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Co2(CO)8 Catalyzed Reactions of Cyclic Ethers with Hydrosilanes and Carbon Monoxide.

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aqueous ZiiC12 solution), Z = 16, R l =0.052, R2=0.063. 1977 unique
,
data ( 1 > 3 ~ ( 1 ) 28<126".
[S] B. C h e w i e r . Th. Diehold. R . Weiss, Inorg. Chim. Acta 19, L57-L58
(1976).
[6] J . L. Hoard in K . .bf. Sniifh. Porphyrins and Metalloporphyrins. Elsevier.
Amsterdam 1975. Chapter 8.
[7] B. M . L. Cken. A . Tulirisky. J. Am. Chem. Soc. 94, 4144 (1972); J.
W Luuher, J . A . Ibe,s, h i d . 95, 5148 (1973); D. L . Cullen, E. F . Meyer,
Jr.. ihid. 96. 2095 (1974); R . G. Lirrlr, J . A . Ibers, ihid. 96, 4440 (1974);
97, 5363 (1975); F . S. Molinaro. J . A . Ibers, Inorg. Chem. I S , 2278
(1976)
C O ~ ( C OCatalyzed
)~
Reactions of Cyclic Ethers with
Hydrosilanes and Carbon Monoxide"]
By Yoshio Seki, Shirtji Murai, Iwao Yamamoto, and Noboru
Sot1oda"I
We recently reported a new reaction of olefins with hydrosilanes and carbon monoxide which leads to enol silyl ethers[*],
and resembles that of hydroformylation. To test the applicability of the new hydrosilane reaction to compounds other than
olefins, we have studied the reaction of cyclic ethers with
hydrosilanes and carbon monoxide.
Hydroformylation of cyclic ethers is known to give hydroxyaldehydes as initial product^'^]. The reaction, however, frequently suffers from undesirable side reactions or further reactions, since the hydroxyaldehydes are very labile compounds.
For example, hydroformylation of tetrahydrofuran did not
afford the expected 4-hydroxybutanal but yielded various products arising from further carbonylati~n[~],
and the hydroformylation of cyclohexene oxide gave only a condensation product of the expected 2-hydroxycyclohexanecarbaldehyde[5!
We have found that the reaction of tetrahydrofuran, oxetane,
or 1,2-epoxycyclohexane with diethyl(methy1)silane and
carbon monoxide in the presence of a catalytic amount of
Co2(COj8gives thesilyl-protected hydroxyaldehydes ( 1 )-(3),
respectively, in reasonable yields['].
id, +
HSiEt,Me
+
CO
CO*(CO)S
EtzMeSiO
0
( 1 ) 53%
1
og
+
HSiEtzMe
+
CO
CO,(CO)*
0
Experimental
Synthesis of ( 1 ) ; A solution of 4 ml(50 mmol) of tetrahydrofuran, 1.02 g (10mmol) of diethyl(methyl)silane, and 0.068 g
(0.2mmol) of C O ~ ( C Oin
) ~20ml of benzene was placed in
a l00ml stainless steel autoclave. The autoclave was flushed
with N 2 (60 kg/cm2) and CO (60 kg/cm2), then charged with
CO (60kg/cm2) and heated at 140°C with stirring. After 20h,
the autoclave was cooled and depressured. Analysis of the
reaction mixture by GLC (Silicon OV-I, 5 % , on Uniport
KS, 3 m x 3 mm, 135°C) with n-tetradecane as an internal
standard showed it to contain ( I ) in 53 % yield. An analytical
sample of (1) was obtained by fractional distillation (b.p.
120-1 30°C/30 torr) followed by preparative GLC (Silicon
OV-I, 5 04,on Uniport KS, 3 m x 8 mm, 140°C).
Received- August 16, 1977 [Z 822 IE]
German version: Angew. Chem. 89, 8 I 8 ( I 977)
CAS Registry numbers:
( I ), 64035-85-4; f 2 J, 64035-86-5; ( 3 ) , 64056-85-5; tetrahydrofuran, 109-99-9;
dietliylmethylsilane. 760-32-7; oxetane. 503-30-0; 7-oxabicyclo[4. I .O]heptane.
286-20-4
[ I ] Part 3 of Transition Metal Reactions of Si1anes.--Part 2: [2].
[2] E Seki. A . Hidaku. S. Murai, N . Sonoda, Angew. Chem. 89, 196 (1977);
Angew. Chem. hit. Ed. Engl. 16, 174(1977); E Srki, A Hidaku, S. Mukir~o.
S. Murai, N . Sorzoda, J. Organomet. Chem., in press.
[3] J . Falhe: Carbon Monoxide in Organic Synthesis. Springer, Berlin 1970.
[4] W Reppe, H . Kroper, H . J . Pistor, 0. Weissborrh, Justus Liehigs Ann.
Chem. 587, 87 (1953).
[5] L. ROOP.R. F. Gorrz, M . Orchiu. J. Org. Chem. 30. 3023 (1965).
[6] This is important from the viewpoint of utility as synthetic intermediates.
Efforts are being made to optimize the yields. Elemental analysis of
all the new compounds gave the expected results. Spectral data: 1R
(without so1vent)for ( I ) to ( 3 ) : 1725cm-I (C=O); IH-NMR (in CCI2;
each s. CHO) for ( 1 ) : 9.60, for ( 2 ) : 9.64, for ( 3 ) : 9.66.
[7] A . J . Cha/k, Chem. Commun. 1970. 847.
Tris(tert-butylimino)sulfur(vr)and
Bis(terr-butylimino)(silylimino)sulfur(vr) ;
The "Y-triene" Structure[**]
By Oskur Glemser, Siegfried Pohl, Frcink-M. Tesky, and Riidigrr
Mewsl*l
Compounds containing tricoordinate sulfur(vr) have only
rarely been reported. The only representatives of proven structure are SO3 and its aza analogs (R,SiN=),S['I
and
(R3SiN=)2S=0[21. As shown by these examples, the trimeth-
( 2 ) : 40%
NSF3
+
LiN(CR3)SiR3
-
7
p
N-S-N
I
F
1
\
3
f
LiF
SiR3
+ LIN(CR~)SIR~
(31, 51%
It is interesting to note that Chalkr7]has already reported
the polymerization of tetrahydrofuran catalyzed by C O ~ ( C O ) ~
and triethylsilane (1 :2) and proposed opening of the tetrahydrofuran ring by a carbonyl(silyl)cobaIt for the initiation step.
No polymerization, however, was observed in the present
reaction.
~
-~
['I, 1. Yamainoto. Prof. Dr. N. Sonoda
Department of Petroleum Chemistry, Faculty of Engineering, Osaka
Cniversity
Suita. Osaka 565 (Japan)
To w>hoincorrespondence should he addressed.
[*] Y Seki. Prof. Dr. S. Murai
[ '3
[*] Prof. Dr. 0. Clemser, Dip1.-Chem. F.-M. Tesky, Priv.-Dor. Dr. R. Mews
Aiiorganisch-Chemischcs lnstitut der UniversitBt
Tammannstrasse 4. D-3400 Giittingen (Ccrmany)
Dr. S. Pohl
Anorganisch-Chemisches lnstitut der Universitht
Postfdach 8640, D-4800 Bielefeld (Germany)
[**I This w o r k was supported by the Dcutsche Forschun%agerneinscli~,ft
and thc Fonds der Chemischen lnduslrie.
789
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cyclic, reaction, ethers, monoxide, co2, hydrosilanes, carbon, catalyzed
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