Cyclo hexanone

Wallach has synthesised i-menthone by condensing 1, 4-methyl-cyclo-hexanone with bromo-isobutyric ester from the condensation product he prepared i-menthene, which was converted into i-menthenone, by means of its nitrosochloride, whence i-menthone resulted by reduction. 

Phosphorus oxychloride, reaction with dimethy Iformamide and cyclo hexanone, 46,18... 

Alkalimetallhydride reduzieren nicht. Man isoliert ausschlieBlich Olefine22. Bei der Umsetzung von Cyclo-hexanon-N-phenyl-N-tosyl-hydrazon mit Lithiumhydrid erhalt man die Azo-Stufe der Bamford-Stevens-Reaktion unter Bildung von Phenylazo-cyclohexen1. ... 

B. 2,2-(Trimethylenedithio)cyclohexanone. A solution of 3.02 g. (0.02 mole) of freshly distilled 1-pyrrolidinocyclohexene, 8.32 g. (0.02 mole) of trimethylene dithiotosylate4 (Note 2), and 5 ml. of triethylamine (Note 3) in 40 ml. of anhydrous acetonitrile (Note 4), is refluxed for 12 hours in a 100-ml., round-bottom flask under a nitrogen atmosphere. The solvent is removed under reduced pressure on a rotary evaporator, and the residue is treated with 100 ml. of aqueous 0.1 N hydrochloric acid for 30 minutes at 50° (Note 5). The mixture is cooled to ambient temperature and extracted with three 50-ml. portions of ether. The combined ether extracts are washed with aqueous 10% potassium bicarbonate solution (Note 6) until the aqueous layer remains basic to litmus, and then with saturated sodium chloride solution. The ethereal solution is dried over anhydrous sodium sulfate, filtered, and concentrated on a rotary evaporator. The resulting oily residue is diluted with 1 ml. of benzene and then with 3 ml. of cyclohexane. The solution is poured into a chromatographic column (13 x 2.5 cm.), prepared with 50 g. of alumina (Note 7) and a 3 1 mixture of cyclohexane and benzene. With this solvent system, the desired product moves with the solvent front, and the first 250 ml. of eluent contains 95% of the total product. Elution with a further 175 ml. of solvent removes the remainder. The combined fractions are evaporated, and the pale yellow, oily residue crystallizes readily on standing. Recrystallization of this material from pentane gives 1.82 g. of white crystalline 2,2-(trimethylenedithio)cyclo-hexanone, m.p. 52-55° (45% yield) (Note 8). 

RuClj(C H )]j was used for deracemisation of alcohols, by oxidation of secondary alcohols to the ketone with [RuCl3(C H )]3/(R)-BINAP/(R,R )-DPEN/cyclo-hexanone/THF/K( BuO)/60°C. The oxidation may occur by transfer hydrogenation, followed by reduction with back to the alcohol [962],... 

Bei der Hydrierung von Isochinolin in Essigsaure in Gegenwart von 1,2 mol-equiv. Cyclo-hexanon und Platin(IV)-oxid als Katalysator bis zur Beendigung der Wasserstoff-Aufnah-me erhalt man unter C-Substitution 4-Cyclohexyl-l,2,3,4-tetrahydro-isochinolin (83%)4 ... 

An early example using this strategy is the cyclization of 2-methyl-2-(tosyloxymethyl)cyclo-hexanone to give l-methylbicyclo[3.1.1]heptan-6-one (1) in 36% yield (see also Table 12).2,3 An undesired product, namely l-methylbicyclo[3.2.0]heptan-6-one (2) was also produced, the formation of 2 can be rationalized by the mechanism shown.2,3... 

Cyclo- hexanone Cyclo- hexenol Cyclo- hexenone Cyclohexene oxide Alcohols mole ratio... 

This transformation can be applied to 2-methoxycydohexanone. The racemic ketone was hydrogenated with the (S)-XylBINAP/(S,S)-DPEN/Ru catalyst in the presence of a base at 5 °C and under 50 atm of H2 to give (1 R,2S)-2-methoxycy-clohexanol in 99% ee (cis trans=99.5 0.5) (Scheme 12) [37]. This alcohol can be converted to the potent antibacterial agent sanfetrinem after it is oxidized to the chiral ketone. In the same manner, racemic 2-(ferf-butoxycarbonylamino)cyclo hexanone was converted with the (S)-XylBINAP/(R)-DAIPEN/Ru catalyst under basic conditions to the 1S.2R alcohol in 82% ee (cis trans=99 l) [33]. 

Conjugation has a great influence on the structure of aliphatic and alicyclic compounds. Thus, the existence of an amino form has been established (in addition to the extreme case of aromatic amines17) for all compounds where the double bond is conjugated with a carbonyl group (or its equivalent),12 with esters12,18 and nitriles of a,/8-un-saturated /8-amino acids,519,20 and with /8-amino-ketones. The /3-keto-esters ethyl 2-cyclopentanone- 1-carboxylate and ethyl 2-cyclo-hexanone-l-carboxylate exist as mixtures containing 95% of the keto... 

Two other nucleophilic substitution reactions of pyridine iV-oxides deserve mention and further study to determine the effects of substituents. Pyridine N-oxide, benzoyl chloride, and the piperidine enamine of cyclohexanone give a good yield of 2-(2 -pyridyl)cyclo-hexanone (155) (63%).360 When W-methoxy-4-picolinium methyl... 

Fig. 17.32. Oxidative cleavage of an asymmetric ketone with complementary regiose-lectivities. Lactone A is obtained by Baeyer-Villiger oxidation of menthone [2-methyl-5-(l- methylethyl)cyclo-hexanone]. Alternatively, one may first convert menthone into the silylenol ether B and cleave its C=C double bond with ozone to obtain a silyl ester containing an a-methoxyhydroperoxide group as a second functional group (which resembles the unstable structural element of the so-called ether peroxides cf. Figure 1.38). The latter is reduced with NaBH4tothe hydroxylated silyl ester C. The hydroxycarboxylic acid is obtained by acid-catalyzed hydrolysis. It cyclizes spontaneously to give lactone D.

Test Isovaler- aldehyde Benz- aldehyde Cyclo- hexanone Acetone Unknown... 

Adipic Acid Nitric acid oxidizes cyclo-hexanone-cyclohexanol mixtures to adipic acid, which goes into nylon 6,6, other resins and plasticizers. 

Wir haben bei unseren Untersuchungen ein anisotherm arbeitendes Kalorimeter verwendet und die Mischungswarmen von TBP, Cyclo-hexanon und MIBK mit Wasser und Mineralsauren bestimmt (297). Die ermittelten Verteilungsenthalpien fiir die Extraktion von Eisen- und Kobaltrhodanid, Wismut-, Quecksilber-, Cadmium- und Zinkjodid sowie Uranylnitrat sind in Tabelle 4 zusammengefaBt. 

Indol 1-Isopropyl-4,5,6,7-tetrahy-dro- E6a, 685 (4-R — 1-oxa-4-aza-spiro[4.5]decan + Cyclo-hexanon)... 

Ar-PdCl) E21b, 2058 (Cyclo-hexanon + Ar —MgX) Cyclohexen 6-Hydroxy-1-phenyl-Vl/la, 1, 50 Cyclopentan... 

Thioxanthylium 1,2,3,4-Tetrahy-dro- -perchlorat E7a, 214 [2-(Arylthio-methylen)-cyclo-hexanon + (H3C —CO)20]... 

Benzimidazol 2-(l-Hydroxy-cyclo-hexyl)- E8c, 358 l-[CH(OR)2-benzimidazol + R —Li/Cyclo-hexanon ... 

Benzothiophen 2-Atnino-6-tert.-butyl-3-cyan- E6a, 223 (Cyclo-hexanon + NC —CH2 —CN/S8)... 

Di-5-bromovanillidene-cyclo- hexanone 7.2- 8.6 yellow-green—orange-red... 

Ruder, S.M., and Kulkarni, V.R., Phase transfer catalysed alkylation of 2-(diethoxyphosphinyl)cyclo-hexanone, Synthesis, 945, 1993. 

Additive Solution (%) Cyclo- hexanone (%) Water (%) Cyclohexanone/ water (-) Water flux (-) Permea- tion (-)... 

Cyclo- hexanone 111 129 1.1 Water, dry chemical, or carbon dioxide Not pertinent Not pertinent 788 No ... 

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