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Ethanethiol → 3,6-Dihydro-4-methyl-6-(3-nitrophenyl)-2-thioxo-1,5(2H)-pyrimidinedicarboxylic acid, 1-methyl 5-(1-methylethyl) ester

HRID 1590289
Notes
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Reaction equation

HRID 1590289 reaction equation
F[C:2](F)(F)[C:3]([OH:5])=[O:4].[CH2:8](S)[CH3:9].C[C:12]1[NH:13][C:14](=[S:33])[N:15](C(O)=O)[CH:16]([C:21]2[CH:26]=[CH:25][CH:24]=[C:23]([N+:27]([O-:29])=[O:28])[CH:22]=2)[C:17]=1C(O)=O.[C:34]([O:37][CH2:38]C)(=[O:36])C.Cl[CH2:41]Cl>>[CH3:17][C:12]1[NH:13][C:14](=[S:33])[N:15]([C:34]([O:37][CH3:38])=[O:36])[CH:16]([C:21]2[CH:26]=[CH:25][CH:24]=[C:23]([N+:27]([O-:29])=[O:28])[CH:22]=2)[C:2]=1[C:3]([O:5][CH:8]([CH3:9])[CH3:41])=[O:4]
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

6

Reactant 5

HCID 6343EthanethiolHCID 6344Dichloromethane2×HCID 6422Trifluoroacetic acidHCID 8857Ethyl AcetateHCID 197695663,6-dihydro-4-methyl-6-(3-nitrophenyl)-2-thioxo-1,5(2H)-pyrimidinedicarboxylic acid

Product 1

HCID 71722732
3,6-Dihydro-4-methyl-6-(3-nitrophenyl)-2-thioxo-1,5(2H)-pyrimidinedicarboxylic acid, 1-methyl 5-(1-methylethyl) ester

Procedure

The ester product from part (b) (7.42 g.) is dissolved in dichloromethane (50 ml.) and treated with trifluoroacetic acid (5 ml.) and ethanethiol (1.5 ml.). The reaction is stirred at room temperature for 16 hours, and then dichloromethane (50 ml.) is added. The organic layer is washed with water (2×150 ml.), saturated sodium bicarbonate (2×150 ml.), saturated sodium carbonate (100 ml.), sodium dihydrogen phosphate (100 ml.), and saturated sodium chloride (100 ml.), dreid over magnesium sulfate, and evaporated in vacuo to give 6.31 g. of product as an oil. Crystallization from ethyl acetate: hexanes gives 3.2 g. of yellow solid 3,6-dihydro-4-methyl-6-(3-nitrophenyl)-2-thioxo-1,5(2H)-pyrimidinedicarboxylic acid, 5-(1-methylethyl 1-methyl ester; m.p. 130.5°-131.5°. TLC (silica gel; ethyl acetate:hexanes, 1:2) Rf =0.30.

Workup

  1. washThe organic layer is washed with water (2×150 ml.), saturated sodium bicarbonate (2×150 ml.), saturated sodium carbonate (100 ml.), sodium dihydrogen phosphate (100 ml.), and saturated sodium chloride (100 ml.)
  2. customevaporated in vacuo
  3. customto give 6.31 g
  4. customCrystallization from ethyl acetate
  5. customhexanes gives 3.2 g

Sources & evidence

ORD record
ord-871afc86ff534278bd57dd380c761dbd
Source dataset
uspto-grants-1993_04
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US05202330

Reaction notes

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