LETTERS TO THE EDITOR HYDRIDE MOBILITY OF
a-ATOMS
HYDROGEN
OF
IN ALCOHOLATES
S. V. V i m m
and
N. S. M a r t i n k o v a
Heteroorganic Compounds Institute, Academy of Sciences USSR Translated from Ivestiya Akademii Nauk SSSR, Otdelenie Khimicheskikh Nauk, No. 5, p. 930, May, 1962 Original article submitted February 10, 1962
We discovered, that alcoholates of secondary alcohols undergo isotopic exchange of hydrogen with donors of hydride ions (deuteride ions) such as LiA1H4 or CHsCD~OH. For instance, the alcoholate of phenylethyl alcohol on heating to 200* in a nitrogen atmosphere reacts with CHsCD2OH by hydrogen exchange. In this case, the exchange reached 50% of the calculated after 15 hours (excess density of water by combustion of nitrobeuzoate formed in the experiment with phenylethyl alcohol - 8650 y / m l ) . It was established that in the molecule of the phenylethyl alcohol the deuterium is concentrated at the carbon atom carrying the hydroxyl group CH~CD~OH Ph--CH--CH~-~Ph--CO--CH~--~Ph--CD--CH3.
I
I
I
0|
0|
OH
It is possible, that the reaction proceeds via intermediate ketone formation. In this way we established that the negatively charged center brings about anionic mobility of the hydrogen adjacent to the carbon atom.
FORMATION
OF M I X E D A L L Y L ESTERS D U R I N G R E A C T I O N OF
H I G H E R O L E F I N S W I T H P A L L A D I U M C H L O R I D E IN A N H Y D R O U S CARBOXYLIC ACID SOLUTIONS M. N. V a r g a f t ~ k ,
I. I. M o i s e e v ,
and
Ya.
K. S y r k i n
M. V. Lomonosov Fine Chemical Technology Institute Translated from Izvestiya Akademii Nauk SSSR, Otdelenie Khimicheskikh Nauk, No. 5, pp. 930-931, May, 1962 Original article submitted February 28, 1962
It was shown earlier [1], that oxidation of ethylene by palladium chloride in anhydrous acetic acid containing sodium acetate or potassium acetate leads to the formation of vinyl acetate. When propylene was oxidized under the same conditions, we obtained isopropenyl acetate in 25% yield. Thus the reaction of lower olefins with PdC12 in an anhydrous carboxylic acid medium leads to the substitution of a H-atom at the double bond of the olefin by the acetoxy group. In the case of higher olefins, the reaction course changes. Reduction of PdC1z by hexene-1 in anhydrous acetic acid yielded the acetate of hexene-2-ole-1, yield: 68%; b. p. 151-152 ~ (739 ram); n2~ 1.4260; dZSzs 0.8877. Found: C 67.81, 67.26; H 9.86, 9.83%0; tool. wt. 142. CsHlzP 2. Calculated: C 67.58; H 9.86%. This same substance was obtained by oxidation of hexene-1 by p-benzoquinone in the presence of PdC12. Analogously, heptene-1 yielded the
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acetate of heptene-2-ole-1; yield: 66%, b . p . 1"/1-172" (745 mm); n2~ 1.4320; d9595 0.8929; decene-1 (decylene-1) gave the acetate of decene-2-ole-1; yield: 53~o, b. p. 212-214" (731 mm); n2~ 1.4393; d~5 0.8793. During reaction of hexene-1 with PdC1z in anhydrous propionic acid containing potassium propionate, the propionate of hexene2-ole-1 was obtained: yield 37%; b. p. "/7-78* (9 ram); nlg"SD 1.4125; d2~5 0.9882. In aU cases the yields of corresponding a-alkenyl esters did not exceed 5~ It is probable, that during these reactions of olefins with PdC12 a complex of lr -allyl type is first formed, which in an acetate medium can exist in tautomeric equilibrium with the organometallic compound of the type RCH = CHCHz -- PdC1. During reaction of that compound with acetate ions: RCH = CHCH~-- PdCI ~ CH3CO0- -- RCH ~ CHCH2 - - OCOCHs -I= Pd -t- CIsubstituted allyl esters are formed.
1.
LITERATURE CITED I. I. Moiseev, M. N. Vargaftik, and Ya. K. Syrkin, Dokl. AN SSSR, 133, No. 2, 377 (1960).
N- E T H Y L E N E I M I N O M E T H Y L A T I O N R. G. K o s t y a n o v s k i i ,
O. A. P a n ' s h i n ,
a n d V. F. B y s t r o v
Chemical Physics Institute, Academy of Sciences USSR Translated from Izvestiya Akademii Nauk SSSR, Otdelenie Khimicheskikh Nauk, No. 5, p. 931, May, 1962 Original article submitted March 1, 1962
The N-ethyieneiminocarbinol described by us earlier [1] appears to be a mild N-ethyleneiminomethylating agent C H ~ - OH -l- HN
--,
-- Ctt2 -- N
R
q- H20. R
The reaction was conducted without solvent or in benzene at 20" (heat evolution 46-78 ~ within 0.5-10 minutes). The products were vacuum distilled over metallic sodium. N, N'-Ethyleneiminomethylamines / " R ~ N - : (CH3)zN- yield: 42.86%, b. p. 54* (99-101 ram); nZ~ 1.4315; d2~4 0.8378; (CzH~)z N - yield 71.06%; b. p. 52.3-58* (21 ram); n~~ 1.4874; dZ~ 0.8340; (CHz = CH - CHz)zN yield 80.28%; m. p. 56-57* (5 mm); n2~ 1.4680; dZ~ 0 . 8 7 6 0 ; ~ N n2~ 1.4626; dZ~ 0.9178; D N
- - yield 88.59%; b. p. 55,3-55.5* (24,5 ram);
- yield 85.17; b. p. 47.5-48.5* (5 ram); n2~ 1.4712; d~~ 0 . 9 2 8 6 ; ( ~ ) I q - yield
57.51%; b. p. 56-56.5* (4.5 ram); n2~ 1.4762; dZ~ 0.9313; C n2~ 1.4821; dZ~ 0.9881; O ~ N
N - yield 65.65%; b. p. 50.8-52.5* (0.7-0.8 ram);
- yield 59.54%; b. p. 50-50.3* (0.6-0.8 ram); nZ~ 1.4778; d~~ 1.0177.
The structure of the compounds was proved by infrared spectra (valence vibrations of the C - H bOnds in the ri.gs was 3050-3060 cm-1), and by spectra of proton magnetic resonance. Signals of protons from
N - were
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