Dimethyl acetylenedicarboxylate → HCID 86690037, compound

HRID 2369332Notes

Reaction equation

HRID 2369332 reaction equation
[Cl:1][C:2]1[CH:20]=[CH:19][C:5]([C:6]([N:8]2[C:12]3[CH:13]=[CH:14][CH:15]=[CH:16][C:11]=3[S:10][CH:9]2C#N)=O)=[CH:4][CH:3]=1.F[B-](F)(F)F.[H+].[C:27]([C:33]([O:35][CH3:36])=[O:34])#[C:28][C:29]([O:31][CH3:32])=[O:30]>ClCCl.CN(C=O)C>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([C:6]2[N:8]3[C:9]([S:10][C:11]4[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=43)=[C:28]([C:29]([O:31][CH3:32])=[O:30])[C:27]=2[C:33]([O:35][CH3:36])=[O:34])=[CH:19][CH:20]=1

Participants

6

Reactant 3

HCID 12980Dimethyl acetylenedicarboxylateHCID 28118Tetrafluoroboric acidHCID 13301274HCID 13301274, compound

Product 1

HCID 86690037HCID 86690037, compound

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolvent

Procedure

To a solution of 3-(4-chlorobenzoyl)-2,3-dihydrobenzo[d]thiazole-2-carbonitrile (9.12 g, 30.0 mmol) in dichloromethane (50 mL) was added dropwise 9 mL of tetrafluoroboric acid (HBF4). The solution was stirred for 3 h at room temperature. The brown precipitates appeared were collected by filtration and the filter cake was washed with ether. The solid salt was added to a solution of dimethyl acetylenedicarboxylate (12.7 g, 90.0 mmol) in DMF (40 mL) and then warmed at 35° C. for 14 h. The reaction mixture was concentrated in vacuo and the residue was crystallized from methanol to give dimethyl 1-(4-chlorophenyl)benzo[d]pyrrolo[2,1-b]thiazole-2,3-dicarboxylate, 2.5 g (21%); mp 172-173° C. 1H NMR (DMSO-d6) δ 3.64 (3H, s, COOMe), 3.83 (3H, s, COOMe), 6.85-6.87 (1H, m, ArH), 7.30-7.42 (2H, m, ArH), 7.60-7.66 (4H, m, 4×ArH), 8.04-8.06 (1H, m, ArH). Anal. Calcd. for (C20H14ClNO4S.0.5H2O): C, 58.75; H, 3.70; N, 3.43; S, 7.84. Found: C, 58.76; H, 3.45; N, 3.59; S, 7.73.

Workup

  1. customThe brown precipitates
  2. filtrationappeared were collected by filtration
  3. washthe filter cake was washed with ether
  4. temperaturewarmed at 35° C. for 14 h
  5. concentrationThe reaction mixture was concentrated in vacuo
  6. customthe residue was crystallized from methanol

Sources & evidence

ORD record
ord-39a1d31b8c674ba7a2c533ca39958f29
Source dataset
uspto-grants-2014_04
Patent number
US08703951B2

Reaction notes

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