Tributylphosphine → HCID 67153617, compound

HRID 1914292Notes

Reaction equation

HRID 1914292 reaction equation
[CH3:1][O:2][C:3](=[O:16])[C:4]1[CH:9]=[CH:8][C:7]([CH:10](O)[CH2:11][CH:12]([CH3:14])[CH3:13])=[CH:6][CH:5]=1.N(C(N1CCCCC1)=O)=NC(N1CCCCC1)=O.C(P(CCCC)CCCC)CCC.[Br:48][C:49]1[CH:54]=[CH:53][C:52]([SH:55])=[CH:51][CH:50]=1>C1(C)C=CC=CC=1>[CH3:1][O:2][C:3](=[O:16])[C:4]1[CH:9]=[CH:8][C:7]([CH:10]([S:55][C:52]2[CH:53]=[CH:54][C:49]([Br:48])=[CH:50][CH:51]=2)[CH2:11][CH:12]([CH3:14])[CH3:13])=[CH:6][CH:5]=1

Participants

6

Reactant 4

HCID 13831TributylphosphineHCID 660494-BromothiophenolHCID 730421,1'-(Azodicarbonyl)dipiperidineHCID 59518172Methyl 4-(1-hydroxy-3-methylbutyl)benzoate

Product 1

HCID 67153617HCID 67153617, compound

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To a solution of 4-(1-hydroxy-3-methyl-butyl)-benzoic acid methyl ester (1240 mg, 5.59 mmol) in toluene (10 mL) is added 1,1′-(azodicarbonyl)dipiperidine (ADDP, 2114 mg, 8.38 mmol) at 0° C., followed by the additions of tributylphosphine (2.09 mL, 8.38 mmol) and 4-bromo-thiophenol (1267 mg, 6.7 mmol). The reaction mixture is warmed up to room temperature and stirred overnight. The mixture is loaded on silica gel, eluted with hexanes with a gradient from 0% of ethyl acetate to 50% of ethyl acetate giving 4-[1-(4-bromo-phenylsulfanyl)-3-methyl-butyl]-benzoic acid methyl ester. 393 mg of the ester product is taken into ethanol (2 mL), treated with sodium hydroxide (5N aqueous, 1 mL) for 3 h at room temperature. The mixture is concentrated, diluted with ethyl acetate, acidified with 5 N HCl (1.1 mL), extracted with ethyl acetate. The organic layers are dried and concentrated giving 4-[1-(4-bromo-phenylsulfanyl)-3-methyl-butyl]-benzoic acid (379 mg).

Workup

  1. washeluted with hexanes with a gradient from 0% of ethyl acetate to 50% of ethyl acetate

Sources & evidence

ORD record
ord-a547b1d3c3ff4a80b25fc1a9fa43c8c5
Source dataset
uspto-grants-2013_12
Patent number
US08609892B2

Reaction notes

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