Triethylamine → N-methyl-1,2,3,4-tetrahydrobenzo[b]thieno[2,3-c]pyridine-3-carboamide

HRID 893858Notes

Reaction equation

HRID 893858 reaction equation
C(OC([CH:8]1[S:20][C:11]23[CH:19]=[CH:18][CH:17]=[CH:16][C:12]2=[N:13][CH2:14][CH2:15][CH:10]3[CH:9]1[C:21]([OH:23])=O)=O)(C)(C)C.Cl.CN.[CH2:27]([N:29](CC)CC)C.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=O)C=CC=CC=1>CN(C)C=O.C(OCC)(=O)C>[CH3:27][NH:29][C:21]([CH:9]1[CH:10]2[C:11]3([CH:19]=[CH:18][CH:17]=[CH:16][C:12]3=[N:13][CH2:14][CH2:15]2)[S:20][CH2:8]1)=[O:23]

Participants

7

Reactant 4

HCID 8471Triethylamine2×HCID 199401P,P-Diphenylphosphinic azideHCID 6364545Methylamine hydrochlorideHCID 699596062-Tert-butoxycarbonyl-1,2,3,4-tetrahydro-benzo[b]thieno[2,3-c]pyridine-3-carboxylic acid

Product 1

HCID 19891213N-methyl-1,2,3,4-tetrahydrobenzo[b]thieno[2,3-c]pyridine-3-carboamideYield 65%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolvent3×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
50 °C

Procedure

In 5 ml of dimethylformamide were dissolved 0.32 g of 2-tert-butoxycarbonyl-1,2,3,4-tetrahydro-benzo[b]thieno[2,3-c]pyridine-3-carboxylic acid, 0.08 g of methylamine.hydrochloride, and 0.17 ml of triethylamine, and after adding dropwise thereto 5 ml of a dimethylformamide solution of 0.33 g of diphenylphosphorylazide under ice-cooling and further adding dropwise thereto 2 ml of a dimethylformamide solution of 0.17 ml of triethylamine, the mixture was stirred for 2 hours at room temperature. To the reaction mixture was added 50 ml of ethyl acetate and the mixture was washed thrice with 10 ml of an aqueous 5% citric acid solution, thrice with an aqueous 5% sodium hydrogencarbonate solution and then twice with a saturated sodium chloride solution, and thereafter dried with sodium sulfate. After filtering away sodium sulfate, 5 ml of a mixture of 1N hydrochloric acid in ethyl acetate were added to the filtrate and the mixture was heated to 50° C. for one hour. Then, the reaction mixture was allowed to stand overnight in a refrigerator and crystals thus deposited were collected by filtration to provide 0.23 g (yield of 65%) of N-methyl-1,2,3,4-tetrahydrobenzo[b]thieno[2,3-c]pyridine-3-carboamide. (See Table 11, Table 12).

Workup

  1. additionafter adding dropwise
  2. additionfurther adding dropwise
  3. washthe mixture was washed thrice with 10 ml of an aqueous 5% citric acid solution, thrice with an aqueous 5% sodium hydrogencarbonate solution
  4. dry with materialtwice with a saturated sodium chloride solution, and thereafter dried with sodium sulfate
  5. filtrationAfter filtering away sodium sulfate, 5 ml of a mixture of 1N hydrochloric acid in ethyl acetate
  6. additionwere added to the filtrate
  7. filtrationthus deposited were collected by filtration

Sources & evidence

ORD record
ord-0f0979f7160842f6a4a075d7c4addaf4
Source dataset
uspto-grants-1992_06
Patent number
US05126448

Reaction notes

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