Title of Invention

PROCESS FOR THE PREPARATION OF A HYDROXYBENZALDEHYDE

Abstract

ABSTRACT HYDROXyBENZALDEHYDE PREPARATION PROCESS The present invention concerns a process for the oxidation of hydroxybenzyl alcohols to the corresponding hydroxybenzaldehydes. The present invention provides a process for the preparation of a hydroxybenzaldehyde by oxidation of the corresponding hydroxybenzyl alcohol in the liquid phase, using molecular oxygen or a gas containing molecular oxygen, in an aqueous medium containing an alkali, in the presence of a platinum based catalyst , characterised in that oxidation is carried out in the presence of a boron derivative and a bismuth derivative.

Full Text

GOVERNMENT OF INDIA, THE PATENT OFFICE 2nd M.S.O. BUILDING, 234/4, ACHARYA JAGADISH CHANDRA BOSE ROAD KOLKATTA - 700 020. COMPLETE SPECIFICATION NO. DATED: . 07-Feb-95 APPLIATION NO. 149 MAS 95 DATED: 07-Feb-95 Convention Mb. 94 01562 on 11th Feb 1994. FEANCE. ACCEPTANCE OF THE COMPLETE SPECIFICATION ADVERTISED ON INDEX AT ACCEPTANCE — 32 F3 C INTERNATIONAL CLASSIFICATION " C 0 7 C 47 / 56 TITLE : " A PROCESS FOR THE PREPARATION OF A HYDROXYBENZALDEHYDE" APPLICANT RHONE-POULENC CHIMIE A FRENCH COMPANY, OF 25 QUAI PAUL DOUMER, 92408 COURBEVOIE CEDEX, FRANCE INVENTORS 1. HELENELEFRANC. THE FOLLOWING SPECIFICATION PARTICULARLY DESCIRBES AND ASCERTAINS THE NATURE OF THIS INVENTION AND THE MANNER IN WHICH IT IS TO BE PERFORMED: - * comparative examole The mixture was distilled for 3 hours and the carrier (toluene) was recycled to separate the theoretical quantity of water. Dilution with 75 g of toluene followed and 16 g of trioxymethylene suspended in 25 g of toluene was added. The mixture was held at 80°C until the reaction with the formaldehyde was complete (about 3 hours). The solution of saligenlne borate in toluene was hydrolysed at, room temperature with a caustic soda solution prepared by adding 200 g of water to 152 g of a 30 % by weight caustic soda solution. This was then decanted and the aqueous solution containing the sodium salts of saligenol and boric acid was separated out. This aqueous solution was oxidized directly using the procedure described in Example 4, except that it was not necessary to add boric acid. Oxygen at atmospheric pressure was passed into the solution, to which the following had been added: 0.8 g of 2 % platinum black (16 mg of platinxim); 0-035 g of bismuth oxide (31 mg of bismuth). until the volume of oxygen absorbed corresponded to the theoretical quantity required to transform the sallgenol into salicylic aldehyde, namely about 1 hour. The catalyst was separated from the reaction mixture and the salicylic aldehyde formed was liberated from Its sodium salt by adding 200 ml of 5N sulphuric acid, then steam distilling or extracting using an appropriate solvent to Isolate the salicylic aldehyde. 43 g of salicylic aldehyde was obtained, representing a field of 68 % with respect to the phenol used. EXAMPLE 6* Example 5 was repeated but without the addition of bismuth oxide to the aqueous solution containing the sodium salts of jsaligenol and boric acid (before oxidation). 23 g of salicylic aldehyde was obtained, i.e., a yield of 37 % with respect to the phenol used. EXAMPLE 7 The following were loaded into a three necked flask provided with a thermometer, a distillation column, a retrograder, a coolant and a separator: salicylic aldehyde (600 mmol) prepared in accordance with Example 5; acetic anhydride (1.90 mmol) in solution in acetic acid » (3.47 g). This was refluxed and sodium acetate (2.1 mmol) was introduced in solution in acetic acid (3.47 g). The acetic acid was distilled by maintaining the reflux until the temperature at the column head was about 118*C. 4. The process according to claim 1, wherein the hydroxybenzyl alcohol is saligenol. 5. The process according to any one of claims 1 to 4, wherein the boron derivative is selected from boric acids, preferably orthobonic acid (or its precursor B2O3) metabornic acid, pyroboric acid and tetrbornic acid; metallic borates, in particular those of alkali or alkaline-earth metals or of ammonium in their anhydrous or hydrated forms, in particular metal tertiary borates, hemiborates, monoborates, diborates, triborates, tetraborates or pentaborates, preferably of alkali metals, or of ammonium; or double salts containing born, in particular metallic fluoborates. 6. The process according to claim 5, wherein the boron derivative is orthoboric acid or boric anhydride. 7. The process according to claim 5 or claim 6, wherein the ratio between the number of moles of boron derivative and the number of moles of hydroxybenzyl alcohol is between 0.1 and 3.0, preferably between 0.9 and 1.1. 8. The process according to any one of claims 1 to 7, wherdn the co-catalyst is an organic or inorganic bismuth derivative selected from: bismuth oxides; bismuth hydroxides; bismuth or bissmu1hyl salts or mineral hydrogen acids, preferably a chloride, bromide, iodide, sulphide, selenide or telluride; bismuth or bismuthyi salts of mineral oxyacids, preferably a sulphite, sulphate, nitrite, nitrate, phosphite, phosphate, pyrophosphate, carbonate, perchlorate, antimonate, arsenate, selenite, or selenate; bismuth or bismuthyl salts of organic aliphatic or aromatic acids, preferably an acetate, propionate, salicylate, benzoate, oxalate, tartrate, lactate or citrate; and bismuth or bismuthyl phenates, preferably the gallate or pyrogallate. 9. The process according to claim 8, wherein the bismuth derivative is selected from: bismuth oxides Bi203 and BiO4; bismuth hydroxide Bi(OH)3; bismuth chloride BiCl3; bismuth bromide BiBr3; bismuth iodide Bil3; neutral bismuth sulphate Bi2(SO4)3; neutral bismuth nitrate Bi(NO3)3; 5H2O; neutral Insmuthyl nitrate (BiO)NO3; bismuthyl carbonate (BiOyCO3, O.5H2O; bismuth acetate Bi(C2H3O2)3; and bismuthyl salicylate QRiCO2CBiO)(OH). 10. The process according to claim 8 or claim 9, wherein the quantity of co-catalyst used is selected such that it provides in the medium; at least 0.1% by weight of metallic bismuth with respect to the weight of platinum used, and 10 to 900 ppm by weight of metallic bismuth with respect to the hydroxyben2yl alcohol. 11. The process according to any one of claims 1 to 10, wherein the platinum catalyst is in the form of platinum black, platinum oxide, or the noble metal itself deposited on a support such as carbon black, calcium carbonate, activated aluminas and silicas, or equivalent materials, preferably carbon black. 12. The process according to claim 11, wherein the quantity of catalyst used, expressed as the weight of metallic platinum with respect to that of the alcohol to be oxidized, is 0.01 % to 4 %, preferably 0.04 % to 2%. 13. The process according to any one of claims 1 to 12, wherein oxidation is carried out in an aqueous medium containing 0.5 to 3 moles of sodium or potassium hydroxide with respect to the hydroxybenzyl alcohol to be oxidized. 14. The process according to any one of claims 1 to 13, wherein oxidation is carried out at a temperature of between 10°C and 100°C, preferably between 20°C and 60°C. 15. The process according to any one of claims 1 to 14, wherein the boron derivative is introduced during oxidation, with the platinum based catalyst and the bismuth based co-catalyst. 16. The process according to any one of claims 1 to 14, wherein the boron derivative is introduced during the preparation of the hydroxybenzyl alcohol. 17. The process according to any one of claims 1 to 14 and 16 wherein the boron derivative contained in the aqueous solution to be oxidized is produced by reacting a phenol with boric acid (or botic anhydride) to form a boric ester, which is then reacted with formaldehyde or a formaldehyde generator, followed by saponification of the hydroxybenzyl alcohol borate obtained using an alkaline base to produce a complex salt of hydroxyrbenzyl alcohol and boric acid. 18. The process for the preparation of salicylic aldehyde according to any one of claims 1 to 14, 16 and 17 wherein phenol and boric acid (or boric anhydride) are reacted to form a boric ester which is reacted with formaldehyde or a formaldehyde generator, followed by saponification of the saligenine borate obtained, using an alkaline base, to produce an aqueous solution of a complex salt or saligenol and boric acid which is oxidized after addition of a platinum based catalyst and a bismuth based co-catalyst. 19. The process according to claim 18, wherein the molar ratio of phenol/boric acid used is between 0.8 and 3.0, preferably between 1.0 and 1.5. 20. A process for the preparation of cumarin from salicylic aldehyde obtained using the process defined in any one of claims 1 to 19, 21. A process for the preparation of cumarin from salicylic aldehyde obtained using the process defined m any one of claims 1 to 19 and by reacting salicylic aldehyde with acetic anhydride, in the presence of sodium acetate. 22. A process for the preparation of a hydroxybenzaldehyde substantially as hereinbefore described with reference to the examples. We Claim: 1. A process for the preparation of a hydroxybenzaldehyde such as herein described by oxidation of the corresponding hydroxybenzyl alcohol in the liquid phase, using molecular oxygen or a gas containing molecular oxygen, in an aqueous medium containing an alkali, in the presence of a platinum based catalyst, wherein oxidation is carried out in the presence of a boron derivative as described herein and a bismuth derivative as described herein. 2. The process according to claim 1, wherein the hydroxybenzyl alcohol has formula (I): where radical -CH2OH is in the ortho, meta or para position with respect to the hydroxy group, the benzene nucleus may be sutstituted by one or more substituents R, which may be identical or different, and n is a number which is less than or equal to 3. 3. The process according to claim 2, wherein the hydroxybenzyl alcohol has formula (I)'where R represents a hydrogen atom or one or more substituents which may be a halogen atom, preferably fluorine, chlorine or bromine, or an alkyl or alkoxy radical preferably containing 1 to 12 carborn atoms, more preferably 1 to 4 carbon atoms. 4. The process according to claim 1, wherein the hydroxybenzyl alcohol is saligenol. 5. The process according to any one of claims 1 to 4, wherein the boron derivative is selected from boric acids, preferably orthoboric acid (or its precursor B2O3), metaboric acid, pyroboric acid and tetraboric acid; metallic borates, in particular those of alkali or alkaline-earth metals or of ammonium in their anhydrous or hydrated forms, in particular metal tertiary borates, hemiborates, monoborates, diborates, triborates, tetraborates or pentaborates, preferably of alkali metals, or of ammonium; or double salts containing boron, in particular metallic fluoborates. 6. The process according to claim 5, wherein the boron derivative is orthoboric acid or boric anhydride. 7. The process according to claim 5 or claim 6, wherein the ratio between the number of moles of boron derivative and the number of moles of hydroxybenzyl alcohol is between 0.1 and 3.0, preferably between 0.9 and 1.1. 8. The process according to any one of claims 1 to 7, wherein the bismuth derivative is an organic or inorganic bismuth derivative selected from: bismuth oxides; bismuth hydroxides; bismuth or bismuthyl salts or mineral hydrogen acids, preferably a chloride, bromide, iodide, sulphide, selenide or telluride; bismuth or bismuthyl salts of mineral oxyacids, preferably a sulphite, sulphate, nitrite, nitrate, phosphite, phosphate, pyrophosphate, carbonate, perchlorate, antimonate, arsenate, selenite, or selenate; bismuth or bismuthyl salts of organic aliphatic or aromatic acids, preferably an acetate, propionate, salicylate, benzoate, oxalate, tartrate, lactate or citrate; and bismuth or bismuthyl phenates, preferably the gallate or pyrogallate. 9. The process according to claim 8, wherein the bismuth derivative is selected from: bismuth oxides Bi2O3 and Bi2O4; bismuth hydroxide Bi(0H)3; bismuth chloride BiCl3; bismuth bromide BiBr3; bismuth iodide Bil3; neutral bismuth sulphate Bi2(SO4)3; neutral bismuth nitrate Bi(NO3)3; 5H2O; neutral bismuthyl nitrate (BiO)NO3; bismuthyl carbonate (BiO)2CO3, O.5H2O; bismuth acetate Bi(C2H3O2)3; and bismuthyl salicylate C6H4CO2(BiO)(OH). 10. The process according to claim 8 or claim 9, wherein the quantity of the said bismuth derivative used is selected such that it provides in the medium; at least 0.1% by weight of metallic bismuth with respect to the weight of platinum used, and 10 to 900 ppm by weight of metallic bismuth with respect to the hydroxybenzyl alcohol. 11. The process according to any one of claims 1 to 10, wherein the platinum catalyst is in the form of platinum black, platinum oxide, or the noble metal itself deposited on a support such as carbon black, calcium carbonate, activated aluminas and silicas, or equivalent materials, preferably carbon black. 12. The process according to claim 11, wherein the quantity of catalyst used, expressed as the weight of metallic platinum with respect to that of the alcohol to be oxidized, is 0.01 % to 4 %, preferably 0.04 % to 2%. 13. The process according to any one of claims 1 to 12, wherein oxidation is carried out in an aqueous medium containing 0.5 to 3 moles of sodium or potassium hydroxide per mole of the hydroxybenzyl alcohol to be oxidized. 14. The process according to any one of claims 1 to 13, wherein oxidation is carried out at a temperature of between 10°C and l00°C, preferably between 20°C and 60°C. 15. The process according to any one of claims 1 to 14, wherein the boron derivative is introduced during oxidation, with the platinum based catalyst and the bismuth derivative. 16. A process for the preparation of a hydroxybenzaldehyde substantially as hereinbefore described and exemplified.

Documents:

149-mas-95 abstract.pdf

149-mas-95 claims.pdf

149-mas-95 correspondence-others.pdf

149-mas-95 correspondence-po.pdf

149-mas-95 description (complete).pdf

149-mas-95 form-2.pdf

149-mas-95 form-26.pdf

149-mas-95 form-29.pdf

149-mas-95 form-4.pdf

149-mas-95 form-8.pdf

149-mas-95 others document.pdf

149-mas-95 others.pdf