Piperonal → (Benzodioxol-5-yl)(3,5-dimethoxyphenyl)methanol

HRID 970961Notes

Reaction equation

BrC1C=C(OC)C=C(OC)C=1.O1C2C=CC(C=O)=CC=2OC1.C([Li])CCC.[O:28]1[C:33]2[CH:34]=[CH:35][C:36]([CH:38]([C:40]3[CH:45]=[C:44]([O:46][CH3:47])[CH:43]=[C:42]([O:48][CH3:49])[CH:41]=3)[OH:39])=[CH:37][C:32]=2[O:31][CH2:30]C1>>[O:28]1[C:33]2[CH:34]=[CH:35][C:36]([CH:38]([C:40]3[CH:45]=[C:44]([O:46][CH3:47])[CH:43]=[C:42]([O:48][CH3:49])[CH:41]=3)[OH:39])=[CH:37][C:32]=2[O:31][CH2:30]1

Participants

Reactant 4

HCID 8438Piperonal

HCID 6391871-Bromo-3,5-dimethoxybenzene

HCID 69202534(2,3-Dihydrobenzo[1,4]dioxin-6-yl)-(3,5-dimethoxyphenyl)methanol

HCID 178418339Butyllithium

Product 1

HCID 69202706(Benzodioxol-5-yl)(3,5-dimethoxyphenyl)methanolYield 81%

Procedure

1-Bromo-3,5-dimethoxybenzene (0.47 g, 3.14 mmol), benzo[1,3]dioxole-5-carbaldehyde (0.75 g, 3.46 mmol), and n-butyl lithium (1.38 ml, 3.46 mmol) were treated in the same manner as described above for the synthesis of (2,3-dihydrobenzo[1,4]dioxin-6-yl)-(3,5-dimethoxyphenyl)methanol. The crude was purified via flash column chromatography (5% EtOAc in hexane gradient to 30% EtOAc in hexane in about 40 min.) to give Benzo[1,3]dioxol-5-yl-(3,5-dimethoxy-phenyl)-methanol as an off-white oil (0.73 g, 81%): 1HNMR (CDCl3) 6.87-6.83 (m, 2H, Ar), 6.77-6.74 (m, 1H, Ar), 6.53 (d, J=2 Hz, 2H, Ar), 6.36 (t, J=2 Hz, 1H), 5.93 (m, 2H, CH2), 5.68 (d, J=3 Hz, 1H, CHOH), 3.77 (s, 6H, 2OCH3), 2.15 (d, J=3 Hz, 1H, OH). The product was carried over to the next step.

Workup

customThe crude was purified via flash column chromatography (5% EtOAc in hexane gradient to 30% EtOAc in hexane in about 40 min.)

Sources & evidence

ORD record: ord-3b7f0ab8559a46bba78ef7ec77690989
Source dataset: uspto-grants-2007_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07312241B2

Reaction notes

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