Tributylphosphine → 4-[1-(4-Bromo-phenoxyl)-heptyl]-benzoic acid methyl ester

HRID 1160897Notes

Reaction equation

HRID 1160897 reaction equation
[CH3:1][O:2][C:3](=[O:18])[C:4]1[CH:9]=[CH:8][C:7]([CH:10]([OH:17])[CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH3:16])=[CH:6][CH:5]=1.N(C(N1CCCCC1)=O)=NC(N1CCCCC1)=O.C(P(CCCC)CCCC)CCC.[Br:50][C:51]1[C:56](C)=[CH:55][C:54](O)=[CH:53][C:52]=1C>C1(C)C=CC=CC=1>[CH3:1][O:2][C:3](=[O:18])[C:4]1[CH:9]=[CH:8][C:7]([CH:10]([O:17][C:54]2[CH:55]=[CH:56][C:51]([Br:50])=[CH:52][CH:53]=2)[CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH3:16])=[CH:6][CH:5]=1

Participants

6

Reactant 4

HCID 13831TributylphosphineHCID 730421,1'-(Azodicarbonyl)dipiperidineHCID 819704-Bromo-3,5-dimethylphenolHCID 595181434-(1-Hydroxy-heptyl)-benzoic acid methyl ester

Product 1

HCID 671535474-[1-(4-Bromo-phenoxyl)-heptyl]-benzoic acid methyl ester

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

To a solution of 4-(1-hydroxy-heptyl)-benzoic acid methyl ester (1000 mg, 4.0 mmol) in toluene (40 mL) is added 1,1′-(azodicarbonyl)dipiperidine (ADDP, 1514 mg, 6.0 mmol) at 0° C., followed by the additions of tributylphosphine (1.49 mL, 6.0 mmol) and 4-bromo-3,5-dimethyl-phenol (965 mg, 4.8 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-phenoxyl)-heptyl]-benzoic acid methyl ester. The ester product (1800 mg) is taken into ethanol (5 mL), treated with sodium hydroxide (5N aqueous, 5 mL) for 3 h at room temperature. The mixture is concentrated, diluted with ethyl acetate, acidified with 5 N HCl (5 mL), extract with ethyl acetate. The organic layers are dried and concentrated giving 4-[1-(4-bromo-3,5-dimethyl-phenoxyl)-heptyl]-benzoic acid (1790 mg).

Workup

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

Sources & evidence

ORD record
ord-9183c4a464d643a69a95a13dfd4c9b84
Source dataset
uspto-grants-2010_10
Patent number
US07816557B2

Reaction notes

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