Hydrochloric Acid → ethyl [2-({2-methyl-3-[methyl(2-thienylsulfonyl)amino]-4H-thieno[3,2-b]pyrrol-5-yl}carbonyl)hydrazino](oxo)acetate

HRID 453591Notes

Reaction equation

HRID 453591 reaction equation
[CH3:1][C:2]1[S:9][C:8]2[CH:7]=[C:6]([C:10](O)=[O:11])[NH:5][C:4]=2[C:3]=1[N:13]([CH3:22])[S:14]([C:17]1[S:18][CH:19]=[CH:20][CH:21]=1)(=[O:16])=[O:15].O.NN.[N:26]1(O)C2C=CC=CC=2N=[N:27]1.Cl.CN(C)CCCN=C=NCC.C(=O)([O-])[OH:49].[Na+].ClC(=O)[CH2:55][C:56]([O:58][CH2:59][CH3:60])=[O:57].Cl>CN(C)C(=O)C.C(#N)C.O1CCCC1>[CH3:1][C:2]1[S:9][C:8]2[CH:7]=[C:6]([C:10]([NH:26][NH:27][C:55](=[O:49])[C:56]([O:58][CH2:59][CH3:60])=[O:57])=[O:11])[NH:5][C:4]=2[C:3]=1[N:13]([CH3:22])[S:14]([C:17]1[S:18][CH:19]=[CH:20][CH:21]=1)(=[O:16])=[O:15]

Participants

11

Reactant 7

HCID 313Hydrochloric AcidHCID 24654Hydrazine hydrate (1:1)HCID 757711-HydroxybenzotriazoleHCID 118931Ethyl 3-chloro-3-oxopropionateHCID 516892Sodium BicarbonateHCID 27239391,3-Propanediamine, N'-(ethylcarbonimidoyl)-N,N-dimethyl-, monohydrochlorideHCID 594113852-methyl-3-[methyl(2-thienylsulfonyl)amino]-4H-thieno[3,2-b]pyrrole-5-carboxylic acid

Product 1

HCID 59411379ethyl [2-({2-methyl-3-[methyl(2-thienylsulfonyl)amino]-4H-thieno[3,2-b]pyrrol-5-yl}carbonyl)hydrazino](oxo)acetateYield 65%

Reagents, catalysts & solvents 3

HCID 6342AcetonitrileSolventHCID 8028TetrahydrofuranSolventHCID 31374DimethylacetamideSolvent

Procedure

To a mixture of 2-methyl-3-[methyl(2-thienylsulfonyl)amino]-4H-thieno[3,2-b]pyrrole-5-carboxylic acid (2.0 g), hydrazine monohydrate (2 mL), 1H-1,2,3-benzotriazol-1-ol (920 mg), tetrahydrofuran (20 mL) and acetonitrile (20 mL) was added N-[3-(dimethylamino)propyl]-N′-ethylcarbodiimide hydrochloride (1.15 g), and the mixture was stirred at room temperature for 30 min. Saturated aqueous sodium hydrogen carbonate solution was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with saturated brine, dried (MgSO4) and concentrated to give a colorless oil. The colorless oil was dissolved in N,N-dimethylacetamide (10 mL), and ethyl 3-chloro-3-oxopropanoate (0.67 mL) was added. The reaction mixture was stirred at room temperature for 1 hr, 1N hydrochloric acid was added, and the mixture was extracted with ethyl acetate. The ethyl acetate layer was washed with saturated brine, dried (MgSO4) and concentrated. Crystallization from diethyl ether gave ethyl [2-({2-methyl-3-[methyl(2-thienylsulfonyl)amino]-4H-thieno[3,2-b]pyrrol-5-yl}carbonyl)hydrazino](oxo)acetate (1.7 g, yield 65%) as colorless crystals. melting point 135° C.

Workup

  1. extractionthe mixture was extracted with ethyl acetate
  2. washThe ethyl acetate layer was washed with saturated brine
  3. dry with materialdried (MgSO4)
  4. concentrationconcentrated
  5. customto give a colorless oil
  6. stirringThe reaction mixture was stirred at room temperature for 1 hr
  7. extractionthe mixture was extracted with ethyl acetate
  8. washThe ethyl acetate layer was washed with saturated brine
  9. dry with materialdried (MgSO4)
  10. concentrationconcentrated
  11. customCrystallization from diethyl ether

Sources & evidence

ORD record
ord-eb4703cd2e3b43e6b1dc17277c84be55
Source dataset
uspto-grants-2013_07
Patent number
US08492405B2

Reaction notes

Loading…