TW593266B - Method for preparing hydroxyphenyl carboxylic acid esters - Google Patents

Abstract

The invention relates to a method for preparing compounds of formula (I), in which R1 and R2, independent of one another, represent C1-C8 alkyl, cyclopentyl or cyclohexyl; m equals 1, 2 or 3, preferably 2; n is an integer ranging from 1 to 30, and; R3 represents an n-valence radical of linear or branched C4-C30 alkyl, which is optionally interrupted by one or more oxygen atoms, or (if n=1-12) represents an n-valence radical of C5-C12 cycloalkyl, or a radical R4-[NR5-CmH2m-]p; R4 represents hydrogen, an n-valence radical of the linear or branched C4-C30 alkyl, which is optionally interrupted by one or more groups -NR5-, or (if n=1-12) represents an n-valence radical of C5-C12 cycloalkyl; R5, independent of one another, represents hydrogen or methyl or -CmH2m-, preferably hydrogen, and; p represents the number of -[NR5-CmH2m-] groups that yield n radicals -CmH2m- per molecule. The compounds of formula (I) are prepared by reacting a compound of formula (II), in which R represents C1-C3 alkyl, with a compound of formula (III) R3(OH)n, in which R3 and n have the cited meanings. The inventive method is characterized in that the reaction occurs with a practically neutral acid value (pH) and in the presence of at least one alkali salt, which is dissolved or suspended in the reaction mixture, of an organic carboxylic acid or in the presence of a mixture of such alkali salts, whereby: (i) this alkali salt is formed from an alkali cation and from an organic carboxylic acid, and; (ii) the organic carboxylic acid is at least partially volatile with the applied reaction conditions. The alkali salts are preferably alkali formate and alkali acetate.

Description

593266 A7 __B7_ V. Description of the invention () [Detailed description of the invention] The present invention relates to a method for producing a hydroxyphenyl intactate using a selected catalyst. The present invention also relates to novel hydroxyphenyl carboxylic acid esters which can be produced by the method of the present invention. Hydroxyphenyl carboxylic acid esters, especially hydroxyphenyl carboxylic acid esters of the formula (I), are preferably used as antioxidants. Many compounds of formula (I) are known. By way of example, they are produced by esterification using suitable catalysts. This method of esterification is mentioned, for example, in U.S.-A-4,716,244, U-A-5,481,023, and US-A-5,563,291. Some of the compounds of formula XI are important commercial products. For example, they protect organic materials such as plastics or lubricants from oxidative or actinic decomposition. In addition, there is a continuing need for such compounds as antioxidants and their preferred manufacturing methods. We have found that we can use unexpectedly selected carboxylic acid alkaline earth metals (such as lithium acetate, sodium acetate, or potassium acetate) in practically neutral media without solvents in conventional esterification methods. A catalyst in which the product is obtained in the form of a colorless melt, and the product in the form of a colorless melt can be used directly without a purification process. Moreover, unexpectedly, the neutralization operation of the catalyst can be omitted, and no esterification reaction will occur, even if the reaction is completed and the cooled reaction material is in contact with the alcohol. One fact is worth noting; under the given conditions, the above catalysts, especially at pH and without solvents, can catalyze n-membered esterification, where η = 1, 2, 3, 4 or more. The opinion of the present invention is in the scope of patent application. The present invention particularly relates to a method for manufacturing a compound of formula VII: 6 Applicable to National Standard (CNS) A4 specification (2ΐϊχ 297 mm) One by one -------- ^ --------- Avi (Please read the notes on the back before filling this page) 593266 A7 B7

CmH2m—C—0- -R3 V. Description of the invention (Λ 0 (I) n where: Heart and r2 are irrelevant to each other to represent c! ~ C8 alkyl, cyclopentyl, or cyclohexyl, m 1, 2, or 3, and preferably an integer of 2 η 1 to 30, and preferably an integer of 1 to 10, especially 1, 3, 4, 5, 6, R3 — a η-valent linear or branched C4 ～ C3Q alkyl radical, this radical can be interrupted by one or several oxygen molecules if necessary, or (for η = 1 ~ 12) is a η-valent C5 ~ C12 cycloalkyl, or an R4— [NR5 —CmH2m—] p radical, R4 hydrogen, a η-valent linear or branched C4 ~ C30 alkyl radical, the radical can be interrupted by one or several NR5- radicals if necessary, or (For n = 1 ~; 12) is an n-valent C5 ~ C12 cycloalkyl group, R5 shows hydrogen, methyl or -CmH2m- independently of each other, and P is equivalent to the number of the group [NR5—CmH2m—], This number produces n one CmH2m—free radicals per molecule; this method involves combining a compound of formula (II) with a compound of formula (III) 7 This paper is in accordance with the Chinese National Standard (CNS) A4 specification (210 X 297g t) ----------- • Installation: -.---- --------- set to 0 (Please read the Notes on the back to fill out this page) 593266 A7 B7 V. invention is described in () reactions:

Formula II

r2 Among them: R means Ci ~ C3 courtyard foundation, (Please read the precautions on the back before filling this page)

Formula III R3 (〇H) n (HI) wherein R3 and η have the same meanings as described above, and are characterized by: The reaction is at a practically neutral pH. The alkali metal salt or at least one organic carboxylic acid has such an alkali metal salt. The alkali metal salt is dissolved or suspended in the reaction mixture, wherein: 混合物 metal salt is composed of an alkali metal cation and an anion of an organic carboxylic acid, (ii) the acid is used in the reaction conditions At least partially volatile. Here, the reaction conditions used in the reaction ... especially temperature and pressure --- temperature is 50 ° C ~ 250 ° C, and preferably 80t ~ 220 ° C, especially 140 ° C ~ 220 ° C, pressure 0.1 mbar to 1 mbar (normal pressure), and preferably 0.1 mbar to 100 mbar, especially 0.1 mbar to 50 mbar, and especially 0.1 mbar to 20 mbar. It is better that the boiling point of the carboxylic acid constituting the salt is within the above temperature and pressure range. 8 This paper size is in accordance with the Chinese National Standard (CNS) A4 specification (210 X 297 public love) 593266 A7 ^ __________ —_B7. . The salt-forming alkali metal cations used are, in particular, lithium, sodium, and potassium cations. Preferred are sodium, potassium, and / or lithium cations or sodium, potassium, and / or lithium salts of organic carboxylic acids. Examples of end acids (when in acid form, which are at least partially volatile under the reaction conditions used) are examples of aliphatic saturated or unsaturated C2 ~ Cl0 (and preferably C2 ~ Q) carboxylic acids, such as: formic acid 'Acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, trimethylacetic acid, hexanoic acid, n-heptanoic acid or nonanoic acid. Other examples are malonic acid, maleic acid, fumaric acid, or monomethyl malonate. Also suitable are halogenated acids, such as: fluoroacetic acid, chloroacetic acid, bromoacetic acid, difluoroacetic acid, dichloroacetic acid, trifluoroacetic acid, trichloroacetic acid, α-chloropropionic acid or cold-chloropropionic acid. Preferred are sodium acetate, potassium acetate, lithium acetate, sodium formate, potassium formate, lithium formate, or a mixture of these compounds. The amount of the catalyst to be added is preferably 0.05 to 5% mole. [Reaction molar amount with respect to the compound of formula]] 〇R] should represent C! ~ C8 alkyl group, wherein the alkyl radical can be linear Or forked. Preferably, Ri represents a C! To C4 alkyl radical, and is preferably methyl, ethyl, propyl, or butyl. Alternatively, R1 preferably represents a branched free group, and is preferably a methyl group or a third butyl group. R2 preferably represents a G ~ c8 alkyl group, wherein the alkyl radical may be linear or branched. Preferably, R2 represents a C1-C4 alkyl radical, and is preferably methyl, ethyl, propyl, or butyl. Alternatively, r2 preferably represents a branched free radical, and is preferably a methyl group or a third butyl group, and is preferably a third butyl group. The compound of formula ⑴ may contain attentiveness and r2 in the same molecule in accordance with 9 Chinese national standards (ΐ4Έϋ ^ 72Ί〇χ 297 mm 1 ------------------- Order --------- (Please read the precautions on the back before filling this page) 593266 A7 ______ __B7 —_ V. Description of the invention () Free radicals substituted in the same way, and in the same phenyl group &Amp; and R2 on the radical may be the same or different. In this regard, for example, 仏 and! ^ May both represent methyl or third butyl, or R] represents methyl, and R2 represents Third butyl. R3 (which can be interrupted by oxygen) in the free radical form of η-valent C4 ~ c3 () alkyl can exist in a straight line or a bifurcation or a mixture of the two. This mixture can be These compounds are composed of, in which, r3 represents a mixture of alkyl radicals which are mainly linear or branched, such as those having 14, 16, 18, and 20 carbon atoms, of which some of the alkyl radicals are also It can be a bifurcation. If R3 represents a R4- [NR5—CmH2m—] p radical, then this radical should preferably be R4 — [NH —CmH2m—fan or R4 — [N ( CmH2m—) 2] p, and it is preferably R4— [NH—CmH2ni—] p radical. Among them, R4 should be a C4 ~ C30 alkyl radical, which can be interrupted by —NR5— and should be interrupted by —NR5—. NH — interrupted, and can be straight or bifurcated, such as those with 14, 16, 18, and 20 carbon atoms. Similarly, R4 can be (for η = 2) an alkylenediamine (such as ethylenediamine or Propylene diamine) or derived from a polyalkylene diamine (and preferably a dialkylene diamine, such as diethylene diamine or dipropylene diamine). If η = 1, then R3 should represent a A monovalent radical, and preferably: n-butyl, isobutyl, third butyl, pentyl, isopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl , Undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptyl, octadecyl, eicosyl, and have increasing To 30 carbon sources 10 national standards (CNS) X4 ϋ7210 X 297 male ----------- install -------- order --------- (please (Please read the notes on the back before filling this page) 593266 A7 ______B7__ 5. Description of the invention ) Related homolog alkyl radicals, or a mixture of these C4 ~ C30 radicals. For η = 1, R3 should also represent a monovalent radical, such as C5 ~ C12 cycloalkyl, It should be cyclopentyl, and cyclohexyl, especially cyclohexyl. R3 should indicate (for η = 1) a monovalent G ~ C3g radical, and it should be isooctyl, 2-ethyl Hexyl, n-hexadecyl, and n-octadecyl, or a mixture of these alkyl radicals. The conditions for R3 described here are also preferred for R4. If η = 2, then R3 should represent C2 ~ C8 alkylene or C4 ~ C12 alkylene interrupted by an oxygen atom. In this regard, R3 (for η = 2) represents an alkylene derived from the removal of the two oxo groups from a divalent alcohol, which can be interrupted by an oxygen atom. Examples of such divalent alcohols are alkylene glycols [e.g. 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1, 6-hexanediol, 1,7-heptanediol, 1,8-octanediol], polyalkylene glycols [eg: diethylene glycol, triethylene glycol, tetraethylene glycol Glycol, dipropylene glycol, tripropylene glycol] or (for η = 1) glycerol, pentaerythritol [C (CH2OH) 4] or similar polyols. Likewise, the n-valent radical R3 interrupted by an oxygen atom may be derived from an etherified polyhydroxy compound, and preferably derived from polyglycerol or polypentaerythritol. Similarly, R4 (for η = 2) should represent an alkylene group derived from a diamine by removing its two fluorene 2N- groups, which can be interrupted by an NR5 — and by an (NH) —. Examples of such diamines are alkylenediamines [e.g. ethylenediamine, or 1,2-propanediamine], or dialkylene diamines [e.g. di (ethylenediamine), or di ( Propylenediamine)]. For example, bis (ethylenediamine) may have a [― (NH) —CmH2m—] group on the intermediate nitrogen atom if necessary. 11 This Chinese National Standard (CNS) Hi ^ (210 X 297 public ^ ^ ^ ----------- install -------- order --------- (please (Please read the notes on the back before filling this page) 593266 A7 _ — _B7__ 5. Description of the invention () If η = 3, R3 is a courtyard derived from the trivalent alcohol by taking off the OH group. In this regard, R3 should be represented by Ayuan-C ^ CV courtyard-trimethylol. Examples of such trivalent alcohols are Shen-jingyuanyiethane (trimethyl alcoholethane), M, 1-gins-hydroxyalkylpropane (trimethylolpropane). If η = 4, R3 is a branched alkyl group derived by removing the 0H group from a tetravalent alcohol or polyol- Alkylene. In this regard, R3 should preferably represent methane-tetramethylene, for example: methyl-hydroxymethyl-methane (pentaerythritol). Alkylene radicals 1 of compounds of formula (I) or (II) CmH2m) —where m is preferably 2, or the alkylene radical is mono (CH2-CH2) —. Among the compounds of formula IX produced, R! Preferably represents a third butyl group, and R2 represents a methyl group. Or third butyl, R3 represents n-octadecyl, a higher alkane having 8 to 30 carbon atoms A mixture of free radicals (C8 to C3o alkyl radicals), or a mixture of 1,6-hexanediol, triethylene glycol, pentaerythritol, 1,1,1-s- (hydrocarbylmethyl) Ethane), 1,1, Phenophenyl- (hydrocarbylmethylpropane) derived radicals, or R4 represents a kind of 1,2-ethylenediamine or 1,2-propylenediamine or such as di (ethylene Diamine) or bis (propylene diamine) derived radicals. The invention also relates to the use of an alkali metal salt of an organic carboxylic acid or such an alkali metal salt mixture, as described above, for use in formulas (II) and The compound of formula (m) is used as a catalyst when the compound of formula VII is initially produced, and sodium acetate, potassium acetate, lithium acetate, sodium formate, potassium formate, or lithium formate, or a mixture of these compounds is preferably used. Amount of catalyst added 0.05 to 5 mole%, and preferably 0.05 to 3 mole%, particularly preferably 0.1 to 1 mole% [relative to the compound of formula (I), 12 paper fi national standards (Cns) a4 彳 ϋ 〇ι〇x 297 — ----------- • equipment; ----------- order --------- stupid (please read the first (Please fill in this page again for attention) 593266 A7 _________B7 __ 5. Description of the invention () Amount used]. According to the present invention, it is preferable to operate without a solvent. However, the esterification reaction can also be carried out in an inert organic aliphatic and / or aromatic solvent or a mixture of these solvents according to the present invention. According to the present invention, the compounds of formula (II) and formula (III) together with the catalyst are heated together under inert conditions, and preferably at a temperature of 90 to 120 ° C and with stirring, until there is a melt. In order to shift the direction of chemical equilibrium towards the esterification reaction, the pressure is then reduced and the temperature is increased. In other words, the reaction should be carried out in a pressure range of 0.1 to 200 mbar and a temperature range of 140 to 220 ° C. The pressure should preferably be 0.1 to 50 mbar, especially 0.1 to 20 mbar. The reaction temperature should be 160 ~ 220 t, especially 165 ~ 185 ° C. The reaction time is related to pressure and temperature, and is generally between 1 to 12 hours, and preferably between 1 to 10 hours, and particularly preferably between 2 to 6 hours. Generally we use a slight excess of the ester of formula (II) [with respect to the hydroxy-functional group of the alcohol of formula (III)]. The ratio of the compound of formula (II) to the compound of formula (III) (calculated in molar equivalents) should preferably be in the range of 0.8: 1 to 1.5: 1, and preferably in the range of 1: 1 to 1.2: 1, particularly preferably The range is from 1.05 to 1.15: 1. If an excess of the compound of formula (II) is used, the excess of the compound of formula (II) should be distilled off at the end of the reaction, and this excess of the compound of formula (II) is also used as a "strip agent" (Schlepper), Take away any inappropriate side ingredients that can affect the color of your product. The product of formula (I) can be directly crystallized or cooled by cooling [animpfen or seedless], so that it can be directly reprocessed without additional purification steps, such as recrystallization. Commodity form. According to the invention, the melt can of course also be absorbed in a suitable solvent and cooled, 13 using Chinese National Standard (CNS) A4 (210 X 297 mm)-* --------- ---------- Order --------- (Please read the notes on the back before filling out this page) 593266 A7 _____ B7______ 5. Description of the invention () and crystallization (can seed seeds) Or not seeding). Examples of suitable solvents are aliphatic hydrocarbons (such as heptane, or cyclohexane, or a mixture thereof), aromatic hydrocarbons (such as toluene and / or xylene), alcohols [such as methanol, ethanol, propanol, and / Or isopropanol and related alcohol / water mixtures (50 ~ 100% alcohol)]. Methanol / or isopropanol and a mixture with water are preferred. The remaining content of the catalyst in the product (for example, before or after the filtration operation of the reaction melt after the reaction in various cases) is generally not hindered when used as a stabilizer. Nonetheless, the alkali metal salt present can also be removed by simple filtration, for example, by conventional filtering through a 20 // filter plate at 90 ~ 130. After filtration, the catalyst content is generally in the ppm range. A particular advantage of the method of the present invention is that the product obtained is "analytical grade", in other words, the reaction melt or product does not contain obstructive colored or staining side components and does not require further purification steps The reaction product can be made into a usable commercial form by using physical methods without adding additives, such as grinding into powder. The compounds of formula (II) and formula (III) used in the method of the present invention are known. And the compound of formula (I) {wherein: n == 3, and R3 is a trivalent radical [it can be derived from 1,1,1-gins-hydroxymethyleneethane (trimethanolethane)], Or in which R3 represents U, l-gins-methylidene} is novel. Similarly, another compound of formula VII [where: η = 3 and R3 is a trivalent radical [which can be derived from U, l-p-s-hydroxymethylenepropane (trimethanolpropane)], or where R3 Representing 1,1,1-ginsane-methylene propane} is also novel. Another compound of formula (I) {wherein: R3 represents a free radical r4 — [NR5—CmH2m] p —, and preferably R4- [NH—CmH2m] p —, of which 14 paper standards are applicable @@ 17. ¾ 2 ^ &quot; (^ \ JS) X4 (210 ~ χ 297 ^ 11 ”— ~ ------------------- Order --------- (Please read the notes on the back before filling this page) 593266 A7 _____B7__ 5. Description of the invention () R4 means a derivative of 1,2-ethylenediamine or propylenediamine or one (ethylene-1 Amine) or free radicals derived from bis (propylene diamine), and R1, R2, and m have the above meaning} are also novelty. These compounds are the subject of the present invention. These compounds can also be used in other conventional The method is manufactured without using the method described by Fangming. Unexpectedly, these compounds show only a minimal tendency to dye in a basic acetone solution. The focus is on the page index (Yellowness In ( jex) is an important proof of the advantages of the application. The following examples are used to further illustrate the invention, but not to limit its scope. <MLi_: Shi- (3,5-Di-Third-Butyl-4-Hydroxyl) Benzene) Propionic acid + Benzyl ester [compound of formula ⑴, where R! And R2 = third butyl, η = 1, m = 2, R3 = n-C18H37]> 109 g (0.364 mole) / 3- (3, 5-Di-tert-butyl-4-hydroxyphenyl) propionic acid methyl ester, 92.5 g (0.34 mol) of stearyl alcohol, and 0.1 g (0.001 mol) of acetic acid. Put it in the form of dihydrate with two crystal waters), and melt and stir at 10 (TC under nitrogen. Once the melt appears, carefully evacuate, and heat it to an internal temperature of 150 ~ 160 t (丨 Ding). The produced methanol is distilled off and condensed in a cooling downcomer. As soon as the internal pressure reaches &lt; 10 mbar, the internal temperature is raised to 170 ~ 180 ° C and evacuated to a pressure &lt; 1 millimeter. Bar. When IT = 170 ~ 180 ° C and pressure &lt; 1 mbar, hold it for one hour, then between 1 ~ 2 hours at IT = 200 ~ 210 ° C will excess ^ ...,- Di-tert-butyl-4-hydroxyphenyl) propionic acid methyl ester is distilled off. At this time, the reaction melt contains only <0.2% of 15 ----------- • pack:- --.---- Order --------- Stupid (Please read the notes on the back before filling this page) Home Standard (~ CNiS) A4 Regulations ϋϋίχ 297 Public Love Γ * &quot; 593266 A7 ------------ B7 ___ V. Description of the Invention () Edukt, and no-(3,5- 二-Content of stearyl trimethyl-4-hydroxyphenyl) propanoate &gt; 98%. The reaction melt was cooled and left to crystallize. Yield: 96.5%, melting point: 51. (:. &Lt; Tertiary butyl-4-hydroxyl benzene) octadecyl propionate [compound of formula ，, where Ri and R2 = third butyl, η = 1, m = 2, R3 = n _c18h37] &gt; Put 109 g (0.364 mol) of κ3,5-di-third-butyl-4-hydroxyphenyl) propanoic acid methyl ester, 92.5 g (0.34 mol) of stearyl alcohol, Put in 0.2 g (0.003 moles) of sodium formate, and melt and stir under nitrogen (rc) under nitrogen. Once the melt appears, carefully evacuate while heating to an internal temperature of 150 to 160 ° C (IT). The produced methanol is distilled off and condensed in a cooling downcomer. As soon as the internal pressure reaches &lt; 10 mbar, the internal temperature is raised to 170 ~ 180 ° C and evacuated to a pressure &lt; 1 milliliter. Bar. When it reaches 180 ° C and the pressure is <1 mbar, it is held for one hour, and then between 2 hours at the temperature of IT = 200 ~ 210 ° C, the point of excess will be-(3,5- Di-third butyl-4- via methylphenyl) propionate is distilled off. At this time, the reaction melt contains only <0.2% of the educt, and /? _ (3,5-di- Tributyl-4-hydroxyphenyl) stearyl ester propionate content &gt; 98%. Melt the reaction Cool and allow to crystallize. Yield: 96.5%, melting point: 51t. <亶 JLi_: triethyleneaminoethyl fluorene-bisdi-third-butyl- [compound of formula ，, where R ^ R2 = third butyl , Η = 2, m = 2, R3 = — (CH2CH20) 2CH2CH2-]> Put 76 grams (0.26 mole) of / 3- (3,5-di-third-butyl-4-hydroxyphenyl) propane Acid methyl ester, 15 g (0.1 mol) of triethylene glycol, and 0.17 g 16 This paper size is applicable to Chinese standard (21〇χΐ9Γ5 ^^ --------- -• Equipment -------- Order --------- (Please read the precautions on the back before filling this page) 593266 A7 _____ B7____ V. Description of the invention () (0.0015 mole) Lithium acetate was put in and melted and stirred under 100t under nitrogen. Once the melt appeared, carefully evacuate it while heating to an internal temperature (IT) of 160 ~ 180 ° C. Distill off the produced methanol and Condensate in a cooling downcomer. As soon as the internal pressure reaches &lt; 10 mbar, the internal temperature will be raised to 180 ~ 190 ° C and then evacuated to a pressure &lt; 1 mbar. When IT = 190 ° C, And pressure &lt; 1 mbar, hold for one hour, and then between 1 and 2 hours at 1 D = 20 The temperature of 0 ~ 220 ° (: will distill the excess of / 3- (3,5-di-third-butyl-4-hydroxyphenyl) propanoic acid methyl ester. At this time, the reaction melt contains only &lt; 0.2% of the educt (Edukt), and the content of triethyleneamine ethylacetamidine-bis- / 5-(3,5-di · tertiarybutyl-4-hydroxyphenyl) propionate> 97% . The reaction melt was cooled and left to crystallize. Yield 94%, melting point 113 ~ 115 ° C. <Example 4: Triethylene amine, a Z-bis- / 3 third butyl 5-methyl-4- mesitylphenyl) propionate [compound of formula (I), wherein R! And R2 = the Tributyl, η = 1 5 m = 2, R3 =-(CH2CH20) 2CH2CH2-]> Put 65 g (0.26 mole) of / 3- (3-third butyl 5-methyl-4-hydroxybenzene Methyl) propionate, 15 g (0.1 mol) of triethylene glycol, and 0.17 g (0.0015 mol) of lithium acetate) were placed, and at 100 it was melted and stirred under nitrogen. Once the melt appears, carefully evacuate it and heat it to an internal temperature (IT) of 160 to 170 ° C. The methanol produced was distilled off and condensed in a cooling downcomer. As soon as the internal pressure reaches &lt; 10 mbar, the internal temperature is raised to 170 ~ 180 ° C and a vacuum is applied to the pressure &lt; 1 mbar. When IT = 180 ° C is reached, and the pressure is <1 mbar, it is held for one hour, and then between 1 and 2 hours at the temperature of IT = 190 ~ 200 ° C, the excess of / 5- (3-third Butyl-5-methyl-4- is distilled off via methyl phenyl) propanoate. At this time, the reaction melt was only 17 copies of the national standard &quot; T5Ss) A4 specifications. 71 ^^ 97 public issue 1,------------ load ------- -Order --------- (Please read the precautions on the back before filling out this page) 593266 A7 _______B7_ V. Description of the invention () Contains <0.2% of Edukt and triethyleneamine The content of acetofluorene · bis-cold- (3-thirdbutyl-5-methyl-4-hydroxyphenyl) propionate> 97%. The reaction melt was cooled and left to crystallize. Yield: 94.5%, melting point: 74 ~ 77 ° C. 〇 <Example, ..__ 5_J_LJ, 1->-f / 9 43,5-Di-Pindibutyl-4-hydroxyphenyl) propanylmethoxy 1 Propane [compound of formula (I), in which R! And R2 = third butyl, η = 3, m = 2, R-CH-CH3CH2C (CH2) 3]> 85.5 g (0.293 mole) of yj-( 3,5-Di-tert-butyl-4-hydroxyphenyl) propanoic acid methyl ester, 10.1 g (0.075 mol) of stilbene, i, stilbene-(-hydroxymethyl) -propane, Place with 0.25 g (0.002 mol) of lithium acetate (in the form of a dihydrate with two crystal waters) and melt and stir at 12 ° C under nitrogen. Once the melt appears, carefully Evacuate while heating to an internal temperature of 16 ° C. The produced methanol is distilled off and condensed in a cooling downcomer. As soon as the internal pressure reaches &lt; 10 mbar, the internal temperature is raised to 180 ° C And evacuate again to a pressure of <1 mbar. When it reaches IT = 18 (TC, and the pressure is <1 mbar, it is held for one hour, and then between 1 and 2 hours at IT = 200 to 210 ° C. The excess of / 3- (3,5-di-third-butyl-4-hydroxyphenyl) propanoate was distilled off at a temperature. The melt should contain &lt; 0.2% of / S- (3,5-di-third-butyl-4-hydroxyphenyl) propanoic acid methyl ester, and ^^ _ [a _ (3,5_ Di-third-butyl-4-hydroxyphenyl) propanylmethoxy] propane content &gt; 97%. This colorless reaction melt was filtered, cooled and allowed to solidify / crystallize. Yield 95% ^ Melting point 66 ~ 79 ° C. [Amorphous (amorphous) form] <Example__LL1-gins- (3,5-di-third-butyl-4-mercaptobenzene) Ξ. 醯. 棊 methoxyl 1 Propane [Compound of formula (I), where R! And R2 = the third 18 This paper size applies to the Chinese National Standard (CNS) A4 specification (ϋχ 297 公 爱) _ ~ '** --------- ---------- Order · -------- (Please read the notes on the back before filling this page) 593266 A7 _____ _ B7 V. Description of the invention () Butyl, n = 3 M = 2, R3 = —CH3CH2C (CH2) 3]> 85.5 grams (0.293 Wu Er) of _ (3,5_di_third butyl-cardiohydroxyphenyl) propionate Base ester, 10.1 g (0.075 mol) of Bishen_ (hydroxymethyl) -propane, and 0.19 g (0.002 mol) of sodium acetate were placed, and melted and stirred at 12.0 under nitrogen. .Once the melt appears, carefully evacuate, When heated to an internal temperature of 160 C in methanol produced was distilled off and swing in a cooled downcomer condensed.俟 Internal pressure-reach &lt; 10 milliseconds = just = temperature rise to 180 C and then evacuate to pressure &lt; 丨 millibar. When it reaches ΙΓ = 18〇C, and the pressure is <1 bar, it is kept for one hour, and then between 丨 and 2 hours at an IT = 200 ~ 210C temperature, an excessive amount of _ (3,5- 二 _ 第Tributyl ice was distilled off with methyl phenyl) propionate. At this time, the reaction melt contained only &lt; 0.2% of cold- (3,5-di-third-butyl-4-hydroxyphenyl) propionic acid methyl ester, and ^, ^ 参 _ [冷- The content of (3,5-di-third-butyl-4-hydroxyphenyl) propanylmethoxy] propane &gt; 97%. This colorless reaction melt was filtered, cooled, and allowed to solidify / crystallize. Yield: 95.5%, melting point: 66 ~ 79. 〇. [Amorphous (amorphous) form] <Shili 7: __ ΙΛΔζ ^ Ι-π · 5 -—- Third-butyl-4-methylphenylphenyl ^ 1 ethane [Compound of formula (I), wherein R, and r2 = third butyl, η = 3, m = 2, R3 =-CH3C (CH2) 3]> 85.5 g (0.293 mole) of K3,5_di-third-butyl- 4-Hydroxyphenyl) methyl propionate, 9 g (0.075 mol) of ι, ΐ, ΐ, ΐ-ginsyl- (hydroxymethyl) -ethoxylate, and 0.23 g (0.002 mol) of lithium acetate (present Dihydrate form), and melted and stirred at 120 ° C under nitrogen. Once a melt appeared, carefully evacuate while heating to an internal temperature of 160 ° C. The methanol produced was distilled off and condensed in a cooling downcomer. As soon as the internal pressure reaches <10 19 this paper standard Chinese national standard one ----------- installed -------- order --------- (Please read first Note on the back, please fill out this page again) 593266 A7 __B7 V. Description of the invention () 耄 bar, the internal temperature will be raised to 180 ° C and evacuated to a pressure of <1 mbar. When IT = 180 ° C is reached, and the pressure is q mbar, it is held for one hour, and then between 1 and 2 hours, the temperature at IT = 200 ~ 2100 ° C will be excessively called _ (3,5- 二-第Dibutyl I was distilled off with methyl phenyl) propionate. At this time, the reaction melt contained only <0.2% methyl- (3,5, di-third-butyl-4-hydroxyphenyl) propionate, and dream-[/ 3-(3,5 -Di-Third-Butylhydroxyphenyl) Methylformate: IZ ^ MΛ &gt; 97%. This colorless reaction melt was filtered, cooled and allowed to solidify / crystallize. Yield: 9S%, melting point: 55 ~ 78 ° C. [Amorphous (amorphous) form] '〈Real I-8 ″ ~~ m (3'54 awning tributyl-4-hydroxy benzene) propyl 醯 棊 $$$]] _ "兀 [式 ⑴ 的Compounds, where &amp; and r2 = third butyl, η = 4, m = 2, R3 = C (CH2) 4]> 75.9 g (0.26 旲) million, (3,5_second · third Butyl 4-hydroxyphenyl) methyl propionate, 6.8 g (0.05 mol) of pentaerythritol, and 0.16 g (0.002 mol) of sodium acetate were placed, and at 12 (rc in Melt and stir under nitrogen. Once the melt appears, carefully evacuate while heating to an internal temperature of 160 ~ 170 ° C. Distill off the produced methanol and condense in a cooling downcomer. Once the internal pressure reaches &lt; 10 mbar, raise the internal temperature to 180 ° C and evacuate to pressure &lt; 1 mbar. When IT = 180 ° C and pressure &lt; 1 mbar, hold for one hour, The excess /?-(3,5-di-third-butyl-4-hydroxyphenyl) propanoic acid methyl ester was distilled off at a temperature of IT = 200 to 210 ° C between 1 and 2 hours. At this time The reaction melt contained <0.2% methyl- (3,5-di-third-butyl-4-hydroxyphenyl) propanoate only, and-[/ 5- (3,5- Di-Third-Butyl-4-hydroxyphenyl) propanylmethoxy] methane content> 96%. 20 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) --- -------- Installation -------- Order --------- (Please read the notes on the back before filling this page) 593266 A7 ______ B7 ____ V. Description of the invention ( ) This colorless reaction melt is filtered, cooled and allowed to solidify / crystallize. Yield 96%, melting point 55 ~ 85 ° C. [Amorphous (amorphous) form] This paper size applies Chinese National Standard (CNS) A4 specifications (210 X 297 male f) ----------- install -------- order --------- (Please read the precautions on the back before filling this page)

Claims (1)

593266 r2 A3 B8 C8 D8 VI. Patent application scope Formula II —CmH2m—C—0—R (π) Where: R represents α ~ (: 3 alkyl group, Formula III R3 (〇H) n (Hi) where R3 and η The meaning is the same as above, characterized in that the reaction is carried out at a practically neutral pH in the presence of at least one alkali metal salt of an organic carboxylic acid or a mixture of such alkali metal salts, and the alkali metal salt is dissolved or Suspended in the reaction mixture, wherein: (i) the metal detection salt is composed of an alkali metal cation and an anion of an organic carboxylic acid, and (ii) the organic carboxylic acid is at least partially volatile under the reaction conditions used. 2. The method according to item 1 of the patent application, wherein: the alkali metal salt of the organic acid is a sodium, potassium, and / or lithium salt. 3. The method according to item 1 or 2 of the patent application, wherein : The residual acid used to form the alkali metal salt is an aliphatic saturated or unsaturated c2 ~ c10 (and preferably C2 ~ C6) carboxylic acid. 4. The method according to item 3 of the scope of patent application, wherein: Carboxylic acid consists of the following _______ 2 ------------------------------------------ Order ..... ......... ΙΜΦ (Please read the precautions on the back before copying this page) This paper size is applicable to China Standard (CNS) A4 specifications (⑽χ 297 mm factory one — 593266 A8 B8 C8 D8 VI. Scope of patent application ------------------------- Double · ί! (Please read the notes on the back before writing this page) Selection: Formic acid , Acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-pentanoic acid, trimethylacetic acid, hexanoic acid, n-heptanoic acid or nonanoic acid, malonic acid, maleic acid, fumaric acid, or Monomethyl malonate, fluoroacetic acid, chloroacetic acid, bromoacetic acid, difluoroacetic acid, dichloroacetic acid, trifluoroacetic acid, trichloroacetic acid, α-chloropropionic acid or chloropropionic acid. The method according to item 1 or 2, wherein: the catalyst used is sodium acetate, potassium acetate, lithium acetate, sodium formate, potassium formate, lithium formate, or a mixture of these compounds. 6. If the scope of patent application is the first or second Method, wherein: R! Represents a radical of C1 ~ C4. 7. The method according to item 1 or 2 of the scope of patent application, wherein: R2 represents a linear or branched G ~ C4 alkyl radical 8. The method of claim 6 or 7, wherein: the compound of formula (I) may contain phenyl radicals substituted with K and R2 in different ways in the same molecule. The method of item 1 or 2, wherein: the R4- [NR5—CmH2m—] P radical represents one R4 — [NH —CmH2m—] p or R4 — [N (—CmH2m—) 2] p, and R4 is derived from an alkylene diamine or from a polyalkylene diamine. 10. The method of claim 1 or 2, wherein: R3 represents n-butyl, isobutyl, third butyl, pentyl, isopentyl, hexyl, heptyl, octyl, 2- Ethylhexyl, nonyl, decyl, decyl, dodecyl, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen Decadecyl, and has an increasing number of 30 carbon atoms 3 This paper size applies to Chinese National Standard (CNS) A4 specification (~ 2ϋmm) 593266 B8 C8 D8 Six, related homologous alkyl radicals for patent scope _ Or a mixture of these c4 ~ C3G free radicals, or cyclopentyl and cyclohexyl. 11. The method according to item 1 or 2 of the scope of patent application, wherein: R3 represents an alkylene radical derived by removing the two 0H groups from a divalent alcohol, wherein the alcohol is 1,2- Ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol] , Diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol], glycerol, pentaerythritol [C (CH2OH) 4] Or a similar polyol, polyglycerol, polypentaerythritol. 12. The method of claim 1 or 2, in which: FU represents an alkylene group derived from a diamine by removing its two H2N- groups, which can be interrupted by an NR5-, where the The diamine is 1,2-ethylenediamine, 1,2-propylenediamine, bis (ethylenediamine), or bis (propylenediamine). 13. The method of claim 1 or 2, wherein: R3 represents a branched alkyl-alkylene group derived from the 0H group by removing a trivalent alcohol (polyol), wherein the The alcohol is 1,1,1, -p-hydroxyalkylethane (trimethylolethane) or 1,1,1-p-hydroxyalkylpropane (trimethylolpropane). 14. The method of claim 1 or 2, wherein: R3 represents methane-tetramethylene. 15. The method of claim 1 or 2, wherein: in the compound of formula (I), R! Represents a third butyl group, R2 represents a methyl group or a third butyl group, and R3 represents n-octadecane. Base, a mixture of higher alkyl radicals (C8 to C30 alkyl radicals) with 8 to 30 carbon atoms, or a 4-size paper that applies the Chinese National Standard (CNS) A4 specification (210 &gt; &lt; 297 mm) (Please read the notes on the back before copying this page) 593266 A8 B8 C8 D8 VI. The scope of patent application includes 1,6-hexanediol, triethylene glycol, pentaerythritol, U, l-gins- (hydrocarbylmethylethane), 1, U- Phenyl- (hydrocarbylmethylpropane) derived radicals. 16. The method of claim 1 or 2, wherein: In the formula (I), R4 represents a compound consisting of 1,2,2-ethylenediamine or 1,2-propylenediamine, or di (ethylene Diamine) or bis (propylenediamine) derived radicals. 17. The method of claim 1 or 2, wherein: the compounds of formula (Π) and formula (ΠΙ) together with the catalyst are in an inert condition at a temperature of 90 ~ 120 ° C and under agitation The mixture is heated until there is a melt, and then an esterification reaction is performed under a reduced pressure in a pressure range of 0.1 to 200 mbar and a high temperature range of 14 to 220 ° C. 18. The method according to item 1 or 2 of the scope of patent application, wherein: the ratio of the compound of formula (π) to the compound of formula (II) (calculated using Moire equivalent) is 0.8: 1 to 1.5: 1 range. 19 The method according to the first or second scope of the patent application, wherein: the product of formula (I) can be directly crystallized or cooled by cooling [can seed or not seed], so it can be added without additional Purification steps, such as recrystallization, and reprocessing directly into commercial form. 20. A method as claimed in claim 1 or 2, wherein an alkali metal salt of an organic carboxylic acid or a mixture thereof is used as a catalyst in the production of a compound of formula (I), wherein: the alkali metal of the organic carboxylic acid The salt is preferably sodium acetate, potassium acetate, lithium acetate, sodium formate, potassium formate, lithium formate, or a mixture of these compounds. 21. The method as claimed in claim 20, wherein the catalyst is used in an amount of 0.05 to 3% moles [relative to the amount of the compound of formula ⑴]. _ ____ 5 ^ __ This paper size applies to China National Standard (CNS) A4 (210 X 297 mm). ..........— ΜΦ, (Please read the precautions on the back before filling out this page) 593266 A8 B8 C8 D8 ___ — ™ ———-— VI. Application for Patent Scope 22. —Such as application The compound of formula (I) prepared by the method of item 1 of the patent scope, wherein: η = 3, and R3 represents 1,1,1-shen- (Meganyiyuan), and Ri, R2 and m have patent applications Significance of Scope Item 1. 23. A compound of formula (I) prepared by the method of claim 1 in the scope of patent application, wherein: η = 3, and R3 represents 1,1,1-gins- (methylenepropane), and R15R2 and m It has the meaning of the first scope of patent application. 24. A compound of formula (I) prepared by the method of claim 1 in the scope of patent application, wherein R3 represents a radical Rf [NR5—CmH2m—] p, and R4 is composed of an alkylene diamine or A radical derived from a polyalkylene diamine, and R !, R2 and m have the meaning of the first scope of the patent application. ------------------------ Double .. [丨 丨 丨! 1T ---------------- (Please read the notes on the back before filling out this page) This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) Please apply for W period ~ ^ όΛΙιΊ Case No. category 〇ac6i / 〇 ^ (The above items are to be filled in by the Bureau) 92. 12. 17 #! ^ A4 C4 593266 II Patent Specification Invention I. U-name new Chinese method for producing hydroxyphenyl hexanoate English- Invention I. Creation last name _ First name Nationality Residence and residence Christopher Kreiner Switzerland Switzerland 5073 Giff- No. 10, Brumanstic, Oberkirch City III. Name of applicant (name) Nationality residence, residence (office) Representative name Cibaat Chemicals Holding Company Switzerland, Basel City, Switzerland 4057 No. 141 Bay Street (1) Hans Pett Wittlin Nicole Cork-j- line ------ 1-- This paper size applies to China National Standard (CNS) A4 (210X 297) Mm) loaded, 593266 For making compound of formula VII 〇II 'CmH2m—C—0- -R3 (I) η 1 and r2 are irrelevant to each other to represent c! ~ C8 alkyl, cyclopentyl, or cyclohexyl, m 1, 2, or 3, n 1 ~ 30 ^ Integer R3 — a η-valent linear or branched C4 ~ C30 radical, which can be interrupted by one or several oxygen molecules, or (for η = 1 ~ 12) is a η valent C5 ~ C〗 2 Yunyuan, or a R4-[NR5—CmH2m a] P radical, R4 hydrogen, a η valent linear or branched C4 ~ C3O alkyl radical, the The radical may be interrupted by one or several NR5- groups if necessary, or (for η = 1-12) is a η-valent C5 ~ C12 cycloalkyl group, R5 independently of each other represents hydrogen, methyl or- CmH2m-, P is equivalent to the number of the group [NR5—CmH2m—], this number produces n one CmH2m—free radicals per molecule; this method is to combine a compound of formula (Π) with a compound of formula (ΠΙ) Compound reaction: Using Chinese standard (CNS) A4 specification (210 X 297 mm) ........--------------- · τ ------ -r——Order ---------------- (Please read the notes on the back first to fill in this page)