Pyridine → HCID 21062529, compound

HRID 1242274

Reaction equation

HRID 1242274 reaction equation
[CH:1]([C:3]1[CH:11]=[CH:10][C:6]([C:7](Cl)=[O:8])=[CH:5][CH:4]=1)=[CH2:2].[OH:12][CH2:13][CH:14]1[CH2:18][O:17][C:16](=[S:19])[NH:15]1.N1C=CC=CC=1>C1COCC1>[S:19]=[C:16]1[NH:15][CH:14]([CH2:13][O:12][C:7](=[O:8])[C:6]2[CH:10]=[CH:11][C:3]([CH:1]=[CH2:2])=[CH:4][CH:5]=2)[CH2:18][O:17]1

Participants

5

Reactant 3

HCID 1049PyridineHCID 110520284-Vinylbenzoyl chlorideHCID 21939074HCID 21939074, compound

Product 1

HCID 21062529HCID 21062529, compoundYield 73%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of 4-vinylbenzoyl chloride (21.0 g, 126 mmol) in dry THF (50 mL) was added to a solution of 4-hydroxymethyl-1,3-oxazolidine-2-thione (14.0 g, 105 mmol) in dry THF (250 mL) and pyridine (10.2 mL, 126 mmol) at 0° C. After 12 hours of stirring at room temperature, pyridine hydrochloride was filtered off, and the solvent was evaporated out in vacuo. The residue was purified by silica gel column chromatography eluted with ethyl acetate/acetone (1/1=v/v), followed by recrystallization from a mixed solvent [n-hexane/ethyl acetate (3/1=v/v)] to afford 4-vinylbenzoic acid 2-thioxo-oxazolidin-4-ylmethyl ester as a colorless solid. Yield 73% (24.1 g, 91.5 mmol). 1H NMR (DMSO-d6): δ=4.25–4.77 (5H, >CH—, —CH2—O(CO)—, and —(SC)O—CH2—), 5.45 (d, J=10.8 Hz, 1H, —CH═CH2), 6.03 (d, J=17.8 Hz, 1H, —CH═CH2), 6.84 (dd, J=11.3 and 17.7 Hz, 1H, —CH═CH2), 7.64 (d, J=8.1 Hz, 2H, —C6H4—), 8.01 (d. J=8.1 Hz, 2H, —C6H4—), 10.3 (broad s, 1H, —NH—) ppm. 13C NMR (DMSO-d6): δ=55.0 (CO—CH2—CH<), 65.1 (>CH—), 71.8 (—CH2—O(CO)—), 117.7 (—CH═CH2), 126.5, 128.6, 130.1 (—C6H4—), 136.0 (—CH═CH2), 142.2 (—C6H4—), 165.6 (—O(CO)—C6H4—), 189.3 (>C═S) ppm. IR (KBr): 3185, 1712 (—OCOPh), 1504 (C═S), 1280, 1180, 1110, 971 cm−1.

Workup

  1. filtrationpyridine hydrochloride was filtered off
  2. customthe solvent was evaporated out in vacuo
  3. customThe residue was purified by silica gel column chromatography
  4. washeluted with ethyl acetate/acetone (1/1=v/v)
  5. customfollowed by recrystallization from a mixed solvent [n-hexane/ethyl acetate (3/1=v/v)]

Sources & evidence

ORD record
ord-e294491d536149cc9dabcbaa57e13a54
Source dataset
uspto-grants-2006_10
Patent number
US07115705B2

Linked notes

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