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Cyclododecanone Oxime and Cyclo-octanone Oxime from Cyclododecatriene and Cyclo-octadiene.

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azotized and added dropwise over 1 hour at 10°C to a
solution of 1.06 g of NazC03 in 500 ml of water. Judging
from paper chromatograms (isoamyl alcohol/pyridine/5 %
ammonia l : l : l ) , the cyclic disazo compound (2) is
obtained almost exclusively (RF = 0.07; RF for (I) is
similar) with only traces of polymeric dyes (RF = 0). After
evaporating the solution to one-tenth of the original
volume, the product was precipitated with NaCl and recrystallized from water. When the second coupling is carried out
in a 50 times more concentrated solution, the yield falls to
about 50 %. The remainder consists of polymer.
., S G N a
example, proceeds smoothly to give cyclododecanone oxime
as major product. Palladium is especially suitable as catalyst;
if platinum is used, cyclododecylamine may be the major
Incontrast, hydrogenation of(2) or ofa-chlorocyclo-octanone
oxime with palladium or platinum affords a mixture of cyclooctanone oxime and cyclo-octanone together with cyclooctylamine, the Schiff's base from cyclo-octylamine and
cyclo-octanone, and traces of cc-aminoethylcyclohexane.
Received, August 23rd, 1963 [Z 5771408 IE]
German version: Angew. Chem. 75, 980 (1963)
[I] German Published Patent Application 1094741 (1959) Studiengesellschaft Kohle, invenlors: E. W i k e , E. W. Muller, and
J, Stedefeder. Our results indicate that the NOCl adducts described by L. I. Zakhurkin, 1J.S.S.R. Pat. 139317 (1960), are
dimeric nitroso compounds.
A Photochemical 1,2-Hydrogen Shift in the
Cyclohepta-1,3,5-triene Molecule
By Dr. R. Roth
lnstitut fur Organische Chemie der Universitat K61n
Dyestuff (2) forms red-brown needles (tetrahydrate after
drying at 130"C), dissolves in water to give a red solution
(maxima at 333 and 490 mp). Upon hydrolysis of (2) with
10 % hydrochloric acid, one or both amide bonds are split
to give free carboxylic acids (3) or (4). Reductive cleavage
with sodium dithionate yields only one product, viz. 1-(mAminobenzoylamino)-7-amim-8naphthol - 3,6 - disulfonic
acid. In contrast to (I), (2) does not react with naphthalenediazonium-4-sulfonic acid. Compounds (I), (3). and (4) and
the polymeric dyestuffs dissolve in water to give bordeauxred solutions.
Received, August 19th, 1963 [Z 575/400 IE]
German version: Angew. Chem. 75, 979 (1963)
[l] I. E. Balaban and H. King, J. chem. SOC.(London) 1927.
Cyclododecanone Oxime and Cyclo-octanone
Oxime from Cyclododecatriene and
By Dr. H. Metzger
Hauptlaboratorium der Badischen Anilin- & Soda-Fabrik AG,
Ludwigshafen am Rhein (Germany)
The addition of nitrosyl chloride onto cyclododecatriene normally yields a mixture of positional isomers of bis(ch1oronitrosocyclododecadiene)with the nitroso group and chlorine
atom on adjacent positions [I]. In the presence of hydrogen
chloride, however, nitrosyl chloride reacts with cyclododecatriene to give structural isomers of chlorohydroximinocyclododecadiene (I), likewise with adjacent substituents.
In the case of the trans,trans,cis-compound, a trrins-bond is
preferentially attacked. Cyclo-octa-l,5-diene behaves in
exactly the same way; only one mole of nitrosyl chloride is
added and 1-cI iloro-2-hydroximinocyclo-octene
(2) is formed.
Both rx-chloro-oximescan be converted into the hydroximinoamines ( S o ) or ( 3 b ) by treatment with secondary amines.
3;:: 3~'
Hydrogenation of (I) in the presence of noble-metal catalysts at 40 50 "C and atmospheric pressurc in methanol, for
Although thermal excitation of cyclohepta-l,3,5-triene gives
primarily a 1,Shydrogen shift [I], bicyclo[3,2,0]hepta-2,6diene [21 and toluene [3] have been described as the products
of photochemical excitation. By irradiating 7-deuterocyclohepta-1,3,5-triene (95 % C7H7D) in methanol with a highpressure mercury lamp in a Pyrex apparatus, we were able to
show that the valence isomcriiation is preceded by a 1,2hydrogen shift.
The first change in the NMR spectrum of the 7-deuterocyclohepta-I ,3,5-triene was observed after an irradiation time of
30min and is the superposilion of a doublet, the lines of
which have a fine structure, on the 1 :2: I-triplet of the aliphatic hydrogen atoms (split at this stage into a 1: 1: 1-triplet
by D(7)-H(7)-coupling).Theintensity ofthis new signal reaches
a maximum after ca. 4 hours; it then falls off to a constant
valuecorresponding to statistical distribution ofthedeuterium.
The primary occurrence of a doublet is characteristic for a
methylene group which posscsses only one a-hydrogen atom
and indicates a I ,2-hydrogen shift, the intramolecular character of which was demonstrated by mass-spectroscopic
analysis of the photolysis products.
Similarly, photolysis of 7-methyl- and 7-ethylcyclohepta1,3,5-triene(1 % in methanol, Pyrex apparatus, high-pressure
Hg lamp) gives primarily 1-methyl- and l-ethylcyclohepta1,3,5-triene; the structures of these compounds were proved
by hydrogenation to methyl- and ethylcycloheptane respectively, and by their NMR spectra which contained a doublet at
7.65 and 7.757 due to the two H(7)-hydrogen atoms. Irradiation of 7-vinylcyclohepta-I,3,5-triene even for a short time
gives only traces of 1-vinykycloheptatriene, as this is very
rapidly converted by a 1,Zhydrogen shift into the 2- and
7-vinyl isomers as a result of its ultraviolet absorption at
longer wavelength (hmax = 298 nip; E = 7000).
Hydrogen migration during the gas-phase photolysis of 7methoxycyclohepta-I ,3,5-trienc was also recently observed [4].
Received, August 28th. 1963
[Z 578/407
German version: Angew. Chem. 75, 921 (1963)
[ l ] C. Grundmann and G. Otfinann, Liebigs Ann. Chem. 582,
163 (1953); G. Biichi and E. M . Birrgcs, J. Amcr. chem. SOC.84,
3104 (1962); A . P.Ter Borg, H . Klou,slcrzicl, and N . Van Meurs,
Proc. chom. SOC.(London) I Y 6 2 , 350.
[2] W. G. Dairben and R. L. Corgill, Tetrahedron 12, 186 (1961).
[3] R. Srinivasan, J . Amer. chem. SOL84, 3432 (1962).
[4]0.L. Chapman and G.W.Borclen, Proc. chem. SOC. (London)
1963, 221.
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octanone, cyclododecatriene, octadiene, cyclododecanone, cycle, oximes
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