1-Chloro-4-(chloromethyl)benzene → HCID 86676534, compound

HRID 73505Notes

Reaction equation

HRID 73505 reaction equation
[Cl:1][C:2]1[CH:9]=[CH:8][C:5]([CH2:6]Cl)=[CH:4][CH:3]=1.[OH:10][C:11]1[CH:12]=[C:13]([CH:16]=[CH:17][C:18]=1[O:19][CH2:20][C:21]1[CH:26]=[CH:25][C:24]([O:27][CH3:28])=[CH:23][CH:22]=1)[CH:14]=[O:15].C(=O)([O-])[O-].[K+].[K+]>[I-].C([N+](CCCC)(CCCC)CCCC)CCC.CC(C)=O>[Cl:1][C:2]1[CH:9]=[CH:8][C:5]([CH2:6][O:10][C:11]2[CH:12]=[C:13]([CH:16]=[CH:17][C:18]=2[O:19][CH2:20][C:21]2[CH:26]=[CH:25][C:24]([O:27][CH3:28])=[CH:23][CH:22]=2)[CH:14]=[O:15])=[CH:4][CH:3]=1

Participants

6

Reactant 3

HCID 77231-Chloro-4-(chloromethyl)benzeneHCID 11430Potassium CarbonateHCID 112306483-Hydroxy-4-[(4-methoxyphenyl)methoxy]benzaldehyde

Product 1

HCID 86676534HCID 86676534, compoundYield 73.6%

Reagents, catalysts & solvents 2

HCID 67553Tetrabutylammonium IodideCatalystHCID 180AcetoneSolvent

Procedure

A solution of 4-chlorobenzyl chloride (67.9 g), 3-hydroxy-4-(4-methoxy-benzyloxy)-benzaldehyde (40) (99 g) and tetrabutylammonium iodide (14.1 g) was heated at reflux in acetone (0.4 L) over solid potassium carbonate (39.1 g) for 3 hours. Excess acetone was removed by rotary evaporation under reduced pressure and the resulting residue partitioned between ethyl acetate and dilute hydrochloric acid (0.5 N). The organic layer was washed with water and brine and then dried over magnesium sulphate. Ethyl acetate was removed by rotary evaporation under reduced pressure to afford the crude product. The crude oil was triturated with a 50/50 mixture of diethyl ether and hexane accompanied by vigorous stirring to afford the product as a colourless solid (108 g, 73% yield, retention time 3.70 mins, poor ionization, ES− m/z 538.05). 1H NMR (400 MHz, CDCl3) δ 9.84 (s, 1H), 7.51-7.43 (m, 2H), 7.42-7.32 (m, 6H), 7.07 (d, J=8.1 Hz, 1H), 6.97-6.89 (m, 2H), 5.19 (s, 2H), 5.17 (s, 2H), 3.85 (s, 3H).

Workup

  1. customExcess acetone was removed by rotary evaporation under reduced pressure
  2. customthe resulting residue partitioned between ethyl acetate and dilute hydrochloric acid (0.5 N)
  3. washThe organic layer was washed with water and brine
  4. dry with materialdried over magnesium sulphate
  5. customEthyl acetate was removed by rotary evaporation under reduced pressure
  6. customto afford the crude product
  7. customThe crude oil was triturated with a 50/50 mixture of diethyl ether and hexane

Sources & evidence

ORD record
ord-ce12807a553c4e0aa6516372fa81cd19
Source dataset
uspto-grants-2014_09
Patent number
US08829184B2

Reaction notes

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