(R)-(+)-1-Phenylethyl isocyanate → HCID 14074449, compound

HRID 2309230Notes

Reaction equation

HRID 2309230 reaction equation
[F:1][C:2]([F:19])([F:18])[CH:3]([C:5]1[CH:10]=[CH:9][CH:8]=[C:7]([O:11][C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)[N:6]=1)[OH:4].[C:20]1([C@H:26]([N:28]=[C:29]=[O:30])[CH3:27])[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=1>CN(C)C1C=CN=CC=1.C1C=CC=CC=1.CCOCC>[O:11]([C:7]1[N:6]=[C:5]([CH:3]([O:4][C:29](=[O:30])[NH:28][CH:26]([C:20]2[CH:25]=[CH:24][CH:23]=[CH:22][CH:21]=2)[CH3:27])[C:2]([F:1])([F:18])[F:19])[CH:10]=[CH:9][CH:8]=1)[C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=1

Participants

6

Reactant 2

HCID 7018262(R)-(+)-1-Phenylethyl isocyanateHCID 15592688HCID 15592688, compound

Product 1

HCID 14074449HCID 14074449, compound

Reagents, catalysts & solvents 3

HCID 142844-(Dimethylamino)pyridineCatalystHCID 241BenzeneSolventHCID 3283Diethyl EtherSolvent

Procedure

A stirred solution of 2.40 g (8.91 mmol) of α-trifluoromethyl-6-phenoxy-2-pyridinemethanol, 1.38 g (9.36 mmol) of (R)-(+)-1-phenylethyl isocyanate, and 22 mg (0.18 mmol) of 4-dimethylaminopyridine in 9 ml of benzene under a nitrogen atmosphere was heated at 50° C. for 17 hours. The reaction mixture was then diluted with 150 ml of ether and washed with 25 ml of 1N aqueous HCl, 25 ml of saturated aqueous NaHCO3, and 25 ml of saturated aqueous NaCl. The organic layer was dried (MgSO4) and concentrated under reduced pressure. Repeated chromatography of the residue on silica gel with benzene afforded first 1.77 g (48%) of the [R-(R*,R*)] diastereomer: Rf =0.10 (SiO2, benzene); 1H NMR (CDCl3) δ 1.52 (d, 6.8 Hz, 3H), 4.83 (quintet, 7.1 Hz, 1H), 6.01 (q, 6.1 Hz, 1H), 6.83 (d, 8.2 Hz, 1H), 7.11-7.37 (br m, 12H), and 7.68 (t, 7.8 Hz, 1H); and then 1.77 g (48%) of the [S-(R*,S*)] diastereomer: Rf =0.09 (SiO2, benzene); 1H NMR (CDCl3) δ 1.47 (d, 6.8 Hz, 3H), 4.80 (quintet, 7.0 Hz, 1H), 5.98 (q, 6.9 Hz, 1H), 6.86 (d, 8.3 Hz, 1H), 7.13-7.42 (br m, 12H), and 7.72 (t, 7.8 Hz, 1H).

Workup

  1. washwashed with 25 ml of 1N aqueous HCl, 25 ml of saturated aqueous NaHCO3, and 25 ml of saturated aqueous NaCl
  2. dry with materialThe organic layer was dried (MgSO4)
  3. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-b8d0ce855b8e47a28a88047a0275d587
Source dataset
uspto-grants-1987_09
Patent number
US04694013

Reaction notes

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