1-Chloroethyl 1-methylethyl carbonate → HCID 86628908, compound

HRID 1919439Notes

Reaction equation

HRID 1919439 reaction equation
[Cl:1][CH2:2][CH2:3][CH2:4][S:5]([O:8][CH2:9][C:10]([CH3:26])([CH3:25])[C@@H:11]([O:15][CH2:16][C:17]1[CH:22]=[CH:21][C:20](OC)=[CH:19][CH:18]=1)[C:12]([OH:14])=[O:13])(=[O:7])=[O:6].[CH3:27][CH:28]([O:30][C:31]([O:33][CH:34](Cl)[CH3:35])=[O:32])[CH3:29]>C1(C)C=CC=CC=1.C(=O)([O-])[O-].[Ag+2]>[Cl:1][CH2:2][CH2:3][CH2:4][S:5]([O:8][CH2:9][C:10]([CH3:25])([CH3:26])[C@@H:11]([O:15][CH2:16][C:17]1[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=1)[C:12]([O:14][CH2:35][CH2:34][O:33][C:31]([O:30][CH:28]([CH3:29])[CH3:27])=[O:32])=[O:13])(=[O:6])=[O:7]

Participants

5

Reactant 2

HCID 117895851-Chloroethyl 1-methylethyl carbonateHCID 86628873HCID 86628873, compound

Product 1

HCID 86628908HCID 86628908, compoundYield 50%

Reagents, catalysts & solvents 2

HCID 178418647HCID 178418647, compoundCatalystHCID 1140TolueneSolvent

Procedure

Following the general procedure for the preparation of acyloxyalkyl/alkoxycarbonyloxyalkyl carboxylic esters from carboxylic acids of Description 22, (2R)-4-[(3-chloropropyl)sulfonyloxy]-3,3-dimethyl-2-(phenylmethoxy)butanoic acid (11) (34.0 g, 89.7 mmol) dissolved in 300 mL of anhydrous toluene was reacted with 30 g (179.5 mmol) of commercially available 1-chloroethyl methylethoxyformate in the presence of 47 g (179.5 mmol) of silver carbonate (Ag2CO3). After work-up, the crude material was purified by silica gel column chromatography using a mixture of ethyl acetate (EtOAc) and hexane (Hxn) (EtOAc/Hxn=1:2) as eluent to provide 23.0 g (50% yield) of the title compound (40a). Rf=0.32 (EtOAc/Hxn=1:4). 1H NMR (400 MHz, CDCl3, both diastereomers): δ=1.06-1.08 (m, 6H), 1.24-1.35 (m, 6H), 1.57 (d, J=5.2 Hz, 3H), 2.24-2.31 (m, 2H), 3.20-3.26 (m, 2H), 3.63-3.66 (m, 2H), 3.85-3.86 (2s, 1H), 3.94-3.97 (2d, J=9.6, 9.6 Hz, 1H), 4.19-4.23 (2d, J=9.2, 9.6 Hz, 1H), 4.33-4.38 (2d, J=11.2, 11.6 Hz, 1H), 4.64 (t, J=11.2 Hz, 1H), 4.81-4.97 (m, 1H), 6.81-6.87 (m, 1H), 7.30-7.37 (m, 5H) ppm. MS (ESI) m/z 531.02 (M+Na)+. The analytical data was consistent with the proposed structure.

Workup

  1. customAfter work-up, the crude material was purified by silica gel column chromatography
  2. additiona mixture of ethyl acetate (EtOAc) and hexane (Hxn) (EtOAc/Hxn=1:2) as eluent

Sources & evidence

ORD record
ord-c94b12572736493585c3c9a7150c34a9
Source dataset
uspto-grants-2012_05
Patent number
US08168617B2

Reaction notes

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