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On the Preparation of the Dimorpholide of Dithiomalonic Acid.

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KHI4C03(2x LO7 counts per min/ymole) according to equation (a); the complex ( 1 0 . 8 ~105 counts per minute) was separated from the reaction mixture by filtration on “Sephadex”.
Brief treatment with trypsin, followed by methylation of the
cleavage products with CHzNz at pH 6.5-7, yielded a mixture of stable methoxy-14C-carbonyl compounds ( 9 . 6 ~10-5
counts per minute). N(1)-methoxy-14C-~arbonyl-(+)-biotin
was obtained in 9 3 % yield (calculated on radio-activity) by
hydrolysis of the water-soluble fraction (6x 105 counts/pin)
with biotinidase [3]. The compound was identified, for
example, as its dimethyl ester by chromatographic comparison
with the methyl ester of N(1)-methoxycarbonylbiotin and the
methyl ester of N(3)-methoxycarbonylbiotin [4].
We used biotinidase that had been enriched 200 times from
pig kidney extract. The enzyme, which is inhibited by iodoacetamide and diisopropylfluorophosphate, specifically
hydrolyses amides and esters of (+)-biotin; to a small extent
also their carboxy-derivatives. KM for N-(biotiny1)aminobenzoate 5x 10-6 M, for N-[N(1)-methoxyca1%onylbiotinyl]aminobenzoate 8 x 1 0 4 M.
Our attempts to obtain the apoenzyme of methylcrotonyl
carboxylase by elimination of biotin were unsuccessful. The
bond between vitamin and protein can be attacked only after
denaturation or degradation of the enzyme protein.
Received, May 14th. 1962
On the Preparation of the Dimorpholick of
Dithiomalonic Acid
By Dr. B. Brahler, Dr. J. Reese and Dr. Rolf Zimmermann
Chemische Werke Albert, Abteilung Allgemeine Organica
Wiesbaden-Biebrich (Germany)
A method for the preparation of the dimorpholide (I) from
propenyl alkyl ethers, morpholine and sulfur is already
known [l]:
+ 4 S + 2 HN/ o\-
R = alkyl
This is a special case of the Willgerodt-Kindler reaction with
attack at both ends of the C3-chain [2].
We have now found that a similar reaction occurs with the
more easily accessible allyl compounds. The preparation of
(I) can be carried out even with simple compounds such as
allyl alcohol or allyl chloride, and with better yields as when
working with allyl ethers or esters:
+ 4 S + 2 HN/
\ -/
+ 2 HzS
( R = OH, CI efc.)
The smooth course of the reaction i s surprising. Compound
(I), m.p. 208 “C, is obtained in yields up to 47 %.
(11): yellowish needles, m.p. 250-260 “C (decomp.)
(111): yellow-brown needles, m.p. 250 “C.
Received, May
16th. 1962
[Z 282/117 IE]
[ l ] German Patent 1003212 (H. Feichtinger, Ruhrchemie A.G.).
[2] R. WegZer et al., Angew. Chem. 70,351 (1958).
[3] U. Schmidt, Chem. Ber. 92, 1171 (1959).
The Reaction of Diazomethane with Silanes
By Dr. K. Kramer and Dr. A. Wright
Shell Research Ltd., Thornton Research Centre.
Chester, (Great Britain)
[Z 276/116 I€]
[*I Dedicated to Prof. Dr. G. Wittig on the occasion of his 65th.
[ l ] F. Lynen et al., Biochem. Z. 335, 123 (1961).
[2] We are grateful to Prof. Lynen for the communication of an
improved isolation technique.
[3] R. W. Thoma and W. H . Peterson, J. biol. Chemistry 210, 569
[4] J. Knapne, E. Ringelmann, and F. Lynen, Biochem. Z . 335,
168 (1961).
In analogy to the work by U. Schmidt [3], we have subjected
(1) to cyclising oxidation and obtained 3,5-dimorpholino-l,2dithiacyclopentadienylium halides (11, 111).
By the reaction of phenylsilane with excess diazomethane we
have obtained phenylmethylsilane (I) as the major product,
together with phenyldimethylsilane (11).
+ CHzNz
+ CHzNz
The products (I and 11) were characterized by gas chromatography, mass and infrared spectroscopy and (I) also by microanalysis. No reaction occurred in the absence of catalysts or
light, although phenyltrichlorosilane reacts readily with diazomethane, in the same way as silicon tetrachloride [ I , 21,
giving phenylchloromethyldichlorosilane and phenyl-bis(ch1oromethyl)chlorosilane. Low yields of (I) were obtained
when a copper catalyst was used. When the reaction mixture
was photolysed with a “Hanau” mercury arc lamp in a
quartz dip-tube, up to 70 % (I) and 5 % (11) were formed. No
phenyltrimethylsilane could be detected by mass spectrometry or gas chromatography. In all the photolyses in diethyl
ether solutions, n-propyl and iso-propyl ethyl ethers were
also formed [3], as is to be expected in a reaction involving
free carbene. However, methylenation of the phenyl group did
not occur, as was shown by gas chromatography and the
infra-red spectrum.
Under the same conditions, diphenylsilane gave diphenylmethylsilane (50 %) as the only product. Triphenylsilane did
not react readily, although a mass spectrometric examination
suggested that traces of triphenylmethylsilane were formed.
Germanes also react similarly. Diphenylgermane givss both
diphenylmethylgermane and diphenyldimethylgermane. Triethylgermane gives 9 % triethylmethylgermane on photolysis, but none is formed in the presence of a copper catalyst
of the type used in the preparation of organogermanium
esters from diazoacetic ester [4].
Received, May 16th. 1962 [Z 290/121 I€]
[ l ] A. Ya. Yakubovitch et al., Dokl. Akad. Nauk S.S.S.R. 72,
69 (1950).
[Z] D. Seyferth and E. G . Rochow, J. Amer. chem. SOC.77,907
131 H . Meerwein, H. Rarhjen, and H. Werner, Ber. dtsch. chem.
Ges. 75, 1610 (1942).
[4] M.Lesbre and J. Satge, C. r. hebd. Stances Acad. Sci. 247,
471 (1958):
Angew. Chem. inferiint. Edit.
Vol. I (1962) /No. 7
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acid, preparation, dimorpholide, dithiomalonic
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