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Methane, dichloromethoxy- → 2-Deoxy-4-o-diphenylphosphono-3-o-[(r)-3-tetradecanoyloxytetradecanoyl]-6-o-(2,2,2-trichloro-1,1-dimethylethoxycarbonyl)-2-(2,2,2-trichloroethoxycarbonylamino)-alpha-d-glucopyranosyl chloride

HRID 849622
ノート
印刷プレビュー

反応式

HRID 849622 の反応式
[C:1]1([O:7][P:8]([O:17][C@@H:18]2[C@@H:30]([CH2:31][O:32][C:33]([O:35][C:36]([CH3:42])([CH3:41])[C:37]([Cl:40])([Cl:39])[Cl:38])=[O:34])[O:29][C@@H:21](OCC[Si](C)(C)C)[C@H:20]([NH:43][C:44]([O:46][CH2:47][C:48]([Cl:51])([Cl:50])[Cl:49])=[O:45])[C@H:19]2[O:52][C:53](=[O:83])[CH2:54][C@H:55]([O:67][C:68](=[O:82])[CH2:69][CH2:70][CH2:71][CH2:72][CH2:73][CH2:74][CH2:75][CH2:76][CH2:77][CH2:78][CH2:79][CH2:80][CH3:81])[CH2:56][CH2:57][CH2:58][CH2:59][CH2:60][CH2:61][CH2:62][CH2:63][CH2:64][CH2:65][CH3:66])([O:10][C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)=[O:9])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.COC(Cl)[Cl:87]>C(Cl)(Cl)Cl.CCOC(C)=O.[Cl-].[Cl-].[Zn+2]>[C:1]1([O:7][P:8]([O:17][C@@H:18]2[C@@H:30]([CH2:31][O:32][C:33]([O:35][C:36]([CH3:41])([CH3:42])[C:37]([Cl:38])([Cl:40])[Cl:39])=[O:34])[O:29][C@H:21]([Cl:87])[C@H:20]([NH:43][C:44]([O:46][CH2:47][C:48]([Cl:50])([Cl:49])[Cl:51])=[O:45])[C@H:19]2[O:52][C:53](=[O:83])[CH2:54][C@H:55]([O:67][C:68](=[O:82])[CH2:69][CH2:70][CH2:71][CH2:72][CH2:73][CH2:74][CH2:75][CH2:76][CH2:77][CH2:78][CH2:79][CH2:80][CH3:81])[CH2:56][CH2:57][CH2:58][CH2:59][CH2:60][CH2:61][CH2:62][CH2:63][CH2:64][CH2:65][CH3:66])([O:10][C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)=[O:9])[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1
参加物実験手順後処理出典と根拠反応ノート

参加物

6

反応物 2

HCID 21004Methane, dichloromethoxy-HCID 229523932-(Trimethylsilyl)ethyl 2-deoxy-4-o-diphenylphosphono-3-o-[(r)-3-tetradecanoyloxytetradecanoyl]-6-o-(2,2,2-trichloro-1,1-dimethylethoxycarbonyl)-2-(2,2,2-trichlorethoxycarbonylamino)-beta-d-glucopyranoside

生成物 1

HCID 117684072-Deoxy-4-o-diphenylphosphono-3-o-[(r)-3-tetradecanoyloxytetradecanoyl]-6-o-(2,2,2-trichloro-1,1-dimethylethoxycarbonyl)-2-(2,2,2-trichloroethoxycarbonylamino)-alpha-d-glucopyranosyl chloride収率 89.6%

試薬・触媒・溶媒 3

HCID 3007855Zincchloride触媒HCID 6212Chloroform溶媒HCID 8857Ethyl Acetate溶媒

実験手順

A solution of the compound 8 (6.5 g, 4.84 mmol) and dichloromethyl methyl ether (2.18 ml, 24.2 mmol) in CHCl3 (60 ml) at 0°C. was treated with ZnCl2 (1.0 M in ether; 2.41 ml, 2.41 mmol) and then allowed to warm slowly and stir at room temperature overnight. The reaction mixture was diluted with EtOAc, washed with saturated aq. NaHCO3, dried (Na2SO4) and then concentrated. The light yellow oil obtained was purified by flash chromatography on silica gel eluting with 10% EtOAc-hexanes to give 5.4 g (88%) of 2-deoxy-4-O-diphenylphosphono-3-O-[(R)-3-tetradecanoyloxytetradecanoyl]-6-O-(2,2,2-trichloro-1,1-dimethylethoxycarbonyl)-2-(2,2,2-trichloroethoxycarbonylamino)-α-D-glucopyranosyl chloride (compound 9) as an amorphous solid: 1H NMR (CDCl3) δ 0.88 (~t, 6H), 1.1-1.6 (m, 42H), 1.78 (s, 3H), 1.88 (s, 3H), 2.18 (t, 2H, J=7.6 Hz), 2.34-2.52 (m, 2H), 4.2-4.4 (m, 4H), 4.70 (d, 1H, J=12 Hz), 4.73 (d, 1H J=12 Hz), 4.83 (~q, 1H, J=9 Hz), 5.09 (m, 1H), 5.51 (~t, 1H, J=10 Hz), 5.79 (d, 1H, J=8.0 Hz), 6.26 (d, 1H, J=3.6 Hz), 7.1-7.4 (m, 10H).

後処理

  1. temperatureto warm slowly
  2. washwashed with saturated aq. NaHCO3
  3. dry with materialdried (Na2SO4)
  4. concentrationconcentrated
  5. customThe light yellow oil obtained
  6. customwas purified by flash chromatography on silica gel eluting with 10% EtOAc-hexanes

出典と根拠

ORDレコード
ord-419ed6841492409d941c596776a4e3ff
出典データセット
uspto-grants-2000_01
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US06013640

反応ノート

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