Hydrazine → HCID 10456060, compound

HRID 2393109Notes

Reaction equation

HRID 2393109 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH2:9][C:10]([N:12]([CH3:29])[C@@H:13]([C:20]2[CH:25]=[CH:24][CH:23]=[C:22]([N+:26]([O-])=O)[CH:21]=2)[CH2:14][N:15]2[CH2:19][CH2:18][CH2:17][CH2:16]2)=[O:11])[CH:5]=[CH:6][C:7]=1[Cl:8].NN>CCO.[Ni]>[Cl:1][C:2]1[CH:3]=[C:4]([CH2:9][C:10]([N:12]([CH3:29])[C@@H:13]([C:20]2[CH:25]=[CH:24][CH:23]=[C:22]([NH2:26])[CH:21]=2)[CH2:14][N:15]2[CH2:19][CH2:18][CH2:17][CH2:16]2)=[O:11])[CH:5]=[CH:6][C:7]=1[Cl:8]

Participants

5

Reactant 2

HCID 9321Hydrazine2×HCID 10005038HCID 10005038, compound

Product 1

HCID 10456060HCID 10456060, compound

Reagents, catalysts & solvents 2

HCID 935NickelCatalyst2×HCID 702EthanolSolvent

Conditions

Temperature
55 °C

Procedure

A mixture of 14 (1.17 g, 2.68 mmol), hydrazine (1 mL, 32 mmol), and Raney-Ni in 95% EtOH (75 mL) was heated at 55° C. Small portions of Raney-Ni and hydrazine were added until TLC indicated completion of the reaction (2.5 h). The reaction was filtered through celite, and the Raney-Ni was washed with hot MeOH. The combined filtrates were evaporated under reduced pressure to yield 15 in quantitative yield. Further purification was achieved by gravity column chromatography with CHCl3 :1% MeOH:2% NH3 :mp (15.2HCl) softens at 149° C. and melts at 223°-224° C.; [α]D25°C. +143.7° (c=0.45, 15.2HCl, MeOH); 1H NMR (15.2HCl, DMSO-d6) δ 1.9-2.0 (m, 4H, --CH2CH2 --), δ 2.82 (s, 3H, NCH3), δ 3.07-4.07 (complex, 6H, 3 --CH2N), δ 3.77 (d, J=16 Hz, 1H, ArCH2CO), δ 4.10 (d, J=16 Hz, 1H, ArCH2CO), δ 6.05 (d of d, J=12.5 Hz and 2.5 Hz, 1H, CH), δ 6.87 (br s, 2H, m-NH2C6H4), δ 6.92 (d, J=8 Hz, 1H, m-NH2C6H4), δ 7.26 (t, J=8 Hz, 1H, m-NH2C6H4), δ 7.29-7.31 (m, 1H, Cl2C6 H3 --), δ 7.55-7.59 (m, 2H, Cl2C6H3 --). MS (FAB) m/z 406.2. Anal. (C21H25N3OCl2.2HCl) calcd.: C 52.62, H 5.68, N 8.77, Cl 29.59; found: C 52.43, H 5.58, N 8.50, Cl 29.47.

Workup

  1. customcompletion of the reaction (2.5 h)
  2. filtrationThe reaction was filtered through celite
  3. washthe Raney-Ni was washed with hot MeOH
  4. customThe combined filtrates were evaporated under reduced pressure

Sources & evidence

ORD record
ord-93e1eb11ca434bd0a37bcfaaf1436d86
Source dataset
uspto-grants-1998_09
Patent number
US05804595

Reaction notes

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