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Cyclopropylacetylene → 5-Cyclopropylethynyl-3-(dimethylaminomethyleneamino)thiophene-2-carboxylic acid methyl ester

HRID 532458
Notes
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Reaction equation

HRID 532458 reaction equation
[CH3:1][O:2][C:3]([C:5]1[S:6][C:7](Br)=[CH:8][C:9]=1[N:10]=[CH:11][N:12]([CH3:14])[CH3:13])=[O:4].[C:16]([CH:18]1[CH2:20][CH2:19]1)#[CH:17]>C(N(CC)CC)C.C1COCC1.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I>[CH3:1][O:2][C:3]([C:5]1[S:6][C:7]([C:17]#[C:16][CH:18]2[CH2:20][CH2:19]2)=[CH:8][C:9]=1[N:10]=[CH:11][N:12]([CH3:14])[CH3:13])=[O:4]
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

7

Reactant 2

HCID 138823CyclopropylacetyleneHCID 600270405-Bromo-3-(dimethylaminomethyleneamino)thiophene-2-carboxylic acid methyl ester

Product 1

HCID 689443485-Cyclopropylethynyl-3-(dimethylaminomethyleneamino)thiophene-2-carboxylic acid methyl ester

Reagents, catalysts & solvents 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)Catalyst
HCID 178418476
HCID 178418476, compound
Catalyst
HCID 8028TetrahydrofuranSolvent
HCID 8471TriethylamineSolvent

Procedure

Firstly bis(triphenylphosphine)palladium(II) chloride (602 mg) and then copper(I) iodide (164 mg) were added to a mixture of 5-bromo-3-(dimethylaminomethyleneamino)thiophene-2-carboxylic acid methyl ester (1 g), ethynylcyclopropane (463 mg) in triethylamine (9.5 mL) and THF (4.5 mL). After one hour, the reaction mixture was partitioned between water and ethyl acetate. The organic phase was dried and concentrated. The crude product was purified by preparative HPLC. The product with the molecular weight of 276.36 (C14H16N2O2S) was obtained in this way; MS (ESI): 277 (M+H+).

Workup

  1. customthe reaction mixture was partitioned between water and ethyl acetate
  2. customThe organic phase was dried
  3. concentrationconcentrated
  4. customThe crude product was purified by preparative HPLC
  5. customThe product with the molecular weight of 276.36 (C14H16N2O2S) was obtained in this way

Sources & evidence

ORD record
ord-e65d043a33094806a62df4ce247fbcf9
Source dataset
uspto-grants-2014_10
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US08853208B2

Reaction notes

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On this pageParticipantsProcedureWorkupSources & evidenceReaction notes