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Carbon-Free Metal Chelate Rings Containing Boron.

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Whether or not the imene acts as a diradical, or as an electrophilic agent, cannot yet be decided [4]. It is unlikely that
pyrroline formation occurs through the isomerisation of a
vinylethylene imine (I) formed by 1,2-addition since we have
By Prof. Dr. P. L. Pauson and Dr. W. H. Stubbs
Department of Chemistry, The Royal College of Science
and Technology, Glasgow (Scotland)
Isonitrile Complexes of Manganese, Iron and Nickel
never found aziridines in the reaction of olefines with the
imene produced according to equation (I); on the contrary,
hydrogenation alone is always observed [5]. The 1,4-addition
that we have noted is a further important argument for the
appearance of the imene as an intermediate in the alkaline
break-down of hydroxylamine-0-sulphonicacid and chloramine [4].
[Z 255/74 IE]
Received, April 6th. 1962
[*I Dedicated to Prof. Dr. G. Witrig on the occasion of his 65 th
[ I ] V. Franzen, Chem. Ber. 95, 571 (1962).
[2] 0. Eiichner, Diploma Thesis, Universitat Heidelberg (1960).
[3] According to nomenclature proposals by A . Liittringhaus,
J. Jander, and R. Schneider, Chem. Ber. 92, 1756 (1959), the name
"imene" (Imen) forNH should be applied in place of "imine"
(Imin) (German nomenclature in brackets).
[4] See also: R . Appel and W. Biichner, Liebigs Ann. Chem., in
[ 5 ] 0.Buchner, Ph. D. Thesis, Universitat Heidelberg (1962).
A Fragmentation Reaction in the Adamantane
By Prof. Dr. H. Stetter and Dip1.-Chem. P. Tacke
Institut fur Organische Chemie, Technische Hochschule,
Aachen (Germany)
acid [I], which is easily ob3 -Bromoadamantane-I-carboxylic
tained by direct bromination of adamantane- 1-carboxylic
acid, was converted to the amide by way of its acid chloride.
Hofmann degradation yields N-[3-bromo-l-adamantyl]methylurethane (I), which on alkali treatment undergoes
fragmentation, whereby 3-methylenebicyclo[l,3,3]nonan-7one (11) is formed in high yield. Ozonolysis gives the previously unknown bicyclo[l,3,3]nonane-3,7-dione(Ill), which on
Wolff-Kishner reduction gives rise to bicyclo[I,3,3]nonane.
Despite the widespread current interest in both hydrocarbon
[I] and isonitrile derivatives [2] of transition metals, no
complexes have been described which contain both types of
group. We now report cyclopentadienyl metal isonitriles of
manganese, iron and nickel, analogous to the corresponding
hydrocarbon metal carbonyls.
Tris(pheny1 isocyanide) cyclopentadienylmanganese(I) was
obtained in 20 % yield as yellow crystals, m.p. 97 "C (from
pentane), when a solution of hexakis(pheny1 isocyanide)manganese iodide in dimethylformamide was added to cyclopentadienylsodium in tetrahydrofuran.
I .
The iron complex (11) was formed by direct displacement of
one molecule of carbon monoxide when dicarbonylcyclopentadienyliron iodide was treated with phenyl isocyanide in
tetrahydrofuran solution. This behaviour contrasts with the
reaction of the corresponding chloride with triphenylphosphine, whereby the halide ion is displaced rather than a
carbonyl group [3]. The product (11) was isolated by chromatography and formed blacK crystals m.p. 89"C, from
methylene chloride and ligroin; vmax. in the CNR and CO
stretching region: 2137 cm-1, 2058 cm-1 and 2000 cm-1.
Like carbon monoxide, phenyl isocyanide displaces both
cyclopentadienyl groups from dicyclopentadienyinickel,but
the desired mixed-complex was formed (again by analogy to
the corresponding carbonyl [4]) when dicyclopentadienylnickel and tetrakisbhenyl isocyanide)nickel were allowed to
react together in refluxing benzene. The ptoduct, deep red
plates, m.p. 91 OC (from pentanef, shows a single band at
2174 cm-1, i.e. the normal region for isonitrile groupings
bonded to single metal atoms [1,5]. No isonitrile-bridged
complexes appear to be known, but they would be expected
to absorb at lower frequency. The nickel complex is, therefore, formulated as having structure (III), whereas its
carbonyl analogue has two bridging CO groups.
Received, April 16th. 1962
[277/106 IE]
[I] H. Zeiss: Organometallic Chemistry. Reinhold, New York
I1 m.p. &O*C
I m.p. 80-81 OC
I11 m.p. 249"C, decomp.
IV m.p. 225°C
On reducing (IIi) with lithium aluminum hydride, bicyclo[1,3,3]nonane-3,7-diol (m.p. 231-234 "C) was isolated as an
isomeric mixture. Analogous to the preparation of 6,6-dimethyl-2-oxa-adamantane [2], treatment with sulfuric acid
gave the hitherto unknown' cyclic ether, 2-oxa-adamantane
(IV). On condensation with nitromethane [2] compound (111)
gives 1,3-dihydroxy-2-nitroadamantane
(m.p. 167 "C).
Received, April 1 Ith. 1962
[Z 262/90 IE]
[l] H . Stetter and J. Mayer, Chem. Ber. 95, 667 (1962).
[2] H. Stetter and J. Mayer, Angew. Chem. 71,430 (1959); Chern.
Ber. 92, 2664 (1959).
Angew. Chem. internat. Edit.
[2] L. Malatesta in F. A . Cotton: Progress in Inorganic Chemistry.
Interscience, New York 1959, Vol. I, p. 283.
[3] A . Davison, M . L. H. Green and G . Wilkinson, J. chem. SOC.
(London) 3172 (1961).
[4] E. 0 .Fischer and C. Palm, Chem. Ber. 91, 1725 (1958).
[ 5 ] F. A . Cotton and R . V . Parish, J. chem. SOC.(London) 1440
(1960); F. A . Cotton and F. Zingales, J. Amer. chem. SOC.83,351
1 Vol. 1 (1962)
No. 6
Carbon-Free Metal Chelate Rings
Containing Boror
By Priv.-Doz. Dr. F. Umland and DipLChem. D. Thierig
Institut fur Anorganische Chemie, Technische Hochschule
Hannover (Germany
Chelate rings with the basic structure (I) are obtained by the
reaction of borinic acid esters or anhydrides with certain
metal salts and oximes [I].
Example: An aqueous solution of a nickel salt, arnyl alcohol,
and methanolic s'olutions of dimethylglyoxime and of
Flavognost @ [diphenylborinic acid aminoethyl ester complex (Hey1 and Co., Hildesheim, West Germany)] are mixed
in the volume ratio 1:3 : 1 : 1, and the mixture is boiled for 1 to
2 minutes. A yellow solution of (11) results. The reaction can
be carried out on a microanalytical scale. On a preparative
scale, it is better to fuse nickel dimethylglyoximate with excess Flavognost for a short time at approximately 200'C.
Compound (11) is then extracted from the solidified melt with
benzene and, for further purification, recrystallized from a
methanol-chloroform mixture. Depenidng on the proportions
of this mixture, fine yellow-orange needles or coarse redorange rods are obtained. Compound(I1) is readily soluble
in non-polar solvents, sparingly soluble in polar solvents,
and insoluble in water. Even in the presence of wetting
agents it is not perceptibly saponified by hot water. After
Tosylated 42-cyclopentenylmethanol(I; X = OTs), m.p.
3-4 "C, likewise reacts to form a three-membered ring
through solvolysis in abs. methanol with the addition of
CaC03. A mixture of the stereoisomers of methyl bieyclo[3,1,0]hex-2-yl ether (11; X = OCH3), b.p. 6O0C/5O mm., is
formed in 80% yield, alongside other products.
Az-Cyclopentenylmethanol(I; X = OH) was prepared both by reaction
of Az-cyclopentenyl chloride with Mg and paraformaldehyde (yield 20 %,
b.p. 50-51 "C/IZ mm., alongside 50 % hydrocarbon), and through
reduction of ethyl A2-cyclopentenylcarboxylate(I; X = COzCzHs) with
LiAlH4. The ethyl ester (I: X = C02CzHS) is accessible from the nitrile
(I: X = CN) via the iminoether chloride.
Received, April 19th. 1962
[Z 271/100 IE]
[ 11 M. Hanack and X.ANmendinger, unpublished results.
[2] Cf. N. P. Buu-Hoiand P. Caignant, Bull. SOC.chim. France
12, 978 (1945).
By Prof. Dr. H. Bredereck, Dr. B. Fohlisch
and cand. chem. K.Walz
Institut fur Organische Chernie and Organisch-Chemische
Technologie der Technischen Hochschule Stuttgart (Germany)
M = metal
R', Rz = aryl, halogen (F, Cl)
R3, R4 = alkyl, aryl
dissolving (11) in concentrated sulfuric acid, followed by
neutralization, nickel dimethylglyoximate is regenerated. On
heating to 3O5-31O0C, the compound turns dark and
The corresponding olive-green palladium chelate, the violet
copper(1I) chelate, and the reddish iron(I1) chelate are obtained similarly.
Received, April 16th. 1962
In the course of our investigations on acid amide-acid chloride
complexes, we have synthesised representatives of the previously unknown dialkylaminoisocyanides (11). The action
of phosgene on an ice-cooled solution of N,N-disubstituted
formylhydrazine (I) in methylene chloride and in the presence
of a tertiary amine, preferably trimethylamine, leads to the
formation of dialkylaminoisocyanides (11; R = C2H5, b.p.
39 "C/16 mm.; R = n-C4Hg, b.p. 42 "Cl0.l mm.).
+ COClz + 2 (CHs)3N
[Z 2641103 IE]
[l] G. N. Schruuzer has prepared similar compounds (personal
communication; Chem. Ber. in the press).
Rearrangements of A 2-Cyclopentenylmethane
Dialkylaminoisocyanides - which can formally be considered
as diallcylamides of fulminic acid - are highly reactive,
unstable, evil-smelling liquids. If a solution of formic acid
in ethyl acetate is added, compound (0 is re-formed with
evolution of carbon monoxide. The infrared spectra of (11)
show a characteristic band at 2100 cm-1.
Received, April 24th. 1962
[Z 269/99 IE]
By Priv.-Doz. Dr. M. Hanack
and cand. chem. H. J. Schneider
Pharmazeutisch-chemisches Institut
der Universitat Tubingen (Germany)
As a result of homoallyl resonance, 4 7 cyclopentenylmethylamine (I; X = NH2) forms a three-membered ring on reaction
with HNOz (in 10 % acetic acid, 60 "C, 5 hrs.). A mixture
composed of the stereoisomers (58 %) of bicyclo[3,1,0]hexan-2-01 (11; X = OH), 12 % Az-cyclopentenylmethanol
(I; X = OH) and 12% A3-cyclohexenol is obtained alongside
the acetates (18 %). The nuclear magnetic resonance spectrum of (11) shows a three-membered ring; the infrared spectra of the alcohols separated by preparative ,gas chromatography are identical with independent preparations 111.
For the preparation of (I; X = N H d , Dz-cyclopentenyl chloride (in
aqueous acetone) is allowed to react with KCN 121 and, after removal
of Az-cyclopentenol (cu. 20 %), the Az-cyclopentenyl nitrile (yield 50 %:
b.p. 55-57 "C/12mm.) is reduced with LiAIH4 to give the required
product in 50 % yield (b.p. 48-50 9 1 2 mm.). The amine is pure by
gas chromatography. Benzoyl compound, m. p. 120-104°C.
Stereospecific Formation of Cyclopropanes by
Reaction of Diphenyldibromomethane with
Methyllithium and Olefins
By Prof. Dr. Gerhard L. Closs and Dr. Liselotte E. Closs [*I
Department of Chemistry, The University of Chicago,
Chicago, Illinois (USA)
According to SkeNet al. [l], the photolysis of diphenyldiazomethane leads to a carbene whose addition to olefins is not
stereospecific [2]. Accordingly, a triplet ground-state was
ascribed to diphenylmethylene.
While investigating the reactivity of carbenes as a function
of their method of preparation, it was of interest to prepare
diphenylcarbene by another route.
Reaction of diphenyldibromomethane with methyllithium at
-10 "C in the presence of olefins [3]leads to 1,l-diphenylcyclopropane in moderate yields (10-15 %), alongside larger
amounts of tetraphenylethylene.
Mixtures resulting from reaction with trans- and cis-but-2enes were analysed by gas chromatography; this showed that
the additions are completely stereospecific. Both isomers of
l,l-diphenyl-2,3-dimethylcyclopropane were charactensed
Angew. Chem. internat. Edit. 1 Vol. I (1962) / No. 6
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containing, free, metali, ring, carbon, boron, chelate
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