ester compounds

Abstract

The present invention has an object to provide an internal donor component capable of producing a propylene polymer having extremely high stereoregularity at high productivity, mainly for a solid titanium catalyst component. The solution of the present invention is a polyol ester compound having a specific polycyclic structure represented by the following formula (1). It is an ester compound having a structure characterized by satisfying a specific relationship at a site having a C-R 3 structure and a C-R 4 structure.

Description

TECHNICAL FIELD

[0001] The present application relates to a novel ester compound. BACKGROUND

[0002] As prior art on ester compounds, many have been disclosed on the use of additives such as resin additives, cosmetics, skin external agents, bactericide compositions, antioxidants, chelating agents, etc. As one of the uses thereof, it is known to be used for a mode of Mg compound-supported titanium catalyst used in olefin polymerization.

[0003] With respect to catalysts for olefin polymerization, it is one of the technologies that have been greatly developed so far, taking the discovery of so-called Ziegler-Natta catalyst as a turning point, which is: in 1953, Ziegler reported that by combining titanium tetrachloride with an organic aluminum compound, ethylene can be polymerized even at low pressure, and then, Natta first reported that propylene can be polymerized by combining titanium trichloride with a halogen-containing organic aluminum compound. Among them, it was found that a catalyst containing titanium tetrachloride, a magnesium compound, and a Lewis base, which is called a third-generation catalyst, can achieve both high polymerization activity (high productivity) and high stereoregularity in the polymerization of propylene. This discovery became an opportunity for the spread of propylene polymers (polypropylene) in the world.

[0004] In addition, it was found that a Lewis base (hereinafter also referred to as "internal donor") as one of the main components of the above-mentioned third-generation catalyst component (hereinafter also referred to as "solid titanium catalyst component") has a great influence on catalyst performance, and various Lewis bases have been developed so far.

[0005] As a Lewis base for Ziegler-Natta catalysts, for example, ethyl benzoate, phthalate, 1,3-diketone (Patent Literature 1), malonate (Patent Literature 2), succinate (Patent Literature 3), 2,4-pentanediol diester (Patent Literature 4), naphthalenediol diester (Patent Literature 5), catechol diester (Patent Literature 6), etc. are reported, and it is currently a field in which research and development are actively conducted by enterprises.

[0006] In addition, with respect to elementary reactions for synthesizing various ester compounds, many methods have been disclosed (for example, Patent Literatures 7 to 10, Non-Patent Literatures 1 to 19).

[0007] PRIOR ART DOCUMENTS

[0008] PATENT LITERATURES

[0009] Patent Literature 1: Japanese Patent Application Laid-Open No. 2005-226076

[0010] Patent Literature 2: Japanese Patent Application Laid-Open No. 2000-516987

[0011] Patent Literature 3: Japanese Patent Application Laid-Open No. 2002-542347

[0012] Patent Literature 4: Japanese Patent Application Laid-Open No. 2005-517746

[0013] Patent Literature 5: Japanese Patent Application Laid-Open No. 2011-529888

[0014] Patent Literature 6: Japanese Patent Application Laid-Open No. 2014-500390

[0015] Patent Literature 7: Japanese Patent Application Laid-Open No. 2008-247796

[0016] Patent Literature 8: International Publication No. 2008 / 062553

[0017] Patent Literature 9: U.S. Patent Application Publication No. 2018 / 0149973

[0018] Patent Literature 10: U.S. Patent Application Publication No. 2002 / 0162991

[0019] Non-Patent Literature

[0020] Non-Patent Literature 1: Journal of Organic Chemistry, 1969, 34, 3579-3582

[0021] Non-Patent Literature 2: Journal of Organic Chemistry, 1971, 36, 3979-3987

[0022] Non-Patent Literature 3: Organic Letters, 2004, 6, 1589-1592

[0023] Non-Patent Literature 4: Journal of the American Chemical Society, 1957, 79, 2822-2824

[0024] Non-Patent Literature 5: Organic Synthesis, 1991, 70, 47-53

[0025] Non-Patent Literature 6: Organic Synthesis, 1997, 75, 153-160

[0026] Non-Patent Literature 7: Catalysis Letters, 2012, 142, 124-130

[0027] Non-Patent Literature 8: Organic Synthesis, 1997, 74, 91-100

[0028] Non-Patent Literature 9: 20. Organic Synthesis II Alcohol-Amine p39 of Experimental Chemistry Course 4th ed.

[0029] Non-Patent Literature 10: Journal of Organic Chemistry, 1959, 24, 54-55

[0030] Non-Patent Literature 11: Angewandte Chemie International Edition, 1978, 17, 522-524

[0031] Non-Patent Literature 12: Bulletin of the Chemical Society of Japan, 1967, 40, 2380-2382

[0032] Non-Patent Literature 13: Organic Synthesis, 1952, 32, 41

[0033] Non-Patent Literature 14: Macromolecules, 2017, 50, 580-586

[0034] Non-Patent Literature 15: Journal of Organic Chemistry, 1980, 45, 2301-2304

[0035] Non-Patent Literature 16: Journal of Organic Chemistry, 2009, 74, 405-407

[0036] Non-Patent Literature 17: Journal of Organic Chemistry, 1988, 53, 2120-2122

[0037] Non-Patent Literature 18: Journal of Organic Chemistry, 1963, 28, 2572-2577

[0038] Non-Patent Literature 19: European Journal of Organic Chemistry, 2017, 24, 3501-3504 SUMMARY

[0039] PROBLEMS TO BE SOLVED BY THE INVENTION

[0040] The propylene polymer has heat resistance and rigidity close to general-purpose engineering plastics and is composed of almost only carbon and hydrogen, and thus has the advantage that no toxic gas is generated even if combustion treatment is performed.

[0041] With recent progress in molding technology, if a propylene polymer having higher stereoregularity than ever before is used, it is possible to exhibit higher physical properties (rigidity, heat resistance, etc.). For this reason, from the market perspective, a propylene polymer having higher stereoregularity is required. In addition, from the viewpoint of resource saving and environmental protection, a production method of a propylene polymer with high productivity is also required.

[0042] Therefore, the object of the present application is to provide an internal donor component for a solid titanium catalyst component, which is capable of producing a propylene polymer having extremely high stereoregularity at high productivity (high activity) when mainly used for a solid titanium catalyst component.

[0043] METHOD FOR SOLVING THE PROBLEMS

[0044] The present inventors etc. have made intensive studies in order to solve the above problems, and as a result, have found that an ester compound having a specific cyclic structure is suitable as a Lewis base for a solid titanium catalyst component, for example, and thus have completed the present application. The present application relates to, for example, the following [1] to [4].

[0045] [1] A cyclic polybasic ester group-containing compound (A) represented by the following formula (1).

[0046] [Chem. 1]

[0047]

[0048] [In formula (1), m and n are integers of 1 to 5, and satisfy the relationship of m + n > 4.

[0049] R 1 and R 2 each are substituted or unsubstituted hydrocarbon groups having 1 to 20 carbon atoms, a plurality of R 3 , a plurality of R 4 , R 5 to R 8 each are groups selected from a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, or a halogen atom, R 1 to R 8 The hydrogen atom, the carbon atom, or both of R 3 to R8 Each is an independent relation, but adjacent R 3 They can directly bond to each other to form multiple bonds. Additionally, adjacent R... 4 They can directly bond together to form multiple bonds. Multiple R atoms bonded to the same carbon atom... 3 Multiple R 4 They can combine to form a ring structure.

[0050] [2] The ester compound (A) as described in item [1], wherein m is 2 or more and n is 2 or more.

[0051] [3] As described in item [1], ester compound (A), R 1 and R 2 It can be a substituted or unsubstituted alkyl, a substituted or unsubstituted alkenyl, a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted aryl, or a substituted or unsubstituted heteroaryl.

[0052] [4] As described in item [1], ester compound (A), R 3 ~R 8 Each of the following groups is selected from hydrogen atom, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted cycloalkenyl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkenoxy, substituted or unsubstituted cycloalkoxy, substituted or unsubstituted cycloalkenoxy, substituted or unsubstituted aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted heteroaryl, or substituted or unsubstituted heteroaryloxy.

[0053] Invention Effects

[0054] The ester compounds of the present invention can be used, for example, as resin additives, cosmetics, topical skin agents, bactericidal compositions, antioxidants, chelating agents, and Ziegler-Natta catalysts. Detailed Implementation

[0055] The ester compounds of the present invention will be described in further detail below.

[0056] The ester compound of the present invention (hereinafter also referred to as "ester compound (A)") is represented by the following general formula (1).

[0057] [Chemistry 2]

[0058]

[0059] In the above formula (1), R 1 and R 2 Each of the above R groups consists of a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. 1 R 2The hydrogen atom, carbon atom, or both may be replaced by at least one atom selected from the group consisting of nitrogen atom, oxygen atom, phosphorus atom, halogen atom and silicon atom (hereinafter, sometimes referred to as heteroatoms). As the heteroatom group mentioned above, it is preferably the group consisting of nitrogen atom, oxygen atom, phosphorus atom and silicon atom, more preferably the group consisting of nitrogen atom, oxygen atom and silicon atom, and even more preferably the group consisting of oxygen atom and silicon atom.

[0060] As substituents containing heteroatoms, heteroatom-containing hydrocarbon groups are preferred examples, with heteroatom-containing aryl groups being particularly preferred examples. Furthermore, examples of heteroatom-containing aryl groups include groups with a basic skeleton consisting of a heteroatom in the aryl structure itself, such as a pyrrole ring or a pyran ring, or groups with heteroatom-containing hydrocarbon groups such as alkoxy groups bonded to a benzene ring.

[0061] In addition, the above R 1 and R 2 Preferably, the hydrocarbon group has 2 to 20 carbon atoms, more preferably a lower limit of 4 carbon atoms, and even more preferably 6 carbon atoms. More detailed structural information will be described later.

[0062] It should be noted that in this invention, the description of substituents as "~ atoms" such as halogen atoms and hydrogen atoms undoubtedly sometimes refers to a bonded manner as represented in the structural formula, such as "H-" or "Cl-".

[0063] Examples of the aforementioned hydrocarbon groups include, for example, substituted or unsubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted alkynyl groups, and substituted or unsubstituted aryl groups.

[0064] Examples of heteroatom-containing hydrocarbon groups (hereinafter sometimes referred to as heteroatom-containing hydrocarbon groups) include substituted or unsubstituted heteroatom-containing alkyl groups and substituted or unsubstituted heteroaryl groups.

[0065] Examples of the aforementioned hydrocarbon groups and heteroatom-containing hydrocarbon groups include alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroatom-containing alkyl, and heteroaryl groups. 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. In the case of aryl groups, the preferred lower limit is 6. On the other hand, the upper limit is preferably 18, more preferably 15, further preferably 10, and particularly preferably 6. In the case of heteroaryl groups, it is preferable to have one or more 5-membered ring structures, more preferably one or more 5- to 7-membered ring structures, and even more preferably one or more 5- or 6-membered ring structures.

[0066] Preferred R 1 and R 2each 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.

[0067] More preferred R 1 and R 2 each is 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.

[0068] Particularly preferred R 1 and R 2 each is 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. It is particularly preferable to be a group selected from a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.

[0069] The above R 1 , R 2 in the present application can be combined with R 3 to R 8 described later to form a monocyclic structure, a polycyclic structure. In addition, the above R 1 , R 2 may be combined with each other to form a cyclic structure.

[0070] R 3 to R 8 >

[0071] In the above formula (1) and the like, R 3 to R 8 each is selected from a hydrogen atom, a halogen atom, a hydrocarbon group, or a heteroatom-containing hydrocarbon group.

[0072] As the group of the above heteroatom, a preferable example is a group consisting of a nitrogen atom, an oxygen atom, a phosphorus atom, a halogen atom, and a silicon atom. More preferable is a group consisting of a nitrogen atom, an oxygen atom, a phosphorus atom, and a silicon atom, further preferable is a group consisting of a nitrogen atom, an oxygen atom, and a silicon atom, particularly preferable is a group consisting of an oxygen atom and a silicon atom. In the case of a substituent containing an oxygen atom, an ether type (a substituent containing a C-O-C type structure) is preferable, and a structure containing an oxygen double bond is preferably avoided.

[0073] Examples of the aforementioned hydrocarbon groups include, for example, substituted or unsubstituted alkyl groups, substituted or unsubstituted cycloalkyl groups, substituted or unsubstituted alkenyl groups, substituted or unsubstituted alkynyl groups, and substituted or unsubstituted aryl groups.

[0074] Examples of heteroatom-containing hydrocarbon groups include substituted or unsubstituted heteroatom-containing alkyl groups and substituted or unsubstituted heteroaryl groups. Furthermore, examples of heteroatom-containing aryl groups include groups with a basic framework consisting of heteroatoms in the aryl structure itself, such as pyrrole rings or pyran rings, and groups with substituents such as heteroatom-containing hydrocarbon groups bonded to a benzene ring.

[0075] Examples of the aforementioned hydrocarbon groups and heteroatom-containing hydrocarbon groups include alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroatom-containing alkyl, and heteroaryl groups. The number of carbon atoms in these groups is preferably 1 to 20. The lower limit is preferably 2, more preferably 3. In the case of aryl groups, the preferred lower limit is 6. On the other hand, the upper limit is preferably 18, more preferably 15, further preferably 10, and particularly preferably 6. In the case of heteroaryl groups, it is preferable to have one or more 5-membered ring structures, more preferably one or more 5- to 7-membered ring structures, and even more preferably one or more 5- or 6-membered ring structures.

[0076] The above-mentioned R is preferred 3 ~R 8 At least one of them is a substituent of the preferred embodiment described above, and more preferably all of them are substituents of the preferred embodiment described above.

[0077] Sometimes the above-mentioned R is preferred 3 ~R 8 At least one substituent is a substituent other than hydrogen. Further, it is sometimes preferred that two or more substituents are substituents other than hydrogen. In this case, it can be a mixture of two or more substituents, or it can be all of the same type of substituent. Further, it is sometimes preferred that one or more carbon atoms forming the cyclic structure are quaternary carbons. More preferably, it is sometimes preferred that R... 7 and / or R 8 Substituents other than hydrogen. R is particularly preferred. 7 and / or R 8 The group is a hydrocarbon group, or a hydrocarbon group containing heteroatoms, especially a hydrocarbon group. If it is in the manner described above, for example, when the ester compound of the present invention is used as a component of a catalyst for olefin polymerization, the performance balance is sometimes improved. Specific examples of the aforementioned performance include reaction control properties such as activity, stereospecificity, and molecular weight control.

[0078] The above R 3 Sometimes multiple exist. In this case, R is bound to different carbons. 3 They are independent of each other, but R is bound to adjacent carbons.3 They can directly combine to form a multiple key. Here, the so-called independent relation refers to multiple Rs. 3 As structural formulas, they can be clearly distinguished from each other; specifically, for example, multiple Rs bound to different carbons. 3 A structure in which the elements do not combine to form a ring structure of 3 or more members.

[0079] The above R 4 Sometimes multiple exist. In this case, R is bound to different carbons. 4 They are independent of each other, bound to the R of adjacent carbons. 4 They can directly combine to form a multiple bond. Here, the so-called independent relation is the same as the R mentioned above. 3 The same rule applies to multiple Rs. 4 As structural expressions, they can be clearly distinguished from each other; specifically, for example, multiple R... 4 A structure in which rings do not bond together to form 3-membered or more ring structures. R-membered rings bonded to the same carbon atom. 3 They can combine with each other to form monocyclic or polycyclic rings. Additionally, R atoms bonded to the same carbon atom... 4 They can combine with each other to form single or multiple rings.

[0080] The above formula (1) includes CR 3 Structure, CR 4 The carbon chain structure can be any of single, double, or triple bonds, with single bonds being the most preferred. Furthermore, heteroatoms can be connected between the carbon chain bonds. A preferred example of such a chain structure is a (divalent) structural formula as shown below.

[0081] [Chemistry 3]

[0082]

[0083] (where l is a natural number)

[0084] The above R 5 ~R 8 There is one substituent. R 5 ~R 8 With R 3 R 4 It is also an independent relationship, but it is bound to the substituent (R) of the adjacent carbon. 3 ~R 8 They can also be directly combined to make R 5 ~R 8 Multiple bonds are formed.

[0085] In equation (1), m and n are selected from integers from 1 to 5, satisfying the relationship m+n≥4.

[0086] The above m, n are values related to the size and balance of the cyclic structure. The lower limit of m, n is preferably 2. Further, it is preferable that both m, n are 2 or more. The upper limit of m, n is 5, and the preferable upper limit is 4. The values of m, n can be the same or different.

[0087] As the above halogen atom, for example, fluorine, chlorine, bromine, iodine can be given.

[0088] As the above substituted or unsubstituted alkyl group, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, neopentyl, n-hexyl, 2,3-dimethyl-2-butyl (thexyl group), cumyl group, triphenylmethyl group, and the like can be given.

[0089] As the above substituted or unsubstituted alkenyl group, for example, vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, pentenyl group, hexenyl group, and the like can be given.

[0090] As the above substituted or unsubstituted alkynyl group, for example, ethynyl group, propynyl group, butynyl group, pentynyl group, hexynyl group, heptynyl group, octynyl group, and the like can be given.

[0091] As the above substituted or unsubstituted cycloalkyl group, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, methylcyclohexyl group, cycloheptyl group, cyclooctyl group, adamantyl group, cyclopentadienyl group, indenyl group, fluorenyl group, and the like can be given.

[0092] As the above substituted or unsubstituted aryl group, for example, phenyl group, methylphenyl group, dimethylphenyl group, diisopropylphenyl group, dimethylisopropylphenyl group, n-propylphenyl group, n-butylphenyl group, t-butylphenyl group, di-t-butylphenyl group, naphthyl group, tetrahydronaphthyl group, biphenyl group, terphenyl group, phenanthryl group, anthryl group, and the like can be given as aromatic hydrocarbon groups, and methoxyphenyl group, dimethylaminophenyl group, nitrophenyl group, trifluoromethylphenyl group, and the like can be given as heteroatom-substituted aryl groups.

[0093] Among the above heteroatom-containing substituents, an aryl group containing an oxygen-containing substituent is preferable, and specifically, examples of the preferable structure include an oxygen-containing substituent such as an alkoxy group, an aryloxy group, an alkoxyalkyl group, an aryloxyalkyl group, a substituent in which the oxygen of the above substituent is replaced with a carbonyl group, a carboxyl group, and the like, which is bound to the aromatic skeleton. Among the above, a substituent in which an alkoxy group or an aryloxy group is bound to the aromatic skeleton is preferable, and a substituent in which an alkoxy group is bound to the aromatic skeleton is more preferable. The number of carbon atoms of the above oxygen-containing substituent is preferably 1 to 10, more preferably 1 to 8, and further preferably 1 to 6. More specifically, examples of the preferable structure other than the above methoxyphenyl group include ethoxyphenyl group, propoxyphenyl group, isopropoxyphenyl group, butoxyphenyl group, phenoxyphenyl group, and the like. An aryl group containing such an oxygen-containing substituent is sometimes particularly preferable for R 1 , R2 .

[0094] As the above-mentioned substituted or unsubstituted heteroatom-containing hydrocarbon group, for example, there can be mentioned: a heteroatom-containing alkyl group such as methoxymethyl, methoxyethyl, benzyloxy, ethoxymethyl, ethoxyethyl, acetyl, benzoyl, and the like; a heteroaromatic group such as furanyl, pyrrolyl, thienyl, pyrazolyl, pyridyl, carbazolyl, imidazolyl, dimethylfuranyl, N-methylpyrrolyl, N-phenylpyrrolyl, diphenylpyrrolyl, thiazolyl, quinolyl, benzofuranyl, triazolyl, tetrazolyl, and the like.

[0095] In the above-mentioned R 3 ~R 8 In the case where R 3 ~R 8 is a substituent other than a hydrogen atom, it can be selected from the substituents exemplified above in R 3 ~R 8 . It is more preferable to be a substituent selected from a hydrocarbon group, a heteroatom-containing hydrocarbon group, and further a hydrocarbon group.

[0096] <Specific Examples of Ester Compound (A)>

[0097] Hereinafter, specific examples of the ester compound (A) of the present application will be shown, but the ester compound (A) of the present application is not limited to these specific examples.

[0098] [Chemical Formula 4]

[0099]

[0100] [Chemical Formula 5]

[0101]

[0102] [Chemical Formula 6]

[0103]

[0104] [Chemical Formula 7]

[0105]

[0106] [Chemical Formula 8]

[0107]

[0108] [Chemical Formula 9]

[0109]

[0110] [Chemical Formula 10]

[0111]

[0112] [Chemical Formula 11]

[0113]

[0114] [Chemical Formula 12]

[0115]

[0116] [Chemical Formula 13]

[0117]

[0118] Note that in the above structural formulas, methyl is represented as "Me", ethyl as "Et", propyl as "Pr", butyl as "Bu", and phenyl as "Ph". In addition, [n] represents "normal", [i] represents "iso", and [t] represents "tertiary".

[0119] In addition, in the ester compound of the present application, the OCOR 1 group and the OCOR 2 group that are bonded to the alicyclic structure sometimes form an ester compound in which the cis structure, trans structure, or the like derived from the alicyclic structure is the main component. Here, the main component means that the cis structure is contained at a rate of more than 50 mol%, and preferably at a rate of more than 70 mol%.

[0120] One of the preferred uses of the ester compound (A) of the present application is a Lewis base (internal donor) component of a solid titanium catalyst component. The reason why the above-mentioned internal donor component is suitable is not clear at present, but the present inventors and others have conjectured as follows.

[0121] The ester compound (A) used in the present application has a special polycyclic structure as shown above, and thus it is conjectured that the compound has a moderate rigidity and a small displacement of the structure. On the other hand, it is understood that there is also a structure in which a part moves slightly flexibly. Therefore, it is considered that when the ester compound (A) is coordinated to a titanium compound and a magnesium compound described later, a stable structure is maintained, and the stereospecificity and the polymerization activity as a catalyst in an olefin polymerization reaction are less likely to change. In addition, it is expected that the above-mentioned flexible structure part reduces the generation of strain from the cyclic structure, and it is possible to exhibit a function as a buffer material against changes in the reaction environment. From these viewpoints, it is considered that a polymer having a high stereoregularity is provided with a high activity. In addition, from such a viewpoint, it is conjectured that there is a potential to easily provide a component having a high molecular weight.

[0122] On the other hand, in the case of the stable structure with less displacement of the above structure, there was initially a concern that the molecular weight distribution would become narrow, but as shown in the examples described later, a polymer with a wide molecular weight distribution could be produced according to the method of the present application. The present inventors presume that the reason for this is that in the case of the ester compound (A), it is possible that a slight change in the cyclic structure, a combination of changes in the respective ring structures, has a large effect on the molecular weight of the resulting polymer; and because there are a plurality of ring structures, it is possible that the combination of stereoisomer structures (for example, chair form, boat form, etc.) that can be taken by each ring becomes diverse.

[0123] <Method for producing ester compound (A)>

[0124] The method for producing the ester compound (A) of the present application is not particularly limited, and for example, a corresponding olefin can be obtained via diolization reaction, diesterization reaction. In addition, for example, it can also be obtained via carbonation reaction, diolization reaction, diesterization reaction using a specific polycyclic compound such as cyclohexadiene. More specifically, it can be produced as follows.

[0125] <Synthesis of olefin>

[0126] The olefin can be synthesized by, for example, Diels-Alder reaction of cyclohexadiene and methyl vinyl ketone (non-patent literature 1). The diene can also use a dimer of the diene as a precursor (for example, dicyclopentadiene) as a raw material.

[0127] <Synthesis of diol>

[0128] The diol as a precursor of the ester can be produced using a corresponding olefin as a raw material. For example, the diol can be directly obtained by reaction of the olefin with potassium permanganate (non-patent literature 4) or osmium tetroxide (non-patent literature 5).

[0129] As another method, the olefin site can be epoxidized by using meta-chloroperbenzoic acid (non-patent literature 6), t-butyl peroxide (non-patent literature 7), dimethyl dioxirane (non-patent literature 8), formic acid and hydrogen peroxide water (non-patent literature 9), hydrogen peroxide water and molybdenum catalyst, or hydrogen peroxide water and tungsten catalyst (non-patent literature 10), followed by acid hydrolysis or base hydrolysis reaction, thereby obtaining the diol.

[0130] In addition, the diol compound can also be obtained by performing hydrolysis after performing cyclic carbonation of the above diene. The details are as follows.

[0131] The cyclic carbonate as a precursor of the diol can be produced by Diels-Alder reaction of a corresponding diene and vinylene carbonate (non-patent literature 19). As with the above, the diene can also use a dimer of the diene as a precursor as a raw material.

[0132] Diols can be obtained by hydrolyzing cyclic carbonates with acid or base (Non-Patent Document 19).

[0133] Esters Synthesis

[0134] The ester corresponding to formula (1) above can be synthesized by reacting the diol with an acyl chloride in the presence of a base. There are no particular limitations on the base; for example, sodium hydroxide, potassium hydroxide, or an amine base can be used. Alternatively, it can be synthesized by reacting the 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). When one equivalent of acyl chloride or carboxylic acid is reacted with the diol, an isomer can be generated, but if the acyl chloride or carboxylic acid is then reacted, a compound equivalent to formula (1) can be obtained. In this case, R... 1 and R 2 They can be the same or different. Alternatively, they can be synthesized by reacting the diol with a carboxylic acid in the presence of an azocarboxylic acid ester and triphenylphosphine (Non-Patent Literature 12).

[0135] The ester compound (A) of the present invention is suitable as a Lewis base component of a solid titanium catalyst, as described above, but is not limited to this use. Undoubtedly, it has the potential to be used as a known additive in various resins, cosmetics, topical skin agents, bactericidal compositions, antioxidants, chelating agents, and so on.

[0136] Example

[0137] The following examples illustrate methods for synthesizing the ester compounds of the present invention. The compounds disclosed in the following examples show a portion of the stereoisomers, and sometimes include other stereoisomers.

[0138] It should be noted that in the structural formula, "Me" represents methyl, "n-Pr" represents n-propyl, "iPr" represents isopropyl, "n-Bu" represents n-butyl, "tBu" represents tert-butyl, and "Ph" represents phenyl.

[0139] exist 1 For H NMR measurements, a JNM-EX270 nuclear magnetic resonance apparatus manufactured by Nippon Electron Ltd. was used, with deuterated chloroform as the solvent and a small amount of tetramethylsilane added.

[0140] The measurement temperature was set to room temperature, and the observation kernel was set to... 1 The sequence was set to H (270MHz), single pulse, 45° pulse, repetition time greater than 5.5 seconds, and cumulative count greater than 16-64. The reference chemical shift was set to 0 ppm for hydrogen in tetramethylsilane. (Source: Organic acid compounds) 1 H peaks were determined using conventional methods.

[0141] [Example 1] (Synthesis of ester compound)

[0142] <Synthesis of Compound 1>

[0143] Compound 1 shown below was synthesized by the method described later.

[0144] [Chemical Formula 1]

[0145]

[0146] Under a nitrogen atmosphere, 8.0 g of 1,3-cyclohexadiene and 8.6 g of vinylene carbonate were added to a 30-ml pressure-resistant vessel, heated and stirred to bring the internal temperature to 220°C, and stirring was continued for 6 hours. After cooling to room temperature, 5 ml of hexane was added, and after stirring, the solid was filtered out. The obtained solid was washed with hexane and dried to obtain 8.5 g of Compound 1.

[0147] <Synthesis of Compound 2>

[0148] Compound 2 shown below was synthesized by the method described later.

[0149] [Chemical Formula 15]

[0150]

[0151] To a 50-ml 3-necked flask, 16.6 g of the above Compound 1, 40.0 g of sodium hydroxide, and 100 ml of pure water were added, heated and stirred to bring the internal temperature to 100°C, and stirring was continued for 6 hours. After cooling to room temperature, neutralization was performed by adding 12 mol / L concentrated hydrochloric acid at 50°C or lower. The reaction liquid was extracted 3 times with ethyl acetate, and the organic layer was dried with sodium sulfate and concentrated to obtain 14.0 g of Compound 2.

[0152] <Synthesis of Compound 3>

[0153] Compound 3 shown below was synthesized by the method described later.

[0154] [Chemical Formula 16]

[0155]

[0156] Under a nitrogen atmosphere, 14.0 g of the above Compound 2, 42.2 g of benzoyl chloride, and 200 ml of pyridine were added to a 200-ml 3-necked flask, heated and stirred to bring the internal temperature to 60°C, and stirring was continued for 6 hours. After distilling off the pyridine, chloroform was added, washed with 2 mol / L hydrochloric acid and 2 mol / L aqueous sodium hydroxide solution, and the organic layer was dried with magnesium sulfate. After concentration, recrystallization was performed from hexane to obtain 13.1 g of Compound 3.

[0157] 1 H NMR (270 MHz, CDC13, with TMS as an 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).

[0158] The melting point of the obtained compound 3 was measured using a differential scanning calorimeter (DSC-60A, manufactured by Shimadzu Corporation, initial temperature: 25°C, final temperature: 300°C, temperature increase rate: 10°C / min), and the result was a melting point of 95°C.

[0159] [Example 2] (Synthesis of ester compound)

[0160] The compound 4 shown below was synthesized by the method described later.

[0161] [Compound 17]

[0162]

[0163] Under a nitrogen atmosphere, 7.0 g of the compound 3 obtained in Example 1, 3.6 g of Pd / C (manufactured by Nippon Carbon Co., Ltd., 5% Pd, water content 58.6%), and 100 ml of ethyl acetate were added to a 300-ml 3-necked flask, and stirring was performed at room temperature. One atmosphere of hydrogen gas was introduced into the reaction vessel to change to a hydrogen atmosphere, and stirring was continued for 15 hours. After filtration was performed using diatomaceous earth, the filtrate was concentrated. Recrystallization was performed using hexane, and 6.6 g of the compound 4 was obtained.

[0164] 1 H NMR (270 MHz, CDC13, with TMS as an 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).

[0165] The melting point of the obtained compound 4 was measured using a differential scanning calorimeter (DSC-60A, manufactured by Shimadzu Corporation, initial temperature: 25°C, final temperature: 300°C, temperature increase rate: 10°C / min), and the result was a melting point of 105°C.

[0166] [Example 3] (Synthesis of ester compound)

[0167] <Compound 5>

[0168] The following compound 5 shown below was synthesized by the method described later.

[0169] [Chemical Formula 18]

[0170]

[0171] Under a nitrogen atmosphere, 13.6 g of α-terpinene and 8.6 g of vinylene carbonate were added to a 30-ml pressure-resistant vessel, heated and stirred to bring the internal temperature to 220°C, and stirring was continued for 6 hours. After cooling to room temperature, 5 ml of hexane was added, and after stirring, the solid was filtered off. The obtained solid was washed with hexane and dried to obtain 14.7 g of compound 5.

[0172] <SYNTHESIS OF COMPOUND 6>

[0173] The following compound 6 shown below was synthesized by the method described later.

[0174] [Chemical Formula 19]

[0175]

[0176] In a 50-ml 3-necked flask, 4.5 g of the above compound 5, 8.0 g of sodium hydroxide, and 30 ml of pure water were added, heated and stirred to bring the internal temperature to 100°C, and stirring was continued for 6 hours. After cooling to room temperature, neutralization was performed by adding 12 mol / L concentrated hydrochloric acid at 50°C or lower. The reaction liquid was extracted 3 times with ethyl acetate, the organic layer was dried with sodium sulfate and concentrated, and the solid was recovered to obtain 3.9 g of compound 6.

[0177] <SYNTHESIS OF COMPOUND 7>

[0178] The following compound 7 shown below was synthesized by the method described later.

[0179] [Chemical Formula 20]

[0180]

[0181] Under a nitrogen atmosphere, 3.9 g of the above compound 6, 8.4 g of benzoyl chloride, and 100 ml of pyridine were added to a 200-ml 3-necked flask, heated and stirred to bring the internal temperature to 60°C, and stirring was continued for 6 hours. After distilling off the pyridine, chloroform was added, washed with 2 mol / L hydrochloric acid and 2 mol / L aqueous sodium hydroxide solution, and the organic layer was dried with magnesium sulfate. After concentration, the solid was filtered off, washed with hexane, and dried to obtain 3.0 g of compound 7.

[0182] 1H NMR (270 MHz, CDC13, internal standard TMS): 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, IH), 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).

[0183] The melting point of the obtained compound 7 was measured by a differential scanning calorimeter (DSC-60A, manufactured by Shimadzu Corporation, initial temperature: 25°C, final temperature: 300°C, temperature increasing rate: 10°C / min), and the result was 137°C.

[0184] [Example 4] (Synthesis of ester compound)

[0185] < Synthesis of compound 8 >

[0186] The compound 8 shown below was synthesized by the method described later.

[0187] [Compound 21]

[0188]

[0189] In a 200-ml 3-necked flask, 4.5 g of the above compound 5, 4.3 g of Pd / C (manufactured by Nippon Catalysis Co., 5% Pd, water content 58.6%), and 100 ml of ethyl acetate were added, and stirred at room temperature. Hydrogen gas was introduced into the reaction vessel to change the atmosphere to hydrogen, and the stirring was continued for 15 hours. After filtration using celite, the filtrate was concentrated, and the solid was recovered to obtain 4.5 g of compound 8.

[0190] < Synthesis of compound 9 >

[0191] The compound 9 shown below was synthesized by the method described later.

[0192] [Compound 22]

[0193]

[0194] In a 50-ml 3-necked flask, 4.5 g of the above compound 8, 8.0 g of sodium hydroxide, and 30 ml of pure water were added, and heated and stirred to bring the internal temperature to 100°C, and the stirring was continued for 6 hours. After cooling to room temperature, neutralization was performed by adding 12 mol / L concentrated hydrochloric acid at 50°C or lower. The reaction liquid was extracted 3 times with ethyl acetate, and the organic layer was dried with sodium sulfate and concentrated to obtain 3.8 g of compound 9.

[0195] Synthesis of Compound 10

[0196] Compound 10 shown below was synthesized by the method described later.

[0197] [Compound 23]

[0198]

[0199] Under 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 3-necked flask, heated and stirred to bring the internal temperature to 60°C, and stirring was continued for 6 hours. After distilling off the pyridine, chloroform was added, washed with 2 mol / L hydrochloric acid and 2 mol / L aqueous sodium hydroxide solution, and the organic layer was dried over magnesium sulfate. After concentration, purification was performed using a silica gel column and dried to obtain 3.6 g of Compound 10.

[0200] 1 H NMR (270 MHz, CDC13, with TMS as an internal standard): 7.87-7.74 (m, 4H), 7.45-7.12 (m, 6H), 5.49-5.46 (m, IH), 5.26-5.25 (m, IH), 2.10-0.82 (m, 18H).

[0201] The melting point of the obtained Compound 10 was measured using a differential scanning calorimeter (DSC-60A, manufactured by Shimadzu Corporation, initial temperature: 25°C, final temperature: 300°C, temperature increase rate: 10°C / min), and the result was a melting point of 107°C.

[0202] [Example 5] (Synthesis of ester compound)

[0203] Synthesis of Compound 11

[0204] Compound 11 shown below was synthesized by the method described later.

[0205] [Compound 24]

[0206]

[0207] Under a nitrogen atmosphere, 4.0 g of the above Compound 9, 9.3 g of 4-methylbenzoyl chloride and 50 ml of pyridine were added to a 200 ml 3-necked flask, heated and stirred to bring the internal temperature to 60°C, and stirring was continued for 6 hours. After distilling off the pyridine, chloroform was added, washed with 2 mol / L hydrochloric acid and 2 mol / L aqueous sodium hydroxide solution, and the organic layer was dried over magnesium sulfate. After concentration, purification was performed using a silica gel column and dried to obtain 2.9 g of Compound 11.

[0208] 1H NMR (270 MHz, CDC13, with TMS as an 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).

[0209] [Example 6] (Synthesis of ester compound)

[0210] < Synthesis of Compound 12 >

[0211] Compound 12 shown below was synthesized by the method described later.

[0212] [Compound 25]

[0213]

[0214] Under 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 3-necked flask, heated and stirred to bring the internal temperature to 60°C, and stirring was continued for 6 hours. After distilling off the pyridine, chloroform was added, washed with 2 mol / L hydrochloric acid and 2 mol / L aqueous sodium hydroxide solution, and the organic layer was dried over magnesium sulfate. After concentration, purification was performed using a silica gel column and dried to obtain 2.3 g of Compound 12.

[0215] 1 H NMR (270 MHz, CDC13, with TMS as an 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).

[0216] The melting point of the obtained Compound 12 was measured using a differential scanning calorimeter (DSC-60A manufactured by Shimadzu Corporation, initial temperature: 25°C, final temperature: 300°C, temperature increase rate: 10°C / minute), and the result was a melting point of 70°C.

[0217] [Example 7] (Synthesis of ester compound)

[0218] < Synthesis of Compound 13 >

[0219] Compound 13 shown below was synthesized by the method described later.

[0220] [Chemical 26]

[0221]

[0222] Under a nitrogen atmosphere, 4.0 g of the above compound 9, 11.8 g of 4- n-butylbenzoyl chloride and 50 ml of pyridine were added to a 200 ml 3-necked flask, heated and stirred to bring the internal temperature to 60°C, and stirring was continued for 6 hours. After distilling off the pyridine, chloroform was added, washed with 2 mol / L hydrochloric acid and 2 mol / L aqueous sodium hydroxide solution, and the organic layer was dried over magnesium sulfate. After concentration, purification was performed using a silica gel column chromatograph and dried to obtain 7.9 g of compound 13.

[0223] 1 H NMR (270 MHz, CDC13, with TMS as an 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).

[0224] [Example 8] (Synthesis of ester compound)

[0225] <Synthesis of compound 14>

[0226] Compound 14 shown below was synthesized by the method described later.

[0227] [Chemical 27]

[0228]

[0229] Under a nitrogen atmosphere, 4.0 g of compound 9, 11.8 g of 4-tert- butylbenzoyl chloride and 50 ml of pyridine were added to a 200 ml 3-necked flask, heated and stirred to bring the internal temperature to 60°C, and stirring was continued for 6 hours. After distilling off the pyridine, chloroform was added, washed with 2 mol / L hydrochloric acid and 2 mol / L aqueous sodium hydroxide solution, and the organic layer was dried over magnesium sulfate. After concentration, purification was performed using a silica gel column chromatograph and dried to obtain 1.7 g of compound 14.

[0230] 1H NMR (270 MHz, CDC13, with 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).

[0231] The melting point of the obtained compound 14 was measured by a differential scanning calorimeter (DSC-60A, manufactured by Shimadzu Corporation, initial temperature: 25°C, final temperature: 300°C, temperature increasing rate: 10°C / min) and the result was 137°C.

[0232] [Example 9] (Synthesis of ester compound)

[0233] <Synthesis of compound 15>

[0234] The compound 15 shown below was synthesized by the method described later.

[0235] [Compound 28]

[0236]

[0237] Under 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 3-necked flask, heated and stirred to bring the internal temperature to 60°C, and stirring was continued for 6 hours. After distilling off the pyridine, chloroform was added, washed with 2 mol / L hydrochloric acid and 2 mol / L aqueous sodium hydroxide solution, and the organic layer was dried over magnesium sulfate. After concentration, purification was performed using a silica gel column and dried to obtain 4.7 g of compound 15.

[0238] 1 H NMR (270 MHz, CDC13, with 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).

[0239] The melting point of the obtained compound 15 was measured by a differential scanning calorimeter (DSC-60A, manufactured by Shimadzu Corporation, initial temperature: 25°C, final temperature: 300°C, temperature increasing rate: 10°C / min) and the result was 60°C.

[0240] [Example 10] (Synthesis of ester compound)

[0241]

[0242] The compound 16 shown below was synthesized by the method described later.

[0243] [Compound 29]

[0244]

[0245] Under a nitrogen atmosphere, 4.0 g of the above compound 9, 10.1 g of 3,4- dimethylbenzoyl chloride and 50 ml of pyridine were added to a 200 ml 3-necked flask, heated and stirred to bring the internal temperature to 60°C, and stirring was continued for 6 hours. After distilling off the pyridine, chloroform was added, washed with 2 mol / L hydrochloric acid and 2 mol / L aqueous sodium hydroxide solution, and the organic layer was dried over magnesium sulfate. After concentration, purification was performed using a silica gel column and dried to obtain 1.2 g of the compound 16.

[0246] 1 H NMR (270 MHz, CDC13, with TMS as an 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).

[0247] The melting point of the obtained compound 16 was measured using a differential scanning calorimeter (DSC-60A, manufactured by Shimadzu Corporation, initial temperature: 25°C, final temperature: 300°C, temperature increase rate: 10°C / min), and the result was a melting point of 92°C.

[0248] [Example 11] (Synthesis of ester compound)

[0249]

[0250] The compound 17 shown below was synthesized by the method described later.

[0251] [Compound 30]

[0252]

[0253] Under a nitrogen atmosphere, 4.0 g of the above compound 9, 10.1 g of 3,4- dimethylbenzoyl chloride and 50 ml of pyridine were added to a 200 ml 3-necked flask, heated and stirred to bring the internal temperature to 60°C, and stirring was continued for 6 hours. After distilling off the pyridine, chloroform was added, washed with 2 mol / L hydrochloric acid and 2 mol / L aqueous sodium hydroxide solution, and the organic layer was dried over magnesium sulfate. After concentration, purification was performed using a silica gel column and dried to obtain 1.2 g of the compound 16.

[0254] ​​1 H NMR (270 MHz, CDC13, internal standard TMS): 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).

[0255] The melting point of the obtained compound 17 was measured by a differential scanning calorimeter (DSC-60A, manufactured by Shimadzu Corporation, initial temperature: 25°C, final temperature: 300°C, temperature increasing rate: 10°C / min) and the result was 133°C.

[0256] [Example 12] (Synthesis of ester compound)

[0257] < Synthesis of compound 18, compound 19 >

[0258] The compounds 18 and 19 shown below were synthesized by the following method.

[0259] [Chemical 31]

[0260]

[0261] Under a nitrogen atmosphere, 3.3 g of anhydrous aluminum chloride and 25 ml of dehydrated toluene were added to a 50 ml 2-necked flask and stirred at room temperature. 4 ml of dehydrated THF was slowly added to dissolve the aluminum chloride, thereby preparing an aluminum chloride solution. Under a nitrogen atmosphere, 8.6 g of methyl vinyl ketone, 20.1 g of α-terpinene and 60 ml of dehydrated toluene were added to a 300 ml 3-necked flask and stirred while cooling in an ice bath. The previously prepared aluminum chloride solution was slowly added to the 300 ml flask, and then warmed to room temperature and stirred overnight. The reaction was stopped by cooling again with an ice bath and adding 100 ml of water. After separating the organic layer from the aqueous layer, the organic layer was washed sequentially with 50 ml of water, saturated aqueous sodium bicarbonate solution, and saturated brine, dried over magnesium sulfate, and concentrated with a rotary evaporator. The obtained crude product was purified by silica gel column chromatography to obtain 18.4 g of an isomer mixture of compound 18 and compound 19.

[0262] < Synthesis of compound 20, compound 21 >

[0263] The compounds 20 and 21 shown below were synthesized by the following method.

[0264] [Chemical 32]

[0265]

[0266] In a 1000 ml 3 -necked flask equipped with a dropping funnel, 7 g of a mixture of compound 18 and compound 19, 132 ml of t-butyl alcohol and 33 ml of water were added and cooled to 0°C. An aqueous potassium permanganate solution was prepared by adding 7.91 g of potassium permanganate, 1.79 g of sodium hydroxide and 165 ml of water to another flask and added to the dropping funnel. The potassium permanganate was added dropwise at a rate such that the internal temperature did not exceed 5°C. After the addition was complete, stirring was continued for 1 hour and a saturated aqueous sodium thiosulfate solution was added dropwise until the purple-red color of the aqueous layer disappeared. 350 ml of ethyl acetate was added and allowed to stand. The supernatant organic layer was removed and 350 ml of ethyl acetate was added to the aqueous layer and allowed to stand. The supernatant was removed and combined with the previous organic layer. The organic layer was washed with saturated brine, dried over magnesium sulfate and concentrated using 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.

[0267]

[0268] Compound 22 and 23 shown below were synthesized by the methods described later.

[0269] [Compound 33]

[0270]

[0271] In a 50 ml 3 -necked flask, 1.93 g of a mixture of compound 20 and compound 21 and 8 ml of anhydrous pyridine were added under a nitrogen atmosphere. After cooling in an ice bath, 2 ml of benzoyl chloride was added dropwise slowly and allowed to warm to room temperature while stirring overnight. Dichloromethane and water were added to the reaction mixture and the organic layer was separated and the aqueous layer was extracted with dichloromethane three times. The organic layer was washed with saturated brine, dried over magnesium sulfate and concentrated using a rotary evaporator. The reaction mixture was purified by silica gel column chromatography to obtain 2.34 g of a mixture of compound 22 and compound 23 (an isomer mixture in a mixture ratio of 71:29).

[0272] 1 ​H NMR (270 MHz, CDC13, internal standard TMS): δ 7.87-7.71 (m, 4H), 7.50-7.27 (signals overlapped with CHC13, m, 4H), 7.15-7.09 (m, 2H), 6.20 (dd, J = 7.6 Hz, 1.3 Hz, IH, major isomer), 5.79 (dd, J = 7.9 Hz, 2.3 Hz, IH, minor isomer), 5.65-5.63 (m, IH, minor isomer), 5.49 (dd, J = 7.9 Hz, 2.0 Hz, IH, major isomer), 3.02 (dd, J = 11.9 Hz, 4.9 Hz, IH, major isomer), 2.81 (t, J = 9.2 Hz, IH, minor isomer), 2.27 (s, 3H, major isomer), 2.26 (s, 3H, minor isomer), 2.17-1.23 (m, 7H), 0.94-0.81 (m, 9H).

[0273] [Example 13] Synthesis of ester compound

[0274] <Synthesis of Compound 24, Compound 25>

[0275] The compounds 24 and 25 shown below were synthesized by the method described later.

[0276] [Compound 34]

[0277]

[0278] Under a nitrogen atmosphere, 2.0 g of anhydrous aluminum chloride and 18 ml of dehydrated toluene were added to a 50 ml two-necked flask and stirred at room temperature. 2.3 ml of dehydrated THF was slowly added to dissolve the aluminum chloride, thereby preparing an aluminum chloride solution. Under a nitrogen atmosphere, 9.4 g of phenyl vinyl ketone, 11.6 g of α-terpinene and 40 ml of dehydrated toluene were added to a 300 ml three-necked flask and stirred while cooling in an ice bath. After the previously prepared aluminum chloride solution was slowly added to the 300 ml flask, the temperature was raised to room temperature and stirred overnight. The reaction was stopped by cooling again with an ice bath and adding 150 ml of water. The organic layer was separated from the aqueous layer, and the organic layer was washed successively with 100 ml of water, saturated aqueous sodium bicarbonate solution, and saturated brine, dried with magnesium sulfate, and concentrated with a rotary evaporator. The resulting crude product was purified with silica gel column chromatography to obtain 10.9 g of an isomer mixture of the compound 24 and the compound 25.

[0279] <Synthesis of Compound 26, Compound 27>

[0280] The compounds 26 and 27 shown below were synthesized by the method described later.

[0281] [Compound 34]

[0282]

[0283] In a 1000 ml 3-necked flask equipped with a dropping funnel, 10.8 g of a mixture of compound 24 and compound 25, 200 ml of t-butyl alcohol and 40 ml of water were charged and cooled to 0°C. An aqueous potassium permanganate solution was prepared by charging 6.98 g of potassium permanganate, 1.93 g of sodium hydroxide and 160 ml of water in another flask and charged into the dropping funnel. The potassium permanganate was added dropwise at a rate so that the internal temperature did not exceed 6°C. After the addition was completed, stirring was continued for 1 hour and saturated aqueous sodium thiosulfate was added dropwise until the purple-red color of the aqueous layer disappeared. 350 ml of ethyl acetate was added and allowed to stand with stirring. The supernatant organic layer was drawn off and 350 ml of ethyl acetate was again added to the aqueous layer and allowed to stand with stirring. The supernatant was drawn off and combined with the previous organic layer. The organic layer was washed with saturated brine, dried over magnesium sulfate and concentrated using a rotary evaporator to obtain a crude product. The crude product was purified by silica gel column chromatography to obtain 4.0 g of a mixture of isomers of compound 26 and compound 27.

[0284] < Synthesis of compound 28, compound 29 >

[0285] Compound 28 and 29 shown below were synthesized by the method described later.

[0286] [Chem. 36]

[0287]

[0288] In a 50 ml 3-necked flask, 3.6 g of a mixture of compound 26 and compound 27 and 5 ml of anhydrous pyridine were charged under a nitrogen atmosphere. After cooling in an ice bath, 2.9 ml of benzoyl chloride was added dropwise slowly and then allowed to warm to room temperature and stirring was continued overnight. To the reaction solution, dichloromethane and water were added and the organic layer was separated and the aqueous layer was extracted with dichloromethane three times. The organic layer was washed with saturated brine, dried over magnesium sulfate and concentrated using a rotary evaporator. The reaction mixture was purified by silica gel column chromatography to obtain 3.42 g of a mixture of compound 28 and compound 29 (a mixture of isomers in a ratio of 76:24).

[0289] 1H NMR (270 MHz, CDC13, internal standard TMS): δ 8.03-7.09 (m, 15H), 6.51 (dd, J = 7.6 Hz, 1.3 Hz, IH, major isomer), 6.08 (dd, J = 7.9 Hz, 1.6 Hz, IH, minor isomer), 5.74 (dd, J = 7.9 Hz, 1.0 Hz, IH, minor isomer), 5.70 (dd, J = 7.6 Hz, 2.0 Hz, IH, major isomer), 3.84 (dd, J = 11.9 Hz, 4.9 Hz, IH, major isomer), 3.70 (t, J = 9.2 Hz, IH, minor isomer), 2.25-1.23 (m, 7H), 0.93-0.75 (m, 9H).

[0290] The melting point of the mixture of the obtained compound 28 and compound 29 was measured by a differential scanning calorimeter (DSC 7020, Hitachi High-Technologies Corporation, initial temperature: 25°C, final temperature: 300°C, temperature increasing rate: 10°C / min) and the result was 130°C.

[0291] [Example 14]

[0292] Preparation of solid titanium catalyst component [α1]

[0293] After a 1 L glass container was sufficiently replaced with nitrogen, 85.8 g of anhydrous magnesium chloride, 321 g of decane and 352 g of 2-ethylhexyl alcohol were put in the container, and a uniform solution was prepared by heating the mixture at 130°C for 3 hours. 241 g of the solution and 6.43 g of ethyl benzoate were put in the glass container, and the mixture was stirred at 50°C for 1 hour.

[0294] After the thus obtained homogeneous solution was cooled to room temperature, 38.3 ml of the homogeneous solution was added dropwise to 100 ml of titanium tetrachloride kept at -20°C under stirring at a stirring speed of 350 rpm for 45 minutes. After the addition was completed, the temperature of the mixture was increased to 80°C over 3.8 hours, and after the temperature reached 80°C, 1.26 g of the above-mentioned compound 10 was added to the mixture. The temperature was again increased to 120°C over 40 minutes, and the mixture was kept at the same temperature under stirring for 35 minutes. After the reaction was completed, the solid fraction was collected by hot filtration, and after the solid fraction was again suspended in 100 ml of titanium tetrachloride, the reaction was again carried out at 120°C for 35 minutes. After the reaction was completed, the solid fraction was again collected by hot filtration, and washed with 100°C decane and room temperature decane in a washing liquid until free titanium compounds were not detected. The solid titanium catalyst component [αl] containing the compound 10 prepared by the above operation was stored as a decane slurry, but a part of it was dried for the purpose of investigating the catalyst composition. The composition of the solid titanium catalyst component [αl] obtained by the above operation was 0.28 mass% of titanium, 1.5 mass% of magnesium, and 0.13 mass% of 2-ethylhexyl alcohol residue.

[0295] <Official polymerization>

[0296] In a polymerizer having a content volume of 2 liters, after 500 g of propylene and 1 NL of hydrogen were added at room temperature, a mixture liquid obtained by mixing 7 ml of heptane, 0.35 mmol of triethylaluminum, 0.07 mmol of cyclohexylmethyldimethoxysilane, and 0.0028 mmol (in terms of titanium atoms) of the solid titanium catalyst component [αl] at 25°C for 10 minutes was added, and the temperature inside the polymerizer was rapidly increased to 70°C. After the polymerization was carried out at 70°C for 1.5 hours, the reaction was stopped with a small amount of methanol, and the propylene was removed. Further, the obtained polymer particles were dried under reduced pressure at 80°C overnight. The activity, the bulk specific gravity, the MFR, the amount of decane-insoluble component, the Tm, the Tmf, the ΔH, the MWD (molecular weight distribution), and the like are shown in Table 1.

[0297] [Table 1]

[0298] Table 1

[0299]

[0300] The measuring methods of the above-mentioned properties are as follows.

[0301] (1) Bulk specific gravity:

[0302] It was measured according to JIS K-6721.

[0303] (2) Melt flow rate (MFR):

[0304] The temperature setting was set to 230°C in the case of propylene polymers, as determined in accordance with ASTM D1238E.

[0305] (3) Amount of decane-soluble (insoluble) component:

[0306] In a glass measuring vessel, about 3 g of the propylene polymer (measured to the nearest 10 -4 mg unit. In addition, the weight is represented as b (g) in the following formula.), 500 ml of decane, and a small amount of a heat-resistant stabilizer soluble in decane were charged, and the propylene polymer was dissolved by raising the temperature to 150°C over 2 hours under a nitrogen atmosphere while stirring with a stirrer, and after keeping at 150°C for 2 hours, it was slowly cooled to 23°C over 8 hours. The liquid containing the precipitate of the obtained propylene polymer was subjected to reduced-pressure filtration using a 25G-4 standard glass filter manufactured by Tokyo Rikakiki Co., Ltd. 100 ml of the filtrate was selected, and it was reduced-pressure dried to obtain a part of the decane-soluble component, and the weight was measured to the nearest 10 -4 mg unit (the weight is represented as a (g) in the following formula.). After this operation, the amount of the decane-soluble component was determined using the following formula.

[0307] Decane-soluble component content rate = 100 x (500 x a) / (100 x b)

[0308] Decane-insoluble component content rate = 100 - 100 x (500 x a) / (100 x b)

[0309] (4) Molecular weight distribution:

[0310] Gel permeation chromatography: HLC-8321 GPC / HT manufactured by Tosoh Corporation

[0311] Detector: differential refractometer

[0312] Column: TSKgel GMH6-HT x 2 manufactured by Tosoh Corporation and TSKgel GMH6-HTL x 2 were connected in series.

[0313] Mobile phase medium: o-dichlorobenzene

[0314] Flow rate: 1.0 ml / min

[0315] Measurement temperature: 140°C

[0316] Method for preparing standard curve: standard polystyrene samples were used

[0317] Sample concentration: 0.1% (w / w)

[0318] Sample solution amount: 0.4 ml

[0319] The obtained chromatogram was analyzed by a known method under the above conditions, whereby the weight average molecular weight (Mw), the number average molecular weight (Mn), the Z average molecular weight (Mz), and the Mw / Mn value, the Mz / Mw value as an index of the molecular weight distribution (MWD) were calculated. The measurement time for each 1 sample was 60 minutes.

[0320] (5) Melting point (Tm) of the polymer:

[0321] The melting point (Tm), the crystallization temperature (Tc), and the heat of fusion (ΔH) of the polymer in the present application were measured by a differential scanning calorimeter (DSC) in a DSC220C apparatus manufactured by Seiko Instruments Inc. A sample of 3 to 10 mg was sealed in an aluminum pan, and heated from room temperature to 200°C at a rate of 100°C / min. The sample was held at 200°C for 5 minutes, and then cooled to 30°C at a rate of 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 to 200°C at a rate of 10°C / min for the second time. In this second heating test, the peak temperature was taken as the melting point (Tm), and the heat of fusion was taken as the heat of fusion (ΔH).

[0322] The final melting point (Tmf) of the polymer in the present application was measured by a differential scanning calorimeter (DSC) in a DSC220C apparatus manufactured by Seiko Instruments Inc. A sample of 3 to 10 mg was sealed in an aluminum pan, and heated from room temperature to 240°C at a rate of 80°C / min. The sample was held at 240°C for 1 minute, and then cooled to 0°C at a rate of 80°C / min. After being held at 0°C for 1 minute, the sample was heated to 150°C at a rate of 80°C / min, and held for 5 minutes. Finally, the sample was heated to 180°C at a rate of 1.35°C / min, and the intersection of the tangent line of the inflection point on the high temperature side of the peak obtained in this final heating test and the base line was taken as the final melting point (Tmf).

[0323] The Tmf can be considered as a parameter for evaluating the ease of crystallization, the firmness of the crystalline structure, the firmness of the crystalline structure of a component having a very high crystallinity, and the like, of a polymer considered to have a tendency to be difficult to crystallize. More specifically, it can be considered that the higher the Tmf value, the more easily a super high molecular weight polymer component forms a crystalline structure that is firm and has a high heat resistance.

[0324] [Example 15] (Synthesis of ester compound)

[0325] <Synthesis of Compound 30>

[0326] Compound 30 shown below was synthesized by the method described later.

[0327] [Compound 37]

[0328]

[0329] (Synthesis of the precursor (cycloalkene compound))

[0330] Under a nitrogen atmosphere, 4.5 g of anhydrous aluminum chloride, 90 ml of dehydrated toluene were added to a 200 ml 2-necked flask and stirred at room temperature. 5.6 ml of dehydrated THF was slowly added to dissolve the aluminum chloride, thereby preparing an aluminum chloride solution. Under a nitrogen atmosphere, 24.3 g of phenyl-l-propenyl ketone, 28.0 g of α-terpinene and 170 ml of dehydrated toluene were added to a 500 ml 3-necked flask and stirred while cooling in an ice bath. After slowly adding the previously prepared aluminum chloride solution to the 500 ml flask, the temperature was raised to room temperature and stirred overnight. The reaction was stopped by cooling again with an ice bath and adding 150 ml of water. The reaction solution was added to a separatory funnel, followed by 300 ml of dichloromethane. After separating the organic layer from the aqueous layer, the organic layer was washed with 300 ml of water and separated again. The organic layer was washed with saturated sodium bicarbonate solution and saturated brine, dried with magnesium sulfate, and concentrated with a rotary evaporator. The resulting crude product was purified with silica gel column chromatography to obtain 12.0 g of a Diels-Alder adduct (cycloalkene compound).

[0331] (Synthesis of the diol compound)

[0332] A 1000 ml 3-necked flask was charged with 12.0 g of the above Diels-Alder adduct, 167 ml of t-butyl alcohol and 42 ml of water, a dropping funnel was attached, and cooled to 0°C. An aqueous permanganate solution was prepared by charging 10.0 g of potassium permanganate, 2.2 g of sodium hydroxide and 209 ml of water in another flask and adding to the dropping funnel. The potassium permanganate was slowly added so that the internal temperature did not exceed 5°C. After the addition was completed, stirring was continued for 1 hour, and saturated aqueous sodium thiosulfate solution was added until the purple-red color of the aqueous layer disappeared. After stirring with 350 ml of ethyl acetate, the supernatant was allowed to stand. The supernatant organic layer was drawn off, 350 ml of ethyl acetate was added to the aqueous layer and stirred, and the supernatant was again allowed to stand. The supernatant organic layer was similarly drawn off and combined with the previous organic layer. The organic layer was washed with saturated brine, dried with magnesium sulfate, and concentrated with a rotary evaporator to obtain 14.0 g of a crude product. The crude product was purified with silica gel column chromatography to obtain 3.84 g of a diol.

[0333] (Synthesis of ester compound 30)

[0334] To a 50-ml 3-necked flask, 3.84 g of the above diol and 12.4 ml of dry pyridine were added under a nitrogen atmosphere. After cooling in an ice bath, 2.5 ml of benzoyl chloride was added dropwise, and then the temperature was raised to room temperature, and stirring was continued overnight. To the reaction solution, dichloromethane and water were added to separate the organic layer, and the aqueous layer was extracted with dichloromethane three times. The organic layer was washed with saturated brine, dried over magnesium sulfate, and concentrated using a rotary evaporator. The reaction mixture was purified by silica gel column chromatography to obtain 2.11 g of compound 30 as a main product.

[0335] 1 H NMR (270 MHz, CDC13, with TMS as an internal standard): δ 8.08-8.01 (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 = 7.6 Hz, IH), 5.72-5.61 (m, IH), 3.42 (d, J = 5.3 Hz, IH), 2.16-1.93 (m, 2H), 1.86-1.44 (m, 4H), 1.12 (d, J = 6.9 Hz, 3H), 0.87-0.69 (m, 9H).

[0336] The melting point of the mixture of the obtained compound 30 was measured using a differential scanning calorimeter (Hitachi High-Technologies Corporation DSC7020, initial temperature: 25°C, final temperature: 300°C, temperature increase rate: 10°C / min), and the result was a melting point of 60°C.

[0337] Industrial applicability

[0338] The novel ester compound of the present application is a compound useful in the production of a resin additive, a cosmetic material, a skin external agent, a bactericidal composition, an antioxidant, a chelating agent, a Ziegler-Natta catalyst. In particular, it can be used as a catalyst component for a Ziegler-Natta catalyst, and a catalyst that provides excellent stereoregularity and productivity in the polymerization of polypropylene can be produced. As described above, the ester compound of the present application has a very high industrial value.

Claims

1. A cyclic compound (A) containing a polyester group, represented by the following formula (1), [Chemistry 1] In equation (1), m and n are integers from 1 to 5, satisfying the relationship m + n ≥ 4. R 1 and R 2 Each aryl group is either substituted or unsubstituted with 6 to 20 carbon atoms. When the aryl group is a heteroatom-substituted aryl group, the heteroatom-substituted aryl group is an oxygen-containing substituent with 1 to 10 carbon atoms. Multiple R groups... 3 Multiple R 4 R 5 ~R 8 Each group is selected from hydrogen atoms, halogen atoms, hydrocarbon groups, and heteroatom-containing hydrocarbon groups. When the heteroatom-containing hydrocarbon group is a substituent containing an oxygen atom, it is an ether type, that is, a substituent containing a COC type structure. R 3 ~R 8 Each is an independent relation, but adjacent R 3 They can directly combine to form multiple bonds; in addition, adjacent R 4 They can also directly combine to form multiple bonds; multiple R bonds bonded to the same carbon atom 3 Multiple R 4 They can combine with 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. The ester compound (A) according to claim 1, R 3 ~R 8 Each of the groups is selected from hydrogen atom, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted cycloalkenyl, substituted or unsubstituted alkoxy, substituted or unsubstituted alkenoxy, substituted or unsubstituted cycloalkoxy, substituted or unsubstituted cycloalkenoxy, substituted or unsubstituted aryl, substituted or unsubstituted aryloxy, substituted or unsubstituted heteroaryl, and substituted or unsubstituted heteroaryloxy.

4. The ester compound (A) according to claim 1, wherein R 1 and R 2 Each is a substituted or unsubstituted aryl group with 6 to 15 carbon atoms. When the aryl group is a heteroatom-substituted aryl group, the heteroatom-substituted aryl group is an oxygen-containing substituent with 1 to 8 carbon atoms.

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