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Gold Complexes of Cycloalkenes and Cycloalkadienes.

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The compound ( 5 ) can also be copolymerized with ethylene
oxide or propylene oxide.
Received: March 23rd, 1965
[ Z 957/784 IE]
German version: Angew. Chem. 77, 455 (1965)
[ I ] The compound ( I ) is obtained from 3-chloro-2-chloromethylpropene and formaldehyde (molar ratio 1 : 3 ) in 809:)
H2SO4 by a Prins reaction [2] in 68y0 yield; b.p. l2O0C/12 rnm,
n$ = 1,4927. The byproduct 3-chloro-4-chloromethyl-4-hydroxytetrahydropyran, m.p. 104,5 "C, is formed with a yield of 11 %,.
[2] E . Arundnle and C. A . Mikenka, Chem. Rev. Sf, 505 (1952).
pounds: ethylene diisocyanate ( I ) reacts with dimethylbis(dimethy1amino)silane (2) to give I-dimethylcarbamoyl-3[dimethyl(dirnethylamino)silyl~imidazolidinone (3) and dimethylbis(1-dimethylcarbamoyl-2-oxoimidazolidin - 3 - y1)silane ( 4 ) .
8 9
( C H 3 ) ~ N - t i - y'r-C-N(CH3)2
H3C C H S H z
Gold Complexes of Cycloalkenes and
By Prof. Dr. R. Hiittel and Dipl.-Chem. H. Diet1
Institut fur Organische Chemie
der Universitat Munchen (Germany)
Gold complexes of olefins were recently described for the
first time [I]. We have found that cyclopentene, cyclohexene,
cis-cyclooctene, and trans-cyclodecene react with aqueous
solutions of HAuC14 or NaAuC14 or with finely pulverized
HAuC14.4 H20 to form gold(1) complexes. These are colorless
crystalline substances. When aqueous solutions of the inorganic gold compounds are used, they precipitate only
slowly because their formation is preceded by the reduction
of Au(II1) to Au(1). They decompose at relatively low temperatures, e.g. the cyclopentene complex at 55-60 "C, and
the cyclooctene complex at 81-85 "C. The olefin evaporates
off to a considerable extent from the cyclopentene and cyclohexene complexes even during drying.
Cyclooctenegold(1) chloride is obtained in 74 % yield with
aqueous solutions of HAuC14 or in practically quantitative
yield from the dry tetrahydrate. It crystallizes in rectangular
prisms (C8H14AuClr molecular weight = 308 by cryoscopy
in bromoform). Its infrared spectrum resembles that of
(CsH14PdC12)2 121 and exhibits a characteristic shift of the
double-bond absorption of the cyclooctene moiety from 1655
to 1512 cm-1.
Cyclodecenegold(1) chloride (CloHlsAuC1) separates in 78 %
yield in the form of needles, m.p. 75-8OoC (decomp.),
on shaking an aqueous solution of HAuCI4 with excess
olefin. Its molecular weight measured in a vapor pressure
osmometer in chloroform is 386.
I ,5-Cyclooctadiene reacts immediately with HAuCl4 or
NaAuCl4 in water to give a 68 % yield of yellow quadratic
platelets or cubes of a substance ( C ~ H ~ ~ A U C I )rn.p.
85-90 OC (decomp.), which does not resemble the compound
described by Chalk [I] in color, melting point, or composition.
The compound is so insoluble that its molecular weight could
not be determined. On reduction with methanolic sodium
hydroxide solution [3], it reaffords 1,5-cyclooctadiene. Here,
too, the infrared spectrum contains the double-bond absorption at 1515 cm-1.
Received: March 24th, 1965
[Z 947/773 IE]
German version: Angew. Cheni. 77, 456 (1965)
[I] A. J . Chalk, J. Amer. chem. SOC.86, 4733 (1964).
[2] R. Hiittel, H. Diefl, and H. Christ, Chem. Ber. 97,2037 (1964).
[3] H. Christ and R. Hiittel, Angew. Chem. 75, 921 (1963);
Angew. Chem. internat. Edit. 2, 626 (1963).
New N-Silylimidazolidinones
By Dr. 0.J. Scherer and Prof. Dr. Max Schmidt
Institut fur Anorganische Chemie der Universitat Marburg
Cyclic ureas can be directly silylated [I]. Other N-silylimidazolidinones are accessible by ring extension [2]. We have
found a simple new route to this little-known class of com-
After slow, dropwiseaddition of a solution of ( I ) in ether to
an etheral solution of the stoichiometric amount of (2) at
-1OOC and removal of the solvent, (3) can be distilled in
about 70 % yield from ( 4 ) (yield about 20 %); (3) has m. p.
67-69OC, b.p. 108-109°C/0,1 mm, (4) has m.p. 172 to
175 ' C . Both compounds crystallize well and are sensitive to
solvolysis. They were characterized by analysis and infrared
and proton magnetic resonance spectra
On reversing the order of adding the reagents, i.e. o n adding
(2) to ( I ) . only little (3) can be isolated, and apart from ( 4 )
polymers are formed, which have not yet been finally characterized. The relative yields of ( 3 ) , (4), and polymer depend strongly on the conditions of reaction.
With anhydrous ethanol, (3) and ( 4 ) react quantitatively at
room temperature with formation of l-dimethylcarbamoylimidazolidin-2-one, m.p. 126- 128 "C.
The reaction of bis(trimethylsily1)methylaniine with (I) is
simjlar to that of (2) with ( I ) .
Received: March 25th. 1965
[Z9631789 IE]
German version: Angew. Chem. 77, 456 (1965)
[I1 P. L . De Benneville and M. J. Hurwitr, U.S. Pat. 2876209
[ 2 ] 0.J . Scherer and M. Schmidt, Chem. Ber., in the press.
Reaction of Sodium Bistrimethylsilylamide with
Carbon Monoxide and Metal CarbonyIs [l]
By Prof. Dr. U. Wannagat and Dipl.-Chem. H. Seyffert
Institut fur Anorganische Chemie
der Technischen Hochschule Graz (Austria)
Carbon monoxide reacts with sodium bistrimethylsilylamide
( I ) in petroleum ether or benzene at 80°C and 100 atm to
give sodium cyanide and bistrimethylsilyl ether in yields of
over 80 %. The same products are formed in 95 % yield in
the reaction of trimethylsilyl cyanide (2) and sodium trimethylsiloxide (3) in benzene at 80 O C . It is therefore possible
that the reaction of ( I ) and CO proceeds via (2) and (3) as
intermediates, (2) reacting as trimethylsilyl isocyanide.
CO iNaN[Si(CH&]2
+ NaCN
(CH3)3SiCN+ NaOSi(CH&
The reaction of carbon dioxide with ( I ) rapidly leads
bistrimethylsilyl ether, and
NaOCN [Z]. Here, trimethylsilyl isocyanate occurs as an
intermediate; this was shown by passing CO2 over molten
( I ) at 200 O C and distilling off the trimethylsilyl isocyanate
before it could react with ( I ) or ( 3 ) , which is also formed
as an intermediate.
Both iron pentacarbonyl and nickel tetracarbonyl react
vigorously with ( I ) , bistrimethylsilyl ether being produced
Aiigew. Cheni. interticit. Edit.
Vol. 4 (1965) No. 5
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cycloalkenyl, cycloalkadienes, gold, complexes
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