Phenol → HCID 68968754, compound

HRID 2116104Notes

Reaction equation

HRID 2116104 reaction equation
[C:1]([C:5]1[CH:10]=[C:9]([O:11][CH3:12])[CH:8]=[CH:7][C:6]=1[OH:13])([CH3:4])([CH3:3])[CH3:2].[C:14]([C:18]1C=C(O)C=C[C:23]=1[O:24]C)(C)(C)C.C(=O)([O-])[O-].[K+].[K+].C(Br)C=C.C(OCC=C)C=C.C1(C)C=C(C)C=C(C)C=1.C(C1C=C(OC)C=C(C(C)(C)C)C=1O)C=C.C(C1C=C(OC)C(C(C)(C)C)=CC=1O)C=C.C1(O)C=CC=CC=1.ClC1C=C(C=CC=1)C(OO)=O>>[C:1]([C:5]1[C:6]2[O:13][CH:18]([CH2:23][OH:24])[CH2:14][C:7]=2[CH:8]=[C:9]([O:11][CH3:12])[CH:10]=1)([CH3:4])([CH3:2])[CH3:3]

Participants

11

Reactant 10

HCID 996PhenolHCID 69322-tert-Butyl-4-hydroxyanisoleHCID 7841Allyl bromideHCID 7947MesityleneHCID 8456Butylated HydroxyanisoleHCID 11194Diallyl etherHCID 11430Potassium Carbonate2×HCID 70297m-Chloroperbenzoic acidHCID 19820128HCID 19820128, compoundHCID 68965704HCID 68965704, compound

Product 1

HCID 68968754HCID 68968754, compoundYield 14%

Procedure

Treatment of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol (18.25 g, 0.101 mol) with potassium carbonate (55.28 g, 0.400 mol) and allyl bromide (14.69 g, 0.121 mol) followed by treatment of the resultant allyl ether in refluxing mesitylene generally according to the procedure described for Intermediate 8 provided 2-allyl-6-tert-butyl-4-methoxyphenol and 2-allyl-5-tert-butyl-4-methoxyphenol. Treatment of the phenol with 3-chloroperoxybenzoic acid (49.58 g, 0.287 mol, 77%) and potassium carbonate (33.0 g, 0.238 mol) generally according to the procedure described for Intermediate 9 gave 3.23 g (14%) of (±)-(7-tert-butyl-5-methoxy-2,3-dihydro-1-benzofuran-2-yl)methanol as a white solid. Treatment of the benzofuran with p-toluenesulfonyl chloride (2.86 g, 0.015 mol) generally according to the procedure described for Intermediate 10 afforded (±)-(7-tert-butyl-5-methoxy-2,3-dihydro-1-benzofuran-2-yl)methyl 4-methylbenzenesulfonate. Treatment of the tosylate with sodium azide (1.46 g, 22.5 mmol) generally according to the procedure described for Intermediate 98 gave (±)-2-(azidomethyl)-7-tert-butyl-5-methoxy-2,3-dihydro-1-benzofuran. Treatment of the azide with palladium on carbon (0.14 g, 10 wt. %) generally according to the procedure described for Example 1 afforded 1.5 g (40%) of (±)-(7-tert-butyl-5-methoxy-2,3-dihydro-1-benzofuran-2-yl)methylamine) as a white solid, hydrochloride salt. mp 174-176° C.; Anal calcd. for C14H21O2NHCl: C, 61.87; H, 8.16; N, 5.15. Found C, 61.67; H, 8.37; N, 4.93.

Sources & evidence

ORD record
ord-03c69a7730554d49b18742cff019c71b
Source dataset
uspto-grants-2008_10
Patent number
US07435837B2

Reaction notes

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