US3256336A - Cleavage of alkyl o-hydroxyphenyl ethers - Google Patents

Cleavage of alkyl o-hydroxyphenyl ethers Download PDF

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US3256336A
US3256336A US118514A US11851461A US3256336A US 3256336 A US3256336 A US 3256336A US 118514 A US118514 A US 118514A US 11851461 A US11851461 A US 11851461A US 3256336 A US3256336 A US 3256336A
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chloride
aluminum chloride
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Robert G Lange
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Monsanto Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C313/00—Sulfinic acids; Sulfenic acids; Halides, esters or anhydrides thereof; Amides of sulfinic or sulfenic acids, i.e. compounds having singly-bound oxygen atoms of sulfinic or sulfenic groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C313/08—Sulfenic acids; Derivatives thereof
    • C07C313/10—Sulfenic acids; Esters thereof
    • C07C313/16—Sulfenic acids; Esters thereof having sulfur atoms of sulfenic groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/44—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by —CHO groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
    • C07C303/22—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof from sulfonic acids, by reactions not involving the formation of sulfo or halosulfonyl groups; from sulfonic halides by reactions not involving the formation of halosulfonyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C313/00—Sulfinic acids; Sulfenic acids; Halides, esters or anhydrides thereof; Amides of sulfinic or sulfenic acids, i.e. compounds having singly-bound oxygen atoms of sulfinic or sulfenic groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C313/02—Sulfinic acids; Derivatives thereof
    • C07C313/04—Sulfinic acids; Esters thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
    • C07C319/12—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by reactions not involving the formation of mercapto groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
    • C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
    • C07C39/17—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings containing other rings in addition to the six-membered aromatic rings, e.g. cyclohexylphenol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/673—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C65/01—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups
    • C07C65/03—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups monocyclic and having all hydroxy or O-metal groups bound to the ring

Definitions

  • alkyl o-hydroxyphenyl ethers of the formula where R represents an alkyl radical of from 1 to 4 carbon atoms, R representsa member of the groupconsisting of hydrogen, halogen, alkyl and alkenyl radicals of from 1 to 4 carbon atoms and alkoxy radicals of from 1 to 4 carbon atoms, R" represents a member of the group consisting of halogen, nitro, sulfomethyl, sulfinomethyl, mercaptomethyl, sulfenomethyl, hydroxyl, hydrocarbons of from 1 to 18 carbon atoms and oxygenated hydrocarbons of from 1 to 18 carbon atoms, and n represents an integer from 0 to 3.
  • the alkyl o-hydroxyphenyl ethers of this formula can be cleaved by reaction with a tertiary amine and anhydrous aluminum chloride in the presence of an inert organic solvent.
  • the intermediate product which is formed is then hydrolyzed with aqueous acid to yield a product of the formula (Rm W wherein R, R and n have the same meaning as above.
  • halogen includes chlorine, bromine, iodine and fluorine.
  • hydrocarbon includes both the aliphatic and aromatic radicals consisting solely of carbon and hydrogen. Illustrative of such hydrocarbons are methyl, ethyl, propyl, isopropyl, n-butyl,
  • Patented June 14, 1966 isobutyl, sec.-butyl, tert.-butyl, n-amyl, isoamyl, n-hexyl, isohexyl, heptyl, Z-ethylhexyl, octyl, isooctyl, Z-ethylheptyl, isononyl, decyl, isodecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, octadecyl, cyclobutyl, cyclopentyl, 2- methylcyclopentyl, 3-methylcyclopentyl, 2,4-dimethylcyclopentyl, cyclohexyl, 3,5-dimethylcyclohexyl, cyclohexylmethyl, cyclohexylpropyl, methylcyclohexylethyl, 2-propyl
  • oxygenated hydrocarbon includes not only those radicals wherein a hydrocarbon contains a terminal oxygen atom having a free valence thereon, but also other and different radicals consisting solely of carbon, hydrogen and oxygen wherein the latter forms part of a carbonyl, hydroxyl or alkoxy group.
  • oxygenated hydrocarbon radicals are methoxy, ethoxy, propoxy, butoxy, pentoxy, octoxy, decoxy, tetradecoxy, hexadecoxy, octadecoxy, cyclo-propoxy, cyclobutoxy, cyclohexoxy, methyl cyclopentoxy, cyclohexyl methoxy, cyclohexyl propoxy, cycloheptoxy, 3-dodecyl cyclohexoxy, phenoxy, naphthoxy, 3- phenylpropoxy, benzyloxy, Z-phenylethoxy, phenyldecoxy, ethyl phenoxy, toloxy, formyl, carboxy, hydroxyrnethyl, acetyl, acetoxy, allyloxy, benzoyl, 2,4-dihydroxyphenyl and the like.
  • the substituents represented by R encompass a very extensive group of radicals.
  • the moieties which occupy the meta positions and the para position, in respect to the ortho hydroxy group of the alkyl o-hydroxyphenol ether have not been found to interfere with the desired ether cleavage in any way.
  • the diverse nature of such moieties, particularly in the case of the oxygenated hydrocarbons, will be further exemplified below.
  • alkyl o-hydroxyphenyl ethers which can be cleaved in accordance with this invention are guaiacol, vanillin, isovanillin, acetovanillone, 3-ethoxy-4-hydroxybenzaldehyde, ferualdehyde, syringaldehyde, vanilloyl acetyl, eugenol, chavibetol, isoeugenol, o-eugenol, o-isoeugenol, isochavibetol, ferulic acid, isoferulic acid, hydroferulic acid, hydroisoferulic acid, hydroxyferulic acid, vanillic acid, isovanillic acid, homovanillic acid, 4-npropyl guaiacol, S-iodoguaiacol, S-bromovanillim-Z-nitrovanillin, 6-nitrovanillin, coniferyl alcohol, vanillyl alcohol,
  • cleavage process of this invention is not applicable to ethers which do not conform to the structural formula set forth above.
  • ethers as veratraldehyde, 3,4-diethoxybenzaldehyde, resorcinol monomethyl ether, m-methoxybenzaldehyde and anisole remain virtually unchanged in the pres- For ex- 7 ence of the reagents of this invention.
  • alkyl o-hydroxyphenyl ethers remain virtually unchanged when the other ortho position contains a substituent outside the scope of R. An example of such a situation is the case of orthovanillin.
  • the first pro-- cedure consists of slow addition of anhydrous aluminum chloride to the amine while cooling and stirring, followed by addition of the ether and then the solvent.
  • this method is somewhat inconvenient since it produces a viscous slurry before addition of the solvent.
  • Another procedure involves preforming an aminealuminum chloride complex by adding the amine slowly and with cooling to anhydrous aluminum chloride slurried in a solvent such as pentane. The pentane is distilled off and the remaining solid is added to the ether and the solvent.
  • a solvent such as pentane
  • a preferred procedure comprises adding a solution of an ether in a solvent to anhydrous aluminum chloride to form a stirrable slurry.
  • the amine is then added slowly and with cooling to complete the charge of reactants.
  • This last procedure has the particular advantage of permitting close control of the temperature during the complex formation because addition of liquids at a uniform rate is much easier than addition of solids and, also, the time required for complex formation is reduced due to dilution of the reactants with the solvent..
  • tertiary amines which can be used in the present process are the heterocylic tertiary amines such as pyridine, a-picoline, 'y-picoline, fl-picoline, quinoline, isoquinoline, 2-methyl quinoline, 3-methyl quinoline, 4-methyl quinoline, S-methyl quinoline, 6-methyl quinoline, 7- methyl quinoline, 8-methyl quinoline, Z-ethyl quinoline, 4- ethyl quinoline, 2,3-dimethyl quinoline, 2,4-dimethyl quinoline, 2,8-dimethyl quinoline, 3,4-dimethyl quinoline, 4,6-
  • methyl--ethyl pyridine pyrimidine, 2,3-dimethyl pyridine, 2,4-dimethyl pyridine, 2,5-dimethyl pyridine, 2,6-dimethyl pyridine, 3,4-dimethyl pyridine, 3,5-dimethyl pyridine, 2- ethyl pyridine, 3-ethyl pyridine, 4-ethyl pyridine, 2,4,6- trimethyl pyridine, Z-propyl pyridine; the aromatic tertiary amines such as N,N-dimethylaniline, N,N-diethylaniline, and the like; and the aliphatic tertiary amines such as trimethylamine, trie'thylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-tert.-butylamine, triisoamylamine, tri-n-amylamine, trihexyl
  • the anhydrous aluminum chloride used in the process of this invention can be prepared by any of a number of methods well known to those skilled in the art. For example, such methods of preparation include chlorination of aluminum metal with chlorine, hydrogen chloride, and metal chlorides, i.e. lead chloride, copper chloride, and silver chloride.
  • Aluminum chloride can also be prepared by the reaction of alumina and aluminiferous ores with chlorine, hydrogen chloride, metal chlorides and the like.
  • Anhydrous aluminum chloride is extremely hygroscopic and consequently caution should be taken to minimize the exposure of aluminum chloride to the air to avoid premature reaction of said aluminum chloride.
  • Suitable solvents in which the reaction can be conducted include saturated aliphatic'hydrocarbons such as n-penethylcyclobutane, cyclopentane, methylcyclopentane, methylcyclohexane, cyclohexane and the like; halogenated aliphatic hydrocarbons such as ethyl chloride, ethyl bromide, ethyl iodide, n-propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, propyl iodide, ethylene dichloride, methylene chloride, methylene bromide, chloroform, carbon tetrachloride and the like; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, n-propylbenzene and the like; halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenz
  • reaction temperature of 0 C. can be maintained, for example, by employing a cooling bath comprising a slurry of ice in water and using methylene chloride or chloroform as a reaction solvent.
  • rate of reaction at temperatures 0 C. to 10 C. will be somewhat slow.
  • the minimum temperature for the process of this invention is therefore the temperature just above that at which no reaction takes place between the alkyl o-hydroxyphenyl ether, tertiary amine and aluminum chloride.
  • Temperatures such as those greater than 105 C. can i also be used in the process of this invention. However, degradation results in considerable tar in the reaction product. At higher temperatures shorter reaction periods may be used to overcome the degradation problem. The yield of product falls off with the longer reaction time at higher temperatures, i.e. greater than 105 C. Temperatures within the range of from about 0 C. to about 55 C. can be most advantageously used, while temperatures within the range of from about 40 C. to 45 C. are especially preferred.
  • the tertiary amine, anhydrous aluminum chloride and ether employed in the practice of this invention can be used in ratios which vary over a rather wide range. For example, with each mole of the ether, from 1.4 to about 14.0 moles of the amine can be added. Similarly, with each mole of the ether, there can be added from 0.5 to about 3.5 mole of the aluminum chloride. It should be pointed out that a molar ratio of about 4.4:1.1 .:1.0 (aminezaluminum chloridezether) is particularly preferred.
  • the product of the ether-amine-aluminum chloride reaction is then hydrolyzed with an aqueous acid.
  • a wide range of acids can be employed for such hydrolysis, it has been found that optimum yields are obtained with acids such as sulfuric, phosphoric, hydrochloric and the like.
  • the product can be recovered by any method well known to those skilled in and efiicient separation of the reaction product and any unreacted alkyl o-hydroxyphenyl ether.
  • the reaction mixture is permitted to settle into two phases, i.e. an organic phase and an aqueous phase. It is generally found upon separation of the two phases that the aqueous phase contains in efiect all of the desired reaction product, and the organic phase contains all of the unreacted alkyl o-hydroxyphenyl ether.
  • the aqueous phase is treated by a solvent extraction technique to isolate the desired product. Any unreacted components are recovered from the organic phase for reuse in the process by evaporation.
  • the organic phase can be dried by azeotropic distillation and recycled to the process.
  • Example I A suitable reaction vessel, designed to exclude atmospheric moisture, is equipped with agitation means, means for measuring the temperature of liquids and vapors, heating and cooling means, and means for condensing vapors. Said vessel is charged with 152 grams (1.0 mole) of vanillin and 1500 ml. of methylene chloride, and
  • the methylene chloride phase contains substantially all of the unreacted vanillin, Said vanillin may be recovered by evaporation.
  • the methylene chloride phase can be dried by azeotropic distillation and recycled to the process.
  • Example 11 A reaction vessel as described in Example I is charged with 166 grams (1.0 mole) of acetovanillone and 1500 ml. of methylene chloride, and 146.8 grams 1.1 moles) of anhydrous aluminum chloride is suspended 'in the charged materials. 348.0 grams (4.4 moles) of pyridine is then added with agitation and cooling at such a rate as to maintain the reaction temperature at -35 C. The resulting solution of the reaction complex in the solvent is heated to the reflux temperature of the solvent (44 C) and maintained at said temperature for about 24 hours. Said solution is then cooled to 20 C. and hydrolyzed with cooling by the addition of dilute (15- 20%) hydrochloric acid until the solution is acidic to a Congo red indicator.
  • the aqueous phase and the methylene chloride phase are separated.
  • the former is extracted with four 500 ml. portions of ether.
  • the combined ether extracts are evaporated to obtain crystalline 3,4-dihydroxyacetophenone in a yield of 70% of theory and having a M.P. 110-112" C.
  • the methylene chloride phase contains substantially all of the unreacted acetovanillone; Said acetovanillone may be recovered by evaporation. As an alternative, the methylene chloride phase can be dried by azeotropic distillation and recycled to the process.
  • Example III Following the procedure of Example I, 124 grams (1.0 mole) of guaiacol, 146.8 grams (1.1 moles) of anhydrous aluminum chloride, 1500 m1. of methylene chloride and 348.0 grams (4.4 moles) of pyridine are utilized to prepare catechol, M.P. 103105 C., in a yield of 78% of theory.
  • Example IV Following the procedure of Example I, 152 grams (1.0 mole) of isovanillin, 146.8 grams (1.1 moles) of anhydrous aluminum chloride, 1500 ml. of methylene chloride and 348 grams (4.4 moles) of pyridine are utilized to pre- 6 pare protocatechualdehyde, M.P. 153-154 C., in a yield of 88% of theory.
  • the chloroform phase contains substantially all of the unreacted vanillin. Said vanillin may be recovered by evaporation. As an alternative, the chloroform phase can be dried by azeotropic distillation and recycled to the process.
  • Example XI A reaction vessel as described in Example I is charged with 152 grams (1.0 mole) of vanillin and 1500 ml. of chloroform, and 146.8 grams (1.1 moles) of anhydrous aluminum chloride is suspended in the charged materials. 348.0 grams (4.4 moles) of pyridine is then added with agitation and cooling at such a rate as to maintain the reaction temperature at 30-35" C. The resulting solution of the reaction complex in the solvent is heated to a temperature of 45 C. and maintained at said temperature for about 24 hours. Said solution is then cooled to 20 C. and hydrolyzed with cooling by the addition of dilute (IS-20%) hydrochloric acid until the solution is acidic to a Congo red indicator.
  • dilute IS-20% hydrochloric acid
  • the aqueous phase and the chloroform phase are separated.
  • the former is extracted with four 500 ml. portions of ether.
  • the combined ether extracts are evaporated to obtain crystalline protocatechualdehyde in a yield of 76% of theory and having a M.P. 152153 C.
  • the chloroform phase contains substantially all of the unreacted vanillin. Said vanillin may be recovered by evaporation. As an alternative, the chloroform phase can be dried by azeotropic distillation and recycled to the process.
  • Example XII A reaction vessel as described in Example I is charged with 152 grams (1.0 mole) of vanillin and 1500 ml. of ethyl bromide, and 146.8 grams (1.1 moles) of anhydrous aluminum chloride is suspended in the charged materials. 348.0 grams (4.4 moles) of pyridine is then added with agitation and cooling at such a rate as to maintain the reaction temperature at 3035 C. The resulting solution of the reaction complex in the solvent is heated to the reflux temperature of the solvent (40 C.) and maintained at said temperature for about 24 hours. Said solution is then cooled to 20 C. and hydrolyzed with cooling by the addition of dilute (IS-20%) hydrochloric acid until the solution is acidic to a Congo red indicator.
  • the aqueous phase and the ethyl bromide phase are separated.
  • the former is extracted with four 500 ml. portions of ether.
  • the combined ether extracts are evaporated to obtain crystalline protocatechualdehyde in a yield of 87% of theory and having a M.P. l53l54 C.
  • the ethyl bromide phase contains substantially all of the unreacted vanillin. Said vanillin may be recovered by evaporation. As an alternative, the ethyl bromide phase can be dried by azeotropic distillation and recycled to the process.
  • Example XIII Following the procedure of Example I, 182 grams (1.0 mole) of syringaldehyde, 146.8 grams (1.1 mole) of anhydrous aluminum chloride, 1500 ml. of methylene chloride and 348.0 grams (4.4 moles) of pyridine are utilized to prepare 3-methoxy-4,S-dihydroxybenzaldehyde, M.P. 131-l33 C., in a yield of 79% of theory.
  • Example XIV A reaction vessel as described in Example I is charged with 152 grams (1.0 mole) of vanillin and 1500 ml. of ethylene dichloride, and 146.8 (1.1 moles) of anhydrous aluminum chloride is suspended in the charged mate-rials. 348.0 gram (4.4 moles) of pyridine is then added With agitation and cooling at such a rate as to maintain the reaction temperature at 3035 C. The resulting solution of the reaction complex in the solvent is heated to a temperature of 45 C. and maintained at said temperature for about 24 hours. Said solution is then cooled to 20 C. and hydrolyzed with cooling by the addition of dilute (-20%) hydrochloric acid until the solution is acidic to a Congo red indicator.
  • the aqueous phase and the ethylene dichloride phase are separated.
  • the former is extracted with four 500 ml. portions of ether.
  • the combined ether extracts are evaporated tdobtain crystalline protocatechualdehyde in a yield of 76% of theory and having a M.P. l49l51 C.
  • the ethylene dichloride phase contains substantially all of the unreacted vanillin. Said vanillin may be recovered by evaporation. As an alternative, the ethylene dichloride phase can be dried by azeotropic distillation and recycled to the process.
  • Example XV Following the procedure of Example I, 152 grams (1.0 mole) of vanillin, 146.8 grams (1.1 moles) of anhydrous aluminum chloride, 1500 ml. of methylene chloride, and 410 grams (4. 4 moles) of 'y-picoline are utilized to prepare protocatechualdehyde in a yield of 73% of theory.
  • Example XVI Following the procedure of Example 1,152 grams (1.0 mole) of vanillin, 146.8 grams (1.1. moles) of anhydrous aluminum chloride, 1500 ml. of methylene chloride, and
  • Example XVII Following the procedure of Example I, 152 grams (1.0 mole) of vanillin, 146.8 grams (1.1 moles) of anhydrous aluminum chloride, 1500 ml. of methylene chloride, and 567 grams (4.4 moles) of quinoline are utilized to prepare protocatechualdeliyde in a yield of 23% of theory.
  • Example XVIII Following the procedure of Example I, 15 2 grams (1.0 mole) of vanillin, 146.8 grams 1.1 moles) of anhydrous aluminum chloride, 1500 ml. of methylene chloride, and 532 grams (4.4 moles) of N,N-dimethylaniline are utilized to prepare protocatechualdehyde in a yield of 33% of theory.
  • Example XIX A reaction vessel as described in Example I is charged with 166 grams (1.0 mole) of 3-ethoxy-4-hydroxybenzaldehyde and 1500 ml. of methylene chloride, and 146.8 grams (1.1 moles) of anhydrous aluminum chloride is suspended in the charged materials. 348.0 grams (4.4 moles) of pyridine is then added with agitation and cooling at such a rate as to maintain the reaction temperature at 3035 C. The resulting solution of the reaction complex in the solvent is heated to the reflux temperature of the solvent (44 C.) and maintained at said temperature ride phase can be dried by azeotropic distillation and recycled to the process.
  • Example XXV Following the procedure of Example I, 152.0 grams (1.0 mole) of vanillin, 146.8 grams (1.1 moles) of an- 9 hydrous aluminum chloride, 1500 ml. of methylene chloride and 444 grams (4.4 moles) of triethylam-ine are utilized to prepare protocatechualdehyde, M.P. 152-154 C., in a yield of 62% of theory.
  • Example XXI/H 1 A process which comprises reacting an alkyl o-hyd roxyphenyl ether of formula Following the procedure of Example I, 164 grams (1.0 (RH) mole) of eugenol, 146.8 grams (1.1 moles) of anhydrous aluminum chloride, 1500 ml. of methylene chloride, and 348 grams (4.4 moles) ofpyridine are utilized to prepare 4-allyl catechol, M.P. 4850 C., in good yield.
  • Example II Following the procedure of Example I, 197 grams (1.0 g mole) of Z-nitrovanillin, 146.8 grams (1.1 moles) of anwhere alkyl radical contammg from 1 to 4 l l atoms, R is a radical selected from the group consisting hydrous aluminum chloride, 1500 ml.
  • Example XXX 37 about 1.4 to about 14.0 moles of tertiary hydrocarbyl Following the procedure f
  • Example 1 3 grams 1 0 0 amine and from about 0.5 to about 3.5 moles of aluminum mole) of vanillyl sulfenic acid, 146.8 grams (1.1 moles) chlfmde P mole 9 etherof anhydrous aluminum chloride, 1500 ml.
  • Example XXXI Following the procedure of Example I, 170 grams (1.0 mole) of vanillyl mercaptan, 146.8 grams (1.1 moles) of anhydrous aluminum chloride, 1500 ml. of methylene B chloride, and 348 grams (4.4 moles) of pyridine are uti- 1 1 lized to prepare 3,4-dihydroxybenzyl mercaptan in good where R is an alkyl radical containing from 1 to 4 caryield.
  • R is a radical selected from the group con- Example X XX II sisting of hydrogen, halogen and alkyl, a-lkenyl and alkoxy 90 radicals containing froml to 4 carbon atoms
  • R" is a Following the procedure of Example I, 218 grams (1.0 radical selected from the group consisting of halogen, mole) of 4-hydroxy-3-methoxytoluene-w-sulfonic acid, nitro, sulfomethyl, sulfinomethyl, mercaptomethyl, sul- 146.8 grams (1.1 moles) of anhydrous aluminum chlofenomethyl, hydroxyl and hydrocarbon and oxygenated ride, 1500 ml.
  • cyclic tertiary hydrocarbyl amine and anhydrous alumi- The following table represents additional examples num chloride in the presence of an inert organic solvent, of the present invention, wherein the apparatus of Exand thereafter hydrolyzing the product of said reaction ample I is utilized, and the procedure and reactants emwith aqueous acid, there being from about 1.4 to about ployed are as specified.
  • this invention provides a simple and inexpensive method 0.5 to about 3.5 moles of aluminum chloride per mole of ether.
  • a process of preparing protocatechualdehyde which comprises reacting vanillin with a tertiary hydrocarbyl .amine and anhydrous aluminum chloride in the presence of an inert organic solvent and thereafter hydrolyzing the product of said reaction with an aqueous acid,
  • a process of preparing 3,4-dihydroxyacetophenone which comprises reacting acetovanillone with a tertiary hydrocarbyl amine and anhydrous aluminum chloride in the presence of an inert organic solvent and thereafter hydrolyzing the product of said reaction with an aqueous acid, there being from about 1.4 to about 14.0 moles of tertiary hydrocarbyl amine and from about 0.5 to about 3.5 moles of aluminum chloride per mole of acetovanillone.
  • a process of preparing 3,4-dihydroxy-5-methoxybenzaldehyde which comprises reacting syringaldehyde with a tertiary hydrocarbyl amine and anhydrous alu minum chloride in the presence of an inert organic solvent and thereafter hydrolyzing the product of said reaction with an aqueous acid, there being from about 1.4 to about 14.0 moles of tertiary hydrocarbyl amine and from about 0.5 to about 3.5 moles of aluminum chloride per mole of syringaldehyde.
  • a process of preparing S-bromoprotocatechualdehyde which comprises reacting S-bromovanillin with a tertiary hydrocanbyl amine and anhydrous aluminum chloride in the presence of an inert organic solvent and thereafter hydrolyzing the product of said reaction with an aqueous acid, there being from about 1.4 to about 14.0 moles of tertiary hydrocarbyl amine and from about 0.5 to about 3.5 moles of aluminum chloride per mole of 5-bromovanillin.

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FR901022A FR1330382A (fr) 1961-06-21 1962-06-18 Procédé de clivage des éthers d'alcoyle o-hydroxyphényle et de préparation simultanée de composés 1-alkyl-2,3-dihydroxyphényliques
DE1962M0053259 DE1182662B (de) 1961-06-21 1962-06-19 Verfahren zur Spaltung von Alkyl-o-hydroxy-phenyläthern.
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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3642622A (en) * 1970-10-27 1972-02-15 Texaco Inc Drilling fluid
US3970707A (en) * 1974-04-11 1976-07-20 Vasily Ivanovich Shvedov Method for preparing 3,5,3',5'-tetrabromo-2,4,2',4'-tetraoxydiphenyl
US4060561A (en) * 1976-09-20 1977-11-29 Continental Oil Company Method for the preparation of trimethylhydroquinone
US4093667A (en) * 1977-03-14 1978-06-06 Continental Oil Company Preparation of 4-n-hexylresorcinol
US4172960A (en) * 1975-06-28 1979-10-30 Fisons Limited Process for preparing pyrogallol
US4473713A (en) * 1981-09-29 1984-09-25 Rhone-Poulenc Specialites Chimiques Hydrolysis of aryl-aliphatic ethers
US4476330A (en) * 1978-08-16 1984-10-09 Mobil Oil Corporation Conversion of ethers using a zeolite catalyst
US4618627A (en) * 1983-05-13 1986-10-21 Yamanouchi Pharmaceutical Co., Ltd. Catechol derivatives and pharmaceutical compositions thereof for inhibiting anaphylaxis (SRS-A)
US5710343A (en) * 1994-09-23 1998-01-20 Orion-Yhtyma Oy Method for the preparation of 3,4-dihydroxy-5-nitrobenzaldehyde
FR2921921A1 (fr) * 2007-10-03 2009-04-10 Clariant Specialty Fine Chem Procede de synthese de composes polyhydroxystilbeniques.
CN104072362A (zh) * 2014-07-15 2014-10-01 吴学民 一种抗病毒化合物原儿茶酸的合成工艺
CN107118128A (zh) * 2017-04-25 2017-09-01 常州佳德医药科技有限公司 3,4‑二羟基苯甲腈的制备方法
CN108821955A (zh) * 2018-05-24 2018-11-16 荆楚理工学院 一种通过脱除邻香兰素的甲基制备2,3-二羟基苯甲醛的方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE458033B (sv) * 1984-10-22 1989-02-20 Chemical Dynamics Dev Ab Metod foer dealkylering av alkyl-aryl-etrar
US5236952A (en) * 1986-03-11 1993-08-17 Hoffmann-La Roche Inc. Catechol derivatives
GB9113431D0 (en) * 1991-06-20 1991-08-07 Orion Yhytma Oy Method for the preparation of 3,4-dihydroxy-5-nitrobenzaldehyde
US9567292B2 (en) 2012-07-19 2017-02-14 Laurus Labs Private Limited Process for preparation of 2,3-dihydroxy benzonitrile

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2100228A (en) * 1936-05-27 1937-11-23 Du Pont Process for the dealkylation of alkyl-aryl ethers
US2878292A (en) * 1955-06-20 1959-03-17 Crown Zellerbach Corp Purification of bourbonal

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2100228A (en) * 1936-05-27 1937-11-23 Du Pont Process for the dealkylation of alkyl-aryl ethers
US2878292A (en) * 1955-06-20 1959-03-17 Crown Zellerbach Corp Purification of bourbonal

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3642622A (en) * 1970-10-27 1972-02-15 Texaco Inc Drilling fluid
US3970707A (en) * 1974-04-11 1976-07-20 Vasily Ivanovich Shvedov Method for preparing 3,5,3',5'-tetrabromo-2,4,2',4'-tetraoxydiphenyl
US4172960A (en) * 1975-06-28 1979-10-30 Fisons Limited Process for preparing pyrogallol
US4060561A (en) * 1976-09-20 1977-11-29 Continental Oil Company Method for the preparation of trimethylhydroquinone
US4093667A (en) * 1977-03-14 1978-06-06 Continental Oil Company Preparation of 4-n-hexylresorcinol
US4476330A (en) * 1978-08-16 1984-10-09 Mobil Oil Corporation Conversion of ethers using a zeolite catalyst
US4473713A (en) * 1981-09-29 1984-09-25 Rhone-Poulenc Specialites Chimiques Hydrolysis of aryl-aliphatic ethers
US4618627A (en) * 1983-05-13 1986-10-21 Yamanouchi Pharmaceutical Co., Ltd. Catechol derivatives and pharmaceutical compositions thereof for inhibiting anaphylaxis (SRS-A)
US5710343A (en) * 1994-09-23 1998-01-20 Orion-Yhtyma Oy Method for the preparation of 3,4-dihydroxy-5-nitrobenzaldehyde
FR2921921A1 (fr) * 2007-10-03 2009-04-10 Clariant Specialty Fine Chem Procede de synthese de composes polyhydroxystilbeniques.
US20100324342A1 (en) * 2007-10-03 2010-12-23 Clariant Specialty Fine Chemicals (France) Process for the synthesis of polyhydroxystilbene compounds
US8399714B2 (en) 2007-10-03 2013-03-19 Clariant Speciality Fine Chemicals (France) Process for the synthesis of polyhydroxystilbene compounds
CN104072362A (zh) * 2014-07-15 2014-10-01 吴学民 一种抗病毒化合物原儿茶酸的合成工艺
CN107118128A (zh) * 2017-04-25 2017-09-01 常州佳德医药科技有限公司 3,4‑二羟基苯甲腈的制备方法
CN107118128B (zh) * 2017-04-25 2020-04-21 常州佳德医药科技有限公司 3,4-二羟基苯甲腈的制备方法
CN108821955A (zh) * 2018-05-24 2018-11-16 荆楚理工学院 一种通过脱除邻香兰素的甲基制备2,3-二羟基苯甲醛的方法
CN108821955B (zh) * 2018-05-24 2021-05-18 荆楚理工学院 一种通过脱除邻香兰素的甲基制备2,3-二羟基苯甲醛的方法

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GB967605A (en) 1964-08-26

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