Benzene → HCID 86747406, compound

HRID 326317Notes

Reaction equation

HRID 326317 reaction equation
[CH3:1][O:2][C:3]1C2C(=O)[CH2:10][C:11]3([O:17][C:7]=2[CH:6]=[C:5]([O:19][CH2:20][C:21]([O:23][CH2:24][CH3:25])=[O:22])[CH:4]=1)[CH2:16][CH2:15][CH2:14][CH2:13][CH2:12]3.[CH:26]([SH:29])([SH:28])[CH3:27].[CH:30]1C=CC=C[CH:31]=1>C1(C)C=CC(S(O)(=O)=O)=CC=1>[CH3:1][O:2][C:3]1[C:27]2[C:26]3([CH2:10][C:11]4([O:17][C:7]=2[CH:6]=[C:5]([O:19][CH2:20][C:21]([O:23][CH2:24][CH3:25])=[O:22])[CH:4]=1)[CH2:16][CH2:15][CH2:14][CH2:13][CH2:12]4)[S:29][CH2:31][CH2:30][S:28]3

Participants

5

Reactant 3

HCID 241BenzeneHCID 336451,1-EthanedithiolHCID 9863129HCID 9863129, compound

Product 1

HCID 86747406HCID 86747406, compoundYield 82.1%

Reagents, catalysts & solvents 1

HCID 6101p-Toluenesulfonic acidCatalyst

Procedure

A mixture of ethyl {(5-methoxy-3,4-dihydro-4-oxospiro[2H-1-benzopyran-2,1'-cyclohexan]-7-yl)oxy}acetate (prepared in Preparation 49) (0.5 g, 1.44 mmol), ethanedithiol (0.149 g, 1.59 mmol), dry benzene (10 ml), and p-toluenesulfonic acid (0.013 g, 0.076 mmol) is heated to reflux for 12 hours under conditions for azeotropic dehydration. The solvent is removed under reduced pressure. The residue is applied to a silica gel column and eluted with a mixture of ethyl acetate and dichloromethane (1:9). The eluate is applied to a Lober column and eluted with a mixture of ethyl acetate and hexane (1:2) to obtain ethyl {(5-methoxy-3,4-dihydrodispiro[2H-1-benzopyran-2,1'-cyclohexan-4,2"-[1,3]dithiolan]-7-yl)oxy}acetate as an oil (0.50 g, 82.1%). A mixture of the ester (0.49 g, 1.16 mmol), 1N sodium hydroxide (1.27 ml, 1.27 mmol), and ethanol (5 ml) is stirred at room temperature for 0.5 hours. The reaction mixture is made acid with 1N HCl and distilled under reduced pressure at room temperature to remove ethanol. The residue is extracted with diethyl ether. The extract is washed with saturated brine, dried, and the solvent is removed under reduced pressure. The residue is treated with a mixture of diethyl ether and hexane to obtain the title compound as a crystalline soild (0.43 g, 93.7%). Recrystallization from ethyl acetate gives a product having a melting point of 189°-190° C.

Workup

  1. temperatureis heated
  2. temperatureto reflux for 12 hours under conditions for azeotropic dehydration
  3. customThe solvent is removed under reduced pressure
  4. washeluted with a mixture of ethyl acetate and dichloromethane (1:9)
  5. washeluted with a mixture of ethyl acetate and hexane (1:2)

Sources & evidence

ORD record
ord-13a2c05274ac4952bf3f2366f635ea92
Source dataset
uspto-grants-1993_12
Patent number
US05268386

Reaction notes

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