Hydrochloric Acid → (2-Chloro-5-methylpyrimidin-4-yl)(3,4-dichlorophenyl)amine

HRID 1357542Notes

Reaction equation

HRID 1357542 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH:6]=[CH:7][C:8]=1[Cl:9])[NH2:5].Cl.[CH3:11][C:12]1[C:13](Cl)=[N:14][C:15]([Cl:18])=[N:16][CH:17]=1.C(Cl)Cl>C(O)CCC>[Cl:18][C:15]1[N:16]=[C:17]([NH:5][C:4]2[CH:6]=[CH:7][C:8]([Cl:9])=[C:2]([Cl:1])[CH:3]=2)[C:12]([CH3:11])=[CH:13][N:14]=1

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 6344DichloromethaneHCID 72573,4-DichloroanilineHCID 74508Pyrimidine, 2,4-dichloro-5-methyl-

Product 1

HCID 18186461(2-Chloro-5-methylpyrimidin-4-yl)(3,4-dichlorophenyl)amineYield 29.9%

Reagents, catalysts & solvents 1

HCID 2631-ButanolSolvent

Procedure

3,4-Dichloroaniline (639 mg, 3.94 mmol) and concentrated hydrochloric acid (ca. 12M, 0.2 ml, ca. 2.4 mmol) were sequentially added to a solution of 5-methyl-2,4-dichloropyrimidine (643 mg, 3.94 mmol) in n-butanol (20 ml). The mixture was stirred at ambient temperature for 20 hours, after which time a gelatinous precipitate had fallen out of solution. DCM was added until a solution was obtained, and silica (2.5 g) was added. Volatile material was removed by evaporation and the residue was loaded on a Varian Mega Bond Elut column pre-conditioned with ethyl acetate. The column was eluted with 0-10% methanol solution in ethyl acetate containing 0.5% aqueous ammonia. The appropriate fractions were concentrated, and the residue was triturated with n-butanol (20 ml). The filtrate was evaporated onto silica (2.5 g) and loaded on a Varian Mega Bond Elut column pre-conditioned with isohexane. The column was eluted with 0-50% ethyl acetate solution in isohexane. Concentration of the appropriate fractions gave the product as a white solid (340 mg, 26%). NMR: 2.17 (s, 3H), 7.60 (d, 1H), 7.70 (dd, 1H), 8.00 (d, 1H), 8.11 (s, 1H), 8.97 (s, 1H); MS (MH+): 288.1, 290.1, 292.1.

Workup

  1. customwas obtained
  2. additionsilica (2.5 g) was added
  3. customVolatile material was removed by evaporation
  4. washThe column was eluted with 0-10% methanol solution in ethyl acetate containing 0.5% aqueous ammonia
  5. concentrationThe appropriate fractions were concentrated
  6. customthe residue was triturated with n-butanol (20 ml)
  7. customThe filtrate was evaporated onto silica (2.5 g)
  8. washThe column was eluted with 0-50% ethyl acetate solution in isohexane

Sources & evidence

ORD record
ord-ccdda1e220a64e4fae41f771bdccb380
Source dataset
uspto-grants-2003_07
Patent number
US06593326B1

Reaction notes

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