Bromine → HCID 19915369, compound

HRID 1090445Notes

Reaction equation

HRID 1090445 reaction equation
[C:1]([O:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][CH:18]([Br:23])[C:19](Br)([F:21])[F:20])(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.BrBr.C(OCCCCCCCCC=C(F)F)(=O)C1C=CC=CC=1.[H-].[Na+]>O1CCCC1>[C:1]([O:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][C:18]([Br:23])=[C:19]([F:21])[F:20])(=[O:8])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 4

HCID 24408BromineHCID 24758Sodium hydrideHCID 19915372HCID 19915372, compound2×HCID 19915373HCID 19915373, compound

Product 1

HCID 19915369HCID 19915369, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

After ester formation, additional reactions, most of which are described above, were utilized to further modify the esters themselves. For example, 9,10-dibromo-10,10-difluorodecyl benzoate (XXVI) was prepared by adding elemental bromine to 10,10-difluoro-9 decenyl benzoate (XXV). Subsequently, 9,10-dibromo-10,10-difluorodecyl benzoate was dehydrobrominated using sodium hydride in tetrahydrofuran, yielding 9-bromo-10,10-difluoro-9-decenyl benzoate (XXVII). In order to extend a hydrocarbon chain by three carbon atoms, an unsaturated ester, e.g., 9-decenyl acetate, was reacted with borane-tetrahydrofuran complex and then with acrolein in the presence of hydrochloric acid, producing 13-oxotridecyl acetate (XXIX). As an alternative to catalytic hydrogenolysis to remove a bromine atom, a brominated compound, e.g., 2,4-dibromo-4,4-difluorobutyl acetate (XXXVI), tributyltin hydride, and 1,1'-azobisisobutyronitrile were heated at 120° C., yielding 4-bromo-4,4-difluorobutyl acetate. These reactions are detailed in Examples 12-23.

Sources & evidence

ORD record
ord-90d41a982f9f44b09204bcaa31fac351
Source dataset
uspto-grants-1992_01
Patent number
US05081287

Reaction notes

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