2,4,5-Trichloronitrobenzene → (+/-)-(1R*,2S*,3R*)-3-(4,5-Dichloro-2-nitroanilino)-1,2-cyclopentanediol

HRID 1609028Notes

Reaction equation

HRID 1609028 reaction equation
[NH2:1][C@@H:2]1[CH2:6][CH2:5][C@@H:4]([OH:7])[C@H:3]1[OH:8].[Cl:9][C:10]1[CH:15]=[C:14]([N+:16]([O-:18])=[O:17])[C:13](Cl)=[CH:12][C:11]=1[Cl:20].C(N(CC)CC)C>C(O)(C)(C)C>[Cl:9][C:10]1[C:11]([Cl:20])=[CH:12][C:13]([NH:1][C@@H:2]2[CH2:6][CH2:5][C@@H:4]([OH:7])[C@H:3]2[OH:8])=[C:14]([N+:16]([O-:18])=[O:17])[CH:15]=1

Participants

5

Reactant 3

HCID 69832,4,5-TrichloronitrobenzeneHCID 8471TriethylamineHCID 13497976(1R,2S,3R)-3-aminocyclopentane-1,2-diol

Product 1

HCID 57087546(+/-)-(1R*,2S*,3R*)-3-(4,5-Dichloro-2-nitroanilino)-1,2-cyclopentanediol

Reagents, catalysts & solvents 1

HCID 6386tert-ButanolSolvent

Procedure

(±)-(1R*,2S*,3R*)-3-Amino-1,2-cyclopentanediol (7.10 g, 50.0 mmol), 1,2,4-trichloro-5-nitrobenzene (11.67 g, 50.0 mmol as 97%, Aldrich), triethylamine (10 mL) and t-butanol (50 mL) were refluxed under nitrogen for 7 hours. Volatiles were removed in vacuo and the black residue chromatographed on silica gel. Title compound was eluted with methanol:chloroform/1:24 as an orange solid (6.45 g, 42%). Crystallization of such a sample from ethanol-water gave title compound as yellow needles, m.p. 137°-140° C.; 1H-NMR (DMSO-d6) δ: 8.26 and 7.49 (both s, 1 each, 2 aromatic CH), 8.06 (d, J=7.0 Hz, 1, NH), 5.04 (d, J=6.1 Hz, 1, OH), 4.65 (d, J=4.1 Hz, 1, OH), 4.0-3.7 (m, 3,2 OCH and NCH), 2.2-2.1, 2.0-1.8, 1.7-1.3 (all m, 4, 4 CH).

Workup

  1. customVolatiles were removed in vacuo
  2. customthe black residue chromatographed on silica gel
  3. washTitle compound was eluted with methanol
  4. customCrystallization of such a sample from ethanol-water

Sources & evidence

ORD record
ord-5b691ed11e954ec286136c60ed865b90
Source dataset
uspto-grants-1995_03
Patent number
US05399580

Reaction notes

Loading…