One pot, one step process for the halogenation of aromatics using solid acid catalysts

Patent metadata

Field	Value
Publication number	US-11111207-B2
Application number	US-201716086831-A
Country	US
Kind code	B2
Filing date	Mar 17, 2017
Priority date	Mar 21, 2016
Publication date	Sep 7, 2021
Grant date	Sep 7, 2021

Abstract

The present invention disclosed an improved one pot, one step process for halogenation of compound of formula (II) to afford corresponding halogenated compound of formula (I) having improved yield and increased selectivity under very mild conditions.

First claim

The invention claimed is:

1. An improved one pot, one step process for the halogenation of substituted aromatic compound selected from hydroxy aromatic compound, aromatic aldehyde compound, halo substituted aromatics, amide substituted aromatic compound and amino aromatic compound, said process consists of:
addition of halogenating agent selected from chlorine, bromine or iodine and solid acid catalyst to the mixture of substituted aromatic compound in solvent selected from ethylene dichloride, methanol, hexane, toluene, ethanol, higher alcohols, dimethylsulfoxide, dioxane, dimethylformamide, acetone, diethyl ether, butanol and benzylalcohol followed by stirring the reaction mixture at temperature in the range of 25 to 85° C. and at atmospheric pressure of 14 psig for the period in the range of 2 to 6 hrs to afford corresponding halogenated compound wherein said solid acid catalyst is selected from MoO 3 /TiO 2 , MoO 3 /SiO 2 , WO 3 /TiO 2 , WO 3 /SiO 2 , and Mo Si/Al (7.5);
wherein no mixed halogenated products are produced;
wherein said catalyst is recyclable.

2. The process as claimed in claim 1 , wherein said aminoaromatic compound is selected from aniline, 4-Chloroaniline, 4-Bromoaniline, 2,6 dimethyl aniline, anthranilamide, 2,6 diethyl aniline.

3. The process as claimed in claim 1 , wherein said hydroxy aromatic compound is selected from phenol.

4. The process as claimed in claim 1 , wherein said aromatic aldehyde compound benzaldehyde.

5. The process as claimed in claim 1 , wherein said corresponding halogenated compound is selected from 4-chloro-2-iodoaniline, 2-iodoaniline, 4-bromo-2-iodoaniline, 4-iodo-2,6-dimethylaniline, 3-iodobenzaldehyde, 2-iodophenol, 2-amino-3-iodobenzamide, 2,6-diethyl-4-iodoaniline, 4-chloro-2,6-dimethylaniline and 4-bromo-2,6-dimethylaniline.

6. The process as claimed in claim 1 , wherein selectivity towards corresponding ortho-halogenated compound is in the range of 50 to 100%.

7. The process as claimed in claim 1 , wherein said process is carried out in batch mode or continuous mode.

8. The process as claimed in claim 1 , wherein aniline conversion to bromination is 100% and selectivity for 2-bromo aniline, 4-bromo aniline and 2,4-dibromo aniline is 40%, 50% and 10% respectively.

9. The process as claimed in claim 1 , wherein aniline conversion to chlorination is 100% and selectivity for 4-chloro aniline and 2,4-dichloro aniline is 40% and 60% respectively.

Assignees

• Council Scient Ind Res

Inventors

• Umbarkar Shubhangi Bhalchandra
• Kulal Atul Balasaheb
• Deshmukh Amar Jaywant

Classifications

• C07C45/63

  by introduction of halogen; by substitution of halogen atoms by other halogen atoms · CPC title

• B01J23/30

  Tungsten · CPC title

• C07C211/52

  the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups · CPC title

• C07C231/12

  by reactions not involving the formation of carboxamide groups · CPC title

• C07C37/62

  by introduction of halogen; by substitution of halogen atoms by other halogen atoms · CPC title