2-Methyl-5-nitrobenzaldehyde → 1-(2-Methyl-5-nitro-phenyl)ethanol

HRID 1053690Notes

Reaction equation

HRID 1053690 reaction equation
[CH3:1][Li].[CH3:3][C:4]1[CH:11]=[CH:10][C:9]([N+:12]([O-:14])=[O:13])=[CH:8][C:5]=1[CH:6]=[O:7]>C(OCC)C.[Ti](Cl)(Cl)(Cl)Cl>[CH3:3][C:4]1[CH:11]=[CH:10][C:9]([N+:12]([O-:14])=[O:13])=[CH:8][C:5]=1[CH:6]([OH:7])[CH3:1]

Participants

5

Reactant 2

HCID 126541452-Methyl-5-nitrobenzaldehydeHCID 178418348HCID 178418348, compound

Product 1

HCID 205638201-(2-Methyl-5-nitro-phenyl)ethanolYield 100.8%

Reagents, catalysts & solvents 2

HCID 24193Titanium TetrachlorideCatalystHCID 3283Diethyl EtherSolvent2×

Procedure

Following the General Procedure of Description 8, MeTiCl3 was freshly prepared prior to use from commercial titanium tetrachloride (TiCl4) (10.0 mL, 17.3 g, 91.0 mmol) and methyl lithium (MeLi) (1.6 M in Et2O, 57.0 mL, 91.0 mmol) in anhydrous diethyl ether (Et2O) (400 mL). A solution of 2-methyl-4-nitro-benzaldehyde (5j) (12.4 g, 75.01 mmol) in anhydrous Et2O (200 mL) was added. Aqueous work-up afforded 13.7 g (99% yield) of the target compound (5k) as a yellow solid. The material was of sufficient purity to be used directly in the next step without further isolation and purification procedures. Rf: ˜0.47 (EtOAc/Hxn=1:2 v/v). 1H NMR (300 MHz, CDCl3): δ 8.41 (d, J=2.4 Hz, 1H), 8.00 (dd, J=8.4, 2.4 Hz, 1H), 7.27 (d, J=9.0 Hz, 1H), 5.16 (q, J=6.3 Hz, 1H), 2.43 (s, 3H), 1.96 (br. s, 1H), 1.50 (d, J=6.3 Hz, 3H) ppm. The analytical data correspond to the data of compound (5b) of Method A.

Workup

  1. customwas freshly prepared

Sources & evidence

ORD record
ord-f258cdf85f30432c8147b34acb870e5c
Source dataset
uspto-grants-2016_07
Patent number
US09394236B2

Reaction notes

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