1 -Methyl-1 -nitrocyclohexane

In addition to the present method,2 1-amino-1-methylcyclo-hexane has been synthesized by the following procedures Ritter reaction, e.g., with 1-methylcyclohexanol (76%, 67%)3i 4 or 1-methylcyclohexene (35%,) 4 5 Hofmann reaction with 1-methyl-cyclohexanecarboxamide (80% as hydrochloride) 6 reduction of 1-methyl-l-nitrocyclohexane (63%) 6 Schmidt reaction with 1-methylcyclohexanecarboxylic acid (42%).6... 

On treatment of glutaraldehyde with 2-hydroxy-3-nitropropionic acid, only 2-nitrocyclohexane-l,3-diol could be isolated in 10% yield, indicating that, under the conditions used, a retro-aldol degradation takes place with liberation of nitromethane. However, when using methyl 2-methoxy-3-nitropropionate, which cannot undergo a retro-nitro-methane addition", products (101) and (102) are obtained in yields of 7 and 13% respectively... 

Alkynyl(phenyl)iodonium salts can be used for the preparation of substituted alkynes by the reaction with carbon nucleophiles. The parent ethynyliodonium tetrafluoroborate 124 reacts with various enolates of /J-dicarbonyl compounds 123 to give the respective alkynylated products 125 in a high yield (Scheme 51) [109]. The anion of nitrocyclohexane can also be ethynylated under these conditions. A similar alkynylation of 2-methyl-1,3-cyclopentanedione by ethynyliodonium salt 124 was applied in the key step of the synthesis of chiral methylene lactones [110]. 

We found that Michael addition of nitroalkanes had limited success with nitromethane owing to its nitroaldol reaction with the products formed from methyl vinyl ketone and cyclohexenone, for example. (It may be noted in this regard that although the product obtained in the reaction of methyl vinyl ketone with nitromethane was achieved in 78% yield [127], a recent report [128] described a 98 % yield by employing the less basic catalyst TBD at a higher temperature 0°C). However, 2-nitropropane and nitrocyclohexane were much better candidates for pro-azaphosphatrane-catalyzed reactions for which DBU and TMG typically require longer reaction times and afford only poor to modest product yields [127]. 

Integrated line intensities obtained from low-temperature n.m.r. spectra of cyclohexanol, nitrocyclohexane, and methylcyclohexane have been used to determine their conformational energies for the substituents OH, NO, and Me, A = 4.27, 5.31, and >7.5 kJ mol" S respectively. A similar low-temperature study of the conformational energies of MeS, MeSO, and MeSOj groups in cis-4-methyl-cyclohexanes has given. 4-values for these substituents of 4.18, 5.02, and 10.46 kJmol" respectively. 4-values of NHj, MeNH, and NMOj substituents in cyclo-... 

Very little has been done on the use of iron compounds in the synthesis of carbamates and ureas from nitro compounds. It has long been known [191] that heating aliphatic nitro compounds with an excess of Fe(CO)s (1.4 mol for 1.0 mol of nitro compound) in diglyme at 120-132 °C for 15-17 h affords low yields of formamides and ureas, but the yield of urea is at best 18.5 % (in the case of nitrocyclohexane yields were even lower for 1- or 2-nitropropane, 2-methyl-2-nitropropane, and 1-nitroadamantane). These experiments were among the first... 

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