Dimethyl acetylenedicarboxylate → HCID 86690038, compound

HRID 2369335Notes

Reaction equation

HRID 2369335 reaction equation
[CH3:1][O:2][C:3]1[CH:21]=[CH:20][C:6]([C:7]([N:9]2[C:13]3[CH:14]=[CH:15][CH:16]=[CH:17][C:12]=3[S:11][CH:10]2C#N)=O)=[CH:5][CH:4]=1.F[B-](F)(F)F.[H+].[C:28]([C:34]([O:36][CH3:37])=[O:35])#[C:29][C:30]([O:32][CH3:33])=[O:31]>ClCCl.CN(C=O)C>[CH3:1][O:2][C:3]1[CH:4]=[CH:5][C:6]([C:7]2[N:9]3[C:10]([S:11][C:12]4[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=43)=[C:29]([C:30]([O:32][CH3:33])=[O:31])[C:28]=2[C:34]([O:36][CH3:37])=[O:35])=[CH:20][CH:21]=1

Participants

6

Reactant 3

HCID 12980Dimethyl acetylenedicarboxylateHCID 28118Tetrafluoroboric acidHCID 86690039HCID 86690039, compound

Product 1

HCID 86690038HCID 86690038, compoundYield 24%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolvent

Procedure

To a solution of 3-(4-methoxybenzoyl)-2,3-dihydrobenzo[d]thiazole-2-carbonitrile (5.3 g, 17.9 mmol) in dichloromethane (50 mL) was added dropwise 5 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 (7.6 g, 54.0 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-methoxyphenyl)benzo[d]pyrrolo[2,1-b]thiazole-2,3-dicarboxylate 1.7 g (24%); mp 167-168° C. 1H NMR (DMSO-d6) δ 3.63 (3H, s, COOMe), 3.82 (3H, s, COOMe), 3.86 (3H, s, Me), 6.84-6.86 (1H, m, ArH), 7.12 (2H, d, J=8.4 Hz, 2×ArH), 7.28-7.32 (1H, m, ArH), 7.37-7.40 (1H, m, ArH), 7.48 (2H, d, J=8.4 Hz, 2×ArH), 8.03-8.05 (1H, m, ArH). Anal. Calcd. for (C21H17NO5S): C, 63.79; H, 4.33; N, 3.54; S, 8.11.

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-29d7868c57704278ba93f6c05f15514f
Source dataset
uspto-grants-2014_04
Patent number
US08703951B2

Reaction notes

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