Method for producing compound, and compound

Abstract

The present invention addresses the problem of providing a method for producing a compound, with which it is possible to easily produce an intermediate that is useful for producing a compound having a siloxane structure. A method for producing a compound according to the present invention comprises: a step 1 for reacting a compound represented by formula (1) with a compound represented by formula (2) so as to obtain a compound represented by formula (3); and a step 2 for obtaining a compound represented by formula (4) from the compound represented by formula (3).

Description

Method for producing compound, compound

[0001] The present invention relates to a method for producing a compound and the compound.

[0002] Compounds containing fluorine atoms (e.g., compounds containing a perfluoroalkyl group) have been utilized in a variety of applications such as surfactants, alignment agents, leveling agents, antireflection agents, surface treatment agents, water repellents, etc., due to their properties such as water repellency, oil repellency, surface uneven distribution, low surface tension, low refractive index, and heat resistance. For example, Patent Document 1 discloses compounds containing a perfluoroalkyl group or a fluoroalkyl group that can be used as alignment agents.

[0003] JP 2013-047204 A

[0004] Recently, restrictions on PFAS (perfluoroalkyl compounds and polyfluoroalkyl compounds) have been put in place due to their persistence and toxicity, and there is an increasing demand for alternative compounds that do not contain fluorine atoms.

[0005] The present inventors focused on compounds having a siloxane structure, which is a compound containing a Si atom, as such compounds, and produced compounds having a siloxane structure by hydrosilylation. However, they found that the above method had problems such as the production of a large amount of by-products and an insufficient yield of the target compound.

[0006] Therefore, an object of the present invention is to provide a method for producing a compound that can easily produce an intermediate useful in producing a compound having a siloxane structure. Another object of the present invention is to provide a compound produced by the method for producing a compound.

[0007] As a result of extensive research into solving the above problems, the present inventors have found that the problems can be solved by the following configuration.

[0008] [1] A method for producing a compound, comprising: Step 1, in which a compound represented by formula (1) described below is reacted with a compound represented by formula (2) described below to obtain a compound represented by formula (3) described below; and Step 2, in which a compound represented by formula (4) described below is obtained from the compound represented by formula (3). [2] A method for producing a compound, comprising Step 3, in which a compound represented by formula (4) described above, produced by the method for producing a compound according to [1], is reacted with a compound represented by formula (5) described below to obtain a compound represented by formula (6) described below. [3] A method for producing a compound according to [1] or [2], in which L is an n-propylene group. [4] A method for producing a compound according to [1] or [2], in which R, R １ , and R ２ [5] A compound represented by the formula (7) described later. [6] The compound according to [5], wherein L is an n-propylene group. [7] A method for producing a compound according to any one of [1] to [3], wherein R, R １ , and R ２ is a methyl group.

[0009] According to the present invention, a method for producing a compound can be provided that can easily produce an intermediate useful in producing a compound having a siloxane structure. Furthermore, according to the present invention, a compound useful in producing a compound having a siloxane structure can also be provided.

[0010] The present invention will be described in detail below. The following description of the components may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0011] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits. Furthermore, in this specification, when two or more types of a certain component are present, the "content" of that component means the total content of those two or more components. In this specification, in a numerical range described in stages, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in a numerical range described in this specification, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the Examples. In this specification, a combination of two or more preferred embodiments is a more preferred embodiment.

[0012] In this specification, when a formula showing a chemical structure contains a plurality of identical symbols indicating the type or number of groups, the contents of the plurality of identical symbols are independent of each other, and the contents of the plurality of identical symbols may be the same or different, unless otherwise specified. In this specification, when a formula showing a chemical structure contains a plurality of groups of the same type (e.g., alkyl groups, etc.), the specific contents of the plurality of groups of the same type are independent of each other, and the specific contents of the plurality of groups of the same type may be the same or different, unless otherwise specified.

[0013] The bonding direction of divalent groups represented in this specification is not limited unless otherwise specified. For example, when Y is -COO- in a compound represented by the formula "X-Y-Z", Y may be -CO-O- or -O-CO-. In addition, the compound may be "X-CO-O-Z" or "X-O-CO-Z".

[0014] Unless otherwise specified herein, after each reaction, the obtained crude product may be purified, if necessary, by one or more operations selected from washing, extraction, drying, filtration, concentration, recrystallization, reprecipitation, crystallization, centrifugation, adsorption, column purification, and sublimation purification.

[0015] [Method for Producing Compound] The method for producing the compound of the present invention will be described in detail below. The method for producing the compound of the present invention includes step 1 of reacting a compound represented by formula (1) (also referred to as "compound (1)") described below with a compound represented by formula (2) (also referred to as "compound (2)") described below to obtain a compound represented by formula (3) (also referred to as "compound (3)") described below, and step 2 of obtaining a compound represented by formula (4) (also referred to as "compound (4)") described below from compound (3).

[0016] A common method for introducing silicon atoms into compounds is the hydrosilylation reaction, in which a hydrosilane is added to an unsaturated bond present in a given compound. However, when hydrosilylation is applied to compounds containing moieties such as carbonyl groups, it is difficult to control side reactions. As described above, the compound production method of the present invention includes step 1, in which a compound (1) having a siloxane structure is reacted with a compound (2) to synthesize a compound (3). This facilitates the formation of a desired siloxane structure, which may have a branched structure. Furthermore, compound (4) obtained by converting compound (3) in step 2 has a leaving group represented by X linked to the siloxane structure obtained in step 1 via an alkylene group. Therefore, compound (4) can react simply and efficiently with nucleophilic functional groups (e.g., carboxy groups and hydroxy groups). In other words, the compound production method of the present invention allows the production of an intermediate compound that can be used to easily synthesize a compound having a desired siloxane structure.

[0017] [Step 1] Step 1 is a step of reacting compound (1) with compound (2) to obtain compound (3). Each compound and specific steps will be described below in this order.

[0018] <Compound (1)>

[0019]

[0020] In formula (1), each R independently represents an alkyl group. The alkyl group may be linear, branched, or cyclic, with linear being preferred. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, even more preferably 1 to 3, and preferably 1. Multiple R groups may be the same or different. R is preferably a linear alkyl group having 1 to 6 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group.

[0021] In formula (1), R １ and R ２ are each independently an alkyl group or —(O—SiR ３ R ４ ) ｌ —O—Si(R ５ ) ３ Represents R １ and R ２ The preferred embodiments of the alkyl group represented by —(O—SiR ３ R ４ ) ｌ —O—Si(R ５ ) ３ In the group represented by the formula (hereinafter also referred to as "substituent SI"), each l independently represents an integer of 0 or more. As l, an integer of 0 to 20 is preferred, an integer of 0 to 10 is more preferred, and an integer of 0 to 6 is even more preferred. In the substituent SI, R ３ ~R ５ R each independently represents an alkyl group. ３ ~R ５ The preferred embodiments of the alkyl group represented by R are the same as those of the alkyl group represented by R. １ and R ２ is a linear alkyl group having 1 to 3 carbon atoms, or R ３ ~R ５ is preferably a linear alkyl group having 1 to 3 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group.

[0022] In formula (1), m represents an integer of 0 or greater. m is preferably an integer of 0 to 20, more preferably an integer of 0 to 15, and even more preferably an integer of 0 to 10.

[0023] Examples of compound (1) are shown below, but the present invention is not limited thereto. In the examples below, Et represents an ethyl group, and iPr represents an isopropyl group.

[0024]

[0025] <Compound (2)>

[0026]

[0027] In formula (2), each R independently represents an alkyl group. The definition and preferred embodiments of R in formula (2) are the same as those of R in formula (1).

[0028] In formula (2), L represents an alkylene group. The alkylene group may be linear, branched, or cyclic, but is preferably linear in terms of the reaction efficiency of step 1 and the availability of raw materials. The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, even more preferably 2 to 4, and particularly preferably 3. The alkylene group is preferably a linear alkylene group having 1 to 6 carbon atoms, more preferably a linear alkylene group having 2 to 4 carbon atoms, and even more preferably an n-propylene group.

[0029] n represents an integer of 1 to 3.

[0030] Examples of compound (2) are shown below, but the present invention is not limited thereto.

[0031]

[0032] <Compound (3)>

[0033]

[0034] R and R in formula (3) １ , R ２ , and m are R and R in formula (1), respectively. １ , R ２, and m are the same as n and L in formula (3), respectively.

[0035] Examples of compound (3) are shown below, but the present invention is not limited thereto. In the examples below, Et represents an ethyl group, and iPr represents an isopropyl group.

[0036]

[0037] <Procedure of Step 1> The specific procedure of Step 1 is not particularly limited as long as compound (3) can be obtained from compound (1) and compound (2). For example, reaction conditions for a conventionally known nucleophilic substitution reaction can be appropriately adopted.

[0038] The reaction in step 1 is preferably carried out in a solvent. The solvent is not particularly limited, and examples thereof include aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, and cyclohexane; ketone solvents such as acetone, methyl ethyl ketone, and cyclopentanone; ether solvents such as ethylene glycol dimethyl ether, tetrahydrofuran, diethyl ether, and dioxane; ester solvents such as ethyl acetate and butyl acetate; aprotic polar solvents such as acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; and chlorinated hydrocarbon solvents such as chloroform and dichloromethane. The solvents may be used singly or in combination of two or more.

[0039] The reaction in step 1 is preferably carried out in the presence of a base. Examples of the base include organic and inorganic bases. Examples of the organic base include nitrogen-containing aromatic heterocyclic compounds such as pyridine and pyrimidine, nitrogen-containing aliphatic compounds such as triethylamine, trimethylamine, N,N-diisopropylethylamine, and 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), and metal alkoxides such as potassium tert-butoxide. Examples of the inorganic base include sodium carbonate, sodium bicarbonate, potassium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium phosphate, potassium phosphate, and sodium acetate.

[0040] The amounts of compound (1) and compound (2) used are not particularly limited, but the amount of compound (1) used relative to 1 mole of compound (2) is preferably 1n to 2n moles, more preferably 1n to 1.5n moles, and even more preferably 1n to 1.2n moles. Note that n is n in formula (2), and when n=2, for example, the amount of compound (1) used relative to 1 mole of compound (2) is preferably 2 to 4 moles, more preferably 2 to 3 moles, and even more preferably 2 to 2.4 moles.

[0041] The reaction temperature can be appropriately adjusted depending on the compound, solvent, etc. used, and is preferably −20 to 50° C., more preferably 0 to 30° C. The reaction time can be appropriately adjusted depending on the compound, solvent, etc. used, and is preferably 0.5 to 10 hours, more preferably 1 to 5 hours.

[0042] [Step 2] Step 2 is a step of obtaining compound (4) from compound (3). Compound (4) and specific procedures will be described below in this order.

[0043] <Compound (4)>

[0044]

[0045] R and R in formula (4) １ , R ２ , m, n, and L are R, R in formula (3), respectively. １ , R ２, m, n, and L. X represents a bromine atom or an iodine atom. X is preferably an iodine atom, since the reactivity of the compound represented by formula (4) is superior.

[0046] Examples of the compound (4) include compounds represented by the following formulas (4-1) to (4-3).

[0047]

[0048] R and R in formulas (4-1) to (4-3) １ , R ２ , m, L, and X are R, R in formula (4), respectively. １ , R ２ , m, L, and X.

[0049] As described above, the group represented by X in compound (4) can function as a leaving group. Therefore, it is useful as an intermediate that can easily introduce a siloxane structure into a compound containing a nucleophilic functional group (e.g., a carboxy group and a hydroxy group). The compound represented by formula (4) may also be used for purposes other than as an intermediate.

[0050] Examples of compound (4) are shown below, but the present invention is not limited thereto. In the examples below, Et represents an ethyl group, and iPr represents an isopropyl group.

[0051]

[0052] <Procedure of Step 2> The specific procedure of Step 2 is not particularly limited as long as compound (4) can be obtained from compound (3). For example, conditions for a conventionally known conversion reaction of a leaving group can be appropriately adopted. Specific examples include a method of reacting compound (4) with an iodide or bromide.

[0053] Examples of the iodide include metal iodides such as sodium iodide, potassium iodide, calcium iodide, and magnesium iodide. Examples of the bromide include metal bromides such as sodium bromide, potassium bromide, calcium bromide, and magnesium bromide. The amount of the iodide or bromide used is not particularly limited, but is preferably 1 to 20 mol, and more preferably 1.5 to 15 mol, per mol of compound (3).

[0054] The reaction is preferably carried out in a solvent, such as the solvent used in Step 1 above.

[0055] The reaction temperature can be appropriately adjusted depending on the compound, solvent, etc. used, and is preferably 30 to 150° C., more preferably 60 to 100° C. The reaction time can be appropriately adjusted depending on the compound, solvent, etc. used, and is preferably 1 to 48 hours, more preferably 3 to 30 hours.

[0056] [Uses] The compound production method of the present invention is preferably used to produce a compound having a siloxane structure. In other words, compound (4) produced by the compound production method of the present invention is preferably used to produce a compound having a siloxane structure. For example, a compound having a siloxane structure can be produced by a nucleophilic substitution reaction between compound (4) and a compound containing a nucleophilic functional group such as a hydroxy group or a carboxy group. An example of the use of the compound production method of the present invention is a method for producing a compound having a siloxane structure and an aromatic ring by step 3 shown below.

[0057] [Step 3] Step 3 is a step in which compound (4) is reacted with a compound represented by formula (5) (also referred to as "compound (5)") to obtain a compound represented by formula (6) (also referred to as "compound (6)"). Each compound and specific steps will be described below in this order.

[0058] <Compound (5)>

[0059]

[0060] In formula (5), Ar represents an aromatic ring. The aromatic ring may be either a monocyclic or polycyclic ring. The aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring. The number of ring atoms in the aromatic ring is preferably 5 to 20, more preferably 5 to 12, and even more preferably 6 to 10. Examples of the aromatic ring include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, an anthracene ring, a pyrene ring, a phenanthrene ring, and a fluorene ring, as well as pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, triazine ring, tetrazine ring, quinoxaline ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, benzopyrrole ring, benzofuran ring, benzothiophene ring, benzimidazole ring, benzoxazole ring, benzothiazole ring, naphthopyrrole ring, naphthopyrrole ring, and naphthopyrrole ring. Examples of aromatic heterocycles include a furan ring, a naphthothiophene ring, a naphthoimidazole ring, a naphthoxazole ring, a pyrroloimidazole ring, an imidazoxazole ring, a thienothiazole ring, a benzothiadiazole ring, a benzodithiophene ring, a thienothiophene ring, a thiazolothiazole ring, a naphthodithiophene ring, and a benzothienobenzothiophene ring. A benzene ring, a naphthalene ring, an anthracene ring, a pyridine ring, a pyrimidine ring, a pyrrole ring, a furan ring, or a thiophene ring is preferred, and a benzene ring is more preferred.

[0061] In formula (5), Y's each independently represent a hydroxy group or a carboxy group. When a plurality of Y's are present, the plurality of Y's are preferably the same group. That is, in formula (5), it is preferable that all of the p Y's represent a hydroxy group or all of the p Y's represent a carboxy group.

[0062] In formula (5), p represents an integer of 1 or greater. p is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2.

[0063] In formula (5), each A independently represents a substituent other than a carboxy group. However, when A represents a hydroxy group, Y represents a carboxy group. Examples of the substituent other than a carboxy group represented by A include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a hydroxy group, an alkoxy group, an amino group, an aryloxy group, a formyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio ... group, arylthio group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, silyloxy group, heterocyclic oxy group, carbamoyl group, carbamoyloxy group, heterocyclic thio group, sulfamoyl group, arylazo group, heterocyclic azo group, imido group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, hydrazino group, imino group, cyano group, nitro group, mercapto group, sulfo group, hydroxamic acid group, sulfino group, boronic acid group (-B(OH) ２ ), phosphato group (—OPO(OH) ２ ), phosphono group (-PO(OH) ２ ), and a sulfato group (—OSO ３ H). The above-mentioned substituent may further have a substituent exemplified above. Among them, the above-mentioned substituent is preferably a hydroxy group, a formyl group, an acyl group, an alkyl group, or a halogen atom.

[0064] In formula (5), q represents an integer of 0 or more. q is preferably an integer of 0 to 6, and more preferably an integer of 0 to 3.

[0065] Examples of compound (5) are shown below, but the present invention is not limited thereto.

[0066]

[0067] <Compound (6)>

[0068]

[0069] R and R in formula (6) １ , R ２ , m, n, and L are R, R in formula (4). １ , R ２ , m, n, and L are the same as those in formula (6), and p, Ar, A, and q are the same as those in formula (5).

[0070] In formula (6), Z represents —O— or —OCO—. In formula (5), when Y is a hydroxy group, Z is —O—, and when Y is a carboxy group, Z is —OCO—.

[0071] The use of the compound represented by formula (6) is not particularly limited, and it may be used, for example, as a surfactant and a surface modifier, or as an intermediate.

[0072] Examples of compound (6) are shown below, but the present invention is not limited thereto. In the examples below, Et represents an ethyl group, and iPr represents an isopropyl group.

[0073]

[0074]

[0075]

[0076]

[0077]

[0078] <Procedure of Step 3> The specific procedure of Step 3 is not particularly limited as long as compound (6) can be obtained from compound (4) and compound (5). For example, reaction conditions for a conventionally known nucleophilic substitution reaction can be appropriately adopted.

[0079] The reaction in the above step 3 is preferably carried out in a solvent. Examples of the solvent include the solvents that can be used in the above step 1.

[0080] The reaction in the above step 3 is preferably carried out in the presence of a base. Examples of the base include the bases that can be used in the above step 1.

[0081] The amounts of compound (5) and compound (4) used are not particularly limited, but the amount of compound (4) used is preferably 1 p to 2 pmol, more preferably 1 p to 1.5 pmol, and even more preferably 1 p to 1.2 pmol, relative to 1 mole of compound (5). p is p in formula (5). For example, when p=2, the amount of compound (4) used is preferably 2 to 4 mol, more preferably 2 to 3 mol, and even more preferably 2 to 2.4 mol, relative to 1 mole of compound (5).

[0082] The reaction temperature can be adjusted appropriately depending on the compound and solvent used, etc., and is preferably 20 to 150°C, more preferably 40 to 100°C, and even more preferably 50 to 80°C. The reaction time can be adjusted appropriately depending on the compound and solvent used, etc., and is preferably 1 to 48 hours, and more preferably 5 to 24 hours.

[0083] When compound (4) produced by the compound production method of the present invention is used as an intermediate, the reaction is not limited to step 3, and compound (4) may be used in a reaction with a compound other than compound (5). The use of the compound having a siloxane structure obtained using compound (4) as an intermediate is not particularly limited, and examples thereof include surfactants, leveling agents, surface treatment agents, alignment agents, antireflection agents, and water repellents.

[0084] [Compound] The present invention includes a compound represented by formula (7).

[0085]

[0086] In formula (7), R, R １ , R ２ The definitions and preferred embodiments of m, n, and L are respectively defined as R, R in formula (3). １ , R ２ , m, n, and L.

[0087] In formula (7), X ２ represents a chlorine atom, a bromine atom, or an iodine atom. In formula (7), m is preferably an integer of 1 or more, more preferably an integer of 1 to 20, even more preferably an integer of 1 to 15, and particularly preferably an integer of 1 to 10. ２When is a chlorine atom, it is preferable that m satisfies the above preferred range.

[0088] Examples of the compound represented by formula (7) include the compound represented by formula (3) and the compound represented by formula (4) described above.

[0089] The present invention will be described in more detail below based on examples. The materials, amounts used, ratios, treatment details, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the examples shown below. The abbreviations used in the following explanation are as follows: DMF: N,N-dimethylformamide DMAc: N,N-dimethylacetamide DIPEA: N,N-diisopropylethylamine THF: tetrahydrofuran

[0090] Compounds A-1 to A-7 were synthesized according to the following procedure.

[0091] [Synthesis Example] [Synthesis of Compound A-1]

[0092]

[0093] <Step 1> A solution of compound 1a (26.1 mmol) in tetrahydrofuran was added dropwise to a solution of trimethylsilanol (54.8 mmol) and pyridine (54.8 mmol) in tetrahydrofuran (50 mL) under ice cooling, and the mixture was stirred at room temperature for 1 hour. After stirring, the resulting reaction suspension was filtered, and hexane and water were added for liquid separation. The solvent was distilled off to obtain compound 1b (yield 91%). １ The results of the H NMR measurement are shown below. １ H NMR (400MHz, CDCl ３ ) δppm: 0.03 (s, 3H), 0.10 (s, 18H), 0.55-0.59 (m, 2H), 1.75-1.83 (m, 2H), 3.51 (t, 2H)

[0094] <Step 2> Compound 1b (26.1 mmol) and sodium iodide (261 mmol) were dissolved in acetone (94 mL) and stirred at 60°C for 27 hours. After stirring, the resulting reaction suspension was filtered, and hexane and water were added for liquid separation. The solvent was distilled off, and the mixture was purified by silica gel column chromatography (hexane / ethyl acetate = 19 / 1) to obtain Compound A-1 (yield 63%). １ The results of the H NMR measurement are shown below. １ H NMR (400MHz, CDCl ３ ) δppm: 0.02 (s, 3H), 0.94 (s, 18H), 0.54-0.58 (m, 2H), 1.82-1.88 (m, 2H), 3.19 (t, 2H)

[0095] [Synthesis of Compound A-2]

[0096]

[0097] <Step 1> A solution of compound 2a (19.1 mmol) in tetrahydrofuran was added dropwise to a solution of 1,1,3,3,3-pentamethyl-1-disiloxanol (21.0 mmol) and pyridine (21.0 mmol) dissolved in tetrahydrofuran (30 mL) under ice cooling, and the mixture was stirred at room temperature for 2 hours. After stirring, the resulting reaction suspension was filtered, and hexane and water were added for liquid separation. The solvent was distilled off, and the residue was purified by silica gel column chromatography (hexane / ethyl acetate = 19 / 1) to obtain compound 2b (yield 72%). １ The results of the H NMR measurement are shown below. １ H NMR (400MHz, CDCl ３ ) δppm: 0.03 (s, 6H), 0.08 (s, 9H), 0.09 (s, 6H), 0.62-0.65 (m, 2H), 1.78-1.83 (m, 2H), 3.51 (t, 2H)

[0098] <Step 2> Compound 2b (13.7 mmol) and sodium iodide (137 mmol) were dissolved in acetone (51 mL) and stirred at 60°C for 26 hours. After stirring, the resulting reaction suspension was filtered, and hexane and water were added for liquid separation. The solvent was distilled off, and the mixture was purified by silica gel column chromatography (hexane / ethyl acetate = 19 / 1) to obtain Compound A-2 (yield 80%). １ The results of the H NMR measurement are shown below. １ H NMR (400MHz, CDCl ３ ) δppm: 0.04 (s, 6H), 0.09 (s, 9H), 0.10 (s, 6H), 0.62-0.66 (m, 2H), 1.83-1.91 (m, 2H), 3.20 (t, 2H)

[0099] [Synthesis of Compound A-3]

[0100]

[0101] <Synthesis of Raw Materials> A toluene solution of compound 3a (31.5 mmol) was added dropwise to a solution of trimethylsilanol (34.7 mmol) and pyridine (34.7 mmol) dissolved in toluene (50 mL) under ice-cooling, followed by stirring at room temperature for 1 hour. After stirring, the resulting reaction suspension was filtered, and hexane and water were added for liquid separation. The solvent was evaporated to obtain compound 3b (yield 94%). Water (40.3 mmol) was added to an ethyl acetate suspension of Pd / C (0.134 mmol), and an ethyl acetate solution of compound 3b (13.4 mmol) was added dropwise under ice-cooling, followed by stirring at room temperature for 5 hours. After stirring, the resulting reaction suspension was filtered through Celite, and the solvent was evaporated to obtain compound 3c (yield 98%).

[0102] <Step 1> A toluene solution of compound 2a (16.4 mmol) was added dropwise to a solution of compound 3c (17.2 mmol) and pyridine (24.5 mmol) dissolved in toluene (28 mL) under ice cooling, and the mixture was stirred at room temperature for 1 hour. After stirring, the resulting reaction suspension was filtered, and hexane and water were added for liquid separation. The solvent was distilled off, and the residue was purified by silica gel column chromatography (hexane / ethyl acetate = 9 / 1) to obtain compound 3d (yield 72%). １The results of the H NMR measurement are shown below. １ H NMR (400MHz, CDCl ３ ) δppm: 0.05-0.09 (m, 39H), 0.62-0.66 (m, 2H), 1.76-1.84 (m, 2H), 3.51 (t, 2H)

[0103] <Step 2> Compound 3d (11.7 mmol) and sodium iodide (117 mmol) were dissolved in acetone (75 mL) and stirred at 60°C for 24 hours. After stirring, the resulting reaction suspension was filtered, and hexane and water were added for liquid separation. The solvent was distilled off, and the mixture was purified by silica gel column chromatography (hexane / ethyl acetate = 12 / 1) to obtain Compound A-3 (yield 83%). １ The results of the H NMR measurement are shown below. １ H NMR (400MHz, CDCl ３ ) δppm: 0.05-0.09 (m, 39H), 0.61-0.66 (m, 2H), 1.82-1.90 (m, 2H), 3.19 (t, 2H)

[0104] [Synthesis of Compound A-4]

[0105]

[0106] <Synthesis of Raw Materials> A toluene solution of compound 3a (30.9 mmol) was added dropwise to a solution of compound 3c (32.5 mmol) and pyridine (34.0 mmol) dissolved in toluene (49 mL) under ice-cooling, followed by stirring at room temperature for 2 hours. After stirring, the resulting reaction suspension was filtered, and hexane and water were added for liquid separation. The solvent was evaporated to obtain compound 4a (yield 99%). Water (89.7 mmol) was added to an ethyl acetate suspension of Pd / C (0.762 mmol), and an ethyl acetate solution of compound 4a (29.9 mmol) was added dropwise under ice-cooling, followed by stirring at room temperature for 5 hours. After stirring, the resulting reaction suspension was filtered through Celite, the solvent was evaporated, and the mixture was purified by silica gel column chromatography (hexane / ethyl acetate = 4 / 1) to obtain compound 4b (yield 47%).

[0107] <Step 1> A toluene solution of compound 2a (13.4 mmol) was added dropwise to a solution of compound 4b (14.1 mmol) and pyridine (20.2 mmol) dissolved in toluene (23 mL) under ice cooling, and the mixture was stirred at room temperature for 1 hour. After stirring, the resulting reaction suspension was filtered, and hexane and water were added for liquid separation. The solvent was distilled off, and the residue was purified by silica gel column chromatography (hexane / ethyl acetate = 9 / 1) to obtain compound 4c (yield 80%). １ The results of the H NMR measurement are shown below. １ H NMR (400MHz, CDCl ３ ) δppm: 0.05-0.09 (m, 63H), 0.62-0.66 (m, 2H), 1.76-1.84 (m, 2H), 3.51 (t, 2H)

[0108] <Step 2> Compound 4c (11.7 mmol) and sodium iodide (117 mmol) were dissolved in acetone (75 mL) and stirred at 60°C for 24 hours. After stirring, the resulting reaction suspension was filtered, and hexane and water were added for liquid separation. The solvent was distilled off, and the mixture was purified by silica gel column chromatography (hexane / ethyl acetate = 12 / 1) to obtain Compound A-4 (yield 83%). １ The results of the H NMR measurement are shown below. １ H NMR (400MHz, CDCl ３ ) δppm: 0.05-0.09 (m, 63H), 0.61-0.65 (m, 2H), 1.82-1.90 (m, 2H), 3.19 (t, 2H)

[0109] [Synthesis of Compound A-5]

[0110]

[0111] <Step 1> A solution of compound 1a (7.31 mmol) in tetrahydrofuran was added dropwise to a solution of 1,1,3,3,3-pentamethyl-1-disiloxanol (15.3 mmol) and pyridine (15.3 mmol) in tetrahydrofuran (14 mL) under ice cooling, and the mixture was stirred at room temperature for 1 hour. After stirring, the resulting reaction suspension was filtered, and hexane and water were added for liquid separation. The solvent was evaporated to obtain compound 5a quantitatively. １ The results of the H NMR measurement are shown below. １ H NMR (400MHz, CDCl ３ ) δppm: 0.05-0.11 (m, 33H), 0.59-0.63 (m, 2H), 1.78-1.86 (m, 2H), 3.51 (t, 2H)

[0112] <Step 2> Compound 5a (14.6 mmol) and sodium iodide (146 mmol) were dissolved in acetone (78 mL) and stirred at 60°C for 27 hours. After stirring, the resulting reaction suspension was filtered, and hexane and water were added for liquid separation. The solvent was distilled off to obtain Compound A-5 (yield 86%). １ The results of the H NMR measurement are shown below. １ H NMR (400MHz, CDCl ３ ) δppm: 0.06-0.10 (m, 33H), 0.59-0.63 (m, 2H), 1.84-1.92 (m, 2H), 3.19 (t, 2H)

[0113] [Synthesis of Compound A-6]

[0114]

[0115] <Step 1> A toluene solution of compound 1a (9.5 mmol) was added dropwise to a solution of 1,1,3,3,5,5,5-heptamethyl-1-trisiloxanol (19.5 mmol) and pyridine (20.0 mmol) dissolved in toluene (18 mL) under ice cooling, and the mixture was stirred at room temperature for 1 hour. After stirring, the resulting reaction suspension was filtered, and hexane and water were added for liquid separation. The solvent was distilled off to obtain compound 6a (yield 96%). １The results of the H NMR measurement are shown below. １ H NMR (400MHz, CDCl ３ ) δppm: 0.05-0.11 (m, 45H), 0.63-0.65 (m, 2H), 1.79-1.87 (m, 2H), 3.51 (t, 2H)

[0116] <Step 2> Compound 6a (9.1 mmol) and sodium iodide (91.1 mmol) were dissolved in acetone (78 mL) and stirred at 60°C for 26 hours. After stirring, the resulting reaction suspension was filtered, and hexane and water were added for liquid separation. The solvent was distilled off, and the mixture was purified by silica gel column chromatography (hexane / ethyl acetate = 12 / 1) to obtain Compound A-6 (yield 87%). １ The results of the H NMR measurement are shown below. １ H NMR (400MHz, CDCl ３ ) δppm: 0.05-0.09 (m, 45H), 0.59-0.63 (m, 2H), 1.83-1.91 (m, 2H), 3.19 (t, 2H)

[0117] [Synthesis of Compound A-7]

[0118]

[0119] <Step 1> A toluene solution of compound 1a (6.3 mmol) was added dropwise to a solution of compound 3c (13.2 mmol) and pyridine (13.2 mmol) dissolved in toluene (12 mL) under ice cooling, and the mixture was stirred at room temperature for 2 hours. After stirring, the resulting reaction suspension was filtered, and hexane and water were added for liquid separation. The solvent was distilled off, and the residue was purified by silica gel column chromatography (hexane / ethyl acetate = 6 / 1) to obtain compound 7a (yield 90%). １ The results of the H NMR measurement are shown below. １ H NMR (400MHz, CDCl ３ ) δppm: 0.05-0.10 (m, 69H), 0.60-0.64 (m, 2H), 1.80-1.84 (m, 2H), 3.50 (t, 2H)

[0120] <Step 2> Compound 7a (5.7 mmol) and sodium iodide (56.5 mmol) were dissolved in acetone (64 mL) and stirred at 60°C for 41 hours. After stirring, the resulting reaction suspension was filtered, and hexane and water were added for liquid separation. The solvent was distilled off, and the mixture was purified by silica gel column chromatography (hexane / ethyl acetate = 6 / 1) to obtain Compound A-7 (yield 64%). １ The results of the H NMR measurement are shown below. １ H NMR (400MHz, CDCl ３ ) δppm: 0.05-0.09 (m, 69H), 0.59-0.63 (m, 2H), 1.83-1.89 (m, 2H), 3.18 (t, 2H)

[0121] Example 1 Compound D-2 was synthesized according to the following procedure.

[0122]

[0123] Compound A-1 (46.1 mmol) was added to a solution prepared by dissolving compound B-2 (21.9 mmol) and DIPEA (48.3 mmol) in DMAc (40 mL), and the mixture was stirred at 55°C for 24 hours. After stirring, ethyl acetate, aqueous hydrochloric acid, and brine were added to the resulting reaction solution for separation, and the solvent was distilled off. The residue was then purified by silica gel column chromatography (hexane / ethyl acetate = 9 / 1) to obtain compound D-2 (yield 64%). １ The results of the H NMR measurement are shown below. １ H NMR (400MHz, CDCl ３ ) δppm: 0.04-0.10 (m, 42H), 0.52-0.57 (m, 4H), 1.75-1.82 (m, 4H), 4.28 (t, 4H), 7.72 (d, 2H), 8.27 (t, 1H)

[0124] Example 2 Compound D-3 was synthesized according to the following procedure.

[0125]

[0126] Compound A-2 (5.2 mmol) was added to a solution of compound B-3 (4.7 mmol) and potassium carbonate (7.0 mmol) dissolved in DMF (23 mL), and the mixture was stirred at 55°C for 24 hours. After stirring, ethyl acetate, aqueous hydrochloric acid, and brine were added to the resulting reaction solution for separation, and the solvent was distilled off. The residue was purified by silica gel column chromatography (hexane / ethyl acetate = 9 / 1) to obtain compound D-3 (yield 63%). １ The results of the H NMR measurement are shown below. １ H NMR (400MHz, CDCl ３ ) δppm: 0.04-0.10 (m, 21H), 0.52-0.56 (m, 2H), 1.76-1.83 (m, 2H), 4.28 (t, 2H), 5.12 (s, 2H), 6.99 (d, 2H), 7.32-7.42 (m, 5H), 8.00(d, 2H)

[0127] Example 3 Compound D-4 was synthesized according to the following procedure.

[0128]

[0129] Compound D-4 was synthesized in the same manner as in the above-mentioned [Synthesis of Compound D-3], except that Compound A-2 was replaced with Compound A-3 and Compound B-3 was replaced with Compound B-4. １ The results of the H NMR measurement are shown below. １ H NMR (400MHz, CDCl ３ ) δppm: 0.05-0.09 (m, 78H), 0.52-0.56 (m, 4H), 1.76-1.83 (m, 4H), 4.28 (t, 4H), 5.12 (s, 2H), 7.32-7.47 (m, 5H), 7.74 (t, 2H), 8.27(t, 1H)

[0130] Example 4 Compound D-5 was synthesized according to the following procedure.

[0131]

[0132] Compound D-5 was synthesized in the same manner as in the synthesis of compound D-3, except that compound A-2 was replaced with compound A-4 and compound B-3 with compound B-5. １ The results of the H NMR measurement are shown below. １ H NMR (400MHz, CDCl ３ ) δppm: 0.05-0.09 (m, 63H), 0.56-0.61 (m, 2H), 1.80-1.87 (m, 2H), 4.00 (t, 2H), 6.98 (d, 2H), 7.82 (d, 2H), 9.87 (s, 1H)

[0133] Example 5 Compound D-6 was synthesized according to the following procedure.

[0134]

[0135] Compound D-6 was synthesized in the same manner as in the synthesis of compound D-3, except that compound A-2 was replaced with compound A-5 and compound B-3 was replaced with compound B-5. １ The results of the H NMR measurement are shown below. １ H NMR (400MHz, CDCl ３ ) δppm: 0.06-0.10 (m, 33H), 0.56-0.61 (m, 2H), 1.80-1.87 (m, 2H), 4.00 (t, 2H), 6.98 (d, 2H), 7.82 (d, 2H), 9.87 (s, 1H)

[0136] Example 6 Compound D-7 was synthesized according to the following procedure.

[0137]

[0138] Compound D-7 was synthesized in the same manner as in the synthesis of compound D-3, except that compound A-2 was replaced with compound A-6 and compound B-3 with compound B-5. １ The results of the H NMR measurement are shown below. １ H NMR (400MHz, CDCl ３) δppm: 0.05-0.11 (m, 45H), 0.56-0.61 (m, 2H), 1.80-1.87 (m, 2H), 4.00 (t, 2H), 6.98 (d, 2H), 7.82 (d, 2H), 9.87 (s, 1H)

[0139] Example 7 Compound D-8 was synthesized according to the following procedure.

[0140]

[0141] Compound D-8 was synthesized in the same manner as in the synthesis of compound D-3, except that compound A-2 was replaced with compound A-7 and compound B-3 with compound B-6. １ The results of the H NMR measurement are shown below. １ H NMR (400MHz, Acetone-d6) δppm: -0.03-0.07 (m, 69H), 0.59-0.64 (m, 2H), 1.77-1.85 (m, 2H), 4.24 (t, 2H), 8.00 (d, 2H), 8.11 (d, 2H), 10.1 (s, 1H)

[0142] Comparative Example 1 Compound D-1 was synthesized according to the following procedure.

[0143]

[0144] Under a nitrogen atmosphere, compound C (47.0 mmol) and compound B-1 (22.9 mmol) were dissolved in tetrahydrofuran (50 mL), and Karsted's catalyst (2% Pt xylene solution, 100 μL) was added under water cooling. The resulting reaction solution was stirred at room temperature for 2 hours, and then the solvent was distilled off. The mixture was purified by silica gel column chromatography (hexane / ethyl acetate=9 / 1) to obtain compound D-1 (yield 29%). １ The results of the H NMR measurement are shown below. １ H NMR (400MHz, CDCl ３) δppm: 0.04-0.10 (m, 42H), 0.56-0.60 (m, 4H), 1.82-1.93 (m, 4H), 4.00-4.06 (m, 4H), 6.94 (d, 1H), 7.38-7.43 (m, 2H), 9.83 (s, 1H)

[0145] The compounds used in the synthesis of compounds D-1 to D-8 and their yields are shown in Table 1. Compound C and compound B-1 are comparative compounds, and are different from compounds (4) and (5), respectively. The results shown in the table below confirm that the compound production method of the present invention can produce useful intermediates that can be used to synthesize compounds having a siloxane structure in high yield.

[0146]

Claims

1. Step 1 involves reacting a compound represented by formula (1) with a compound represented by formula (2) to obtain a compound represented by formula (3), A method for producing a compound, comprising step 2 of obtaining a compound represented by formula (4) from a compound represented by formula (3). 【Chemistry 1】 In formulas (1) to (4), R independently represents an alkyl group. In formula (1) and formulas (3) to (4), R １ and R ２ each independently represents an alkyl group or -(O-SiR ３ R ４ ) ｌ -O-Si(R ５ ) ３ . l represents an integer of 0 or more. R ３ to R ５ each independently represents an alkyl group. m represents a non-negative integer. In formulas (2) to (4), L represents an alkylene group. n represents an integer between 1 and 3. In equation (4), X represents a bromine atom or an iodine atom.

2. A method for producing the compound according to Claim 1, wherein n = 2 or 3 and m = 2 or more, or n = 1 and m = 8 or more.

3. A method for producing a compound, comprising step 3, in which a compound represented by formula (4), produced by the method for producing a compound according to claim 1, is reacted with a compound represented by formula (5) to obtain a compound represented by formula (6). 【Chemistry 2】 In formula (5), Y independently represents either a hydroxyl group or a carboxyl group. In formulas (5) and (6), Ar represents an aromatic ring. Each A independently represents a substituent other than a carboxyl group. However, if A represents a hydroxyl group, then Y represents a carboxyl group. p represents an integer greater than or equal to 1. q represents an integer greater than or equal to 0. In equation (6), Z represents -O- or -OCO-. Each R independently represents an alkyl group. R １ and R ２ Each is independently an alkyl group, or -(O-SiR ３ R ４ ) ｌ -O-Si(R ５ ) ３ This represents l, which represents a non-negative integer. ３ ~R ５ Each of these independently represents an alkyl group. m represents a non-negative integer. L represents an alkylene group. n represents an integer between 1 and 3.

4. A method for producing the compound according to claim 3, wherein n = 2 or 3 and m = 2 or more, or n = 1 and m = 8 or more integers.

5. A method for producing the compound according to claim 3, wherein Y in formula (5) represents a carboxyl group.

6. A method for producing the compound according to claim 1 or 3, wherein L is an n-propylene group.

7. R, R １ , and R ２ A method for producing the compound according to claim 1 or 3, wherein the compound is a methyl group.

8. A compound represented by formula (7). 【Transformation 3】 In formula (7), R independently represents an alkyl group. R １ and R ２ Each is independently an alkyl group, or -(O-SiR ３ R ４ ) ｌ -O-Si(R ５ ) ３ This represents l, which represents a non-negative integer. ３ ~R ５ Each of these independently represents an alkyl group. m represents a non-negative integer. L represents an alkylene group. n represents an integer between 1 and 3. X ２ This represents a chlorine atom, a bromine atom, or an iodine atom.

9. The compound according to claim 8, wherein n = 2 or 3 and m = 2 or more, or n = 1 and m = 8 or more.

10. The compound according to claim 8 or 9, wherein L is an n-propylene group.

11. R, R １ , and R ２ The compound according to claim 8 or 9, wherein the compound is a methyl group.

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