(+/-)-2-(Azidomethyl)-7-tert-butyl-5-methoxy-2,3-dihydro-1-benzofuran → (+/-)-(7-Tert-butyl-5-methoxy-2,3-dihydro-1-benzofuran-2-yl)methylamine

HRID 2116106

Reaction equation

HRID 2116106 reaction equation
[N:1]([CH2:4][CH:5]1[CH2:9][C:8]2[CH:10]=[C:11]([O:18][CH3:19])[CH:12]=[C:13]([C:14]([CH3:17])([CH3:16])[CH3:15])[C:7]=2[O:6]1)=[N+]=[N-]>[Pd]>[C:14]([C:13]1[C:7]2[O:6][CH:5]([CH2:4][NH2:1])[CH2:9][C:8]=2[CH:10]=[C:11]([O:18][CH3:19])[CH:12]=1)([CH3:17])([CH3:15])[CH3:16]

Participants

3

Reactant 1

HCID 86599178(+/-)-2-(Azidomethyl)-7-tert-butyl-5-methoxy-2,3-dihydro-1-benzofuran

Product 1

HCID 68961710(+/-)-(7-Tert-butyl-5-methoxy-2,3-dihydro-1-benzofuran-2-yl)methylamineYield 40%

Reagents, catalysts & solvents 1

HCID 23938PalladiumCatalyst

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-a93e6d7c5be548e8b08cfd8b70e2c6f6
Source dataset
uspto-grants-2008_10
Patent number
US07435837B2

Linked notes

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