Hydrochloric Acid → (+)-6-[(4-chlorophenyl)hydrazinomethyl]-1-methyl-1H-benzotriazole monohydrochloride

HRID 1376824Notes

Reaction equation

HRID 1376824 reaction equation
C[C:2]([N:5](C([O-])=O)[N:6]=[C:7](C1C=CC([Cl:24])=CC=1)[C:8]1[CH:9]=[CH:10][C:11]2[N:15]=[N:14][N:13]([CH3:16])[C:12]=2[CH:17]=1)([CH3:4])[CH3:3].[ClH:28].O.O1C[CH2:33][CH2:32][CH2:31]1>>[ClH:24].[Cl:28][C:32]1[CH:33]=[CH:3][C:2]([NH:5][NH:6][CH2:7][C:8]2[CH:9]=[CH:10][C:11]3[N:15]=[N:14][N:13]([CH3:16])[C:12]=3[CH:17]=2)=[CH:4][CH:31]=1

Participants

5

Reactant 4

HCID 313Hydrochloric AcidHCID 962WaterHCID 8028Tetrahydrofuran2×HCID 1317201711,1-dimethylethyl[(4-chlorophenyl)(1-methyl-1H-benzotriazol-6-yl)-methylene]hydrazine carboxylate

Product 1

HCID 18924324(+)-6-[(4-chlorophenyl)hydrazinomethyl]-1-methyl-1H-benzotriazole monohydrochloride

Conditions

Temperature
22 °C

Procedure

To a suspension of 10 g of intermediate 1-b in 60 ml of tetrahydrofuran under a nitrogen atmosphere were added dropwise over 15 minutes 26 ml of a borane tetrahydrofuran complex in tetrahydrofuran (1M). After stirring for 15 minutes at ±22° C. there were added 13 ml of hydrochloric acid (6N). The whole was heated to reflux and refluxed for 1.5 hours. The mixture was cooled to room temperature and 50 ml of water were added. After stirring for 1 hour, the reaction mixture was filtered. The filtrate was mixed with 75 ml of methylbenzene. The layers were separated and the aqueous layer was basified (pH 7.5-8) with NH4OH. The product was extracted with dichloromethane and the extract was dried, filtered and evaporated. The residue was converted into the hydrochloride salt in 2-propanol by adding 3 ml of a mixture of hydrochloric acid in 2-propanol (4.8N). After stirring for 2 hours the product was filtered off, washed with 2-propanol and dried in vacuo at 50° C., yielding 2.1 g of (±)-6-[(4-chlorophenyl)hydrazinomethyl]-1-methyl-1H-benzotriazole monohydrochloride (interm. 2-e).

Workup

  1. temperatureThe whole was heated
  2. temperatureto reflux
  3. temperaturerefluxed for 1.5 hours
  4. temperatureThe mixture was cooled to room temperature
  5. stirringAfter stirring for 1 hour
  6. filtrationthe reaction mixture was filtered
  7. additionThe filtrate was mixed with 75 ml of methylbenzene
  8. customThe layers were separated
  9. extractionThe product was extracted with dichloromethane
  10. customthe extract was dried
  11. filtrationfiltered
  12. customevaporated
  13. additionby adding 3 ml of a mixture of hydrochloric acid in 2-propanol (4.8N)
  14. stirringAfter stirring for 2 hours the product
  15. filtrationwas filtered off
  16. washwashed with 2-propanol
  17. customdried in vacuo at 50° C.

Sources & evidence

ORD record
ord-dff8e6340dfc430497203261c956222f
Source dataset
uspto-grants-1997_09
Patent number
US05663354

Reaction notes

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