2-Amino-4-methylphenol → N-(4-Bromophenyl)-5-methyl-1,3-benzoxazol-2-amine

HRID 30904

反応式

HRID 30904 の反応式
BrC1C=CC(N=C=S)=CC=1.NC1C=C(C)C=CC=1O.[Br:20][C:21]1[CH:26]=[CH:25][C:24]([NH:27][C:28]([NH:30][C:31]2[CH:36]=[C:35]([CH3:37])[CH:34]=[CH:33][C:32]=2[OH:38])=S)=[CH:23][CH:22]=1.Cl.CN(C)CCCN=C=NCC>C(O)C.CCOCC>[Br:20][C:21]1[CH:26]=[CH:25][C:24]([NH:27][C:28]2[O:38][C:32]3[CH:33]=[CH:34][C:35]([CH3:37])=[CH:36][C:31]=3[N:30]=2)=[CH:23][CH:22]=1

参加物

7

反応物 4

HCID 72642-Amino-4-methylphenolHCID 161334-Bromophenyl isothiocyanateHCID 27239391,3-Propanediamine, N'-(ethylcarbonimidoyl)-N,N-dimethyl-, monohydrochlorideHCID 21985832N-(4-bromophenyl)-N'-(2-hydroxy-5-methylphenyl)thiourea

生成物 1

HCID 21985825N-(4-Bromophenyl)-5-methyl-1,3-benzoxazol-2-amine収率 60%

試薬・触媒・溶媒 2

HCID 702Ethanol溶媒HCID 3283Diethyl Ether溶媒

実験手順

In a 250-mL round-bottom flask, 1-bromo-4-isothiocyanatobenzene (4.28 g, 20 mmol) and 2-amino-4-methyl-phenol (2.46 g, 20 mmol) were stirred in 120 mL ethanol at rt overnight. The formation of N-(4-bromophenyl)-N′-(2-hydroxy-5-methylphenyl)thiourea was confirmed by LC-MS. To the mixture, 1.5 eq. 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDCI) was added, and the reaction was stirred at rt for another 2 h. The reaction mixture was then heated at reflux for 6 h. The mixture was cooled to rt and the solvent was removed under reduced pressure. The solid was dissolved in EtOAc and washed with 2 N aqueous HCl and H2O. The organic layer was dried (MgSO4) and the solvent was removed under reduced pressure. The solid obtained was ultrasonicated in 30 mL ether and filtered to give the desired compound (3.64 g, 60%). 1H NMR (400 MHz, DMSO-d6) δ 10.70 (s, 1H), 7.70 (m, 2H), 7.55 (m, 2H), 7.35 (d, 1H), 7.25 (s, 1H), 6.95 (d, 1H), 2.40 (s, 3H). LC-MS m/z 303.3 (MH+), ret. time 3.46 min.

後処理

  1. temperatureThe reaction mixture was then heated
  2. temperatureat reflux for 6 h
  3. temperatureThe mixture was cooled to rt
  4. customthe solvent was removed under reduced pressure
  5. dissolutionThe solid was dissolved in EtOAc
  6. washwashed with 2 N aqueous HCl and H2O
  7. dry with materialThe organic layer was dried (MgSO4)
  8. customthe solvent was removed under reduced pressure
  9. customThe solid obtained
  10. filtrationfiltered

出典と根拠

ORDレコード
ord-6ec68b7d671742119a40ab019e4facc7
出典データセット
uspto-grants-2008_09
特許番号
US07423156B2

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