1-(Azidomethyl)-4-methoxybenzene → Ethyl 5-[hydroxy-(2-nitrophenyl)methyl]-1-(4-methoxybenzyl)-1,2,3-triazole-4-carboxylate

HRID 357641ノート

反応式

HRID 357641 の反応式
[OH:1][CH:2]([C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=1[N+:16]([O-:18])=[O:17])[C:3]#[C:4][C:5]([O:7][CH2:8][CH3:9])=[O:6].[CH3:19][O:20][C:21]1[CH:30]=[CH:29][C:24]([CH2:25][N:26]=[N+:27]=[N-:28])=[CH:23][CH:22]=1>C1(C)C=CC=CC=1>[OH:1][CH:2]([C:10]1[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=1[N+:16]([O-:18])=[O:17])[C:3]1[N:26]([CH2:25][C:24]2[CH:29]=[CH:30][C:21]([O:20][CH3:19])=[CH:22][CH:23]=2)[N:27]=[N:28][C:4]=1[C:5]([O:7][CH2:8][CH3:9])=[O:6]

参加物

4

反応物 2

HCID 109317671-(Azidomethyl)-4-methoxybenzeneHCID 18937810Ethyl 4-hydroxy-4-(2-nitrophenyl)-2-butynoate

生成物 1

HCID 21476163Ethyl 5-[hydroxy-(2-nitrophenyl)methyl]-1-(4-methoxybenzyl)-1,2,3-triazole-4-carboxylate

試薬・触媒・溶媒 1

HCID 1140Toluene溶媒

反応条件

温度
100 °C

実験手順

To a solution of diisopropylamine (6.6 ml, 47.1 mmole) in tetrahydrofuran (80 ml) at -78° C. under an argon atmosphere was added 2.5 N butyllithium (17.4 ml, 43.5 mmole), and the mixture was stirred for 30 minutes. To this reaction mixture were next added a solution of ethyl propionate (4.0 ml, 39.5 mmole) in tetrahydrofuran (20 ml) and a solution of 2-nitrobenzaldehyde (4.0 g, 26.5 mmole) in tetrahydrofuran (20 ml) in this sequence, and the resulting mixture was further stirred at -78° C. for 30 minutes. To the reaction mixture were added tetrahydrofuran (10 ml) followed by water, and the mixture was extracted with ethyl acetate. The organic layer was washed with dilute hydrochloric acid, a saturated aqueous sodium hydrogen carbonate solution and a saturated aqueous saline in this sequence. After the organic layer was dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure to give ethyl 4-hydroxy-4-(2-nitrophenyl)-2-butynoate as an oily product. After the ethyl 4-hydroxy-4-(2-nitrophenyl)-2-butynoate thus obtained was dissolved in toluene (80 ml), 4-methoxybenzylazide (13.0 g, 79.7 mmole) was added to the solution and stirred under heating at 100° C. for 3 hours. The reaction mixture was then cooled to room temperature. Precipitates were collected by filtration, washed with toluene and desiccated to give ethyl 5-[hydroxy-(2-nitrophenyl)methyl]-1-(4-methoxybenzyl)-1,2, 3-triazole-4-carboxylate (a-2: highly polar product (MP)) (2.55 g, 15.7%). Furthermore, the filtrate was concentrated and purified by silica gel column chromatography (toluene : ethyl acetate =1:1) to give a 3:1 mixture (6.09 g, 37.4%) of ethyl 4-(hydroxy-(2-nitrophenyl)methyl)-1-(4-methoxybenzyl)-1, 2,3-triazole-5-carboxylate (a-1: low polar product (LP)) and a compound a-2.

後処理

  1. temperatureThe reaction mixture was then cooled to room temperature
  2. customPrecipitates
  3. filtrationwere collected by filtration
  4. washwashed with toluene

出典と根拠

ORDレコード
ord-e4b44ab7ba0948cbaf5e8abdcb10c8b5
出典データセット
uspto-grants-1998_11
特許番号
US05840895

反応ノート

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