Chloroform → 5-Chloro-6-hydroxymethyl-3,3a,7,7a-tetrahydro-1H-4-thia-2-aza-cyclopenta[alpha]pentalene-2-carboxylic acid ethyl ester

HRID 1013356Notes

Reaction equation

HRID 1013356 reaction equation
[CH2:1]([O:3][C:4]([N:6]1[CH2:13][CH:12]2[CH:8]([CH2:9][C:10]3[C:16]([CH2:17][OH:18])=[CH:15][S:14][C:11]=32)[CH2:7]1)=[O:5])[CH3:2].C(Cl)(Cl)[Cl:20]>C(Cl)Cl>[CH2:1]([O:3][C:4]([N:6]1[CH2:13][CH:12]2[CH:8]([CH2:9][C:10]3[C:16]([CH2:17][OH:18])=[C:15]([Cl:20])[S:14][C:11]=32)[CH2:7]1)=[O:5])[CH3:2]

Participants

4

Reactant 2

HCID 6212Chloroform2×HCID 58624945HCID 58624945, compound

Product 1

HCID 1317270275-Chloro-6-hydroxymethyl-3,3a,7,7a-tetrahydro-1H-4-thia-2-aza-cyclopenta[alpha]pentalene-2-carboxylic acid ethyl esterYield 45%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

The product of step c) (185 mg, 0.74 mmol) was dissolved in CHCl3 (2.7 ml) and a solution of SO2Cl2 (59.5 μl, 0.74 mmol) in CHCl3 (1 ml) was added dropwise over 10 minutes and the contents were stirred for 1 hour. Next, the mixture was diluted with CH2Cl2 (10 ml), washed with H2O (2×25 ml), sat. NaHCO3 (25 ml) and dried (MgSO4). The crude residue was purified by preparative TLC (hexanes/EtOAc-1:3) to give the subtitle compound (99.7 mg, 45%). 1H NMR (300 MHz, CDCl3, ppm) 1.20 (t, J=7 Hz, 3H); 2.37 (br s, 1H); 2.65-2.71 (m, 1H); 2.90-3.05 (m, 1H); 3.08-3.18 (br m, 1H); 3.28-3.42 (br m, 1H); 3.52-3.72 (br m, 2H); 3.75-3.88 (m, 2H); 4.09 (q, J=7 Hz, 2H); 4.54 (s, 2H).

Workup

  1. washwashed with H2O (2×25 ml), sat. NaHCO3 (25 ml)
  2. dry with materialdried (MgSO4)
  3. customThe crude residue was purified by preparative TLC (hexanes/EtOAc-1:3)

Sources & evidence

ORD record
ord-669601ae18de4776a170c0e9d98fc691
Source dataset
uspto-grants-2011_07
Patent number
US07981919B2

Reaction notes

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