Ester Compounds

Abstract

[Problem] To provide an internal donor component capable of producing, with high productivity, a propylene polymer having extremely high stereoregularity when used mainly as a solid titanium catalyst component. [Solution] A polyol ester compound having a specific polycyclic structure represented by formula (1). This ester compound is characterized in that sites including a C-R3 structure and a C-R4 structure satisfy a specific relationship.

Description

[Technical field]

[0001] The present invention relates to novel ester compounds. [Background technology]

[0002] As prior art related to ester compounds, there are many disclosures related to their use as additives such as resin additives, cosmetics and topical skin preparations, bactericidal compositions, antioxidants, chelating agents, etc. One of the known uses is that of Mg compound-supported titanium catalysts for olefin polymerization.

[0003] Olefin polymerization catalysts are one of the technologies that have made great advances since the discovery of the so-called Ziegler-Natta catalyst in 1953, when Ziegler reported that ethylene could be polymerized at low pressure by combining titanium tetrachloride with an organoaluminum compound, followed by Natta's report of the first propylene polymerization by combining titanium trichloride with a halogen-containing organoaluminum compound. Among them, it was discovered that a catalyst containing titanium tetrachloride, a magnesium compound, and a Lewis base, called the third generation catalyst, can achieve both high polymerization activity (high productivity) and high stereoregularity in propylene polymerization. This became one of the opportunities for propylene polymers (polypropylene) to spread around the world.

[0004] In addition, it has been found that Lewis bases (hereinafter also referred to as "internal donors"), which are one of the main components of the above-mentioned third-generation catalyst components (hereinafter also referred to as "solid titanium catalyst components"), have a significant effect on the catalytic performance, and various Lewis bases have been developed to date.

[0005] Examples of Lewis bases used in Ziegler-Natta catalysts include ethyl benzoate, phthalate esters, 1,3-diketones (Patent Document 1), malonate esters (Patent Document 2), succinate esters (Patent Document 3), 2,4-pentanediol diesters (Patent Document 4), naphthalenediol diesters (Patent Document 5), and catechol diesters (Patent Document 6). Even now, this is a field in which research and development is being actively conducted, primarily by private companies. Furthermore, many methods have been disclosed for elementary reactions for synthesizing various ester compounds (for example, Patent Documents 7 to 10, Non-Patent Documents 1 to 19). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2005-226076 A [Patent Document 2] Special Publication No. 2000-516987 [Patent Document 3] Special Publication No. 2002-542347 [Patent Document 4] Special Publication No. 2005-517746 [Patent Document 5] Special Publication No. 2011-529888 [Patent Document 6] Special Publication No. 2014-500390 [Patent Document 7] JP2008-247796Publication [Patent Document 8] International Publication No. 2008 / 062553 [Patent Document 9] US Patent Application Publication No. 2018 / 0149973 [Patent Document 10] US Patent Application Publication No. 2002 / 0162991 [Non-patent literature]

[0007] [Non-Patent Document 1] Journal of Organic Chemistry,1969,34,3579-3582 [Non-licensed document 2] Journal of Organic Chemistry,1971,36,3979-3987 [Non-licensed document 3] Organic Letters,2004,6,1589-1592

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Non-licensed literature 9

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Non-licensed Document 14

[0008] Propylene polymers have heat resistance and rigidity similar to those of general-purpose engineering plastics, while being composed almost entirely of carbon and hydrogen, and therefore have the advantage of producing less toxic gases even when burned.

[0009] Due to recent advances in molding technology, it is possible to achieve higher physical properties (rigidity, heat resistance, etc.) by using propylene polymers with higher stereoregularity than ever before. Therefore, the market demands propylene polymers with higher stereoregularity. In addition, from the viewpoints of resource conservation and environmental protection, there is also a demand for a method for producing propylene polymers with high productivity.

[0010] Therefore, an object of the present invention is to provide an internal donor component suitable for a solid titanium catalyst component, which can produce a propylene polymer with extremely high stereoregularity with high productivity (high activity) when used in the solid titanium catalyst component. [Means for solving the problem]

[0011] As a result of intensive research aimed at solving the above problems, the present inventors have found that an ester compound having a specific cyclic structure is suitable as, for example, a Lewis base for a solid titanium catalyst component, and have completed the present invention. The present invention relates to, for example, the following [1] to [4].

[0012] [1] A cyclic polyvalent ester group-containing compound (A) represented by the following formula (1):

[0013] [ka] [In formula (1), m and n are integers of 1 to 5 and satisfy the relationship m+n≧4. R 1 and R 2 are each a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, 3 , multiple R 4 , R 5 ~R 8 are each a group selected from a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom; R 1 ~R 8 R may have a hydrogen atom, a carbon atom, or both substituted with at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, a phosphorus atom, a halogen atom, and a silicon atom. 3 ~R 8 are independent of each other, but adjacent R 3 They may be directly bonded to each other to form a multiple bond. 4 They may be directly bonded to each other to form a multiple bond. 3 , multiple R 4 may be bonded to each other to form a ring structure.

[0014] [2] The ester compound (A) according to item [1], wherein m is 2 or more and n is 2 or more. [3] R 1 and R2 is a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, the ester compound (A) according to item [1].

[0015] [4] R 3 ~R 8 are each a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkenyloxy group, a substituted or unsubstituted cycloalkyloxy group, a substituted or unsubstituted cycloalkenyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, or a substituted or unsubstituted heteroaryloxy group. The ester compound (A) according to item [1]. Effect of the Invention

[0016] The ester compound of the present invention can be used, for example, as a resin additive, a cosmetic or external skin preparation, a germicidal composition, an antioxidant, a chelating agent, or a Ziegler-Natta catalyst. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] The ester compound according to the present invention will be described in more detail below. The ester compound according to the present invention (hereinafter also referred to as "ester compound (A)") is represented by the following general formula (1).

[0018] [ka]

[0019] In the above formula (1), R 1 and R 2 Each of R is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms.1 , R 2 The hydrogen atom, the carbon atom, or both of them may be substituted with at least one atom selected from the group consisting of nitrogen atoms, oxygen atoms, phosphorus atoms, halogen atoms, and silicon atoms (hereinafter, sometimes referred to as heteroatoms). The heteroatom group is preferably the group consisting of nitrogen atoms, oxygen atoms, phosphorus atoms, and silicon atoms, more preferably the group consisting of nitrogen atoms, oxygen atoms, and silicon atoms, and even more preferably the group consisting of oxygen atoms and silicon atoms.

[0020] The substituent containing a heteroatom is, for example, a heteroatom-containing hydrocarbon group, a heteroatom-containing aryl group is a preferred example, and an oxygen-containing aryl group is a particularly preferred example.The heteroatom-containing aryl group may, for example, be a pyrrole ring, a pyran ring, or the like, which has a structure in which the aryl structure itself contains a heteroatom as a basic skeleton, or a heteroatom-containing hydrocarbon group such as an alkoxy group is bonded to a benzene ring.

[0021] In addition, the R 1 and R 2 is preferably a hydrocarbon group having 2 to 20 carbon atoms, and the lower limit of the number of carbon atoms is more preferably 4, and even more preferably 6. A more detailed structure will be described later.

[0022] In the present invention, the description of an "atom" such as a halogen atom or a hydrogen atom in the description of a substituent may of course refer to an embodiment having a bond, such as "H-" or "Cl-", as represented in a structural formula.

[0023] Examples of the hydrocarbon group include a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, and a substituted or unsubstituted aryl group.

[0024] Examples of the hydrocarbon group containing a heteroatom (hereinafter sometimes referred to as a heteroatom-containing hydrocarbon group) include a substituted or unsubstituted heteroatom-containing alkyl group and a substituted or unsubstituted heteroaryl group.

[0025] Examples of the hydrocarbon group and the heteroatom-containing hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroatom-containing alkyl group, and a heteroaryl group. The number of carbon atoms in these groups is preferably 1 to 20. The lower limit is preferably 2, more preferably 3, and particularly preferably 4. However, in the case of an aryl group, the preferred lower limit is 6. On the other hand, the upper limit is preferably 18, more preferably 15, even more preferably 10, and particularly preferably 6. In the case of a heteroaryl group, it is preferable that the heteroaryl group has at least one 5-membered ring structure, more preferably has at least one 5- to 7-membered ring structure, and even more preferably has at least one 5- or 6-membered ring structure.

[0026] Preferred R 1 and R 2 each is a group selected from a substituted or unsubstituted alkyl group having 4 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 4 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 4 to 20 carbon atoms, a substituted or unsubstituted alkynyl group having 4 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted heteroatom-containing alkyl group having 4 to 20 carbon atoms, or a substituted or unsubstituted heteroaryl group having 4 to 20 carbon atoms.

[0027] More preferred R 1 and R 2 are each a group selected from a substituted or unsubstituted alkyl group having 4 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, a substituted or unsubstituted heteroatom-containing alkyl group having 4 to 10 carbon atoms, or a substituted or unsubstituted heteroaryl group having 4 to 15 carbon atoms.

[0028] Particularly preferred R1 and R 2 are each a substituted or unsubstituted aryl group having 6 to 10 carbon atoms and a substituted or unsubstituted heteroaryl group having 4 to 10 carbon atoms. Particularly preferably, it is a group selected from substituted or unsubstituted aryl groups having 6 to 10 carbon atoms. The R 1 , R 2 is R 3 ~R 8 may be bonded to form a monocyclic structure or a polycyclic structure. 1 , R 2 may be bonded to each other to form a ring structure.

[0029] <R 3 ~R 8 > In the above formula (1), R 3 ~R 8 are each selected from a hydrogen atom, a halogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group.

[0030] As the heteroatom group, a preferred example is a group consisting of a nitrogen atom, an oxygen atom, a phosphorus atom, a halogen atom and a silicon atom. More preferably, it is a group consisting of a nitrogen atom, an oxygen atom, a phosphorus atom and a silicon atom, further preferably, it is a group consisting of a nitrogen atom, an oxygen atom and a silicon atom, and particularly preferably, it is a group consisting of an oxygen atom and a silicon atom. When it is an oxygen atom-containing substituent, it is preferably an ether type (a substituent containing a COC type structure), and it is preferable to avoid a structure containing an oxygen double bond.

[0031] Examples of the hydrocarbon group include a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, and a substituted or unsubstituted aryl group.

[0032] Examples of the heteroatom-containing hydrocarbon group include a heteroatom-containing aryl group such as a substituted or unsubstituted heteroatom-containing alkyl group, a substituted or unsubstituted heteroaryl group, etc. Examples of the heteroatom-containing aryl group include a group having a basic skeleton in which the aryl structure itself contains a heteroatom, such as a pyrrole ring or a pyran ring, and a group in which a substituent such as a heteroatom-containing hydrocarbon group, such as an alkoxy group, is bonded to a benzene ring.

[0033] Examples of the hydrocarbon group and the heteroatom-containing hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroatom-containing alkyl group, and a heteroaryl group. The number of carbon atoms in these groups is preferably 1 to 20. The lower limit is preferably 2, and more preferably 3. However, in the case of an aryl group, the preferred lower limit is 6. On the other hand, the upper limit is preferably 18, more preferably 15, even more preferably 10, and particularly preferably 6. In the case of a heteroaryl group, it is preferable that the heteroaryl group has at least one 5-membered ring structure, more preferably has at least one 5- to 7-membered ring structure, and even more preferably has at least one 5- or 6-membered ring structure.

[0034] At least one of R3 to R8 is preferably a substituent according to the above-mentioned preferred embodiment, and more preferably all of them are a substituent according to the above-mentioned preferred embodiment.

[0035] R 3 ~R 8 At least one of the substituents may be a substituent other than hydrogen. Furthermore, it may be preferable that two or more of the substituents are substituents other than hydrogen. In this case, two or more types may be mixed, or all may be a single substituent. Furthermore, it may be preferable that one or more of the carbon atoms forming the ring structure is a quaternary carbon. More preferably, R 7 and / or R 8 In some cases, it may be preferable that R is a substituent other than hydrogen. 7and / or R 8 is a hydrocarbon group, a heteroatom-containing hydrocarbon group, and particularly a hydrocarbon group. In the above-mentioned embodiment, for example, when the ester compound of the present invention is used as a component of an olefin polymerization catalyst, the performance balance may be improved. Specific examples of the above-mentioned performance include reaction control performance such as activity, stereospecificity, and molecular weight controllability.

[0036] The above R 3 There may be multiple Rs. In that case, Rs bonded to different carbons 3 Although they are independent of each other, R bonded to adjacent carbons 3 may be directly bonded to each other to form a multiple bond. Here, the independent relationship means that there are multiple R 3 This means that the structural formulas can be clearly distinguished from each other. Specifically, for example, there are multiple R 3 They do not bond to each other to form a ring structure with three or more members.

[0037] The above R 4 There may be multiple Rs. In that case, Rs bonded to different carbons 4 Although they are independent of each other, R bonded to adjacent carbons 4 may be directly bonded to each other to form a multiple bond. Here, the independent relationship means that the above R 3 The same as the provisions in 4 This means that the structural formulas can be clearly distinguished from each other. Specifically, for example, 4 The R bonded to the same carbon atom do not bond to each other to form a ring structure of three or more members. 3 may be bonded to each other to form a monocyclic or polycyclic ring. 4 They may be bonded to each other to form a monocyclic or polycyclic ring.

[0038] CR of the above formula (1) 3 Structure and CR 4The carbon chain structure may be a single bond, a double bond, or a triple bond, but preferably is mainly a single bond. A heteroatom may be connected between the carbon chain bonds. As a preferred example of such a chain structure, the following (divalent) structural formula can be exemplified.

[0039] [ka]

[0040] The above R 5 ~R 8 is a substituent that occurs once. 5 ~R 8 is R 3 , R 4 Similarly, they are independent, but R 5 ~R 8 is a substituent (R 3 ~R 8 ) may be directly bonded to each other to form a multiple bond.

[0041] The above m and n in the formula (1) are selected from integers of 1 to 5 and satisfy the relationship m+n≧4. The above m and n are values ​​related to the size and balance of the cyclic structure. The preferred lower limit of m and n is 2. Furthermore, it is preferred that both m and n are 2 or more. The upper limit of m and n is 5, and the preferred upper limit is 4. The above values ​​of m and n may be the same or different.

[0042] Examples of the halogen atom include fluorine, chlorine, bromine, and iodine. Examples of the substituted or unsubstituted alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, a thexyl group, a cumyl group, and a trityl group.

[0043] Examples of the substituted or unsubstituted alkenyl group include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a pentenyl group, and a hexenyl group.

[0044] Examples of the substituted or unsubstituted alkynyl group include an ethynyl group, a propynyl group, a butynyl group, a pentynyl group, a hexynyl group, a heptynyl group, and an octynyl group.

[0045] Examples of the substituted or unsubstituted cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantyl group, a cyclopentadienyl group, an indenyl group, and a fluorenyl group.

[0046] Examples of the substituted or unsubstituted aryl group include aromatic hydrocarbon groups such as a phenyl group, a methylphenyl group, a dimethylphenyl group, a diisopropylphenyl group, a dimethylisopropylphenyl group, an n-propylphenyl group, an n-butylphenyl group, a tert-butylphenyl group, a di-tert-butylphenyl group, a naphthyl group, a tetrahydronaphthyl group, a biphenyl group, a terphenyl group, a phenanthryl group, and an anthracenyl group, and heteroatom-substituted aryl groups such as a methoxyphenyl group, a dimethylaminophenyl group, a nitrophenyl group, and a trifluoromethylphenyl group.

[0047] Among the heteroatom-containing substituents, an aryl group containing an oxygen-containing substituent is preferred, and specifically, a structure in which an oxygen-containing substituent such as an alkoxy group, an aryloxy group, an alkoxyalkyl group, an aryloxyalkyl group, or a substituent in which the oxygen of the substituent is replaced by a carbonyl group or a carboxyl group is bonded to an aromatic group is preferred. Among the above, a substituent in which an alkoxy group or an aryloxy group is bonded to an aromatic skeleton is preferred, and a substituent in which an alkoxy group is bonded to an aromatic skeleton is more preferred. The number of carbon atoms of the oxygen-containing substituent is preferably 1 to 10, more preferably 1 to 8, and even more preferably 1 to 6. More specifically, in addition to the above methoxyphenyl group, an ethoxyphenyl group, a propyloxyphenyl group, an isopropyloxyphenyl group, a butoxyphenyl group, a phenoxyphenyl group, and the like are preferred examples. Such an aryl group containing an oxygen-containing substituent is R 1 , R 2 In some cases, it is particularly preferable to use

[0048] Examples of the substituted or unsubstituted heteroatom-containing hydrocarbon group include heteroatom-containing alkyl groups such as a methoxymethyl group, a methoxyethyl group, a benzyloxy group, an ethoxymethyl group, an ethoxyethyl group, an acetyl group, and a benzoyl group, and heteroaryl groups such as a furyl group, a pyrrolyl group, a thienyl group, a pyrazolyl group, a pyridyl group, a carbazolyl group, an imidazolyl group, a dimethylfuryl group, an N-methylpyrrolyl group, an N-phenylpyrrolyl group, a diphenylpyrrolyl group, a thiazolyl group, a quinolyl group, a benzofuryl group, a triazolyl group, and a tetrazolyl group.

[0049] R 3 ~R 8 When R is a substituent other than a hydrogen atom, 3 ~R 8 The substituent can be selected from those exemplified in 1. More preferred are substituents selected from a hydrocarbon group and a heteroatom-containing hydrocarbon group, and further preferred are hydrocarbon groups.

[0050] <Specific examples of ester compound (A)> Specific examples of the ester compound (A) of the present invention are shown below, but the ester compound (A) of the present invention is not limited to these.

[0051] [ka]

[0052] [ka]

[0053] [ka]

[0054] [ka]

[0055] [ka]

[0056] [ka]

[0057] [ka]

[0058] [ka]

[0059] [ka]

[0060] [ka]

[0061] In the above structural formula, the methyl group is represented as "Me", the ethyl group as "Et", the propyl group as "Pr", the butyl group as "Bu", and the phenyl group as "Ph". [n] stands for "normal", [i] stands for "iso", and "t" stands for "tertia". r It shows "y".

[0062] In addition, the ester compound of the present invention has an OCOR bonded to an alicyclic structure. 1 Group and OCOR 2 Although the group may form a cis structure or a trans structure derived from the alicyclic structure, it is preferable that the ester compound has a cis structure as the main component, where the main component means that the content of the compound having a cis structure exceeds 50 mol %, preferably 70 mol % or more.

[0063] One of the suitable applications of the ester compound (A) of the present invention is as a Lewis base (internal donor) component of a solid titanium catalyst component. The reason why it is suitable as the internal donor component is unclear at present, but the present inventors speculate as follows.

[0064] Since the ester compound (A) used in the present invention has a special polycyclic structure as described above, it is presumed that the compound has a moderate rigidity and relatively little structural displacement. On the other hand, it can be understood as a structure in which a portion having a somewhat flexible movement also exists. Therefore, when the ester compound (A) is coordinated to a titanium compound or magnesium compound described later, it is considered that the compound maintains a stable structure, and the stereospecificity as a catalyst during the olefin polymerization reaction and the polymerization reaction activity fluctuate little. In addition, the flexible structural portion is expected to mitigate the occurrence of distortion derived from the cyclic structure, and may function like a buffer against changes in the reaction environment. From these viewpoints, it is considered that the compound gives a polymer with high stereoregularity with high activity. From such a viewpoint, it can be presumed that the compound has the potential to easily give a component with a high molecular weight.

[0065] On the other hand, in the case of a stable structure with little structural displacement, there was initially a concern that the molecular weight distribution would be narrow, but as shown in the examples described below, the method of the present invention makes it possible to produce a polymer with a wide molecular weight distribution. The present inventors speculate that this is because, in the case of this ester compound (A), minute fluctuations in the cyclic structure and the combination of fluctuations in each of the cyclic structures may have a high effect on the molecular weight of the resulting polymer, and because the compound has multiple cyclic structures, the combinations of stereoisomeric structures (e.g., chair type, boat type, etc.) that each ring can take may become more diverse.

[0066] <Method for producing ester compound (A)> The method for producing the ester compound (A) of the present invention is not particularly limited, and for example, the corresponding olefin can be obtained through a diolation reaction or a diesterification reaction. In addition, for example, the ester compound (A) can be obtained through a carbonation reaction, a diolation reaction, or a diesterification reaction using a specific polycyclic compound such as cyclohexadienes. More specifically, the ester compound (A) can be produced as follows.

[0067] <Olefin synthesis> O The olefin can be synthesized, for example, by the Diels-Alder reaction of cyclohexadiene and methyl vinyl ketone (Non-Patent Document 1). The diene can also be used from a precursor diene dimer (e.g., dicyclopentadiene) as a raw material.

[0068] <Synthesis of diol> Diols, which are precursors of esters, can be produced from the corresponding olefins as raw materials. For example, diols can be obtained directly by reacting olefins with potassium permanganate (Non-Patent Document 4) or osmium tetroxide (Non-Patent Document 5).

[0069] Alternatively, the olefin moiety can be epoxidized using metachloroperbenzoic acid (Non-Patent Document 6); tert-butyl peroxide (Non-Patent Document 7); dimethyldioxirane (Non-Patent Document 8); formic acid and hydrogen peroxide (Non-Patent Document 9); hydrogen peroxide and a molybdenum catalyst; or hydrogen peroxide and a tungsten catalyst (Non-Patent Document 10), followed by acid or alkali hydrolysis to obtain a diol. In addition, the diene can be converted into a cyclic carbonate and then hydrolyzed to obtain a diol compound. The details are as follows.

[0070] Cyclic carbonates, which are precursors of diols, can be produced by the Diels-Alder reaction of the corresponding dienes with vinylene carbonate (Non-Patent Document 19). As in the above, the diene can also be used as a raw material in the form of a diene dimer, which is the precursor of the diene. ring The diol is obtained by hydrolyzing the carbonate with acid or alkali. Body It is possible to obtain (Non-Patent Document 19).

[0071] <Synthesis of ester> The ester corresponding to the above formula (1) is a diol Body and It can be synthesized by reacting an acid chloride in the presence of a base. do. The base is not particularly limited, and for example, sodium hydroxide, potassium hydroxide, or an amine base can be used. In addition, it can also be synthesized by a method of reacting a diol with a carboxylic acid in the presence of an acid catalyst, or by using a condensing agent such as DCC (Non-Patent Document 11). do. Diol On the body When reacted with 1 equivalent of acid chloride or carboxylic acid , different However, by reacting with an acid chloride or a carboxylic acid, a compound corresponding to formula (1) can be obtained. 1 and R 2may be the same or different. Alternatively, the diol may be reacted with a carboxylic acid in the presence of an azocarboxylate and triphenylphosphine to synthesize the diol (Non-Patent Document 12).

[0072] As described above, the ester compound (A) of the present invention is suitable as a Lewis base component of a solid titanium catalyst component, but is not limited to this use. Needless to say, it may be applicable to known additive uses such as additives for various resins, cosmetics and skin external preparations, bactericidal compositions, antioxidants, chelating agents, etc. EXAMPLES

[0073] The following examples illustrate the synthesis of the ester compounds of the present invention. The compounds disclosed in the following examples represent some of the stereoisomers and may contain other stereoisomers. In the structural formula, "Me" is a symbol representing a methyl group, "n-Pr" is a normal propyl group, "iPr" is an isopropyl group, "n-Bu" is a normal butyl group, "tBu" is a tertiary butyl group, and "Ph" is a phenyl group.

[0074] 1 In the case of 1 H NMR measurement, a nuclear magnetic resonance apparatus of JNM-EX270 manufactured by JEOL Ltd. was used, the solvent was deuterated chloroform, and a small amount of tetramethylsilane was added. The measurement temperature was room temperature, and the observed nucleus was 1 The conditions were H (270 MHz), sequence was single pulse, 45° pulse, repetition time was 5.5 seconds or more, and the number of accumulations was 16 to 64 times or more. The reference chemical shift was set to 0 ppm for hydrogen of tetramethylsilane. 1 Peaks such as H were assigned by standard methods.

[0075] [Example 1] (Synthesis of ester compound) <Synthesis of Compound 1> Compound 1 shown below was synthesized by the method described below.

[0076] [ka]

[0077] In a nitrogen atmosphere, 8.0 grams of 1,3-cyclohexadiene and 8.6 grams of vinylene carbonate were added to a 30 ml pressure vessel, and the vessel was heated and stirred until the internal temperature reached 220° C., and the stirring was continued for 6 hours. After cooling to room temperature, 5 ml of hexane was added and stirred, and the solid was filtered off. The solid obtained was washed with hexane and then dried, to obtain 8.5 grams of compound 1.

[0078] <Synthesis of compound 2> Compound 2 shown below was synthesized by the method described below.

[0079] [ka]

[0080] 50 0 In a 3-neck flask of 16.6 g of the compound 1, 40.0 g of sodium hydroxide, and 100 ml of pure water were added, and the mixture was heated and stirred so that the internal temperature reached 100° C., and stirring was continued for 6 hours. After cooling to room temperature, 12 mol / L concentrated hydrochloric acid was added at 50° C. or less to neutralize. The reaction solution was extracted three times with ethyl acetate, and the organic layer was dried over sodium sulfate and concentrated to obtain 14.0 g of compound 2.

[0081] <Synthesis of compound 3> Compound 3 shown below was synthesized by the method described below.

[0082] [ka]

[0083] In a nitrogen atmosphere, 14.0 g of the compound 2, 42.2 g of benzoyl chloride, and 200 ml of pyridine were added to a 200 ml three-neck flask, and the mixture was heated and stirred so that the internal temperature reached 60° C., and stirring was continued for 6 hours. After distilling off the pyridine, chloroform was added, and the mixture was washed with 2 mol / L hydrochloric acid and 2 mol / L aqueous sodium hydroxide solution, after which the organic layer was dried over magnesium sulfate. After concentration, the mixture was recrystallized from hexane to obtain 13.1 g of compound 3.

[0084] 1 H NMR (270 MHz, CDCl 3 , TMS as internal standard):7.83-7.80 (m, 4H), 7.44-7.41 (m, 2H), 7.28-7.20 (m, 4H), 6.41-6.39 (m, 2H),5.35 (s, 2H), 3.00 (s, 2H), 1.71-1.40 (m,4H).

[0085] The melting point of the obtained compound 3 was measured by a differential scanning calorimeter (DSC-60A manufactured by Shimadzu Corporation, starting temperature: 25°C, ending temperature: 300°C, heating rate: 10°C / min) and was found to be 95°C.

[0086] [Example 2] (Synthesis of ester compound) Compound 4 shown below was synthesized by the method described below.

[0087] [ka]

[0088] In a nitrogen atmosphere, 7.0 grams of compound 3 obtained in Example 1, 3.6 grams of Pd / C (manufactured by Evonic, 5% Pd, water content 58.6%), and 100 ml of ethyl acetate were added to a 300 ml three-neck flask and stirred at room temperature. Hydrogen was introduced at one atmospheric pressure into the reaction vessel to change the atmosphere to hydrogen, and stirring was continued for 15 hours. After filtration using Celite, the filtrate was concentrated. Recrystallization was performed from hexane to obtain 6.6 grams of compound 4.

[0089] 1 H NMR (270 MHz, CDCl 3 , TMS as internal standard): 7.91-7.88 (m, 4H), 7.49-7.42 (m, 2H), 7.30-7.24 (m, 4H), 5.34 (s, 2H), 3.00 (s, 2H), 2.09-2.05 (m, 4H), 1.71 (brs, 4H), 1.54-1.52 (m, 2H).

[0090] The melting point of the obtained compound 4 was measured by a differential scanning calorimeter (DSC-60A manufactured by Shimadzu Corporation, starting temperature: 25°C, ending temperature: 300°C, heating rate: 10°C / min) and was found to be 105°C.

[0091] [Example 3] (Synthesis of ester compound) <Synthesis of compound 5> Compound 5 shown below was synthesized by the method described below.

[0092] [ka]

[0093] In a nitrogen atmosphere, 13.6 g of α-terpinene and 8.6 g of vinylene carbonate were added to a 30 ml pressure vessel, and the mixture was heated and stirred so that the internal temperature reached 220° C. for 6 hours. After cooling to room temperature, 5 ml of hexane was added and stirred, and the solid was filtered off. The solid was washed with hexane and then dried to obtain 14.7 g of compound 5.

[0094] <Synthesis of compound 6> Compound 6 shown below was synthesized by the method described below.

[0095] [ka]

[0096] 4.5 g of the compound 5, 8.0 g of sodium hydroxide, and 30 ml of pure water were added to a 50 ml three-neck flask, and the mixture was heated and stirred so that the internal temperature reached 100° C., and stirring was continued for 6 hours. After cooling to room temperature, 12 mol / L concentrated hydrochloric acid was added at 50° C. or less to neutralize. The reaction solution was extracted three times with ethyl acetate, the organic layer was dried and concentrated with sodium sulfate, and the solid was collected to obtain 3.9 g of compound 6.

[0097] <Synthesis of compound 7> Compound 7 shown below was synthesized by the method described below.

[0098] [ka]

[0099] In a nitrogen atmosphere, 3.9 g of the compound 6, 8.4 g of benzoyl chloride, and 100 ml of pyridine were added to a 200 ml three-neck flask, and the mixture was heated and stirred so that the internal temperature reached 60° C., and the stirring was continued for 6 hours. After distilling off the pyridine, chloroform was added, and the mixture was washed with 2 mol / L hydrochloric acid and 2 mol / L aqueous sodium hydroxide solution, and then the organic layer was dried over magnesium sulfate. After concentration, the solid was filtered off, washed with hexane, and dried to obtain 3.0 g of compound 7.

[0100] 1 H NMR (270 MHz, CDCl 3 , TMS as internal standard):7.79-7.68 (m, 4H), 7.43-7.29 (m, 2H), 7.25-7.07 (m, 4H), 6.28-6.09 (m, 2H), 5.42-5.34 (m, 2H), 2.23-2.12 (m, 1H), 1.63-1.25 (m, 4H), 1.17 (s, 3H), 1.02 (d, J = 7.0 Hz, 3H), 0.92 (d, J = 7.0 Hz, 3H).

[0101] The melting point of the obtained compound 7 was measured by a differential scanning calorimeter (DSC-60A manufactured by Shimadzu Corporation, starting temperature: 25°C, ending temperature: 300°C, heating rate: 10°C / min) and was found to be 137°C.

[0102] [Example 4] (Synthesis of ester compound) <Synthesis of compound 8> Compound 8 shown below was synthesized by the method described below.

[0103] [ka]

[0104] In a nitrogen atmosphere, 4.5 g of the compound 5, 4.3 g of Pd / C (manufactured by Evonic, 5% Pd, water content 58.6%), and 100 ml of ethyl acetate were added to a 200 ml three-neck flask and stirred at room temperature. One atmosphere of hydrogen was introduced into the reaction vessel to change the atmosphere to hydrogen, and stirring was continued for 15 hours. After filtration using Celite, the filtrate was concentrated to recover a solid, and 4.5 g of compound 8 was obtained.

[0105] <Synthesis of compound 9> Compound 9 shown below was synthesized by the method described below.

[0106] [ka]

[0107] 4.5 g of the compound 8, 8.0 g of sodium hydroxide, and 30 ml of pure water were added to a 50 ml three-neck flask, and the mixture was heated and stirred so that the internal temperature reached 100° C., and stirring was continued for 6 hours. After cooling to room temperature, 12 mol / L concentrated hydrochloric acid was added at 50° C. or less to neutralize. The reaction solution was extracted three times with ethyl acetate, and the organic layer was dried over sodium sulfate and concentrated to obtain 3.8 g of compound 9.

[0108] <Synthesis of compound 10> Compound 10 shown below was synthesized by the method described below.

[0109] [ka]

[0110] In a nitrogen atmosphere, 2.0 g of compound 9, 3.2 g of benzoyl chloride, and 50 ml of pyridine were added to a 200 ml three-neck flask, and the mixture was heated and stirred so that the internal temperature reached 60° C. for 6 hours. After distilling off pyridine, chloroform was added, and the mixture was washed with 2 mol / L hydrochloric acid and 2 mol / L aqueous sodium hydroxide solution, after which the organic layer was dried over magnesium sulfate. After concentration, the mixture was purified by silica gel column chromatography and dried to obtain 3.6 g of compound 10.

[0111] 1 H NMR (270 MHz, CDCl 3 , TMS as internal standard):7.87-7.74 (m, 4H), 7.45-7.12 (m, 6H), 5.49-5.46 (m, 1H), 5.26-5.25 (m, 1H), 2.10-0.82 (m, 18H).

[0112] The melting point of the obtained compound 10 was measured by a differential scanning calorimeter (DSC-60A manufactured by Shimadzu Corporation, starting temperature: 25°C, ending temperature: 300°C, heating rate: 10°C / min) and was found to be 107°C.

[0113] [Example 5] (Synthesis of ester compound) <Synthesis of compound 11> Compound 11 shown below was synthesized by the method described below.

[0114] [ka]

[0115] In a nitrogen atmosphere, 4.0 g of the compound 9, 9.3 g of 4-methylbenzoyl chloride, and 50 ml of pyridine were added to a 200 ml three-neck flask, and the mixture was heated and stirred so that the internal temperature reached 60° C., and the stirring was continued for 6 hours. After distilling off the pyridine, chloroform was added, and the mixture was washed with 2 mol / L hydrochloric acid and 2 mol / L aqueous sodium hydroxide solution, and then the organic layer was dried over magnesium sulfate. After concentration, the mixture was purified by silica gel column chromatography and dried to obtain 2.9 g of compound 11.

[0116] 1 H NMR (270 MHz, CDCl 3 , TMS as internal standard):7.76 (d, J = 7.8 Hz, 2H), 7.66 (d, J= 7.8 Hz, 2H), 7.09 (d, J = 8.6 Hz, 2H), 6.96 (d, J = 8.4 Hz, 2H), 5.47-5.23 (m, 2H), 2.36 (s, 3H), 2.30 (s, 3H), 2.09-1.26 (m, 11H), 0.95-0.81 (m, 6H).

[0117] [Example 6] (Synthesis of ester compound) <Synthesis of compound 12> Compound 12 shown below was synthesized by the method described below.

[0118] [ka]

[0119] In a nitrogen atmosphere, 4.0 g of compound 9, 11.0 g of 4-n-propylbenzoyl chloride, and 50 ml of pyridine were added to a 200 ml three-neck flask, and the mixture was heated and stirred so that the internal temperature reached 60° C., and the stirring was continued for 6 hours. After distilling off pyridine, chloroform was added, and the mixture was washed with 2 mol / L hydrochloric acid and 2 mol / L aqueous sodium hydroxide solution, and then the organic layer was dried over magnesium sulfate. After concentration, the mixture was purified by silica gel column chromatography and dried to obtain 2.3 g of compound 12.

[0120] 1 H NMR (270 MHz, CDCl 3 , TMS as internal standard): 7.76 (d, J = 8.4 Hz, 2H), 7.67 (d, J= 8.4 Hz, 2H), 7.07 (d, J = 7.8 Hz, 2H), 6.93 (d, J = 8.1 Hz, 2H), 5.47-5.23 (m, 2H), 2.51-2.48 (m, 4H), 2.10-1.26 (m, 16H), 0.94-0.80 (m, 12H).

[0121] The melting point of the obtained compound 12 was measured by a differential scanning calorimeter (DSC-60A manufactured by Shimadzu Corporation, starting temperature: 25°C, ending temperature: 300°C, heating rate: 10°C / min) and was found to be 70°C.

[0122] [Example 7] (Synthesis of ester compound) <Synthesis of compound 13> Compound 13 shown below was synthesized by the method described below.

[0123] [ka]

[0124] In a nitrogen atmosphere, 4.0 g of the compound 9, 11.8 g of 4-n-butylbenzoyl chloride, and 50 ml of pyridine were added to a 200 ml three-neck flask, and the mixture was heated and stirred so that the internal temperature reached 60° C., and the stirring was continued for 6 hours. After distilling off the pyridine, chloroform was added, and the mixture was washed with 2 mol / L hydrochloric acid and 2 mol / L aqueous sodium hydroxide solution, and then the organic layer was dried over magnesium sulfate. After concentration, the mixture was purified by silica gel column chromatography and dried to obtain 7.9 g of compound 13.

[0125] 1 H NMR (270 MHz, CDCl 3, TMS as internal standard): 7.76 (d, J = 7.8 Hz, 2H), 7.66 (d, J= 8.1 Hz, 2H), 7.08 (d, J = 7.8 Hz, 2H), 6.93 (d, J = 8.4 Hz, 2H), 5.47-5.23 (m, 2H), 2.64-2.51 (m, 4H), 2.10-1.23 (m, 20H), 0.96-0.81 (m, 12H).

[0126] [Example 8] (Synthesis of ester compound) <Synthesis of compound 14> Compound 14 shown below was synthesized by the method described below.

[0127] [ka]

[0128] In a nitrogen atmosphere, 4.0 g of compound 9, 11.8 g of 4-t-butylbenzoyl chloride, and 50 ml of pyridine were added to a 200 ml three-neck flask, and the mixture was heated and stirred so that the internal temperature reached 60° C., and the stirring was continued for 6 hours. After distilling off pyridine, chloroform was added, and the mixture was washed with 2 mol / L hydrochloric acid and 2 mol / L aqueous sodium hydroxide solution, and then the organic layer was dried over magnesium sulfate. After concentration, the mixture was purified by silica gel column chromatography and dried to obtain 1.7 g of compound 14.

[0129] 1 H NMR (270 MHz, CDCl 3 , TMS as internal standard): 7.79 (d, J = 8.6 Hz, 2H), 7.68 (d, J= 8.6 Hz, 2H), 7.31 (d, J = 8.1 Hz, 2H), 7.14 (d, J = 8.4 Hz, 2H), 5.47-5.23 (m, 2H), 2.09-1.24 (m, 30H), 0.85-0.81 (m, 6H).

[0130] The melting point of the obtained compound 14 was measured by a differential scanning calorimeter (DSC-60A manufactured by Shimadzu Corporation, starting temperature: 25°C, ending temperature: 300°C, heating rate: 10°C / min) and was found to be 137°C.

[0131] [Example 9] (Synthesis of ester compound) <Synthesis of compound 15> Compound 15 shown below was synthesized by the method described below.

[0132] [ka]

[0133] In a nitrogen atmosphere, 4.0 g of compound 9, 10.2 g of 4-methoxybenzoyl chloride, and 50 ml of pyridine were added to a 200 ml three-neck flask, and the mixture was heated and stirred so that the internal temperature reached 60° C., and the stirring was continued for 6 hours. After distilling off pyridine, chloroform was added, and the mixture was washed with 2 mol / L hydrochloric acid and 2 mol / L aqueous sodium hydroxide solution, and then the organic layer was dried over magnesium sulfate. After concentration, the mixture was purified by silica gel column chromatography and dried to obtain 4.7 g of compound 15.

[0134] 1 H NMR (270 MHz, CDCl 3 , TMS as internal standard):7 . 82 (d, J = 8.9 Hz, 2H), 7.73 (d, J = 8.6 Hz, 2H), 6.78 (d, J = 8.9 Hz, 2H), 6.65 (d, J = 8.9 Hz, 2H), 5.44-5.20 (m,2H), 3.82 (s, 3H), 3.77 (s, 3H), 2.54-0.79 (m, 18H).

[0135] The melting point of the obtained compound 15 was measured by a differential scanning calorimeter (DSC-60A manufactured by Shimadzu Corporation, starting temperature: 25°C, ending temperature: 300°C, heating rate: 10°C / min) and was found to be 60°C.

[0136] [Example 10] (Synthesis of ester compound) <Synthesis of compound 16> Compound 16 shown below was synthesized by the method described below.

[0137] [ka]

[0138] In a nitrogen atmosphere, 4.0 g of the compound 9, 10.1 g of 3,4-dimethylbenzoyl chloride, and 50 ml of pyridine were added to a 200 ml three-neck flask, and the mixture was heated and stirred so that the internal temperature reached 60° C., and the stirring was continued for 6 hours. After distilling off the pyridine, chloroform was added, and the mixture was washed with 2 mol / L hydrochloric acid and 2 mol / L aqueous sodium hydroxide solution, and then the organic layer was dried over magnesium sulfate. After concentration, the mixture was purified by silica gel column chromatography and dried to obtain 1.2 g of compound 16.

[0139] 1 H NMR (270 MHz, CDCl 3 , TMS as internal standard):7.65-7.45 (m, 4H), 7.09-6.94 (m, 2H), 5.46-5.23 (m, 2H), 2.67-1.30 (m, 24H), 0.84-0.75 (m, 6H).

[0140] The melting point of the obtained compound 16 was measured by a differential scanning calorimeter (DSC-60A manufactured by Shimadzu Corporation, starting temperature: 25°C, ending temperature: 300°C, heating rate: 10°C / min) and was found to be 92°C.

[0141] [Example 11] (Synthesis of ester compound) <Synthesis of compound 17> Compound 17 shown below was synthesized by the method described below.

[0142] [ka]

[0143] In a nitrogen atmosphere, 4.0 g of compound 9, 11.7 g of 5,6,7,8-tetrahydronaphthalene-2-carbonyl chloride, and 50 ml of pyridine were added to a 200 ml three-neck flask, and the mixture was heated and stirred so that the internal temperature reached 60° C., and the stirring was continued for 6 hours. After distilling off pyridine, chloroform was added, and the mixture was washed with 2 mol / L hydrochloric acid and 2 mol / L aqueous sodium hydroxide solution, and then the organic layer was dried over magnesium sulfate. After concentration, the mixture was purified by silica gel column chromatography and dried to obtain 3.8 g of compound 17.

[0144] 1 H NMR (270 MHz, CDCl 3 , TMS as internal standard):7.63-7.37 (m, 4H), 7.02-6.88 (m, 2H), 5.45-5.22 (m, 2H), 2.76-1.27 (m, 28H), 0.84-0.80 (m, 6H).

[0145] The melting point of the obtained compound 17 was measured by a differential scanning calorimeter (DSC-60A manufactured by Shimadzu Corporation, starting temperature: 25°C, ending temperature: 300°C, heating rate: 10°C / min) and was found to be 133°C.

[0146] [Example 12] (Synthesis of ester compound) <Synthesis of Compound 18 and Compound 19> Compounds 18 and 19 shown below were synthesized by the method described below.

[0147] [ka]

[0148] Under a nitrogen atmosphere, 3.3 grams of anhydrous aluminum chloride and 25 ml of dehydrated toluene were added to a 50 ml two-neck flask and stirred at room temperature. An aluminum chloride solution was prepared by slowly dropping 4 ml of dehydrated THF to dissolve the aluminum chloride. Under a nitrogen atmosphere, 8.6 grams of methyl vinyl ketone, 20.1 grams of α-terpinene, and 60 ml of dehydrated toluene were added to a 300 ml three-neck flask and stirred while cooling in an ice bath. The aluminum chloride solution prepared above was slowly dropped into the 300 ml flask, then warmed to room temperature and stirred overnight. The mixture was cooled again in an ice bath and 100 ml of water was added to stop the reaction. After separating the organic layer and the aqueous layer, the organic layer was washed with 50 ml of water, saturated aqueous sodium bicarbonate solution, and saturated saline in that order, dried over magnesium sulfate, and then concentrated with a rotary evaporator. The obtained crude product was purified by silica gel column chromatography to obtain 18.4 grams of an isomer mixture of compound 18 and compound 19.

[0149] <Synthesis of Compound 20 and Compound 21> Compounds 20 and 21 shown below were synthesized by the method described below.

[0150] [ka]

[0151] A 1000 ml three-neck flask equipped with a dropping funnel was charged with 7 grams of a mixture of compound 18 and compound 19, 132 ml of tert-butyl alcohol, and 33 ml of water, and cooled to 0°C. In a separate flask, 7.91 grams of potassium permanganate, 1.79 grams of sodium hydroxide, and 165 ml of water were added to prepare an aqueous permanganate solution, which was then added to the dropping funnel. Potassium permanganate was slowly dripped in so that the internal temperature did not exceed 5°C. After completion of the dripping, stirring was continued for 1 hour, and a saturated aqueous sodium thiosulfate solution was dripped in until the red-purple color of the aqueous layer disappeared. 350 ml of ethyl acetate was added and the mixture was allowed to stand. After the organic layer of the supernatant was extracted, 350 ml of ethyl acetate was added again to the aqueous layer and the mixture was allowed to stand. The supernatant was combined with the organic layer from which it was extracted, the organic layer was washed with saturated saline, dried over magnesium sulfate, and then concentrated with a rotary evaporator to obtain a crude product. The crude product was purified by silica gel column chromatography to obtain 2.1 g of a mixture of Compound 20 and Compound 21 as an isomer mixture.

[0152] <Synthesis of Compound 22 and Compound 23> Compounds 22 and 23 shown below were synthesized by the method described below.

[0153] [ka]

[0154] Under a nitrogen atmosphere, 1.93 grams of a mixture of compound 20 and compound 21 and 8 ml of dehydrated pyridine were added to a 50 ml three-neck flask. After cooling in an ice bath, 2 ml of benzoyl chloride was slowly added dropwise, and the mixture was warmed to room temperature and stirred overnight. Dichloromethane and water were added to the reaction solution to separate the organic layer, and the aqueous layer was extracted three times with dichloromethane. The organic layer was washed with saturated saline, dried over magnesium sulfate, and then concentrated with a rotary evaporator. The reaction mixture was purified by silica gel column chromatography to obtain 2.34 grams of a mixture of compound 22 and compound 23 (a mixture of isomers with a mixing ratio of 71:29).

[0155] 1H NMR (270 MHz, CDCl 3 , TMS as internal standard): δ 7.87-7.71 (m, 4H), 7.50-7.27 (CHCl 3 , m, 4H), 7.15-7.09(m, 2H), 6.20(dd, J = 7.6Hz, 1.3Hz, 1H, major isomer), 5.79(dd, J = 7.9Hz, 2.3Hz, 1H, minor isomer), 5.65-5.63(m, 1H, minor isomer), 5.49(dd, J = 7.9Hz, 2.0Hz, 1H, major isomer), 3.02(dd, J = 11.9Hz, 4.9Hz, 1H, major isomer), 2.81(t, J = 9.2Hz, 1H, minor isomer), 2.27(s, 3H, major isomer), 2.26(s, 3H, minor isomer) isomer), 2.17-1.23(m,7H), 0.94-0.81(m,9H)

[0156] [Example 13] (Synthesis of ester compound) <Synthesis of Compound 24 and Compound 25> Compounds 24 and 25 shown below were synthesized by the method described below.

[0157] [ka]

[0158] Under a nitrogen atmosphere, 2.0 grams of anhydrous aluminum chloride and 18 ml of dehydrated toluene were added to a 50 ml two-neck flask and stirred at room temperature. An aluminum chloride solution was prepared by slowly dropping 2.3 ml of dehydrated THF to dissolve the aluminum chloride. Under a nitrogen atmosphere, 9.4 grams of phenyl vinyl ketone, 11.6 grams of α-terpinene, and 40 ml of dehydrated toluene were added to a 300 ml three-neck flask and stirred while cooling in an ice bath. The aluminum chloride solution prepared above was slowly dropped into the 300 ml flask, then warmed to room temperature and stirred overnight. The mixture was cooled again in an ice bath and 150 ml of water was added to stop the reaction. The organic layer and the aqueous layer were separated, and the organic layer was washed with 100 ml of water, saturated aqueous sodium bicarbonate solution, and saturated saline in that order, dried over magnesium sulfate, and then concentrated with a rotary evaporator. The obtained crude product was purified by silica gel column chromatography to obtain 10.9 grams of an isomer mixture of compound 24 and compound 25.

[0159] <Synthesis of Compound 26 and Compound 27> Compounds 26 and 27 shown below were synthesized by the method described below.

[0160] [ka]

[0161] A 1000 ml three-neck flask equipped with a dropping funnel was charged with 10.8 g of a mixture of compound 24 and compound 25, 200 ml of tert-butyl alcohol, and 40 ml of water, and cooled to 0°C. A separate flask was charged with 6.98 g of potassium permanganate, 1.93 g of sodium hydroxide, and 160 ml of water to prepare an aqueous permanganate solution, which was then added to the dropping funnel. Potassium permanganate was slowly dripped in so that the internal temperature did not exceed 6°C. Stirring was continued for 1 hour after the dropwise addition was completed, and a saturated aqueous sodium thiosulfate solution was dripped in until the red-purple color of the aqueous layer disappeared. 350 ml of ethyl acetate was added and the mixture was stirred and left to stand. After the organic layer of the supernatant was extracted, 350 ml of ethyl acetate was added to the aqueous layer again and the mixture was stirred and left to stand. The organic layer was combined with the organic layer from which the supernatant was extracted, washed with saturated saline, dried over magnesium sulfate, and then concentrated with a rotary evaporator to obtain a crude product. The crude product was purified by silica gel column chromatography to obtain 4.0 g of an isomer mixture of Compound 26 and Compound 27.

[0162] <Synthesis of Compound 28 and Compound 29> Compounds 28 and 29 shown below were synthesized by the method described below.

[0163] [ka]

[0164] In a nitrogen atmosphere, 3.6 grams of a mixture of compound 26 and compound 27 and 5 ml of dehydrated pyridine were added to a 50 ml three-neck flask. After cooling in an ice bath, 2.9 ml of benzoyl chloride was slowly added dropwise, and the mixture was warmed to room temperature and stirred overnight. Dichloromethane and water were added to the reaction solution to separate the organic layer, and the aqueous layer was extracted three times with dichloromethane. The organic layer was washed with saturated saline, dried over magnesium sulfate, and then concentrated with a rotary evaporator. The reaction mixture was purified by silica gel column chromatography to obtain 3.42 grams of a mixture of compound 28 and compound 29 (a mixture of isomers with a mixing ratio of 76:24).

[0165] 1H NMR (270 MHz, CDCl 3 , TMS as internal standard): δ8.03-7.09(m,15H), 6.51(dd,J=7.6Hz, 1.3Hz,1H, major isomer), 6.08(dd,J=7.9Hz, 1.6Hz,1H, minor isomer), 5.74(dd,J=7.9Hz, 1.0Hz,1H, minor isomer), 5.70(dd,J=7.6Hz, 2.0Hz,1H, major isomer), 3.84(dd,J=11.9Hz, 4.9Hz,1H, major isomer), 3.70(t,J=9.2Hz, 1H, minor isomer), 2.25-1.23(m,7H), 0.93-0.75(m,9H)

[0166] The melting point of the mixture of the obtained compounds 28 and 29 was measured using a differential scanning calorimeter (DSC7020 manufactured by Hitachi High-Tech Science Corporation, starting temperature: 25°C, ending temperature: 300°C, heating rate: 10°C / min), and the melting point was 130°C.

[0167] [Example 14] <Preparation of solid titanium catalyst component [α1]> After thoroughly replacing the atmosphere in a 1L glass container with nitrogen, 85.8g of anhydrous magnesium chloride, 321g of decane, and 352g of 2-ethylhexyl alcohol were added and reacted at 130°C for 3 hours to obtain a homogeneous solution. 241g of this solution and 6.43g of ethyl benzoate were added to the glass container and mixed with stirring at 50°C for 1 hour.

[0168] The homogeneous solution thus obtained was cooled to room temperature, and then 38.3 ml of this homogeneous solution was added dropwise to 100 ml of titanium tetrachloride kept at -20°C over a period of 45 minutes while stirring at a stirring speed of 350 rpm. After the addition, the temperature of this mixture was raised to 80°C over a period of 3.8 hours, and when it reached 80°C, 1.26 g of the compound 10 was added to the mixture. The temperature was raised again to 120°C over a period of 40 minutes, and the mixture was kept at the same temperature for 35 minutes while stirring. After the reaction was completed, the solid portion was collected by hot filtration, and the solid portion was resuspended in 100 ml of titanium tetrachloride, and then the heating reaction was carried out again at 120°C for 35 minutes. After the reaction was completed, the solid portion was collected by hot filtration again, and thoroughly washed with 100°C decane and room temperature decane until no free titanium compound was detected in the washings. The solid titanium catalyst component [α1] containing compound 10 prepared by the above procedure was stored as a decane slurry, and a portion of it was dried for the purpose of examining the catalyst composition. The composition of the solid titanium catalyst component [α1] thus obtained was 0.28 mass% titanium, 1.5 mass% magnesium, and 0.13 mass% 2-ethylhexyl alcohol residue.

[0169] <Main Polymerization> After adding 500g of propylene and 1NL of hydrogen to a 2-liter polymerization vessel at room temperature, a mixture of 7ml of heptane, 0.35mmol of triethylaluminum, 0.07mmol of cyclohexylmethyldimethoxysilane, and 0.0028mmol of solid titanium catalyst component [α1] (titanium atom equivalent) mixed for 10 minutes at 25°C was added, and the temperature inside the polymerization vessel was quickly raised to 70°C. After polymerization at 70°C for 1.5 hours, the reaction was stopped with a small amount of methanol, and propylene was purged. The obtained polymer particles were further dried under reduced pressure at 80°C overnight. Activity, bulk density, MFR, amount of decane insoluble component, Tm, Tmf, ΔH, MWD (molecular weight distribution), etc. are shown in Table 1.

[0170] [Table 1]

[0171] The methods for measuring the above physical properties are as follows. (1) Bulk density: Measurements were performed in accordance with JIS K-6721. (2)Melt flow rate (MFR): The method was based on ASTM D1238E, and the measurement temperature was 230° C. for propylene polymers.

[0172] (3) Amount of decane soluble (insoluble) components: Approximately 3 grams (10 -4 The weight was measured to the nearest gram. This weight was expressed as b (grams) in the formula below. 500 ml of decane and a small amount of a heat stabilizer soluble in decane were added, and the mixture was heated to 150°C over 2 hours while stirring with a stirrer under a nitrogen atmosphere to dissolve the propylene polymer. The mixture was then held at 150°C for 2 hours and then gradually cooled to 23°C over 8 hours. The resulting liquid containing the propylene polymer precipitate was Tokyo Glass Instruments Co., Ltd. The mixture was filtered under reduced pressure using a 25G-4 standard glass filter. 100 ml of the filtrate was collected and dried under reduced pressure to obtain a portion of the decane-soluble components. -4 The weight was measured to the nearest gram (this weight is represented as a (gram) in the formula below). After this operation, the amount of decane soluble components was determined by the formula below. Decane soluble component content = 100 × (500 × a) / (100 × b) Decane insoluble content = 100 - 100 × (500 × a) / (100 × b)

[0173] (4)Molecular weight distribution: Gel permeation chromatograph: Tosoh Corporation HLC-8321 GPC / HT type Detector: Differential refractometer Columns: Two TSKgel GMH6-HT columns and two TSKgel GMH6-HTL columns manufactured by Tosoh Corporation were connected in series. Mobile phase medium: o-dichlorobenzene Flow rate: 1.0ml / min Measurement temperature: 140℃ How to create a calibration curve: Standard polystyrene samples were used Sample concentration: 0.1% (w / w) Sample volume: 0.4ml The measurement was performed under the above conditions, and the obtained chromatogram was analyzed by a known method to calculate the weight average molecular weight (Mw), number average molecular weight (Mn), Z average molecular weight (Mz), and the Mw / Mn and Mz / Mw values, which are indices of molecular weight distribution (MWD). The measurement time for one sample was 60 minutes.

[0174] (5) Melting point of polymer (Tm): The melting point (Tm), crystallization temperature (Tc), and heat of fusion (ΔH) of the polymer in the present invention were measured by differential scanning calorimetry (DSC) using a Seiko Instruments Inc. DSC220C device. 3 to 10 mg of sample was sealed in an aluminum pan and heated from room temperature to 200°C at 100°C / min. The sample was held at 200°C for 5 minutes and then cooled to 30°C at 10°C / min. In this cooling test, the peak temperature was taken as the crystallization temperature (Tc). After being left at 30°C for 5 minutes, the sample was heated a second time to 200°C at 10°C / min. In this second heating test, the peak temperature was taken as the melting point (Tm) and the heat generated was taken as the heat of fusion (ΔH).

[0175] The final melting point (Tmf) of the polymer in the present invention was measured by differential scanning calorimetry (DSC) using a Seiko Instruments DSC220C device. 3 to 10 mg of the sample was sealed in an aluminum pan and heated from room temperature to 240°C at 80°C / min. The sample was held at 240°C for 1 minute and then cooled to 0°C at 80°C / min. After holding at 0°C for 1 minute, the sample was heated to 150°C at 80°C / min and held for 5 minutes. Finally, the sample was heated to 180°C at 1.35°C / min, and the intersection of the tangent of the inflection point on the high temperature side of the peak obtained in this final heating test and the baseline was adopted as the final melting point (Tmf).

[0176] Tmf can be considered as one parameter for evaluating the ease of crystallization and the strength of the crystal structure of a polymer in the ultra-high molecular weight region, which is considered to be difficult to crystallize, and the strength of the crystal structure of a component with extremely high crystallinity, etc. More specifically, it can be considered that the higher the Tmf value, the easier it is for the ultra-high molecular weight polymer component to form strong, highly heat-resistant crystals.

[0177] [Example 15] (Synthesis of ester compound) <Synthesis of compound 30> Compound 30 shown below was synthesized by the method described below.

[0178] [ka]

[0179] (Synthesis of precursor (cyclic olefin compound)) Under a nitrogen atmosphere, 4.5 grams of anhydrous aluminum chloride and 90 ml of dehydrated toluene were added to a 200 ml two-neck flask and stirred at room temperature. An aluminum chloride solution was prepared by slowly dropping 5.6 ml of dehydrated THF to dissolve the aluminum chloride. Under a nitrogen atmosphere, 24.3 grams of phenyl-1-propenyl ketone, 28.0 grams of α-terpinene, and 170 ml of dehydrated toluene were added to a 500 ml three-neck flask and stirred while cooling in an ice bath. The aluminum chloride solution prepared above was slowly dropped into the 500 ml flask, then the temperature was raised to room temperature and stirred overnight. The mixture was cooled again in an ice bath and 150 ml of water was added to stop the reaction. The reaction solution was added to a separatory funnel, followed by 300 ml of methylene chloride. After separating the organic layer and the aqueous layer, the organic layer was washed with 300 ml of water and separated again. The organic layer was washed with a saturated aqueous sodium bicarbonate solution and saturated saline, dried over magnesium sulfate, and concentrated with a rotary evaporator. The resulting crude product was purified by silica gel column chromatography to obtain 12.0 g of a Diels-Alder adduct (cyclic olefin compound).

[0180] (Synthesis of diol compounds) In a 1000 ml three-neck flask, 12.0 g of the Diels-Alder adduct, 167 ml of tert-butanol, and 42 ml of water were added, a dropping funnel was attached, and the flask was cooled to 0°C. In another flask, 10.0 g of potassium permanganate, 2.2 g of sodium hydroxide, and 209 ml of water were added to prepare an aqueous permanganic acid solution, which was then added to the dropping funnel. Potassium permanganate was slowly dripped in so that the internal temperature did not exceed 5°C. After completion of the dripping, stirring was continued for 1 hour, and a saturated aqueous sodium thiosulfate solution was dripped in until the red-purple color of the aqueous layer disappeared. 350 ml of ethyl acetate was added and stirred, and the supernatant was allowed to stand. After extracting the organic layer of the supernatant, 350 ml of ethyl acetate was added to the aqueous layer and stirred, and the supernatant was allowed to stand again. Similarly, the organic layer of the supernatant was extracted and combined with the previous organic layer. The organic layer was washed with saturated saline, dried over magnesium sulfate, and then concentrated with a rotary evaporator to obtain 14.0 g of crude product. The crude product was purified by silica gel column chromatography to obtain 3.84 g of a diol compound.

[0181] (Synthesis of ester compound 30) In a nitrogen atmosphere, 3.84 g of the diol compound and 12.4 ml of dehydrated pyridine were added to a 50 ml three-neck flask. After cooling in an ice bath, 2.5 ml of benzoyl chloride was slowly added dropwise, and the mixture was warmed to room temperature and stirred overnight. Dichloromethane and water were added to the reaction solution to separate the organic layer, and the aqueous layer was extracted three times with dichloromethane. The organic layer was washed with saturated saline, dried over magnesium sulfate, and then concentrated using a rotary evaporator. The reaction mixture was purified by silica gel column chromatography to obtain 2.11 g of compound 30 as the main product.

[0182] 1 H NMR (270 MHz, CDCl 3, TMS as internal standard): δ8.08-8.01(m,2H), 7.91-7.83(m,2H), 7.82-7.72(m,2H), 7.65-7.23(m,7H), 7.20-7.07(m,2H), 6.38(d,J=7.6Hz, 1H), 5.72-5.61(m,1H), 3.42(d,J=5.3Hz, 1H), 2.16-1.93(m,2H), 1.86-1.44(m,4H), 1.12(d,J=6.9Hz, 3H), 0.87-0.69(m,9H)

[0183] The melting point of the obtained mixture of compounds 30 was measured using a differential scanning calorimeter (DSC7020 manufactured by Hitachi High-Tech Science Corporation, starting temperature: 25°C, ending temperature: 300°C, heating rate: 10°C / min), and was found to be 60°C. [Industrial Applicability]

[0184] The novel ester compound according to the present invention is useful for the production of resin additives, cosmetic materials, skin care products, antibacterial compositions, antioxidants, chelating agents, and Ziegler-Natta catalysts. In particular, it can be used as a catalyst component for Ziegler-Natta catalysts, and can produce catalysts that provide excellent stereoregularity and productivity when polypropylene is polymerized. As described above, the ester compound according to the present invention is extremely valuable industrially.

Claims

1. A cyclic polyvalent ester group-containing compound (A) represented by the following formula (1): 【Chemistry 1】 [In formula (1), m and n are integers of 1 to 5, and satisfy the relationship m+n≧4. R 1 and R 2 are each a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and when the aryl group is a heteroatom-substituted aryl group, the heteroatom substituent is an oxygen-containing substituent having 1 to 10 carbon atoms; 3 , multiple R 4 , R 5 ~R 8 are each a group selected from a hydrogen atom, a halogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group (provided that when the heteroatom-containing hydrocarbon group is an oxygen atom-containing substituent, it is an ether type (a substituent containing a C—O—C structure)). 3 ~R 8 are independent of each other, but adjacent R 3 They may be directly bonded to each other to form a multiple bond. 4 Multiple R groups bonded to the same carbon atom may be bonded directly to each other to form a multiple bond. 3 , multiple R 4 may be bonded to each other to form a ring structure.

2. The ester compound (A) according to claim 1, wherein m is 2 or more and n is 2 or more.

3. R 3 ~R 8 are each a group selected from a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted cycloalkenyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkenyloxy group, a substituted or unsubstituted cycloalkyloxy group, a substituted or unsubstituted cycloalkenyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, and a substituted or unsubstituted heteroaryloxy group.

4. The ester compound (A) described in claim 1, wherein R 1 and R 2 are each a substituted or unsubstituted aryl group having 6 to 15 carbon atoms, and when the aryl group is a heteroatom-substituted aryl group, the heteroatom substituent is an oxygen-containing substituent having 1 to 8 carbon atoms.

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