Pyridine → (+/-)-trans-4-Nitro-benzenesulfonic acid 2-azidocyclohexyl ester

HRID 1744834Notes

Reaction equation

HRID 1744834 reaction equation
[N:1]([C@@H:4]1[CH2:9][CH2:8][CH2:7][CH2:6][C@H:5]1[OH:10])=[N+:2]=[N-:3].N1C=CC=CC=1.[N+:17]([C:20]1[CH:25]=[CH:24][C:23]([S:26](Cl)(=[O:28])=[O:27])=[CH:22][CH:21]=1)([O-:19])=[O:18]>C(Cl)Cl>[N:1]([C@@H:4]1[CH2:9][CH2:8][CH2:7][CH2:6][C@H:5]1[O:10][S:26]([C:23]1[CH:22]=[CH:21][C:20]([N+:17]([O-:19])=[O:18])=[CH:25][CH:24]=1)(=[O:27])=[O:28])=[N+:2]=[N-:3]

Participants

5

Reactant 3

HCID 1049PyridineHCID 74044-Nitrobenzenesulfonyl chlorideHCID 11094719(1R,2R)-2-azidocyclohexan-1-ol

Product 1

HCID 59122973(+/-)-trans-4-Nitro-benzenesulfonic acid 2-azidocyclohexyl esterYield 72.8%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A solution of (±)-trans-2-azidocyclohexan-1-ol (11.3 g, 80.0 mmol) (Zhang, Z. da; Scheffold, R. Helv. Chim. Acta 1993, 76, 2602] in CH2Cl2 (110 mL) at 0° C. was treated successively with pyridine (14.2 mL, 176 mmol) and 4-nitro-benzenesulfonyl chloride (35.6 g, 160 mmol), allowed to warm to room temperature slowly, stirred for 4 d, and partitioned between CH2Cl2 and 1 N HCl. The aqueous phase was extracted with CH2Cl2 and the extracts were washed with saturated NaHCO3, dried and concentrated. Chromatography of the residue with 10:1–1:1 hexanes:EtOAc gave the product (19 g, 72%) as a cream solid: 1H NMR δ 1.19–1.39 (m, 3H), 1.53–1.82 (m, 3H), 2.00–2.10 (m, 1H), 2.26 (m, 1H), 3.36 (m, 1H), 4.35 (ddd, J=4.7, 9.2, 10.8 Hz, 1H), 8.17 (m, 2H), 8.41 (m, 2H).

Workup

  1. custompartitioned between CH2Cl2 and 1 N HCl
  2. extractionThe aqueous phase was extracted with CH2Cl2
  3. washthe extracts were washed with saturated NaHCO3
  4. customdried
  5. concentrationconcentrated

Sources & evidence

ORD record
ord-a713596184624c1ebc5dbb613452ff7d
Source dataset
uspto-grants-2006_03
Patent number
US07019007B2

Reaction notes

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