4-Toluenesulfonyl chloride → (+/-)-2-(Azidomethyl)-7-tert-butyl-5-methoxy-2,3-dihydro-1-benzofuran

HRID 2116105

Reaction equation

HRID 2116105 reaction equation
O1C2C=CC=CC=2C=C1.C1(C)C=CC(S(Cl)(=O)=O)=CC=1.CC1C=CC(S(O[CH2:32][CH:33]2[CH2:37][C:36]3[CH:38]=[C:39]([O:46][CH3:47])[CH:40]=[C:41]([C:42]([CH3:45])([CH3:44])[CH3:43])[C:35]=3[O:34]2)(=O)=O)=CC=1.S(C1C=CC(C)=CC=1)([O-])(=O)=O.[N-:59]=[N+:60]=[N-:61].[Na+]>>[N:59]([CH2:32][CH:33]1[CH2:37][C:36]2[CH:38]=[C:39]([O:46][CH3:47])[CH:40]=[C:41]([C:42]([CH3:45])([CH3:44])[CH3:43])[C:35]=2[O:34]1)=[N+:60]=[N-:61]

Participants

6

Reactant 5

HCID 73974-Toluenesulfonyl chlorideHCID 9223BenzofuranHCID 33557Sodium AzideHCID 85570p-ToluenesulfonateHCID 86599179HCID 86599179, compound

Product 1

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

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-91a78b251ca94395b11cce5c5f9b1b90
Source dataset
uspto-grants-2008_10
Patent number
US07435837B2

Linked notes

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