Formaldehyde → 2-(4-Methoxycarbonyl-2-nitrophenyl)propanol

HRID 2095230Notes

Reaction equation

HRID 2095230 reaction equation
CO[C:3](=[O:15])[C:4]1[CH:9]=[CH:8][C:7]([CH2:10][CH3:11])=[C:6]([N+:12]([O-:14])=[O:13])[CH:5]=1.[CH2:16]=[O:17].C[C:19](C)([O-:21])C.[K+]>CS(C)=O>[CH3:16][O:17][C:3]([C:4]1[CH:9]=[CH:8][C:7]([CH:10]([CH3:11])[CH2:19][OH:21])=[C:6]([N+:12]([O-:14])=[O:13])[CH:5]=1)=[O:15]

Participants

5

Reactant 3

HCID 712FormaldehydeHCID 21938352Methyl 4-ethyl-3-nitrobenzoateHCID 23665647Potassium tert-butoxide

Product 1

HCID 684541792-(4-Methoxycarbonyl-2-nitrophenyl)propanolYield 38%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Procedure

To a suspension of 4-ethyl-3-nitrobenzoic acid methyl ester (11d) (10 g, 48 mmol) and paraformaldehyde (1.8 g, 60 mmol) in DMSO (10 mL) was added in portions potassium tert-butoxide (1.46 g, 12 mmol), during which the colour of the reaction mixture was changing from yellow to purple. After stirring for 2.5 hours at room temperature, the reaction mixture was directly applied to the silica gel bed of a chromatography column (100 g silica, 3.5×14 cm) and eluted with hexane/ethyl acetate (EA) (3:1, v/v). The slightly yellow product (4d) was obtained in 38% yield (4.42 g, 18 mmol). Rf=0.24 (hexanes/EtOAc 7:3). 1H NMR (250 MHz, CDCl3) δ 8.36 (d, 1H, arom. H(3)), 8.18 (dd, 1H, arom. H(5)), 7.58 (d, 1H, arom. H(6)), 3.93 (s, 3H, COOCH3), 3.78 (m, 2H, α-CH2), 3.54 (sextet, 1H, β-CH), 1.69 (d, 3H, CH3).

Workup

  1. washeluted with hexane/ethyl acetate (EA) (3:1

Sources & evidence

ORD record
ord-e63b3aa471a947daa96ab680cb18d9fb
Source dataset
uspto-grants-2013_05
Patent number
US08445734B2

Reaction notes

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