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Comment on the Publication Entitled УSynthesis of a Stable 1 3 4-DioxazolidineФ.

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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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