Ethyl Acetate → HCID 86599792, compound

HRID 131178Notes

Reaction equation

HRID 131178 reaction equation
[OH:1][C:2]1[C:3]([C:12]#[N:13])=[CH:4][C:5]2[CH2:6][CH2:7][CH2:8][CH2:9][C:10]=2[CH:11]=1.[OH-].[K+].[CH3:16][N:17]([CH3:21])[C:18](Cl)=[S:19].C(OCC)(=O)C>CC(C)=O.O>[C:12]([C:3]1[C:2]([O:1][C:18](=[S:19])[N:17]([CH3:21])[CH3:16])=[CH:11][C:10]2[CH2:9][CH2:8][CH2:7][CH2:6][C:5]=2[CH:4]=1)#[N:13]

Participants

7

Reactant 4

HCID 8857Ethyl AcetateHCID 14797Potassium HydroxideHCID 27871Dimethylthiocarbamoyl chlorideHCID 21864957HCID 21864957, compound

Product 1

HCID 86599792HCID 86599792, compoundYield 64.3%

Reagents, catalysts & solvents 2

HCID 180AcetoneSolvent2×HCID 962WaterSolvent2×

Procedure

To a solution of 3-hydroxy-5,6,7,8-tetrahydronaphthalene-2-carbonitrile prepared in method II-2 (3.00 g, 17.3 mmol) in acetone (60 mL) was added dropwise a solution of potassium hydroxide (1.07 g, 19.1 mmol, 1.1 eq) in water (40 mL) at 0° C. After stirring for 45 min, a solution of dimethylthiocarbamoyl chloride (2.35 g, 19.1 mmol, 1.1 eq) in acetone (40 mL) was added at 0° C. over 30 min. The reaction mixture was then stirred at room temperature for 16 h, and poured into ethyl acetate and water. The organic layer was washed with saturated aqueous ammonium chloride, water, and brine. The combined aqueous wash was re-extracted with ethyl acetate, and the organic washes were dried over magnesium sulfate and evaporated at reduced pressure. The crude oil was crystallized from ether/hexane to give dimethyl-thiocarbamic acid O-(3-cyano-5,6,7,8-tetrahydro-naphthalene-2-yl) ester (2.90 g, 64.3%) as a beige solid. 1H-NMR (Acetone-d6) δ 7.46 (s, 1H), 6.98 (s, 1H), 3.43 (d, J=4.2 Hz, 6H), 2.80 (m, 4H), 1.81 (m, 4H); MS ES (MH+=261). Rf=0.70 (30% ethyl acetate-hexane).

Workup

  1. stirringThe reaction mixture was then stirred at room temperature for 16 h
  2. washThe organic layer was washed with saturated aqueous ammonium chloride, water, and brine
  3. washThe combined aqueous wash
  4. extractionwas re-extracted with ethyl acetate
  5. dry with materialthe organic washes were dried over magnesium sulfate
  6. customevaporated at reduced pressure
  7. customThe crude oil was crystallized from ether/hexane

Sources & evidence

ORD record
ord-523d16a8332849eaad83f6601e28442e
Source dataset
uspto-grants-2008_06
Patent number
US07384947B2

Reaction notes

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