Hydrochloric Acid → 2-Sulfanylidene-2,3-dihydro-1,3-benzothiazole-6-carbonitrile

HRID 1847973Notes

Reaction equation

HRID 1847973 reaction equation
[NH2:1][C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][C:3]=1Cl.[C:11]([S-:16])(=[S:15])OCC.[K+].Cl>CN(C=O)C>[SH:16][C:11]1[S:15][C:3]2[CH:4]=[C:5]([C:6]#[N:7])[CH:8]=[CH:9][C:2]=2[N:1]=1

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 5198964-Amino-3-chlorobenzonitrileHCID 2735045Potassium ethylxanthate

Product 1

HCID 1785095042-Sulfanylidene-2,3-dihydro-1,3-benzothiazole-6-carbonitrileYield 84%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of 4-amino-3-chlorobenzonitrile (12.2 g, 80.2 mmol) from Step 1 of this Example in DMF (60 mL) was added potassium O-ethyl carbonodithioate (28.9 g, 180.7 mmol) at rt. The mixture was refluxed for 4 h. After cooling to rt, the reaction mixture was poured into ice water and acidified with 2N aq HCl. The tan solids were collected and dried in vacuum oven overnight. Then the solids were refluxed with 500 mL of CHCl3 for 10 min. After cooling to rt, the mixture was treated with 200 mL of hexanes and sonicated for 20 min. The pale brown solid was collected by filtration to give 2-mercaptobenzo[d]thiazole-6-carbonitrile (12.9 g, 84%). 1H NMR (300 MHz, DMSO-d6) δ 14.16 (br s, 1H), 8.23 (d, J=0.9 Hz, 1H), 7.83 (dd, J=1.3, 8.5 Hz, 1H), 7.31-7.51 (m, 1H).

Workup

  1. customat rt
  2. temperatureThe mixture was refluxed for 4 h
  3. customThe tan solids were collected
  4. customdried in vacuum oven overnight
  5. temperatureThen the solids were refluxed with 500 mL of CHCl3 for 10 min
  6. temperatureAfter cooling to rt
  7. additionthe mixture was treated with 200 mL of hexanes
  8. customsonicated for 20 min
  9. filtrationThe pale brown solid was collected by filtration

Sources & evidence

ORD record
ord-60b96e40329847bc9bd47d100e9bfe25
Source dataset
uspto-grants-2015_02
Patent number
US08952058B2

Reaction notes

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