V ictor Meyer R eaction.

To a s lu rry of

6.7 g* (0.0J*3 mole) of s ilv e r n i t r i t e in 20 ml. o f benzene was added slowly 9 g. (0.032 mole) o f the d ia c e ta te of 2-bromo-2 - n it r o - 1 ,3propanediol while s t i r r in g continuously a t 25°.

The m ixture was then

heated slowly to 1*0° and s tir r e d fo r 16 hours.

The m ixture was f i l t e r e d

and the s o lid residue washed with hot benzene.

The benzene so lu tio n was

then d i s t i l l e d under vacuum to give a 90% recovery of the e s te r . Experiment 38 - P reparation o f 2 ,2-D initro-1,3-propanediol by the Method o f Shechter and Kaplan.

In a 2 1. round-bottom fla s k provided

w ith a s t i r r e r and thermometer a so lu tio n of 108 g. (0.755 mole) o f the sodium s a l t of 2- n itro -1 ,3 -p ro p an ed io l, 1*8 g. (0.695 mole) o f sodium n i t r i t e and 1*80 ml. o f w ater was cooled to 7°*

S tir r in g c o n stan tly , a

so lu tio n of 201* g. (1.2 mole) o f s ilv e r n i tr a te in 600 ml. o f w ater was

52

added a l l a t once.

The tem perature Immediately rose to 15° and the solu­

tio n ra p id ly darkened u n til i t became black.

A fter about 90 seconds,

the tem perature rose fu rth e r ( 19°) and a s ilv e r m irror was deposited on the sides of the fla s k .

Mien the tem perature s ta r te d dropping again in

a minute o r so, the fla s k was removed from the ice bath and allowed to stand a t room tem perature (25°) fo r an a d d itio n a l f if te e n m inutes.

The

s ilv e r residue was f i l t e r e d and washed with about 100 ml. o f warm w ater. The combined f i l t r a t e and washing was then e x tra cted 5 times w ith 200 ml. p o rtio n s o f e th e r. orange, viscous o i l .

The e th e r e x tra c t was then evaporated to give an On standing th is o i l yielded a white so lid lèiich

was r e c iy s ta lliz e d from benzene to give the 2 ,2 -d in itro -l,3 -p ro p a n e d io l, m.p. 139° ( l i t . v a lu e ^ 11*0°).

I n r e c r y s ta lliz in g w ith benzene, th e re

was always some yellow o i l l e f t which would not go in to s o lu tio n .

A fter

decanting th e benzene, th is o i l , on standing fo r se v e ra l days, would y ie ld more c ry s ta llin e product which was r e c r y s ta lliz e d from benzene. Total y ie ld of p u rifie d d io l was $0%»

PART 17.

THE ATTEMPTED REACTION OF NITRO PARAFFINS WITH ISOCYANATES In tro d u ctio n

.In the course o f rocket p ro p e lla n t research , much time has been spent on th e study o f the p rep a ratio n and re a ctio n s of isocyanates as one of th e type compounds capable of being used as monomers.

I t has

been known fo r some time th a t compounds containing a c tiv e hydrogen atoms w ill undergo ad d itio n to iso c y an a te s.

Since n itr o p a ra ffin s undergo

some re a c tio n s involving an a c tiv e hydrogen, i t was assumed th a t they might also add to isocyanates in the follow ing manners

R~N-C=0 +

R H 0 R1 H-C-NOg ------- ) R-N-C-C-NCL I, 1* R R

R ■ a lk y l o r arom atic R = H, alk y l o r NO 2

Such a re a c tio n w ith diisocyanates and p o ly n itro p a ra ffin s would give another means of preparing both monomers and polymers. 29 Steinkopf and Daege had rep o rte d previously th a t n i tromethane 21 i t s e l f did not re a c t with phenyl iso cy an ate. Also Michael found th a t the actio n o f phenyl isocyanate on the potassium s a l t of ni tr o form re ­ su lte d only in th e decomposition o f the potassium s a l t .

However, the

claim o f S a n t e l l i ^ to have obtained ad d itio n products between nitroform or dinitrom ethane and various isocyanates again aroused an i n t e r e s t in the re a c tio n o f n itr o p a ra ffin s with iso cy an ates. In order to c la r if y these c o n flic tin g d ata, experiments were per­ formed, th e r e s u lts o f which s u b s ta n tia te the work as rep o rted by the

e a r l ie r in v e s tig a to rs .

These experiments in d ic a te th a t n itromethane

does not add to isocyanates and th a t decomposition occurs in the re ­ actio n of nitroform w ith iso cy an ates. D iscussion Since S a n t e l l i ^ had rep o rted rea ctio n s between nitroform and is o ­ cyanates, i t was o f i n te r e s t to know i f the re a c tio n a lso occurred w ith simple n itr o p a ra ffin s .

To determine t h is , n i tromethane was reacted

w ith phenyl isocyanate.

The f i r s t attem pts re s u lte d in th e is o la tio n

o f a s o lid product which on in v e s tig a tio n proved to be diphenylurea. This product was due to the re a c tio n of the isocyanate with tra c e s of w ater contained in the n itromethane. ArN=C=0 + H20

> ArNH-C02H ------->

ArN=C“0 + ArNH2 ------- >

ArNH

-|~

CO^

0 ArNH-C-NH-Ar

Following t h is , fre s h ly p u rifie d ni tromethane was used and g re a t care taken to exclude m oisture from the re a c tio n m ixture.

No re a c tio n

occurred in th is case even when the m ixture was refluxed fo r a period of s ix h ours.

The experiment was repeated using n i tromethane and

oC-

naphthyl isocyanate and again no re a c tio n took p lac e. Having found t h a t simple n itr o p a ra ffin s did not re a c t with is o ­ cyanates, a tte n tio n was then d ire c te d toward the behavior of nitroform in t h is re a c tio n .

I t had been reported th a t potassium nitroform did not

re a c t with arom atic isocyanates 21 but no referen ces could be found to th e re a c tio n w ith an a lip h a tic iso cy an ate.

Therefore potassium n itr o ­

form was reacted w ith eth y l isocyanate in dry e th e r and allowed to stand

55

fo r te n days.

At the end o f th a t time potassium nitroform was recovered

unreacted from th e m ixture. With th e f a ilu r e of these experiments the re a ctio n reported by S a n t e l l i ^ between nitroform and phenyl isocyanate was repeated.

4

small amount o f a green p r e c ip ita te was is o la te d from the mixture but i t became an o il on prolonged exposure to a i r .

This p re c ip ita te

did not melt below 330° ( S a n te lli rep o rted m.p. above 250°)5 i t was soluble i n acetone but in so lu b le in oth er organic solvents aid w ater. When th e remaining re a c tio n mixture was s e t a sid e , i t decomposed during the n ig h t, blowing the step p er from the fla s k and leaving a black t a r as a resid u e. From the r e s u lts o f t h is experiment and the fa c t th a t none of the analyses o f S a n t e l l i's product checked fo r any conceivable a d d itio n product, i t seems reasonable to assume th a t the re a c tio n gives only decomposition. Since t h is type o f re a c tio n held l i t t l e hope o f success, work was discontinued along th is lin e in fav o r o f more promising re a c tio n s . Experimental The n i tromethane used in the follow ing re a c tio n s was p u rifie d by washing i t f i r s t with a 30% so lu tio n o f sodium b i s u l f i t e , then with a 10% so lu tio n o f sodium bicarbonate.

I t was d i s t i l l e d through a packed

column and f in a lly d ried over calcium c h lo rid e . Experiment 39 - Attempted Reaction o f Nitromethane with Phenyl Iso cy an ate.

In a completely dry 100 ml. round bottom fla s k provided

with a condenser with a calcium chloride tube i n the open end was

56

placed 16 g* ( 0.26 mole) of n itromethane and k g. (0.03U mole) o f phenyl iso cy an ate.

Upon re fluxing the m ixture fo r 6 hours, and then

allowing i t to cool and stand f o r sev era l days a t 30° , no re a c tio n occurred. I t was found th a t i f the s lig h te s t tra c e o f w ater were p resen t in these re a c tio n s , diphenylurea formed as a white s o lid , m.p. 238° ( l i t . value 238-239°) •

No oth er produce was ever is o la te d .

Experiment I4O - Attempted Reaction o f Ni tromethane with OCNaphthyl Iso cy an ate.

In a completely dry $0 ml. round-bottom fla s k

provided with a condenser w ith a calcium ch lo rid e tube in the open end was placed 3 g. ( 0 . 0U8 mole) of nitrom ethane and 8 .I4. g. (0.01*8 mole) o f OC-naphthyl isocyanate.

A fter re fluxing fo r 2 hours and then

allowing to stand fo r several days a t 30°, no re a c tio n occurred. I t was found t h a t th e s lig h te s t tra c e of water i n t h i s re a c tio n re s u lte d in the form ation o f o c , ec'-dinaphthylurea, a w hite s o lid , m.p. 285° ( sublimes) ( l i t . value 288°-sublim es). P rep aration of Ethyl Isocy anate. S lo tta and L o re n z .^

This i s the procedure o f

To a mixture o f 10 g. (0.12 mole) o f potassium

cyanate and 2 g. ( 0.019 mole) of anhydrous sodium carbonate in a 125 ml. d i s t i l l i n g fla s k was added 16 g. (0.101* mole) of eth y l s u lf a te .

The

fla s k was heated to a tem perature s u f f ic ie n t to drive o ff eth y l is o ­ cyanate, which was condensed and c o lle c te d in a receiving f la s k .

A

y ie ld o f !*.!* g. ( 60$) of eth y l isocyanate was obtained; b .p . 59-60°. Experiment 1*1 - Attempted Reaction o f Ethyl Isocyanate and Potassium N itroform .

The potassium nitroform used i n th ese experiments was p re­

pared according to th e procedure o f G illila n d

57

The e th e r used in th is experiment was d ried over calcium hydride. A mixture of 2 g. (0.01 mole) o f potassium nitroform , 2 g. (0.03 mole) o f ethyl isocyanate and 15 ml. o f anhydrous e th e r was s e t aside in a t ig h t l y stoppered Erlenmeyer fla s k fo r a period o f 11 days.

At

the end o f th a t time the potassium nitroform was recovered q u a n tita tiv e ­ ly by f i l t r a t i o n .

The f i l t r a t e s t i l l had the strong odor o f e th y l is o ­

cyanate and y ield ed no s o lid on c h illin g in dry ic e . Experiment li2 - Reaction of Nitroform with Phenyl Isocyanate.

Five

grams (0.033 mole) o f nitroform , h g. (0.03U mole) of phenyl isocyanate and 20 ml. o f e th e r were placed in a tig h tly stoppered Erlenmeyer fla s k . A fter 21* hours the so lu tio n had turned a dark green w ith the form ation o f a sm all amount o f dark green p r e c ip ita te .

This p re c ip ita te was

f i l t e r e d and on standing in a i r fo r sev eral hours, i t became an o i l . I t was so lu b le i n acetone, in so lu b le in o th er organic solvents and w ater; m.p. above 330°.

The remaining re a c tio n m ixture decomposed

overnight, blowing the stopper from the fla s k and leaving a black t a r in the bottom o f the f la s k .

BIBLIOGRAPHY 1.

Abderhalden and Guggenheim, B er., 1*1, 2853 (1908) •

2.

Adams, "Organic R eactions,* Vol. I , p . 305, 313, New York, John Wiley and Sons, I n c ., 191*2.

3.

A erojet Eng. Corp. Q uarterly Report, No. 31*5, p . 62 (191*9).

U.

A erojet Eng. Coip. Q uarterly Report, No. 371, p . 22 (191*9) •

5.

A erojet Eng. Corp. Monthly Report, No. 1*831-18, p . 5, May, 1950.

6 . Alexander and U nderhill, J . Am. Chem. Soc., 71, 1*011* (191*9) • 7.

Buchner, B e r., 25, 1157 (1892).

8.

F ischer, i b i d ., 31*, 1*33 (1901).

9.

Frankel and C ornelius, i b i d ., 51» 1651* (1918).

10.

Frankel and K atchalaki, J . Am. Chem. Soc. , 61*, 2261* (191*2)•

11.

G illila n d , Report on th e Synthesis and Testing o f High Explosives, A rthur D. L i t t l e , I n c ., p . 101* ( 191*9)•

12 .

Gilman and B la tt, "Organic Synthesis, " Col. Vol. I , p . 168, New York, John Wiley and Sons, I n c ., 191*1#

13.

Gilman and B la tt, i b id . , Col. Vol. I I , p . 1*76.

11*.

Gresham, e t a l . , J . Am. Chem. Soc., 70, 1000 (191*8).

15.

H arris and Weiss, Ann. , 327, 365 (1903)•

16 . Johnson, J . Am. Chem. Soc. , 68, 12 (191*6). 17.

Kispersky, J . P ., Ph. D. Thesis, Purdue U n iv ersity , 1950.

18 . R o lle r, C. R ., Ph. D. T hesis, Purdue U niversity, 1950. 19.

Liebermann and Wagner, J . Org. Chem., 11*, 1001 (191*9)•

20 .

Lipp and Wldmann, Ann. , 1*09, 79 (1915)•

21

.

22 .

Michael, B er., 38, 1*1 (1905)# 0. S. R. D. Report No. 3992, "Rocket Fundamentals," p. 121.

59

23*

Boy, D r., P riv a te Communication, General Tire and Rubber Co., Akron, Ohio.

2lt.

S a n te lli, T. R., Ph. D. Thesis, Purdue U n iv ersity , 19U8»

2$.

Senkus, M., J . Am. Chem. Soc., 68, 10 (19U6).

26.

Shechter and Kaplan, Bui. of the S ixth Meeting o f Army-Navy S olid P ropellan t Group, Vol. I I , p . 169 (1950).

27*

S hriner and Young, J . Am. Chem.Soc., £2, 3337 (1930).

28.

S lo tta and Lorenz, Ber., 5QB, 1320 (1925)«

29.

Steinkopf and Daege, i b i d . , 1+k, 1*97 (1911).

30.

Urbanski, e t a l . , J . Chem. Soc., 921* (191*7).

31-

Van Tamelea and Van Zyl, J . Am. Chem. Soc. , 71, 835(191*9).

32.

Whitmore, "Organic Chem istry," p. 73, New York, D.Van Co., 1937.

33.

Whitmore, i b i d ., p . 539.

Nostrand

60

VITA

Wayne May was born September 21*> 1919, in New C a stle , Indiana. He graduated from New C astle High School, New C astle, Indiana, i n June o f 1937 and received an A. B. degree from De Pauw U niversity in June o f 191*1 •

Ffrom October o f 191*2 u n t i l January o f 191*6 he served

as an o f f ic e r i n the United S ta te s Naval Reserve.

He received th e

Ph. D. degree in August o f 1950 from Purdue U n iv ersity . member o f Phi Lambda Upsilon and Sigma I i .

He i s a