USSR TRENDS IN WORK ON ORGANIC FLOURINE COMPOUNDS AND RELATED WORK IN SOME OTHER COUNTRIES

• Document Type: CREST
• Collection: General CIA Records
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• Release Decision: RIPPUB
• Original Classification: S
• Document Page Count: 5
• Document Creation Date: December 22, 2016
• Document Release Date: August 31, 2011
• Sequence Number: 153
• Publication Date: October 19, 1954
• Content Type: REPORT

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CLASSIFICATION 5-E-r, _R-E-T
CENTRAL INTELLIGENCE AGENCY
INFORMATION FROM REPORT
FOREIGN DOCUMENTS OR RADIO BROADCASTS CD NO.
COUNTRY
USSR
SU
GATE OF
BJECT
Scientific -Chemistry, organic fluorine
INFORMATION 1954
HOW
c ompounds
PUBLISHED
Book; monthly and bimonthly periodicals;
DATE DIST. iq Oct 1954
semimonthly periodical
WHERE
PUBLISHED
Moscow, Berlin, Leipzig, Budapest
,,,, ?_ _.___
DATE
PUBLISHED
1949-1954
LANGUAGE
Russian, Germsn, Er.~!lish
SUPPLEMENT TO
REPORT N0.
THIS IS UNEVALUATED INFORMATION
USSR TRENI).i iN WORK ON ORGANIC FLUORINE COMPOUNDS
AND RII.ATED WORK IN SCME GTRER COUNTRIES
P,ecent USSR publications indicate that there is a considerable interest
in that country in the technical application of fluorocarbons as heat-resist-
ant and fire-resistant lubricants and as chemically inert plastics.(1) The
advisability of expanding research that will lead to the production of ficoro-
o r~Trnic plastics has been mentioned in an address dealing with Ukrainian
cnemical developments and given at the 3d Ukrainian SSR Conference on Organic
Chemistry.(2)
The most prominent USSR worker in the field of fluoroorganic compounds is
I. L. Knunyants, who in cooperation with members of his group has worked on
the polymerization of fluoroolefins.
extensive investigations on the intera'tionstot allphaticnoxides}~withahydrogenr
fluoride.(4) In tl~e course of this work he developed a method for the synthesis
of ethylene fluoraliydrin by reacting ethylene oxide with hydrogen fluoz?ide in
ether containing 1.5-~';b of water. The availability of ettLylene fluorohydrin
and of its analogs prepared in the same Inannar modem pos~ibh the synthesis of
many other fluoroorganic compoundc,(3, II, 5,) In the introduction to an -article
reviewing USSR and foreign wort: on the addition of hydrogen sulfide and
mercaptans to olefins, Knunyants indicates his range of interest in work of
this type and the standpoint from which the available information on the sub-
ject has been systematized by saying that research in this field leads to
physiologically active compounds (e.g., mercaptoamino acids, vitamins, and
antibiotir_s) and that it furthermore is of importance in connection with the
study of rubber vulcanization and the synthesis cf technically valuable
elsstamers.(6) One may conclude on the basis of this statement that one of
the aims of an extensive series of investigations launched by Knunyants which
deal with the addition of alcohols and mercaptans to fluorcolefins (q g) i~
presumably the synthesis of technically useful mscromolecular ccmpounris
STATE
ARMY
NAVY
AIR
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c wrtzining fluorine and sulfur, and that Knunyants furthermore must pay close
attention to ;lie physiological activity of the compounds synthesized by him
in the course of this xork? Some of these compounds may be assumed to have
toxic properties on the basis of the constitution given by Knunyants In
connection with his prior investigations on the interaction of alkyl.ene oxides
with hydroger, fluoride, Knunyants has synthesized toxic and irritant compounds,
scme of them organophosphorus compounds containing fluorine.
lishecl account of this woe}; (5) In tiro pub-
irritant nropert.ies of the co unyants explicitly refers to the toxic and
mpounds in question.
The assumption that Knun ants must be interested ir. ~
Po-Yin=_ izabl~_
that contain fluarine and sulfur and that may form a suitable starting material
for the production of technically useful macromolecular compounds is burr. out
by his ex}:eriments on tiro dehydrofluorination of corresponding saturated
co.~ounds.(?)
Althou3h Knunyants has investigated the addition of thiophenoi Lo
f'_uorocoomccundsvinLl M7)Y,ahis work hitherto has been msinly on aliphatic
P gupol sY.iy and id. I. Mn.n~ko of the Institute of
Grganic Chemistry, Aogdem,,, of Sciences Ln:rainian SSR, have nutlished a paper
that describes s new mcthai of synthesizing ortho derivatives of trifluoromethyl-
benzene by introducinG a nitrile grouF com?er'ir:g this group into a carbaxylsmide
group, acrd then transforming the latter into a ,:arboxyl grow or an amino
gro~,:p.(3) A, I. Titov and A. T7. Baryshnikova have described the preparation of
l~rafiuorasniline by tiro reaction of phenylhydroxylamine xith anh?rdrous hydro-
fluoric acid.(10) Titov points out that prior to that the only !mown method
of introduc}n,; a fluorine atom into ar. aromatic nucleus has been diazotizstion
of an aromatic amine followed by decomposition of the diazomcmc fiuor:de or
diazonium borofluoride.
It is ]mown on the basis of work done in Germany that introduct.on of a
nitro group ic;to an aromatic compo.md in the ortho or Para pose?;o^ to a
flucrine a+,om makes the fluorine atom more mobile.(11) The effect of the amino
Troup in the compound synthesized by Titov will p;eeumably be opposite to that
of a intro P,roup, i.e., the mobility and reactivity of the f'uerine atom in
the Ik.ra position wi].i be :?educed. In other words, paraf.luoroaniline cynthecized
by 'I'itores method will be a useful intermediate for the syrthosis of compounds
containing parafluorophenyl groups.
On the basin of dam published by a group of HunGarian irn?estigatcrs,
introduction of fluorine atoms into organic compounds by the exchange reaction
of clcloro derivatives and bromo derivatives with potassium fluoride is effective,
at. leant as far as aliphatic compounds are conce:?red, when the reaction mixture
is irradiated with ultraviolet light. +lith the use of this method, ethyl.
chloroformiate has been converted into ethyl 1'luoroformiate, methyl bromoacetate
into methyl fluoroacetate, ethyl chloraacetate into ethyl fluoroacetate, 1,
2-dichioroethane into 1-fluoro-2-chloroethare 1 2-dibromoethsne into 1-
2-bromnethane~ and diisopropyl chlorophospha.te Into diisooro i r fluoro-
(~, 13) ?la?thermore, the Hun;;ar;an investigators u_e p?~- ]ccorophosphate,
2-t1~.or~ethanol from ethylene chlorohydrin?(15 '~ pared by this method
et.harm: by the reduction of methyl fluoroacetate3)ithelithiumnae,:minum~hydride
(15, 1~) Iu a subsequent stage of the investigation, t}:ey prepared fluornm?tha.^.ol
by .educing ethyl fluorofa,?miete o :o,-rgv2 fluoride with lii.hium alucninam
hydride.{14 13) `
Excerpt for the use of ultraviolet light, the preparation of 2-fiuoroethanol
from eL'iiylene chlorohydrin is very similar to a procedure used earlier by
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Knunyants, who reacted ethylene chlorohydrin with anhydrous potassium fluoride
under pressure and used the ethylene fluorohydrin obtained in this manner to
synthesize a great number of other compounds, including the tris-(2_fluoroethyl)
ester of phosphorous acid, the mono-(2-fluoroethyl) ester of dichlorophosphoric
acid, and the tris-(2_fluoroethyl) ester of phosphoric aMd.(5} Some of the
other syntheses involving replacement of chlorine or bromine wit?: fluorine had
also beery carried out before with the use of pressure and in some instances
applied indr;sr.rially? Nevertheless, the yew method of carrying out the re-
actions at atmospheric pressure and at relatively Lose temnerat.ures represents
sr. improvement.
Si;nilarly to Knunyents and his collaborators, the Hungarians have synthesized
compounds which are toxic cr can be used as intermediates in the synthesis of
toxic compounds? Their research on 1-fluoro-2-chloroethane and 1-fluoro-2-bromo-
e*hnr.= is preliminary work leading to an investigation of the possibilities of
producing freons with the use of the method proposed ty them. They intend to
continue prior work dealing with the addition of acid fluorides to cerbonyl
groups. Tire synthesis of fluoromethanoi was carried cut by them wirh the tur-
Fose of developing a simple method for its preparation, so that it will be
possible to use this compound in industrial iluoromethylations?(13) 'Tito
Hungarian investigators have actually prerrired benzyl fluoride by ra.acting
benzine with i?luoromethnnol.(14) They furthermore fluoromethylated benzene
with parafonraldchyde and hydrogen fluoride, but were unable to isolate benzyl
fluoride under the e.?cperimental conditions used, because cnly diphEry:uretlinne
derivatives and resinous polymerization products had formed By condensing
monof?uorobenzene with f]uoromethanol, they prepared p-fluorebenzylfluoride.
(161 On the heals of this description of the -experimental work, ore ,ray a=sumE
tt;st the great reactivity of the fl.uoromethyl group can possibly be us.;d to
advantage in prrpering hi~ir polymers containing fluerinste3 aromatic nuclei.
While the research done by the Rungaris.n group, just as *.he wor'r, cf
Knunyantr, which it. parallels in many respects, leads to both toxic and nontoxic
substances, a Gernan investigation on trifluoromethyl arsiras {l;j deg].. with a
class of substances which are strictly toxic.
-? A. L. Petrov, KhLniya Mctornyl?,h Topliv (Chemistry of Motor Y~.;els), Mosrow,
1953, pp 150-'F53
2? The Diost important Directions of Research in Orf;nnic Chemistry frorn the
Standpoint of the Decisions of the 19th Congress, Communist Party of the
Soviet Union, and the September 1953 Plenary Session, Central Committee
of the Communist Party of the Soviet Union, UkrainsY,iy Blrlmicheskiy
Zhurnrrl, Vol 20, I}o 1, 195t~, p 7
3? Elections of idembers nrd Correspc::dingy btembers of the Academy of Science=
USSR (I. L. Knunyants's Work on Het
erocyclic Compounds, Fluoroorganir_
Compounds, A1lanolphosphines, an3 Other Substances), Izvestivn Akademii
d 1 .ni ? Khimiches}~ikh IJa
l
u
c No 1 1954 n 105
4. I. L. }:nunynnts, 0. V, Kll'disheva, I. P. Peteov, Reactions of Frliphatic
Oxides with Hydrogen Fluoride, Communication I, Zhuinal Obshchey fQrimii,
Vcl 19, IQo 1, 19?~9, FF 95-100
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5? I. L. Knunyants, 0. V. Kil'disheva, E. Bykhovskaya, Reactions of Aliphatic
Oxides xith Hydrogen Fluoride, Communication II, Zhurnal Obshchey Khimii,
Vol lg, No 1, 1949, PP 101-113
6. I. L. Knunyants, A. V. Fokin, Addition of Hydrogen Sulfide and of Mercaptans
to Olefins, Uspekhi Khimii, Vol 19, No 5, 1950, pp 545-564
7? I. L. Knur~yanta, A. V. Fokin, Addition Reactions of Perfluoroolefins,
Izvestiya Akademii Nauk SSSR, Otdeleniye Khimicheskilch Nauk, No 2, 1952,
pp 261-267
8? I. L. Knunyants, A. I. Shchekotikhin, A. V. Fokin, Addition Reactions of
Perfluoroolefins. II. Addition of Alcohols and Tliiols to Perfluoroproperie,
Izvestiya Akademii Nauk SSSR, Otdeleniye Khimicheskikh Nauk, No 2, 1953,
pP 282-289
9? L. M. Yagupol'skiy, N. I. Man'ko, A New Method of Synthesizing Ortho-
Derivatives of Benzoic Acid Trifluoride, Zhurnal Obshchey Khimii, Vol 23,
No 6, 1953, pp 988-991
10. A. I. Titov, A. N. Baryshnikova, A New Method of Introducing Fluorine
Into Aromatic Nuclei, Zhurnal Obshchey i4~imii, Vol 23, No 2, 1953,
PP 346-347
11. $, Zahn, H. Zuber, On Some Reactive Fluorine Compounds of the Aromatic
Series, Chemische Berichte, Vol 86, No 2, 1953, PP 172-180; as abstracted
in Referativt~yy Zhurnal Khimiys, No 1, 1954, p 133 (Abstract No 10557)
12.~G.-0lah, A, pavlath, Synthesis of Organic Fluorine Compounds. Z. A Nex
Method for the Preparation of Aliphatic Fluorine Compounds, Acta Chimica
Academiae Scientarium $un~aricae, Vol 3, No 2, 1953, pp 191-197; as
abstracted in Referativnyy Zhurnal Khimiya, No 1, 1954, p 132, (Abstract
No 10553)
13? G. Olah, A. Pavlath, Synthesis of Organic Fluorine Comnounds (A New
Method for the Preparation of Aliphatic Fluorine Compounds), Acta Chimica
Academiae Scientarium Hungaricae, Vol 3, 1953, pp 191-207 as summarized
by $. D. Schmidt, Chemische Technik, Vol 5, No 10, 1953, Pp 599-600
lk. G. Olah, A? Pavlath, Synthesis of Organic Fluorine Compounds, III, The
Preparation .of Fluoromethanol, Acta Chimica Academiae Scientarium Hungaricae,
Vol 3, No 2, 1953, PP 203-207; as abstracted in Referativnyy Zhurnal Khimiya,
No 1, 1954, pp 132-133, (Abstract No 10555)
15? G. Olah, A. Pavlath, Synthesis of Organic Fluorine Compounds.' II. The
Preparation of 2-Fluoroethanol, Actrs Chimica Academiae Scientarium
Hungaricae, Vol 3, No 2, 1953, pp 199-202; as abstracted in Referativnyy
Zhurnal Khimiya, No 1, 1954, p 132 (Abstract No 10554)
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16. 'G. Olah, A. PavA t~t13c'nCoesis of Organic Fluorine Compounds. Fluoro-
methylation of
Hungaricae Vol 3, 1953, PP~2~4p' Acta Chimica Academlae Scientarium
Vol 6, 1954, p 347 5- 9 as abstracted in Chemische Technik,
~7? E? G. Walaschewski, The Reaction Between Trifluorometh 1
? Arsenic and the Interaction of the Trifluoromethylarsine Iodides Formed
in This Reaction with Silver Salts and Mercu S y Iodide and
~~ , No 2, 1953, pp 272_p7? as abstractedrin Referatiemische Berichte,
ya, fto 1, 1954, p 135 (Abstract No 10559) v~'3' Zhurnal
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