WO2014073672A1 - アルデヒド化合物の製造方法 - Google Patents
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- WO2014073672A1 WO2014073672A1 PCT/JP2013/080344 JP2013080344W WO2014073672A1 WO 2014073672 A1 WO2014073672 A1 WO 2014073672A1 JP 2013080344 W JP2013080344 W JP 2013080344W WO 2014073672 A1 WO2014073672 A1 WO 2014073672A1
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- UMRZSTCPUPJPOJ-UHFFFAOYSA-N C(C1)C2CC1CC2 Chemical compound C(C1)C2CC1CC2 UMRZSTCPUPJPOJ-UHFFFAOYSA-N 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N C1C2C=CC1C=C2 Chemical compound C1C2C=CC1C=C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 0 CC1CC(CCCCC*)C(C)CC1 Chemical compound CC1CC(CCCCC*)C(C)CC1 0.000 description 1
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- C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
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- C07C211/34—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of rings other than six-membered aromatic rings of a saturated carbon skeleton
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- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Definitions
- the present invention relates to a method for producing an aldehyde compound, a method for producing an amine compound and a method for producing an isocyanate compound using the aldehyde compound obtained by the production method.
- Patent Documents 1 to 3 As a method for producing an aldehyde compound using a norbornene compound, for example, methods described in Patent Documents 1 to 3 are known.
- Patent Documents 1 to 3 disclose a process for producing formylcyanorbornane by hydroformylating cyanorbornene using a H 2 / CO mixed gas in the presence of a catalyst.
- Patent Documents 1 and 2 disclose examples using a metal compound as a catalyst.
- a rhodium complex is preferably used as the catalyst because the target compound can be obtained with high selectivity and the reaction pressure can be suppressed low.
- Patent Document 1 describes that the catalyst can be 0.1 to 10% by weight with respect to cyannorbornene.
- Patent Document 2 describes that the catalyst concentration is 0.5 to 10 mmol / l, and triarylphosphine can be used in the range of 3 to 300 mol with respect to 1 mol of rhodium.
- Patent Document 4 discloses a method for hydroformylating an olefinic compound using a H 2 / CO mixed gas in the presence of a transition metal catalyst and a trivalent phosphorus compound.
- the content of the metal catalyst is described as a free metal content of 10 to 1000 ppm based on the weight or volume of the catalyst composition.
- Patent Document 5 describes a metal ligand complex catalyst, and mentions rhodium as a metal and an organic phosphorus ligand as a ligand.
- the amounts used are described as a metal concentration in the range of about 1 ppm to 10,000 ppm and a ligand: metal molar ratio of 1: 1 to 200: 1, calculated as free metal.
- Patent Documents 6 and 7 disclose a method for producing an aldehyde compound by hydroformylating a chain olefin compound.
- Patent Document 6 describes an example in which 7-octenal is hydroformylated in the presence of a rhodium catalyst and a bisphosphite. It is described that rhodium is used in an amount of about 3 ppm mol with respect to 1 mol of 7-octenal, and the rhodium atom / phosphorus atom is 1/20 in molar ratio. On the other hand, paragraph 0084 of Patent Document 6 describes that 2 to 1000 mol in terms of phosphorus atom is preferable with respect to 1 mol of metal, and the reaction rate tends to be extremely low when it exceeds 1000 mol.
- Patent Document 7 there is a description that a substance such as a halogenated organic compound should be excluded from the reaction in hydroformylation of olefin, but there is no description regarding the amount thereof.
- the present invention has been made in view of the above problems, and in producing an aldehyde by reducing the amount of a metal that is an expensive catalyst, even if the amount of the metal is reduced, it is possible to suppress a decrease in the reaction rate. It is to provide an industrially advantageous method that can be performed.
- X represents a hydrogen atom, cyano group, aldehyde group, —CH ⁇ NR group, and R represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group.
- the group 8 to 10 metal is 1 to 5 ppm mol per 1 mol of the compound represented by the general formula (a1) or (a2) [1] to [3] The manufacturing method of the aldehyde compound as described in any one of these. [5] The method for producing an aldehyde compound according to any one of [1] to [4], wherein the phosphorus compound is a trivalent phosphorus compound. [6] Using the compound represented by the general formula (a1), the compound is represented by the following general formula (1).
- a process comprising reacting an aldehyde compound obtained by the production method according to any one of [1] to [6] with ammonia and reacting with hydrogen in the presence of a catalyst.
- a method for producing an amine compound A method for producing an isocyanate compound, comprising a step of reacting the amine compound obtained by the production method according to [7] with a carbonylating agent.
- the “phosphorus compound” in the present invention means a phosphorus compound that can form a complex with a metal.
- the amount of the substance B is expressed as 1 ppm mol.
- the method for producing an aldehyde compound of the present invention even if the amount of metal as a catalyst is reduced, the reaction rate is prevented from being lowered, and an industrially advantageous aldehyde can be produced. Since the method for producing an amine compound and the method for producing an isocyanate compound of the present invention include the method for producing an aldehyde compound as one step, the present invention has the effect of further improving the productivity and yield of the isocyanate compound and the amine compound. give.
- FIG. 2 is a 1 H-NMR chart of the compound obtained in Example 1.
- FIG. 2 is a 1 H-NMR chart of the compound obtained in Example 2.
- FIG. 2 is a 1 H-NMR chart of the compound obtained in Example 3.
- a compound represented by the following general formula (a1) or the following general formula (a2) is treated with hydrogen in the presence of a metal compound containing a Group 8-10 metal and a phosphorus compound. And a step of reacting with carbon monoxide, and the amount of chlorine atoms in the reaction system in the step is 1.5 parts by weight or less with respect to 1 part by weight of the Group 8-10 metal.
- X represents a hydrogen atom, a cyano group, an aldehyde group, —CH ⁇ NR group, and R represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms. .
- X is preferably a cyano group or an aldehyde group, and more preferably a cyano group.
- n represents 0, 1 or 2, preferably 0 or 1, and more preferably 1.
- the compound represented by general formula (a1) may be either an endo isomer or an exo isomer, and may be a mixture containing these in an arbitrary ratio.
- Specific examples of the compound represented by the general formula (a1) include the following compounds.
- n 1 compound
- Bicyclo [2.2.1] hepta-2,5-diene can be mentioned.
- Bicyclo [2.2.2] octa-2,5-diene can be mentioned.
- n is more preferably 1.
- a compound represented by the following general formula (1) can be preferably used.
- X is synonymous with general formula (a1), and is preferably a cyano group or an aldehyde group, and more preferably a cyano group.
- the compound represented by the general formula (1) may be either an endo isomer or an exo isomer, and may be a mixture containing these at an arbitrary ratio.
- the metal compound containing a Group 8-10 metal used in the reaction of this embodiment is a rhodium compound, a cobalt compound, a ruthenium compound, or an iron compound.
- Examples of the rhodium compound include Rh (acac) (CO) 2 , Rh (acac) 3 , Rh 2 (CO) 8 , Rh 4 (CO) 12 , Rh 6 (CO) 16 and the like.
- Examples of the cobalt compound include HCo (CO) 3 , HCo (CO) 4 , Co 2 (CO) 8 , HCo 3 (CO) 9, and the like.
- Examples of the ruthenium compound include Ru (CO) 3 (PPh 3 ) 2 and Ru 3 (CO) 12 .
- As the iron compounds for example, Fe (CO) 5, Fe ( CO) 4 PPh 3, Fe (CO) 4 (PPh 3) 2 and the like.
- “Acac” means acetylacetonate.
- the rhodium compound used in the reaction of the present embodiment is not particularly limited as long as it is a compound containing a monovalent rhodium metal, but dicarbonylacetylacetonatodium (Rh (acac) (CO) 2 ), dodecacarbonyltetrarhodium.
- examples thereof include rhodium carbonyl catalysts such as (Rh 4 (CO) 12 ), hexadecacarbonyl hexarhodium (Rh 6 (CO) 16 ), and octacarbonyl dirhodium (Rh 2 (CO) 8 ).
- R 1 and R 2 may be the same or different and each represents an optionally substituted alkyl group having 1 to 16 carbon atoms or an aryl group having 6 to 16 carbon atoms.
- phosphorus compounds include triphenyl phosphite, triphenylphosphine, trimethylphosphine, triethylphosphine, tripropylphosphine, tri (methylbenzene) phosphine, tri (ethylbenzene) phosphine, 1,2-bis (diphenylphosphino ) Ethylene, 1,3-bis (diphenylphosphino) propane, 2,2-bis (diphenylphosphino) -1,1-binaphthyl, trimethoxy phosphite, triethoxy phosphite, tripropoxy phosphite, triisopropoxy Examples thereof include trivalent phosphorus compounds such as phosphite, trimethylphenyl phosphite, and tris (2,4-ditertiarybutylphenyl) phosphite. In this embodiment, triphenyl phosphite is preferably used
- phosphorus compounds are generally synthesized by reacting phosphorus trichloride or phosphorus pentachloride with an aromatic compound, alicyclic compound, aliphatic compound or the like which may contain a substituent. Therefore, the phosphorus compound contains chlorine such as phosphorus trichloride and phosphorus pentachloride as raw materials, chlorine such as by-produced hydrogen chloride and chlorine, and chlorine-containing intermediates produced as a by-product in the reaction. Although the chlorine atom present in the reaction system is considered to be derived from the phosphorus compound, it does not exclude chlorine contained in other raw materials.
- the metal compound containing a Group 8 to 10 metal does not contain a chlorine atom in the structure, since the chlorine-containing compound is not used in the synthesis process for the raw materials other than the phosphorus compound, It is thought to be derived from a compound. That is, in this case, the phosphorus compound contains a chlorine atom in an amount described later with respect to 1 part by weight of the Group 8-10 metal.
- the amount of chlorine contained in the phosphorus compound is the above-mentioned predetermined amount, it is not necessary to reduce the chlorine content of the phosphorus compound, but a metal compound containing a Group 8-10 metal contains a chlorine atom in the structure.
- the amount of chlorine contained in the phosphorus compound can be reduced by a method such as topping or activated carbon treatment.
- the method of reducing the quantity of chlorine content is not limited to these.
- the amount of the Group 8-10 metal used is 0.01-10 ppm mol with respect to 1 mol of the compound represented by formula (a1) or formula (a2).
- Group 8 to 10 metals preferably 1 to 10 ppm mol, more preferably 1 to 5 ppm mol. If it is the said numerical range, advancing of smooth reaction can be ensured, without using an expensive catalyst excessively.
- the amount of the phosphorus compound used is 100 times mol or more, more preferably 100 times mol or more and 10000 times mol or less with respect to the Group 8 to 10 metal. In addition, said numerical range can be combined arbitrarily.
- the amount of chlorine atoms in the reaction system is 1.5 parts by weight or less, preferably 1.2 parts by weight or less, relative to 1.0 part by weight of the Group 8-10 metal.
- the lower limit is not particularly limited, but is 0.1 parts by weight or more, preferably 0.5 parts by weight or more with respect to 1.0 part by weight of the Group 8-10 metal. If it is the said lower limit, since the process of reducing a chlorine content does not become complicated and does not affect productivity, it is preferable.
- the upper limit value and the lower limit value can be appropriately combined.
- the synthesis of the aldehyde compound can be performed as follows. First, a rhodium compound, a phosphorus compound, and a compound represented by the general formula (a1) or (a2) as a raw material are inserted into a container. While supplying hydrogen and carbon monoxide gas, the reaction can be performed at a temperature of 30 to 120 ° C., a pressure of 0.1 to 1.0 MPa, and a reaction time of 1 to 8 hours. In addition, the hydroformylation reaction can be carried out by appropriately selecting a homogeneous reaction system comprising only an oil phase or a two-layer reaction system comprising an aqueous layer and an oil layer. Thereby, the compound represented by the general formula (a1) or (a2) is hydroformylated to synthesize an aldehyde compound.
- the hydroformylation reaction can also be performed in a solvent-free manner, and a substituted or unsubstituted aromatic compound, a substituted or unsubstituted aliphatic hydrocarbon compound, and an alcohol can be used.
- a substituted or unsubstituted aromatic compound a substituted or unsubstituted aliphatic hydrocarbon compound, and an alcohol
- toluene, benzene, hexane It can also be carried out in a solvent such as octane, acetonitrile, benzonitrile, ethanol, pentanol, octanol. Since the hydroformylation reaction in this embodiment is also excellent in reactivity at a high concentration, the hydroformylation reaction can be performed in the absence of a solvent. This eliminates the need for a step of distilling off the solvent, which makes the step simple, improves the volumetric efficiency, and improves the production efficiency.
- the aldehyde compound represented by the following general formula (b1) is synthesized from the compound of the general formula (a1) by the production method of the present embodiment.
- An aldehyde compound represented by the following general formula (b2) is synthesized from the compound of the general formula (a2).
- the compound represented by the general formula (b1) or (b2) is “a compound in which the 2-position and the 5-position are substituted with a predetermined group (hereinafter, 2 , 5 forms) "or” compounds substituted at the 2-position and 6-position with a predetermined group (hereinafter 2,6 forms) ", or a mixture containing these in an arbitrary ratio.
- the 2,5 and 2,6 isomers can be obtained as either an endo-endo isomer, an endo-exo isomer, or an exo-exo isomer depending on the configuration of substituents, or at least two of these. It can also be obtained as a mixture containing seeds in any proportion.
- the compound represented by the general formula (b1) or (b2) can be obtained as either a cis type or a trans type, and these can be obtained at any ratio. It can also be obtained as a mixture comprising In general formula (b1) or (b2), X and n are synonymous with general formula (a1) or (a2).
- a compound represented by the general formula (b1) is preferably obtained, and examples of the compound include a compound represented by the following general formula (2).
- the aldehyde compound represented by the general formula (2) is a compound in which the 2-position of bicyclo [2.2.1] heptane is substituted with a substituent X and the 5-position is substituted with an aldehyde group (hereinafter referred to as 2 , 5 forms) "or" a compound in which the 2-position is substituted with a substituent X and the 6-position is substituted with an aldehyde group (hereinafter, 2,6 forms) ", or a mixture containing these in an arbitrary ratio Can be obtained as
- the 2,5 and 2,6 isomers can be obtained as either an endo-endo isomer, an endo-exo isomer, or an exo-exo isomer depending on the configuration of substituents, or at least two of these. It can also be obtained as a mixture containing seeds in any proportion.
- a predetermined purification step can be performed to obtain the target alde
- the manufacturing method of the amine compound of this embodiment includes the manufacturing method of the above-mentioned aldehyde compound as a process (a). Therefore, since the productivity and yield of the aldehyde compound are excellent in the step (a), the productivity and yield of the target amine compound are also excellent. In addition, since the process (a) is the same as the process in the above “method for producing an aldehyde compound”, the description thereof is omitted.
- the aldehyde compound represented by the general formula (b1) or the following general formula (b2) obtained in the step (a) is reacted with ammonia to iminate and in the presence of a catalyst.
- An amine compound is synthesized by hydrogenation.
- a metal catalyst such as nickel, platinum, palladium, ruthenium or the like can be used.
- the aldehyde compound has a cyano group as a substituent, a —CH 2 —NH 2 group is generated by hydrogen reduction.
- the aldehyde group of the aldehyde compound becomes an amino group by imination, and the cyano group also becomes an amino group by hydrogen reduction. Therefore, in the following general formula (c1) having two amino groups, The amine compound represented is synthesized. In addition, when X is a hydrogen atom, the amine compound represented by the following general formula (c2) is synthesized.
- n has the same meaning as in general formula (a1) or (a2).
- the compound represented by the general formula (c1) is “a compound in which 2-position and 5-position are substituted with a predetermined group (hereinafter, 2,5-body)” or “2-position” It can be obtained as any of “compounds substituted at the 6-position with a predetermined group (hereinafter, 2,6)” or a mixture containing these in an arbitrary ratio.
- the 2,5 and 2,6 isomers can be obtained as either an endo-endo isomer, an endo-exo isomer, or an exo-exo isomer depending on the configuration of substituents, or at least two of these. It can also be obtained as a mixture containing seeds in any proportion.
- the compound represented by the general formula (c1) can be obtained as either a cis type or a trans type, and can also be obtained as a mixture containing these at an arbitrary ratio.
- the compound represented by the general formula (c2) can be obtained as an endo isomer or an exo isomer, and can also be obtained as a mixture containing these in an arbitrary ratio.
- a compound represented by the general formula (c1) is preferably obtained, and examples of the compound include compounds represented by the following chemical formula (3) in which n is 1.
- the amine compound represented by the chemical formula (3) is “a compound in which the 2- and 5-positions of bicyclo [2.2.1] heptane are substituted with aminomethyl groups (hereinafter, 2,5)”, or Any of “compounds substituted with aminomethyl groups at the 2-position and 6-position” (hereinafter, 2,6 compounds), or a mixture containing these in an arbitrary ratio can be obtained.
- the 2,5 and 2,6 isomers can be obtained as either an endo-endo isomer, an endo-exo isomer, or an exo-exo isomer depending on the configuration of substituents, or at least two of these. It can also be obtained as a mixture containing seeds in any proportion.
- the above imination and hydrogenation reaction can be performed as follows. First, an aldehyde compound, a solvent, and a catalyst are charged into a reaction vessel, and ammonia gas is blown into the reaction vessel. Then, hydrogen is injected to a pressure of about 1 MPa, the temperature is raised to about 100 ° C., and the reaction is performed for about 1 to 10 hours under the temperature and pressure while supplying hydrogen.
- the solvent for example, alcohol having 1 to 8 carbon atoms, water and the like are preferably used.
- the target amine compound can be obtained by performing normal catalyst filtration, solvent removal, purification steps, and the like after completion of the reaction.
- the manufacturing method of the isocyanate compound of this embodiment includes the manufacturing method of the above-mentioned aldehyde compound as a process (a). Therefore, in the step (a), the productivity and yield of the aldehyde compound are excellent, and hence the productivity and yield of the isocyanate compound as the target compound are also excellent.
- step (a) is the same as the step in the “method for producing an aldehyde compound”, and the step (b) is the same as the step in the “method for producing an amine compound”.
- the amine compound represented by the general formula (c1) or (c2) obtained in the step (b) is reacted with a carbonylating agent under a predetermined condition, whereby the following general formula (d1) Alternatively, an isocyanate compound represented by (d2) is synthesized.
- a carbonylating agent phosgene, urea derivatives, carbonate derivatives, carbon monoxide and the like can be used.
- n has the same meaning as in general formula (a1) or (a2).
- the compound represented by the general formula (d1) is “a compound in which 2-position and 5-position are substituted with a predetermined group (hereinafter, 2,5-body)” or “2-position” It can be obtained as any of “compounds substituted at the 6-position with a predetermined group (hereinafter, 2,6)” or a mixture containing these in an arbitrary ratio.
- the 2,5 and 2,6 isomers can be obtained as either an endo-endo isomer, an endo-exo isomer, or an exo-exo isomer depending on the configuration of substituents, or at least two of these. It can also be obtained as a mixture containing seeds in any proportion.
- the compound represented by the general formula (d1) can be obtained as either a cis type or a trans type, and can also be obtained as a mixture containing these at an arbitrary ratio.
- the compound represented by the general formula (d2) can be obtained as an endo isomer or an exo isomer, and can also be obtained as a mixture containing these in an arbitrary ratio.
- a compound represented by the general formula (d1) is preferably obtained. Examples of the compound include compounds represented by the following chemical formula (4) in which n is 1.
- the isocyanate compound represented by the chemical formula (4) is “a compound in which 2- and 5-positions of bicyclo [2.2.1] heptane are substituted with an isocyanatomethyl group (hereinafter, 2,5)”, Alternatively, it can be obtained as any one of “compounds substituted with isocyanatomethyl groups at the 2nd and 6th positions (hereinafter, 2,6)”, or a mixture containing these in an arbitrary ratio.
- the 2,5 and 2,6 isomers can be obtained as either an endo-endo isomer, an endo-exo isomer, or an exo-exo isomer depending on the configuration of substituents, or at least two of these. It can also be obtained as a mixture containing seeds in any proportion.
- step (c) when phosgene is used as the carbonylating agent, specifically, a method in which an amine compound and a solvent are first charged in a reaction vessel and hydrochloric acid is converted to hydrochloric acid with hydrochloric acid and then reacted with phosgene, Examples thereof include a method in which a carbamoyl chloride compound is obtained by direct reaction with phosgene and then thermally decomposed. Furthermore, the target isocyanate compound can be obtained by performing a normal purification process after the reaction is completed.
- the reaction solvent in the case of using phosgene as the carbonylating agent is not particularly limited, but has a high solubility in hydrochloric acid during the salt formation reaction, a high solubility of phosgene in the phosgenation reaction, and a low solubility in hydrochloric acid. It is preferable to use an organic aromatic compound or an ester compound.
- Examples of high-boiling organic aromatic compounds include 1,2-diethylbenzene, 1,3-diethylbenzene, 1,4-diethylbenzene, isopropylbenzene, 1,2,4-trimethylbenzene, amylbenzene, diamylbenzene, triamylbenzene, Examples include dodecylbenzene, p-cymene, cumene methylphenyl ether, ethylphenyl ether, diisoamyl ether, n-hexyl ether, orthodichlorobenzene, parachlorotoluene, bromobenzene, 1,2,4-trichlorobenzene and the like.
- the ester compound is not particularly limited, but is preferably an acetate such as isoamyl acetate or isooctyl acetate. Among these exemplified solvents, aromatic solvents are particularly preferred for carrying out the present invention.
- the isocyanate compound obtained by this embodiment can be used as a raw material for optical materials and a paint.
- the amine compound obtained by this embodiment can also be used as a raw material for paints and curing agents.
- the obtained reaction solution containing bicyclo [2.2.1] -5-heptene-2-carbonitrile was 355.6 g, and analysis showed that bicyclo [2.2.1] -5-heptene-2- It contained 331.2 g (2.78 mol) of carbonitrile. 352.4 g of the reaction solution containing 328.2 g (2.75 mol) of the obtained bicyclo [2.2.1] -5-heptene-2-carbonitrile was charged into a 500 ml flask, Distillation was performed to obtain 300.7 g (2.52 mol) of bicyclo [2.2.1] -5-heptene-2-carbonitrile as the main fraction.
- the chlorine content (chlorine atomic weight) in triphenyl phosphite was quantified by coulometric titration.
- the coulometric titration method is a method in which a sample is oxidized and burned using an oxygen gas in an argon gas stream, a chlorine compound is converted into hydrogen chloride, and the generated hydrogen chloride is quantitatively subjected to silver titration.
- the measuring instruments used are as follows. Autosampler device: ASC-250L Horizontal electric furnace: HF-210 Coulometer: MDC-210 Mitsubishi Chemical Gas Injector: GI-100 Auto boat controller: ABC-210
- Raney cobalt catalyst obtained by developing a cobalt-aluminum alloy containing 89.5 g (0.6 mol) of heptane, 89.5 g of methanol, and manganese (94% by mass of cobalt, 3.5% by mass of aluminum, Manganese (2.1% by mass) 4.5 g (dry mass) was charged, and ammonia gas 24.5 g (1.44 mol) was blown.
- Example 3 [Synthesis of 2,5-bisisocyanatomethyl-bicyclo [2.2.1] heptane and 2,6-bisisocyanatomethyl-bicyclo [2.2.1] heptane] 958 g of orthodichlorobenzene was charged into a 2-liter 5-neck reaction flask equipped with a reflux condenser, a stirring blade, a thermometer, a gas blowing tube, and a raw material charging tube, and obtained in Example 2 in the raw material tank.
- aging was performed for 1 hour while charging hydrochloric acid gas at 20 g / hr.
- the hydrochloride reaction mass was then heated to 160 ° C., and then phosgene was blown from the phosgene blowing tube at 100 g / hr (1.0 mol / hr) and reacted for 6 hours while maintaining the temperature.
- unreacted phosgene and hydrochloric acid gas in the system were purged with nitrogen, and the solvent was removed to remove 2,5-bisisocyanatomethyl-bicyclo [2.2.1] heptane and 2,6-bis.
- Rh catalyst adjustment liquid 221.3 g of an Rh catalyst adjustment liquid. It was 370 ppm (2.093 mg) as a result of measuring the chlorine atom amount in the triphenyl phosphite used at this time by the said analysis method. This amount was 2.3 parts by weight based on 1 part by weight of rhodium. Rhodium usage amount: 5 ppm mol per 1 mol of bicyclo [2.2.1] -5-heptene-2-carbonitrile
- the reaction was terminated when 5 hours had elapsed, and the mixed gas in the system was purged with nitrogen, and 2-cyano-5-formylbicyclo [2.2.1] heptane and 2-cyano-6-formylbicyclo [2. 2.1]
- a reaction solution containing heptane was obtained in an amount of 244.6 g. When the reaction solution was analyzed, it contained 173.2 g (1.16 mol) of the compound. The reaction yield was 64.5 mol%.
- Table 1 The results are shown in Table 1.
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Abstract
Description
特許文献5には、金属リガンド錯体触媒に関して記載されており、金属としてロジウム、リガンドとして有機燐リガンドが挙げられている。これらの使用量としては、遊離の金属として計算した場合、約1ppm~10,000ppmの範囲の金属濃度、およびリガンド:金属のモル比が1:1~200:1と記載されている。
また、特許文献6、7には、鎖状のオレフィン化合物をヒドロホルミル化させ、アルデヒド化合物を製造する方法が開示されている。
本発明は以下に示すことができる。
[1] 下記一般式(a1)
前記工程における反応系内の塩素分の量が、第8~10族金属1重量部に対して、1.5重量部以下であることを特徴とするアルデヒドの製造方法。
[3] 前記第8~10族金属を含む金属化合物が、ロジウム化合物であることを特徴とする[1]または[2]に記載のアルデヒド化合物の製造方法。
[5] 前記リン化合物は、三価のリン化合物であることを特徴とする[1]乃至[4]のいずれか一つに記載のアルデヒド化合物の製造方法。
[6] 前記一般式(a1)で表される化合物を用い、当該化合物が下記一般式(1)
[8] [7]に記載の製造方法により得られたアミン化合物を、カルボニル化剤と反応させる工程を含むことを特徴とするイソシアネート化合物の製造方法。
また、本発明において、物質A 1molに対して、物質Bを1×10-6molの量で用いる場合、物質Bの量を1ppmmolと表記する。
本実施形態のアルデヒド化合物の製造方法は、下記一般式(a1)または下記一般式(a2)で表される化合物を、第8~10族金属を含む金属化合物とリン化合物の存在下で、水素および一酸化炭素と反応させる工程を含み、当該工程における反応系内の塩素原子の量が、第8~10族金属1重量部に対して、1.5重量部以下である。
なお、一般式(a1)で表される化合物は、エンド体またはエキソ体の何れかであってもよく、これらを任意の割合で含む混合物であってもよい。
(1)n:0の化合物として、
シクロヘキセン、4-シアノ-1-シクロへキセン、3-シクロへキセン-1-カルボキシアルデヒド、4-イミノメチル-1-シクロヘキセンを挙げることができる。
(2)n:1の化合物として、
ビシクロ[2.2.1]-2-ヘプテン、ビシクロ[2.2.1]-5-ヘプテン-2-カルボニトリル、ビシクロ[2.2.1]-5-ヘプテン-2-カルボキシアルデヒド、ビシクロ[2.2.1]-5-ヘプテン-2-イルメタンアミンを挙げることができる。
(3)n:2の化合物として、
ビシクロ[2.2.2]-2-オクテン、ビシクロ[2.2.2]-5-オクテン-2-カルボニトリル、ビシクロ[2.2.2]-5-オクテン-2-カルボキシアルデヒド、ビシクロ[2.2.2]-5-ヘプテン-2-イルメタンアミンを挙げることができる。
一般式(a2)で表される化合物として、以下の化合物を挙げることができる。
1,4-シクロヘキサジエンを挙げることができる。
(2)n:1の化合物として、
ビシクロ[2.2.1]ヘプタ-2,5-ジエンを挙げることができる。
(3)n:2の化合物として、
ビシクロ[2.2.2]オクタ-2,5-ジエンを挙げることができる。
なお、一般式(1)で表される化合物は、エンド体またはエキソ体の何れかであってもよく、これらを任意の割合で含む混合物であってもよい。
本実施形態の反応に用いられる第8~10族金属を含む金属化合物は、ロジウム化合物、コバルト化合物、ルテニウム化合物または鉄化合物である。
(R1)3P
(R2O)3P
上記式中、R1、R2は同一又は異なっていてもよく、それぞれ置換基を有していてもよい炭素数1~16のアルキル基または炭素数6~16のアリール基を示す。
リン化合物に含まれる塩素分の量が、上記所定の量となる場合には、リン化合物の塩素分を低減する必要はないが、第8~10族金属を含む金属化合物が構造中に塩素原子を含む場合など、上記所定の量を超える場合には、トッピングや活性炭処理などの方法によりリン化合物に含まれる塩素分の量を低減することができる。なお、塩素分の量を低減する方法は、これらに限定されるものではない。
また、使用するリン化合物の量は、第8~10族金属に対して100倍モル以上、より好ましくは100倍モル以上10000倍モル以下である。なお、上記の数値範囲は任意に組み合わせることができる。
反応系内の塩素原子の量は、本発明の効果の観点から、第8~10族金属1.0重量部に対して、1.5重量部以下、好ましくは1.2重量部以下である。なお、下限値は特に限定されないが、第8~10族金属1.0重量部に対して、0.1重量部以上、好ましくは0.5重量部以上である。上記下限値であれば、塩素分を低減する工程が煩雑とならず、生産性に影響を与えないため好ましい。なお、上限値と下限値は適宜組み合わせることができる。
まず、容器内に、ロジウム化合物と、リン化合物と、原料の一般式(a1)または(a2)で表される化合物を挿入する。そこに、水素および一酸化炭素ガスを供給しながら、温度30~120℃、圧力0.1~1.0MPa、反応時間1~8時間で行うことができる。なお、油相のみの均一反応系また水層および油層からなる二層反応系を適宜選択してヒドロホルミル化反応を行うことができる。
これにより、一般式(a1)または(a2)で表される化合物をヒドロホルミル化し、アルデヒド化合物が合成される。
一般式(b1)または(b2)中、Xおよびnは、一般式(a1)または(a2)と同義である。
本実施形態においては、一般式(b1)で表される化合物が好ましく得られ、当該化合物としては、下記一般式(2)で表される化合物を挙げることができる。
なお、一般式(2)で表されるアルデヒド化合物は、「ビシクロ[2.2.1]ヘプタンの2位が置換基Xで置換され、5位がアルデヒド基で置換された化合物(以下、2,5体)」、または「2位が置換基Xで置換され、6位がアルデヒド基で置換された化合物(以下、2,6体)」の何れか、またはこれらを任意の割合で含む混合物として得ることができる。また、2,5体および2,6体は、各々、置換基の立体配置により、エンド-エンド体、エンド-エキソ体、エキソ-エキソ体の何れかとして得ることができ、またはこれらの少なくとも2種を任意の割合で含む混合物として得ることもできる。
ヒドロホルミル化反応終了後、所定の精製工程を行い、目的とするアルデヒド化合物を得ることができる。
本実施形態のアミン化合物の製造方法は、以下の工程を含む。
工程(a):第8~10族金属を含む金属化合物とリン化合物の存在下で、前記一般式(a1)または(a2)で表される化合物を水素および一酸化炭素と反応させる。
工程(b):工程(a)で得られたアルデヒド化合物をアンモニアと反応させるとともに、触媒の存在下で水素と反応させる。
なお、工程(a)は、上記「アルデヒド化合物の製造方法」における工程と同一であるので、説明を省略する。
触媒としては、ニッケル、白金、パラジウム、ルテニウムなどの金属触媒等を用いることができる。アルデヒド化合物が置換基としてシアノ基を有する場合、水素還元により-CH2-NH2基が生成される。
nが1または2の場合、一般式(c1)で表される化合物は、「2位と5位が所定の基で置換された化合物(以下、2,5体)」、または「2位と6位が所定の基で置換された化合物(以下、2,6体)」の何れか、またはこれらを任意の割合で含む混合物として得ることができる。また、2,5体および2,6体は、各々、置換基の立体配置により、エンド-エンド体、エンド-エキソ体、エキソ-エキソ体の何れかとして得ることができ、またはこれらの少なくとも2種を任意の割合で含む混合物として得ることもできる。
nが1または2の場合、一般式(c2)で表される化合物は、エンド体またはエキソ体として得ることができ、これらを任意の割合で含む混合物として得ることもできる。
本実施形態においては、一般式(c1)で表される化合物が好ましく得られ、当該化合物としては、nが1である、以下の化学式(3)の化合物を挙げることができる。
さらに、反応終了後、通常の触媒ろ過、脱溶媒、精製工程等を行い、目的とするアミン化合物を得ることができる。
本実施形態のイソシアネート化合物の製造方法は、以下の工程を含む。
工程(a):第8~10族金属を含む金属化合物とリン化合物の存在下で、前記一般式(a1)または(a2)で表される化合物を水素および一酸化炭素と反応させる。
工程(b):工程(a)で得られたアルデヒド化合物をアンモニアと反応させるとともに、触媒の存在下で水素と反応させる。
工程(c):工程(b)で得られたアミン化合物を、カルボニル化剤と反応させる。
nが1または2の場合、一般式(d1)で表される化合物は、「2位と5位が所定の基で置換された化合物(以下、2,5体)」、または「2位と6位が所定の基で置換された化合物(以下、2,6体)」の何れか、またはこれらを任意の割合で含む混合物として得ることができる。また、2,5体および2,6体は、各々、置換基の立体配置により、エンド-エンド体、エンド-エキソ体、エキソ-エキソ体の何れかとして得ることができ、またはこれらの少なくとも2種を任意の割合で含む混合物として得ることもできる。
nが1または2の場合、一般式(d2)で表される化合物は、エンド体またはエキソ体として得ることができ、これらを任意の割合で含む混合物として得ることもできる。
本実施形態においては、一般式(d1)で表される化合物が好ましく得られ、当該化合物としては、nが1である、以下の化学式(4)の化合物を挙げることができる。
[ビシクロ[2.2.1]-5-ヘプテン-2-カルボニトリルの合成]
1000mlオートクレーブに、純度95%ジシクロペンタジエン195.0g(1.40モル)と、N-ニトロソジフェニルアミン0.36g(1.8ミリモル)を添加したアクリロニトリル163.6g(3.08モル)を装入し、撹拌下、160℃で5時間反応後、さらに昇温して180℃で2時間反応し終了した。得られたビシクロ[2.2.1]-5-ヘプテン-2-カルボニトリルを含む反応液は、355.6gであり、分析したところビシクロ[2.2.1]-5-ヘプテン-2-カルボニトリルを331.2g(2.78モル)含有していた。得られたビシクロ[2.2.1]-5-ヘプテン-2-カルボニトリル328.2g(2.75モル)を含む反応液352.4gを、500ミリリットルのフラスコに装入し、減圧下、蒸留を行い、主留分としてビシクロ[2.2.1]-5-ヘプテン-2-カルボニトリル300.7g(2.52モル)を得た。
[2-シアノ-5-ホルミルビシクロ[2.2.1]ヘプタンおよび2-シアノ-6-ホルミルビシクロ[2.2.1]ヘプタンの合成]
内容積0.1リットルのガラス容器に、ロジウムアセチルアセトナトジカルボニル50.0mg(0.194mmol)、参考例で得られたビシクロ[2.2.1]-5-ヘプテン-2-カルボニトリル16.0g(0.133mol)、トリフェニルホスファイト1.2g(3.87mmol)を装入し、25℃で攪拌し、触媒マスター液を調整した。次に、内容積0.5リットルのSUS316L製電磁攪拌式オートクレーブに、触媒マスター液0.81g(Rh換算で0.926mg)、参考例で得られたビシクロ[2.2.1]-5-ヘプテン-2-カルボニトリル214.8g(1.8mol)、トリフェニルホスファイト5.656g(18.23mmol)を装入し、25℃で攪拌し、Rh触媒調整液221.3gを得た。このとき使用したトリフェニルホスファイト中の塩素分を下記分析方法にて測定した結果、110ppm(0.622mg)含有していた。この量は、ロジウム1重量部に対し0.7重量部であった。
・ロジウム使用量:ビシクロ[2.2.1]-5-ヘプテン-2-カルボニトリル 1molに対して、5ppmmol
トリフェニルホスファイト中の塩素分(塩素原子量)は電量滴定法で定量した。電量滴定法とは、試料をアルゴンガス気流中で酸素ガスを用いて酸化燃焼させ、塩素化合物を塩化水素に変換し、生成した塩化水素を定量的に銀滴定する方法である。
用いた測定機器は以下の通りである。
オートサンプラー装置 :ASC-250L
横型電気炉 :HF-210
クーロメーター :MDC-210
三菱化学ガスインジェクター:GI-100
オートボートコントローラー:ABC-210
結果を表1に示す。
加水分解溶液に20重量%の炭酸水素カリウム水溶液を6.4g(0.012mol)を、25℃でpH7.0になるまで滴下した。
[2,5-ビスアミノメチル-ビシクロ[2.2.1]ヘプタンおよび2,6-ビスアミノメチル-ビシクロ[2.2.1]ヘプタンの合成]
内容積0.5リットルのステンレス製電磁攪拌式オートクレーブに、実施例1で得られた2-シアノ-5-ホルミルビシクロ[2.2.1]ヘプタンおよび2-シアノ-6-ホルミルビシクロ[2.2.1]ヘプタン89.5g(0.6mol)、メタノール89.5g、およびマンガンを含有したコバルト-アルミニウム合金を展開して得たラネーコバルト触媒(コバルト94質量%、 アルミニウム3.5質量%、マンガン2.1質量%)4.5g(乾燥質量)を仕込み、アンモニアガス24.5g(1.44mol)を吹き込んだ。
[2,5-ビスイソシアナトメチル-ビシクロ[2.2.1]ヘプタンおよび2,6-ビスイソシアナトメチル-ビシクロ[2.2.1]ヘプタンの合成]
還流冷却管、攪拌翼、温度計、ガス吹込み管、原料装入管が付属した内容積2リットルの5つ口反応フラスコにオルソジクロロベンゼン958gを装入し、原料槽に実施例2で得られた2,5-ビスアミノメチル-ビシクロ[2.2.1]ヘプタンおよび2,6-ビスアミノメチル-ビシクロ[2.2.1]ヘプタン154.2g(1.0モル)及び、オルソジクロロベンゼン702gを仕込んだ。次に、0.1MPa下にて、反応容器を120℃に昇温後、塩酸吹き込み管より塩酸ガスを43.8g/hrの速度で、原料槽より溶媒で希釈したアミンを、原料装入ポンプにて428.1g/hrの速度で、同時に装入を始め、2時間掛けて全量を装入した。更に塩酸ガスを20g/hrで装入しながら、1時間熟成を行った。反応終了後、次に、塩酸塩反応マスを160℃に昇温後、ホスゲン吹き込み管より,ホスゲンを100g/hr(1.0モル/hr)で吹き込み、温度を保ちながら6時間反応した。反応終了後、窒素にて系内の未反応ホスゲン及び、塩酸ガスをパージし、脱溶媒して、2,5-ビスイソシアナトメチル-ビシクロ[2.2.1]ヘプタンおよび2,6-ビスイソシアナトメチル-ビシクロ[2.2.1]ヘプタンを含む溶液200.9gを得た。更に、減圧下蒸留を行い、純度99.0%の2,5-ビスイソシアナトメチル-ビシクロ[2.2.1]ヘプタンおよび2,6-ビスイソシアナトメチル-ビシクロ[2.2.1]ヘプタンの混合物175.7gを得た。1H-NMRチャートを図3に示す。
[2-シアノ-5-ホルミルビシクロ[2.2.1]ヘプタンおよび2-シアノ-6-ホルミルビシクロ[2.2.1]ヘプタンの合成]
実施例1と同様に触媒マスター液を調整後、内容積0.5リットルのSUS316L製電磁攪拌式オートクレーブに、触媒マスター液0.81g(Rh換算で0.926mg)、参考例の方法で得られたビシクロ[2.2.1]-5-ヘプテン-2-カルボニトリル214.8g(1.8mol)、トリフェニルホスファイト5.656g(18.23mmol)を25℃で攪拌し、Rh触媒調整液221.3gを得た。このとき使用したトリフェニルホスファイト中の塩素原子量を上記分析方法にて測定した結果、160ppm(0.905mg)であった。この量は、ロジウム1重量部に対し1.0重量部であった。
・ロジウム使用量:ビシクロ[2.2.1]-5-ヘプテン-2-カルボニトリル 1molに対して、5ppmmol
反応収率は、96.2モル%であった。
結果を表1に示す。
[2-シアノ-5-ホルミルビシクロ[2.2.1]ヘプタンおよび2-シアノ-6-ホルミルビシクロ[2.2.1]ヘプタンの合成]
実施例1と同様に、触媒マスター液を調整した。次に、内容積0.5リットルのSUS316L製電磁攪拌式オートクレーブに、触媒マスター液0.81g(Rh換算で0.926mg)、参考例の方法で得られたビシクロ[2.2.1]-5-ヘプテン-2-カルボニトリル214.8g(1.8mol)、トリフェニルホスファイト5.656g(18.23mmol)を25℃で攪拌し、Rh触媒調整液221.3gを得た。このとき使用したトリフェニルホスファイト中の塩素原子量を上記分析方法にて測定した結果、260ppm(1.471mg)であった。この量は、ロジウム1重量部に対し1.6重量部であった。
・ロジウム使用量(条件(1)):ビシクロ[2.2.1]-5-ヘプテン-2-カルボニトリル 1molに対して、ロジウムアセチルアセトナトジカルボニルに含まれるロジウムが5ppmmol
結果を表1に示す。
[2-シアノ-5-ホルミルビシクロ[2.2.1]ヘプタンおよび2-シアノ-6-ホルミルビシクロ[2.2.1]ヘプタンの合成]
実施例1と同様に、触媒マスター液を調整した。次に、内容積0.5リットルのSUS316L製電磁攪拌式オートクレーブに、触媒マスター液0.81g(Rh換算で0.926mg)、参考例の方法で得られたビシクロ[2.2.1]-5-ヘプテン-2-カルボニトリル214.8g(1.8mol)、トリフェニルホスファイト5.656g(18.23mmol)を25℃で攪拌し、Rh触媒調整液221.3gを得た。このとき使用したトリフェニルホスファイト中の塩素原子量を上記分析方法にて測定した結果、370ppm(2.093mg)であった。この量は、ロジウム1重量部に対し2.3重量部であった。
・ロジウム使用量:ビシクロ[2.2.1]-5-ヘプテン-2-カルボニトリル 1molに対して、5ppmmol
結果を表1に示す。
Claims (8)
- 前記第8~10族金属を含む金属化合物が、ロジウム化合物、コバルト化合物、ルテニウム化合物または鉄化合物であることを特徴とする請求項1に記載のアルデヒド化合物の製造方法。
- 前記第8~10族金属を含む金属化合物が、ロジウム化合物であることを特徴とする請求項1または2に記載のアルデヒド化合物の製造方法。
- 前記第8~10族金属は、一般式(a1)または(a2)で表される化合物1モルに対して、1~5ppmモルであることを特徴とする請求項1乃至3のいずれか一項に記載のアルデヒド化合物の製造方法。
- 前記リン化合物は、三価のリン化合物であることを特徴とする請求項1乃至4のいずれか一項に記載のアルデヒド化合物の製造方法。
- 請求項1乃至6のいずれか一項に記載の製造方法により得られたアルデヒド化合物を、アンモニアと反応させるとともに、触媒の存在下で水素と反応させる工程を含むことを特徴とするアミン化合物の製造方法。
- 請求項7に記載の製造方法により得られたアミン化合物を、カルボニル化剤と反応させる工程を含むことを特徴とするイソシアネート化合物の製造方法。
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