Carbon Dioxide → (+)-2-Cyano-2-methylhexanol

HRID 1198330Notes

Reaction equation

C1CC[CH:4]([N:7]=C=NC2CCCCC2)CC1.[CH2:16]([O:23][C:24]1[CH:29]=[CH:28][C:27]([C:30]2[C:31]([F:40])([C:37]([OH:39])=O)[CH:32]([F:36])[CH:33]=[CH:34][CH:35]=2)=[CH:26][CH:25]=1)[CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH3:22].FC1C(F)=CC=CC=1C1C=CC(OCCCCCCC)=CC=1.CN(CCN(C)C)C.[C:71](=[O:73])=[O:72]>C(Cl)Cl.C1COCC1.CCCCCC>[CH2:16]([O:23][C:24]1[CH:25]=[CH:26][C:27]([C:30]2[CH:35]=[CH:34][C:33]([C:71]([OH:73])=[O:72])=[C:32]([F:36])[C:31]=2[F:40])=[CH:28][CH:29]=1)[CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH3:22].[C:4]([C:31]([CH3:30])([CH2:32][CH2:33][CH2:34][CH3:35])[CH2:37][OH:39])#[N:7]

Participants

Conditions

Temperature: -78 °C

Procedure

0.1 mol of DCC, dissolved in methylene chloride, is added to a mixture of 0.1 mol of 4'-heptyloxy-2,3-difluorobiphenylcarboxylic acid (preparation: 0.1 mol of 2,3-difluoro-4'-heptyloxybiphenyl and 0.1 mol of TMEDA are dissolved in 200 ml of THF and the solution is cooled to -78° C. and reacted with 0.105 mol of a 1.6 N solution of Buli in hexane at this temperature. The reaction mixture is stirred at -78° C. for 3 hours and is then poured all at once onto 200 g of crushed dry ice. Customary working up gives 4'-heptyloxy-2,3-difluoro-biphenyl-4-carboxylic acid), 0.1 mol of optically active 2-cyano-2-methylhexan-1-ol (which can be prepared from optically active ethyl 2-methyl-2-butylcyanoacetate by reduction with LiBH4) and a catalytic amount of 4-N,N'-dimethylaminopyridine (DMAP) in 200 ml of methylene chloride at 0° C. The mixture is then stirred at room temperature for 12 hours. It is worked up in the customary manner and the product is purified by crystallization. Optically active 2-cyano-2-methylhexyl 4'-heptyloxy-2,3-difluorobiphenyl-4-carboxylate is obtained.

Workup

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Sources & evidence

ORD record: ord-96e07dc9a6534c00875e0fd16b2fe978
Source dataset: uspto-grants-1994_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05279764

Reaction notes

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