Methyl isothiocyanate → HCID 19780562, compound

HRID 2081732Notes

Reaction equation

HRID 2081732 reaction equation
[C:1]1([CH:7]2[CH2:12][CH2:11][CH2:10][CH2:9][C:8]2=[O:13])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[K].[O-]CCCC.[CH3:20][N:21]=[C:22]=[S:23]>O1CCCC1.C(Cl)(Cl)Cl.O>[CH3:20][NH:21][C:22]([C:7]1([C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=2)[CH2:12][CH2:11][CH2:10][CH2:9][C:8]1=[O:13])=[S:23]

Participants

8

Reactant 4

HCID 11167Methyl isothiocyanateHCID 955922-PhenylcyclohexanoneHCID 5462222PotassiumHCID 12476378Butan-1-olate

Product 1

HCID 19780562HCID 19780562, compoundYield 35.5%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6212ChloroformSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

A solution of (±)-2-phenylcyclohexanone (3.0 g, 17.2 mmol) at -15° C. in tetrahydrofuran (40 ml) was treated with potassium t.-butoxide (1.9 g, 17.2 mmol) during 2 minutes. After 15 minutes at -15° C., a solution of methyl isothiocyanate (1.38 g, 19 mmol) in tetrahydrofuran (20 ml) was added dropwise during 2 minutes and the resulting solution was stirred for 3 hours at 0° C. Water (200 ml) followed by chloroform (200 ml) were added to the reaction mixture and the aqueous layer was extracted with chloroform (200 ml). The combined organic extracts were washed with brine (150 ml) then dried over sodium sulphate. Concentration in vacuo (30° C.; 14 mm Hg) afforded a crude oil (4.2 g) which was purified by flash chromatography over silica gel eluting with a 1:1 mixture of diethyl ether and hexane to give (±)-N-methyl-2-oxo-1-phenylcyclohexanecarbothioamide (1.5 g, 6.1 mmol) m.p. 86° C. N.M.R. (CDCl3) 1.62-2.05 (c, 4H), 2.42-2.56 (m, 2H), 2.64-2.84 (ddd, 1H), 3.0-3.18 (c, 4H), 7.23-7.45 (c, 5H) 8.72-9.06 (broad singlet, 1H). Found C, 68.3; H, 7.2; N, 5.8; S, 13 0%, C14H17NOS requires C, 68.0; H, 6.9; N, 5.7; S, 13.0%.

Workup

  1. additionwere added to the reaction mixture
  2. extractionthe aqueous layer was extracted with chloroform (200 ml)
  3. washThe combined organic extracts were washed with brine (150 ml)
  4. dry with materialthen dried over sodium sulphate
  5. concentrationConcentration in vacuo (30° C.; 14 mm Hg)
  6. customafforded a crude oil (4.2 g) which
  7. customwas purified by flash chromatography over silica gel eluting with a 1:1 mixture of diethyl ether and hexane

Sources & evidence

ORD record
ord-e4c62619dab746f38734fdfc62940c80
Source dataset
uspto-grants-1993_02
Patent number
US05185375

Reaction notes

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