WO2006109654A1 - トリカルボン酸トリス(アルキル置換シクロヘキシルアミド)の製造方法 - Google Patents
トリカルボン酸トリス(アルキル置換シクロヘキシルアミド)の製造方法 Download PDFInfo
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- WO2006109654A1 WO2006109654A1 PCT/JP2006/307246 JP2006307246W WO2006109654A1 WO 2006109654 A1 WO2006109654 A1 WO 2006109654A1 JP 2006307246 W JP2006307246 W JP 2006307246W WO 2006109654 A1 WO2006109654 A1 WO 2006109654A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/36—Oxygen or sulfur atoms
- C07D207/40—2,5-Pyrrolidine-diones
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
- C07C233/04—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C233/06—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a ring other than a six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/16—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
- C07C233/23—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by a carbon atom of a ring other than a six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Definitions
- the present invention relates to a novel process for producing tricarboxylic acid tris (alkyl-substituted cyclohexylamide), and more specifically, tricarboxylic acid tris (alkyl-substituted cyclohexane) by an amidation reaction of tricarboxylic acid and alkyl-substituted cyclohexylamine. It relates to a method for producing (hexylamide).
- Polyolefin resin is excellent in moldability, mechanical properties, electrical properties, etc.! / As a material for film molding, sheet molding, blow molding, injection molding, etc., it can be applied in various fields. It has been.
- Patent Document 2 1,2,3-propanetricarboxylic acid and cyclohexylamine or 2-methylcyclohexylamine in the presence of triphosphite phosphite and pyridine.
- Patent Document 2 1,2,3-propanetricarboxylic acid tris (cyclohexylamide) and 1,2,3-propanetricarboxylic acid tris (2-methylcyclohexylamide) by reaction with.
- the phosphite triphosphite which is an activator of the carboxyl group
- the force must be used in a large amount, that is, in a stoichiometric amount.
- phosphorus-containing waste liquid is generated, so environmental measures are also required.
- Patent Document 1 Japanese Patent No. 3401868
- Patent Document 2 Japanese Patent Laid-Open No. 7-242610
- Patent Document 3 International Publication No. WOOOZ52089 Pamphlet
- Patent Document 4 Japanese Patent Laid-Open No. 7-309821
- Patent Document 5 Japanese Patent Laid-Open No. 61-000050
- Patent Document 6 Japanese Patent Laid-Open No. 2001-187769
- An object of the present invention is to provide a simple tricarboxylic acid that solves problems such as production and cost associated with the conventional method for producing tricarboxylic acid tris (alkyl-substituted cyclohexylamide) s.
- An object of the present invention is to provide a method for producing tris (alkyl-substituted cyclohexylamide).
- R 2 and R 3 are synonymous with R 2 and IT in the following general formula (2), respectively.
- a side reaction product represented by the following (hereinafter referred to as “amide-imide”) is produced.
- amide-imide A side reaction product represented by the following (hereinafter referred to as “amide-imide”) is produced.
- the present inventors converted tricarboxylic acid and alkyl-substituted cyclohexylamine as a boric acid compound to diboron trioxide in accordance with the method described in JP-A-2001-187769. , And 2-ethyl hexanol as an aliphatic alcohol, and subjected to an amidy reaction, it was found to be extremely low compared to the target tricarboxylic acid tris (alkyl-substituted cyclohexylamide) 1S Seven yields (about 2%) were not obtained.
- the target tricarboxylic acid tris (alkyl-substituted cyclohexyla) is obtained. It was revealed that it was difficult to obtain (mid) in high yield. Therefore, when using boric acid compounds, it seemed impossible to obtain the desired tricarboxylic acid tris (alkyl-substituted cyclohexylamide) in a yield exceeding 20%.
- the crude target product thus obtained includes an amide-imide represented by the general formula (4) as an impurity, a boric acid compound and a phenolic compound used as a catalyst, or phenol.
- These compounds contain borates of oleic compounds, modified di or triamine salts (hereinafter referred to as “amine salts”), which are intermediates of amidation reactions between tricarboxylic acids and alkyl-substituted cyclohexylamines. It has also been found that can be easily purified by a very industrially advantageous method of simply washing with a solvent.
- the present invention has been completed based on these findings, and has been completed.
- the following method for producing tricarboxylic acid tris (alkyl-substituted cyclohexylamide) and purified tricarboxylic acid tris (alkyl-substituted cyclohexane) are described below.
- a method for producing hexylamide) is provided.
- R 1 is a carbon number of 3 to: a trivalent saturated aliphatic hydrocarbon group of L0, a trivalent saturated alicyclic hydrocarbon group of 5 to 15 carbon atoms, or a carbon number of 6 to 15 represents a trivalent aromatic hydrocarbon group.
- R 2 and R 3 are the same or different and each represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms.
- a tricarboxylic acid tris (alkyl-substituted cyclohexylamide) represented by the following general formula (1)
- R 1 has the same meaning as R 1 in the general formula (3).
- R 2 and R 3 have the same meanings as R 2 and R 3 in formula (3), respectively.
- Item 2 The method according to item 1, wherein the boric acid compound power is at least one selected from the group power of orthoboric acid, metaboric acid, pyroboric acid, tetraboric acid, and diboron trioxide.
- Item 3 The method according to Item 1 or 2, wherein the phenol compound is phenol or talesol (that is, o-, m- or p-talesol or a mixture of isomers thereof).
- the borate ester is orthoboric acid, metaboric acid, pyroboric acid, tetraboric acid, and triacid.
- Item 2 The method according to Item 1 above, which is a borate ester of at least one selected boric acid compound and phenol or cresol.
- Item 5 The method according to any one of Items 1 to 4, wherein the amido reaction is carried out at a reaction temperature of 98 ° C to 180 ° C.
- Item 6 The method according to any one of Items 1 to 5, wherein the amidation reaction is carried out in the presence of an azeotropic dehydrating solvent.
- Item 7 The method according to Item 6, wherein the azeotropic dehydration solvent is a saturated aliphatic hydrocarbon, a saturated alicyclic hydrocarbon, an aromatic hydrocarbon, or a mixture thereof.
- Item 8 The method according to Item 7, wherein the azeotropic dehydrating solvent has a boiling point of 120 to 160 ° C.
- boiling point refers to the boiling point under latm unless otherwise specified.
- Tricarboxylic acid tris (alkyl-substituted cyclohexylamide) force 1, 2, 3-propanetricarboxylic acid tris (cyclohexylamide), 1, 2, 3-propanetricarboxylic acid tris (2-methylcyclohexylamide) ), Trimesic acid tris (cyclohexylamide), trimesic acid tris (2-methylcyclohexylamide), 1, 3, 5-cyclohexanetricarboxylic acid tris (cyclohexylamide), or 1, 3, 5-cyclo 9.
- Trimesic acid tris (cyclohexylamide), trimesic acid tris (2-methylcyclohexylamide), 1, 3, 5-cyclohexanetricarboxylic acid tris (cyclohexylamide), or 1, 3, 5-cyclo 9.
- Item 10 The method according to Item 9, wherein the tricarboxylic acid tris (alkyl-substituted cyclohexylamide) force is 1,2,3-propantricarboxylic acid tris (2-methylcyclohexylamide).
- Item 11 The method according to any one of Items 1 to 10, further comprising a step of purifying crude tricarboxylic acid tris (alkyl-substituted cyclohexylamide).
- Item 12 Purifying Process Power Step of washing crude tricarboxylic acid tris (alkyl-substituted cyclohexylamide) with a mixture of an aliphatic alcohol having 1 to 3 carbon atoms or water and an aliphatic alcohol having 1 to 3 carbon atoms Item 12.
- Item 13 The purification step is carried out by measuring the boron content in tricarboxylic acid tris (alkyl-substituted cyclohexylamide) by ICP emission analysis (ie, inductively coupled plasma atomic emission spectrometry). lOOppm or less Item 13. The method according to Item 11 or 12 performed in
- Item 14 A method for producing purified tricarboxylic acid tris (alkyl-substituted cyclohexyl amide), comprising a step of washing crude tricarboxylic acid tris (alkyl-substituted cyclohexyl amide) with a purified solvent.
- Item 15 The method according to Item 14, wherein the purification solvent is an aliphatic alcohol having 1 to 3 carbon atoms or a mixture of water and an aliphatic alcohol having 1 to 3 carbon atoms.
- Item 16 The impurities contained in the crude tricarboxylic acid tris (alkyl-substituted cyclohexylamide) are represented by the general formula (4):
- R 2 and R 3 are the same or different and each represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. ]
- Item 15 The production method according to Item 14, comprising a compound represented by:
- tricarboxylic acid tris (alkyl-substituted cyclohexamide) useful as a transparent glaze agent for polypropylene-based resin is more easily compared with the case where it is produced by a conventional method. And with good productivity.
- the purification of the target product thus obtained is industrially advantageous because it is a very simple method of washing with alcohol or a mixture of water and alcohol.
- the present invention is advantageous in that an object having a good hue (white) can be obtained.
- an object having a good hue (white)
- propanetricarboxylic acid produced by a hydrogen peroxide oxidation reaction in the presence of a phosphotungsten catalyst is used, the reaction solution turns yellow to green, and there is a concern that colored components are adsorbed on the target compound crystals. It was done.
- the production method and purification method of the present invention are adopted. As a result, the desired product (white solid) having a good hue can be obtained.
- the tricarboxylic acid in the present invention has the following general formula (1)
- R 1 is a trivalent saturated aliphatic hydrocarbon group having 3 to 10 carbon atoms, preferably 3 to 8 carbon atoms, more preferably 3 to 6 carbon atoms, 5 to 15 carbon atoms, preferably 5 to 5 carbon atoms. 10, more preferably a trivalent saturated alicyclic hydrocarbon group having 5 to 8 carbon atoms, or a trivalent aromatic hydrocarbon group having 6 to 15 carbon atoms, preferably 6 to 10, more preferably 6 to 8 carbon atoms .
- tricarboxylic acid examples include saturated aliphatic tricarboxylic acid, saturated alicyclic tricarboxylic acid, and aromatic tricarboxylic acid.
- These tri-force rubonic acids represented by the general formula (1) are compounds that are well known and easily available, or can be easily produced by known methods.
- R 1 represents a trivalent organic group obtained by removing three carboxyl groups from the tricarboxylic acid represented by the general formula (1). More specifically, R 1 is a residue formed by removing three carboxyl groups from a saturated aliphatic tricarboxylic acid having 6 to 13, preferably 6 to 11, and more preferably 6 to 9 carbon atoms. To 18, preferably 8 to 13, more preferably 8 to: a residue formed by removing three carboxyl groups from a saturated alicyclic tricarboxylic acid of L 1, or a carbon number of 9 to 18, preferably 9 to 13, more preferably 9 to: represents a residue formed by removing three carboxyl groups from the aromatic tricarboxylic acid of L1.
- saturated aliphatic tricarboxylic acid examples include 1, 2, 3-propanetricarboxylic acid, 1-methinoleol 1, 2, 3-pronone tricanolevonic acid, 2-methinoleol 1, 2, 3— Protontricarboxylic acid, 1-ethyl-1,2,3-propanetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, etc. I can get lost.
- 1,2,3-propanetricarboxylic acid is particularly preferable.
- the Japanese aliphatic tricarboxylic acid may be a monoanhydride in which two of the three carboxyl groups form an acid anhydride group! /.
- the saturated alicyclic tricarboxylic acid may be substituted with a saturated aliphatic group, or may be substituted with a cyclopentane tricarboxylic acid, a saturated aliphatic group, cyclohexane tricarboxylic acid, Substitution with a saturated aliphatic group may be exemplified by decahydronaphthalene tricarboxylic acid and the like.
- examples of the saturated aliphatic group include an alkyl group having 1 to 3 carbon atoms. When the substituent is present, the number thereof is 1 or 2, particularly 1.
- Saturated alicyclic tricarboxylic acids include 1, 2, 4 cyclopentane tricarboxylic acid, 1, 2, 3-cyclohexane tricarboxylic acid, 4-methyl 1, 2, 3 cyclohexane tricarboxylic acid, 1, 2, 4 Cyclohexanetricarboxylic acid, 6-methyl 1, 2, 4 Cyclohexanetriforce Rubonic acid, 1, 3, 5 Cyclohexanetricarboxylic acid, 1, 2, 4 Decahydronaphthalene Recarboxylic acid, 1, 2, 5 Examples include decahydronaphthalene tricarboxylic acid. Of these, 1,3,5 cyclohexanetricarboxylic acid is particularly preferable.
- saturated alicyclic tricarboxylic acids may be monoanhydrides in which two of the three carboxyl groups form an acid anhydride group.
- aromatic tricarboxylic acid examples include trimellitic acid, trimesic acid, 1,2,3-benzenetricarboxylic acid, 1,2,4 naphthalenetricarboxylic acid, 1,2,5 naphthalenetricarboxylic acid 1, 4, 5 naphthalene tricarboxylic acid, 2, 3, 6 naphthalene tricarboxylic acid, 1, 3, 6 naphthalene tricarboxylic acid and the like.
- aromatic ring of these aromatic tricarboxylic acids is substituted with a saturated aliphatic group are also included.
- examples of the saturated aliphatic group include an alkyl group having 1 to 3 carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and the like.
- the number thereof is 1 or 2, particularly 1.
- aromatic tricarboxylic acids may also be monoanhydrides in which two of the three carboxyl groups form an acid anhydride group. Of these, trimesic acid is particularly preferable.
- R 2 and R 3 each represent a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, which may be the same or different.
- the linear or branched alkyl group having 1 to 4 carbon atoms represented by R 2 and R 3 includes a methyl group, an ethyl group, and a propyl group. Examples thereof include isopropyl group, butyl group, isobutyl group, sec butyl group, and tert butyl group. Among these, an alkyl group having 1 to 3 carbon atoms, particularly a methyl group, an ethyl group, an n-propyl group, and an i-propyl group are preferable.
- one of R 2 and R 3 is preferably a hydrogen atom, and the other is preferably an alkyl group having 1 to 4 carbon atoms, particularly a methyl group, an ethyl group, an n-propyl group, or an i-propyl group.
- the substitution position of the alkyl group is not particularly limited, but it is preferably the 2-position or 4-position with respect to the amino group.
- both R 2 and R 3 are hydrogen atoms.
- alkyl-substituted cyclohexylamines represented by the general formula (2) are compounds that are well-known and easily available, or can be easily produced by known methods.
- alkyl-substituted cyclohexylamine represented by the general formula (2) include cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, 2-ethylcyclohexamine.
- alkyl-substituted cyclohexylamines can be used singly or in combination of two or more. Accordingly, in the present specification and claims, the three force rubamoyl groups in the general formula (3) may be the same or different.
- Trimesic acid tris (2-methylcyclohexylamide),
- Trimesic acid tris (4-methylcyclohexylamide) and the like.
- Trimesic acid tris (2-methylcyclohexylamide) is preferred.
- 1,2,3-propanetricarboxylic acid tris (2-methylcyclohexylamide) and trimesic acid tris (cyclohexylamide) are more preferable, in particular, 1,2,3-propanetricarboxylic acid tris ( 2-Methylcyclohexylamide) is preferred!
- the method for producing tricarboxylic acid tris (alkyl-substituted cyclohexylamide) according to the present invention can be prepared by, for example, preparing a boric acid compound and a phenolic compound in a mixed solution of a tricarboxylic acid and an alkyl-substituted cyclohexylamine or a conventional method in advance. Simply add the boric acid ester of the boric acid compound and phenolic compound, and heat in the presence or absence of the azeotropic dehydration solvent. Hexylamide) can be produced.
- the above alkyl-substituted cyclohexylamine is a reaction substrate, it is considered to function as a reaction solvent.
- the phenol compound is a component of the catalyst, but is considered to function as a reaction solvent.
- the heating temperature during the reaction is preferably 98 to 180 ° C, more preferably 120 to 160 ° C.
- the reaction is promoted as the heating temperature is higher, in order to remove water produced by the reaction, and a temperature of 100 ° C. or higher is preferred, but 120 to 160 ° C. is particularly preferred in order to suppress side reactions.
- a temperature at which reflux continuously occurs in the reaction system is preferable.
- the reaction can usually be performed at atmospheric pressure, but the reaction system may be depressurized in order to promote the removal of moisture from the reaction mixture.
- the reaction atmosphere is not particularly limited, but it is performed in the presence of an inert gas such as nitrogen or argon, or in an inert gas stream. It is preferable.
- the reaction time is preferably 0.1 to 50 hours, and more preferably 1 to 30 hours.
- the azeotropic dehydrating solvent may or may not be used, but the azeotropic dewatering agent is preferably used for promoting the reaction.
- the azeotropic dehydration solvent saturated aliphatic hydrocarbons, saturated alicyclic hydrocarbons or aromatic hydrocarbons having a boiling point (boiling point below 1 atm, hereinafter the same) are preferred.
- azeotropic dehydrating solvent having a boiling point in the range of 120 to 160 ° C is preferred.
- an azeotropic dehydrating solvent mixture adjusted to have a boiling point of 130 to 150 ° C by appropriately mixing xylene and these solvents.
- U ⁇ Prefer U ⁇ .
- the amount used is not particularly limited, but is usually 500 to 5000 parts by weight, preferably ⁇ 800 to 2500 parts by weight with respect to 100 parts by weight of tricarboxylic acid. It is a range.
- the ratio of the tricarboxylic acid and the alkyl-substituted cyclohexylamine used is more preferably 3 to 50 mol of the alkyl-substituted cyclohexylamine with respect to 1 mol of the tricarboxylic acid. Is in the range of 3-10 mol, particularly preferably in the range of 3-6 mol.
- the alkyl-substituted cyclohexylamine used in excess can be reused after separation from the target product produced after the reaction.
- a boric acid compound capable of forming a phenolic compound and a phosphonic acid ester particularly an inorganic boric acid compound
- specific examples include orthoboric acid, metaboric acid, pyroboric acid, tetraboric acid, and diboron trioxide. Of these, orthoboric acid and boron trioxide are particularly preferred.
- Orthoboric acid is particularly preferable because it can be easily dissolved in a purification solvent used in the purification step described later and easily separated from the target product. These may be used alone or in combination of two or more.
- the amount of the boric acid compound to be used is not particularly limited, but is usually in the range of 0.1 to 10 mol, preferably 0.5 to 5 mol, with respect to 1 mol of the tricarboxylic acid.
- the amount is less than 1 mol, the reaction promoting effect tends to be insufficient.
- the amount exceeds 10 mol, the reaction promoting effect corresponding to the amount used tends to be difficult to obtain. It is done.
- the phenolic compound is not particularly limited as long as it can form a boric acid ester with the boric acid compound, but generally 1-2 hydroxy groups, in particular, One is preferable, and benzene which may further have 1 to 3, more preferably 1 to 2 substituents is preferable.
- substituents include an alkyl group having 1 to 3 carbon atoms, specifically, a methyl group, an ethyl group, and an iso-propyl group.
- phenol compound examples include phenol, m-cresol, o-cresol, p-cresol, p-methoxyphenol, xylenol, catechol, and the like. These may be used alone or in combination of two or more. It can also be used. Of these, phenol and cresol are particularly preferred.
- the amount of the phenol compound used is not particularly limited, but is usually in the range of 0.5 to 20 mol, preferably 1.0 to 10 mol, per 1 mol of the tricarboxylic acid.
- the amount is less than 0.5 mol, the reaction promoting effect tends to be insufficient.
- the amount exceeds 20 mol, the reaction promoting effect corresponding to the amount used tends to be difficult to obtain. Is seen.
- boric acid ester of boric acid compound and phenolic compound examples include boric acid ester of boric acid compound and phenolic compound, and boric acid, among others.
- a borate ester of a compound and talesol is particularly preferred.
- the boric acid ester can be easily prepared by dehydrating and condensing a boric acid compound and a phenol compound in the presence of an azeotropic dehydrating solvent according to a conventional method (see Example 4 described later).
- azeotropic dehydration solvent those exemplified with respect to the amidation reaction, and deviations can be used.
- the amount of the boric acid ester used is not particularly limited, but is usually in the range of 0.1 to 10 mol, preferably 0.5 to 5 mol, per 1 mol of the tricarboxylic acid. 0. If less than 1 mole On the other hand, there is a tendency that the reaction promoting effect is not sufficient. On the other hand, even if the amount exceeds 10 mol, there is a tendency that it is difficult to obtain the reaction promoting effect corresponding to the amount used.
- the method for recovering the desired tricarboxylic acid tris (alkyl-substituted cyclohexylamide) after completion of the reaction can be appropriately selected.
- the reaction mixture force after completion of the amidation reaction can be isolated using a conventional method such as filtration or centrifugation.
- the yield of crude tricarboxylic acid tris (alkyl-substituted cyclohexylamide) having a high conversion rate of the starting tricarboxylic acid is satisfactory.
- the use of a mixture of boric acid compounds and phenolic compounds or a phenolic folate ester compared with the case where the boric acid compound is used alone, the imide ring Formation is suppressed and the yield of tricarboxylic acid tris (alkyl-substituted cyclohexylamide) is significantly improved.
- the reaction mother liquor obtained by filtering the target product contains tricarboxylic acid, alkyl-substituted cyclohexylamine, and an azeotropic dehydration solvent, if necessary. Can be added to the amidy reaction again.
- the obtained solid that is, crude tricarboxylic acid tris (alkyl-substituted cyclohexylamide), as impurities, an amide-imide represented by the general formula (4), a fluoric acid compound and a phenol compound used as a catalyst, or It contains boric acid esters and amine salts of phenolic compounds.
- the impurities contain both organic and inorganic substances! /, It was considered difficult to remove by a conventional purification method such as recrystallization or a long operation time. However, according to the study by the present inventors, unexpectedly, these impurities were removed all at once by a simple method of washing with a solvent, and high-purity tricarboxylic acid tris (alkyl-substituted cyclohexane) was obtained. It has been found that (xylamide) can be produced.
- the present invention provides the above-mentioned crude tricarboxylic acid tris (alkyl-substituted cyclohexyla).
- the present invention also provides a method for producing purified tricarboxylic acid tris (alkyl-substituted cyclohexylamide) including a step of washing (mid) with a solvent.
- the solvent used for the purification is not particularly limited as long as it is a solvent that can dissolve the impurities contained in the crude tricarboxylic acid tris (alkyl-substituted cyclohexylamide). .
- Examples of the purification solvent include lower aliphatic alcohols having 1 to 3 carbon atoms such as methanol, ethanol, and isopropanol, or mixed alcohols thereof, or mixed solvents of water and lower aliphatic alcohols having 1 to 3 carbon atoms.
- lower aliphatic alcohols having 1 to 3 carbon atoms such as methanol, ethanol, and isopropanol, or mixed alcohols thereof, or mixed solvents of water and lower aliphatic alcohols having 1 to 3 carbon atoms.
- methanol and ethanol are preferable.
- the ratio of water and lower alcohol can be appropriately selected from a wide range.
- water: lower alcohol 9: 1 to 1: 9, especially 5: 5 It is preferable to be about ⁇ 1: 9.
- the amount of the lower alcohol used is not particularly limited, but is usually preferably 200 to 5000 parts by weight with respect to 100 parts by weight of crude tricarboxylic acid tris (alkyl-substituted cyclohexylamide).
- crude tricarboxylic acid tris alkyl-substituted cyclohexylamide.
- the amount used when a mixture of water and a lower alcohol is not particularly limited, but is usually 200 to 5,000 weight repulsive force with respect to 100 parts by weight of crude tricarboxylic acid tris (alkyl-substituted cyclohexylamide). I like it!
- the target product (crude tricarboxylic acid tris (alkyl-substituted cyclohexylamide)) separated by filtration is dispersed in a purification solvent, and the temperature is within the range of room temperature to the boiling temperature of the purification solvent.
- a method of stirring and mixing at a temperature generally room temperature to 100 ° C, preferably room temperature to 90 ° C, more preferably about room temperature to 80 ° C
- purifying a target solvent with a purified solvent etc.
- the degree of purification in the purification step can be appropriately selected according to the type and amount of the purification solvent, the washing time, the washing temperature, and the like.
- the resulting tricarboxylic acid tris alkyl ICP emission analysis (i.e., inductively coupled plasma atomic emission spectrometry) of 7-boron boron content of lOOppm or less, preferably 50ppm or less, more preferably It is industrially preferable to purify to 20 ppm or less.
- the yield is based on the starting tricarboxylic acid. It has been confirmed from FT-IR that the raw material triforce rubonic acid forms an amine salt that is a reaction intermediate with 2-methylcyclohexylamine, and the conversion rate is 100%. Since the obtained target product is almost insoluble under the following reaction conditions, the yield is almost equal to the selectivity.
- Carrier gas He, 150kPa
- Measurement was performed using an ICP emission spectrometer (trade name “Optima 2000 DV”, manufactured by Perkin Elma Co., Ltd.).
- 1, 2, 3-propanetricarboxylic acid (manufactured by Nacalai Tester Co., Ltd.) 3 in a 200m 1 4-separable flask equipped with a mechanical stirrer, thermometer, and water separator fitted with a reflux condenser 52 g (20 mmol), 2-methylcyclohexylamine (13.6 g, 120 mmol), Talesol (manufactured by Nacalai Testa) 6.5 g (60 mmol), diboron trioxide 0.5 g (7.2 mmol) and xylene 80 g was heated at the reflux temperature of the azeotropic solvent for 3 hours under a nitrogen atmosphere, and the amidy reaction was carried out while continuously removing the produced water azeotropically. After completion of the reaction, the precipitated solid was filtered under reduced pressure to obtain crude 1,2,3-propanetricarboxylic acid tris (2-methylcyclohexylamide) as a white solid.
- the resulting white solid was stirred and washed in 100 ml of methanol at room temperature for 1 hour, filtered, and dried under reduced pressure at 120 ° C. for 2 hours to obtain purified 1,2,3-propanetricarboxylic acid tris (2 — 4.61 g (yield 49.9%) of methylcyclohexylamide) was obtained.
- the obtained white solid had a GC purity of 99.7%, and the structure thereof was confirmed to have the structure of the target product by the following measurement.
- 1, 2, 3-propanetricarboxylic acid 3.52 g (20 mmol), 2-methylcyclohexylamine 13.6 g (120 mmol), trimesic acid 4.20 g instead of 1.0 g (14 mmol) (20 mmol), cyclohexylamine (17.8 g, 180 mmol) and orthoboric acid (1.0 g, 16 mmol) and boric acid as in Example 4 except that the reaction time of the amidation reaction was 8 hours. Preparation of ester, amidation reaction and purification were carried out to obtain 7.18 g (yield 79.2%) of white solid trimesic acid tris (cyclohexylamide).
- 1,2,3-Prononetricanolevonic acid 3.52 g (20 mmol)
- 1,3,5-cyclohexanetricarboxylic acid 4.32 g (20 mmol) instead of 1.0 g (14 mmol)
- the boric acid ester was prepared, amidated, and purified in the same manner as in Example 4 to obtain 1,3,5-cyclohexanetricarboxylic acid tris as a white solid.
- (2-Methylcyclohexylamide) 8.02g (yield 80.3%) was obtained.
- Tricarboxylic acid tris (alkyl-substituted cyclohexyl amide) requires expensive processes that require a complicated process until the production of the tricarboxylic acid tris (alkyl-substituted cyclohexylamide) until now, or a large amount of phosphorus-containing waste is generated. There was a need.
- tricarboxylic acid tris (alkyl-substituted cyclohexylamide) is industrially simple, high purity, high yield, and industrially advantageous productivity. It became possible to manufacture by an excellent method.
- This tricarboxylic acid tris (alkyl-substituted cyclohexylamide) exhibits excellent thermal stability, and can act as a transparent glaze agent and impart excellent transparency to polypropylene-based resin. .
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
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KR1020077025695A KR101230177B1 (ko) | 2005-04-07 | 2006-04-05 | 트리카르복실산 트리스(알킬 치환 시클로헥실아미드)의제조 방법 |
BRPI0610700-1A BRPI0610700A2 (pt) | 2005-04-07 | 2006-04-05 | processo para a produção de tris(ciclohexilamida substituida com alquila) de ácido tricarboxìlico |
EP06731194A EP1867630B1 (en) | 2005-04-07 | 2006-04-05 | Process for producing tricarboxylic acid tris(alkyl-substituted cyclohexylamide) |
US11/911,054 US7745661B2 (en) | 2005-04-07 | 2006-04-05 | Process for producing tricarboxylic acid tris (alkyl-substituted cyclohexylamide) |
DE602006017671T DE602006017671D1 (de) | 2005-04-07 | 2006-04-05 | Verfahren zur herstellung von tricarbonsäuretris(alkylsubstituiertes cyclohexylamid) |
JP2007512939A JP4978466B2 (ja) | 2005-04-07 | 2006-04-05 | トリカルボン酸トリス(アルキル置換シクロヘキシルアミド)の製造方法 |
CN2006800114769A CN101155776B (zh) | 2005-04-07 | 2006-04-05 | 三羧酸三(烷基取代的环己酰胺)的制造方法 |
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EP (1) | EP1867630B1 (ja) |
JP (1) | JP4978466B2 (ja) |
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CN (1) | CN101155776B (ja) |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008255325A (ja) * | 2006-11-22 | 2008-10-23 | Japan Polypropylene Corp | プロピレン系樹脂組成物およびその成形品 |
JP2009120803A (ja) * | 2007-10-24 | 2009-06-04 | Japan Polypropylene Corp | プロピレン系樹脂組成物およびその成形品 |
CN101909889B (zh) * | 2008-03-06 | 2013-10-16 | 三得为株式会社 | 热成形薄板层压用薄膜 |
Families Citing this family (3)
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CN104230739B (zh) * | 2014-08-23 | 2016-07-20 | 山西省化工研究所(有限公司) | 用均苯三甲酸生产n, nˊ,nˊˊ-三环己基-1,3,5-苯酰胺的工艺 |
CN107793325B (zh) * | 2017-11-10 | 2020-01-24 | 河南省化工研究所有限责任公司 | 一种制备合成辣椒素的方法 |
CN113024398B (zh) * | 2021-03-15 | 2023-12-19 | 遂宁晶安科技有限公司 | 辣椒素的制备方法及利用该方法制备得到的辣椒素 |
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JPH07242610A (ja) * | 1994-03-07 | 1995-09-19 | New Japan Chem Co Ltd | 新規なアミド系化合物 |
JP2001187769A (ja) * | 1999-10-20 | 2001-07-10 | Ajinomoto Co Inc | N−アシルアミノ酸アミドの製造方法 |
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JPS6150A (ja) * | 1984-02-17 | 1986-01-06 | Ajinomoto Co Inc | Ν−アシルアミノ酸アミドの製造方法 |
JP3401868B2 (ja) | 1992-10-22 | 2003-04-28 | 新日本理化株式会社 | ポリプロピレン系樹脂組成物 |
JP2985662B2 (ja) | 1994-05-19 | 1999-12-06 | 新日本理化株式会社 | 脂肪族多価カルボン酸アミド類の製造方法 |
US5973076A (en) * | 1995-05-31 | 1999-10-26 | New Japan Chemical Co., Ltd. | Polybutene-1 resin composition and a method of accelerating the crystal transformation thereof |
JP3567533B2 (ja) * | 1994-06-01 | 2004-09-22 | 新日本理化株式会社 | ポリブテン−1樹脂組成物 |
KR20020010578A (ko) | 1999-03-05 | 2002-02-04 | 시바 스폐셜티 케미칼스 홀딩 인코포레이티드 | 결정성 열가소성 중합체용 핵생성제 |
US6335468B1 (en) | 1999-10-20 | 2002-01-01 | Ajinomoto Co., Inc. | Process for production N-acyl amino acid amide |
CN100591716C (zh) | 2000-12-06 | 2010-02-24 | 西巴特殊化学品控股有限公司 | 聚丙烯树脂组合物 |
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- 2006-04-05 WO PCT/JP2006/307246 patent/WO2006109654A1/ja active Application Filing
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- 2006-04-05 DE DE602006017671T patent/DE602006017671D1/de active Active
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JPH07242610A (ja) * | 1994-03-07 | 1995-09-19 | New Japan Chem Co Ltd | 新規なアミド系化合物 |
JP2001187769A (ja) * | 1999-10-20 | 2001-07-10 | Ajinomoto Co Inc | N−アシルアミノ酸アミドの製造方法 |
JP2002265472A (ja) * | 2001-03-13 | 2002-09-18 | Japan Science & Technology Corp | アミド脱水縮合触媒として有用なパーフルオロアルキルフェニルホウ酸 |
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JP2009120803A (ja) * | 2007-10-24 | 2009-06-04 | Japan Polypropylene Corp | プロピレン系樹脂組成物およびその成形品 |
CN101909889B (zh) * | 2008-03-06 | 2013-10-16 | 三得为株式会社 | 热成形薄板层压用薄膜 |
TWI451971B (zh) * | 2008-03-06 | 2014-09-11 | Sun Tox Co Ltd | As a film for thermoforming sheet laminates |
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EP1867630A4 (en) | 2009-05-06 |
TWI364411B (ja) | 2012-05-21 |
CN101155776A (zh) | 2008-04-02 |
DE602006017671D1 (de) | 2010-12-02 |
KR20070116690A (ko) | 2007-12-10 |
US20090069599A1 (en) | 2009-03-12 |
KR101230177B1 (ko) | 2013-02-06 |
US7745661B2 (en) | 2010-06-29 |
JPWO2006109654A1 (ja) | 2008-11-13 |
TW200642993A (en) | 2006-12-16 |
JP4978466B2 (ja) | 2012-07-18 |
EP1867630A1 (en) | 2007-12-19 |
BRPI0610700A2 (pt) | 2010-07-20 |
EP1867630B1 (en) | 2010-10-20 |
CN101155776B (zh) | 2011-05-04 |
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