Dimethyl acetylenedicarboxylate → HCID 60165811, compound

HRID 2369326Notes

Reaction equation

HRID 2369326 reaction equation
[C:1]([N:4]1[C:8]2[CH:9]=[CH:10][CH:11]=[CH:12][C:7]=2[S:6][CH:5]1C#N)(=O)[CH3:2].F[B-](F)(F)F.[H+].[C:21]([C:27]([O:29][CH3:30])=[O:28])#[C:22][C:23]([O:25][CH3:26])=[O:24]>ClCCl.CN(C=O)C>[CH3:2][C:1]1[N:4]2[C:5]([S:6][C:7]3[CH:12]=[CH:11][CH:10]=[CH:9][C:8]=32)=[C:22]([C:23]([O:25][CH3:26])=[O:24])[C:21]=1[C:27]([O:29][CH3:30])=[O:28]

Participants

6

Reactant 3

HCID 12980Dimethyl acetylenedicarboxylateHCID 28118Tetrafluoroboric acidHCID 60165810HCID 60165810, compound

Product 1

HCID 60165811HCID 60165811, compound

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolvent

Procedure

To a solution of 3-acetyl-2,3-dihydrobenzo[d]thiazole-2-carbonitrile (5 g, 24.5 mmol) in dichloromethane (50 mL) was added dropwise 7 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 (10.4 g, 73.0 mmol) in DMF (30 mL) and then warmed at 35° C. for 13 h. The reaction mixture was concentrated in vacuo and the residue was recrystallized from methanol to give dimethyl 1-methylbenzo[d]pyrrolo[2,1-b]thiazole-2,3-dicarboxylate, 1.7 g (23%); mp 143-144° C. 1H NMR (DMSO-d6) δ 2.85 (3H, s, Me), 3.83 (3H, s, COOMe), 3.85 (3H, s, COOMe), 7.50 (1H, t, J=7.6 Hz, ArH), 7.58 (1H, t, J=7.6 Hz, ArH), 8.07 (1H, d, J=8.0 Hz, ArH), 8.12 (1H, d, J=8.0 Hz, ArH). Anal. Calcd. for (C15H13NO4S): C, 59.39; H, 4.32; N, 4.62; S, 10.57. Found: C, 59.02; H, 4.23; N, 4.87; S, 10.42.

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 13 h
  5. concentrationThe reaction mixture was concentrated in vacuo
  6. customthe residue was recrystallized from methanol

Sources & evidence

ORD record
ord-3be759f8ff9c4f2fa9b756d86d7a9497
Source dataset
uspto-grants-2014_04
Patent number
US08703951B2

Reaction notes

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