Tosylhydrazone camphor

Camphor tosylhydrazone, with methyllithium to give 2-bor-nene, 51, 66... 

Methylcyclohexene, from 2-methyl-cyclohexanone tosylhydrazone and methyllithium, 51,69 Methylenecyclopropanes, 50,30 Methyl iodide, with triphenyl phosphite and cyclohexanol, 51,45 with triphenyl phosphite and neopentyl alcohol, 51,44 METHYL ftrans-2-IODO-l-TETRA-LIN)CARBAMATE, 51,112 Methyl (frans-2-iodo-l-tetralin)carba-mate, with potassium hydroxide to give 1,2,3,4-tetrahydronaph-thalene(l,2)imine, 51,53 Methyllithium, with camphor tosylhydrazone to give 2-bomene, 51, 66... 

Reduction of tosyl- and trisylhydrazones.3 The reagent (1 equivalent) reduces tosylhydrazones of ketones to alkanes in yields of 60-85% (GLC). The reduction is Subject to sleric hindrance and so is not effective with the tosylhydrazone of camphor. Tosylhydrazones of aldehydes are reduced in moderate yield (about 50%). The reagent does not reduce tosylhydrazones of aromatic or a,/)-unsaturated aldehydes or ketones. 

Camphor tosylhydrazone is prepared in the following manner. To a 1-1. one-necked round-bottomed flask are added 44 g. (0.24 mole) of p-toluenesulfonylhydrazide, 31.6 g. (0.20 mole) of camphor, and 300 ml. of 95% ethanol. One milliliter of concentrated hydrochloric acid is added, and the flask is fitted with a reflux condenser. The solution is heated under reflux for 2 hours. The resulting solution is cooled in an ice bath, and the colorless needles are collected by suction filtration and dri( d in air (Note 11). Recrystallization from ethanol yields 50 g. (73 ), ) of [)ni( camphor tosylhydrazonc, m.p. 163-164°. 

Shapiro and Duncan01 have described use of the method for the synthesis of 2-bornene (6) from camphor tosylhydrazone (5). 

The carbene nature of this intermediate was detected by examination of camphor tosylhydrazone, which on heating with hydroxide gives a mixture ofcamphene and tricyclene. When the reaction was performed in acidic alcohols, such as ethylene... 

A new hydroxycamphene (566) has been found in two species of chrysanthemum. [2- H J-2-bornene can be made by the action of BuLi on camphor tosylhydrazone in hexane followed by DjO quench. In ether proton abstraction from solvent occurs before work-up. However, with less hindered hydrazones, deuterium incorporation is much reduced since the vinyl anion can apparently act as the base (B) in (567) and so capture a proton. ... 

The bicyclo[2,2,l]heptane system also continues to find employment for the assessment of new synthetic procedures, or for testing the efficacy of new reagents. Isolated yields of 50—65 % of ap-unsaturated aldehydes have been obtained by reaction of alkyl tosylhydrazones with butyl-lithium, addition of DMF, and hydrolysis however, reaction of camphor tosylhydrazone (381 X = NNHTs) according to this procedure only gave 10 % of the aldehyde (382 X = CHO), presumably because of unfavourable steric effects. " Trimethylsilyl trifluoromethanesulphonate is a mild reagent for converting carbonyl compounds into trimethylsilyl enol ethers, for example the production of (382 X = OSiMcj) from camphor (381 X = Experimental details... 

---