Process for the preparation of oxethylmercaptobenzaldehydes and their oxidation products

• US 4,922,014 A
• Filed: 09/20/1988
• Issued: 05/01/1990
• Est. Priority Date: 09/22/1987
• Status: Expired due to Fees

• Current Assignee: Hoechst Aktiengesellschaft (Sanofi )
• Original Assignee: Hoechst Aktiengesellschaft (Sanofi )
• Inventors: Papenfuhs, Theodor
• Primary Examiner(s): Shippen, Michael L.
• Application Number:
  US07/246,802
• Time in Patent Office: 588 Days
• Field of Search: 562/418, 562/31, 562/41
• US Class Current: 562/418
• CPC Class Codes: C07C 317/00 Sulfones; Sulfoxides
• CPC Class Codes: C07C 323/00 Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups

Abstract

Process for the preparation of oxethylmercaptobenzaldehydes and their oxidation products of the formula (I) ##STR1## in which R denotes a hydrogen, fluorine, chlorine, bromine or iodine atom, m denotes the number 0 or 2, n denotes the number 1 or 2, and p denotes the number 0 or 1, with the proviso that p is 0 if m is 0, and the side-chain --S(0)_m --CH₂ --CH₂ --OH is in the ortho and/or para position to the aldehyde or carboxyl group, can be prepared by condensing 1 mole of a halobenzaldehyde of the general formula (II) ##STR2## in which R, X, Y and Z represent hydrogen, fluorine, chlorine, bromine or iodine atoms, with the proviso that R, X, Y and Z can be in total 1, 2 or 3 halogen atoms, where R is a halogen atom if R, X, Y and Z together represent 3 halogen atoms, in aqueous medium with about 1.0 to 1.5 moles of mercaptoethanol (per halogen atom to be exchanged) in the presence of the acid-binding agents at or about 70° C. about 150° C., to give the oxethylmercaptobenzaldehydes and oxidizing these to give the oxethylsulfonylbenzoic acids using at least the amount of hydrogen peroxide necessary in each case at about 40° C. to about 110° C. in the presence of a tungsten(VI) compound as a catalyst.

Claims

1. A process for the preparation of an oxethylmercaptobenzaldehyde of the formula (1) ##STR8## in which R denotes a hydrogen, fluorine, chlorine, bromine or iodine atom, m denotes the number 0, n denotes the number 1 or 2 and p denotes the number 0, and the side-chain --S(O)_m --CH₂ --CH₂ --OH is in the ortho and para, or ortho or para position to the aldehyde group, which comprises condensing 1 mole of a halobenzaldehyde of the formula (II), ##STR9## in which R, X, Y and Z represent hydrogen, fluorine, chlorine, bromine or iodine atoms, with the proviso that R, X, Y and Z can be in total 1, 2 or 3 halogen atoms, where R is a halogen atom, if R, X, Y and Z together represent 3 halogen atoms, in aqueous medium with about 1.0 to 15 moles of mercaptoethanol, per halogen atom to be exchanged, in the presence of an acid-binding agent at a temperature of about 70°

C. to about 150°

C., to give the corresponding oxethylmercaptobenzaldehyde.

2. The process as claimed in claim 1,

wherein the condensation is carried out in the presence of caustic soda, sodium hydroxide solution, caustic potash, potassium hydroxide solution or magnesium oxide.

3. The process as claimed in claim 1,

wherein the condensation is carried out at temperatures of about 90°

C. to about 120°

C.

4. The process as claimed in claim 1,

wherein 1 mole of the starting compound of the formula (II) mentioned therein is condensed with 1.25 to 1.4 moles of mercaptoethanol.

5. A process for the preparation of an oxethylsulfonylbenzaldehyde of the formula (I) ##STR10## in which R denotes a hydrogen, fluorine, chlorine, bromine or iodine atom, m denotes the number 2, n denotes the number 1 or 2, and p denotes the number 0, and the side-chain --S(O)_m --CH₂ --CH₂ --OH is in the ortho and para, or ortho or para, position to the aldehyde group, which comprises condensing 1 mole of a halobenzaldehyde of the formula (II) ##STR11## in which R, X, Y and Z represent hydrogen, fluorine, chlorine bromine or iodine atoms with the proviso that R, X, Y and Z can be total 1, 2 or 3 halogen atoms, where R is a halogen atom is R, X, Y and Z together represent 3 halogen atoms, in aqueous medium with about 1.0 to 1.5 moles of mercaptoethanol, per halogen, atoms to be exchanged, in the presence of an acid-binding agent at a temperature of about 70°

C. to about 150°

C., to give the corresponding oxethylmercaptobenzaldehyde and oxidizing this aldehyde to give the corresponding oxethylsulfonylbenzaldehyde with at least 2 moles of hydrogen peroxide per oxethylmercapto group at a pH<

5 at temperature of about 40°

C. to about 110°

C. in the present of a tungsten (VI) compound as a catalyst.

6. The process as claimed in claim 5,

wherein the oxidation is carried out at temperatures of about 60°

C. to about 95°

C.

7. The process as claimed in claim 5,

wherein the oxidation of the oxethylmercaptobenzaldehyde first obtained to give the corresponding oxethylsulfonylbenzaldehyde is performed at a pH between 1 and 4, and wherein said oxidation to give the corresponding oxethylsulfonylbenzoic acid is performed at a pH between 9 and 13.

8. The process as claimed in claim 5,

wherein the oxidation is performed in the presence of sodium tungstate or tungsten trioxide as a catalyst.

9. A process for the preparation of an oxethylsulfonylbenzoic acid of the formula ##STR12## in which R denotes a hydrogen, fluorine, chlorine, bromine or iodine atom, m denotes the number 2, n denotes the number 1 or 2, and p denotes the number 1, and the side-chain --S(O)_m --CH₂ --CH₂ --OH is in the ortho and para, or ortho or para position to the carboxyl group, which comprises condensing 1 mole of a halogenzaldehyde of the formula (II) ##STR13## in which R, X, y and Z represent hydrogen, fluorine, chlorine, bromine or iodine atoms, with the proviso that R, X, Y and Z can be total 1, 2 or 3 halogen atoms where R is a halogen atom is R, X, Y and Z together represent 3 halogen atoms, in aqueous medium with about 1.0 to 1.5 moles of mercaptoethanol, per halogen atom to be exchanged, in the presence of an acid-binding agent at temperatures of about 70°

C. to about 150°

C., to give the corresponding oxethylmercpatobenzaldehyde and oxidizing this aldehyde to give the corresponding oxethylsulfonylbenzoic acid with at least 1 mole of hydrogen peroxide for the oxidation of the aldehyde group and at least 2 moles of hydrogen peroxide per oxethylmercapto group at a pH>

8 at temperatures of about 40°

C. to about 110°

C. in the presence of a tungsten (VI) compound as a catalyst.

10. The process as claimed in claim 9, wherein the oxidation is carried out at temperatures of about 60°

C. to about 95°

C.

11. The process as claimed in claim 9, wherein the oxidation of the oxethylmercaptobenzaldehyde first obtained to give the corresponding oxethylsulfonylbenzaldehyde is performed at a pH between 1 and 4, and wherein said oxidation to give the corresponding oxethylsulfonylbenzoic acid is performed at a pH between 9 and 13.

12. The process as claimed in claim 9, wherein the oxidation is performed in the presence of sodium tungstate or tungsten trioxide as a catalyst.