Hydrochloric Acid → ({1-[(2-chlorophenyl)methyl]-3,5-dimethyl-1H-pyrazol-4-yl}methyl)(methyl)amine

HRID 238122ノート

反応式

HRID 238122 の反応式
[Cl:1][C:2]1[CH:15]=[CH:14][CH:13]=[CH:12][C:3]=1[CH2:4][N:5]1[C:9]([CH3:10])=[CH:8][C:7]([CH3:11])=[N:6]1.C=O.[CH3:18][NH2:19].Cl.[CH3:21]O>>[Cl:1][C:2]1[CH:15]=[CH:14][CH:13]=[CH:12][C:3]=1[CH2:4][N:5]1[C:9]([CH3:10])=[C:8]([CH2:18][NH:19][CH3:21])[C:7]([CH3:11])=[N:6]1

参加物

6

反応物 5

HCID 313Hydrochloric AcidHCID 712FormaldehydeHCID 887MethanolHCID 6329MethylamineHCID 6618091-(2-chlorobenzyl)-3,5-dimethyl-1H-pyrazole

生成物 1

HCID 2466725({1-[(2-chlorophenyl)methyl]-3,5-dimethyl-1H-pyrazol-4-yl}methyl)(methyl)amine収率 62%

反応条件

温度
60 °C

実験手順

A solution of 1-(2-chlorobenzyl)-3,5-dimethyl-1H-pyrazole (1.00 g, 4.53 mmol), paraformaldehyde (0.82 g, 27.20 mmol) and methylamine.HCl (0.92 g, 13.59 mmol) dissolved in methanol (9.06 ml) was stirred at 60° C. for 24 hrs. The mixture was cooled to room temperature and quenched with aqueous NaHCO3 (15 mL). The aqueous layer was extracted 3 times with ether (15 mL) and the combined organic layers washed with brine (30 mL). The organic layer was dried with MgSO4 and concentrated under reduced pressure. The resulting yellow oil was purified using flash column chromatography with 1:4:0.01 ethyl acetate:hexanes:triethylamine as eluting solvent yielding 0.73 g (62%) of 1-(1-(2-chlorobenzyl)-3,5-dimethyl-1H-pyrazol-4-yl)-N-methylmethanamine as a clear oil. 1H NMR (300 MHz, CDCl3) δ 7.40-7.31 (m, 1H), 7.23-7.08 (m, 2H), 6.54-6.43 (m, 1H), 5.32 (s, 2H), 3.31 (s, 2H), 2.91 (s, 1H), 2.25 (s, 3H), 2.16 (s, 3H), 2.12 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 148.12, 138.48, 135.57, 131.94, 129.42, 128.72, 127.61, 127.41, 114.38, 50.24, 49.08, 40.68, 12.36, 9.75. HRMS (m/z): [MH]+ calc for C14H18ClN3, 264.13. found 264.1253.

後処理

  1. temperatureThe mixture was cooled to room temperature
  2. customquenched with aqueous NaHCO3 (15 mL)
  3. extractionThe aqueous layer was extracted 3 times with ether (15 mL)
  4. washthe combined organic layers washed with brine (30 mL)
  5. dry with materialThe organic layer was dried with MgSO4
  6. concentrationconcentrated under reduced pressure
  7. customThe resulting yellow oil was purified
  8. washhexanes:triethylamine as eluting solvent

出典と根拠

ORDレコード
ord-f9d761060b3d416ebab19dc2b5f2d1ff
出典データセット
uspto-grants-2014_02
特許番号
US08642614B2

反応ノート

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