Reaktionsgleichung
NC1C=C(N)C=C(N)C=1C1C=CC(C)=CC=1.[C:17]([O:20][CH:21]1[O:35][C@H:34]([CH2:36][O:37][C:38](=[O:40])[CH3:39])[C@@H:29]([O:30][C:31](=[O:33])[CH3:32])[C@H:24]([O:25][C:26](=[O:28])[CH3:27])[C@H:22]1[NH2:23])(=[O:19])[CH3:18].[I:41][C:42]1[C:47]([CH2:48][CH3:49])=[C:46]([I:50])[C:45]([CH2:51][CH3:52])=[C:44]([I:53])[C:43]=1[C:54]1[CH:59]=[CH:58][C:57]([C:60](Cl)=[O:61])=[C:56]([N+:63]([O-:65])=[O:64])[CH:55]=1>>[N+:63]([C:56]1[CH:55]=[C:54]([C:43]2[C:44]([I:53])=[C:45]([CH2:51][CH3:52])[C:46]([I:50])=[C:47]([CH2:48][CH3:49])[C:42]=2[I:41])[CH:59]=[CH:58][C:57]=1[C:60]([C:21]1([O:35][C@H:34]([CH2:36][O:37][C:38](=[O:40])[CH3:39])[C@@H:29]([O:30][C:31](=[O:33])[CH3:32])[C@H:24]([O:25][C:26](=[O:28])[CH3:27])[C@H:22]1[NH2:23])[O:20][C:17](=[O:19])[CH3:18])=[O:61])([O-:65])=[O:64]Komponenten
Versuchsvorschrift
Freidel-Crafts acylation is performed on 2′,4′,6′-triiodo-3′-ethyl-3-nitrobiphenyl-4-carboxylic acid (13) in the presence of AlCl3 and CH3COCl to yield 2′,4′,6′-triiodo-3′-ethyl-5′-acetyl-3-nitrobiphenyl-4-carboxylic acid (17). 2′,4′,6′-triiodo-3′-ethyl-5′-acetyl-3-nitrobiphenyl-4-carboxylic acid (17) is then reacted with a zinc mercury amalgam and hydrochloric add and heated to yield 2′,4′,6′-triiodo-3′,5′-bis(ethyl)-3-nitrobiphenyl-4-carboxylic acid (18). C 15 H 10 I 3 N O 4 → C H 3 C O Cl Al Cl 3 → Δ Zn ( Hg ) , H Cl C 17 H 14 I 3 N O 4 2′,4′,6′-triiodo-3′,5′-bis(ethyl)-3-nitrobiphenyl-4-carboxylic acid (18) is reacted with thionyl chloride to yield 2′,4′,6′-triiodo-3′,5′-bis(ethyl)-3-nitrobiphenyl-4-carbonyl chloride (19). C 17 H 14 I 3 N O 4 → S O Cl 2 C 17 H 13 Cl I 3 N O 3 1,3,4,6-tetra-O-acetyl-D-glucosamine (9) is reacted with 2′,4′,6′-triiodo-3′5′-bis(ethyl)-3-nitrobiphenyl-4-carbonyl chloride (19) to yield 2-nitro-4-[3′,5′-bis(ethyl)-2′,4′,6′-triiodophenyl]-benzoyl-1,3,4,6-tetra-O-acetyl-D-glucosamine (20). C14H21NO9+C17H13ClI3NO3→C31H33I3N2O12 2-nitro-4-[3′,5′-bis(ethyl)-2′,4′,6′-triiodophenyl]-benzoyl-1,3,4,6-tetra-O-acetyl-D-glucosamine (20) is oxidized with potassium permanganate to yield 2-nitro-4-[3′,5′-bis(carboxylic acid)-2′,4′,6′-triiodophenyl]-benzoyl-1,3,4,6-tetra-O-acetyl-D-glucosamine (21). C 31 H 33 I 3 N 2 O 12 → K Mn O 4 C 29 H 25 I 3 N 2 O 16 2-nitro-4-[3′,5′-bis(carboxylic acid)-2′,4′,6′-triiodophenyl]-benzoyl-1,3,4,6-tetra-O-acetyl-D-glucosamine (21) is reacted with ethanol and weak hydrochloric acid and heated to yield 2-nitro-4-[3′,5′-bis(ethoxycarbonyl)-2′,4′,6′-triiodophenyl]-benzoyl-1,3,4,6-tetra-O-acetyl-D-glucosamine (22). C 29 H 25 I 3 N 2 O 16 → Δ Et O H , H Cl C 33 H 33 I 3 N 2 O 16 2-nitro-4-[3′,5′-bis(ethoxycarbonyl)-2′,4′,6′-triiodophenyl]-benzoyl-1,3,4,6-tetra-O-acetyl-D-glucosamine (22) is reacted with methylamine to yield 2-nitro-4-[3′,5′-bis(N-methylcarboxamide)-2′,4′,6′-triiodophenyl]-benzoyl-1,3,4,6-tetra-O-acetyl-D-glucosamine (23). C 33 H 33 I 3 N 2 O 16 → C H 3 N H 2 C 31 H 31 I 3 N 4 O 14 2-nitro-4-[3′,5′-bis(N-methylcarboxamide)-2′,4′,6′-triiodophenyl]-benzoyl-1,3,4,6-tetra-O-acetyl-D-glucosamine (23) is treated with stannous chloride and hydrochloric acid to yield 2-amino-4-[3′,5′-bis(N-methylcarboxamide)-2′,4′,6′-triiodophenyl]-benzoyl-D-glucosamine (24). C 31 H 31 I 3 N 4 O 14 → Sn Cl 2 , H Cl C 23 H 25 I 3 N 4 O 8
Quellen und Nachweise
- ORD-Eintrag
- ord-12765312a5a24eb2a7badd61b1c61689
- Quelldatensatz
- uspto-grants-2005_08
- Patentnummer
- US06923950B2
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