SCIENTIFIC ABSTRACT LUTSENKO, I.F. - LUTSENKO, M.N.

• Document Type: CREST
• Collection: Scientific Abstracts
• Document Number (FOIA) /ESDN (CREST): CIA-RDP86-00513R001030920020-4
• Release Decision: RIF
• Original Classification: S
• Document Page Count: 100
• Document Creation Date: November 2, 2016
• Document Release Date: March 13, 2001
• Sequence Number: 20
• Publication Date: December 31, 1967
• Content Type: SCIENTIFIC ABSTRACT

S-J 6,3 0
AUTHORS3 Lutseqkq,j_j,.,,,,&, Kraytey Zo S.
S/02Y60/132/03/34/066
Boll B008
TITLEt Arbuzov's Regrouping of the Vinyl Eaters of Phosp orous
and Phenylphosphinic Acids
PERIODICALs Doklady Akademii nauk SSSR, 19609 Vol. 1329 No- 39
pp. 612-614
TEM The authors state that the vinyl eaters of the phosphorous acid can,
as expeotedv be isomerized only very difficultly to vinyl esters of the
phosphinio acids, as compared with the trialkyl phosphites. A 4 to 6-hour
heating with methyl iodide was necessary for the isomerization of the
various dialkyl vinyl phosphites produced by the authors. The same process
takes 20 hours at 10000 when using ethyl- and butyl iodide and is
oonoluded to less than 50~. The reaction had therefore to be carried out
in soldered tubes at 120-1500C for 8 hours. In this way the authors
obtained the following alkylvinyl esters of the phosphinic acids (Table 1.).
ethylvinyl eater of the methylphosphinic acid, butylvinyl eater of the
butylphosphinio acid, divinyl ester of the methylphosphinio acid, di-iao-
Card 1/3

Arbuzov's Regrouping of the Vinyl Eaters
of Phosphorous and Phenylphosphinic Acids
B/020/60/132/03/34/066
B011/BO08
propenyl eater of the ethylphosphinic acid# ethylvinyl eater of the
acathylphosphinic acid, divinyl eater of the benzoylphosphinic acid, and
div*nyl eater of the phenylphosphinio acid. Furthermore, the addition
product of the methyl iodide to the divinyl eater of the last mentioned
acid was produced. Alky1divinyl phosphites are isomerized to divinyl esteza
of the alkylphosphinio acids only under sharper conditions. Divinyl ester
of the ethyl-9 propyl- and butylpboophinic acids were obtained by heating
of alkyldivinyl phosphites in soldered tubes at 130-1600C (for 8 hours)
with alkyl iodide which contains the same radical as the phosphite. When
the radical of the halogen-alkyl was a different one, a mixture of the
phosphinic-aoids-eaters developed. Trivinyl phosphite is not isomerize4
with methyl iodide. Resinification takes place in t'he soldered tube at
120-12~00. Arbuzov's regrouping thus takes its course in the case of the
monovinyl--~ and divinyl phoophites under splitting off of the alkyl
radical. The vinyl radical,howeverlwas split off in no case. Based on
these data it could be expected that Arbuzov's regrouping of the diviny!
ester of phenylphosphirtio acid will also be impeded. A crystalline
addition product develops from the
Card 2/3

Arbuzov's Regrouping of the Vinyl Estero S/020/60/132/03/34/066
of Phosphorous and Phenylphosphinic Acids Boil/BOO8
reaction of this ester with methyl iodide. Iodine is precipitated at the
heating of this addition product and resinification sets in, Slight
heating occurs when dialkylvinyl phosphite and acyl halides are mixed.
The reaction is terminated at room temperature within 46 hours. Vinyl
esters and a-ketophosphinio acids were produced by distilling off
(Table 1). Still sharper conditions are necessary for the reaction of
the alkyldivinyl phosphites with acyl halides (benzoyl chloride with
butyldivinyl phosphite, for example). There are 1 table and 2 Soviet
references.
ASSOCIATION; Moskovskiy gosudarstvennyy universitet im. M. V.
Lomonosova (Moscow State University imeni M. V. Lomonosov)
PRESENTED: January 7, 1960, by As X. Nesmeyanov# Academician
SUBMITTED: January 6, 1960
Card 313

S/020/60/132/04/30/064
0 BO11/BOO3
AUTHORS: Lutsenko, I. F. p Kinii-oa-M.-
.I - I
TITLE: Pboophorylated Chlorovinylketones. Primary Products of the
Reaction of Phosphorus Pentoxide With Enolacetates
PERIODICAL: Doklady Akademii nauk SSSRv 19609 Vol. 1329 No. 4,
pp. 842-845
TEXT: In a previous paper (Ref. 1) the authors described the production
of phosphorylated 0-chlorovinylketones by the reaction of phosphorus
pentachloride with enolacetates. In the present paper they continued
to study this reaction and ascertained conditions under which this
reaction can be stopped in the primary stageg i.e.9 in the stage of
addition of phosphorus pentachloride to the double bond of the
unsaturated ester. 2 moles of PCI are used for one mole of ester M.
The composition of the addition pLduct was proven by the example of
the analysis of vinylacetate. Since the products indicated are easily
hydrolyzed by atmospheric moisture, and are unstable at room temperature,
Card 1/3

Phosphorylated Chlorovinylketones. S/02o/6o/132/04/3o/o64
Primary Products of the Reaction of B0111FB003
Phosphorus Pentoxide With Enolacetates
they were further treated with sulfur dioxide at low temperature, thus
avoiding that they be isolated. Thus, acid chlorides of 0-acetoxy-p-
-chloroalkylphoBphinic acids were formed. They were sufficiently
resistant for isolation in pure state (II). The yields of acid chlorides
of the P-acetoxy-p-ohloroethyl- and of the A-acetoxy-o-ohloropropyl-
phosphinic acids were 85 and 70 per centq respectively. At a ratio of
enolacetate - FC1 - I t I the yield of the acid chloride does not
exceed 40% in* botR cases. This is another indirect proof that the
product added to the vinyl acetate and, apparently, also to the
isopropenylacetate possesses a structure as shown in (I). The two
latter reactions are to be performed at different temperatures; the
former at 7-80, the Tatter at -250, since the addition products have
a different stability. A similar difference in resistance is shown by
the acid chlorides (III) obtained from addition products. The cor-
responding diethyl eater was obtained by the action of alcohol on the
acid chloride of the P-acetoxy-p-ohloroethylphoaFhinic acid in the
presence of pyridine. By way of hydrolysis, this ester yields
Card 2/3

Phosphorylated Chlorovinylketones. S/020/60/132/04/30/064
Primary Products of the Reaction of BO11/BOO3
Phosphorus Pentoxide With Enolacetates
phosphonic acetaldehyde by the action of water and by heating within
several hours, or within 3 - 4 days at r9om temperature. The authors
failed to obtain the diethylester of ~-acetoxy-p-chloropropylphosphinic
acid in the presence or absence of pyridine. In both cases only
phosphonic acetone could be obtained. The same process takes place by
the action of alcohol on the acid chloride of acetonyl-phosphinic acid
in the presence of pyridine. The above reactions substantiate the
indicated structure of the carbon radical of the addition products.
They further prove that addition occurs in accordance with
Markovnikov's law. There are 2 tables and 2 Soviet references.
ASSOCIATION: Moskovskiy gosudarstvennyy universitet im. M. V.
L.omonosova (Moscow State University imeni M. V.
Lomonosov)
PRESENTED: January 7, 1960, by A. N. Nesmeyanov, Academician
SUBMITTED: January 6, 1960
Card 3/3

S/020/60/135/004/024/037
B016/Bo66
AUTEORS: Lutsenko. I. P.. and Krayts, Z. S.
TITLE: Phosphoric and Phosphinic Esters of Enols
PERIODICAM Doklady Akademii nauk SSSR, 1960) Vol. 135, No-4 PP. 860-863
TEXT: In addition of their papers (Ref. 1) the authors studied the effect
of acid ol!lorides of phosphoric and phoephinic acid upon 0~-mercurized
aldehydes and ketones. They found that the acid chlorides of phosphoric
acid do not react with organomercury compounds in ethereal or benzenic
medium contrary to the chlorides of acids of trivalent phosphorus. They
proved, on the other hand, that salts (NaI, KC1 and others) readily split
the metal - carbon bond in the mercurized aldehydes and ketones (Ref. 2).
The authors used this variant in the case of acid chlorides of phosphoric
and phosphinic acid. The salt obtained by dissolving these acid chlorides
in pyridine reacts easily, already in the cold, not only with mercury
bisacetaldehyde, but also with the organomercury salts of ketones. The
ester of phosphoric or phosphinic acid with the enol form of the carbonyl
compound is formed in this connection
Card 1/7

Phosphoric and Phosphinic Esters of Enols S/020/60/135/004/024/037
B016/BO66
H N+ ClHgCH COCH --4(RO ~0) 0C //CH2 +C H N-HgCl
(RO )2P (0) Cl'C5 5 2 3- )2P( \CH 3 ~ 5 5 2'
This reaction obtained by the authors permits the formation of phosphoric
acid esters with one, with two, and with three unsaturated groups, and of
phosphinic acid esters both with one and with two of these groups in a
yield of 50 - 85 %. The authors carried out this reaction with 0~-mercurized
derivatives of the following compounds: acetaldehyde, acetone, diethyl
ketone, cyclopentanone, cyclohexanone. Further with the following halogen
phosphorus compounds: methyl-, ethyl-, and butyl-dichlorophosphates, di-
ethyl- and dibutyl chlorophosphates, the acid chloride of ethyl phosphinic
acid and of ethoxy-ethyl phosphinic acid, and phosphorus oxychloride. It
is difficult to isolate the enol esters from the reaction mixture in the
presence of the mercury salts, since the latter cause polymerization and
resinification. The authors removed these salts in the following manner:
the principal amount of the mercury salt which was precipitated after
termination of the reaction as a pyridine complex, was filtered off.
Hydrogen sulfide was bubbled through the filtrate with pyridine excess:
Card 2/7 H92012 + H2S +2C5H5 N---tHgS+2C 5H 5N-HCl

Phosphoi!ic and Phosphinio Esters of Epols S/020/60/135/004/024/037
B016/BO66
Mercurio sulfide and pyridine hydrochloride were filtered, the filtrate
0 was decomposed by distillation. Table 1 gives yields and constants of
the resultant enol-esters. There are 1 table and 3 Soviet references.
~ASS~OCIATION: -Moskovskiy gosudarstvennyy universitet im. M. V. Lomonosova
(Moscow State University imeni M. V. Lomonosov)
PRESENTED: June 23, 1960, by A. N. Nesmeyanov,*Academician
SUBMITTED: Junq 22, 1960

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