Preparation of Certain Perhalopropionic Acids and Derivatives and Certain (Perhaloalkyl)triazines and Polytriazines

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P U B D U B UNIVERSITY

THIS IS T O CERTIFY T H A T T H E THESIS P R E P A R E D U N D E R M Y SUPERVISION

Addison H, Williamson

by

ENTITLED PREPARATION OF CERTAIN PERHALOPROPIONIC ACIDS AND

DERIVATIVES AND CERTAIN (PEREALOAIKYL)TRIAZINES AND POLYTRIAZINIS COMPLIES W I T H T H E UNIVERSITY R E G U L A T I O N S O N G R A D U A T I O 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 FULFILLING THIS P A R T O F T H E R E Q U I R E M E N T S

FOR THE DEGREE OF

Doetor of Philosophy

P

H

August,

19

r o f e s s o r in

Charge

ead o f sc h o o l or

D

of

T h e s is

epa rtm en t

49

T O T H E LIBRARIAN:--

-IS-. THIS THESIS IS N O T T O B E R E G A R D E D A S CONFIDENTIAL.

PB0FBS6OB U S f OBABOB

GRAD. SOBOOL FORM 9—3-40—IM

PREPAEA.TIOK OP CERTAIN PERHALOPROPIONIC ACIDS AND DERIVATIVES AND CERTAIN (PERHALOALm.)TRIAZlNES AND POLYTRIAZINES A Thesis Submitted to

the Faculty

of Purdue University by A. E. m

Williamson

Partial Fulfillment of the

Requirements for the Degree of

Doctor of Philosophy August, 1949

ProQuest Number: 27712213

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 27712213 Published by ProQuest LLO (2019). C opyright of the Dissertation is held by the Author. All rights reserved. This work is protected against unauthorized copying under Title 17, United States C o d e M icroform Edition © ProQuest LLO. ProQuest LLO. 789 East Eisenhower Parkway P.Q. Box 1346 Ann Arbor, Ml 4 8 1 0 6 - 1346

AomowLmmmr

The author is greatly Indebted to Dr. E. T. MoBee, who has been in direct charge of this research. This research was conducted as a Purdue Research Foundation Fellowship sponsored in turn by the Ethyl Corpora­ tion and by the Westinghouse Electric Corporation.

TART.T3 OF CONTENTS

ABSTRACT PART

-TRICHIORO-Ï^^/? -DIFLUOROPROPIONYL FLUORIDE M ù A à

-DICHLORO-//^^^ -TRI-

FLUOROPROPIONYL

FLUORIDE AND THEIR

DERIVATIVES.

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

i

PART 2. THE SYNTHESIS OF PERHALOALKYLTRIAZIüŒS AND PERHALOALKYLPOLYTRIAZINES. ...... INTRODUCTION...............

ix 1

PART I PERHALOPROPIONIC ACID DERIVATIVES INTRODUCTION..............................

5

EXPERBÆENTAL AND DISCUSSION.................

7

PART II PREPARATION OF TRXAZINES INTRODUCTION.....................

21

EXPERIMENTAL AND DISCUSSION.................

26

PART III MISCELLANEOUS: THE FLÜORINATION OF PBNTA-

CHLOROETH%L PHENYI KETONE; THE SYNTHE­ SIS OF l-GHLOROHEPTADECAFLUORODECAHYDRONAPHTEALSNE; A NEW SYNTHESIS OF 1,4BIS (PBNTACHLOROETHYL) BENZENE........ INTRODUCTION..............................

55

BIBLIOGRAPHY.................................

62

VITA

LIST OF TABLES AND FIGURES List of Tables 1#

2*

To follow Page Physical Properties of Derivatives of Halogenated Propionyl Fluorides*......****.#

3

Physical Properties of Triazines .

List of Figures 1#

Lead Tetrafluoride Reactor

7

2*

100 Ampere Fluorine Cell*.

7

3#

Chlorination Apparatus.•••

29

4«

Fluorination Apparatus....

30

5*

One Liter Autoclave.......

35

6*

Small Nickel Autoclave....

44

-TKIOHtOBO-1^,0 -KCPLÜOBOPBOPIOHÏI. ÏXUORIDB JU9D /i, 6 - DIOBLOEÔ-/,«^.J - TRIPLUOROPRÔPIONYL BLBOEIDB jM) THBXR HEBIVATIVBS By S. T. MoBee aad A. E. Williamson (1)

1*

Present address, Chambers Works, S« X« duPont de meurs and Company, Pennsgrove, N. J.. m

this study, chloro-fluoro-propionyl fluorides

were prepared by

the vapor-phase fluorination of triohloro-

aerylyl chloride, CClgsOOl-OOOl, with lead tetrafluoride. The triohloroacrylyl chloride was passed over lead tetrafluoride at temperatures of from I 50® to 250®. At temperatures below 200®, the primary products are -trichloro-/,. CM 3

3 w\

♦

»A

Cf\

vO

vO

i

» »

CM

to

A

CM c>-

-4-

o

o%

CM

#

H

♦ CN UN

H

CM CM §CM o Ph o m O ëCMëCM ëCM CM #4 o •4 H « 4 H O O O S o 8 O O O O O

• ON

to «4

O •

CM

IN i4

«

O CM

#

O CM

-4

• CN. UN

H

CM # UN UN

ON

•

C OOlgrCOlOOOl, was

prepared by the method of Boesekin et. a Boese

l

.

.

The fol-

lowing experiments are typical.

Bxperiment 8844 Twelve moles of tetrachloroethylene (1990 g.) was slowly added to a mixture of 30 moles of carbon tetrachloride {4613 g.) and 2.8 moles of aluminum chloride (374 g.) con­ tained in a 12-liter 3-neoked flask equipped with three efficient reflux condensers and heated on a steam bath. Tetrachloroethylene was added as fast as the reflux con­ densers could absorb the heat of reaction.

After all of the

tetrachloroethylene had been added, the reaction mixture was heated at reflux temperature for two hours.

The contents of

the flask were then poured over ice, washed thoroughly with water, dried, and rectified.

The yield of unsymmetrical

heptachloropropane was 83^.

Bxperiment 8344-2 Ten moles of unsymmetrical heptachloropropane (2482 g.) was treated with 10.3 moles of alcoholic sodium hydroxide in a 3-liter 3-necked flask equipped with two reflux condensers, a Hirschberg stirrer and a dropping fun­ nel.

After all the alkali had been added, the mixture was

steam-distilled and the water-insoluble material dried and rectified.

A yield and conversion of 98^ was obtained.

Bxperlmeàt 81144-2 Hexaciiloropropene was hydrolyzed to triohloroaeryllc acid by treatment with concentrated sulfuric acid (Baker Technical Grade, 63*3®-66®Be).

Seven and seven-

tenths moles of hexachloropropene (1917 g.) and 13*7 moles of concentrated sulfuric acid were placed in a 12-liter 3-necked flask equipped with a Hirschberg stirrer, a thermometer, and two 14-mm. vent tubes*

The mixture was

stirred vigorously at room temperature until the evolution of hydrogen chloride ceased, then heated gradually to 130® C. with vigorous stirring.

After the contents of the

flask had been stirred at 130^ C. for 6 hours, the material was allowed to cool overnight and then it was poured slowly onto a large quantity of crushed ice. water was violent.

The reaction with

Most of the trichloroacrylic acid sep­

arated as a solid, but, because of its solubility in water, the solution was extracted with carbon tetrachloride.

The

solid trichloroacrylic acid and the carbon tetrachloride solution were placed in a distilling flask and the carbon tetrachloride-water azeotrope was distilled to ensure com­ plete removal of water. further purified.

The trichloroacrylic acid was not

The yield and conversion were 94«7^*

It should be noted that the reaction between hexa­ chloropropene and concentrated sulfuric acid can be ex­ tremely violent if the temperature is raised too fast, or if a temperature much over I30® 0. is attained.

Also,

10

since there is considerable foaming at the beginning of the reaction, extreme care must be exercised in the per­ formance of this reaction*

Experiment 11347 The hydrolysis of hexachloropropene was repeated using 39 moles of hexachloropropene, (Hooker, 9*7 kg.) and 30 moles of 96.7^ sulfuric acid (Baker C. P.) in a 12-liter flask equipped with 2 West condensers and a Hirschberg stirrer.

A lOg. portion of aluminum sulfate

was added as a catalyst.

The hydrolysis proceeded smoothly

to completion at room temperature in 24 hours.

This is a

notable improvement over the use of 93*2ÿ sulfuric acid (Baker technical grade, 6$.3®-66® Be), as it obviates the possibility of a violent reaction, such as occurred in one instance using the elevated temperature method.

The use

of aluminum sulfate had no detectable action in the previous method, whereas in this method the addition of aluminum sul­ fate visibly accelerated the evolution of hydrogen chloride* The product of this reaction was treated by the same method as was used in the preceeding experiment.

Experiment 71444-2 Another method of hydrolyzing hexachloropropene to trichloroacrylic acid was also used^^). Two moles (500 g.) of hexachloropropene, 5 moles (987 g*) of barium

11

carbonate and a sufficient quantity of water to make a thick slurry were placed in a 3-liter round-bottomed flask and heated at reflux temperature until no more carbon di­ oxide was evolved, about 24 hours.

The entire reaction

mixture was filtered while hot, and the solid material was washed with water and the washings combined with the original filtrate.

Sulfuric acid was added to the washings to liber­

ate free trichloroacrylic acid, and to precipitate the barium ion as barium sulfate.

The resulting solution was extracted

with carbon tetrachloride.

On evaporating the carbon tetra­

chloride solution, trichloroacrylic acid crystallized out in clear rhombic plates.

The yield and conversion of the acid

was only 20^.

Experiment 81644 Trichloroacrylic acid was converted to the chloride by treatment with excess thionyl chloride.

acid Six and

sixteen-hundredths moles of trichloroacrylic acid, (1153g*) and 12.6 moles of thionyl chloride (Paragon, 1500g.), were placed in a round-bottomed flask and heated at the reflux temperature for 2 to 3 hours.

The excess thionyl chloride

was then distilled off, followed by the trichloroacrylyl chloride.

A yield and conversion of 96^ were obtained.

The trichloroacrylyl chloride was sealed in Pyrex ampoules for storage until use.

12

The Fluorination of Trichloroacrylyl Chloride The fluorination of trichloroacrylyl chloride pro­ ceeds by two essentially different paths, depending upon the reagents and temperatures employed.

Using silver(II) fluo­

ride at temperatures in the range of l$0°-200O 0., tri­ chloroacrylyl chloride is converted to the fluorinolysis products carbonyl fluoride and various chlorofluoroethanes. The same products are obtained when lead(IV) fluoride is employed in the temperature range of 200^ to 250^ 0. However when trichloroacrylyl chloride is passed over lead(XV) fluo­ ride near the boiling point of the organic acid chloride, that is, from 15O® to 200® G., the predominant reaction products are the fluorination products -trifluoropropionyl fluoride and fluo ropropionyl fluoride. product of the reaction.

-dichloro- % -trichloro-a(,'(^di-

In all cases chlorine is a by­ Since chlorine is also obtained

in the exit gases during the reactivation of the fluorinating agents with fluorine, these reactions are postulated as: 150® C.

O2GI3OOCI+ PbFj^---- ^ C^Gl^FgOOF +- GgOlgF^GOF "hOl^^

0gCl,0001 +

250® 0. ---- CgCXjJô-i

OOFg + PbFyOlg

(6)

Preliminary experiments using iron reactors indi­ cated that the continued presence of chlorine and perhaps other corrosive reaction products at the elevated tempera­ tures involved in alternate passage of trichloroacrylyl

13

ehlorida and fluorine throu^ the reactors corroded through the welds which were used in the construction of these re­ actors from sheet steel.

Therefore many of the subsequent

fluorination experiments were conducted in reactors con­ structed out of sheet nickel.

These nickel reactors gave

satisfactory service over a period of 3 years. The apparatus used in the fluorination of trichlo­ roacrylyl chloride with silver(II) fluoride and with lead(Hr) fluoride is as follows.

 tee connection to the inlet of

the reactor system was fitted with a dropping funnel, the stopcock plug of which was notched in order that close con­ trol of the dropping rate could be obtained, and a nitrogen line for use in purging the system.

The reactors consisted

of two flat nickel tray reactors as shown in Figure 1, li” X 8** X 48”. An integral air jacket served to cool the reactor when necessary.

Adjacent to the inlet and outlet

connections in the reactor was a 24-inch long thermocouple well.

The exit connection was connected to a trap system

consisting of three cylindrical nickel containers.

The

first of these containers was cooled in an ice bath, while the two succeeding traps were immersed in a mixture of dryice and trlchloroethylene.

Following the dry-iee traps in

the exit system, a large glass test tube cooled in liquid air served to indicate that no condensable gases escaped from the dry-ice-cooled traps under the usual operating conditions*

14

The fluorination of triohloroaorylyl chloride with silver(II) and lead(IV) fluorides is exemplified toy the typical reactions.

Experiment 2645 Two and one-half moles of trichloroacrylyl chloride (351g*) was passed over 40 moles of silver(II) fluoride con­ tained in two flat nickel reactors connected in series. reactors were maintained at 155® to 160® 0.

The

The products of

the reaction were condensed in ice and dry-ice traps.

The

contents of the traps were rectified in a low temperature column.

Fractions were obtained which

to 4® C., and 47^ C.

boil at -46® 0.-2®C.

The lowest boiling fraction could not

be identified by halogen analysis because of contamination by chlorine.

The fraction boiling in the range -2® to 4® C.

is composed of dichlorotetrafluoroethanes.

The identity of

these compounds was established by boiling points and by halogen analyses.

The theoretical percentages of chlorine

and fluorine in dichlorotatraf1uoroethane are 41*5 and 44*4 respectively. Analysis of this material showed a chlorine content of 4O.4 and 40.6^, and a fluorine content of 45*0 and 44.6^.

The higher boiling fraction is 1,1,2-trichloro-1,

2,2-trifluoroethane, as evidenced by boiling point and by halogen analysis.

The theoretical percentages of chlorine

and fluorine in trlchlorotrifluoroethane are 52.8 and 30.4 respectively.

The values obtained by analysis are 53*1^

15

ehlorlme and 30*4^ fluorine*

Experiment 11845 Two and one-half moles of trichloroacrylyl chloride (354g.) was passed over 40 moles of silver(II) fluoride con­ tained in two flat reactors connected in series.

The first

reactor was heated at 160® to 170® 0*; the second was heated #t #6#® tp

6«

The products of the reaction were recti­

fied throu^ a low-temperature column.

The fractions ob­

tained were the same as those for the previously described reaction with silver(II) fluoride.

Experiment 2345 One and four-tenths moles of trichloroacrylyl chloride (340g.) was passed over 20 moles of lead(IV) flu­ oride.

The reactor was maintained at a temperature of

160® - 5® G.

The gaseous reaction products passed from the

reactor to a series of nickel traps.

These traps were

cooled by ice, dry-ice, and liquid air respectively.

At

the conclusion of the introduction of the trichloroacrylyl chloride, dry nitrogen was passed through the reactor and trap system for four hours to sweep out organic material* The contents of the ice and dry-ice traps were combined and rectified.

No material was found in the liquid air trap.

After removal of chlorine, the product separated into two fractions consisting of 171g* of

-dichloro-

^^-tri-

fluoropropionyl fluoride, b.p. 47.0® 0. and 299g. of

-

16

trie]iloro-«(/î-fluoropropionyl fluoride, b.p. 74.2® 0., representing yields of 36^ and 58^ respectively.~ The cal­ culated percentages of chlorine and fluorine for dichlorotrifluoropropionyl fluoride are 35.6^ and 38.2% respective­ ly.

Analysis of this material showed a chlorine and fluo­

rine content of 35.8 and 37.9% respectively.

The calculat­

ed percentages of chlorine and fluorine in trichlorodifluoropropionyl fluoride are 49.5 and 26.4 respectively. Analysis for chlorine and fluorine gave 49.6 and 27.4% respectively.

Experiment 8945 The above procedure was repeated, the only dif­ ference being that the reaction was run at 210®-220® 0. The products consisted of carbonyl fluoride, triohlorotrifluoroethane and two isomeric dichlorotetrafluoroethanes. Thus it is seen that lead(II) fluoride at elevated temper­ atures has the same action as silver(II) fluoride at moder­ ate temperatures.

The Preparation of Perhalopropionic Acid Derivatives The various derivatives of perhalopropionic acids were prepared because of their own inherent interest as possible heat transfer agents and dielectrics, and also for use in verifying the composition of the perhalopropionic acid fluorides.

Because of the difficulties involved in

17

the purification and handling of acid fluorides, such physical constants as refractive index and density were not determined.

Two of the derivatives of particular in­

terest , 2,4,6-tris(dichlorotrifluoroethyl)-1,3,5-triazine, and 2,4,6-tris(trichlorodifluoroethyl)-1,3,5-triazine, are discussed subsequently.

Preparation of Esters Experiment 41847 Eight moles (l604g. )

/^-dichloro-

trifluoropxopionyl fluoride was placed in a 3-liter roundbottomed flask equipped with an indented West condenser arranged for reflux and a dropping funnel.

Ten moles

(4ô3g.) of anhydrous ethyl alcohol was added. was vigorous and exothermic.

The reaction

As soon as the reaction sub­

sided, after about 5 Ainutes, the mixture was heated at the reflux temperature for one hour.

No catalyst was added, as

the hydrogen fluoride evolved served to make the reaction proceed with satisfactory rapidity.

The mixture was then

cooled, washed with cold water, aqueous sodium bicarbonate, and again with water.

Rectification of the product gave

1490g. of ethyl /^/