WO2015107987A1 - 5-ノルボルネン-2-スピロ-α-シクロアルカノン-α'-スピロ-2''-5''-ノルボルネン類の製造方法 - Google Patents
5-ノルボルネン-2-スピロ-α-シクロアルカノン-α'-スピロ-2''-5''-ノルボルネン類の製造方法 Download PDFInfo
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
- C07C49/613—Unsaturated compounds containing a keto groups being part of a ring polycyclic
- C07C49/617—Unsaturated compounds containing a keto groups being part of a ring polycyclic a keto group being part of a condensed ring system
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- C07C2602/50—Spiro compounds
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- C07C2603/94—Spiro compounds containing "free" spiro atoms
Definitions
- the present invention relates to a process for producing 5-norbornene-2-spiro- ⁇ -cycloalkanone- ⁇ ′-spiro-2 ′′ -5 ′′ -norbornenes.
- wholly aromatic polyimide (trade name “Kapton”) is known as an indispensable material for advanced industries such as space and aviation.
- a wholly aromatic polyimide has a brown color due to intramolecular charge transfer (CT) between the aromatic ring-based tetracarboxylic dianhydride unit and the aromatic ring-based diamine unit, and is transparent.
- CT intramolecular charge transfer
- it could not be used for optical applications and the like. Therefore, in recent years, attention has been paid to alicyclic polyimides which do not cause intramolecular CT and have high light transmittance, and various compounds (such as raw material compounds) that can be used for the production have been developed. .
- alicyclic tetracarboxylic dianhydrides are used for the production of such alicyclic polyimides.
- a compound and its manufacturing method which can be utilized suitably in order to manufacture such alicyclic tetracarboxylic dianhydride for example, it is specific to international publication 2011/099517 (patent document 1).
- a 5-norbornene-2-spiro- ⁇ -cycloalkanone- ⁇ ′-spiro-2 ′′ -5 ′′ -norbornene represented by the general formula and a method for producing the same are disclosed.
- an alicyclic tetracarboxylic dianhydride is obtained using the 5-norbornene-2-spiro- ⁇ -cycloalkanone- ⁇ ′-spiro-2 ′′ -5 ′′ -norbornene. It is also disclosed that an alicyclic polyimide having a high light transmittance and a sufficiently high heat resistance can be produced when an alicyclic polyimide is produced.
- the present invention has been made in view of the problems of the prior art, and includes 5-norbornene-2-spiro- ⁇ -cycloalkanone- ⁇ ′-spiro-2 ′′ -5 ′′ -norbornenes.
- a method for producing 5-norbornene-2-spiro- ⁇ -cycloalkanone- ⁇ ′-spiro-2 ′′ -5 ′′ -norbornenes which can be produced more efficiently with a higher yield. The purpose is to do.
- the method comprises a formaldehyde derivative and has the formula: HX, wherein X is F, Cl, Br, I, CH 3 COO, CF 3 COO, CH 3 SO 3 , CF 3 SO 3 , C 6 H 5 SO 3 , one selected from the group consisting of CH 3 C 6 H 4 SO 3 , HOSO 3 and H 2 PO 4 ) in an acidic solvent containing an acid represented by the following general formula (1 ) And an amine compound represented by the following general formula (2) are reacted to form a Mannich base represented by the following general formula (3), and the Mannich base is added to the acidic solvent.
- an organic solvent, a base having a molar equivalent of 1.0 to 20.0 times the acid, and a diene compound represented by the following general formula (4) are added and heated.
- the Mannich base and the diene compound are reacted to give 5-norbornene-2-spiro- ⁇ -cycloalkanone- ⁇ ′-spiro-2 ′′ -5 ′′-represented by the following general formula (5):
- a second step of forming norbornene and the content of the acid in the acidic solvent used in the first step is 0.01 to 0.075 with respect to the ketone group of the carbonyl compound.
- the process for producing 5-norbornene-2-spiro- ⁇ -cycloalkanone- ⁇ ′-spiro-2 ′′ -5 ′′ -norbornenes of the present invention contains a formaldehyde derivative and has the formula: HX (formula Wherein X is F, Cl, Br, I, CH 3 COO, CF 3 COO, CH 3 SO 3 , CF 3 SO 3 , C 6 H 5 SO 3 , CH 3 C 6 H 4 SO 3 , HOSO 3 and 1 type selected from the group consisting of H 2 PO 4 ), in an acidic solvent containing an acid represented by the following general formula (1):
- R 1 and R 2 each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, and n is 0 to 12 Indicates an integer.
- each R 3 independently represents a linear saturated hydrocarbon group having 1 to 20 carbon atoms, a branched saturated hydrocarbon group having 3 to 20 carbon atoms, or the number of carbon atoms. 1 type selected from the group consisting of 3 to 20 saturated cyclic hydrocarbon groups and saturated hydrocarbon groups having 1 to 10 carbon atoms having a hydroxyl group, and two R 3 are bonded to each other to form a pyrrolidine ring or piperidine ring
- X ⁇ represents F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , CH 3 COO ⁇ , CF 3 COO ⁇ , and may form one ring selected from the group consisting of a piperazine ring and a morpholine ring.
- R 4 represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom.
- the diene compound represented by formula (5) is added and heated to react the Mannich base with the diene compound, and the following general formula (5):
- the acid content in the acidic solvent used in the first step is 0.01 to 0.075 molar equivalents relative to the ketone group of the carbonyl compound.
- the acidic solvent used in the first step More preferably, the acid content is 0.01 to 0.070 molar equivalents relative to the ketone group of the carbonyl compound.
- 5-norbornene-2-spiro- ⁇ -cycloalkanone- ⁇ ′-spiro-2 ′′ -5 ′′ -norbornenes can be produced more efficiently with higher yields. It is possible to provide a process for producing 5-norbornene-2-spiro- ⁇ -cycloalkanone- ⁇ ′-spiro-2 ′′ -5 ′′ -norbornene capable of forming
- the process for producing 5-norbornene-2-spiro- ⁇ -cycloalkanone- ⁇ ′-spiro-2 ′′ -5 ′′ -norbornenes of the present invention contains a formaldehyde derivative and is represented by the above formula: HX.
- an acidic solvent containing an acid the carbonyl compound represented by the above general formula (1) and the amine compound represented by the above general formula (2) are reacted to form the above general formula (3).
- a 0-fold molar equivalent of the base and the diene compound represented by the above general formula (4) are added and heated to react the Mannich base with the diene compound, and represented by the above general formula (5).
- the acid content in the acidic solvent used in the first step is 0.01 to 0.075 molar equivalents relative to the ketone group of the carbonyl compound.
- the 5-norbornene-2-spiro- ⁇ -cycloalkanone- ⁇ ′-spiro-2 ′′ -5 ′′ -norbornenes represented by the above general formula (5) may be simply referred to in some cases. It is called “bis (spironorbornene)”.
- the first step is represented by the general formula (3) by reacting the carbonyl compound represented by the general formula (1) with the amine compound represented by the general formula (2) in the acidic solvent. Forming a Mannich base to obtain a reaction solution containing the Mannich base in the acidic solvent.
- the acid content in the acidic solvent is 0.01 to 0.075 molar equivalents relative to the ketone group of the carbonyl compound.
- the acidic solvent used in such a first step contains a formaldehyde derivative.
- a formaldehyde derivative is not particularly limited as long as it can be used when producing a so-called Mannich base, and “formaldehyde” used for producing a Mannich base in a reaction system.
- a known compound for example, a compound that can be decomposed in an acidic solvent and can supply formaldehyde into an acidic solvent in addition to formaldehyde itself) can be used as appropriate.
- Examples of compounds that can supply such formaldehyde into the reaction system include, for example, formaldehyde, formaldehyde cyclic bodies (such as trioxane and 1,3-dioxolane), and formaldehyde multimers (such as paraformaldehyde) as appropriate. Available.
- formaldehyde derivatives include formalin, paraformaldehyde, trioxane, 1,3-dioxolane, 1,3-dioxole, 1,3-dioxane, 1,3-dioxin, 1,3-dioxepane, dihydro -1,3-dioxepin, 1,3-dioxepin, 1,3-dioxocan, dihydro-1,3-dioxocin, 1,3-dioxocin, formaldehyde dimethyl acetal, formaldehyde diethyl acetal, formaldehyde dipropyl acetal, formaldehyde dibutyl acetal, Examples include formaldehyde diphenylacetal.
- formaldehyde derivatives formalin, paraformaldehyde, trioxane, and 1,3-dioxolane are preferable from the viewpoint of availability, and formalin and paraformaldehyde are more preferable.
- Such formaldehyde derivatives may be used singly or in combination of two or more, but it is preferable to use one alone from the viewpoint of purification.
- the content of such a formaldehyde derivative is preferably 2.0 to 50.0% by mass in the acidic solvent, and more preferably 4.0 to 25.0% by mass. If the content of the formaldehyde derivative is less than the lower limit, the yield of the Mannich base represented by the general formula (3) tends to decrease. On the other hand, if the content exceeds the upper limit, the yield decreases. Tends to be difficult to purify.
- the acidic solvent used in the first step, together with the formaldehyde derivative is represented by the formula: HX (where X is F, Cl, Br, I, CH 3 COO, CF 3 COO, CH 3 SO 3 , CF 3 1 type selected from the group consisting of SO 3 , C 6 H 5 SO 3 , CH 3 C 6 H 4 SO 3 , HOSO 3 and H 2 PO 4 .
- HX The type of acid (HX) is not particularly limited as long as it is represented by the above formula: HX, but the Mannich base represented by the above general formula (3) in an acidic solvent. From the viewpoint of stability, an acid in which X in the formula is F, Cl, Br, CH 3 COO, or CF 3 COO is more preferable, and an acid in which X in the formula is Cl or CH 3 COO is more preferable.
- the content of the acid (HX) needs to be 0.01 to 0.075 molar equivalents relative to the ketone group of the carbonyl compound represented by the general formula (1). . If the acid content is less than the lower limit, it is difficult to efficiently produce iminium ions, and Mannich base cannot be efficiently produced at a sufficiently high level. As a result, bis (spironorbornene is not produced. ) Cannot be produced at a sufficiently high level with good yield. On the other hand, if the content of the acid exceeds the upper limit, it is difficult to produce bis (spirononorbornene) at a sufficiently high level with a high yield.
- the molar equivalent of such an acid is the value of the total molar amount of the acid in the reaction system ([total molar amount of acid] / [ketone] relative to the total molar amount of the ketone group of the carbonyl compound in the reaction system.
- the content of the acid (HX) in such an acidic solvent is 0.01 to 0.070 molar equivalents relative to the ketone group of the carbonyl compound represented by the general formula (1). Is more preferably 0.012 to 0.050 molar equivalent.
- the content ratio of the acid (HX) in such an acidic solvent is 0.01 mol / L or more (more preferably 0.01 to 0.4 mol / L, still more preferably 0.02 to 0.2 mol / L). L) is preferred.
- the acid content is less than the lower limit, the yield of the Mannich base prepared in the first step is not sufficient, and the bis (spironorbornene) represented by the general formula (1) is sufficient. Therefore, it tends to be impossible to prepare efficiently.
- the content rate of the said acid (HX) exceeds the said upper limit, it exists in the tendency for a yield to fall or refinement
- such an acidic solvent may contain a solvent in addition to the formaldehyde derivative and the acid.
- a solvent include water, alcohol, glycol, ethylene glycol, glycerin, ether, cellosolve, nitrile, amide, and methylcyclohexane.
- the boiling point is 85 to 110 ° C. and the Mannich base is dissolved from the viewpoint of suppressing the formation of by-products during the production of the Mannich base.
- an organic solvent that is not used hereinafter sometimes simply referred to as “first organic solvent”.
- the reaction temperature tends to be difficult to control if the heat of reaction is rapidly generated compared to a container with a small capacity, but the first organic solvent is used.
- the temperature during heating can be easily controlled to a temperature in the vicinity of the temperature range of the boiling point of the first organic solvent, when using a reactor with a larger capacity, It is particularly preferred to use the first organic solvent.
- Mannich base does not dissolve means that 1 wt% or more of the Mannich base represented by the general formula (3) is not dissolved in an organic solvent under the conditions of 20 to 65 ° C. .
- the temperature of the boiling point of the first organic solvent refers to the temperature of the boiling point under conditions where the pressure is normal pressure (0.1 MPa).
- a hydrocarbon solvent having 3 to 20 carbon atoms (more preferably 3 to 10) is preferable. If the number of carbon atoms is less than the lower limit, it tends to be a gas at normal temperature and normal pressure, whereas if it exceeds the upper limit, it tends to be a solid at normal temperature and normal pressure.
- Such hydrocarbon solvents having 3 to 20 carbon atoms are more preferably saturated hydrocarbons which may have a side chain consisting of hydrocarbon groups. 6-20 isoparaffinic hydrocarbons, cyclohexane and n-heptane are more preferred.
- isoparaffinic hydrocarbons examples include 2-methylheptane and 2,2,4-trimethylpentane.
- a commercially available product may be used, for example, a trade name “IP Solvent” manufactured by Idemitsu Kosan Co., Ltd. may be appropriately used.
- IP Solvent manufactured by Idemitsu Kosan Co., Ltd.
- examples of the hydrocarbon solvent having 3 to 20 carbon atoms include methylcyclohexane, IP solvent (trade name: manufactured by Idemitsu Kosan Co., Ltd.), cyclohexane, n-heptane, and 2,2,4-trimethylpentane. Is particularly preferred. In addition, you may use such a solvent individually by 1 type or in combination of 2 or more types.
- the content of such a solvent is preferably 20 to 60% by mass, more preferably 30 to 50% by mass in the acidic solvent. preferable. If the content of such a solvent is less than the lower limit, mixing tends to be uneven, and the yield of Mannich base tends to decrease.On the other hand, if the upper limit is exceeded, the reaction rate decreases and the yield decreases. It tends to end up.
- the content of the first organic solvent in the acidic solvent is preferably 5 to 30% by mass, and more preferably 10 to 20% by mass. preferable. If the content of the first organic solvent is less than the lower limit, the effect of suppressing the temperature rise cannot be sufficiently obtained, and it becomes difficult to sufficiently suppress the production of by-products, resulting in a decrease in yield. On the other hand, when the upper limit is exceeded, the yield of the target compound tends to be reduced in the purification step.
- the formaldehyde derivative is contained and the acid (formula: acid represented by HX) is 0 with respect to the ketone group of the carbonyl compound represented by the general formula (1).
- the acidic solvent contained in a range of 0.01 to 0.075 molar equivalent the carbonyl compound and the amino compound can be reacted under acidic conditions in which an acid is excessively present, This makes it possible to efficiently produce a Mannich base represented by the above general formula (3), which is a reaction intermediate used for the preparation of bis (spironorbornene) s.
- the carbonyl compound used in the first step is represented by the following general formula (1):
- R 1 and R 2 each independently represents one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms and a fluorine atom, and n is 0 to 12 Indicates an integer.
- It is a carbonyl compound represented by these.
- the alkyl group that can be selected as R 1 and R 2 in the general formula (1) is an alkyl group having 1 to 10 carbon atoms.
- the number of carbon atoms of the alkyl group that can be selected as R 1 and R 2 is preferably 1 to 5 from the viewpoint that higher heat resistance can be obtained when a polyimide is produced. 3 is more preferable.
- such an alkyl group that can be selected as R 1 and R 2 may be linear or branched.
- substituents that can be selected as R 1 and R 2 in the general formula (1) from the viewpoint of ease of purification, among the above substituents, among the above substituents, a hydrogen atom, a carbon number of 1 to 10 (more preferably The alkyl group is preferably 1-5, more preferably 1-3), and particularly preferably a hydrogen atom or a methyl group.
- the plurality of R 1 when a plurality of R 1 are present (when n is 2 or more), the plurality of R 1 may be the same or different. From the viewpoint of easiness of purification and the like, it is preferable that they are the same.
- the plurality of R 2 when a plurality of R 2 are present (when n is 2 or more), the plurality of R 2 may be the same or different. From the viewpoint of easiness of purification and the like, it is preferable that they are the same. Moreover, as R ⁇ 1 >, R ⁇ 2 > in General formula (1), it is more preferable that it is the same from viewpoints, such as the ease of refinement
- n represents an integer of 0 to 12.
- the upper limit of the numerical range of n in the general formula (1) is more preferably 5 and more preferably 3 from the viewpoint of facilitating the purification of bis (spironorbornene) s. Is particularly preferred.
- the lower limit of the numerical range of n in the general formula (1) is more preferably 1 and particularly preferably 2 from the viewpoint of the stability of the raw material.
- n in the general formula (1) is particularly preferably an integer of 2 to 3.
- Examples of the carbonyl compound represented by the general formula (1) include carbonyl compounds exemplified in International Publication No. 2011/099517 (cyclopropanone, cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, Cyclooctanone etc.) may be used as appropriate.
- the preparation method of the carbonyl compound represented by the general formula (1) is not particularly limited, and a known method can be appropriately employed. Moreover, you may use a commercially available compound represented by such General formula (1).
- the amine compound used in the first step is represented by the following general formula (2):
- each R 3 independently represents a linear saturated hydrocarbon group having 1 to 20 carbon atoms, a branched saturated hydrocarbon group having 3 to 20 carbon atoms, or the number of carbon atoms. Any one selected from the group consisting of a saturated cyclic hydrocarbon group having 3 to 20 carbon atoms and a saturated hydrocarbon group having 1 to 10 carbon atoms having a hydroxyl group, wherein two R 3 are bonded to each other, One ring selected from the group consisting of a piperidine ring, a piperazine ring and a morpholine ring may be formed, and X ⁇ represents F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , CH 3 COO ⁇ , CF 3.
- the linear saturated hydrocarbon group that can be selected as R 3 in the general formula (2) is one having 1 to 20 carbon atoms. Such a linear saturated hydrocarbon group preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. If the number of carbon atoms of such a linear saturated hydrocarbon group exceeds the upper limit, purification tends to be difficult.
- the linear saturated hydrocarbon group that can be selected as R 3 is more preferably a methyl group or an ethyl group from the viewpoint of ease of purification.
- such a branched saturated hydrocarbon group that can be selected as R 3 has 3 to 20 carbon atoms.
- Such a branched saturated hydrocarbon group preferably has 3 to 10 carbon atoms, and more preferably 3 to 5. If the number of carbon atoms of such a branched chain saturated hydrocarbon group exceeds the upper limit, purification tends to be difficult.
- the branched saturated hydrocarbon group that can be selected as R 3 is more preferably an isopropyl group from the viewpoint of ease of purification.
- the saturated cyclic hydrocarbon group that can be selected as R 3 has 3 to 20 carbon atoms. Such a saturated cyclic hydrocarbon group preferably has 3 to 10 carbon atoms, and more preferably 5 to 6. If the number of carbon atoms of such a saturated cyclic hydrocarbon group exceeds the upper limit, purification becomes difficult. On the other hand, if the number is less than the lower limit, chemical stability tends to decrease.
- the saturated cyclic hydrocarbon group that can be selected as R 3 is more preferably a cyclopentyl group or a cyclohexyl group from the viewpoint of ease of purification and chemical stability.
- the saturated hydrocarbon group having a hydroxyl group that can be selected as R 3 is a hydrocarbon group having 1 to 10 carbon atoms.
- the number of carbon atoms is more preferably 2 to 10, and further preferably 2 to 5. If the number of carbon atoms of the saturated hydrocarbon group having such a hydroxyl group exceeds the upper limit, purification becomes difficult. On the other hand, if it is less than the lower limit, the chemical stability tends to be inferior.
- the saturated hydrocarbon group having a hydroxyl group that can be selected as R 3 is more preferably a 2-hydroxyethyl group from the viewpoint of ease of purification and chemical stability.
- R ⁇ 3 > in General formula (2) these may couple
- R ⁇ 3 > mutually couple
- R 3 in the general formula (2) is more preferably a methyl group, an ethyl group, a 2-hydroxyethyl group, or morpholine from the viewpoint of ease of purification. Moreover, when two R ⁇ 3 > in the said General formula (2) does not form the ring, it is preferable that two R ⁇ 3 > is the same from a viewpoint of availability.
- X ⁇ in the general formula (2) is a so-called counter anion.
- X ⁇ in the formula (2) is F ⁇ , Cl ⁇ , Br ⁇ , I ⁇ , CH 3 COO ⁇ , CF 3 COO ⁇ , CH 3 SO 3 ⁇ , CF 3 SO 3 ⁇ , C 6 H. 5 SO 3 ⁇ , CH 3 C 6 H 4 SO 3 ⁇ , HOSO 3 — and H 2 PO 4 — .
- Such X - include, from the viewpoint of stability of the Mannich base represented by the resulting formula (3), F -, Cl -, Br -, CH 3 COO -, CF 3 COO - are preferred, Cl -, CH 3 COO - is more preferable.
- Examples of the amine compound represented by the general formula (2) include amine compounds (dimethylamine, diethylamine, di-n-propylamine and the like exemplified in International Publication No. 2011/099517). Secondary amine salts and the like) may be used as appropriate. Moreover, the manufacturing method in particular of such an amine compound is not restrict
- the carbonyl compound represented by the general formula (1) is reacted with the amine compound represented by the general formula (2) in the acidic solvent.
- the amount of the carbonyl compound used in such a reaction is preferably 0.01 to 5.0 mol / L, more preferably 0.1 to 2.0 mol / L in the acidic solvent. If the amount of such a carbonyl compound is less than the lower limit, the production efficiency of the Mannich base represented by the general formula (3) tends to be reduced. It tends to increase.
- the amount of the amine compound used is preferably 2 molar equivalents or more, more preferably 2 to 10 molar equivalents relative to the carbonyl compound. If the amount used is less than the lower limit, the yield of Mannich base tends to decrease. On the other hand, if the amount exceeds the upper limit, by-product reactants due to side reactions tend to increase.
- the amine product is supplied by supplying the commercially available product into the system. You may supply a compound and the said acid simultaneously in an acidic solvent. In this case, the concentration of the acid in the acidic solvent is appropriately measured by a known method, and the relationship between the amount of the carbonyl compound used in the reaction and the amount of the acid is appropriately adjusted by adding an acid as necessary. That's fine.
- reaction conditions for reacting the carbonyl compound and the amine compound in the acidic solvent are not particularly limited, and the conditions can be appropriately changed according to the type of the solvent used.
- the atmosphere in contact with the acidic solvent during such a reaction is not particularly limited, but is preferably an inert gas atmosphere such as nitrogen gas.
- the acidic solvent is brought to a temperature of 30 to 180 ° C. (more preferably 80 to 120 ° C., more preferably 85 to 110 ° C.) for 0.5 to 10 hours (more preferably 4 to 8). It is preferable to adopt heating conditions that hold the time).
- the heating temperature condition is preferably controlled to a lower temperature within the temperature range. From such a viewpoint, the boiling point is 85 to 110 ° C.
- an organic solvent preferably a hydrocarbon solvent having 3 to 20 carbon atoms (more preferably 3 to 10 carbon atoms)
- a solvent in an acidic solvent at a temperature and not dissolving the Mannich base It is preferable to control the temperature at a temperature close to the boiling point.
- the pressure condition during heating is not particularly limited, but is preferably 0.10 to 10 MPa, and more preferably 0.10 to 1 MPa. If the pressure condition is less than the lower limit, the thermal energy reduction effect at the time of solvent recycling tends to be low. On the other hand, if it exceeds the upper limit, the equipment tends to be difficult to implement.
- R 1, R 2, n in the formula (3) have the same meanings as R 1, R 2, n in the formula (1) (also synonymous what its suitable.), Equation (3) the R 3, X - is R 3 in the formula (2), X - synonymous (also synonymous what its suitable.). ]
- R ⁇ 3 > in Formula (3) may respectively be same or different, it is preferable that it is the same from a viewpoint of availability.
- the plurality of X ⁇ in the formula (3) may be the same or different, but are preferably the same from the viewpoint of availability.
- the Mannich base represented by the general formula (3) can be formed in a sufficiently high yield.
- the production efficiency and yield of the reaction intermediate (Mannich base) are more sufficiently improved in the first step.
- the Mannich base can be used efficiently. The rate is estimated to improve.
- the reaction solution obtained in the first step is used.
- the Mannich base since the Mannich base is not isolated from the reaction solution in the second step, the Mannich base, which is a reaction intermediate existing in the reaction solution, is used with high efficiency.
- the process can be simplified, and bis (spironorbornene) can be produced sufficiently efficiently.
- an organic solvent for convenience, sometimes simply referred to as “second organic solvent” is added to the reaction solution.
- an organic solvent is not particularly limited, and an organic solvent that can be used for the so-called Diels-Alder reaction can be appropriately used. Examples include alcohol solvents (including glycol solvents, glycerol solvents, and other polyhydric alcohol solvents), cellosolve solvents, ether solvents, amide solvents, and nitrile solvents.
- a suitable organic solvent can be appropriately selected and used depending on the type of norbornene).
- organic solvent used in the second step in the case where bis (spironorbornene) is separated from the reaction solution by the extraction step after the reaction, a carbon atom is used from the viewpoint of simplifying the extraction step.
- An organic solvent immiscible with the saturated hydrocarbon of several 5 to 30 can be suitably used.
- the organic solvent immiscible with the saturated hydrocarbon having 5 to 30 carbon atoms include methanol, methyl cellosolve, dimethylacetamide, dimethyl sulfoxide, ethylene glycol, propylene glycol, 1,3-propanediol, glycerin, propylene glycol monomethyl.
- Ether, ethyl cellosolve, dimethylformamide, acetonitrile and the like are preferable, and methanol and methyl cellosolve are more preferable from the viewpoint of simplicity of extraction operation.
- “immiscible” means that the mixture is separated into two layers when added at an arbitrary ratio to the reaction solution.
- a second organic solvent in the case where the above-mentioned first organic solvent is used as the acidic solvent, when the bis (spironorbornene) is separated and taken out by the crystallization step after the reaction, From the viewpoint of simplification of the crystallization process, it is more preferable to use an organic solvent in which the solubility of bis (spironorbornene) varies greatly depending on the temperature.
- organic solvent in which the solubility of bis (spironorbornene) varies greatly depending on the temperature
- bis (spirononorbornene) is dissolved at 5 wt% or more under the conditions of 40 to 80 ° C., while -25 to An organic solvent that does not dissolve 2 wt% or more of bis (spironorbornene) under the condition of 0 ° C.
- an organic solvent methanol, ethanol, isopropanol, an aqueous solution thereof and the like are preferable.
- methanol, Ethanol is more preferred.
- the amount of the organic solvent (second organic solvent) added to the reaction solution is not particularly limited, but is 10 with respect to the total amount of the reaction solution and the organic solvent (second organic solvent) to be added. It is preferable to set it to ⁇ 80% by mass (more preferably 20 to 60% by mass). If the concentration of the organic solvent (second organic solvent) is less than the lower limit, by-products such as vinyl ketone dimer tend to increase, and the yield of the target product tends to decrease. The rate tends to decrease and the yield tends to decrease.
- a base is added to the reaction solution.
- amine alkali metal hydroxide, and alkaline earth metal hydroxide can be preferably used from the viewpoint of basicity.
- dimethylamine, diethylamine, dipropylamine, and dibutylamine are preferable from the viewpoint of purification, and dimethylamine is particularly preferable.
- the amount of such base added is 1.0 to 20.0 times molar equivalents (more preferably 1.0 to 10.0 times molar equivalents, and still more preferably) with respect to the acid contained in the reaction solution. 1.0 to 5.0 times molar equivalent). If the amount of the base added is less than the lower limit, decomposition of the Mannich base is suppressed, and it is difficult to produce a bis (vinyl ketone) intermediate as a raw material of the target product. A large amount of neutralizing agent is required at the time of analysis, making recovery difficult.
- the reaction solution is neutral or basic, and the Mannich base and the diene compound are reacted to produce a by-product (for example, the Mannich base to the amino compound).
- Bis (vinylketone) formed by elimination of bismuth sufficiently suppresses the formation of dimerization product (dimer) dimerized by hetero-Diels-Alder reaction, and the desired bis (spironorbornene) is sufficiently It is possible to manufacture with high selectivity.
- reaction solution contains the following general formula (4):
- R 4 represents at least one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and a fluorine atom.
- a diene compound represented by the formula is added.
- the alkyl group that can be selected as R 4 in the general formula (4) is an alkyl group having 1 to 10 carbon atoms. When carbon number of such an alkyl group exceeds 10, when it uses as a monomer of a polyimide, the heat resistance of the polyimide obtained will fall. Further, the number of carbon atoms of the alkyl group that can be selected as R 4 is preferably 1 to 5, and preferably 1 to 3, from the viewpoint that higher heat resistance can be obtained when a polyimide is produced. It is more preferable. Such an alkyl group that can be selected as R 4 may be linear or branched.
- R 4 in the general formula (4) is more preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms from the viewpoint of obtaining high heat resistance when a polyimide is produced.
- a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group is more preferable, and a hydrogen atom or a methyl group is preferable. Is particularly preferred.
- the addition amount of such a diene compound is preferably 2 molar equivalents or more, more preferably 2 to 10 molar equivalents relative to the Mannich base represented by the general formula (3). If the addition amount of such a diene compound is less than the lower limit, the yield of bis (spironorbornene) tends to decrease. On the other hand, if it exceeds the upper limit, the by-products due to side reactions tend to increase. In addition, as such a diene compound, you may use individually by 1 type, or may be used in combination of 2 or more type.
- the organic solvent, the base, and the diene compound are added to the reaction solution, and then the resulting mixture is heated to produce the Mannich base and the diene compound. And react.
- Such heating is performed by reacting the Mannich base with the diene compound in the mixed solution to produce bis (spironorbornene) represented by the general formula (5). Any condition is possible.
- the heating temperature for reacting such a Mannich base with the diene compound is preferably 30 to 180 ° C. (more preferably 50 to 140 ° C.). If the heating temperature is less than the lower limit, the decomposition rate of Mannich base tends to decrease and the yield of the target product tends to decrease.On the other hand, if the upper limit is exceeded, vinyl ketone dimer or diene is already present in the target product. By-products such as tetracyclododecene added with single-molecule Diels-Alder increase, and the selectivity of the target product tends to decrease.
- the heating time for reacting the Mannich base with the diene compound is preferably 0.01 to 10 hours, more preferably 0.01 to 7.0 hours, More preferably, it is ⁇ 5.0 hours.
- the atmosphere in the case of this heating is inert gas atmosphere, such as nitrogen gas, from a viewpoint of coloring prevention or safety
- a heating method a method in which a mixed liquid of the Mannich base, the diene compound, the base, and the organic solvent is dropped into a reaction vessel that is heated in advance to the heating temperature may be employed.
- a part of the organic solvent may be put in a reaction vessel in advance. This also makes it possible to proceed the reaction more safely.
- a pressurized container such as an autoclave may be adopted.
- heating may be started at normal pressure, or heating may be started from a certain predetermined pressure.
- various types of organic solvents can be used, and the thermal energy during solvent recycling can be reduced.
- the pressure condition during heating is not particularly limited, but is preferably 0.10 to 10 MPa, and more preferably 0.10 to 1.0 MPa. If the pressure condition is less than the lower limit, the thermal energy reduction effect at the time of solvent recycling tends to be low. On the other hand, if it exceeds the upper limit, the equipment tends to be difficult to implement.
- R 1, R 2, n in the formula (5) have the same meanings as R 1, R 2, n in the above formula (1), R 4 in the formula (5) is of the formula (4) it is synonymous with R 4.
- 5-norbornene-2-spiro- ⁇ -cycloalkanone- ⁇ ′-spiro-2 ′′ -5 ′′ -norbornenes represented by the formula:
- R 1, R 2, n in the general formula (5) have the same meanings as R 1, R 2, n in the formula (1) (also synonymous what its suitable.)
- R 4 in the general formula (5) has the same meaning as R 4 in the general formula (4) (also synonymous what its suitable.).
- the plurality of R 1 when a plurality of R 1 are present (when n is 2 or more), the plurality of R 1 may be the same or different. From the viewpoint of easiness of purification and the like, it is preferable that they are the same.
- the plurality of R 2 when a plurality of R 2 are present (when n is 2 or more), the plurality of R 2 may be the same or different.
- the plurality of R 4 in the general formula (5) may be the same or different from each other, but are the same from the viewpoint of ease of purification and the like. Is preferred.
- the mixture obtained by adding the organic solvent, the base and the diene compound to the reaction solution is heated.
- the amine compound is eliminated from the Mannich base represented by the general formula (3), and the following general formula (6):
- R 1, R 2, n in the formula (6) have the same meanings as R 1, R 2, n in the above formula (1).
- a compound having a bis (vinyl ketone) structure represented by the following formula is formed, and then the compound having the bis (vinyl ketone) structure and the diene compound represented by the general formula (4) are subjected to a so-called Diels-Alder reaction.
- Diels-Alder reaction By reacting, the bis (spirononorbornene) represented by the general formula (5) is formed.
- the reaction proceeds under neutral or basic conditions as described above, the formation of by-products is suppressed at a higher level, and bis (spironorbornene) is produced more efficiently.
- the abundance of the compound having the bis (vinyl ketone) structure in the mixed solution after the reaction is bis (spirononorbornene) ( It is preferable that it is 2 mol% or less with respect to the target object. If the abundance of the compound having such a bis (vinyl ketone) structure exceeds the upper limit, the target product tends to be colored or the product tends to become viscous due to dimerization. From the viewpoint of ensuring that the abundance of the compound having the bis (vinyl ketone) structure is 2 mol% or less, the content of the base is changed to the acid contained in the reaction solution in the second step. It is preferable that the molar equivalent is 2.0 to 5.0 times, the heating temperature is 50 to 125 ° C., and the heating time is 0.5 to 10 hours.
- a dimerization product in which the compound having the bis (vinyl ketone) structure is dimerized in the mixed solution after the reaction.
- a dimerization product Is preferably 2 mol% or less with respect to the bis (spironorbornene) (target product). If the abundance ratio of such a dimer exceeds the upper limit, the product tends to become viscous. From the viewpoint of more surely making the abundance of the dimer 2 mol% or less, in the second step, the content of the base is 2.0 to 5 with respect to the acid contained in the reaction solution.
- the molar equivalent is 0.0
- the heating temperature is 50 to 125 ° C.
- the heating time is 0.5 to 10 hours.
- the presence rate of the compound and dimer which have a bis (vinyl ketone) structure in such a liquid mixture can be measured by what is called HPLC analysis. A well-known thing can be utilized suitably for the apparatus etc. which are used for such HPLC analysis.
- bis (spirononorbornene) can be obtained more efficiently and can be easily obtained. It is more preferable to employ a crystallization method (including a crystallization step) from the viewpoint of improving the properties. That is, it is preferable to employ a crystallization method as a step of purifying bis (spironorbornene) s.
- a specific method for such crystallization is not particularly limited, and a known method can be appropriately employed.
- a crystallization method for cooling the mixed liquid after the reaction to precipitate crystals is appropriately employed. May be. In such a crystallization process, a seed crystal may be used as appropriate.
- the temperature conditions and the like during such a crystallization step vary depending on the type of the target bis (spirononorbornene) and are not particularly limited, but are preferably ⁇ 25 to 25 ° C. (more preferably Is preferably crystallized by adopting the condition of cooling for 5 to 12 hours under the temperature condition of -20 to 0 ° C. If such a temperature condition exceeds the above upper limit, crystal precipitation is insufficient and the yield tends to decrease. On the other hand, if the temperature condition is less than the lower limit, purity tends to decrease due to precipitation of by-products.
- the crystallization step From the viewpoint of efficiently obtaining bis (spirononorbornene), after preparing bis (spirononorbornene), a pretreatment step of removing the solvent having high solubility of bis (spirononorbornene) from the reaction solution. It is preferable to crystallize bis (spironorbornene) after application.
- the mixed solution contains a solvent having high solubility of bis (spirononorbornene) (for example, the first organic solvent)
- a solvent having high solubility of bis (spirononorbornene) for example, the first organic solvent
- Such a pretreatment step is not particularly limited as long as it is a method capable of removing a solvent having high solubility of bis (spirononorbornene) (for example, the first organic solvent).
- a known method can be appropriately employed. For example, a method of azeotropic removal with other components and the like may be appropriately employed.
- a solvent having high solubility of bis (spirononorbornene) contained in the reaction solution (the mixed solution after the reaction) for example, the first organic solvent
- a removal amount (removal ratio) is less than the lower limit, the amount of the product precipitated during crystallization decreases, and the yield tends to decrease.
- the reaction solution after removing the solvent (for example, the first organic solvent) having high solubility of bis (spironorbornene) in the pretreatment step.
- concentration of the solvent (for example, said 1st organic solvent) with high solubility of these bis (spiro norbornene) is 5 mass% or less (more preferably 3 mass% or less).
- concentration exceeds the above upper limit, the amount of the product precipitated during crystallization decreases, and the yield tends to decrease.
- the said acidic solvent contains said 1st organic solvent, it is more preferable to remove a 1st organic solvent by the above-mentioned ratio ⁇ removal amount) in the said pretreatment process.
- the solvent of the mixed solution after the reaction is changed. It is more preferable to use a solvent (poor solvent) having low solubility of bis (spironorbornene) s.
- the property of the solvent “low solubility of bis (spironorbornene)” here is determined based on the solubility at 20 ° C. in the solvent mainly used during the reaction. Further, the low solubility of such bis (spironorbornene) s varies depending on the temperature conditions during crystallization, and is not particularly limited. The solubility at 20 ° C.
- an organic solvent in which the solubility of bis (spirononorbornene) varies greatly depending on the temperature is preferable. Under conditions of 40 to 80 ° C., bis (spirononorbornene) is dissolved by 5 wt% or more. On the other hand, an organic solvent that does not dissolve 2 wt% or more of bis (spironorbornene) under the condition of ⁇ 20 to 0 ° C. is more preferable. By using such a solvent, it becomes possible to precipitate crystals more efficiently under a temperature condition of ⁇ 25 to 25 ° C. (more preferably ⁇ 20 to 0 ° C.).
- a solvent with low solubility of such bis (spiro norbornene) methanol, ethanol, isopropanol, and those aqueous solution etc. are mentioned, for example.
- the solubility of bis (spirononorbornene) is high by the pretreatment step.
- the solvent of the mixed solution after the reaction is changed to bis (spironorbornene).
- a solvent with low solubility may be used.
- the ratio of endo / exo in the configuration of substituents in the bis (spironorbornene) can be 10/90 to 30/70 (more preferably 15/85 to 25/75).
- the Mannich base is decomposed in the second step and at the same time the Diels-Alder reaction is caused to produce bis (spironorbornene), but the heating temperature (reaction temperature) in the second step is In the case of the above-mentioned preferable range (for example, 30 to 180 ° C.), the variable endo / exo ratio naturally falls within the above range.
- the bis (spironorbornene) s of the present invention have a ketone group, and since the ketone group is given priority in naming, it becomes an endo adduct in the reaction, but the bis (spironorbornene) s obtained by the reaction Is an exo body for naming purposes.
- the bis (spironorbornene) represented by the above general formula (5) thus obtained can be suitably used as a raw material compound for producing an acid dianhydride monomer for polyimide production
- Colorless and transparent polyimides starting from such bis (spironorbornene) s are flexible wiring board films, heat-resistant insulating tapes, wire enamels, semiconductor protective coatings, liquid crystal alignment films, transparent conductive films for organic EL, Flexible substrate film, flexible transparent conductive film, transparent conductive film for organic thin film solar cell, transparent conductive film for dye-sensitized solar cell, flexible gas barrier film, touch panel film, interlayer insulating film, sensor substrate, printer transfer It is particularly useful as a material for manufacturing a belt or the like.
- such bis (spironorbornene) s can be made into a desired polymer or cross-linked product by metathesis reaction, addition polymerization, radical polymerization, cationic polymerization, anionic polymerization, etc. alone. Accordingly, it is also possible to obtain a copolymer or a crosslinked copolymer by copolymerizing with any copolymerizable compound. Further, acid dianhydrides obtained from such bis (spironorbornenes) are useful as epoxy curing agents and maleimide raw materials in addition to polyimide monomers.
- the molecular structure of the compound obtained in each example is identified by an IR measuring instrument (manufactured by JASCO Corporation, trade names: FT / IR-460, FT / IR-4100) and an NMR measuring instrument ( The measurement was carried out by measuring IR and NMR spectra using VARIAN, trade name: UNITY INOVA-600 and JEOL Ltd. JNM-Lambda500).
- IR measuring instrument manufactured by JASCO Corporation, trade names: FT / IR-460, FT / IR-4100
- NMR measuring instrument The measurement was carried out by measuring IR and NMR spectra using VARIAN, trade name: UNITY INOVA-600 and JEOL Ltd. JNM-Lambda500).
- Example 1 First, 30.86 g (378.5 mmol) of dimethylamine hydrochloride was added to a 1 L three-necked flask. Next, 12.3 g (385 mmol) of paraformaldehyde, 23.9 g (385 mmol) of ethylene glycol, and 12.95 g (154 mmol) of cyclopentanone were further added to the three-necked flask. Next, after adding 16.2 g (165 mmol) of methylcyclohexane to the three-necked flask, 0.4 g of 35 mass% hydrochloric acid (HCl: 3.85 mmol) was added to obtain a first mixed solution.
- HCl 35 mass% hydrochloric acid
- ⁇ Second step> After cooling the reaction solution in the three-necked flask to 50 ° C., methanol (250 ml) and 4.17 g of a 50 mass% dimethylamine aqueous solution (dimethylamine: 46) with respect to the reaction solution in the three-necked flask. 0.2 mmol) and 30.5 g (461.5 mmol) of cyclopentadiene were added to obtain a second mixed solution. Next, the inside of the three-necked flask is replaced with nitrogen, the temperature in the three-necked flask is set to 65 ° C. at normal pressure (0.1 MPa), and the second mixed solution is heated and stirred at 65 ° C.
- the second mixed solution in the three-necked flask was concentrated by azeotropic distillation of methylcyclohexane and methanol, and 100 mL of the liquid was removed from the second mixed solution. By removing 100 mL of such liquid, most of methylcyclohexane (75% by mass with respect to the total amount of methylcyclohexane in the second mixed solution before concentration) was removed from the second mixed solution.
- the second mixed liquid after the removal of methylcyclohexane was cooled for 12 hours under a temperature condition of ⁇ 20 ° C. to precipitate crystals, and then filtered under reduced pressure to obtain crystals.
- the crystal thus obtained was subjected to a washing step with 20 mL of methanol at ⁇ 20 ° C. three times, and then the methanol was removed by evaporation to give a compound (5-norbornene-2-spiro- 17.4 g (2% -cyclopentanone-5′-spiro-2 ′′ -5 ′′ -norbornene) (final yield 47%) was obtained.
- Example 2 5-Norbornene-2-spiro-similar to Example 1 except that the amount of 35 mass% hydrochloric acid used was changed from 0.4 g (HCl: 3.85 mmol) to 0.2 g (HCl: 1.93 mmol).
- 2′-Cyclopentanone-5′-spiro-2 ′′ -5 ′′ -norbornene was obtained.
- content of the acid (HCl) in said 1st liquid mixture was 0.0125 molar equivalent with respect to the ketone group in cyclopentanone.
- the structure of the compound was confirmed in the same manner as in Example 1.
- the obtained compound was 5-norbornene-2-spiro-2′-cyclopentanone-5′-spiro-2 ′′ -5 ′′ -norbornene. It was confirmed that the reaction yield was 70%.
- Example 3 5-Norbornene-2-spiro- was prepared in the same manner as in Example 1 except that the amount of 35% by mass hydrochloric acid was changed from 0.4 g (HCl: 3.85 mmol) to 1.1 g (HCl: 10.8 mmol). 2′-Cyclopentanone-5′-spiro-2 ′′ -5 ′′ -norbornene was obtained. In addition, content of the acid (HCl) in said 1st liquid mixture was 0.070 molar equivalent with respect to the ketone group in cyclopentanone. Further, the structure of the compound was confirmed in the same manner as in Example 1. As a result, the obtained compound was 5-norbornene-2-spiro-2′-cyclopentanone-5′-spiro-2 ′′ -5 ′′ -norbornene. The reaction yield was 71%.
- Example 4 5-Norbornene-2-spiro- was prepared in the same manner as in Example 1 except that the amount of 35% by mass hydrochloric acid was changed from 0.4 g (HCl: 3.85 mmol) to 0.8 g (HCl: 7.7 mmol). 2′-Cyclopentanone-5′-spiro-2 ′′ -5 ′′ -norbornene was obtained. In addition, content of the acid (HCl) in said 1st liquid mixture was 0.050 molar equivalent with respect to the ketone group in cyclopentanone. Further, the structure of the compound was confirmed in the same manner as in Example 1. As a result, the obtained compound was 5-norbornene-2-spiro-2′-cyclopentanone-5′-spiro-2 ′′ -5 ′′ -norbornene. It was confirmed that the reaction yield was 70%.
- 5-norbornene-2-spiro- ⁇ -cycloalkanone- ⁇ ′-spiro-2 ′′ -5 ′′ -norbornene is obtained in a higher yield. It is possible to provide a process for producing 5-norbornene-2-spiro- ⁇ -cycloalkanone- ⁇ ′-spiro-2 ′′ -5 ′′ -norbornenes that can be more efficiently produced. Therefore, the method for producing 5-norbornene-2-spiro- ⁇ -cycloalkanone- ⁇ ′-spiro-2 ′′ -5 ′′ -norbornenes of the present invention is used for flexible wiring boards that require heat resistance.
- Polyimide polyimide for heat-resistant insulating tape, polyimide for wire enamel, polyimide for semiconductor protective coating, polyimide for liquid crystal alignment film, polyimide for organic EL transparent electrode substrate, polyimide for transparent electrode substrate of solar cell, Manufacture raw material compounds (raw material monomers) for manufacturing polyimide for transparent electrode substrates of electronic paper, various gas barrier film substrate materials, polyimide for interlayer insulation films, polyimide for sensor substrates, polyimide for printer transfer belts, etc. It is particularly useful as a method for doing so.
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Abstract
Description
で表されるカルボニル化合物と、下記一般式(2):
で表されるアミン化合物とを反応させて、下記一般式(3):
で表されるマンニッヒ塩基を形成せしめ、前記酸性溶媒中に前記マンニッヒ塩基を含有する反応液を得る第一工程と、前記反応液中に、有機溶媒と、前記酸に対して1.0~20.0倍モル当量の塩基と、下記一般式(4):
で表されるジエン化合物とを添加し、加熱して、前記マンニッヒ塩基と前記ジエン化合物とを反応せしめ、下記一般式(5):
で表される5-ノルボルネン-2-スピロ-α-シクロアルカノン-α’-スピロ-2’’-5’’-ノルボルネン類を形成せしめる第二工程とを含み、かつ、
前記第一工程に用いる前記酸性溶媒中の前記酸の含有量が、前記カルボニル化合物のケトン基に対して0.01~0.075モル当量である、方法である。
前記第一工程に用いる前記酸性溶媒中の前記酸の含有量が、前記カルボニル化合物のケトン基に対して0.01~0.075モル当量である、方法である。以下、各工程を分けて説明する。なお、以下において、上記一般式(5)で表される5-ノルボルネン-2-スピロ-α-シクロアルカノン-α’-スピロ-2’’-5’’-ノルボルネン類を、場合により、単に「ビス(スピロノルボルネン)類」という。
第一工程は、前記酸性溶媒中、上記一般式(1)で表されるカルボニル化合物と上記一般式(2)で表されるアミン化合物とを反応させて、上記一般式(3)で表されるマンニッヒ塩基を形成せしめ、前記酸性溶媒中に前記マンニッヒ塩基を含有する反応液を得る工程である。なお、このような第一工程においては、前記酸性溶媒中の前記酸の含有量は、前記カルボニル化合物のケトン基に対して0.01~0.075モル当量である。
で表されるカルボニル化合物である。
で表されるアミン化合物である。
で表されるマンニッヒ塩基を形成することができ、これにより前記酸性溶媒中に前記マンニッヒ塩基を含有する反応液を得ることができる。なお、式(3)中の複数のR3は、それぞれ、同一のものであっても異なっていてもよいが、入手性の観点から、同一のものであることが好ましい。また、式(3)中の複数のX-は、それぞれ、同一のものであっても異なっていてもよいが、入手性の観点から、同一のものであることが好ましい。
第二工程は、前記反応液中に、有機溶媒と、前記酸に対して1.0~20.0倍モル当量の塩基と、上記一般式(4)で表されるジエン化合物とを添加し、加熱して、前記マンニッヒ塩基と前記ジエン化合物とを反応せしめ、上記一般式(5)で表されるビス(スピロノルボルネン)類を形成せしめる工程である。
で表されるジエン化合物を添加する。
で表される5-ノルボルネン-2-スピロ-α-シクロアルカノン-α’-スピロ-2’’-5’’-ノルボルネン類が得られる。
で表されるビス(ビニルケトン)構造を有する化合物が形成され、次いで、そのビス(ビニルケトン)構造を有する化合物と、上記一般式(4)で表されるジエン化合物とが、いわゆるディールス・アルダー反応により反応し、上記一般式(5)で表されるビス(スピロノルボルネン)類が形成される。本発明においては、このように中性又は塩基性条件下において反応を進行させるため、副生成物の生成がより高度な水準で抑制され、より効率よくビス(スピロノルボルネン)類が製造される。
<第一工程>
先ず、1Lの三口フラスコにジメチルアミン塩酸塩を30.86g(378.5mmol)添加した。次に、前記三口フラスコ中に、パラホルムアルデヒド12.3g(385mmol)と、エチレングリコール23.9g(385mmol)と、シクロペンタノン12.95g(154mmol)とを更に添加した。次いで、前記三口フラスコ中に、メチルシクロヘキサン16.2g(165mmol)を添加した後、35質量%塩酸0.4g(HCl:3.85mmol)を添加して第一混合液を得た。なお、前記第一混合液中の酸(HCl)の含有量は、シクロペンタノン中のケトン基に対して0.025モル当量(3.85[HClのモル量]/154[シクロペンタノンのモル量]=0.025)であった。
次に、前記三口フラスコ中の前記反応液を50℃に冷却した後、前記三口フラスコ中の前記反応液に対してメタノール(250ml)と、50質量%ジメチルアミン水溶液4.17g(ジメチルアミン:46.2mmol)と、シクロペンタジエン30.5g(461.5mmol)とを添加し、第二混合液を得た。次いで、前記三口フラスコの内部を窒素置換し、常圧(0.1MPa)で前記三口フラスコ内の温度を65℃にして、前記第二混合液を65℃で5時間加熱撹拌して化合物を生成せしめた。このようにして得られた反応液中の化合物(5-ノルボルネン-2-スピロ-2’-シクロペンタノン-5’-スピロ-2’’-5’’-ノルボルネン)を高速液体クロマトグラフィーにより定量したところ、反応収率は76%であった。
35質量%塩酸の使用量を0.4g(HCl:3.85mmol)から0.2g(HCl:1.93mmol)に変更した以外は実施例1と同様にして、5-ノルボルネン-2-スピロ-2’-シクロペンタノン-5’-スピロ-2’’-5’’-ノルボルネンを得た。なお、前記第一混合液中の酸(HCl)の含有量は、シクロペンタノン中のケトン基に対して0.0125モル当量であった。また、実施例1と同様に化合物の構造確認をした結果、得られた化合物は5-ノルボルネン-2-スピロ-2’-シクロペンタノン-5’-スピロ-2’’-5’’-ノルボルネンであることが確認され、また、その反応収率は70%であった。
35質量%塩酸の使用量を0.4g(HCl:3.85mmol)から1.1g(HCl:10.8mmol)に変更した以外は実施例1と同様にして、5-ノルボルネン-2-スピロ-2’-シクロペンタノン-5’-スピロ-2’’-5’’-ノルボルネンを得た。なお、前記第一混合液中の酸(HCl)の含有量は、シクロペンタノン中のケトン基に対して0.070モル当量であった。また、実施例1と同様に化合物の構造確認をした結果、得られた化合物は5-ノルボルネン-2-スピロ-2’-シクロペンタノン-5’-スピロ-2’’-5’’-ノルボルネンであることが確認され、また、その反応収率は71%であった。
35質量%塩酸の使用量を0.4g(HCl:3.85mmol)から0.8g(HCl:7.7mmol)に変更した以外は実施例1と同様にして、5-ノルボルネン-2-スピロ-2’-シクロペンタノン-5’-スピロ-2’’-5’’-ノルボルネンを得た。なお、前記第一混合液中の酸(HCl)の含有量は、シクロペンタノン中のケトン基に対して0.050モル当量であった。また、実施例1と同様に化合物の構造確認をした結果、得られた化合物は5-ノルボルネン-2-スピロ-2’-シクロペンタノン-5’-スピロ-2’’-5’’-ノルボルネンであることが確認され、また、その反応収率は70%であった。
35質量%塩酸の使用量を0.4g(HCl:3.85mmol)から3.2g(HCl:30.8mmol)に変更した以外は実施例1と同様にして、5-ノルボルネン-2-スピロ-2’-シクロペンタノン-5’-スピロ-2’’-5’’-ノルボルネンを得た。なお、前記第一混合液中の酸(HCl)の含有量は、シクロペンタノン中のケトン基に対して0.20モル当量であった。また、実施例1と同様に化合物の構造確認をした結果、得られた化合物は5-ノルボルネン-2-スピロ-2’-シクロペンタノン-5’-スピロ-2’’-5’’-ノルボルネンであることが確認され、また、その反応収率は27%であった。
35質量%塩酸の使用量を0.4g(HCl:3.85mmol)から1.28g(HCl:12.3mmol)に変更した以外は実施例1と同様にして、5-ノルボルネン-2-スピロ-2’-シクロペンタノン-5’-スピロ-2’’-5’’-ノルボルネンを得た。なお、前記第一混合液中の酸(HCl)の含有量は、シクロペンタノン中のケトン基に対して0.080モル当量であった。また、実施例1と同様に化合物の構造確認をした結果、得られた化合物は5-ノルボルネン-2-スピロ-2’-シクロペンタノン-5’-スピロ-2’’-5’’-ノルボルネンであることが確認され、また、その反応収率は60%であった。
35質量%塩酸の使用量を0.4g(HCl:3.85mmol)から1.6g(HCl:15.4mmol)に変更した以外は実施例1と同様にして、5-ノルボルネン-2-スピロ-2’-シクロペンタノン-5’-スピロ-2’’-5’’-ノルボルネンを得た。なお、前記第一混合液中の酸(HCl)の含有量は、シクロペンタノン中のケトン基に対して0.10モル当量であった。また、実施例1と同様に化合物の構造確認をした結果、得られた化合物は5-ノルボルネン-2-スピロ-2’-シクロペンタノン-5’-スピロ-2’’-5’’-ノルボルネンであることが確認され、また、その反応収率は61%であった。
したがって、本発明の5-ノルボルネン-2-スピロ-α-シクロアルカノン-α’-スピロ-2’’-5’’-ノルボルネン類の製造方法は、耐熱性が要求されるフレキシブル配線基板用のポリイミド、耐熱絶縁テープ用のポリイミド、電線エナメル用のポリイミド、半導体の保護コーティング用のポリイミド、液晶配向膜用のポリイミド、有機ELの透明電極基板用のポリイミド、太陽電池の透明電極基板用のポリイミド、電子ペーパーの透明電極基板用のポリイミド、各種のガスバリアフィルム基板材料、層間絶縁膜用のポリイミド、センサー基板用のポリイミド、プリンタ転写ベルト用のポリイミド等を製造するための原料化合物(原料モノマー)を製造するための方法等として特に有用である。
Claims (2)
- ホルムアルデヒド誘導体を含有し且つ式:HX(式中、Xは、F、Cl、Br、I、CH3COO、CF3COO、CH3SO3、CF3SO3、C6H5SO3、CH3C6H4SO3、HOSO3及びH2PO4からなる群から選択される1種を示す。)で表される酸を含有している酸性溶媒中、下記一般式(1):
で表されるカルボニル化合物と、下記一般式(2):
で表されるアミン化合物とを反応させて、下記一般式(3):
で表されるマンニッヒ塩基を形成せしめ、前記酸性溶媒中に前記マンニッヒ塩基を含有する反応液を得る第一工程と、前記反応液中に、有機溶媒と、前記酸に対して1.0~20.0倍モル当量の塩基と、下記一般式(4):
で表されるジエン化合物とを添加し、加熱して、前記マンニッヒ塩基と前記ジエン化合物とを反応せしめ、下記一般式(5):
で表される5-ノルボルネン-2-スピロ-α-シクロアルカノン-α’-スピロ-2’’-5’’-ノルボルネン類を形成せしめる第二工程とを含み、かつ、
前記第一工程に用いる前記酸性溶媒中の前記酸の含有量が、前記カルボニル化合物のケトン基に対して0.01~0.075モル当量である、5-ノルボルネン-2-スピロ-α-シクロアルカノン-α’-スピロ-2’’-5’’-ノルボルネン類の製造方法。 - 前記第一工程に用いる前記酸性溶媒中の前記酸の含有量が、前記カルボニル化合物のケトン基に対して0.01~0.070モル当量である、請求項1に記載の5-ノルボルネン-2-スピロ-α-シクロアルカノン-α’-スピロ-2’’-5’’-ノルボルネン類の製造方法。
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