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Autoxidative Ring Closure of -Bis(triphenylphosphorylidene)alkanes.

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Reaction of two equivalents of potassium xanthate with
diaryldichloromethanes according to Equation (2) gives the
little-known gem-dixanthoylmethanes ( 4 ) , examples of which
are diphenyldixanthoylmethane, m. p. 156 "C and bis-(4methoxyphenyl)dixanthoylmethane, m. p. 146 "C.
These react with one equivalent of ethanolic potassium
hydroxide according to Equation (3) to give thioketones (3),
0-potassium 0'-ethyl thiocarbonate, and xanthic acid, which
decomposes spontaneously into ethanol and CS2. Thermolysis of the above dixanthoylmethanes also yields thio-
ketones (3).
Received, December Znd, 1963 [Z 625/45S I€]
German version: Angew. Chem. 76, 98 (1964)
[*] The recent publications of R . Mayer and H . Berthold, Chem.
Ber. 96, 3096 (1963), and F. Asinger et al., Angew. Chem. 75,
1050 (1963), Angew. Chem. internat. Edit. 3, 19 (1964), prompted us to report some of o u r own results.
metals [I ,4]. Diniethylgermene can be formed from R2GeC12
with Li and added onto olefins analogously.
Received, December 9th, 1963
[Z 633/465 IE]
German version: Angew. Chem. 76, 270 (1964)
-.
~
[ I ] M . E. Volpiti, Yu. D. Koreshkov, V. G. Duiova, and D. N .
Kursanov, Tetrahedron 18, 107 (1962).
[2] P. Vaculik: Chemie der Monomeren (Chemistry of Monomers). Academy of Czechoslovakia, Prague 1956, Vol. I.
[31 V. Franzen, Chem. Ber. 95, 1964 (1962); K. Ziegler and H.-G.
GeNert, Liebigs Ann. Chem. 567, 195 (1950).
[41 0. M . Nefedov, M . N. Manakov, and A. D. Petrov, Izvest.
Akad. Nauk S.S.S.R. Otdel. Khim. Nauk 1961, 1717; 1962,
1228; H. Gilman, Angew. Chem. 74,950 (1962).
o,w
The Formation and Reactions of Dimethylsilylene,
a Silicon-Analogue of the Carbenes
By Dr. 0. M. Nefedov and cand. chem. M. N. Manakov
N. D. Zelinskii Institute of Organic Chemistry of the
Academy of Sciences of the U.S.S.R., Moscow (U.S.S.R.)
Autoxidative Ring Closure of
-Bis(triphenylphosphorylidene)alkanes
By Priv.-Doz. Dr. H. J. Bestmann, Dip1.-Chem. H. Haberlein,
and Dr. 0. Kratzer
lnstitut fur Organische Chemie
der Technischen Hochschule Munchen (Germany)
The action of oxygen on alkylidenetriphenylphosphoranes of
structure R-CH=P(C6H&yields olefins R-CH=HC-R [l].
Under the same conditions, autoxidation of w,w'-bis(tripheny1phosphorylidene)alkanes ( I ) can lead to cycloafkenes
(2). Examples are given in Table 1.
When dimethyldichlorosilane is treated with lithium in tetrahydrofuran at 0-10°C and ethylene is passed through the
reaction mixture, 1,2-dimethyl- 1-silacyclopentane ( 5 ) and
1,1,4,4-tetramethyl-l,4-disilacyclohexane(6) are obtained
in small yields (2-5 %) in addition to solid and liquid high
molecular-weight silicon hydrocarbons (3) and ( 4 ) . Compounds (5) and ( 6 ) are also formed from (H~C)ZS~CIZ,
metallic sodium in benzene, and C2H4 in an autoclave at
temperatures of 105-12OoC, as well as on thermal degradaTable I. Cycloalkenes /2J obtained byautoxidation of w,<,'-bis(triphenyltion of polydimethylsilylene (2) [ l ] at 300 "C in the presence
phoaphorylidenelalkanes ( I ) .
of C2H4. The formation of the Si-containing heterocycles (5)
and ( 6 ) , the telomers (S), and the polymers ( 4 ) can only be
Yield of 12)
11
Cycloalkene (2)
explained by the assumption of transient formation of dimethylsilylene, since Li does not add onto the C = C double
5
Cycloheptene
61
bond of monoolefins under the conditions employed [2], and
4
Cyclohenzne
60
ethylene does not react at 105-120°C with Si-Li bonds such
3
Cyclopentene
68
as those in ( I ) [3].
2
I ,5-Cyclooctadirnr
53
R,SIClZ
HC=CH
K = CH,
When ethylene is replaced by isobutylene, 1,1,2,2,3,3,4,4,5,5decamethyl-l,2,3,4-tetrasilacyclohexane(7), m.p. 44-45 OC,
separates out, whereas the presence of cyclohexene or 1 hexene leads to the formation of liquid telomers containing
oxygen, such as C6H10[Si(CH3)2]402, b.p. 74 "C/0.3 mm, or
C~H14[Si(CH3)21402,b.p. 96 "C/2 mm.
(
71
a: X = CH2
b:X=O
Intermediary formation of silylenes must always be expected
when diaorganyldichlorosilanes are treated with alkali
226
(8)
a: X
=
CH,
b:X=0
Acenaphthylene (4) is obtained in 30
yield from the
naphthalene derivative (31, and phenanthrene (6) in 45
Angew. Chem. internat. Edit.
Vol. 3 (1964) [ No. 3
yield from the biphenyl derivative (5). On autoxidation, (7u)
gives dibenzo[a,e]cyclohepta-1,3,5-triene (Su), m.p. 133 O C
(45 'I;), and (76) gives dibenzo[e,floxepin (Sb), m.p. 111 "C
(52
Received, December 18th, 1963 [Z 643/470 IE]
x).
German version: Angew. Chem. 76, 226 (1964)
.-
[ I ] H. 1. 5esrmnnn and 0. Kratier, Chem. Ber. 96, 1899 (1963).
mouse ears (I. U.), and in the cocarcinogen test on the back
skin of mice, but does not produce any papillomas within
12 weeks without pretreatment with subthreshold doses of a
carcinogen. The substance loses its biological activity on
treatment with acids or alkalies. The parent alcohol ( I ) is not
active in the amounts applied (Table I), while the triacetate
(2) shows a strongly decreased - but still significant - activity compared with A l .
[Z 654/476 IE]
Received, December 27th, 1963
German version: Angew. Chem. 76, 225 (1964)
Publication withheld until now at the request of the authors
Cocarcinogen A 1 - the First Pure, Highly Active
Constituent of Croton Oil
By Doz. Dr. E. Hecker, Dip1.-Chem. H. Bresch.
and Dip1.-Chem. Ch. v. Szczepanski
Max-Planck-Institut fur Biochemie, Munchen (Germany)
The pharmacologically active principle of croton oil [1,2]
contains the substance groups A and B which cause the toxic,
inflammatory, and cocarcinogenic activity [3] of the oil.
Substance group A can be separated further by countercurrent distribution into the inactive component A2, m.p.
72 " C , and the pure, highly active component A l .
The pure cocarcinogen A1 [*I C36H5608 is a colorless resin,
that is insoluble in water but dissolves in nearly all organic
solvents; [a]L4 = + 49" (1 % in dioxan); Amax = 232 and
333 mp, cmax= 5400 and 73 in ethanol; infrared spectrum in
KBr: hydroxyl 2.96 p, ester carbonyl 5.75 p, ketone carbonyl
5.80-5.85 p, C=C double bonds 6.15 p; N M R spectrum 6 =
0.9, 1.3, 1.7, 2.1, 2.5, 3.2, 3.9, 4.3, 5.2, 5.4, 5.6, 7.5 ppm (in
CC14 with tetramethylsilane as internal standard).
Cocarcinogen A1 is not aromatic, contains a n w,P-unsaturated
carbonyl group that does not react with 2,4-dinitrophenylhydrazine or semicarbazide, as well as three free and two
esterified hydroxyl groups. The latter carry an acetic and a
myristic acid residue, respectively [2]. One of the free hydroxyl groups may be esterified practically quantitatively with
4'-nitroazobenzene-4-carbonyl chloride [4]. Fission of this
ester (C49H63011N3), m.p. 86-87 OC [ 2 ] , with K M n 0 4
affords the corresponding ester of glycolic acid. The esterifiable hydroxyl group is therefore primary and occurs in a n
ally1 configuration; the two remaining free hydroxyl groups
are tertiary. Other chemical data (see [5]) have been obtained for compaunds which have riot yet been shown to be pure.
Cocarcinogen A1 may be degraded by fission of the ester
linkages to give a crystalline parent alcohol C20H2806, m.p.
116' (0.4 % in dioxan); A,,
= 234
238-40°C, [a]&9=
and 335 mp, cmaX = 5000 and 75 in ethanol; infrared
spectrum in KBr: hydroxyl 2.87 and 3.05 p, carbonyl 5.88 p,
C=C double bonds 6.10 p ; NMR spectrum: 6 = 0.52, 0.88,
1.10, 1.67, 2.32, 2.91, 3.77, 4.17, 5.44, 7.52 ppm (in perdeuterodimethyl sulfoxide, standard: tetramethylsilane). A triacetate C26H3409, [a]&*= 68 o (1 "/, in dioxan), is obtained
by acetylation. The spectral and chemical properties of the
parent alcohol show that it is not aromatic and contains a
carbonyl as well as five hydroxyl groups, one of which is
primary and allylic; two other are tertiary.
+
+
The natural product A1 proved to be highly active in the
toxicity test in frogs ( L D ~ o ) ,in the inflammation test on
[*I Formerly denoted by "a" (cf. [2]).
[I] E. Hecker, Chemiker-Ztg. 86, 272 (1962).
[2] E. Hecker, Angew. Chem. 74, 722 (1962); Angew. Chem.
internat. Edit. 1 , 602 (1962).
[3] E. Hecker, Z . Krebsforsch. 65, 325 (1963).
[4] E. Hecker, Chem. Ber. 88, 1666 (1955).
[5] 5.L. van Duuren, E. Arroyo, and L. Orris, J. medical Chem.
6 , 616 (1963); Nature (London) 200, 1115 (1963).
Deaminothiamine Pyrophosphate, a Strong
Carboxylase Inhibitor 111
By Dr. habil. A. Schellenberger and Dr. W. Rodel
Institut fur Organische Chemie der Universitat HalleWittenberg (Germany)
Deaminothiamine ( I ) was synthetized as follows : 4-Chloro5-ethoxycarbonylmethyl-2-methylpyrimidine[2] was converted with NaSH into the 4-mercapto compound, m.p.
185"C, in 91 % yield. Elimination of the mercapto group
with Raney nickel in boiling water gave 5-ethoxycarbonylmethyl-2-methylpyrimidine,
b.p. 104 OC/3 mm, in 34 % yield ;
this was converted via the hydrazide, m.p. 160 "C, 98 % yield,
by twofold treatment with NaN02 into 5-hydroxymethyl-2methylpyrimidine, m.p. 105 "C, in 31 % yield. Heating this
with HBr and glacial acetic acid at 100°C gave the bromide
which reacted unpurified with 5-(~-hydroxyethyl)-4-methyl
thiazole to give deaminothiamine bromide (hydrobromide ?).
When this was shaken with a suspension of AgCl in methanol,
the chloride (hydrochloride?) was produced and was purified by chromatography on a cellulose column (Schleicher
and Schull, No. 123a). The product crystallized after standing for several weeks. Deaminothiamine can be obtained
analytically pure as its perchlorate, n1.p. 204 "C (decomp.),
which crystallizes well.
Phosphorylation of ( I ) with anhydrous orthophosphoric
acid [3] yielded a mixture of the mono-, di-, and triphosphoric esters in addition to inorganic phosphate. This mixture was separated using paper or thin-layer electrophoresis.
The separated fractions were eluted with water.
I f deaminDthiamine pyrophosphate is added to resynthetized
carboxylase in a molar ratio cocarboxylase: deaminococarboxylase = 0.96: 1, the activity of the enzyme is reduced
by 8 4 % (optical assay according to [4]). If, however, the
inhibitor is added in the resynthesis of carboxylase before
thiamine pyrophosphate, then the inhibition is almost
complete.
Received, January 2nd, 1964
[Z 644/471 IE]
German version: Angew. Chem. 76, 226 (1964)
Table I. Biological activity of the pure cocarcinogen A l , of its parent
alcohol ( I ) , and of the triacetate ( 2 ) of (I). Tests according to [3].
~~
stance
Al
(1)
(2)
1
1
[wg/50 g]
10
5000
150
1
1
I
1
[ ~ g l e a r ] ~dapplication
Ibl
0.009
2.4
1.5
'
10
500
SO
I
papilloma/mouse
[Cl
1 i.,
[a] Carcinogen: 1 irmole of 9,10-dimethylbenzanthracene.
[ b ] Application: twice weekly for 12 weeks.
[c] Alter I 2 weeks
Angew. Chem. internat. Edit. / Vul. 3 (1964) / No. 3
[I] Investigations into the function of the amino group in cocarboxylase, Part 2. - Part 1 : A . Schellenberger and KI. Winter,
Hoppe-Seylers Z. physiol. Chem. 322, 164 [1960].
[2] H. Andervzg and K . Wesiphal, Chem. Ber. 70, 2035 (1937);
L. R . Cerecedu and F. D . Pickel, J. Amer. chem. SOC. 59, 1714
(1937).
[ 3 ] P . Karrer et al., Helv. chim. Acta 32, 1478 (1949); 34, 1384
(1951).
[4] E. Holzer, H . - D .Soling, H.- W .Goedde, and H . Holzer, in H . U.
Bergmeyer: Methods of enzymatic Analysis. Verlag Chemie.
Weinheim/Bergstr., and Academic Press, New York 1963, p. 602.
227
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triphenylphosphorylidene, closure, autoxidation, ring, alkane, bis
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