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Catalyst-Dependent Product Distribution in the Reaction of 1-Hexene with a Hydrosilane and Carbon Monoxide.

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"I
Et2O
(2) + C 5H 5 ( C 0) 2 M n ( T H F ) - 30 "C
---+
7
C5H5(CO)zMn-N=N-Mn( CO) zC5H5
I
(3)
+ THF
C6H5
(3) can be separated from decomposition products and
any carbene complex still present by chromatography at
-30°C. Contrary to (2), we were able to detect ( 3 ) also in
the mass spectrum. [Spectroscopical data of (3) : vco(CHzClz,
-62°C): 1936, 1848cm-'; 'H-NMR (90MHz, (CD3)2C0,
-62"C, rel. TMS): 15.38 (s, SNH), 7.57 (m, 6C6H5), 5.07 (s,
6C5H5),4.65(s, S C S H ~ MS
) ; (70eV, 20°C): M + at m/e458].
Recrystallization from CHzClz at - 35 "C/- 78 "C affords ( 2 )
and (3) as red-black and blue-black crystals, respectively.
They are extremely sensitive towards oxidation, heat, acids
and bases, and have to be handled at temperatures below
- 30°C. Thermal decomposition of (2) in THF solution yields
the starting N2 complex:
C5H5(CO)2Mn-N=NH
I
THF
C5H5(C0)2Mn-N-N
20 T
+
C6H,
The composition and structure of (2) and (3) have been
confirmed by additional independent syntheses:
I
(4)
Catalyst-Dependent Product Distribution in the Reaction of 1-Hexene with a Hydrosilane and Carbon
Monoxide[']
By Yoshio Seki, Shinji Murai, Akihiko Hidaka, and Noboru
Sonoda[*I
C6H5
C5H5(CO),Mn-NH-NH2
Reactions of Complexed Ligands, Part 23. This work was supported
by the Deutsche Forschungseemcinschaft and the Fonds der Chemischen
Industrie. Part 22. D . S C ~ / / I M I IE.~ I ~, / ~ , ~ J i . \ [ , / i ~ i i ~Z[ ./ r .Naturforscli B
32, lOiO(1977).
P I Cf. J . R . Pobfgrrre 'The Chemistry and Biochemistry of Nitrogen Fixation,
Plenum Press, London 1971.
~ 3 1Cf. J . Chart, A. J . Pearman, R . L. Richards, J . Organomet. Chem. 101,
C 4 5 (1975); J . C h a f f ,ibid. 100, 17 (1975).
M Cf. F . W van der Weij, J . H . Euben, J. Organomet. Chem. 120, 223
(1976).
151 E. 0. Fischer, A. Maasbof, Chem. Ber. 100, 2445 (1967).
C61 Synthesis and proof of structure: ( 4 ) is obtained by reaction of
C5HsMn(CO)2THFwith C6HSN2H3;the coordination of the C6HsNH
group on the Mn center follows from the chemical shifts of N H and
N H 2 protons on coordination.
171 Noti. d d r d iii p r n o / ( l I. I I. 1977): I n the meantime a mass spectrum
of ( 2 ) could be obtained: 15 eV, Ts= - lO"C, M + at m / e 282.
+- HzOz
THF/C~*+
2 HzO
+ (2) + (3)
- 78 "C
6%
f
decomposition
products
Oxidation of the phenylhydrazine complex (4)[61 yields
a mixture of (2) and (3). Separation and reaction of (2)
with CsH5(CO)zMnTHF gives (3) again.
Our findings prove that ligating dinitrogen can be reduced
by base addition under preservation of the N2 coordination
site. Addition reactions of H@-ions are under investigation
to elucidate the relevance of the reaction for the mechanism
of biological NZ fixation.
Procedure
The C~~(CO)~-catalyzed
reaction of cycloalkenes with hydrosilanes and carbon monoxide['] gives only one product,
a siloxymethylenecycloalkane, arid the regioselectivity of this
novel reaction type has yet to be elucidated. We now report
the catalyst-dependent product distribution in the reaction
of a linear n-alkene. Reaction of 1 -hexene with diethyl(methy1)silane and carbon monoxide affords four isomeric derivatives
of siloxymethylene (regio- and stereoisomers); the effective
catalysts found are listed in Table 1.
All of the effective catalysts are also known to be hydroformylation catalysts[3! The total yields and the ratio of straight
chain isomers (Table 1) are also similar to those observed
in hydroformylation. A very good yield was obtained using
RhC1(PPh3),/Et3N.The addition of triethylamine has already
been reported to eliminate the induction period for hydroformylation of I-pentene catalyzed by RhC1(CO)(PPh3)2[41.
A
regioselectivity of 92 % was achieved by the addition of n-Bu3P,
as against 83 "/, for PPh3, in the reaction using C O ~ ( C O ) ~
(cf. Table 1 ; the corresponding proportions of straight chain
AsolutionofC5HsMn(CO)2Nz (1450mg, 7.1 mmo1)in tetrahydrofuran (50ml) is treated at -30°C with a solution of
LiC6Hs (7.1 mmol) indiethyl ether (16 ml). After 2 h the solvent
is removed from the mixture by evaporation. The residue
is dissolved in 40 ml of ether at - 30°C and neutralized by
adding 18ml 0.41 N H2S04; the deep red ether phase is
decanted off and dried over Na2S04 at - 30°C. The solution
is divided into two parts; the first part is evaporated, dissolved
in toluene and chromatographed on SiO2 at -60°C. A yellow
zone of C5HsMn(C0)3is followed by a deep red zone, yielding
after
collection
and
evaporation
60 mg
(5.9 %)
C S H ~ M ~ ( C O ) ~ N ~The
H Csecond
~ H ~ .part of the ether solution is allowed to react with 1240mg (5mmol)
CSH~M~(CO)~T
forH 30min
F
at - 30°C. After evaporation
and warming up to +20"C for 3min, the crude product
is chromatographed on Si02 with toluene at -30°C. After
elution of C5H5Mn(C0)3 and C ~ H ~ M ~ ( C ~ ) Z C ( O aH ) C ~ H ~
blue-black zone is eluted with toluene/THF = 1 : 1, which yields
70mg (4.3 %) [ C ~ H S M ~ ( C O ) ~ ] ~ N Z H
AllC reactions~H~.
carried out under
including the synthesis of LiC&-are
[*] Y.
argon.
Received: October 17, 1977 [ Z 857 IE]
German version: Angew. Chem. 89,918 (1977)
Angew. Chem. I n t . Ed. Engl. 16 ( 1 9 7 7 ) No. 12
['I
+ CO
+
HSiEt,Me
cat.
CbH6. 140°C. 20 h
-
Seki, Prof. Dr. S. Murai ['I. A. Hidaka, Prof. Dr. N. Sonoda
Department of Petroleum Chemistry, Faculty of Engineering,
Osaka University, Suita, Osaka 565 (Japan)
To whom correspondence should be addressed.
881
Table 1. Reaction of I-hexene with Et2MeSiH and CO [a].
Catalyst [mmol]
(WI)
(Z)-f2j
(E)-f2)
c ( 2 1 [.I
["/.I
7
9
13
16
6
10
44
58
56
43
70
59
45
24
23
25
22
24
89
82
79
68
92
83
Product distribution [%]
R ~ d C 0 ) 1 2(0.4)
RhCI(PPh& (0.4)
RhCI(PPhj)3 (0.4) + Et3N (1.0)
Coz(C0)a (0.4)
C O ~ ( C O(0.4)
) ~ + nBu3P (1.0)
C O ~ ( C O(0.4)
) ~ + Ph3P (1.0)
40
41
88
57
18
77
[a] Reaction conditions: 1-hexene (30mmol), EtlMeSiH (lOmmol), CO (50kg/cm2), and catalyst in benzene (20ml),
140"C, 2Oh.
[b] Determined by GLC.
[c] Proportion of straight-chain enol ethers (Z)-(Z j plus (E)-(Zj as determined by GLC in overall product.
isomers in the overall product of analogous hydroformylations
of I-hexene are 89.6 % and 62.4 %, re~pectively[~]).
These results clearly suggest that the new catalyzed reactions
of olefins with hydrosilanes and carbon monoxide have basic
features closely resembling those of hydroformylation.
Experimental :
A solution of 1-hexene (3.7 ml, 30mmol), diethyl(methy1)silane (1.02g, IOmmol), triethylamine (0.1 g, 1 mmol), and
RhCI(PPh& (0.37g, 0.4mmol) in benzene (20ml) is placed
in a 100-ml stainless steel autoclave. The autoclave is flushed
with N2 (50 kg/cm2) and CO (50 kg/cm2), then charged with
CO (50kg/cm2)and heated at 140°C with stirring. After 20h,
the autoclave is cooled and depressured. Analysis of the
.reaction mixture by GLC (Silicon OV-1, 5 % , on Uniport
KS, 6 m, 115"C) with an internal standard (n-tetradecane,
RRT (relative retention time)= 1) showed it to contain enol
silyl ethers [@)-(I
), RRT=0.36; ( E ) - ( I ) , 0.39; (Z)-(2),0.45;
(E)-(2), 0.601 and disiloxane [(Et2MeSi)z0,RRTz0.191 in
88 % (total) and 11 % yields, respectively. The relative yields
ofthe enol silyl ethers are shown in Table 1. Analytical samples
were obtained by fractional distillation (b.p. 105-1 15 "C/12
torr) followed by repeated preparative GLCL6'.
1670 cm-' (C=C); 1.50 (d, CH3C=C), 1.83 (m, CH2C=C), 5.92 (s,
HC=C). ( Z ) - ( 2 ) , 1660 cm-' (C=C); 1.96 (m, CH2C=C), 4.30 (dt, J = 6
and 8 Hz, CH=COSi), 6.02 (d, J = 6 Hz, C=CHOSi). (E)-(2), 1660 cm-'
(C=C); 1.80 (m, CH2C=C), 4.80 (dt, J = 12 and 6 Hz, HC=COSi),
6.08 (d, J = 12 Hz, C=CHOSi).
Comment on the Publication Entitled "Synthesis of
a Stable 1,3,4-Dio~azolidine''~~~
By Gerwalt Zinner and Helmut B l a s s ~ ]
Contrary to the authors' assumption, compound ( I ) described by Varwig and Mews[']is not the first (stable)derivative
of this ring type, correctly designated 1,4,2-dioxazolidine,since
the set of locants 1,4,2 is lower than 1,3,4. The adamantanone
derivate (2)"' and the bicyclic derivative (3)13] were reported
live years ago.
Received: September 2, 1977 [Z 847 IE]
German version: Angew. Chem. 89, 919 (1977)
[l] Transition Metal Reactions of Silanes, Part 4.-Part 3: Y Seki, S. Murai,
1 . Yamamoto, N . Sonoda, Angew. Chem. 89, 818 (1977); Angew. Chem.
Int. Ed. Engl. 16. 789 (1977).
[2] 1: Seki, A . Hidaka, S . Murai, N . Sonoda, Angew. Chem. 89, 196 (1977);
Angew. Chem. Int. Ed. Engl. 16,174 (1977); Y Seki, A . Hidaka, S. Makino,
S . Murai, N . Sonoda, J. Organomet. Chem., in press.
[ 3 ] J. Falbe, Carbon Monoxide in Organic Synthesis. Springer-Verlag. Berlin
1970; F . E. Paulk, Catal. Rev, 6,49 (1972);L. Marko in R. Ugo: Aspects
of Homogeneous Catalysis, Vol. 2. D. Reidel, Dordrecht 1974, p. 1.
[4] D. Evans, J . A. Osborn, G. Wilkinson, J. Chem. SOC.,41968, 3133.
[5] E. R . Tucci, Ind. Eng. Chem. Prod. Res. Dev. 9, 516 (1970).
[6] The IR (neat) and NMR (CCIJ data are: (Z)-(I ), IR 1670 cm-' (C=C);
NMR 1.48 (d, CHsC=C), 2.00 (m, CH2C=C), 5.90 (s, HC=C). (E)-(l),
Received: November 8, 1977 [Z 865 IE]
German version: Angew. Chem. 89, 920 (1977)
p]
Prof. Dr. G. Zinner, H. Blass
Institut fur Pharmazeutische Chemie der Technischen Universitat
Beethovenstrasse 55, D-3300 Braunschweig (Germany)
[l] J. Varwig, R . Mews, Angew. Chem. 89, 675 (1977); Angew. Chem. Int.
Ed. Engl. 16, 646 (1977).
[2] G. Zinner, B. Geister, Chem.-Ztg. 96, 693 (1972); the data given are
supplemented by the mass spectrum (70eV, 170°C): m/e=329 M + (lo),
179 (loo), 162 (loo), 150 (90); we are grateful to Dr. H . - M . Schiebel,
Gesellschaft fur Biotechnologische Forschung, Braunschweig-Stockheim,
for recoding the spectrum.
[3] G . Eikelmann, W Heimberger, G . Nonnenmacher, W M . Weigert, Justus
Liebigs Ann. Chem. 759, 183 (1972).
BOOK REVIEWS
Handbuch der Arzneimittel-Analytik (Handbook of Drug Analysis). By S. Ebel. Verlag Chemie GmbH, Weinheim-New
York 1977. 1st edit., x, 417 pp., 3 figs., 354 tables, plastic
binding , DM 118.-.
This new handbook differs from the earlier works on drug
analysis in that first place has not been given to the analytical
procedure with subsequent treatment of the substances appear882
ing in the various fractions. Instead, extensive lists of analytically important data are provided for some 600 drugs. The
division of the material into pharmacologically important
groups is both novel and useful. In the first place the user
can obtain an impression of the substance in question from
the medical information that is almost always known for
a drug, but he can also see, without a time-wasting search,
Angew. Chem. lnt. Ed. Engl. 16 (1977) N o . 12
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