反应详情

In short, the present invention provides a process for the preparation of substituted trans-cinnamaldehyde, a natural yellow dye, from phenylpropane derivatives wherein R.sup.1 is fixed as a —CH═CH—CHO, however, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6 are independently; i) a hydrogen atoms ii) a alkoxy group but atleast two of them from R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6 are hydrogen atom or a alkoxy group but one methylenedioxy group with combination of either hydroxyl group, alkoxy group, alkyl group having 1-2 carbon atoms, aryl group or hydrogen atom or a alkoxy group but one hydroxyl group with combination of either methylenedioxy group, hydroxyl group, alkoxy group, alkyl group having 1-2 carbon atoms, aryl group or hydrogen atom; iii) a methylenedioxy with atleast three of them from R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6 are combination of either alkoxy, hydroxy group, alkyl group having 1-2 carbon atoms, aryl group and hydrogen atom; iv) a hydroxyl group but atleast one of them from R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6 is hydrogen atom with combination of either alkoxy, hydroxyl group, methylenedioxy group, alkyl group having 1-2 carbon atoms, aryl group or hydrogen atom; v) a protected hydroxyl group such as acetyl, benzyl, etc but atleast one of them from R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6 is hydrogen atom with combination of either alkoxy, hydroxyl group, methylenedioxy group, alkyl group having 1-2 carbon atoms, aryl group and hydrogen atom or the like, obtained from corresponding (R2—R3—R4—R5—R6)phenylpropane derivatives (e.g. dihydro anethole where R2═R3═R5═R6 is H; R4 is —OMe; dihydro methyl eugenol where R2═R5═R6 is H; R3═R4 is —OMe and dihydro asarone where R2═R4═R5 is —OMe; R3═R6 is H etc) and the above process comprising the steps of (a) providing phenylpropane such as but not limited to 2,4,5-trimethoxyphenylpropane (dihydroasarone) in the following solvents namely ether such as but not limited to diethyl ether, tetrahydrofuran, dimethoxyethane, dioxane, diphenylether and the like; chlorinated solvents such as but not limited to dichloromethane, chloroform, o-dichlobenzene; an aromatic hydrocarbon such as but not limited to benzene, toluene, xylene; organic acid such as but not limited to formic acid, acetic acid and the like; (b) oxidation of phenylpropane derivatives in the presence of oxidizing reagents such as but not the limited to 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) or p-chloranil or pyridinium chlorochromate (PCC) or tBuOOH or CrO3 or a combination of reagents and the like and the amount thereof to be used is in the ration of 1-20 times moles, preferably 1.5-8 times moles, reaction temperature varies from −15° C. to +210° C., preferably 30° C. to 140° C., reaction period varies from 30 minutes to 48 hours, preferably 4-16 hours; (c) oxidation step proceeds more smoothly along with higher yield in presence of catalysts mainly mineral acid such as but not limited to hydrochloric acid, sulphuric acid or Cu(I) or Fe(III) salt or periodic acid or organic acid such as but not limited to acetic acid, propionic acid, butyric acid, ion exchange resin such as IR-120H, a sulphonated polystyrene resin, para-toluenesulphonic acid (PTSA) or amberlyst such as amberlyst 15 or absorbed above solution of phenylpropane and oxidising reagent on the following solid support such as but not limited to celite, silica gel, molecular sieve, alumina and the like in a short period ranging from 20 seconds to 12 minutes under microwave irradiation; (d) filtering the mixture and removing the solvent under reduced pressure, where the product is to be isolated in a conventional manner, i.e. extraction, distillation, recrystallization and chromatography and the yield of the product (e.g. 2,4,5-trimethoxycinnamaldehyde where R1 is —CH═CH—CHO, R2═R4═R5 is —OMe; R3═R6 is H; and 3,4-dimethoxycinnamaldehyde where R1 is —CH═CH—CHO, R2═R5═R6═H; R3═R4 is —OMe etc. in the above formula I) varies from 68-82%, preferably more in case of benzoquinone as a oxidising reagent.