Methyl isothiocyanate → HCID 19876107, compound

HRID 1886378Notes

Reaction equation

HRID 1886378 reaction equation
[Cl:1][C:2]1[N:7]=[CH:6][C:5]([CH:8]2[CH2:13][CH2:12][CH2:11][CH2:10][C:9]2=[O:14])=[CH:4][CH:3]=1.CC(C)([O-])C.[K+].[CH3:21][N:22]=[C:23]=[S:24]>O1CCCC1>[CH3:21][NH:22][C:23]([C:8]1([C:5]2[CH:6]=[N:7][C:2]([Cl:1])=[CH:3][CH:4]=2)[CH2:13][CH2:12][CH2:11][CH2:10][C:9]1=[O:14])=[S:24]

Participants

5

Reactant 3

HCID 11167Methyl isothiocyanateHCID 19876135HCID 19876135, compoundHCID 23665647Potassium tert-butoxide

Product 1

HCID 19876107HCID 19876107, compoundYield 52%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A vigorously stirred solution of 2-(6-chloropyrid-3-yl)cyclohexanone (0.36 g 1.7 mmol) in anhydrous tetrahydrofuran (10 ml) under argon at -15° C. was treated with potassium t-butoxide (0.19 g, 1.7 mmol). The resulting mixture was stirred for 2 hours at room temperature before the addition of a solution of methyl isothiocyanate (0.12 g, 1.7 mmol) in dry tetrahydrofuran (2 ml). The mixture was stirred for a further 48 hours at room temperature, concentrated in vacuo and the residue treated with water (30 ml) and extracted with ethyl acetate (50 ml). The organic extract was dried over magnesium sulphate and then concentrated in vacuo (30° C.; 14 mmHg) to give a yellow oil which was purified by flash chromatography over silica gel eluting with ethyl acetate: hexane 4:6 to give (±)-N-methyl-2-oxo-1-(6-chloropyrid-3-yl) -cyclohexanecarbothioamide (0.25 g) m.p. 172°-3° C. NMR (CDCl3) 1.64-2.14(m 4H); 2.4-2.65(m 2H); 2.7-2.8(m 2H); 3.14-3.16(d,3H); 7.26-7.34 (ddd,1H); 7.6-7.66(dd,1H); 8.2(d,1H); 8.84-9.06 (broad singlet, 1H). Calculated for C13H15ClN2OS; C,55.2%; H,5.35%; N,9.91%, C1,12.5%; Found C,55.3%; H,5.3%; N,9.8%;C1,12.6%.

Workup

  1. concentrationconcentrated in vacuo
  2. additionthe residue treated with water (30 ml)
  3. extractionextracted with ethyl acetate (50 ml)
  4. extractionThe organic extract
  5. dry with materialwas dried over magnesium sulphate
  6. concentrationconcentrated in vacuo (30° C.; 14 mmHg)
  7. customto give a yellow oil which
  8. customwas purified by flash chromatography over silica gel eluting with ethyl acetate: hexane 4:6

Sources & evidence

ORD record
ord-1fe11c6efb404a8cb6a96c3f684dd552
Source dataset
uspto-grants-1992_09
Patent number
US05151436

Reaction notes

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