alpha-Hydroxytriazolam → 4-[alpha-Amino-4-chloro-alpha-(o-chlorophenyl)-o-tolyl]-3-hydroxymethyl-5-methyl-4H-1,2,4-triazole

HRID 329220Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 329220
Cl[C:2]1[CH:3]=[CH:4][C:5]2[N:11]3[C:12]([CH2:15][OH:16])=[N:13][N:14]=[C:10]3[CH2:9][N:8]=[C:7]([C:17]3[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=3[Cl:23])[C:6]=2[CH:24]=1.O.NN.NC(C1C=CC=CC=1Cl)C1C=CC([Cl:36])=CC=1N1C(C)=NN=C1C1CC1>C(O)COCCO>[NH2:8][CH:7]([C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=1[Cl:23])[C:6]1[CH:24]=[CH:2][C:3]([Cl:36])=[CH:4][C:5]=1[N:11]1[C:10]([CH3:9])=[N:14][N:13]=[C:12]1[CH2:15][OH:16]

Komponenten

5

Edukt 3

HCID 1963alpha-HydroxytriazolamHCID 24654Hydrazine hydrate (1:1)HCID 867337164-[alpha-amino-4-chloro-alpha(o-chlorophenyl)-o-tolyl]-3-cyclopropyl-5-methyl-4H-1,2,4-triazole2×

Produkt 1

HCID 867337174-[alpha-Amino-4-chloro-alpha-(o-chlorophenyl)-o-tolyl]-3-hydroxymethyl-5-methyl-4H-1,2,4-triazole

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8117Diethylene GlycolLösungsmittel

Versuchsvorschrift

A mixture of 10.776 g. 8-chloro-6-(o-chlorophenyl)-1-hydroxymethyl-4H-s-triazolo[4,3-a] [1,4]benzodiazepine (111) (30.0 mmoles) and 7.50 ml. of hydrazine hydrate in 60 ml. of diethylene glycol is heated to 150°-160° C. for about 18 hours. The reaction is then quenched in a cold aqueous 5% sodium hydroxide solution and the product extracted with chloroform. The extracts thus obtained are dried over anhydrous magnesium sulfate and concentrated in vacuo to give 13.0 g. of oil which is crystallized from methanol/ethyl acetate to give 1.93 g. of a mixture of the A and B isomers (ratio 81/19) of 4-[α-amino-4-chloro-α-(o-chlorophenyl)-o-tolyl]-3-(hydroxymethyl)-5-methyl-4H-1,2,4-triazole (I) m.p. 205°-215° C. The mixture thus obtained is recrystallized from the same solvent mixture to give 0.76 g. of 4-[α-amino-4-chloro-α-(o-chlorophenyl)-o-tolyl]-o-tolyl]-3-(hydroxymethyl)-5-methyl-4H-1,2,4-triazole (I), (isomer A) melting at 218° - 223° C., and having infrared (mull) spectral absorptions at 3330, 3240, 3150, 3060, 2680, 1600, 1570, 1530, 1515 and 1485 cm-1.

Aufarbeitung

  1. additionA mixture of 10.776 g
  2. customThe reaction is then quenched in a cold aqueous 5% sodium hydroxide solution
  3. extractionthe product extracted with chloroform
  4. customThe extracts thus obtained
  5. dry with materialare dried over anhydrous magnesium sulfate
  6. concentrationconcentrated in vacuo
  7. customto give 13.0 g
  8. customof oil which is crystallized from methanol/ethyl acetate
  9. customto give 1.93 g
  10. customThe mixture thus obtained
  11. customis recrystallized from the same solvent mixture
  12. customto give 0.76 g

Quellen und Nachweise

ORD-Eintrag
ord-0dc91a445a504286ac33cca0d4205d3a
Quelldatensatz
uspto-grants-1977_04
Patentnummer
US04020085

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