WO1995021816A1 - Procede de production d'acide acyloxybenzenesulfonique ou de son sel - Google Patents

Procede de production d'acide acyloxybenzenesulfonique ou de son sel Download PDF

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Publication number
WO1995021816A1
WO1995021816A1 PCT/JP1995/000061 JP9500061W WO9521816A1 WO 1995021816 A1 WO1995021816 A1 WO 1995021816A1 JP 9500061 W JP9500061 W JP 9500061W WO 9521816 A1 WO9521816 A1 WO 9521816A1
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Prior art keywords
group
acid
compound
general formula
represented
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PCT/JP1995/000061
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English (en)
French (fr)
Japanese (ja)
Inventor
Yoshio Hatayama
Katsuhisa Inoue
Hiroshi Danjo
Kohshiro Sotoya
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Kao Corporation
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Application filed by Kao Corporation filed Critical Kao Corporation
Priority to US08/530,184 priority Critical patent/US5606104A/en
Priority to JP52110995A priority patent/JP3434298B2/ja
Priority to EP95906500A priority patent/EP0700900B1/en
Priority to KR1019950704322A priority patent/KR0184295B1/ko
Priority to DE69513114T priority patent/DE69513114T2/de
Publication of WO1995021816A1 publication Critical patent/WO1995021816A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/41—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton
    • C07C309/42—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton having the sulfo groups bound to carbon atoms of non-condensed six-membered aromatic rings
    • 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
    • C07C303/04—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 by substitution of hydrogen atoms by sulfo or halosulfonyl groups
    • C07C303/06—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 by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
    • 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
    • C07C303/04—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 by substitution of hydrogen atoms by sulfo or halosulfonyl groups

Definitions

  • the present invention relates to a method for producing acyloxybenzenesulfonic acid or a salt thereof. More specifically, the present invention relates to a method for producing sulfoxybenzene sulfonic acid or a salt thereof having less side reaction and good hue by sulfonating acyloxybenzene with a sulfonating agent in the presence of a specific additive.
  • Acyloxybenzenesulfonate is exposed to hydrogen peroxide-generating substrates such as sodium carbonate (PC) and sodium perborate (PB) and hydrogen peroxide in water at low temperatures. It is a compound that is particularly useful as a bleach activator because it easily generates organic peracids and exhibits effective bleaching performance on clothing stains and stains (EP- corresponding to JP-A 59-22999) A98021).
  • acetic anhydride is allowed to act on phenolsulfonic acid mono-Na salt to form sodium acetyloxybenzenesulfonate, and then a fatty acid having a desired alkyl group is added.
  • a method for causing a transesterification reaction (EP-A105562, corresponding to JP-B4-1739) is known.
  • this method can produce high-purity products, but the production cost is extremely high if there is no use for by-product acetic acid, and is generally unsuitable as a commercial production process.
  • An object of the present invention is to provide an industrial production method capable of producing acyloxybenzenesulfonic acid with higher yield, higher selectivity, better hue, and lower cost than conventional ones.
  • the present invention reduces the side reactions of acyloxybenzenesulphonic acid as compared with the prior art, and provides a high yield, a high selectivity, a good hue, and an inexpensive industrial process. Can also be manufactured.
  • sulfonyloxybenzene (1) is sulfonated to produce the corresponding acyloxybenzenesulfonic acid (5), carboxylic acid or its ester (2), alkyl phosphate (3), polylylate is used as an additive.
  • One of the compound (6) such as acid (4), amide, etc., the carbonate compound (7), and the hydroxy compound are added. Further, it is preferable to use a thin film type sulfonation apparatus.
  • R 1 is a straight-chain or branched alkyl group having a total carbon number of 1 to 35, which may be substituted with halogen, and which may contain an ester group, an ether group, an amide group or a phenylene group. Or an alkenyl group or a phenyl group.
  • R 2 represents a linear or branched alkyl group having 1 to 4 carbon atoms, a methoxy group or an ethoxy group.
  • R 4 having 2 to 35 carbon atoms may be optionally substituted with a halogen, a sulfonic acid group, a carboxyl group, a hydroxyl group o or a funyl group,
  • an ester group, an ether group, an amide group or a phenylene group may have a linear or branched alkyl or alkenyl group which may be inserted, or may be unsubstituted or substituted with a carboxyl group or an alkyl group.
  • X represents a radical.
  • R 5 represents a linear or branched alkyl group having 1 to 22 carbon atoms.
  • R 6 represents a hydrogen atom or a linear or branched alkyl group having 1 to 22 carbon atoms, which may be the same as or different from R 5 . )
  • X represents an oxygen atom or a sulfur atom.
  • the present invention provides a process for producing the above-mentioned acyloxybenzenesulfonic acid, wherein (7) is added in an amount of 2.5 to 200 mol% and (8) is added in an amount of 1 to 100 mol%.
  • the obtained sulfonic acid (5) can be neutralized to obtain a useful salt. It is a sulfonate with a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium, a substituted ammonium, or a quaternary ammonium.
  • sulfonating agent is S0 3
  • R 1 is a halogen straight optionally substituted or branched alkyl group having 5-18 carbon atoms
  • the reaction system Wherein substantially no water is present and the additive is —wherein in general formula (2), R 3 may be replaced by H, R 4 may be replaced by a halogen having 5 to 35 carbon atoms, and an ester group, Ether group or amide Is a linear or branched alkyl group which may have an inserted group, and the additive is represented by the general formula (2), wherein R 3 is H and R 4 is the general formula (1).
  • R 3 in the general formula (2) is H
  • R 5 is a linear or branched alkyl group having 8 to 14 carbon atoms
  • R 6 is a hydrogen atom
  • the sulfonation with a sulfonating agent is performed using a thin film type sulfonation apparatus, and the carboxylic acid or its ester represented by the above general formula (2) or the alkyl lyre represented by the general formula (3) is used.
  • the additives can be added before, during, immediately after or after adding the sulfonating agent. Particularly, it is preferable to add immediately after adding the sulfonating agent.
  • This period is the first step in which the sulfonating agent coordinates to the ester group of the acyloxybenzene (1), thus forming a complex or mixed anhydride.
  • the second step occurs, in which the benzene ring is sulfonated with self-heating, and the sulfonation ends.
  • the second stage is called aging. These two reactions are not temporally separated and both reactions can proceed simultaneously.
  • the additive is added immediately after the addition of the sulfonating agent.
  • the timing of the addition of the additives is determined by analyzing the reaction mixture by liquid chromatography and detecting the amount of the sulfonated compound (5) 'to determine the amount of the complex or mixed anhydride formed by the administration of the sulfonating agent. You can judge by knowing the rate.
  • the sulfonated product (5) production rate is preferably 70% or less.
  • this complex or mixed acid anhydride remains in the reaction mixture effectively in the present invention. The length of this period depends on the type of the reactants of the reaction mixture, It depends on the temperature, the degree of stirring, the presence or absence of the solvent, and the like.
  • Additive was added at low temperature, promoting the sulfonation of the second stage by heating the reaction mixture to 50-60 e C, it can be completed.
  • At least one selected from the group consisting of additives (2), (3) and (4) may be used at any time, but preferably after the sulfonation treatment.
  • R 1 in formula (1) has 1 to 21 carbon atoms
  • R 4 in formula (2) is a halogen, carboxy, hydroxyl or phenyl group having 2 to 21 carbon atoms in total.
  • a straight-chain or branched alkyl or alkenyl group optionally having an ester group, ether group, amide group or phenylene group inserted, or unsubstituted or It includes a phenyl group which may be substituted with a carboxyl group or an alkyl group.
  • At least one selected from the group consisting of additives (6), (7) and (8) is added.
  • the additives are selected from the group consisting of (2), (6) and (8) Adding at least one kind, adding the additive (2) after administering the sulfonating agent, particularly preferably adding the additive (6) after administering the sulfonating agent, immediately after adding the sulfonating agent. , Added.
  • the additive (6) is a urea compound, an amide compound or an imide compound.
  • the additive (8) is added before sulfonation, and the additive (8) is represented by the general formula (9) or (10)
  • R 2 represents a linear or branched lower alkyl group having 1 to 4 carbon atoms, or a methoxy or ethoxy group.
  • sulfonation is performed using a thin film type sulfonation apparatus, two or more additives are used in combination, and two or more additives selected from (2), (6) and (8) are used in combination. be able to.
  • compound (6) is an acyclic monoamide compound, a polyamide Compound, Cyclic amide compound, Acyclic imide compound, Polyimide compound, Cyclic imide compound, Acyclic monourea compound, Polyurea compound, Cyclic urea compound, Acyclic monothioamide compound, Polythioamide Compounds, cyclic thioamide compounds, acyclic thioimide compounds, cyclic thioimide compounds, and thiourea compounds.
  • Compound (8) is a linear or branched monohydric alcohol having 1 to 36 carbon atoms.
  • a divalent to hexavalent polyhydric alcohol or phenolic compound, phenolsulfonic acid or a salt thereof, and compound (6) is acetamido, succinic amide, N, N'-diamine.
  • the present invention provides a method for producing sulfonylbenzene represented by the above general formula (1) by sulfonating with a sulfonating agent to produce the corresponding sulfoxybenzensulfonic acid or a salt thereof.
  • the sulfonation with the agent is performed using a thin-film sulfonation apparatus, and the carboxylic acid or its ester represented by the general formula (2), the alkyl sulfonic acid ester represented by the general formula (3), And at least a part of one or more additives selected from the group consisting of polyphosphoric acids represented by the above general formula (4) are added after the above-mentioned sulfonation treatment, followed by aging. And a method for producing acyloxybenzenesulfonic acid or a salt thereof.
  • the acyloxybenzene used as a raw material of the present invention is represented by the above general formula (1), and R 1 in the general formula (1) is substituted with a halogen having a total carbon number of 1 to 35.
  • R 1 in the general formula (1) is substituted with a halogen having a total carbon number of 1 to 35.
  • R 1 is A straight-chain or branched alkyl group having 5 to 13 carbon atoms is preferred.
  • acyloxybenzene represented by the general formula (1) include phenyl carboxylate, phenyl pelargonate, phenyl carboxylate, phenyl n-undecanoate, phenyl laurate, 3, 5, 5 — phenyl trimethyl carboxylate, 2 — phenyl methyl carboxylate, 2 — phenyl phenyl caprylate, 3, 7 — phenyl dimethyl carboxylate, phenyl 2-ethylhexanoate, isostearic acid
  • Examples include phenyl, phenyl behenate, m-cresol laurate, m-crepe pelargonate, phenyl chlorocabroate, lauroyloxyacetyloxybenzene, and the like.
  • lauric acid ester in terms of the most excellent balance of hydrophilic and lipophilic stains and bleaching performance, and particularly preferable in terms of cost.
  • acyloxybenzenes can be reacted with any of the known reactions such as the reaction of the corresponding fatty acid or acid chloride with phenol (JAOCS, 32, 170 (1955)), but it is preferable to use a direct esterification reaction using a fatty acid, one of the additives of the present invention, as described later, since this leads to shortening of the process. .
  • the sulfonating agent used for sulfonation of the reaction S0 3 is rather preferred, S0 3 is liquid, Moshiku the gas mixture of inert gas and S0 3, such as air dampening N 2 or sufficient removal (hereinafter Gas abbreviated as Jo of S0 3) may be used.
  • the reaction system a batch reaction, Moshiku the flow down type for performing the reaction by the action of gas-like S0 3 in the thin film of reaction substrate exerting S0 3 or gaseous S0 3 liquid into a reaction substrate
  • a known technique such as an ascending continuous thin film reaction can be used.
  • a thin film type sulfonation apparatus as a reaction method, because the raw materials of acyloxybenzene and the sulfonating agent can be mixed in a short time, and heat removal and temperature control can be easily performed.
  • the thin-film type sulfonation apparatus to be used is not particularly limited, and examples thereof include Filing Film Reacter (manufactured by Valestra).
  • a ⁇ sill O carboxymethyl benzene represented by the general formula (1) to be subjected to the reaction be reacted without solvent
  • Moshiku is available to scan sulfonated reaction solvent , for example, dichloromethane, 1.
  • Jikuroroetan, black hole Holm, carbon tetrachloride, CFC halogenated Ru is represented like hydrocarbons or liquid S0 2, may be reaction was diluted in advance. Dilution with these solvents is preferably carried out in order to minimize by-products of ketones during the sulfonation reaction.
  • the amount of solvent used is ⁇ sill O carboxymethyl benzene 20 times by weight or less correct desired (more preferred details, improvements in production efficiency, a reduction in the reaction between the solvent and the S0 3 considered Therefore, it is 0.5 to 5 times by weight.
  • the acyloxybenzene represented by the general formula (1) used for the reaction may be reacted without a solvent. Further, immediately after the action of S0 3 in Ashiruokishibe benzene, diluted mixed with the solvents mentioned can also this to carry out the reaction. However, improvements in production efficiency, solvent and S0 3 reaction reduction of, use the particularly preferred arbitrariness is a This sulfonation reaction is carried out without a solvent from the recovered load or the like of the solvent.
  • the additives used in the present invention include a carboxylic acid or an ester thereof represented by the general formula (2), an alkyl phosphate ester represented by the general formula (3), and a general formula (4).
  • a carboxylic acid or an ester thereof represented by the general formula (2) an alkyl phosphate ester represented by the general formula (3)
  • a general formula (4) One or more selected from the group consisting of polyphosphoric acids.
  • carboxylic acid or its ester represented by the above general formula (2) examples include butyric acid, cabronic acid, enanthic acid, isohexanoic acid, cabrylic acid, and 2-ethylhexanoic acid.
  • those containing a sulfonic acid group and a carboxylic acid or an ester thereof represented by the general formula (2) for example, the carboxylic acid and S0 3 and guard portion reacted compounds, for example ⁇ -position sulfone carboxylic acid Compounds can also be used.
  • lauric acid is used as the raw material, and lauric acid is used as the raw material to give dodecanoyloxybenzenesulfonate having the best balance between hydrophilicity and lipophilicity and exhibiting high bleach activating ability.
  • the alkyl phosphate represented by the general formula (3) may be any of the alkyl phosphates represented by the general formula (3), but is preferably R 5 from the viewpoint of solubility of the neutralized salt in water. Is a linear or branched alkyl group having 1 to 22 carbon atoms, preferably 8 to 14 carbon atoms.
  • R 6 is an alkyl group or hydrogen atom which may be the same as or different from R 5, and preferably, R e is water It is an alkyl phosphate which is an elementary atom.
  • alkyl phosphates can be produced by a known method of reacting an alcohol with a phosphorylating agent.
  • polyphosphoric acid represented by the general formula (4) pyrrolic acid, tripolilic acid, and the like are generally known, but among them, they can be used industrially. Borolinic acid having a concentration of 100% or more in terms of orthophosphoric acid is preferred. Furthermore, in order to minimize the hydrolysis of the ester groups of the compounds (1) and (5), the concentration of the polystyrene should be such that the total amount of water present as an equilibrium composition is 5 mol% or less based on the acyloxybenzene. The use of phosphoric acid is most preferred. These are not generally available as commercial products.
  • the compound (6) such as an amide may be, for example, an amide such as a saturated or unsaturated straight-chain or branched fatty acid amide, an N-lower alkyl (C 4 ) amide, or an amide thereof.
  • ⁇ -di-lower alkyl (C 4 ) amides such as ⁇ -methyl amides, ⁇ , ⁇ ⁇ ⁇ ⁇ -dimethyl amide-containing monoamides, C 4 to C 8 saturated or unsaturated divalent fatty acid amides Dia, including amides, phthalic acid amides, their N-methylamides, ⁇ , ⁇ '-diamides, ⁇ , ⁇ -amides, ⁇ , ⁇ , ⁇ ' ⁇ '-tetraamides Amides, trivalent fatty acid amides-tetravalent fatty acid amides, including polyamides and cyclic amides, more preferably water-soluble monoamides such as formamide and monomethyl Formamide, ⁇ , ⁇ -dimethylformamide, acetamide, ⁇ -methylacetamide, ⁇ ⁇ ⁇ , ⁇ -dimethylacetamide, propionamide, lauramide, ⁇ , ⁇ -dimethyllauramide, ⁇ ,
  • Sesame seed (average molecular weight: 200-3000), including cyclic amides ⁇ including butyralactam and ⁇ -caprolactam ⁇ Acyclic imids, such as diacetylimide, tetraacetylethylenamine, and pen As acetyl acetylene triamine, as cyclic imid
  • cyclic imid Includes imidic acid imid, imidyl lauryl imidic acid, imidated phthalic acid, imidized ethyl phthalic acid, urea, urea, ⁇ , N'-dimethylurea, ⁇ , ⁇ , ⁇ ', ⁇ '—Tetramethylurea, 1,3-Dimethyl 2—Imidazolidinone, Tetraacetyl glycol ⁇ yl, Ethylenurea, Hidantoin, Methylhydantoin, Thiocompound This includes thioamide, thioimid, and thioure
  • the carbonate compound (7) is, for example, dimethyl carbonate, getyl carbonate, dibutyl carbonate pill, dibutyl carbonate, ethylene carbonate, lauryl phenyl carbonate, octyl phenyl carbonate.
  • Hydroxy compounds (8) include, for example, hydroxybenzenes, in particular, phenol, cresol (0-, m-, and p-all), force techol, hydroxyquinone, and monomethylhydroxyquinoline. , Hydroxybenzoic acid (0-, P-, and m-), gallic acid, phenolsulfonic acid (0- and P-), and cresolsulfonic acid (0-, in-, p-) But) Alcohols include carbon as monoalcohol Alcohols having a linear or branched alkyl or alkenyl group of the formulas 1 to 22, such as methanol, ethanol, n-propanol, i-prono, 'nor, and 2-ethylhexano.
  • lauryl alcohol Including stearyl alcohol, 2-octyl dodecyl alcohol, and benzyl alcohol.
  • polyhydric alcohols ethylene glycol. Diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, glycerin, trimethylol brono, and the like. Saccharides such as erythritol, sorbitol, glucose, maltose, etc.-aminoalkylene oxide adducts such as monoethanolamine, methylmonoethanolamine, dimethylmonoethanolamine, Noprono ,.
  • Examples of the alkanol amide include amides of formic acid or carboxylic acids having a linear or branched alkyl group having 1 to 18 carbon atoms with monoethanolamine, amides with diethanolamine, and alkylenes. Oxides (2-4 carbon atoms) Includes amides with 3-5 added moles.
  • the use of the above-mentioned additive may be effected by the fact that the product itself or a neutralized salt thereof is contained in the product, so that the effective component in the product is acyloxybenzenesulfonic acid or In the case of a neutralized product, the apparent purity of the salt is reduced.
  • the amount of the above additive is usually 2.5 to 200 mol% based on the acyloxybenzen represented by the general formula (1). Is preferred, with 5.0 to 100 moles giving the most favorable results.
  • the entire amount of the additive may be added and mixed immediately after the sulfonating agent is allowed to act using a thin-film type sulfonating apparatus, or a part of the additive may be added and mixed with the raw material acryloxybenzene.
  • the sulfonating agent may be allowed to act on the thin film type sulfonating apparatus, and the remaining additives may be added and mixed immediately.
  • the amount of the additive to be added after the action of the sulfonating agent is preferably 2.5 to 200 mol based on the acyloxybenzene represented by the general formula (1).
  • a suitable solvent below + 10 ° C, after preferably reacted with a sulfonating agent at an appropriate temperature in the first 30-0 hand one 10 e C or more, preferably + 10 ° C or higher, more preferable properly is 30-60 Aging at 0.1 ° C. for 0.1 to 20 hours gives acyloxybenzene sulfonic acid.
  • the yield of the obtained acyloxybenzenesulfonic acid or a salt thereof is 0.9 to 1.3 times the molar amount of the acyloxybenzene represented by the general formula (1).
  • S0 3 suppression of side reactions, the S0 3 of 1.0 to 1.2 times by mole is properly preferred for lightening of color, it favored properly is used under conditions where there is substantially no water.
  • S0 3 is used as gaseous S0 3 which has been diluted with an inert gas.
  • Nitrogen or sufficiently dehumidified air is used from the viewpoint of price, etc., but air is preferably used industrially.
  • the S0 3 concentration in the inert gas is industrial productivity, control of treatment temperature, the heat removal and whether we 0.5 to 10 volume, preferably 1-5% by volume.
  • Contact and operating temperature of Ashiruokishi benzene and gaseous S0 3 is not more than 60, to reduce the goodness Ri side reactions, in terms of obtaining good product hue, 0 to 50 e C is more preferred.
  • the temperature of the ripening, 80 e C preferably to obtain a ⁇ sill O carboxymethyl benzenesulfonic acid of interest by aging from 0.1 to 20 hours at 20 to 70.
  • This reaction is preferably carried out under conditions substantially free of water.
  • the hydrolysis of the ester bond of compounds (1) and (5) is markedly increased, and the yield of the desired product is reduced. It is not desirable because the rate decreases.
  • that there is substantially no water does not mean a completely anhydrous state, but means that raw materials commercially available are used as they are. That is, a small amount of water contained in the raw material itself does not affect the yield of the present invention, meaning that water is substantially absent. It is preferable to reduce the water content to 5 mol% or less. Particularly when water is easily mixed, water may be contained in the polyphosphoric acid added as an additive.
  • R 4 in the general formula (2) should be used to obtain good reaction selectivity and reaction yield due to the exchange reaction of the acyl group between the boronic acid species and the acyloxybenzene.
  • the most preferable result is basically the same as R 1 of acyloxybenzene represented by the general formula (1).
  • the corresponding carboxylic acid may be added to the acyloxybenzene afterwards, or when the acyloxybenzene is obtained by esterification from the corresponding carboxylic acid and phenol, the esterification reaction may be used.
  • the esterification reaction may be stopped in the middle so that the composition of the ester may be adjusted at the stage of the esterification reaction, so that a considerable amount of carboxylic acid remains. The overall amount can also be adjusted.
  • R 1 , R 2 and n have the above-mentioned meanings, and M represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium, a substituted ammonium or a quaternary ammonium.
  • alkaline agent examples include an alkali metal, an alkaline earth metal, an ammonium, a substituted ammonium or a quaternary ammonium hydroxide, a carbonate, a bicarbonate, a carboxylate, or a halide.
  • ammonia, substituted Amin like for example NaOH, KOH. L i OH, Mg (0H) 2, Ca (0H) 2, NH4 OH, Na 2 C0 3, K 2 C0 3, NaHC0 3, preparative Rietano Rua Mi emissions, Tetramethylammonium chloride, didecyldimethylammonium chloride and the like are used, and preferably, a water or alcoholic solution or slurry of NaOH or KOH can be used.
  • the additive according to the present invention which is formed by a condensation reaction, a transesterification reaction, or a Friedel's reaction or a freezing rearrangement, which acts as a side reaction accelerating or acts as a catalyst, wherein the additive according to the present invention is in excess or in excess.
  • mixed acid anhydride e.g.,
  • a carboxylic acid and S0 3 are partially reacted, carboxylic acid shed position sul Hong compound RCH the (S0 3 H) C00H
  • the effect of suppressing the same side reaction and improving the yield can be obtained.
  • the present invention is to produce acyloxybenzene sulfonic acid with higher selectivity and higher yield than ever before.
  • the main reaction in the sulfonation of acyloxybenzene can be advantageously and effectively suppressed without inhibiting the main reaction in the sulfonation of acyloxybenzene, and by effectively and effectively suppressing the side reactions which are conventionally inevitable.
  • the selectivity is improved, and it is possible to obtain the desired product, oxybenzene sulfonic acid and its salt in high yield.
  • Representative side-reactants controlled by the present invention are sulfonic ester, ketone phenol, and ketone phenol ester sulfonate.
  • Sulfonate esters and ketone phenols include compounds having a functional group or bond represented by the general formula (6) such as amido, imido, urea, thioamide, thioimid, and thiourea, and carboxylic acid (2 ) Or addition of carbonate ester (7).
  • Ketone phenyl ester sulfonated products can also be effectively suppressed by adding a compound having a functional group represented by general formula (5) represented by phenol.
  • Arsenide Dorokishi compound (8) particularly for phenol, after sulfonation reaction than (S0 3 and immediately after the action), who added in advance to Ashiruokishi benzene of the general formula (1) is better.
  • acyloxybenzene such as dehydration esterification of phenol and carboxylic acid or esterification of phenol with carboxylic acid halide or carboxylic acid anhydride
  • acyloxybenzene such as dehydration esterification of phenol and carboxylic acid or esterification of phenol with carboxylic acid halide or carboxylic acid anhydride
  • It may be contained as a carryover component.
  • phenolsulfonic acid and substituted phenolsulfonic acid they may be prepared and added in advance, or the corresponding phenol or substituted phenol may be added to acyloxybenzene to allow the sulfonating agent to act. And may be formed during the reaction.
  • a carboxylic acid or a carbonic acid ester such as an amide
  • the entire amount may be contained in the acyloxybenzene, but preferably at least a part thereof is added after administration of the sulfonating agent and before aging. The aging method gives better results.
  • fleece dislocations (becomes ⁇ sill O carboxymethyl benzene Ke Tonfuwenoru) and Friedel Crafts reaction ( ⁇ Sil O carboxymethyl benzene 2 minutes operators or, Quai tons full We sulfonyl ester by reaction with ⁇ sill O carboxymethyl benzene and carboxylic acid ⁇ S0 3 mixed acid anhydride is produced. further it scan sulfone Is converted to ketone phenyl ester sulfonate), and at the same time, the target compound, sulfoxybenzenesulfonic acid and amide, which are formed during aging, form a kind of salt. acid further reacted (that is, side reactions) that suppresses.
  • the S0 3 be present in minor amounts to capture single Dan The effect to be similar to A mi earth.
  • a Mi de compound, Lee Mi de compounds, urea compounds obtained by adding together the carboxylic acid or carbonic ester and phenol.
  • mixed acid anhydride A (RC00S0 3 H) is, although present in the reaction, this is what the carboxylic acid once captured the S0 3 in-free, thereby particularly reducing the dewatering capacity This suppresses the by-product of sulfonic acid ester.
  • the mixed anhydride itself acts as an acylating agent and contributes to an increase in ketones.
  • a mi de also additives such as Lee Mi de, is basically should exhibit similar behavior as phenol, as a result, Ami de, but it would produce a complex of Lee Mi de and S0 3, here large difference with Fuwenoru is ⁇ Mi de, in Lee Mi de a complexing to lye, a stable phenol sulfonic as ultimately compound reacts with S0 3 himself in Fuwenoru It is a point that becomes acid.
  • Any hydroxy compound may be used as long as it has a hydroxyl group.
  • transesterification usually occurs during the sulfonation reaction, the yield of the desired product other than phenol decreases. All of the above effects are significant.
  • the phenols may be contained from the standpoint of industrial production as a carrier-over component from the process of producing the acyloxybenzene.
  • the free S0 3 captures temporarily eliminate the Lewis acid catalytic function of S0 3.
  • the amides form a kind of salt with the acyloxybenzenesulfonic acid generated during ripening, and inhibit or suppress the side reaction route derived from the acyloxybenzenesulfonic acid.
  • Sulfonate analysis was performed by liquid chromatography as follows. This was performed using a system, eluent and detector.
  • Solution B CH 3 CN 100%
  • the purity of the neutralized product was measured by liquid chromatography under the same conditions as for the analysis of the sulfonated product.
  • Example 2 Using the same apparatus as in Example 1, weigh 100.0 g of m-cresol perargonic acid ester having a purity of 99.6%, 9.5 g of pelargonic acid, and 100 g of 1,2-dichloroethane, and stir at ⁇ 30 ° C. Then, 34.5 g of sulfan was added dropwise to the well-stirred liquid surface at 132-123 ° C over 10 minutes. The product was kept at -10 ° C for 20 hours, and as a result, the yield of the sulfonated product of m-clebulepelargonic acid ester as the raw material ester was 98.3% and the side reaction rate was 1.6% .
  • Example 2 Using the same apparatus as in Example 1, weigh 100.0 g of m-cresopropyl ester of 99.7 purity, 8.9 g of lauric acid and 100 g of dichloromethane and cool to 130 with stirring. Then, 29.0 g of sulfane was added dropwise to the well-stirred liquid surface at 125 to 120 over 10 minutes. The product was kept at 110 ° C for 20 hours. As a result, the yield of the sulfonated product of m-cresyl laurate ester, which was the starting material ester, was 98.5%. %, And the side reaction rate was 0.3%. Influence of carboxylic acid species on phenyl esters
  • Example 4 Example 5
  • Example 6 Example ⁇ kind of phenyl ester Chlorocapro 2-i-ethylhexisosteari Behenic acid phenyl Sanic acid phenyl acid Phenyl acid phenyl carboxylic acid
  • the amount of carboxylic acid added includes the amount of carboxylic acid contained in the raw phenyl ester.
  • the phenyl ester shown in Table 2 was used as a raw material phenyl ester, and the carboxylic acid shown in Table 2 was added as an additive in an amount of 10 mol% to each phenyl ester, and sulfonation was carried out under the same conditions as in Example 1.
  • the yields of the corresponding sulfonic acids are summarized in Table 2 below.
  • the amount of carboxylic acid added includes the amount of carboxylic acid contained in the raw phenyl ester. Influence of the amount of caulbonic acid added
  • the granulated physical properties of the obtained neutralized product (dried product) at 60 ° C were evaluated according to the following criteria.
  • the raw material phenyl laurate used had a purity of 99.5% or more.
  • Lau Lau-phosphate Fuweniru with a-phosphate is contained 15 mol% at 3.77KgZ, supplied to the thin film flow-down type S0 3 gas contact continuous reactor, managed 1.0% S0 3 concentration of 35 the S0 3 gas dry air dilution which is, was passed through a time 1.05kgZ as S0 3.
  • the temperature of the cooling water supplied to the jacket provided in the reactor was 15 up to the first 2 m section and 20 ° C in the second 3 m section.
  • the temperature of the reaction product separated by the gas-liquid separator was 25.
  • the reaction product was supplied to a continuous extrusion kneader, kneaded well with cooling water at 10 ° C for 30 minutes, and then aged in a continuous extrusion kneader at 40'C for 40 minutes.
  • p- and 0-dodecanyloxybenzenesulfonic acid were obtained in a yield of 97.5%.
  • the secondary reaction rate was 2.3%, mostly ketones.
  • a continuous thin-film reactor (inner diameter: 99.1% phenyl ester, 0.6% lauric acid, 0.4% phenol) at 3.91 kgZ (14.0 mol Z) using a metering pump. 14 mm0, length 4 m). Introducing a concentration of 2.0% by volume of S0 3 diluted in air, allowed to act on a continuous-film reactor is found. S0 3 during 1.14kg Roh in here (14.3 molar Z when, i.e. Lau 1.02 moles per mol-phosphate phenyl) c When this was introduced, the cooling water supplied to the jacket which is provided to the reactor The temperature was 30 ° C. The temperature of the reaction product immediately after separation by the gas-liquid separator was 30 ° C.
  • the completed sulfonated product was subjected to continuous neutralization using an aqueous sodium hydroxide solution while maintaining the temperature at 30 to 40 ° C to a pH of 5 to 7.
  • the retention in neutralization at this time was 99%.
  • the color of the obtained neutralized product was APHA 40 in a 10% concentration solution of the target product.
  • the amount of lauric acid added (post-added) immediately after separation in the gas-liquid separator was as shown in Table 6 with respect to phenyl laurate. Addition and mixing were performed to 50 mol%, 100 mol%, and 150 mol%. The S0 3 in an amount required for these reactions completion is 1.05 times by mole respectively La ⁇ -phosphate phenyl, 1.10 mol times, 1.15 times by mole, introducing the amount to the reactor and used. Table 6 summarizes the yields of the corresponding sulfonic acids (total of 0- and p-forms) and the hue of the neutralized product.
  • Phenyl carboxylate (purity of phenyl ester 92.8%, pupuric acid 6.4%, phenol 0.8%, that is, 10 mol% of phenyl purinate added with capric acid as a pre-addition).
  • S0 3 is introduced in a time 1. 26kgZ (1. 05 molar times the Capri phosphate Fuweniru in time 15.75 mol).
  • concentration of the diluted air S0 3 are as shown in Tables 7.
  • Phenyl laurate (phenyl ester purity 99.0%, lauric acid 0.6%, phenol 0.4%) was introduced into the reactor of Example 25 at 3.91 kgZ (14.0 mol / h) using a metering pump. did. At the same time, introduced in this reaction ⁇ the 1.16kgZ at the S0 3 1.5% by volume diluted with air as S0 3 (14.6 moles time, i.e. 1.04 moles per mol of lauric-phosphate Fuweniru). At this time, the temperature of the cooling water supplied to the jacket provided in the reactor was 20 ° C.
  • the temperature of the reaction product immediately after separation by the gas-liquid separator was 23 ° C, and immediately the ⁇ -sulfonated product of lauric acid was added to the reaction product.
  • the mixture was aged in a continuous extrusion kneader at 50 for 1 hour. Thereafter, neutralization was carried out using sodium hydroxide in a continuous neutralizer while maintaining the pH at 5 to 7 at 30 to 40 ° C.
  • the yields of the p-form and the 0-form dodecanoyloxysulfonic acid were 95%, and the color of the neutralized product was APHA60 in a 10% concentration solution of the target product.
  • Example 39 Under the same conditions as in Example 39, the additive to be added immediately after gas-liquid separation was changed to polyphosphoric acid (condensation degree: 116%), 0.355 kg, hr (4.20 mol / hr as phosphoric acid skeleton) As a result, the yield of the target sulfonic acid in the sulfonation reaction was 95%, and the hue of the neutralized product was APHA40 in a 10% concentration solution of the target product. Atsushi.
  • the target compounds p- and o-decanoyloxybenzenesulfonic acid, were obtained in 92.0% and 7.1%, respectively, in a total yield of 99.1%. Further, this sulfonic acid solution and a 5.0% NaOH aqueous solution were simultaneously dropped and neutralized so as to maintain pH 3 to pH 8 and 30 to 40 ° C. The final pH was 5.2 (10% effective). As a result, a neutralized aqueous solution containing 98.8% of the sulfonic acid was obtained.
  • Example 41 Using the same apparatus as in Example 1, m-clebule pelargonate 100.2 g (0.402 mol) having a purity of 99.6%, pelargonic acid 6.36 g
  • Phenyl phenylate Phenyl phenylate Molar ratio 5 10 10 10 10 10
  • N, N'-Diacetylethylenediamine was used in place of acetamide.
  • the molar ratio is a numerical value based on the amide partial structure.
  • esters used had a purity of 99.5% or more in terms of the total phenyl ester content.
  • Comparative Example 17 A sulfone reaction was carried out under the conditions of JP-A62-30752.
  • Phenyl laurate prepared by esterification of phenol and lauric acid chloride (phenyl ester purity 99.0%, lauric acid 0.61% (vs. phenyl ester 0.85 mol), phenol 0.37% (same as above)
  • Example 53 Thin film sulfonation reaction under the conditions of the present invention
  • Phenyl laurate prepared by dehydration esterification of phenol and lauric acid (phenyl ester purity 91.8%, lauric acid 7.65% (vs. phenyl ester 11.5 moles), phenol 0.47% (1.5 moles using a metering pump at Le%)) of at 3.91KgZ (at 13.0 mol Z), a thin film flow-down type S0 3 gas continuous sulfonation reactor (internal diameter 14 raid, supplied in the pipe length 4 m), which is managed by 40 2.5% concentration (vol / vol, dry air dilution) and S0 3 gas was circulated at the time of 1.14kgZ as S0 3 (at 14.2 Moruno).
  • the temperature of the reaction product was separated by the gas-liquid separator at 33 e C, acid value 186.6, was 37% for the desired product yield at this point.
  • the residence time from the time when the sulfonating agent was acted to the time when the reaction product was obtained through the gas-liquid separator was about 25 seconds.
  • 30.0 g of succinic acid imide was weighed in the same four-neck flask as that used in Example 41, and then cooled in a cold water bath (5 ° C).
  • the conversion of the phenyl ester was 99%, and the by-products (the conversion of the phenyl ester) were 0.8% for the sulfonic acid ester, 0.1% for the ketone phenyl ester, 0.4% for the ketone phenol, and 0.4% for the ketone phenol.
  • Tonhueniruye 1.1% steal sulfonate, 8.1% phenol sulfonic acid, etc., and some other contaminants were observed on the mouth matogram.
  • Example 54 Example 53 + phenol (added to phenyl ester) To the phenyl laurate used in Example 53, phenol was added to prepare phenyl laurate (phenyl ester purity: 89.4%, Quantitative determination of 7.45% of lauric acid (based on 11.5 mol of phenyl ester and 3.05% of phenol (10.0 mol of same)) in S SkgZ at 12.8 mol Z of phenyl ester and 1.28 mol Z of phenol at a temperature of 35 ° C using a pump, thin film flow-down type S0 3 gas continuous sulfonation reactor (internal diameter 14 mm, tube length 4 m) was supplied to a 2.5% strength managed to 40 ° C (vol / vol, dry air dilution) of S0 3 the gas was circulated in a time 1.21kgZ as S0 3 (at 15.1 Moruno).
  • the temperature was controlled (50 ° C at the initial stage, 60 eC at the final stage) so as not to solidify, and the batch was aged while stirring. After one minute, analysis by high performance liquid chromatography revealed that P- and 0-dodecanoyloxybenzenesulfonic acid were obtained at a yield of 8% and 88%, respectively, for a total of 96%. At this time, the conversion of phenyl ester was 99%, and the by-products (phenyl ester conversion) were 1.3% sulfonic acid ester, 0.3% ketone phenyl ester, 0.5% ketone phenol, and 0.5% ketone phenyl ester.
  • the hue of the neutralized product (a 10% effective concentration solution) with an aqueous NaOH solution was APHA30.
  • Example 54 The reaction was carried out in the same manner as in Example 54, except that 30.Og of lauric acid was added instead of 30.Og of succinic acid imid added after gas-liquid separation. However, the aging temperature was 50 e C at the beginning and 70 e C at the end. After aging for 30 minutes in the same manner as in Example 54, analysis by high performance liquid chromatography revealed that p- and 0-dodecanoyloxybenzenesulfonic acid were recovered at 7% and 88%, respectively, for a total of 95%. Rate obtained.
  • the reaction rate of the phenyl ester was 99.9% or more, and the by-products (conversion rate of the phenyl ester) were 0.9% sulfonic acid ester, 0.4% ketone phenyl ester, 0.4% ketone phenol and 0.4% ketone. 0.9% phenyl ester sulfonate, 10% phenol sulfonic acid, etc. (including the product from the added phenol), and the neutralized product neutralized with NaOH aqueous solution has a color (APHA 50) of APHA 50.
  • the temperature of the cooling water supplied to the jacket which is provided to the reactor the first half 0.5m is 15 ° C, the second half 1.5m was managed 30 e C.
  • the temperature of the reaction product separated by the gas-liquid separator was 31 C
  • the acid value was 190.1
  • the yield of the desired product was 32%.
  • the residence time from the reaction of the sulfonating agent to the obtaining of the reactant was about 15 seconds.
  • Phenyl laureate conversion 100 100 100 100 100 100 99 99 99 95 92 Yield of target compound ' 1 92 93 94 95 95 94 94 94 91 85
  • Example 89 Example 53 + phenolsulfonic acid (added to phenylester)
  • composition analysis 78.2% of p-phenolsulfonic acid, 5.0% of 0-phenolsulfonic acid, 9.9% of phenoldisulfonic acid, and Hydroxydiphenyl) sulfone 5.9%, phenol 0.1%, and H 2 SO 4 0.7%.

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PCT/JP1995/000061 1994-02-10 1995-01-20 Procede de production d'acide acyloxybenzenesulfonique ou de son sel WO1995021816A1 (fr)

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US08/530,184 US5606104A (en) 1994-02-10 1995-01-20 Process for the preparation of acyloxybenzenesulfonic acid or salt thereof
JP52110995A JP3434298B2 (ja) 1994-02-10 1995-01-20 アシルオキシベンゼンスルホン酸又はその塩の製造法
EP95906500A EP0700900B1 (en) 1994-02-10 1995-01-20 Process for producing acyloxybenzenesulfonic acid or salt thereof
KR1019950704322A KR0184295B1 (ko) 1994-02-10 1995-01-20 아실옥시벤젠술폰산 또는 그 염의 제조법
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US20030035784A1 (en) * 2001-03-05 2003-02-20 Kao Corporation Hair cosmetic, aminocarboxylic acid amide and method for producing the same
US6790981B2 (en) 2002-12-13 2004-09-14 Clariant Finance (Bvi) Limited Process for the preparation of acyloxybenzenesulfonates
EP1687400A4 (en) 2003-10-08 2009-01-07 Wolf Wilson Mfg Corp METHODS AND DEVICES FOR CELL CULTURE USING GAS PERMEABLE MATERIALS
JP5395171B2 (ja) 2008-07-08 2014-01-22 ウィルソン ウォルフ マニュファクチャリング コーポレイション 気体透過性の細胞培養装置および使用方法

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