1,3-Dibromobenzene → 3-Bromobiphenyl

HRID 1493836Notes

Reaction equation

HRID 1493836 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([Br:8])[CH:3]=1.B(O)O.C([Li])CCC.B(OC(C)C)(OC(C)C)OC(C)C.[OH-].[Na+].I[C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1.C(=O)([O-])[O-].[Na+].[Na+]>C1COCC1.CCOCC.C1(C)C=CC=CC=1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[Br:8][C:4]1[CH:3]=[C:2]([C:33]2[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=2)[CH:7]=[CH:6][CH:5]=1

Participants

12

Reactant 7

HCID 79271,3-Dibromobenzene2×HCID 10340Sodium CarbonateHCID 11575IodobenzeneHCID 14798Sodium HydroxideHCID 21531Triisopropyl borateHCID 61668Boronic Acid2×HCID 178418339Butyllithium

Product 1

HCID 164493-Bromobiphenyl

Reagents, catalysts & solvents 4

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolventHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

Starting with readily available starting materials, 1,3-dibromobenzene and the appropriately substituted iodobenzene, it is possible to prepare biphenyls having 3', 4' and 5' position substitution. Referring to Flow Sheet AE 1,3-dibromobenzene AE1 is converted to boronic acid AE2 by first reacting with butyl lithium in anhydrous THF or ether at about -78° C. followed by addition of triisopropyl borate. The resultant intermediate is worked up with sodium hydroxide and acidified. Boronic acid AE2 is subsequently reacted with the appropriate iodobenzene AE3 in toluene and aqueous sodium carbonate with tetrakistriphenylphosphinepalladium as a catalyst to produce the 3-bromo biphenyl B1. This reaction to B1 is well known in art with reference made herein to N. Miyaura, T. Yanagi and A. Suzuki, Syn. Comm., 11, 513 (1981). ##STR11##

Sources & evidence

ORD record
ord-89144ec834d74ae49c9c1d21cfc7ed84
Source dataset
uspto-grants-1991_06
Patent number
US05025006

Reaction notes

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