JP2006257045A - Method for producing cyclic diamine compound - Google Patents
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- JP2006257045A JP2006257045A JP2005079202A JP2005079202A JP2006257045A JP 2006257045 A JP2006257045 A JP 2006257045A JP 2005079202 A JP2005079202 A JP 2005079202A JP 2005079202 A JP2005079202 A JP 2005079202A JP 2006257045 A JP2006257045 A JP 2006257045A
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- -1 cyclic diamine compound Chemical class 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 17
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 8
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000005984 hydrogenation reaction Methods 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical group [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052731 fluorine Inorganic materials 0.000 abstract description 11
- 239000011737 fluorine Substances 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 6
- 239000004210 ether based solvent Substances 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- BEKFRNOZJSYWKZ-UHFFFAOYSA-N 4-[2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(N)C=C1 BEKFRNOZJSYWKZ-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 2
- 0 C*C(C)(CCC(CC1)C(C)(C(CCC(C)(C)C2)CCC2(C)N)C(F)(F)F)CC1(C)N Chemical compound C*C(C)(CCC(CC1)C(C)(C(CCC(C)(C)C2)CCC2(C)N)C(F)(F)F)CC1(C)N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 2
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- UVUCUHVQYAPMEU-UHFFFAOYSA-N 3-[2-(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]aniline Chemical compound NC1=CC=CC(C(C=2C=C(N)C=CC=2)(C(F)(F)F)C(F)(F)F)=C1 UVUCUHVQYAPMEU-UHFFFAOYSA-N 0.000 description 1
- KIOQWHKRKVBTLT-UHFFFAOYSA-N 4-[2-(4-amino-3-methylphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-methylaniline Chemical compound C1=C(N)C(C)=CC(C(C=2C=C(C)C(N)=CC=2)(C(F)(F)F)C(F)(F)F)=C1 KIOQWHKRKVBTLT-UHFFFAOYSA-N 0.000 description 1
- HJSYPLCSZPEDCQ-UHFFFAOYSA-N 5-[2-(3-amino-4-methylphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-methylaniline Chemical compound C1=C(N)C(C)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(C)C(N)=C1 HJSYPLCSZPEDCQ-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- RPNNPZHFJPXFQS-UHFFFAOYSA-N methane;rhodium Chemical compound C.[Rh] RPNNPZHFJPXFQS-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920002577 polybenzoxazole Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Abstract
Description
本発明は、脂環式ジアミン化合物の製造方法に関する。 The present invention relates to a method for producing an alicyclic diamine compound.
フッ素を含有するジアミン化合物は、例えば電子材料や光学材料用のポリアミド、ポリベンゾオキサゾール、ポリアミドイミド、ポリイミドおよびエポキシ樹脂等の原料として有用である。 A diamine compound containing fluorine is useful as a raw material for, for example, polyamides, polybenzoxazoles, polyamideimides, polyimides and epoxy resins for electronic materials and optical materials.
従来、このような用途では、例えば２，２−ビス（４−アミノフェニル）−ヘキサフルオロプロパン等の芳香族化合物が使用されている。しかし、芳香環を有する化合物は、一般的に電子密度が高く、その結果、特に高周波域での誘電率が高いといった欠点や、芳香環どうしの分子間パッキングが強く、光透過率が低くなるなどの欠点がある。そこで、芳香環を有しない、例えば脂環式のジアミン化合物が新規な材料として検討されているが、このようなフッ素を含有する脂環式ジアミン化合物を効率よく製造する方法は従来知られておらず、従って、その効率的な製造方法の開発が望まれていた。 Conventionally, aromatic compounds such as 2,2-bis (4-aminophenyl) -hexafluoropropane have been used in such applications. However, a compound having an aromatic ring generally has a high electron density, and as a result, a defect such as a high dielectric constant particularly in a high frequency region, a strong intermolecular packing between aromatic rings, and a low light transmittance. There are disadvantages. Thus, an alicyclic diamine compound having no aromatic ring, for example, has been studied as a novel material. However, a method for efficiently producing such an alicyclic diamine compound containing fluorine has not been known. Therefore, development of an efficient manufacturing method has been desired.
そのような要望に応えるべく、ロジウム触媒を用いて含フッ素芳香族ジアミン化合物をアルカリ金属水酸化物およびエーテル系溶媒の存在下に水素化する脂環式ジアミンの製造方法が提案されている（特許文献１参照）が、さらに触媒活性を高度かつ安定に維持し、目的物を安価に高収率で生産することが求められていた。 In order to meet such a demand, a method for producing an alicyclic diamine in which a fluorine-containing aromatic diamine compound is hydrogenated in the presence of an alkali metal hydroxide and an ether solvent using a rhodium catalyst has been proposed (patent) Document 1) has been required to maintain the catalytic activity at a high level and in a stable manner, and to produce the target product at a low yield in a high yield.
本発明は、含フッ素脂環式ジアミン化合物を、安価で、簡便に、収率よく製造する方法を提供することを目的とする。 An object of this invention is to provide the method of manufacturing a fluorine-containing alicyclic diamine compound cheaply, simply and with sufficient yield.
本発明者らは上記課題を解決するため鋭意検討を行った結果、特定の水素化触媒を使用し、含フッ素芳香族化合物を核水素化することにより、容易に含フッ素脂環式ジアミン化合物を製造できることを見出し、本発明を完成した。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have used a specific hydrogenation catalyst, and can easily form a fluorinated alicyclic diamine compound by nuclear hydrogenation of a fluorinated aromatic compound. The present invention was completed by finding that it can be produced.
すなわち、本発明は、一般式（１）： That is, the present invention relates to the general formula (1):
（式中Ｒは、炭素数１〜４のアルキル基、ｎは０〜４の整数を表す。）で表される化合物を、ルテニウム触媒を用いて水素化することを特徴とする一般式（２）： (Wherein R represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 4). The compound represented by the general formula (2) is obtained by hydrogenating a compound represented by ruthenium catalyst. ):
（式中Ｒは、炭素数１〜４のアルキル基、ｎは０〜４の整数を表す。）で表される脂環式ジアミン化合物の製造方法； 一般式（３）： (Wherein R represents an alkyl group having 1 to 4 carbon atoms and n represents an integer of 0 to 4); General formula (3):
で表される化合物を、ルテニウム触媒を用いて水素化することを特徴とする、一般式（４）： The compound represented by the general formula (4) is characterized by hydrogenating using a ruthenium catalyst:
で表される脂環式ジアミン化合物の製造方法、に関する。 The manufacturing method of the alicyclic diamine compound represented by these.
本発明によれば、含フッ素脂環式ジアミン化合物を、収率良く製造することができる。なお、本発明では低温（１５０℃程度）でも反応を進行させることができるため、高温で反応させる場合に比較して、目的物の分解を抑制し、さらには副反応を抑制できるため、目的物を高収率で得ることができる。 According to the present invention, a fluorinated alicyclic diamine compound can be produced with good yield. In the present invention, since the reaction can proceed even at a low temperature (about 150 ° C.), the decomposition of the target product can be suppressed and further the side reaction can be suppressed as compared with the case where the reaction is performed at a high temperature. Can be obtained in high yield.
本発明は一般式（１）： The present invention is a compound represented by the general formula (1):
（式中Ｒは、炭素数１〜４のアルキル基、ｎは０〜４の整数を表す。）で表される含フッ素芳香族ジアミン化合物（以下、含フッ素芳香族ジアミン化合物という。）を、ルテニウム触媒を使用して水素化することを特徴とする。 (Wherein R represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 4), a fluorine-containing aromatic diamine compound (hereinafter referred to as a fluorine-containing aromatic diamine compound), It is characterized by hydrogenation using a ruthenium catalyst.
本発明で用いられる芳香族ジアミン化合物としては、例えば、２，２−ビス（４−アミノフェニル）−ヘキサフルオロプロパン、２，２−ビス（３−アミノフェニル）−ヘキサフルオロプロパン、２，２−ビス（３−アミノ−４−メチルフェニル）−ヘキサフルオロプロパン、２，２−ビス（３−メチル−４−アミノフェニル）−ヘキサフルオロプロパン等が挙げられる。本発明ではこれらの中でも特に一般式（３）： Examples of the aromatic diamine compound used in the present invention include 2,2-bis (4-aminophenyl) -hexafluoropropane, 2,2-bis (3-aminophenyl) -hexafluoropropane, and 2,2- Examples thereof include bis (3-amino-4-methylphenyl) -hexafluoropropane, 2,2-bis (3-methyl-4-aminophenyl) -hexafluoropropane, and the like. In the present invention, among these, the general formula (3):
で表される２，２−ビス（４−アミノフェニル）−ヘキサフルオロプロパンを原料とすることが収率等の点から好ましい。 From the viewpoint of yield and the like, it is preferable to use 2,2-bis (4-aminophenyl) -hexafluoropropane represented by
本発明では水素化触媒としてルテニウム触媒を使用する。ルテニウム触媒としては活性金属種としてのルテニウムを含むものであれば特に限定されないが、取扱いが容易である点から不活性担体に担持したルテニウム担持触媒が好ましい。不活性担体としては例えばカーボン、シリカ、アルミナ、シリカアルミナ、マグネシア等が好ましく、カーボンまたはアルミナが特に好ましい。担体へのルテニウムの担持は含浸法、沈殿法等の公知の方法により行うことができる。ルテニウムの担持量は特に限定されるものではないが、通常０．５〜１０重量％程度とすることが好ましい。また、本発明ではカーボン担持ルテニウム触媒、またはアルミナ担持ルテニウム触媒等として市販されている担持触媒をそのまま使用してもよい。 In the present invention, a ruthenium catalyst is used as the hydrogenation catalyst. The ruthenium catalyst is not particularly limited as long as it contains ruthenium as an active metal species, but a ruthenium-supported catalyst supported on an inert carrier is preferable from the viewpoint of easy handling. As the inert carrier, for example, carbon, silica, alumina, silica alumina, magnesia and the like are preferable, and carbon or alumina is particularly preferable. Ruthenium can be supported on the carrier by a known method such as an impregnation method or a precipitation method. Although the amount of ruthenium supported is not particularly limited, it is usually preferably about 0.5 to 10% by weight. In the present invention, a supported catalyst commercially available as a carbon-supported ruthenium catalyst or an alumina-supported ruthenium catalyst may be used as it is.
水素化反応におけるルテニウム触媒の使用量は特に限定されないが、通常は原料の重量に対し、ルテニウム金属量として０．０１〜２．５重量％程度の範囲とすることが好ましく、０．０５〜１重量％が特に好ましい。 The amount of the ruthenium catalyst used in the hydrogenation reaction is not particularly limited, but it is usually preferably in the range of about 0.01 to 2.5% by weight as the ruthenium metal amount relative to the weight of the raw material, 0.05 to 1 Weight percent is particularly preferred.
本発明では前記ルテニウム触媒に、助触媒としてアルカリ金属水酸化物および／またはアルカリ土類金属水酸化物を使用することが好ましい。アルカリ金属水酸化物および／またはアルカリ土類金属水酸化物をルテニウム触媒と組み合わせて使用することにより、ルテニウム触媒を単独で使用する場合に比較して、目的の核水素化物の選択率や反応速度を改善することができる。使用するアルカリ金属水酸化物としては、例えば、水酸化リチウム、水酸化ナトリウム、水酸化カリウム等が挙げられる。また、アルカリ土類金属水酸化物としては、水酸化カルシウム、水酸化マグネシウム、水酸化バリウム等が挙げられるが、本発明では目的物の収率が最も高くなるという点から、水酸化リチウム、水酸化カルシウムを用いることが特に好ましい。アルカリ金属水酸化物および／またはアルカリ土類金属水酸化物の使用量は特に限定されないが、その添加効果が十分に得られる範囲、および経済的観点から通常は、含フッ素芳香族ジアミン化合物１０重量部に対し０．５〜１０重量部程度用いることが好ましい。なお、ルテニウムカーボン触媒を用いる場合には、含フッ素芳香族ジアミン化合物１０重量部に対し、０．５〜１重量部程度用いることが好ましく、ルテニウムアルミナ触媒を用いる場合には、含フッ素芳香族ジアミン化合物１０重量部に対し、２．５〜１０重量部程度用いることが好ましい。 In the present invention, it is preferable to use an alkali metal hydroxide and / or an alkaline earth metal hydroxide as a promoter for the ruthenium catalyst. By using an alkali metal hydroxide and / or alkaline earth metal hydroxide in combination with a ruthenium catalyst, the selectivity and reaction rate of the target nuclear hydride are compared with the case where the ruthenium catalyst is used alone. Can be improved. Examples of the alkali metal hydroxide to be used include lithium hydroxide, sodium hydroxide, potassium hydroxide and the like. Examples of the alkaline earth metal hydroxide include calcium hydroxide, magnesium hydroxide, barium hydroxide, and the like. In the present invention, lithium hydroxide, water, It is particularly preferable to use calcium oxide. The amount of alkali metal hydroxide and / or alkaline earth metal hydroxide used is not particularly limited, but is usually 10 wt. Of a fluorinated aromatic diamine compound from the range where the effect of addition is sufficiently obtained and from an economic viewpoint. It is preferable to use about 0.5 to 10 parts by weight with respect to parts. In addition, when using a ruthenium carbon catalyst, it is preferable to use about 0.5-1 weight part with respect to 10 weight part of fluorine-containing aromatic diamine compounds, and when using a ruthenium alumina catalyst, fluorine-containing aromatic diamine. It is preferable to use about 2.5 to 10 parts by weight per 10 parts by weight of the compound.
本発明では必要に応じて反応溶媒を用いても良い。反応溶媒としては、原料化合物や触媒等と反応しない公知のものを用いることができる。具体的には、エーテル系溶媒などがあげられる。エーテル系溶媒としては例えば、メチルターシャリーブチルエーテル、ジプロピルエーテル、ジブチルエーテル、メチラール、ジメトキシエタン、ジエトキシエタン、テトラヒドロフラン、テトラヒドロピラン、ジオキサン、ジオキソラン等が挙げられ、これらの中でもテトラヒドロフラン、テトラヒドロピラン、ジオキサン、ジオキソラン等の飽和環状エーテル類が好ましく、テトラヒドロフランまたはジオキサンが収率の点から特に好ましい。 In the present invention, a reaction solvent may be used as necessary. As the reaction solvent, a known solvent that does not react with a raw material compound or a catalyst can be used. Specific examples include ether solvents. Examples of ether solvents include methyl tertiary butyl ether, dipropyl ether, dibutyl ether, methylal, dimethoxyethane, diethoxyethane, tetrahydrofuran, tetrahydropyran, dioxane, dioxolane and the like. Among these, tetrahydrofuran, tetrahydropyran, dioxane Saturated cyclic ethers such as dioxolane are preferred, and tetrahydrofuran or dioxane is particularly preferred from the viewpoint of yield.
反応溶媒を使用する場合の使用量は特に限定されないが、通常は原料の芳香族ジアミン化合物の重量に対し、０．５〜２０重量倍の範囲で使用することが好ましく、２〜１０重量倍がさらに好ましい。 The amount used in the case of using a reaction solvent is not particularly limited, but usually it is preferably used in a range of 0.5 to 20 times by weight, preferably 2 to 10 times by weight, relative to the weight of the starting aromatic diamine compound. Further preferred.
本発明における反応温度および反応圧力（水素圧）は特に限定されず、適宜決定することができるが、通常は、反応温度１３０〜２００℃程度、好ましくは１５０〜１９０℃、水素圧２〜２０ＭＰａ程度、好ましくは７〜１８ＭＰａである。なお、反応時間は特に限定されないが、通常２〜２０時間程度である。 The reaction temperature and reaction pressure (hydrogen pressure) in the present invention are not particularly limited and can be appropriately determined. Usually, the reaction temperature is about 130 to 200 ° C, preferably 150 to 190 ° C, and the hydrogen pressure is about 2 to 20 MPa. , Preferably 7 to 18 MPa. The reaction time is not particularly limited, but is usually about 2 to 20 hours.
以上のような水素化方法によって、一般式（２）： By the hydrogenation method as described above, the general formula (2):
（式中Ｒは、炭素数１〜４のアルキル基、ｎは０〜４の整数を表す。）で表される含フッ素脂環式ジアミン化合物を高濃度に含む反応液が得られ、当該反応液から、触媒および溶媒を分離すれば容易に目的の化合物を得ることができる。特に、前記一般式（３）で表される化合物を原料として用いると、一般式（４）： (Wherein R represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 4), a reaction solution containing the fluorine-containing alicyclic diamine compound at a high concentration is obtained, and the reaction The target compound can be easily obtained by separating the catalyst and the solvent from the liquid. In particular, when the compound represented by the general formula (3) is used as a raw material, the general formula (4):
で表される化合物が、高収率で得られる。なお、反応生成物には少量の水素化分解物や反応中間体が含まれるため、これらは必要に応じて通常の蒸留あるいは再結晶等の手段により精製することにより、更に高純度の含フッ素脂環式ジアミン化合物を得ることができる。 Is obtained in high yield. Since the reaction product contains a small amount of hydrocracked product and reaction intermediate, these can be further purified by means such as ordinary distillation or recrystallization as necessary to obtain a higher purity fluorine-containing fat. A cyclic diamine compound can be obtained.
以下、実施例によって本発明をさらに具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to these Examples.
実施例１
２００ｍｌのオートクレーブに２，２−ビス（４−アミノフェニル）−ヘキサフルオロプロパン１０ｇ、テトラヒドロフラン１００ｍｌ、５％ルテニウム−カーボン担持触媒（エヌイーケムキャット社製５０％含水品）１．０ｇ、水酸化リチウム・１水和物を０．５ｇ仕込み、系内を水素で置換した後、温度を１８０℃、圧力を１８ＭＰａとし、攪拌しながら８時間反応させた。得られた反応溶液を、ろ過して触媒を除去し、ガスクロマトグラフィー（島津製作所製ＧＣ−１７Ａ、ジーエルサイエンス製ＴＣ−１キャピラリーカラム使用）で分析したところ、２，２−ビス（４−アミノシクロヘキシル）−ヘキサフルオロプロパンの選択率は９２．９％であった。なお、選択率は、ガスクロマトグラフィー分析により得られた各成分のピーク面積より計算した値である。
Example 1
In a 200 ml autoclave, 10 g of 2,2-bis (4-aminophenyl) -hexafluoropropane, 100 ml of tetrahydrofuran, 1.0 g of a 5% ruthenium-carbon supported catalyst (50% water-containing product manufactured by NE Chemcat), lithium hydroxide / 1 After charging 0.5 g of the hydrate and replacing the system with hydrogen, the temperature was 180 ° C. and the pressure was 18 MPa, and the reaction was allowed to proceed for 8 hours with stirring. The resulting reaction solution was filtered to remove the catalyst, and analyzed by gas chromatography (using Shimadzu GC-17A, GL Sciences TC-1 capillary column). As a result, 2,2-bis (4-aminocyclohexyl) was obtained. The selectivity of) -hexafluoropropane was 92.9%. The selectivity is a value calculated from the peak area of each component obtained by gas chromatography analysis.
実施例２〜５および比較例１〜３
触媒の種および使用量、反応温度、水酸化リチウムの使用量を表１に記載したように変更した他は実施例１と同様にして反応を行った。なお、実施例５では、水酸化リチウム・１水和物の代わりに水酸化カルシウムを用いた。結果を表１に示す。
Examples 2-5 and Comparative Examples 1-3
The reaction was conducted in the same manner as in Example 1 except that the catalyst seed and amount used, the reaction temperature, and the amount of lithium hydroxide used were changed as described in Table 1. In Example 5, calcium hydroxide was used instead of lithium hydroxide monohydrate. The results are shown in Table 1.
表中、５％Ｒｕ−Ｃは、エヌイーケムキャット社製のルテニウムカーボン担持触媒（５０％含水品）、５％Ｒｕ−Ａｌ２Ｏ３は、和光純薬工業社製のルテニウムアルミナ担持触媒、５％Ｒｈ−Ｃは、エヌイーケムキャット社製のロジウムカーボン担持触媒（５０％含水品）を表す。ＬｉＯＨは水酸化リチウム・１水和物を表す。 In the table, 5% Ru-C is a ruthenium carbon supported catalyst (50% water-containing product) manufactured by NV Chemcat, 5% Ru-Al 2 O 3 is a ruthenium alumina supported catalyst manufactured by Wako Pure Chemical Industries, 5% Rh-C represents a rhodium carbon supported catalyst (50% water-containing product) manufactured by NV Chemcat. LiOH represents lithium hydroxide monohydrate.
Claims (5)
（式中Ｒは、炭素数１〜４のアルキル基、ｎは０〜４の整数を表す。）で表される化合物を、ルテニウム触媒を用いて水素化することを特徴とする、一般式（２）：
(Wherein R represents an alkyl group having 1 to 4 carbon atoms, and n represents an integer of 0 to 4). A compound represented by the general formula (R) is hydrogenated using a ruthenium catalyst. 2):
General formula (3):
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