Hydrogen Bromide → HCID 68966173, compound

HRID 2116289Notes

Reaction equation

HRID 2116289 reaction equation
C[O:2]C1C(C2C=CC=CC=2C)=C(Cl)C=CC=1.Br.[H-].[Na+].C(Br)C=C.C(OCC=C)C=C.[CH2:31]([C:34]1[CH:39]=[CH:38][C:37]([Cl:40])=[C:36]([C:41]2[CH:46]=[CH:45][CH:44]=[CH:43][C:42]=2[Cl:47])[C:35]=1[OH:48])[CH:32]=[CH2:33].ClC1C=C(C=CC=1)C(OO)=O.C(=O)([O-])[O-].[K+].[K+]>C1(C)C=C(C)C=C(C)C=1>[Cl:47][C:42]1[CH:43]=[CH:44][CH:45]=[CH:46][C:41]=1[C:36]1[C:35]2[O:48][CH:32]([CH2:33][OH:2])[CH2:31][C:34]=2[CH:39]=[CH:38][C:37]=1[Cl:40]

Participants

10

Reactant 8

HCID 260Hydrogen BromideHCID 7841Allyl bromideHCID 11194Diallyl etherHCID 11430Potassium CarbonateHCID 24758Sodium hydrideHCID 70297m-Chloroperbenzoic acidHCID 68964104HCID 68964104, compoundHCID 68964218HCID 68964218, compound2×

Product 1

HCID 68966173HCID 68966173, compoundYield 74%

Reagents, catalysts & solvents 1

HCID 7947MesityleneSolvent

Procedure

Treatment of 1-bromo-2-chlorobenzene (5.0 g, 26.88 mmol) with (2-chloro-6-methyoxyphenyl)boronic acid (15.6 g, 80.64 mol) generally according to the procedure described for Intermediate 37 afforded 5.0 g (73%) of 6-chloro-2′-chlorobiphenyl-2-yl methyl ether. Treatment of 6-chloro-2′-methylbiphenyl-2-yl methyl ether with hydrogen bromide (60 mL, 30 wt. % in acetic acid) generally according to the procedure described for Example 395 afforded a brown oil. The oil was reacted with sodium hydride (1.05 g, 26.35 mmol) and allyl bromide (3.19 g, 26.35 mmol) followed by refluxing the resultant allyl ether in mesitylene generally according to the procedure described for Intermediate 8 provided 3-allyl-6-chloro-2′-chlorobiphenyl-2-ol. Treatment of 3-allyl-6-chloro-2′-chlorobiphenyl-2-ol (2.8 g, 10.03 mmol) with m-chloroperoxybenzoic acid (4.6 g, 15.0 mmol, 77%) and potassium carbonate (1.6 g, 12.0 mmol) generally according to the procedure described for Intermediate 9 afforded 2.2 g (74%) of (±)-[7-(2-chlorophenyl)-6-chloro-2,3-dihydro-1-benzofuran-2-yl]methanol. Treatment (±)-[7-(2-chlorophenyl)-6-chloro-2,3-dihydro-1-benzofuran-2-yl]methanol (1.6 g, 5.42 mmol) with p-toluenesulfonyl chloride (1.55 g, 8.13 mmol) generally according to the procedure described for Intermediate 10 gave 2.1 g (86%) of (±)-[6-chloro-7-(2-chlorophenyl)-2,3-dihydro-1-benzofuran-2-yl]methyl 4-methylbenzenesulfonate as a colorless oil. Treatment of (±)-[6-chloro-7-(2-chlorophenyl)-2,3-dihydro-1-benzofuran-2-yl]methyl 4-methylbenzenesulfonate (0.2 g, 0.44 mmol) with sodium azide (0.2 g, 3.08 mmol) generally according to the procedure described for Intermediate 98 afforded 0.14 g, (99%) of (±)-2-(azidomethyl)-7-(2-chlorophenyl)-6-chloro-2,3-dihydro-1-benzofuran. Treatment of (±)-2-(azidomethyl)-7-(2-chlorophenyl)-6-chloro-2,3-dihydro-1-benzofuran (0.14 g, 0.43 mmol) in tetrahydrofuran (10 mL) with polymer-supported triphenylphosphine (0.3 g, 1.14 mmol) generally according to the procedure described for Example 154 provided 0.036 g (24%) of (±)-{[6-chloro-7-(2-chlorophenyl)-2,3-dihydro-1-benzofuran-2-yl]methyl}amine as a white solid, hydrochloride salt. mp 221-223° C.

Workup

  1. customafforded a brown oil

Sources & evidence

ORD record
ord-26cdc53e1fef4c3297aa1bb511902321
Source dataset
uspto-grants-2008_10
Patent number
US07435837B2

Reaction notes

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