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Bis(thioacyl) Sulfides from Acyl Thioacyl Sulfides.

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6 = -9.41, two Si-CH3 signals at 6=0.36 and 0.71 with
a relative intensity of 3 :2. The signal at 6 = 0.71 can be assigned
to the terminally bonded Me2Si group, since all the SiCH3
signals of bridging MezSi groups in dinuclear complexes
appear at lower field[31.
The mass spectrum of (3) (25eV) shows the molecular
ion at mje 272 (5.0 %) and ions corresponding to the successive
loss of CO leading to Me2SiFe+ (m/e= 114, 23.8 %) and
Me3%+ (m/e=73, 100%). In the v C 0 region of ( 3 ) there
appear four bands at 2080 (s), 2030 (s, sh), 2000 (vs), and
1930 (s, sh) cm-'.
Similar reaction of Fez(C0)9and 1,1,2,2-tetramethyldisilane
(2) gave the corresponding yellow-orange complex ( 4 ) ; b. p.
23"C/5 x
torr. IR (neat): 2080 (s), 2030 (s, sh), 2000 (vs),
1930 (s, sh) c m - ' ; MS (25eV): m/e 258 (M', 11.4%), 114
(100%); 'H-NMR (CS,): 6 = -9.4 ( l H , s, Fe-H), 0.30 (6H,
d, 5=4.0Hz, SiH-CH3), 0.7 (6H, s, Si--CH3), 4.0 (1 H, sept.,
J =4.0 Hz, Si-If).
The complex (3) reacts with triphenylphosphane and I ,4diphenylbuta-1,3-diene to give the respective substitution compounds :
Bis(thioacy1) Sulfides from Acyl Thioacyl Sulfides
B y Shinzi Kato, Katsumi Sugino, Masateru Mizuta, and
Tomonori Katada[*l
Bis(thioacy1)sulfides (3) are accessible by reaction of dithiocarboxylic acids and dicyclohexylcarbodiimide['l. In the
course of a study on the synthetic utility of acyl thioacyl
sulfides (I ), it was found that compounds ( 3 ) are obtained
in fair yield by treatment of ( I ) with lithium alkoxides or
alkyl sulfides (2). Preliminary experiments revealed that the
yields of (3) are highly dependent upon the group R and
upon the species (2). The highest yield was obtained on
reaction of (1 a) with lithium ethyl sulfide. The reaction proceeds even on use of '/3 mol of lithium salt per mol of ( 1 a )
to give over 60% of ( 3 a ) (Table 1). This reaction also gives
bis(acy1) sulfide ( 4 ) , which was detected IR spectroscopically.
s
II
o
11
2 R-C-S-C-R'
R
=
R"XLi(2)
s
11
s
11
R-C-S-C-R
0
+
II
0
II
R'-C-S-C-R'
Alkyl, A r y l
R'= A l k y l
x=o,s
Table 1 . Reaction of acyl(thioacy1) sulfides with lithium alkoxides or alkyl
sulfides.
R
The reaction of ( 3 ) with diphenylacetylene results in the
formation of several interesting compounds as shown in the
following scheme:
PhCXPh
(3)
7
Ph,
/Ph
/C
=c\
+
SiMe3
Me3Si
R"X
(1):(2)
M.p.
Yield
YCl
[%I
/Ph
Ph,
,c =c
\H
MeSSi
(6)
(5)
R'
This is the first example of a base-catalyzed disproportionation reaction of acyl thioacyl sulfides.
Experimental
+ Fe(CO)S(PhC-CPh),
(9)
+
Fe~(C0)7(PhC~CPh),
(10)
( 5 ) (6%), (6) (20%), (7) (2%), (8) (5%), (9) (7%), and
(10) (8 %) were isolated by TLC on silica gel.
To a solution of ( I a)[21(0.42g, 2 mmol) in n-hexane (30ml)
was added lithium ethyl sulfide (0.14g, 2 mmol) and the mixture
was stirred for 30min at 0°C under argon. The sky-blue
solution becomes dark blue within 5min, and formation of
small amounts of green crystals is observed. Insoluble EtSLi
is filtered off, and the filtrate is concentrated to ca. 15ml
in uacuo. Cooling to -50°C gave a green precipitate of
( 3 a ) which was isolated by filtration [yield 0.25 g (76 %);
m.p. 74°C (74-75"C['"')] (76 %) and identified by comparison
with an authentic sample['"] (IR, UV, 'H-NMR).
Received: July 4, 1978 [Z 34 IE]
German version: Angew. Chem. YO, 718 (1978)
CAS Registry numbers:
( I ) , 812-15-7; ( 2 ) , 814-98-2; (3). 67505-78-6; ( 4 ) , 67505-77-5; 15),
5351 1-09-4; (6), 57266-93-0; (7), 57266-94-1; ( S ) , 67489-32-1 ; (Y),
67505-79-7; ( l o ) , 67523-52-8; Fe(CO),(PPh&, 14741-34-5;
(Ph-CH=CH-CH=CH-Ph)Fe(CO),,
33593-85-0; Fe2(C0)9, 15321-51 -4;
P h G C P h , 501-65-5
~ . _ _ _-
Chemistry of Organosilicon Compounds, Part 1 15.-Part 114: H . Bock,
U! Kairn, M . K i m , H . Osawa, H . Sukurai, J. Organometal. Chem., in press.
[2] G. S<hmid, E . Wilz, Angew. Chem. 89, 823 (1977); Angew. Chem. Int.
Ed. Engl. 16, 785 (1977).
[ 3 ] D. Kummrr, J. Furrer, Z . Naturforsch. B 2 6 , 162 (1971); A. Brookrs,
S . A. R. Knox, F . G . A . Stone, J. Chem. Soc. A 1971, 3469.
[I]
Anyew. Chem. Int. E d . Engl. 17 ( I 978) N o . Y
Received: April 20, 1978 [Z 992 IE]
German version: Angew. Chem. YO, 71 8 ( 1 978)
a) S. Karo, T Katada, M.Mizuta, Angew. Chem. 88, 844 (1976); Angew.
Chem. Int. Ed. Engl. 15, 766 (1976); b) S . Kato, 7: Takagi, 7: Katada,
M . Mizuta, ibid. SY, 820 (1977) and 16, 786 (1977), respectively.
[2] S. Kato, K . Sugino, M. Yamada, 7: Katada, M. Mizuta,Angew. Chem.
89,917 (1977); Angew. Chem. Int. Ed. Engl. 16, 879 (1977).
[I]
_____
[*I
1'1
Prof. Dr. S. Kato [+I, K. Sugino, Prof. Dr. M. Miznta, T. Katada
Department of Chemistry, Faculty of Engineering, Gifn University
Kagamihara, Gifu 504 (Japan)
Author to whom correspondence should be addressed.
675
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