Dichloromethane → HCID 136348424, compound

HRID 1748734Notes

Reaction equation

HRID 1748734 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([CH:8]2[S:14][CH2:13][CH2:12][NH:11][C:10]3[N:15]([CH3:24])[N:16]=[C:17]([C:18]4[CH:23]=[CH:22][CH:21]=[CH:20][N:19]=4)[C:9]2=3)=[C:4]([CH:25]=[CH2:26])[CH:3]=1.C(Cl)Cl.[H][H]>CO.[OH-].[OH-].[Pd+2]>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([CH:8]2[S:14][CH2:13][CH2:12][NH:11][C:10]3[N:15]([CH3:24])[N:16]=[C:17]([C:18]4[CH:23]=[CH:22][CH:21]=[CH:20][N:19]=4)[C:9]2=3)=[C:4]([CH2:25][CH3:26])[CH:3]=1

Participants

6

Reactant 3

HCID 6344DichloromethaneHCID 136216273HCID 136216273, compoundHCID 178418361HCID 178418361, compound

Product 1

HCID 136348424HCID 136348424, compound

Reagents, catalysts & solvents 2

HCID 9942167Palladium hydroxideCatalystHCID 887MethanolSolvent

Procedure

A mixture of 4-(4-chloro-2-vinyl-phenyl)-1-methyl-3-(2-pyridyl)-4,6,7,8-tetrahydropyrazolo-[3,4-e][1,4]thiazepine (0.100 g, 0.26 mmol, Preparation #18) and palladium hydroxide on carbon (0.073 g, 20 wt % on dry basis, ˜0.1 mmol), in methanol (5 mL) and DCM (2 mL) was treated with hydrogen (1 atm.), at rt, overnight. Then the mixture was filtered over diatomaceous earth and concentrated in vacuo. The residue was purified by prep-HPLC (Table 2, Method b) to give 4-(4-chloro-2-ethyl-phenyl)-1-methyl-3-(2-pyridyl)-4,6,7,8-tetrahydropyrazolo[3,4-e][1,4]thiazepine as an off white solid: LC-MS (Table 1, Method a) Rt=4.03 min; m/z 385 (M+H)+; 1H-NMR (CDCl3, Bruker 400 MHz) δ 1.38 (3 H, t, J=7.5 Hz) 2.71 (1 H, ddd, J=15.1, 6.3, 2.7 Hz) 2.83 (1 H, ddd, J=15.1, 8.8, 2.8 Hz) 2.94 (1 H, dq, J=15.1, 7.5 Hz) 3.10 (1 H, dq, J=15.1, 7.5 Hz) 3.18-3.27 (1 H, m) 3.52-3.60 (1 H, m) 3.79 (1 H, br s) 3.84 (3 H, s) 6.78 (1 H, s) 6.99 (1 H, dd, J=8.4, 2.2 Hz) 7.07 (1 H, ddd, J=7.4, 4.9, 0.9 Hz) 7.13 (1 H, d, J=8.4 Hz) 7.20 (1 H, d, J=2.2 Hz) 7.59 (1 H, td, J=7.8, 1.7 Hz) 7.79 (1 H, dt, J=8.0, 0.9 Hz) 8.44 (1 H, ddd, J=4.8, 1.7, 0.9 Hz).

Workup

  1. filtrationThen the mixture was filtered over diatomaceous earth
  2. concentrationconcentrated in vacuo
  3. customThe residue was purified by prep-HPLC (Table 2, Method b)

Sources & evidence

ORD record
ord-f5d7b50d058048168befe6de6aa44163
Source dataset
uspto-grants-2015_10
Patent number
US09150592B2

Reaction notes

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