Methanethiol → HCID 14372571, compound

HRID 1382976Notes

Reaction equation

HRID 1382976 reaction equation
[NH2:1][C:2]1[C:17]([Cl:18])=[CH:16][C:5]([C:6]([NH:8][CH2:9][CH2:10][N:11]([CH2:14][CH3:15])[CH2:12][CH3:13])=[O:7])=[C:4]([OH:19])[CH:3]=1.Br[CH2:21][CH2:22][CH2:23]Cl.[H-].[Na+].[CH3:27][SH:28]>CN(C=O)C>[NH2:1][C:2]1[C:17]([Cl:18])=[CH:16][C:5]([C:6]([NH:8][CH2:9][CH2:10][N:11]([CH2:12][CH3:13])[CH2:14][CH3:15])=[O:7])=[C:4]([O:19][CH2:21][CH2:22][CH2:23][S:28][CH3:27])[CH:3]=1

Participants

6

Reactant 4

HCID 878MethanethiolHCID 80061-Bromo-3-chloropropaneHCID 24758Sodium hydrideHCID 9817332o-Desmethyl metoclopramide

Product 1

HCID 14372571HCID 14372571, compoundYield 66%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
40 °C

Procedure

To a solution of tetrabutylammonium salt of 4-amino-5-chloro-N-[2-(diethylamino)ethyl]-2-hydroxybenzamide (10.54 g, 20 mmoles) (prepared in Preparation No. 3) in DMF (100 ml) was added 1-bromo-3-chloropropane (3.268 g, 2.2 ml, 20.76 mmoles) and the mixture stirred for 2 hours at ambient temperature and another 30 minutes at 40° C. The mixture was cooled to 0° C and poured over sodium hydride (1.0 g of 60% mineral oil dispersion, 25 mmoles, washed with n-pentane) under nitrogen. The mixture was stirred in the cold while methyl mercaptan gas was bubbled in until evolution of hydrogen ceased. The mixture was heated at 35°-40° C. for 2 hours, poured into water (700 ml) and after standing for 1 hour the resultant solid was isolated by suction to give after drying in air 7.06 g (94%) of crude product, mp. 58°-59° C. This was dissolved in methylene chloride and filtered over a short column packed with silica and alumina. The filtrate was concentrated and the residue crystallized from ether to give 4.95 g (66%) of the title compound as a white solid, mp. 79°-80° C.

Workup

  1. temperatureThe mixture was cooled to 0° C
  2. customwas bubbled in until evolution of hydrogen
  3. temperatureThe mixture was heated at 35°-40° C. for 2 hours
  4. additionpoured into water (700 ml)
  5. waitafter standing for 1 hour
  6. customthe resultant solid was isolated by suction
  7. customto give
  8. dry with materialafter drying in air 7.06 g (94%) of crude product, mp. 58°-59° C
  9. dissolutionThis was dissolved in methylene chloride
  10. filtrationfiltered over a short column
  11. concentrationThe filtrate was concentrated
  12. customthe residue crystallized from ether

Sources & evidence

ORD record
ord-f41a944f962a43a09bbae74db1b0abde
Source dataset
uspto-grants-1989_02
Patent number
US04808624

Reaction notes

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