DIADIC TAUTOMERISM SYNTHESIS OF ORGANIC COMPOUNDS OF PHOSPHORUS AND ARSENIC

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• Document Creation Date: December 22, 2016
• Document Release Date: September 22, 2011
• Sequence Number: 36
• Publication Date: March 10, 1952
• Content Type: REPORT

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DATE OF
COUNTRY USSR
SUBJECT Scientific - Chemistry, toxic compounds
HOW
PUBLISHED monthly periodical
WHERE
PUBLISHED Moscow/Leningrad
DATE
PUBLISHED 1946
LANGUAGE Russian
iNII 00001/18 0017.11/ 111011111111 ?1110010 MI 10001.. 0[71110
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INFORMATION 1946
DATE DIST. ID &,r 1952
NO. OF PAGES 4
SUPPLEMENT TO
REPORT NO.
Zhurnal Obshchey Khimii, Vol XVI, No 9, 1946, pp 1481-1484.
CENTRAL INTELENCE ENCY
INFORMATION FROM
FOREIGN DOCUMENTS OR RADIO BROADCASTS
CLASSIFICATION S-F-C-R-F-T . SEW1Ei
DIADIC TAUTOIIIERISM /SYNTHESIS OF ORGANIC COMPOUNDS
OF PHUZP ORUS AND ARSENIC
0. V. Chelintsev, V K. Kuskov, Org Chem lab
Mil Aced of Chem Defense of the Red Army imeni K. Ye. Voroehtlov
Submitted 16 March 1945
this paper deals with the synthesis Of substances which ma he used as
initial materials in the preparation of chemical warfare agents
The mechanism of the formation of structurally anomalous alkylation prod.
ucts of salts of hydrocyanic, nitrous, sulfurous, and arsenous acids (Meyer
reaction), of the salts of incomplete esters of phosphorous acid (Michaelis -
Arbuzov reaction), and of the arylation of salts of arsenous acid (Barth re-
actior.) are explained by different authors in various ways.
The first explanation is based on the assumption of the iaomerization of
the originally forming normal substitution products, e.g.,
CH3J + Na-6-;As(ONa)2 - CH3-0-As(ONa)2 --p 0 = Ae(ONa)2
CH,
However, the experiments showed that such isomerizations do not take
place under the conditions of the alkylation reaction.
The second explanation is considerably more important. It is based on
the assumption of the formation of intermediate addition products which are
then split up in a different way, e.g.,
CH3J 4 Na-O-AS(ONa)2 -) Na-0-Qs(Na)2.-_3 0 - As(ONa)2 # . NaJ
C/H3 t CH3
STATE NAW NSRS
A' MY ,
tR ~ I Fal
S-E-C-R-E-T
DISTRIBUTION
TT-
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However, tuio method of explanation is inapplicable to the addition reac-
tion of bisul.fite to aldehydes, ketones, or ethylene oxide, in which sulfonic
acids are formed. To convince ourselves of the fact that such addition is not
a characteristic of sulfurous acid only, we performed addition reactions of
? nitrous, arsenous, and phosphorous acid to ethylene oxide and obtained, re-
spectively, a nitro compound, arsonic acid, and phosphonic acid, e.g.,
0\ CH2-CH2_OH
CH2-CH2 + H0-As(ONe)2 -) 0 v As(ONa) 2
2-nitroethanol was determirel in the form of a complex with diazobenzene,
hydroxyethyl arsonic acid in the form of B-chloroethyl-dichloroarsine, and
diethyl ester of .&hydroxyethyl phosphonic acid by opectral analysis. In the
reactions enumerated, there can be no intermediate addition products, and,
consequently, drawing on them for an explanation of the substitution reaction
is meaningless; in all cases the carbon residue reacts directly with the ni-
trogen, arsenic, sulfur, or phosphorus, taking the place of hydrogen or metal.
The third method of explanation of the above reactions is based on the
assumption of participation in them of salts with pseudomeric structures, e.g,,
r Na I CH3
CH3J + [Na-0-As(0Na)2 0 = As(ONa)2J -,~ 0 = As(0Na)2
The possibility of the existence of unmeasurably small quantities of
pseudomeric structures in equilibrium with the main structures cannot be ex-
cluded. However, if it is borne in mind that dissociations of molecules
Na
Na-O-As (ONa)2 _0_As(ONa)2 0 = As(ONa)2 0 = AS(ONa)2 --)O = As(ONa}2
precede the linking of the residues in new arrangements, then it becomes obvi-
ous that due to the equivalence of the third and fifth structures, participa-
tion in the transformation of the fourth structure is not essential.
The best explanation of the structurally anomalous substitution and addi-
tion reaction is obtained by the concept of ion transformation, e.g.,
CH3J [-O-As(0Na) l, CHCH3
Na O-Aa(ONa)2 ' 2) 0 = As(ONa)2' 0 = As(ONa)2
In conclusion, it must be pointed out thnt the concept of a resonance ion
does not exclude isomeric ions whose reality is confirmed by their fixation in
the or'ginal and final molecules.
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Experimental Part
1. .8-Nitroethyl Alcohol
In a flask with an agitator, 23.2 g of magnesium nitrite (0.2 mole)
weite mixed with 200 ml water; then ethylene oxide was paes3d in until the
weight increased by 10 g (0.23 mole); the reaction mass was cooled in such a
manner that the temperature did not exceed 400 C. After standing for 20 hr,
the reaction mass was diluted to three times its volume with water and treated
at 00 C (cooling by ice) with a 0.1 normal solution of phenyl diazonium in a
slightly alkaline medium until the appearance in the solution of an excess of
diazonium (test with ,.I- naphthol). The dyestuff was filtered out, washed
with water, and dried in the desiccator. The yield was 6 g, i.e., 16% of the
theoretical amount calculated on the basis of the nitrite used. After re_
crystallization from ligroin (under treatment with carbon), red needle-like
crystals were obtained, which were insoluble in water, soluble in alcohol and
in ether, and corresponded in their properties to the product obtained by an-
other method by Demuth and Meyer f-71].
Analysis:
3.176 mg substance; 0.61 ml N2 (20?, 736 mm)
Found: 21.62% N
Percentage of N calculated for C H903N3? '
21.54
8
In the condensation of ethylene oxide with sodium nitrite in a weakly
acidic medium, the yield of dyestuff is lower than in the previous case; addi-
tion of magnesium sulfate increases the yield of the product.
2. 4-Rydroxyethyl Arsonic Acid
Twenty grams of arsenous anhydride (0.1 mole) and 34 g of potassium
hydroxide (0.6 g/mol) were stirred in 100 ml water until fully dissolved, and
then ethylene oxide was added durinj; a 2-hr period, until the weight had in-
creased by 10 g (0.23 mole). After the reaction mass had been left standing
for 20 hr, it was diluted with 200 ml water, acidified with 10% sulfuric acid
until the reaction became slightly ac..dic, and filtered and evaporated in vac-
uum (not above 50? C) to a viscous liquid (the inorganic salts precipitati,.g
during evaporation were filtered out). The viscous liquid was treated with
absolute alcohol and the alcohol extract evaporated in vacuum; there was a
residue of 16 g of a viscous transpavent liquid which formed a precipitate
upon heating with magnesia mixture.
For purposes of determination, the product was converted to 4-chlor-
oethyl-dichloroareine. The viscous liquid was diluted with 30 ml water, a
small potassium iodide crystal was added and the solution was saturated with
sulfur dioxide at a temperature below 506 C. After the solution had been left
standing for 48 hr, a stream of SO, was bubbled through it. The light-colored
oil which precipitated was separated and mixed with 20 ml carbon tetrachloride.
The carbon tetrachloride was driven off in vacuum. The residue (7 g) was .
treated with 7 g of thionyl chloride (violent reaction) and the product was
distilled in vacuum. The boiling Point was 79 to 80? C at 12 mm pressure and
93 to 950 C at 32 mm pressure. Six grams of substance were obtained, which
bad the properties of ,4-chloroethyl-dichloroartine[2_7. The yield was ap-
proximately 30 percent of the theoretical.
During the bubbling of ethylene oxide into a Ne2RAs0 solution very
little hydroxyethyl arsonic acid is obtained, and none at alI from ethylene
oxide and NaR2Ae03.
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3. oB-Hydroxyethyl Pbosphonic Acid
To 13.9 g (C.1 mol) of diethyl phosphite dissolved in 120 m1 absolute
alcohol, 2.3 g (0.1 mol) of sodium powder prP;.lred by the Bruell method were
added. Ethylene oxide was passed into the mixture under stirring until the
weight had increased by 4.5 g (0.1 mol), whereupon the precipitate of sodium
diethyl phosphite disappeared. After stirring for one hour, 6.1 g of glacial
acetic acid were added, drop by drop, to the mixture, the sodium acetate pre-
cipitate was filtered out, and the ester was distilled off (on a water bath,
not above 50? C).
The sirupy residue was filtered off under section from a small quan-
tity of acetate and dried in the desiccator over sulfuric acid. A total of
7.6 g of substance were obtained, in which carbon, hydrogen, and pent:vatent
phosphorus were determined qualitatively. The product was sol!ible in alcohol
and ether. It was distilled in vacuum at 9 mm and 120-130? C and distilled
under strong decomposition.
On our request, Gofshteyn and Setkina carried out a spectral analysis.
In the infrared spectrum, the following bands were observed: 800 (strong),
880 (medium), 955 (strong), 980 (strong), 1,040 (strong), 1,080 (strong), 1,210
(strong), 1,250 (weak), 1,400 (medium) 140 (weak). The 1,210-1,250 bands
must be attributed to the P = 0 (P )o) bond, since the same frequency is ob-
served in phosphorus oxychloride and other compounds of P...
Sun~er~r
1. It is shown that ethylene oxide combines with the nitrogen, arsenic,
and phosphorus of nitrous, arsenous, and phosphorous acid, respectively.
2. The question of the mechanism of formation of structurally anomalous
alkylation products (by replacement or addition) of salts of hydrocyanic, ni-
trous, and sulfurous acids, as well as the mechanism of the Meyer-Barth and
Michaelis-Arbuzov reactio:+e, are discussed. Unsatisfactory explanations for
the mechanism of the above reactions were rejected, and the best explanation
was selected.
BIBLIOGRAPHY
1. Demuth and V. Meyer: Liebig's Annalen, Vol 256, p. 28, (1890)
2. Gouch and King: Journ. Chem. Soc., 1928, p 2432; Scherlin and Epstein,
Berichte, Vol 61, p 1921, (1928)
JtCREl
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