N,N-Dimethyloxamic acid → 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(2-(dimethylamino)-2-oxoacetamido)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)benzoic acid

HRID 85572Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 85572
[NH2:1][C@:2]12[CH2:37][CH2:36][C@@H:35]([C:38]([CH3:40])=[CH2:39])[C@@H:3]1[C@@H:4]1[C@@:17]([CH3:20])([CH2:18][CH2:19]2)[C@@:16]2([CH3:21])[C@@H:7]([C@:8]3([CH3:34])[C@@H:13]([CH2:14][CH2:15]2)[C:12]([CH3:23])([CH3:22])[C:11]([C:24]2[CH:33]=[CH:32][C:27]([C:28]([O:30]C)=[O:29])=[CH:26][CH:25]=2)=[CH:10][CH2:9]3)[CH2:6][CH2:5]1.CN(C)CCC(N[C@]12CC[C@@H](C(C)=C)[C@@H]1[C@@H]1[C@@](C)(CC2)[C@@]2(C)[C@@H]([C@]3(C)[C@@H](CC2)C(C)(C)C(C2C=CC(C(O)=O)=CC=2)=CC3)CC1)=O.[CH3:87][N:88]([CH3:94])[C:89](=[O:93])[C:90](O)=[O:91]>>[CH3:87][N:88]([CH3:94])[C:89](=[O:93])[C:90]([NH:1][C@:2]12[CH2:37][CH2:36][C@@H:35]([C:38]([CH3:40])=[CH2:39])[C@@H:3]1[C@@H:4]1[C@@:17]([CH3:20])([CH2:18][CH2:19]2)[C@@:16]2([CH3:21])[C@@H:7]([C@:8]3([CH3:34])[C@@H:13]([CH2:14][CH2:15]2)[C:12]([CH3:23])([CH3:22])[C:11]([C:24]2[CH:33]=[CH:32][C:27]([C:28]([OH:30])=[O:29])=[CH:26][CH:25]=2)=[CH:10][CH2:9]3)[CH2:6][CH2:5]1)=[O:91]

Komponenten

4

Edukt 3

HCID 2760995N,N-Dimethyloxamic acidHCID 683578604-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(3-(dimethylamino)propanamido)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)benzoic acidHCID 68357865methyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-amino-1-isopropenyl-5a,5b,8,8,11a-pentamethyl-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)benzoate

Produkt 1

HCID 683581944-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(2-(dimethylamino)-2-oxoacetamido)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)benzoic acidAusbeute 13 %

Versuchsvorschrift

The title compound was prepared in 13% yield from methyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-amino-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)benzoate following the same procedure as described for the preparation of 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(3-(dimethylamino)propanamido)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-9-yl)benzoic acid, except N,N-dimethyloxamic acid was used instead of 3-(dimethylamino)propionic acid hydrochloride in Step 1. LCMS: m/e 627.6 (M−H)−, 1.91 min (method 5). 1H NMR (500 MHz, 2:1 MeOD:CDCl3) δ=7.93 (d, J=8.2 Hz, 2H), 7.55 (s, 1H), 7.21 (d, J=8.2 Hz, 2H), 5.30 (dd, J=1.7, 6.3 Hz, 1H), 4.77 (d, J=1.2 Hz, 1H), 4.65 (s, 1H), 3.22 (s, 3H), 3.01 (s, 3H), 2.71-2.59 (m, 2H), 2.46 (dd, J=8.2, 11.9 Hz, 1H), 2.14 (dd, J=6.3, 17.2 Hz, 1H), 2.02-1.93 (m, 1H), 1.89 (dt, J=3.4, 12.2 Hz, 1H), 1.79 (d, J=13.1 Hz, 1H), 1.75 (d, J=3.7 Hz, 1H), 1.71 (br. s., 1H), 1.66 (dt, J=3.5, 13.5 Hz, 1H), 1.61-1.54 (m, 2H), 1.54-1.48 (m, 4H), 1.46 (br. s., 1H), 1.45-1.40 (m, 3H), 1.40-1.34 (m, 1H), 1.28 (br. s., 2H), 1.20-1.14 (m, 2H), 1.13 (s, 3H), 1.05 (s, 3H), 1.03 (s, 3H), 0.96 (s, 3H), 0.95 (s, 3H).

Aufarbeitung

  1. customm/e 627.6 (M−H)−, 1.91 min (method 5)

Quellen und Nachweise

ORD-Eintrag
ord-ec3dc0f52a7542fd851fa9fb8ac3373b
Quelldatensatz
uspto-grants-2014_09
Patentnummer
US08846647B2

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