WO1985002178A1 - PROCESS FOR p-ALKENYL PHENOLS AND THEIR SUBSEQUENT OXIDATION FORMING SUBSTITUTED BENZALDEHYDES - Google Patents

PROCESS FOR p-ALKENYL PHENOLS AND THEIR SUBSEQUENT OXIDATION FORMING SUBSTITUTED BENZALDEHYDES Download PDF

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WO1985002178A1
WO1985002178A1 PCT/US1983/001815 US8301815W WO8502178A1 WO 1985002178 A1 WO1985002178 A1 WO 1985002178A1 US 8301815 W US8301815 W US 8301815W WO 8502178 A1 WO8502178 A1 WO 8502178A1
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hydrocarbyl
reaction
substituted
solvent
ethene
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Charles Ray Everly
Jerry Monroe Roper
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Ethyl Corp
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Ethyl Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
    • C07C47/56—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing hydroxy groups
    • C07C47/565—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing hydroxy groups all hydroxy groups bound to the ring
    • 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
    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
    • 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
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
    • C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group

Definitions

  • This invention relates to a novel process for the preparation of p-alkenyl phenols and the subsequent preparation of the corresponding substituted benzaldehydes. More particularly, this invention relates to a novel process for the preparation of 1,1-hydrocarbyl-substituted-2-(3'-hydrocarbyl or 3',5'-dihydrocarby1-4'-hydroxyphenyl)-ethene compounds which are especially useful as interediates in the preparation of phenolic antioxidants for gasoline, lubricants, plastics and rubber.
  • an alkylated phenol having a replaceable hydrogen atom at the 4- position and at least one hydrocarbyl substituent ortho to the hydroxyl group is reacted with an aliphatic aldehyde having two carbon atoms up to at least 20 carbon atoms in the molecule and a secondary amine to form the corresponding 1,1-hydrocarbylsubstituted-2-(3'-hydrocarbyl- or 3',5'-dihydro-carbyl-4'-hydroxyphenyl)-ethene.
  • the invention can best be understood by the following detailed discussion of the reactants and conditions by which the p-alkenyl phenol products of the present process are produced. The structure of these products will, of course, be determined by the nature of the starting phenolic and aldehyde reactants.
  • any monohydroxybenzene compound having a replaceable hydrogen atom on the ring carbon atom para to the hydroxyl substituent and at least one hydrocarbyl substituent ortho to the hydroxyl group will serve as the starting phenol.
  • the hydrocarbyl substituents be alkyl, aralkyl or cycloalkyl groups sufficiently large to offer some degree of hindrance to the phenolic group.
  • the hydrocarbyl substituent be branched on the alpha-carbon atom and have at least 3 carbon atoms and, preferably, up to 8 carbon atoms; although any number of carbon atoms, for example up to about 40 carbon atoms, may be present in the hydrocarbyl substituent as long as the substituents do not interfere with the formation of the desired phenolic styrene.
  • Suitable o-hydrocarbyl phenols meeting these requirements include secondary alkyl-substituted phenols such as o-isopropyl phenol, o-sec-butyl phenol, o-sec-amyl phenol and o-cyclohexyl phenol; while suitable tertiary hydrocarbyl phenols are o-tert-butyl phenol and o-tert- amyl phenol. Additionally, primary hydrocarbyl phenols, such as o-benzylphenol, can serve as starting phenols.
  • phenolic reactants in the process of this invention are dialkyl phenols wherein the phenol has a replaceable hydrogen atom on the para ring carbon atom and two hydrocarbyl substituents ortho to the hydroxyl group.
  • the hydrocarbyl substituents is branched on the alpha-carbon atom and has from 3 to 8 carbon atoms. The substituents need not both be the same hydrocarbyl radical.
  • phenols are represented by 2,6-dimethyl phenol, 2, 6-di-n-butyl phenol, 2,6-di-sec-butyl phenol, 2-isopropyl-6-methyl phenol, 2, 6-diisopropyl phenol, 2, 6-di-tert-butyl phenol, 2,6-di-sec-octyl phenol, 2-methyl-6-cyclohexyl phenol, 2,6-di-(alpha-methylbenzyl)phenol, 2,6-dibenzyl phenol, 2-methyl-6-benzyl phenol and the like.
  • a particularly preferred phenolic reactant for use in the present process is 2,6-di-tert-butyl phenol.
  • Substituent groups other than those previously listed such as aryl, chlorine, bromine, fluorine and nitro groups and the like may be present at any of the ring carbon atoms with the sole exception of the para ring carbon atom in the aromatic phenolic reactant provided they do not adversely affect the formation of the desired 1,1-hydrocarbyl-substituted-2-(3'-hydrocarbyl or 3',5'-dihydrocarbyl-4'-hydroxyphenyl)ethene product.
  • R 1 and R 2 are the same or different and are hydrogen or hydrocarbyl radicals, preferably alkyl, aralkyl or cycloalkyl radicals having up to at least 40 carbon atoms, and preferably from 3 to 8 carbon atoms, at least one of which is branched on the alpha-carbon atom with the provision that at least one of R 1 or R 2 must be other than hydrogen.
  • Aldehydes which are applicable to the present process are those aldehydes having a single aldehyde radical of the general formula
  • R 3 and R 4 can be the same or different and are selected from hydrogen or linear and branched alkyl radicals having up to at least 40 carbon atoms, preferably up to 20 carbon atoms.
  • Typical aldehydes which may be used in the process of the invention include, by way of example only, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, caprylaldehyde, decylaldehyde, tetradecylaldehyde, and the like.
  • Amine reactants which are applicable to the present process are secondary amines; that is, derivatives of ammonia having one hydrogen atom bonded to the amino nitrogen atom and can be represented by the formula
  • R 5 and R 6 are the same or different and are linear or branched alkyl radicals having up to at least 40 carbon atoms. It is deemed, however, that secondary amines containing nitrogen atoms in a ring structure such as piperidine, pyrrolidine, morpholine and the like also may be used. Preferred amines are dimethylamine, diethylamine, dipropylamine, dibutylamine, disecondary propylamine, ethylinethylamine, methylpropylamine, methyl-n-butylamine, ethylisopropylamine and the like.
  • the amino reactant initially combines with the phenolic and aldehyde reactants to yield a Mannich base type of intermediate which upon further reaction spontaneously eliminates the amine component to produce the olefinic final product.
  • the carbonyl carbon atom of the aldehyde reactant along with the organic groups bonded to the carbonyl carbon atom of the aldehyde, becomes bonded to the 4-carbon atom of the phenol ring.
  • R 1 and R 2 are the same or different and are hydrogen or hydrocarbyl radicals selected from the group consisting of alkyl, aralkyl or cycloalkyl radicals having up to at least 40 carbon atoms with the provision that at least one of the R 1 or R 2 radicals must be other than hydrogen and R 3 and R 4 are the same or different and are hydrogen or linear or branched alkyl radicals having up to at least 20 carbon atoms in the molecule with the provision that one of R 3 or R 4 must be other than hydrogen.
  • the process of the invention is carried out by reacting the phenolic starting material with at least one molar equivalent of aldehyde and at least 0.1 molar equivalent of amine. It is preferred, however, that the reaction be conducted with a molar excess of both aldehyde and amine reactants with respect to the starting phenol.
  • a preferred range of aldehyde to phenolic reactant is from 1 to 10 moles of aldehyde per mole of phenol.
  • a preferred molar range of amine reactant to phenolic reactant is from 0.1 to 10 moles of amine per mole of phenol.
  • the reaction can be conducted at a temperature from 50°C. to 250°C. While lower temperatures can be used, the reaction rates are generally too low to be of interest. Temperatures above 250°C. can be used, but excessive decomposition of the reaction components can occur. The preferred reaction temperatures are from 50°C. to 200°C.
  • the reaction can be conducted at atmospheric pressure or at higher pressures, with moderate pressures up to about 300 psig being preferred.
  • a solvent for the reaction mixture is not generally required, though, if desired, a solvent which is inert under the reaction conditions, i.e., those solvents which do not enter into the reaction, may be added to the reaction vessel.
  • Useful solvents comprise aprotic solvents which include ethers such as diethyl ether, dibutyl ether, 1-ethoxyhexane, tetrahydrofuran, 1,4-dioxane, 1, 3-dioxolane, dlglyme, 1, 2-diethoxyethane and tertiary amines such as pyridine, N-ethylpiperidine, triethylamine, tributylamine, N.N-diphenyl-N-methyl amine. N,N-dimethylalanine, etc.
  • ethers such as diethyl ether, dibutyl ether, 1-ethoxyhexane, tetrahydrofuran, 1,4-dioxane, 1, 3-dioxolane, dlglyme, 1, 2-diethoxyethane and tertiary amines such as pyridine, N-ethylpiperidine, triethyl
  • Especially useful solvents are dipolar aprotic solvents such as dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfone, tetramethylene sulfone, N-methylpyrrolidinone, acetonitrile and like materials.
  • dipolar aprotic solvents such as dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfone, tetramethylene sulfone, N-methylpyrrolidinone, acetonitrile and like materials.
  • Other solvents which are inert under the reaction conditions may be used: for example, low boiling hydrocarbons, halogenated hydrocarbons, examples of which are benzene, toluene, tetrachloroethane, the chlorinated benzenes, the chlorinated toluenes, etc.
  • Especially preferred solvents are lower alkanols having up to about 6 carbon atoms. These include methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, secbutyl alcohol, tert-butyl alcohol, n-pentanol, isopentyl alcohol, n-hexanol and isohexyl alcohol.
  • the amount of solvent can be expressed as a volume ratio of solvent to phenolic reactant. Suitable volume ratios of solvent to phenolic reactant can be from 0/1 to 500/1 and preferably from 1/1 to 300/1.
  • the mode of addition in the process is not particularly critical.
  • the reaction is carried out by passing the amine in its gaseous state through the reaction mixture in a reaction vessel with agitation to obtain intimate contact of the reactants.
  • the amount of amine in contact with the other reactants can be controlled by limiting the flow of amine through or into the reaction vessel.
  • the process should be carried out for the time sufficient to convert substantially all of the phenolic reactant to the corresponding p-alkenyl phenol.
  • the length of time for optimum yield will depend primarily upon the reaction temperature and the particular solvent, if any, used in the reactior. In general, excellent yields of p-alkenyl phenol are obtained in from about two to forty-eight hours.
  • substantially anhydrous is meant a reaction system wherein the total amount of water present is no more than about 5 percent by weight, based on the reaction mixture. When the amount of water in the system exceeds this, both reaction rate and yield of product decrease.
  • the process may readily be conducted in a batch-wise, semi-batch or continuous manner and in conventional equipment.
  • the product p-alkenyl phenol is easily separated from the reaction mixture by such means as distillation, extraction, crystallization and other methods obvious to those skilled in the chemical processing art.
  • 2,6-di-tertiary-butyl phenol (4.1 g; 20 mmol) , isobutyraldehyde (3 ml; 33 mmol), dimethylamine (1.5 g; 34 mmol) dissolved in isopropanol (7.5 g) were charged to a 100 ml glass vessel and refluxed at ambient pressure under nitrogen for 48 hours.
  • 1,1-hydrocarbyl-substituted-2-(3'-hydrocarbyl- or 3 ' , 5 ' -dihydrocarbyl-4 ' -hydroxyphenyl) ethene products produced by the process of the present invention can be directly oxidized to the corresponding 3-hydrocarbyl-4- hydroxybenzaldehyde or 3,5-dihydrocarbyl-4-hydroxyben- zaldehyde by contacting with good agitation the aforementioned 1,1-hydrocarbyl-substituted-2-(3'-hydrocarbyl- or 3',5'-dihydrocarbyl-4'-hydroxyphenyl) ethene with at least a stoichiometric amount of oxygen in the presence of a small catalytic quantity of a catalyst selected from the group consisting of a Lewis acid, an alkali metal salt of a weak acid or an alkaline mearth metal salt of a weak acid, an alkali
  • 4,009,210 discloses a method for preparing 3,5-di-tertbutyl-4-hydroxybenzaldehyde, a chemical intermediate for the manufacture of pesticides of the benzylidenemalononitrile type, by reacting 2, 6-di-tert-butylphenol with hexamethylenetetramine or a combination of formaldehyde and ammonium acetate in aqueous acetic acid reaction medium.
  • a new process for the synthesis of 3-hydrocarbyl-4-hydroxybenzaldehydes or 3,5-dihydrocarbyl-4-hydroxy ⁇ benzaldehydes has now been discovered in which these materials can be prepared in a simple and straightforward manner.
  • p-alkenyl phenols in particular 1,1-hydrocarbyl-substituted-2-(3'-hydrocarbyl- or 3',5'-dihydrocarbyl-4'-hydroxyphenyl)ethenes are contacted with oxygen in the presence of a catalyst selected from a Lewis acid, an alkali metal hydroxide or an alkaline earth metal hydroxide, an alkali metal of a weak acid or an alkaline earth metal salt of a weak acid or an amine base.
  • a catalyst selected from a Lewis acid, an alkali metal hydroxide or an alkaline earth metal hydroxide, an alkali metal of a weak acid or an alkaline earth metal salt of a weak acid or an amine base.
  • cleavage of the olefinic bond located at the 4-position of the phenyl ring of the p-alkenyl phenol reactant takes place by a radical process whereby the desired alkylated hydroxyphenyl aldehyde product is produced.
  • 1,1-hydrocarbyl-substituted-2-(3'-hydrocarbyl- or 3',5'-dihydrocarbyl-4'-hydroxyphenyl)ethenes which are oxidized according to the aforementioned process are those compounds described and prepared here-inabove.
  • the process is readily conducted by placing the 1,1-hydrocarbyl-substituted-2-(3'-hydrocarbyl- or 3',5'-dihydrocarbyl-4'-hydroxyphenyl) ethene and other reaction mixture components in a reaction vessel having agitation means, or can be advantagepusly carried out, for example, by passing the 1,1-hydrocarbyl-substituted-2-(3'- hydrocarbyl- or 3',5'-dihydrocarbyl-4'-hydroxyphenyl)ethene through appropriate reaction tubes and simply contacting the same with oxygen or an oxygen containing gas and catalyst.
  • the oxidation reaction should be carried out with agitation and preferably with vigorous agitation or using other means that afford intimate contact between the oxygen containing gas and the reaction mixture.
  • An essential component of the reaction mixture is a catalytic amount of a catalyst, the suitable catalysts being selected from the group consisting of alkali metal hydroxides, alkali metal salts of a weak acid, alkaline earth metal hydroxides, alkaline earth metal salts of a weak acid, amine bases, mixtures of the same and Lewis acid catalysts.
  • Suitable catalysts are sodium hydroxide, potassium hydroxide, barium hydroxide, rubidium hydroxide, cesium hydroxide, potassium carbonate, sodium carbonate, cesium carbonate, rubidium carbonate, potassium sulfite, sodium borate, potassium acetate, diazabicyclononane, pyridine, tetra-methylguanidine, 1,4-diazabicyclo-(2,2,2)-octane, FeCl 3 , BF 3 , ZnCl 2 , TiCl 4 , HF, H 2 SO 4 , H 3 PO 4 , SnCl 2 , SnCl 4 , and CuCl 2 . Copper chloride and ferric chloride are preferred catalysts.
  • the amount of catalyst used is not narrowly critical but only a small amount is sufficient to promote cleavage of the olefinic bond at the 4- position of the 1,1-hydrocarbyl-substituted-2-(3'-hydrocarbyl or 3',5'-dihydrocarby1-4'-hydroxyphenyl) ethene reactant.
  • the amount used can be as little as 0.1 weight percent through amounts up to 1 weight percent, based on the weight of p-alkenyl phenol reactant, and even greater amounts of catalyst may be used if desired.
  • the amount of oxygen employed relative to the 1,1-hydrocarbyl-substi ⁇ tuted-2-(3'-hydrocarbyl- or 3',5'-dihydrocarbyl-4'-hydroxyphenyl) ethene starting reactant is not critical. In general, only an amount of oxygen required for the direct oxidative cleavage of the p-alkenyl phenol to the corresponding benzaldehyde should be used. For best results, however, it is preferable that at least a stoichiometric amount of oxygen or an amount greater than that stoichiometric required is used.
  • the reaction is conducted, for example, by passing oxygen, and preferably an oxygen containing gas such as air , through the reaction mixture in a reaction vessel with agitation to obtain intimate contact of the reactants.
  • oxygen and preferably an oxygen containing gas such as air
  • the reaction is conducted at atmospheric pressure, however , higher pressures up to about 200 psig may be used, if desired.
  • the amount of oxygen reacting with the p-alkenyl phenol reactant can be, in general, easily controlled by limiting the flow of gas through or into the reaction zone.
  • the reaction can be conducted at mildly elevated temperatures of, for example, from 25°C. up to higher temperatures of 250°C. and preferably at a temperature that ranges from 50°C. up to 150°C. Reflux temperature at atmospheric pressure is effective and preferred.
  • a solvent for the reaction mixture is not generally required, though, if desired, a solvent which is inert under the reaction conditions, i.e., those solvents which do not enter into the reaction, may be added. to the reaction vessel.
  • Especially preferred solvents are dipolar aprotic solvents such as dimethyl sulfoxide, N, N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfone, tetramethylene sulfone, N-methylpyrrolidinone, acetonitrile and like materials.
  • solvents which are inert under the reaction conditions may be used: for example, tertiary amines such as pyridine, N-ethylpiperidine, triethylamine, tributyl- amine, N,N-diphenyl-N-methylamine, N,N-dimethylalanine; low boiling hydrocarbons and halogenated hydrocarbons, examples of which are benzene, toluene, tetrachloroethane, the chlorinated benzenes, the chlorinated toluenes, etc, and lower alkanols having up to about 6 carbon atoms which include methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, sec-butyl alcohol, tert-butyl alcohol, n-pentanol, isopentyl alcohol, n-hexanol and isohexyl alcohol.
  • tertiary amines such
  • the amount of solvent can be expressed as a volume ratio of solvent to alkenyl phenol reactant.
  • Suitable volume ratios of solvent to alkenyl phenolic reactant can be from 0/1 to 500/1 and preferably from 1/1 to 300/1.
  • the process should be carried out for a time sufficient to convert substantially all of the paraalkenyl phenol reactant to the corresponding alkylated hydroxyphenyl aldehyde.
  • the length of time for optimum yield depends primarily on the reaction temperature, the type and amount of catalyst and the particular solvent used in the reaction. In general, excellent yields of product are obtained in from 1.5 to 6 hours.
  • the process alternatively may be conducted to continuously produce the benzaldehyde products of the invention.
  • a suitable continuous reactor generally consisting of a length of vertically mounted reactor tubing having heating or cooling means surrounding it may be employed.
  • the product aldehyde can be easily separated from the reactant mixture by such means as distillation, recrystallization and other methods obvious to those skilled in the chemical processing art.
  • the following examples serve to illustrate the formation of alkylated hydroxyphenyl aldehydes from para-alkenyl phenols.
  • Example 19 Preparation of 2, 6-Di-t-Butyl-4-Hyd ⁇ oxybenzaldehyde A 100 ml glass reaction vessel was charged with 1.1 g (4.3 mmols) 1, 1-dimethyl-2-(3',5'-di-t-butyl-4'-hydroxyphenyl)-ethene. Ferric chloride hexahydrate (0.03 g; 0.12 mmols) was suspended in approximately 6 g of N,N-dimethylformamide and added to the reaction vessel. Oxygen ( 17. 7 g ; 550 mmols) was slowly introduced into the solution in the reactor which gradually darkened the solution.

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Abstract

p-alkenyl phenols are prepared by reacting an alkylated phenol having a replaceable hydrogen atom at the 4- position with an aliphatic aldehyde having two carbon atoms up to at least 20 carbon atoms in the molecule and a secondary amine; the p-alkenyl phenols are converted to substituted hydroxybenzaldehydes by direct oxidation in the presence of a catalyst.

Description

PROCESS FOR p-ALKENYL PHENOLS AND THEIR SUBSEQUENT OXIDATION FORMING SUBSTITUTED BENZALDEHYDES
This invention relates to a novel process for the preparation of p-alkenyl phenols and the subsequent preparation of the corresponding substituted benzaldehydes. More particularly, this invention relates to a novel process for the preparation of 1,1-hydrocarbyl-substituted-2-(3'-hydrocarbyl or 3',5'-dihydrocarby1-4'-hydroxyphenyl)-ethene compounds which are especially useful as interediates in the preparation of phenolic antioxidants for gasoline, lubricants, plastics and rubber.
In accordance with one aspect of the invention, an alkylated phenol having a replaceable hydrogen atom at the 4- position and at least one hydrocarbyl substituent ortho to the hydroxyl group is reacted with an aliphatic aldehyde having two carbon atoms up to at least 20 carbon atoms in the molecule and a secondary amine to form the corresponding 1,1-hydrocarbylsubstituted-2-(3'-hydrocarbyl- or 3',5'-dihydro-carbyl-4'-hydroxyphenyl)-ethene. The invention can best be understood by the following detailed discussion of the reactants and conditions by which the p-alkenyl phenol products of the present process are produced. The structure of these products will, of course, be determined by the nature of the starting phenolic and aldehyde reactants.
In general, any monohydroxybenzene compound having a replaceable hydrogen atom on the ring carbon atom para to the hydroxyl substituent and at least one hydrocarbyl substituent ortho to the hydroxyl group, as in the case of o-tert-butyl phenol, will serve as the starting phenol. Since the products of the process are principally useful as antioxidants or as intermediates in the preparation of antioxidants, it is desirable that the hydrocarbyl substituents be alkyl, aralkyl or cycloalkyl groups sufficiently large to offer some degree of hindrance to the phenolic group. It is especially desirable that the hydrocarbyl substituent be branched on the alpha-carbon atom and have at least 3 carbon atoms and, preferably, up to 8 carbon atoms; although any number of carbon atoms, for example up to about 40 carbon atoms, may be present in the hydrocarbyl substituent as long as the substituents do not interfere with the formation of the desired phenolic styrene. Suitable o-hydrocarbyl phenols meeting these requirements include secondary alkyl-substituted phenols such as o-isopropyl phenol, o-sec-butyl phenol, o-sec-amyl phenol and o-cyclohexyl phenol; while suitable tertiary hydrocarbyl phenols are o-tert-butyl phenol and o-tert- amyl phenol. Additionally, primary hydrocarbyl phenols, such as o-benzylphenol, can serve as starting phenols. Most preferred phenolic reactants in the process of this invention are dialkyl phenols wherein the phenol has a replaceable hydrogen atom on the para ring carbon atom and two hydrocarbyl substituents ortho to the hydroxyl group. Preferably, at least one of the hydrocarbyl substituents is branched on the alpha-carbon atom and has from 3 to 8 carbon atoms. The substituents need not both be the same hydrocarbyl radical. Spec if ic examples of particularly appropriate phenols are represented by 2,6-dimethyl phenol, 2, 6-di-n-butyl phenol, 2,6-di-sec-butyl phenol, 2-isopropyl-6-methyl phenol, 2, 6-diisopropyl phenol, 2, 6-di-tert-butyl phenol, 2,6-di-sec-octyl phenol, 2-methyl-6-cyclohexyl phenol, 2,6-di-(alpha-methylbenzyl)phenol, 2,6-dibenzyl phenol, 2-methyl-6-benzyl phenol and the like. A particularly preferred phenolic reactant for use in the present process is 2,6-di-tert-butyl phenol.
Substituent groups other than those previously listed such as aryl, chlorine, bromine, fluorine and nitro groups and the like may be present at any of the ring carbon atoms with the sole exception of the para ring carbon atom in the aromatic phenolic reactant provided they do not adversely affect the formation of the desired 1,1-hydrocarbyl-substituted-2-(3'-hydrocarbyl or 3',5'-dihydrocarbyl-4'-hydroxyphenyl)ethene product.
Preferred starting phenolic reactants may be described by the structure
Figure imgf000006_0001
wherein R1 and R2 are the same or different and are hydrogen or hydrocarbyl radicals, preferably alkyl, aralkyl or cycloalkyl radicals having up to at least 40 carbon atoms, and preferably from 3 to 8 carbon atoms, at least one of which is branched on the alpha-carbon atom with the provision that at least one of R1 or R2 must be other than hydrogen.
Aldehydes which are applicable to the present process are those aldehydes having a single aldehyde radical of the general formula
Figure imgf000006_0002
wherein R3 and R4 can be the same or different and are selected from hydrogen or linear and branched alkyl radicals having up to at least 40 carbon atoms, preferably up to 20 carbon atoms. Typical aldehydes which may be used in the process of the invention include, by way of example only, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, caprylaldehyde, decylaldehyde, tetradecylaldehyde, and the like.
Amine reactants which are applicable to the present process are secondary amines; that is, derivatives of ammonia having one hydrogen atom bonded to the amino nitrogen atom and can be represented by the formula
Figure imgf000007_0001
wherein R5 and R6 are the same or different and are linear or branched alkyl radicals having up to at least 40 carbon atoms. It is deemed, however, that secondary amines containing nitrogen atoms in a ring structure such as piperidine, pyrrolidine, morpholine and the like also may be used. Preferred amines are dimethylamine, diethylamine, dipropylamine, dibutylamine, disecondary propylamine, ethylinethylamine, methylpropylamine, methyl-n-butylamine, ethylisopropylamine and the like. Under the reaction conditions, the amino reactant initially combines with the phenolic and aldehyde reactants to yield a Mannich base type of intermediate which upon further reaction spontaneously eliminates the amine component to produce the olefinic final product. The carbonyl carbon atom of the aldehyde reactant , along with the organic groups bonded to the carbonyl carbon atom of the aldehyde, becomes bonded to the 4-carbon atom of the phenol ring. Some aldol condensation by-product is produced during the reaction.
The 1, 1-hydrocarbyl-substituted-2-(3'-hydrocarbyl or 3',5'-dihydrocarbyl-4'-hydroxyphenyl)ethene products of the process cat. be represented as those compounds having the general formula:
Figure imgf000008_0001
wherein R1 and R2 are the same or different and are hydrogen or hydrocarbyl radicals selected from the group consisting of alkyl, aralkyl or cycloalkyl radicals having up to at least 40 carbon atoms with the provision that at least one of the R1 or R2 radicals must be other than hydrogen and R3 and R4 are the same or different and are hydrogen or linear or branched alkyl radicals having up to at least 20 carbon atoms in the molecule with the provision that one of R3 or R4 must be other than hydrogen.
The process of the invention is carried out by reacting the phenolic starting material with at least one molar equivalent of aldehyde and at least 0.1 molar equivalent of amine. It is preferred, however, that the reaction be conducted with a molar excess of both aldehyde and amine reactants with respect to the starting phenol. A preferred range of aldehyde to phenolic reactant is from 1 to 10 moles of aldehyde per mole of phenol. A preferred molar range of amine reactant to phenolic reactant is from 0.1 to 10 moles of amine per mole of phenol.
The reaction can be conducted at a temperature from 50°C. to 250°C. While lower temperatures can be used, the reaction rates are generally too low to be of interest. Temperatures above 250°C. can be used, but excessive decomposition of the reaction components can occur. The preferred reaction temperatures are from 50°C. to 200°C.
The reaction can be conducted at atmospheric pressure or at higher pressures, with moderate pressures up to about 300 psig being preferred. The use of a solvent for the reaction mixture is not generally required, though, if desired, a solvent which is inert under the reaction conditions, i.e., those solvents which do not enter into the reaction, may be added to the reaction vessel. Useful solvents comprise aprotic solvents which include ethers such as diethyl ether, dibutyl ether, 1-ethoxyhexane, tetrahydrofuran, 1,4-dioxane, 1, 3-dioxolane, dlglyme, 1, 2-diethoxyethane and tertiary amines such as pyridine, N-ethylpiperidine, triethylamine, tributylamine, N.N-diphenyl-N-methyl amine. N,N-dimethylalanine, etc. Especially useful solvents are dipolar aprotic solvents such as dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfone, tetramethylene sulfone, N-methylpyrrolidinone, acetonitrile and like materials. Other solvents which are inert under the reaction conditions may be used: for example, low boiling hydrocarbons, halogenated hydrocarbons, examples of which are benzene, toluene, tetrachloroethane, the chlorinated benzenes, the chlorinated toluenes, etc.
Especially preferred solvents are lower alkanols having up to about 6 carbon atoms. These include methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, secbutyl alcohol, tert-butyl alcohol, n-pentanol, isopentyl alcohol, n-hexanol and isohexyl alcohol. The amount of solvent can be expressed as a volume ratio of solvent to phenolic reactant. Suitable volume ratios of solvent to phenolic reactant can be from 0/1 to 500/1 and preferably from 1/1 to 300/1. The mode of addition in the process is not particularly critical. Accordingly, it is convenient to add the phenolic reactant to a mixture of the other materials, add the aldehyde to a mixture of the other materials, add the amine reactant to a mixture of the other materials, add the reactants to a mixture of the amine and solvent, introduce all ingredients simultaneously into the reaction zone, or the like.
If a gaseous amine is selected for use in the process, the reaction is carried out by passing the amine in its gaseous state through the reaction mixture in a reaction vessel with agitation to obtain intimate contact of the reactants. To ensure that the amount of amine does not exceed that amount required, as hereinabove shown, the amount of amine in contact with the other reactants can be controlled by limiting the flow of amine through or into the reaction vessel.
The process should be carried out for the time sufficient to convert substantially all of the phenolic reactant to the corresponding p-alkenyl phenol. The length of time for optimum yield will depend primarily upon the reaction temperature and the particular solvent, if any, used in the reactior. In general, excellent yields of p-alkenyl phenol are obtained in from about two to forty-eight hours.
Although not required, the process can be conducted in a substantially anhydrous reaction system, and accordingly, the components of the reaction system are brought together and maintained under a substantially dry, inert atmosphere. By "substantially anhydrous" is meant a reaction system wherein the total amount of water present is no more than about 5 percent by weight, based on the reaction mixture. When the amount of water in the system exceeds this, both reaction rate and yield of product decrease.
The process may readily be conducted in a batch-wise, semi-batch or continuous manner and in conventional equipment.
The product p-alkenyl phenol is easily separated from the reaction mixture by such means as distillation, extraction, crystallization and other methods obvious to those skilled in the chemical processing art.
The practice of this aspect of the invention will be still further apparent by the following illustrative examples. Example I
Preparation of 1,1-Dimethy1-2-(3',5'-Di-t-Butyl- 4'-Hydroxyphenyl)Ethene
2,6-di-tertiary-butyl phenol (4.1 g; 20 mmol) , isobutyraldehyde (3 ml; 33 mmol), dimethylamine (1.5 g; 34 mmol) dissolved in isopropanol (7.5 g) were charged to a 100 ml glass vessel and refluxed at ambient pressure under nitrogen for 48 hours. The resultant reaction mixture was allowed to cool to ambient temperature and concentrated to a yellow oil which was recrystallized from a mixture of ethanol and water (90:10) to give yellow crystals (3.7 g; 71% yield) of 1,1-dimethyl-2-(3',5'-di-t-butyl-4'-hydroxyphenyl) ethene as characterized by VPC, mass spectrocopy and NMR. In a manner similar to Example I above, a number of experiments were carried out varying the temperature, reaction time, pressure, reactants and ratio of reactants. The results were analyzed by vapor phase chromotography with internal standards and are shown in the Table below.
Figure imgf000014_0001
Figure imgf000015_0001
Figure imgf000016_0001
In another aspect of this invention , the
1,1-hydrocarbyl-substituted-2-(3'-hydrocarbyl- or 3 ' , 5 ' -dihydrocarbyl-4 ' -hydroxyphenyl) ethene products produced by the process of the present invention can be directly oxidized to the corresponding 3-hydrocarbyl-4- hydroxybenzaldehyde or 3,5-dihydrocarbyl-4-hydroxyben- zaldehyde by contacting with good agitation the aforementioned 1,1-hydrocarbyl-substituted-2-(3'-hydrocarbyl- or 3',5'-dihydrocarbyl-4'-hydroxyphenyl) ethene with at least a stoichiometric amount of oxygen in the presence of a small catalytic quantity of a catalyst selected from the group consisting of a Lewis acid, an alkali metal salt of a weak acid or an alkaline mearth metal salt of a weak acid, an alkali metal hydroxide or an alkaline earth metal hydroxide, or amine bases until a reaction product containig a substantial amount of the corresponding 3-hydrocarbyl-4-hydroxybenzaldehyde or 3,5-dihydrocarbyl-4-hydroxybenzaldehyde is formed.
Alkylated hydroxyphenyl aldehydes and methods for their preparation are known. For example, U.S.
4,009,210 discloses a method for preparing 3,5-di-tertbutyl-4-hydroxybenzaldehyde, a chemical intermediate for the manufacture of pesticides of the benzylidenemalononitrile type, by reacting 2, 6-di-tert-butylphenol with hexamethylenetetramine or a combination of formaldehyde and ammonium acetate in aqueous acetic acid reaction medium. A new process for the synthesis of 3-hydrocarbyl-4-hydroxybenzaldehydes or 3,5-dihydrocarbyl-4-hydroxy¬benzaldehydes has now been discovered in which these materials can be prepared in a simple and straightforward manner. In this new process, p-alkenyl phenols, in particular 1,1-hydrocarbyl-substituted-2-(3'-hydrocarbyl- or 3',5'-dihydrocarbyl-4'-hydroxyphenyl)ethenes are contacted with oxygen in the presence of a catalyst selected from a Lewis acid, an alkali metal hydroxide or an alkaline earth metal hydroxide, an alkali metal of a weak acid or an alkaline earth metal salt of a weak acid or an amine base. In accordance with the process, cleavage of the olefinic bond located at the 4-position of the phenyl ring of the p-alkenyl phenol reactant takes place by a radical process whereby the desired alkylated hydroxyphenyl aldehyde product is produced.
The 1,1-hydrocarbyl-substituted-2-(3'-hydrocarbyl- or 3',5'-dihydrocarbyl-4'-hydroxyphenyl)ethenes which are oxidized according to the aforementioned process are those compounds described and prepared here-inabove.
The process is readily conducted by placing the 1,1-hydrocarbyl-substituted-2-(3'-hydrocarbyl- or 3',5'-dihydrocarbyl-4'-hydroxyphenyl) ethene and other reaction mixture components in a reaction vessel having agitation means, or can be advantagepusly carried out, for example, by passing the 1,1-hydrocarbyl-substituted-2-(3'- hydrocarbyl- or 3',5'-dihydrocarbyl-4'-hydroxyphenyl)ethene through appropriate reaction tubes and simply contacting the same with oxygen or an oxygen containing gas and catalyst. The oxidation reaction should be carried out with agitation and preferably with vigorous agitation or using other means that afford intimate contact between the oxygen containing gas and the reaction mixture.
An essential component of the reaction mixture is a catalytic amount of a catalyst, the suitable catalysts being selected from the group consisting of alkali metal hydroxides, alkali metal salts of a weak acid, alkaline earth metal hydroxides, alkaline earth metal salts of a weak acid, amine bases, mixtures of the same and Lewis acid catalysts. Illustrative of suitable catalysts are sodium hydroxide, potassium hydroxide, barium hydroxide, rubidium hydroxide, cesium hydroxide, potassium carbonate, sodium carbonate, cesium carbonate, rubidium carbonate, potassium sulfite, sodium borate, potassium acetate, diazabicyclononane, pyridine, tetra-methylguanidine, 1,4-diazabicyclo-(2,2,2)-octane, FeCl3, BF3, ZnCl2, TiCl4, HF, H2SO4, H3PO4, SnCl2, SnCl4, and CuCl2. Copper chloride and ferric chloride are preferred catalysts. The amount of catalyst used is not narrowly critical but only a small amount is sufficient to promote cleavage of the olefinic bond at the 4- position of the 1,1-hydrocarbyl-substituted-2-(3'-hydrocarbyl or 3',5'-dihydrocarby1-4'-hydroxyphenyl) ethene reactant. In general, the amount used can be as little as 0.1 weight percent through amounts up to 1 weight percent, based on the weight of p-alkenyl phenol reactant, and even greater amounts of catalyst may be used if desired. In the practice of the invention, the amount of oxygen employed relative to the 1,1-hydrocarbyl-substi¬tuted-2-(3'-hydrocarbyl- or 3',5'-dihydrocarbyl-4'-hydroxyphenyl) ethene starting reactant is not critical. In general, only an amount of oxygen required for the direct oxidative cleavage of the p-alkenyl phenol to the corresponding benzaldehyde should be used. For best results, however, it is preferable that at least a stoichiometric amount of oxygen or an amount greater than that stoichiometric required is used. The reaction is conducted, for example, by passing oxygen, and preferably an oxygen containing gas such as air , through the reaction mixture in a reaction vessel with agitation to obtain intimate contact of the reactants. Typically, the reaction is conducted at atmospheric pressure, however , higher pressures up to about 200 psig may be used, if desired. The amount of oxygen reacting with the p-alkenyl phenol reactant can be, in general, easily controlled by limiting the flow of gas through or into the reaction zone.
The reaction can be conducted at mildly elevated temperatures of, for example, from 25°C. up to higher temperatures of 250°C. and preferably at a temperature that ranges from 50°C. up to 150°C. Reflux temperature at atmospheric pressure is effective and preferred. The use of a solvent for the reaction mixture is not generally required, though, if desired, a solvent which is inert under the reaction conditions, i.e., those solvents which do not enter into the reaction, may be added. to the reaction vessel. Especially preferred solvents are dipolar aprotic solvents such as dimethyl sulfoxide, N, N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfone, tetramethylene sulfone, N-methylpyrrolidinone, acetonitrile and like materials. Other solvents which are inert under the reaction conditions may be used: for example, tertiary amines such as pyridine, N-ethylpiperidine, triethylamine, tributyl- amine, N,N-diphenyl-N-methylamine, N,N-dimethylalanine; low boiling hydrocarbons and halogenated hydrocarbons, examples of which are benzene, toluene, tetrachloroethane, the chlorinated benzenes, the chlorinated toluenes, etc, and lower alkanols having up to about 6 carbon atoms which include methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, sec-butyl alcohol, tert-butyl alcohol, n-pentanol, isopentyl alcohol, n-hexanol and isohexyl alcohol.
The amount of solvent can be expressed as a volume ratio of solvent to alkenyl phenol reactant. Suitable volume ratios of solvent to alkenyl phenolic reactant can be from 0/1 to 500/1 and preferably from 1/1 to 300/1.
The process should be carried out for a time sufficient to convert substantially all of the paraalkenyl phenol reactant to the corresponding alkylated hydroxyphenyl aldehyde. In general, the length of time for optimum yield depends primarily on the reaction temperature, the type and amount of catalyst and the particular solvent used in the reaction. In general, excellent yields of product are obtained in from 1.5 to 6 hours. if desired, the process alternatively may be conducted to continuously produce the benzaldehyde products of the invention. A suitable continuous reactor generally consisting of a length of vertically mounted reactor tubing having heating or cooling means surrounding it may be employed. The product aldehyde can be easily separated from the reactant mixture by such means as distillation, recrystallization and other methods obvious to those skilled in the chemical processing art. The following examples serve to illustrate the formation of alkylated hydroxyphenyl aldehydes from para-alkenyl phenols.
Example 19 Preparation of 2, 6-Di-t-Butyl-4-Hydτoxybenzaldehyde A 100 ml glass reaction vessel was charged with 1.1 g (4.3 mmols) 1, 1-dimethyl-2-(3',5'-di-t-butyl-4'-hydroxyphenyl)-ethene. Ferric chloride hexahydrate (0.03 g; 0.12 mmols) was suspended in approximately 6 g of N,N-dimethylformamide and added to the reaction vessel. Oxygen ( 17. 7 g ; 550 mmols) was slowly introduced into the solution in the reactor which gradually darkened the solution. After 1.75 hours, the black reaction mixture was filtered through a silica gel pad and the filtrate was concentrated to give a black semi-solid product (0.75 g; 74% yield) of 2,6-di-t-butyl-4-hydroxybenzaldehyde as identified by gas chromotography and thin layer chromotography.
In a manner similar to Example 19 above, a number of experiments were carried out varying the temperature, reaction time, solvent and type of catalyst. The results are shown in the Table below.

Claims

1. A process for preparing a 1,1-hydrocarbyl- substituted-2-(3'-hydrocarbyl or 3',5'-dihydrocarbyl-4'- hydroxyphenyl)ethene which comprises reacting an alkylated phenol having a replaceable hydrogen atom at the 4- position and at least one hydrocarbyl substituent ortho to the hydroxy group with an aliphatic aldehyde having from two carbon atoms up to at least 20 carbon atoms in the molecule and a secondary amine and thereafter separating said 1,1-hydrocarbyl-substituted-2- (3'-hydrocarbyl or 3',5'-dihydrocarbyl-4'-hydroxyphenyl) ethene from the resultant reaction mixture. wherein R5 and R6 are the same or different and are linear or branched alkyl radicals having up to at least 40 carbon atoms and thereafter separating the corresponding 1,1-hydrocarbyl-substituted-2-(3'-hydrocarbyl or 3',5'-dihydrocarby1-4'-hydroxy-phenyl) ethene thus formed from the resultant reaction mixture.
2. The process of as clained in Claim 1 in which said aldehyde reactant is selected from acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, caprylaldehyde, decylaldehyde and tetradecylaldehyde.
3. The process as claimed in Claim 1 in which said amine reactant is selected from dimethylamine, diethylamine, dipropylamine, dibutylamine, disecondary-propylamine, ethylmethylamine, methylpropylamine, methyl-n-butylamine and ethylisopropylamine.
4. The process as claimed in Claim 1 in which said reaction is carried out at a temperature of from 50°C. to 250°C.
5. The process as claimed in Claim 1 in which said reaction is carried out under pressure in the range of from atmospheric up to 300 psig.
6. The process as claimed in Claim 1 in which said reaction is carried out in the presence of a solvent which is inert under the reaction conditions.
7. The process as claimed in Claim 6 in which said solvent is a dipolar aprotic solvent.
8. The process as claimed in Claim 7 in which said dipolar aprotic solvent is selected from dimethyl sulfoxide, N,N-dimethyIformamide, N,N-dimethylacetamide, dimethyl sulfone, tetramethylene sulfone, N-methylpyrrolidinone and acetonitrile.
9. The process as claimed in Claim 6 in which said solvent is selected from the group consisting of low boiling hydrocarbons, halogenated hydrocarbons and lower alkanols having up to about 6 carbon atoms.
10. The process for coverting a 1,1-hydrocarbyl-substituted-2-(3'-hydrocarbyl- or 3',5'-dihydrocarby1-4'-hydroxyphenyl) ethene prepared as claimed in Claim 1 to the corresponding 3-hydrocarbyl-substituted- 4-hydroxybenzaldehyde or 3, 5-dihydrocarbyl-4-hydroxybenzaldehyde which comprises intimately contacting said 1, 1-hydrocarbyl-substituted-2-(3'-hydrocarbyl or 3',5'-dihydrocarbyl-4'-hydroxy- phenyl) ethene with at least a stoichiometric amount of oxygen or an oxygen-containing gas in the presence of a catalytic quantity of a catalyst selected from the group consisting of alkali metal hydroxides, alkali metal salts of a weak acid, alkaline earth metal hydroxides, alkaline earth metal salts of a weak acid, amine bases, mixtures of the same or a Lewis acid for the time necessary to react at least a stoichiometric amount of oxygen with said 1,1-hydrocarbyl-substituted-2-(3'-hydrocarbyl- or 3',5'-dihydrocarbyl-4'-hydroxyphenyl)-ethene to form a reaction product containing a substantial amount of the corresponding 3-hydrocarbyl-substituted-4-hydroxybenzaldehyde or 3,5-dihydrocarbyl-4-hydroxybenzaldehyde.
11. The process as claimed in Claim 10 in which said 1,1-hydrocarbyl-substituted-2-(3',5'-dihydro¬carbyl-4'-hydroxyphenyl)ethene is 1,1-dimethyl-2-(3',5'- di-t-butyl-4'-hydroxyphenyl)ethene and the reaction product formed therefrom is the corresponding 2,6-di-t-butyl-hydroxybenzaldehyde.
12. The process as claimed in Claim 10 in which said reaction is carried out at a temperature of from
50°C. to 250°C.
13. The process as claimed in Claim 10 in which the reaction mixture is substantially free of any solvent.
14. The process as claimed in Claim 10 in which said reaction is carried out in the presence of a solvent.
15. The process as claimed in Claim 14 in which said solvent is a dipolar aprotic solvent.
16. The process as claimed in Claim 14 in which said solvent is selected from the group consisting of low-boiling hydrocarbons, halogenated hydrocarbons and lower alkanols having up to about 6 carbon atoms.
PCT/US1983/001815 1983-11-15 1983-11-15 PROCESS FOR p-ALKENYL PHENOLS AND THEIR SUBSEQUENT OXIDATION FORMING SUBSTITUTED BENZALDEHYDES Ceased WO1985002178A1 (en)

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JP50014483A JPS61500547A (en) 1983-11-15 1983-11-15 Process for forming substituted benzaldehydes by p-alkenylphenols and their subsequent oxidation
EP19840900176 EP0163633A4 (en) 1983-11-15 1983-11-15 PROCESS FOR p-ALKENYL PHENOLS AND THEIR SUBSEQUENT OXIDATION FORMING SUBSTITUTED BENZALDEHYDES.

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Citations (7)

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US3413347A (en) * 1966-01-26 1968-11-26 Ethyl Corp Mannich reaction products of high molecular weight alkyl phenols, aldehydes and polyaminopolyalkyleneamines
US3435061A (en) * 1965-01-06 1969-03-25 Standard Oil Co Manufacture of aromatic aldehydes and nitriles
US3592951A (en) * 1967-12-28 1971-07-13 Ethyl Corp Process for alkylating a phenol
DE2363464A1 (en) * 1973-12-20 1975-07-03 Bayer Ag Para-alkenyl-phenol prepn. from para-hydroxy-benzylsulphides - by reaction with alkali hydroxide and use as anti-oxidant inters
US4009210A (en) * 1975-05-07 1977-02-22 Gulf Oil Corporation Process for manufacturing 3,5-ditert.butyl-4-hydroxybenzaldehyde by formylation of 2,6-ditert.butylphenol
US4215229A (en) * 1978-06-15 1980-07-29 Koppers Company, Inc. Process for alkylating phenolic compounds to produce ortho- and para-monoalkylated phenols and 2,4- and 2,6-dialkylated phenols

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2841623A (en) * 1957-05-08 1958-07-01 Shell Dev Process for the alkylation of phenols
US3435061A (en) * 1965-01-06 1969-03-25 Standard Oil Co Manufacture of aromatic aldehydes and nitriles
US3413347A (en) * 1966-01-26 1968-11-26 Ethyl Corp Mannich reaction products of high molecular weight alkyl phenols, aldehydes and polyaminopolyalkyleneamines
US3592951A (en) * 1967-12-28 1971-07-13 Ethyl Corp Process for alkylating a phenol
DE2363464A1 (en) * 1973-12-20 1975-07-03 Bayer Ag Para-alkenyl-phenol prepn. from para-hydroxy-benzylsulphides - by reaction with alkali hydroxide and use as anti-oxidant inters
US4009210A (en) * 1975-05-07 1977-02-22 Gulf Oil Corporation Process for manufacturing 3,5-ditert.butyl-4-hydroxybenzaldehyde by formylation of 2,6-ditert.butylphenol
US4215229A (en) * 1978-06-15 1980-07-29 Koppers Company, Inc. Process for alkylating phenolic compounds to produce ortho- and para-monoalkylated phenols and 2,4- and 2,6-dialkylated phenols

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Organic Chemistry, (1953) FISSCHER) *
See also references of EP0163633A4 *
The Chemistry of Carbony Group, (1966) PATAI see pages 125-127 & 170 *

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