Diisopropylethylamine → HCID 131730627, compound

HRID 1257618Notes

Reaction equation

HRID 1257618 reaction equation
[C:1]1([S:7]([N:10]2[C:14]3=[N:15][CH:16]=[C:17]([N+:20]([O-:22])=[O:21])[C:18](Cl)=[C:13]3[CH:12]=[CH:11]2)(=[O:9])=[O:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[CH2:23]([N:30]1[CH2:35][CH2:34][CH:33]([NH2:36])[CH2:32][CH:31]1[CH3:37])[C:24]1[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=1.C(N(C(C)C)CC)(C)C>CC(O)C>[C:1]1([S:7]([N:10]2[C:14]3=[N:15][CH:16]=[C:17]([N+:20]([O-:22])=[O:21])[C:18]([NH:36][C@H:33]4[CH2:34][CH2:35][N:30]([CH2:23][C:24]5[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=5)[C@@H:31]([CH3:37])[CH2:32]4)=[C:13]3[CH:12]=[CH:11]2)(=[O:9])=[O:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[C:1]1([S:7]([N:10]2[C:14]3=[N:15][CH:16]=[C:17]([N+:20]([O-:22])=[O:21])[C:18]([NH:36][C@@H:33]4[CH2:34][CH2:35][N:30]([CH2:23][C:24]5[CH:29]=[CH:28][CH:27]=[CH:26][CH:25]=5)[C@@H:31]([CH3:37])[CH2:32]4)=[C:13]3[CH:12]=[CH:11]2)(=[O:9])=[O:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

6

Reactant 3

HCID 81531DiisopropylethylamineHCID 219228491-Benzyl-2-methylpiperidin-4-amineHCID 583947741-(benzenesulfonyl)-4-chloro-5-nitro-1H-pyrrolo(2,3-b)pyridine

Product 2

HCID 131730627HCID 131730627, compoundYield 65%HCID 131730628HCID 131730628, compoundYield 21%

Reagents, catalysts & solvents 1

HCID 3776IsopropanolSolvent

Procedure

A mixture of 1-benzenesulfonyl-4-chloro-5-nitro-1H-pyrrolo[2,3-b]pyridine (1.01 g, 3.00 mmol), 1-benzyl-2-methyl-piperidin-4-ylamine (674 mg, 3.30 mmol) and diisopropylethylamine (1.83 mL, 10.5 mmol) in propan-2-ol (30 mL) was heated to reflux for 1 hour. The mixture was filtered through Celite® and the filtrate concentrated under vacuum. Purification by column chromatography on silica gel (gradient: 0 to 30% ethyl acetate in toluene) afforded 990 mg (65%) of racemic cis (1-benzenesulfonyl-5-nitro-1H-pyrrolo[2,3-b]pyridin-4-yl)-(1-benzyl-2-methyl-piperidin-4-yl)-amine as a yellow foam and 320 mg (21%) of racemic trans (1-benzenesulfonyl-5-nitro-1H-pyrrolo[2,3-b]pyridin-4-yl)-(1-benzyl-2-methyl-piperidin-4-yl)-amine as a yellow foam. Analysis for racemic cis: LCMS (Method I, ESI): RT=2.53 min, m+H=506.4; 1H NMR (400 MHz, CDCl3) δ: 9.09 (s, 1H), 8.98 (d, 1H), 8.19 (dd, 2H), 7.61 (m, 2H), 7.54-7.49 (m, 2H), 7.35 (br s, 4H), 7.17 (m, 1H), 6.67 (s, 1H), 4.18 (br s, 1H), 3.94 (br s, 1H), 3.18 (br s, 1H), 2.97 (br s, 1H), 2.36 (s, 1H), 2.21-1.98 (m, 5H), 1.41-1.20 (m, 3H). Analysis for racemic trans: LCMS (Method I, ESI): RT=2.56 min, m+H=506.4; 1H NMR (400 MHz, DMSO) δ: 9.07 (d, 1H), 8.92 (s, 1H), 8.15-8.10 (m, 2H), 7.80 (m, 2H), 7.66 (t, 2H), 7.38-7.19 (m, 4H), 7.02 (d, 1H), 4.42 (s, 1H), 3.89 (d, 1H), 2.80-2.57 (m, 2H), 2.34-2.24 (m, 1H), 1.93-1.58 (m, 4H), 1.15 (d, 3H).

Workup

  1. temperaturewas heated
  2. temperatureto reflux for 1 hour
  3. filtrationThe mixture was filtered through Celite®
  4. concentrationthe filtrate concentrated under vacuum
  5. customPurification by column chromatography on silica gel (gradient: 0 to 30% ethyl acetate in toluene)

Sources & evidence

ORD record
ord-2f38965668d947da9d1868b471ab480c
Source dataset
uspto-grants-2013_06
Patent number
US08461328B2

Reaction notes

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