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4-Chloro-2-(methylthio)pyrimidine-5-carboxylic acid ethyl ester → Ethyl 4-(methylamino)-2-(methylsulfanyl)pyrimidine-5-carboxylate

HRID 336516
Notes
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Reaction equation

HRID 336516 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[C:7](Cl)=[N:8][C:9]([S:12][CH3:13])=[N:10][CH:11]=1)=[O:5])[CH3:2].C[CH2:16][N:17](C(C)C)C(C)C.Cl.CN>C(#N)C>[CH3:16][NH:17][C:7]1[C:6]([C:4]([O:3][CH2:1][CH3:2])=[O:5])=[CH:11][N:10]=[C:9]([S:12][CH3:13])[N:8]=1
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

5

Reactant 3

HCID 800084-Chloro-2-(methylthio)pyrimidine-5-carboxylic acid ethyl esterHCID 81531DiisopropylethylamineHCID 6364545Methylamine hydrochloride

Product 1

HCID 295697Ethyl 4-(methylamino)-2-(methylsulfanyl)pyrimidine-5-carboxylateYield 11.3%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
100 °C

Procedure

4-Chloro-2-methylsulfanyl-pyrimidine-5-carboxylic acid ethyl ester (10 g, 429 mmol) was dissolved in acetonitrile to which DIPEA (4.34 g, 642 mmol) and methylamine hydrochloride (11.10 g, 858 mmol) was added. The reaction mixture was stirred at 100° C. for 3 hours, then cooled to room temperature and poured in to ice water. Off-white crystalline solid precipitated out. The solid was collected by filtration on a Buchner funnel and dried under vacuum to give the desired product (11 g). 1H NMR (DMSO-d6): δ 1.30 (t, J=7 Hz, 3H), δ 2.46 (s, 3H), δ 2.99 (d, J=5 Hz, 3H), δ 4.29 (q, J=7 Hz, 2H), δ 8.09 (br, s, 1H), δ 8.53 (s, 1H).

Workup

  1. additionwas added
  2. temperaturecooled to room temperature
  3. customOff-white crystalline solid precipitated out
  4. filtrationThe solid was collected by filtration on a Buchner funnel
  5. customdried under vacuum

Sources & evidence

ORD record
ord-a4b193244f334bc8b176808aa1d83f85
Source dataset
uspto-grants-2014_11
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US08889696B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes