Benzyl Alcohol → Tert-butyl (2-(benzyloxy)-5-nitrophenyl)carbamate

HRID 2274269ノート

反応式

HRID 2274269 の反応式
N#N.[OH:3][C:4]1[CH:9]=[CH:8][C:7]([N+:10]([O-:12])=[O:11])=[CH:6][C:5]=1[NH:13][C:14](=[O:20])[O:15][C:16]([CH3:19])([CH3:18])[CH3:17].[CH2:21](O)[C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O>C(Cl)Cl.O.CCCCCC.C(OCC)(=O)C>[CH2:21]([O:3][C:4]1[CH:9]=[CH:8][C:7]([N+:10]([O-:12])=[O:11])=[CH:6][C:5]=1[NH:13][C:14](=[O:20])[O:15][C:16]([CH3:17])([CH3:19])[CH3:18])[C:22]1[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=1

参加物

9

反応物 5

HCID 244Benzyl AlcoholHCID 947NitrogenHCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 15252120Tert-butyl 2-hydroxy-5-nitrophenylcarbamate

生成物 1

HCID 86724342Tert-butyl (2-(benzyloxy)-5-nitrophenyl)carbamate

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 6344Dichloromethane溶媒2 回HCID 21226206Ethyl acetate hexane溶媒

反応条件

温度
0 °C

実験手順

In a 50 mL 3-neck RBF equipped with N2-bubbler and thermo pocket, tert-butyl (2-hydroxy-5-nitrophenyl)carbamate (2.0 g), benzyl alcohol (1.02 g) and triphenyl phosphine (2.48 g) were taken in 10 mL DCM. The reaction mixture was cooled to 0° C. Diethyl azodicarboxylate (1.65 g) was dissolved in 10 mL DCM was added dropwise in the reaction. The reaction mixture was stirred at room temperature for 24 h. The reaction mixture was monitored on TLC using hexane:ethyl acetate (6:4) as mobile phase. After completion, the reaction was poured into water and extracted with DCM (3×50 mL). The DCM layer was washed with brine solution, dried over sodium sulfate and concentrated under reduced pressure at 40° C. Purification was carried out by column chromatography. Desired product eluted with 5% ethyl acetate in hexane to give, after concentration, 1.03 g of tert-butyl (2-(benzyloxy)-5-nitrophenyl)carbamate. 1H NMR: DMSO-d6 (400 MHz) 1.48 (s, 9H), 5.34 (s, 2H), 7.26 (d, 1H, J=9.2), 7.35 (m, 1H), 7.41 (m, 2H), 7.54 (d, 2H, J=6.8), 7.95 (dd, 1H, J=2.8, 9.2), 8.51 (s, 1H), 8.64 (d, 1H, J=2.8).

後処理

  1. additionwas added dropwise in the reaction
  2. extractionextracted with DCM (3×50 mL)
  3. washThe DCM layer was washed with brine solution
  4. dry with materialdried over sodium sulfate
  5. concentrationconcentrated under reduced pressure at 40° C
  6. customPurification
  7. washDesired product eluted with 5% ethyl acetate in hexane
  8. customto give
  9. concentrationafter concentration, 1.03 g of tert-butyl (2-(benzyloxy)-5-nitrophenyl)carbamate

出典と根拠

ORDレコード
ord-3869b05b42014160a78281deebd9d54a
出典データセット
uspto-grants-2015_09
特許番号
US09126950B2

反応ノート

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