Cyclododecanone Oxime and Cyclo-octanone Oxime from Cyclododecatriene and Cyclo-octadiene.код для вставкиСкачать
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 Na0.S. 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 product. 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 (Germany) 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. 3068. Cyclododecanone Oxime and Cyclo-octanone Oxime from Cyclododecatriene and Cyclo-octadiene 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. (30) 3;:: 3~' YG" R (36) n Hydrogenation of (I) in the presence of noble-metal catalysts at 40 50 "C and atmospheric pressurc in methanol, for 688 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  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 . Received, August 28th. 1963 [Z 578/407 IE] 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.  W. G. Dairben and R. L. Corgill, Tetrahedron 12, 186 (1961).  R. Srinivasan, J . Amer. chem. SOL84, 3432 (1962). 0.L. Chapman and G.W.Borclen, Proc. chem. SOC. (London) 1963, 221.