Benzonitrile → 2-Aminobenzothiazole-6-carbonitrile

HRID 9102

Reaction equation

HRID 9102 reaction equation
[NH2:1][C:2]1[CH:9]=[CH:8][C:5]([C:6]#[N:7])=[CH:4][CH:3]=1.[S-:10][C:11]#[N:12].[K+].BrBr.C(#N)C1C=CC=CC=1>C(O)(=O)C.O>[NH2:12][C:11]1[S:10][C:3]2[CH:4]=[C:5]([C:6]#[N:7])[CH:8]=[CH:9][C:2]=2[N:1]=1

Participants

7

Reactant 4

HCID 7505BenzonitrileHCID 133964-AminobenzonitrileHCID 24408BromineHCID 516872Potassium thiocyanate

Product 1

HCID 43271392-Aminobenzothiazole-6-carbonitrileYield 67.4%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolvent2×HCID 962WaterSolvent

Conditions

Temperature
16 °C

Procedure

Two grams of 4-aminobenzonitrile was dissolved in about 40 mL acetic acid and the solution was cooled to about 16° C. About 3.3 g of potassium thiocyanate was added and the flask was equipped with an addition funnel. The addition funnel was charged with about 2.7 g bromine and about 5 mL acetic acid. This dark solution was then added to the benzonitrile solution in a dropwise fashion under good agitation and allowed to stir for about 16 hours. The slurry was then drowned into water and filtered. The presscake was washed well with water, reslurried in dilute aqueous alkali and filtered. Again the presscake was washed well with water. After drying in vacuo, about 2 grams of the title compound was isolated. 1H NMR 6.8 (d, 1H, J=8.7 Hz), 6.9 (br s, 2H), 7.6 (dd, 1H, J=2 Hz, J=8.7 Hz), 8.0 (d, 1H, J=2 Hz), LC/MS 2.34 min, 174 (M−H−), RP-HPLC RT 7.7 minutes.

Workup

  1. customthe flask was equipped with an addition funnel
  2. filtrationfiltered
  3. washThe presscake was washed well with water
  4. filtrationfiltered
  5. washAgain the presscake was washed well with water
  6. customAfter drying in vacuo

Sources & evidence

ORD record
ord-5037c9c33a5a49e9b0b5c20797e25f9c
Source dataset
uspto-grants-2006_08
Patent number
US07091227B2

Linked notes

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