Hydrochloric Acid → Isotiquimide

HRID 1974028Notes

Reaction equation

HRID 1974028 reaction equation
C(NC(C)C)(C)C.C([Li])CCC.CCCCCC.[CH3:19][C:20]1[C:29]2[CH2:28][CH2:27][CH2:26][CH2:25][C:24]=2[N:23]=[CH:22][CH:21]=1.C[Si]([N:34]=[C:35]=[S:36])(C)C.Cl>C1C=CC=CC=1.O>[CH3:19][C:20]1[C:29]2[CH2:28][CH2:27][CH2:26][CH:25]([C:35](=[S:36])[NH2:34])[C:24]=2[N:23]=[CH:22][CH:21]=1

Participants

9

Reactant 6

HCID 313Hydrochloric AcidHCID 7912DiisopropylamineHCID 8058HexaneHCID 75297IsothiocyanatotrimethylsilaneHCID 1856675,6,7,8-Tetrahydro-4-methylquinolineHCID 178418339Butyllithium

Product 1

HCID 3037235IsotiquimideYield 19.4%

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 962WaterSolvent

Procedure

A stirred solution of di-isopropylamine (12.2 ml, 0.085 mol) in benzene (100 ml) at 0° C was treated dropwise with a 9% w/v solution of butyl lithium in hexane (62 ml, 0.085 mol). After 1 hour at 0° C, 4-methyl-5,6,7,8-tetrahydroquinoline (12.8 g, 0.085 mol) was added dropwise and then after a further hour the anion was treated dropwise with trimethylsilyl isothiocyanate (12.2 ml, 0.095 mol). After 0.5 hours at 0° C and 0.5 hours at room temperature the reaction mixture was diluted with water (50 ml) and the pH adjusted to 2.0 with conc. HCl. The aqueous layer was separated and adjusted to pH 10.0 with solid sodium carbonate and extracted with chloroform (3 × 50 ml) and the combined extracts were dried over MgSO4, filtered and the solvent was removed in vacuo. The residual oil was triturated with n-hexane to give 4-methyl-5,6,7,8-tetrahydroquinoline-8-thiocarboxamide (3.4g, 19%). The hydrochloride was prepared by dissolving in hot iso-propyl alcohol adding excess ethereal HCl solution and allowing to crystallise to give 4-methyl-5,6,7,8-tetrahydroquinoline-8-thiocarboxamide, hydrochloride m.p. 212-3° C. (Found: C, 54.9; H, 6.4; N, 11.5. C11H14N2S. HCl requires C, 54.4; H, 6.2; N, 11.5%).

Workup

  1. waitAfter 0.5 hours at 0° C
  2. customThe aqueous layer was separated
  3. extractionextracted with chloroform (3 × 50 ml)
  4. dry with materialthe combined extracts were dried over MgSO4
  5. filtrationfiltered
  6. customthe solvent was removed in vacuo
  7. customThe residual oil was triturated with n-hexane

Sources & evidence

ORD record
ord-e28d89be4c414935855c7ac3d274a7ee
Source dataset
uspto-grants-1976_12
Patent number
US04000142

Reaction notes

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