1-Octanethiol → 2-(Octylthio)ethyl 2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-alpha-D-galactopyranosyl)-beta-D-galactopyranoside

HRID 653325노트

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HRID 653325 반응식
[C:1]([O:4][C@@H:5]1[C@@H:14]([O:15][C:16](=[O:18])[CH3:17])[C@@H:13]([O:19][C@H:20]2[O:37][C@H:36]([CH2:38][O:39][C:40](=[O:42])[CH3:41])[C@H:31]([O:32][C:33](=[O:35])[CH3:34])[C@H:26]([O:27][C:28](=[O:30])[CH3:29])[C@H:21]2[O:22][C:23](=[O:25])[CH3:24])[C@@H:12]([CH2:43][O:44][C:45](=[O:47])[CH3:46])[O:11][C@H:6]1[O:7][CH2:8][CH2:9]Br)(=[O:3])[CH3:2].[CH2:48]([SH:56])[CH2:49][CH2:50][CH2:51][CH2:52][CH2:53][CH2:54][CH3:55].C(=O)([O-])[O-].[Cs+].[Cs+].C(O[C@@H]1[C@@H](OC(=O)C)[C@@H](OC(=O)C)[C@@H](COC(=O)C)O[C@H]1OCCSCCCCCCCC)(=O)C>[Cl-].C[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC.C1C=CC=CC=1.O>[C:1]([O:4][C@@H:5]1[C@@H:14]([O:15][C:16](=[O:18])[CH3:17])[C@@H:13]([O:19][C@H:20]2[O:37][C@H:36]([CH2:38][O:39][C:40](=[O:42])[CH3:41])[C@H:31]([O:32][C:33](=[O:35])[CH3:34])[C@H:26]([O:27][C:28](=[O:30])[CH3:29])[C@H:21]2[O:22][C:23](=[O:25])[CH3:24])[C@@H:12]([CH2:43][O:44][C:45](=[O:47])[CH3:46])[O:11][C@H:6]1[O:7][CH2:8][CH2:9][S:56][CH2:48][CH2:49][CH2:50][CH2:51][CH2:52][CH2:53][CH2:54][CH3:55])(=[O:3])[CH3:2]

참가 물질

8

반응물 4

HCID 81441-OctanethiolHCID 10796Cesium carbonateHCID 228870902-Bromoethyl 2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-alpha-D-galactopyranosyl)-beta-D-galactopyranosideHCID 542299382-(Octylthio)ethyl 2,3,4,6-tetra-O-acetyl-beta-D-galactopyranoside

생성물 1

HCID 538927502-(Octylthio)ethyl 2,3,6-tri-O-acetyl-4-O-(2,3,4,6-tetra-O-acetyl-alpha-D-galactopyranosyl)-beta-D-galactopyranoside수율 47.5%

시약·촉매·용매 3

HCID 21218Trioctylmethylammonium chloride촉매HCID 241Benzene용매HCID 962Water용매

실험 절차

Compound 15 (484 mg; 0.65 mmol), octanethiol (110 mg; 0.75 mmol; 130 μl), methyltrioctylammonium chloride (ca 10 mg) and cesium carbonate (245 mg; 0.75 mmol) were dissolved in benzene (1 ml) and water (1 ml). The reaction mixture was treated as for compound 21. Chromatography gave the title compound (23) (250 mg) and starting compound 15 (160 mg). Yield (based on consumed 15): 71%; [α]D21 +65.3° (c 1.4; CHCl3); 1H-NMR (CDCl3, TMS) δ 5.57 (dd, 1H, J4',5' =1 Hz, H4'), 5.39 (dd, 1H, J2', 3'=11 Hz, J3',4' =3.5 Hz, H3'), 5.20 (dd, H1, J1', 2' =3.5 Hz, H2'), 5.19 (dd, 1H, J2,3 =11 Hz, J1,2 =7.5 Hz, H2), 5.01 (d, 1H, J1',2' =3.5 Hz, H1'), 4.81 (dd, 1H, J3,4 =3 Hz, H3), 4.51 (d, 1H, J1,2 =7.5 Hz, H1), 2.73, 2.53 (t, 2H each, J=7 Hz, CH2 --S), 2.13, 2.11, 2.08, 2.08, 2.07, 2.04, 1.99 (s, 3H each, CH3 --CO) ppm. 13C-NMR (CDCl3, TMS) 170.7, 170.6, 170.5, 170.4, 170.1, 169.8, 169.1 (CO), 101.2 (Cl), 99.4 (Cl'), 77.1, 72.7, 71.9, 68.6, 68.6, 67.8, 67.4, 67.1 (C2-C5, C2'-C5'), 69.6 (O--CH2 --CH2 --S), 62.0, 60.5 (C6, C6'), 32.6, 31.8, 31.3, 29.8, 29.2, 28.8, 22.7 (aglycon-CH2), 21.0, 20.8, 20.7 (CH3 --CO), 14.1 (CH3 --CH2) ppm.

출처 및 근거

ORD 기록
ord-5bd2d815e70045b58ccd9587f13fbb9f
출처 데이터셋
uspto-grants-1987_06
특허 번호
US04675392

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