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Hydrazine hydrate (1:1) → 2-(Octadecylthio)ethyl 2-acetamido-2-deoxy-3,6-di-O-acetyl-4-O-[2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-alpha-D-galactopyranosyl)-beta-D-galactopyranosyl]-beta-D-glucopyranoside

HRID 653338
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HRID 653338 반응식
[C:1]([O:4][C@H:5]1[C@H:32]([O:33][C@@H:34]2[O:71][C@H:70]([CH2:72][O:73][C:74](=[O:76])[CH3:75])[C@H:45]([O:46][C@H:47]3[O:64][C@H:63]([CH2:65][O:66][C:67](=[O:69])[CH3:68])[C@H:58]([O:59][C:60](=[O:62])[CH3:61])[C@H:53]([O:54][C:55](=[O:57])[CH3:56])[C@H:48]3[O:49][C:50](=[O:52])[CH3:51])[C@H:40]([O:41][C:42](=[O:44])[CH3:43])[C@H:35]2[O:36][C:37](=[O:39])[CH3:38])[C@@H:31]([CH2:77][O:78][C:79](=[O:81])[CH3:80])[O:30][C@@H:7]([O:8][CH2:9][CH2:10][S:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH3:29])[C@@H:6]1[N:82]1C(=O)C2=CC=CC=[C:84]2[C:83]1=[O:92])(=[O:3])[CH3:2].C[O-].[Na+].O.NN>CO.O1CCCC1>[C:83]([NH:82][C@@H:6]1[C@@H:5]([O:4][C:1](=[O:3])[CH3:2])[C@H:32]([O:33][C@@H:34]2[O:71][C@H:70]([CH2:72][O:73][C:74](=[O:76])[CH3:75])[C@H:45]([O:46][C@H:47]3[O:64][C@H:63]([CH2:65][O:66][C:67](=[O:69])[CH3:68])[C@H:58]([O:59][C:60](=[O:62])[CH3:61])[C@H:53]([O:54][C:55](=[O:57])[CH3:56])[C@H:48]3[O:49][C:50](=[O:52])[CH3:51])[C@H:40]([O:41][C:42](=[O:44])[CH3:43])[C@H:35]2[O:36][C:37](=[O:39])[CH3:38])[C@@H:31]([CH2:77][O:78][C:79](=[O:81])[CH3:80])[O:30][C@H:7]1[O:8][CH2:9][CH2:10][S:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH3:29])(=[O:92])[CH3:84]
참가 물질실험 절차후처리출처 및 근거반응 노트

참가 물질

6

반응물 3

HCID 24654Hydrazine hydrate (1:1)HCID 10942334Sodium MethoxideHCID 186083192-(Octadecylthio)ethyl 3,6-di-O-acetyl-2-deoxy-2-phthalimido-4-O-[2,3,6-tri O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-alpha-D-galactopyranosyl)-beta-D-galactopyranosyl]-beta-D-glucopyranoside

생성물 1

HCID 86741645
2-(Octadecylthio)ethyl 2-acetamido-2-deoxy-3,6-di-O-acetyl-4-O-[2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-alpha-D-galactopyranosyl)-beta-D-galactopyranosyl]-beta-D-glucopyranoside
수율 52.9%

시약·촉매·용매 2

HCID 887Methanol용매2회HCID 8028Tetrahydrofuran용매

실험 절차

Compound 80 (1.46 g, 1.1 mmol) was dissolved in a mixure of methanol (75 ml) and tetrahydrofuran (10 ml) by warming. The clear solution was rapidly cooled to ~40° C. and methanolic sodium methoxide (0.2 M, 5 ml) was added. The mixture was stirred at room temperature for 5 h, after which time the deacetylation was complete. (TLC; SiO2,chloroform:methanol:water 65:35:10, lower phase), neutralized by addition of acidic ion-exchange resin (Duolite C-26), filtered and evaporated. The residue was re-dissolved in refluxing methanol (50 ml) and hydrazine hydrate (0.5 g, 10 mmol) was added. The reflux was continued for 17.5 h, whereafter the solvent was evaporated. The residue was acetylated by stirring for 22 h at room temperature in a mixture of pyridine and acetic anhydride (1:1, 50 ml). After evaporation, the residue was subjected to chromatography (SiO2 -column, 5×18 cm, ethyl acetate: isooctane gradient: 2:1-4:1-ethyl acetate) which gave amorphous 83 (0.72 g, 52%) with [α]D21 +32° (c 1.1, chloroform). 1H-NMR (CDC13, Me4Si) δ 5.67 (d, 1H, J=9.5 Hz, NH), 5.58 (bd, 1H, J=3 Hz, H4"), 5.39 (dd, 1H, J=11 and 3 Hz, H3"), 5.23-5.01 (3H, H2', H2" and H3), 4.99 (d, 1H, J=3.5, H1"), 4.75 (dd, 1H, J=11 and 2.5 Hz, H3') 4.58-4.37 (5H, inter alia H1and H1'), 4.54 and 4.49 (2d, each 1H, J=8 Hz each, H1 and H1'), 4.23-3.90 (7H), 3.85-3.55 (4H), 2.69 (t, 2H, J=7 Hz, OCH2CH2S), 2.51 (t, 2H, J=7 Hz, SCH2), 2.13, 2.12, 2.11, 2.08 (4s, each 3H, MeCO), 2.075, 2.05 (2s, each 6H, MeCO), 1.99, 1.97 (2s, each 3H, MeCO), 1.66-1.20, 0.88 (t, 3H, J=6.5 Hz, CH3CH2). 13C-NMR (CDC13, Me4Si) δ 170.6 (2C), 170.4 (3C), 170.2, 170.1, 169.6, 169.0, 101.1, 101.0 (d, J each 160 Hz, C1 and C1'), 99.6 (d, J=172 Hz, C1"), 76.9, 75.9, 72.7, 72.6 (2C), 71.8, 69.1 (OCH2CH2), 68.9, 68.7, 67.8, 67.1, 67.0, 62.4 (CH2), 61.3 (CH2), 60.2 (CH2), 53.3 (C2), 32.5-28.8, 23.3 (CH3CONH), 22.7 (CH2), 20.9-20.5, 14.1.

후처리

  1. temperatureby warming
  2. temperatureThe clear solution was rapidly cooled to ~40° C.
  3. filtrationfiltered
  4. customevaporated
  5. dissolutionThe residue was re-dissolved
  6. additionwas added
  7. waitThe reflux was continued for 17.5 h, whereafter the solvent
  8. customwas evaporated
  9. stirringby stirring for 22 h at room temperature in a mixture of pyridine and acetic anhydride (1:1, 50 ml)
  10. customAfter evaporation

출처 및 근거

ORD 기록
ord-dce3570b5005459bb4eaef0ed9b98d4b
출처 데이터셋
uspto-grants-1987_06
DOI
10.6084/m9.figshare.5104873.v1
특허 번호
US04675392

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