JP4751644B2 - Method for producing tetraazaporphyrin compound - Google Patents
Method for producing tetraazaporphyrin compoundInfo
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- JP4751644B2 JP4751644B2 JP2005147072A JP2005147072A JP4751644B2 JP 4751644 B2 JP4751644 B2 JP 4751644B2 JP 2005147072 A JP2005147072 A JP 2005147072A JP 2005147072 A JP2005147072 A JP 2005147072A JP 4751644 B2 JP4751644 B2 JP 4751644B2
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- 238000004519 manufacturing process Methods 0.000 title claims description 12
- -1 tetraazaporphyrin compound Chemical class 0.000 title description 15
- 150000001875 compounds Chemical class 0.000 claims description 99
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 45
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 229910021529 ammonia Inorganic materials 0.000 claims description 17
- 125000003545 alkoxy group Chemical group 0.000 claims description 13
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 125000005110 aryl thio group Chemical group 0.000 claims description 10
- 125000004104 aryloxy group Chemical group 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 125000004414 alkyl thio group Chemical group 0.000 claims description 9
- 125000004429 atom Chemical group 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 9
- 125000001072 heteroaryl group Chemical group 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 238000000921 elemental analysis Methods 0.000 description 10
- 238000000434 field desorption mass spectrometry Methods 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 238000004128 high performance liquid chromatography Methods 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 8
- 238000004821 distillation Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000007810 chemical reaction solvent Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 6
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- WADSJYLPJPTMLN-UHFFFAOYSA-N 3-(cycloundecen-1-yl)-1,2-diazacycloundec-2-ene Chemical compound C1CCCCCCCCC=C1C1=NNCCCCCCCC1 WADSJYLPJPTMLN-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- YKENVNAJIQUGKU-UHFFFAOYSA-N tetraazaporphin Chemical class C=1C(C=N2)=NC2=NC(NN2)=NC2=CC(C=C2)=NC2=CC2=NC=1C=C2 YKENVNAJIQUGKU-UHFFFAOYSA-N 0.000 description 2
- KYPOHTVBFVELTG-UPHRSURJSA-N (z)-but-2-enedinitrile Chemical class N#C\C=C/C#N KYPOHTVBFVELTG-UPHRSURJSA-N 0.000 description 1
- QDFXRVAOBHEBGJ-UHFFFAOYSA-N 3-(cyclononen-1-yl)-4,5,6,7,8,9-hexahydro-1h-diazonine Chemical compound C1CCCCCCC=C1C1=NNCCCCCC1 QDFXRVAOBHEBGJ-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Nitrogen Condensed Heterocyclic Rings (AREA)
Description
本発明はＤＶＤ−ＲやＣＤ−Ｒなどの追記型光ディスク用材料、プラズマディスプレイパネルなどの光学フィルター用材料等に有用なテトラアザポルフィリン化合物の製造方法に関する。 The present invention relates to a method for producing a tetraazaporphyrin compound useful for write-once optical disc materials such as DVD-R and CD-R, and optical filter materials such as plasma display panels.
テトラアザポルフィリン化合物は耐光性が高い、吸光係数が高い等有益な物性を有する色素として知られ、近年、電子写真用光導電体、ＤＶＤ-ＲやＣＤ-Ｒなどの追記型光ディスク材料、プラズマディスプレイパネルなどの光学フィルター用材料等への活用に関する研究が活発になされている。このような状況により、テトラアザポルフィリン化合物の製造法に関する研究も盛んに行われるようになってきている。 Tetraazaporphyrin compounds are known as pigments having useful properties such as high light resistance and high extinction coefficient. Recently, photoconductors for electrophotography, write-once optical disk materials such as DVD-R and CD-R, and plasma displays. Research on utilization of optical filter materials such as panels has been actively conducted. Under such circumstances, research on methods for producing tetraazaporphyrin compounds has been actively conducted.
テトラアザポルフィリン化合物の製造法として、例えば、マレオニトリル化合物または２,５−ジイミノピロール化合物を、金属または遷移金属カルボン酸塩等の金属誘導体と、ジアザビシクロウンデセンやジアザビシクロノネン等の有機塩基を反応させる方法が特開平１１−１１６５７４号公報に開示されている（特許文献１を参照。）。また、アルキル置換トリシアノエチレン化合物と、金属または遷移金属ハロゲン化物や遷移金属カルボン酸塩等の金属誘導体と、モリブデン酸アンモニウムを反応させる方法が特開平１１−３５８３７号公報に開示されている（特許文献２を参照。）。
しかしながら、前記のテトラアザポルフィリン化合物の製造方法は収率に改善の余地があること、また、前記の方法で得られるテトラアザポルフィリン化合物は高純度が要求される用途に使用するには再結晶等の精製が必要であることなどの改善すべき余地がある。 However, the production method of the tetraazaporphyrin compound has room for improvement in yield, and the tetraazaporphyrin compound obtained by the above method is recrystallized for use in applications requiring high purity. There is room for improvement, such as the need for purification.
したがって、本発明は、高純度なテトラアザポルフィリン化合物を収率良く製造する方法を提供することを目的とする。 Therefore, an object of the present invention is to provide a method for producing a highly pure tetraazaporphyrin compound with high yield.
本発明者らは、上記課題を解決するために鋭意検討した結果、特定の金属化合物をアンモニアで処理した後、マレオニトリル誘導体と反応させることにより、比較的純度の高いテトラアザポルフィリン化合物が収率良く得られることを見出し本発明に至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors treated a specific metal compound with ammonia, and then reacted with a maleonitrile derivative, whereby a tetraazaporphyrin compound having a relatively high purity was obtained in a high yield. As a result, the present invention was found.
すなわち、本発明は、
後述する一般式（４）で表される化合物と、アンモニアとを、０度から４０度の温度で反応させて、一般式（１）で表される化合物を得る工程と、該工程で得られた一般式（１）
That is, the present invention
A step of obtaining a compound represented by the general formula (1) by reacting a compound represented by the general formula (4), which will be described later, with ammonia at a temperature of 0 to 40 degrees, and obtained in this step. the general formula (1)
［式中、Ｍは１価〜５価の金属原子を表し、Ｒはヒドロキシ基、アルキル基、フェニル基、−ＯＳｉ（ＣＨ３）３又は酸素原子を表し、Ｘはハロゲン原子を表し、ａは０〜４の整数、ｂ及びｃは各々１〜６の整数、ｄは０〜６の整数を表す。］で表される化合物と、一般式（２） [Wherein, M represents a monovalent to pentavalent metal atom, R represents a hydroxy group, an alkyl group, a phenyl group, —OSi (CH 3) 3 or an oxygen atom, X represents a halogen atom, and a represents 0 -4, b and c each represent an integer of 1-6, d represents an integer of 0-6. And a compound represented by the general formula (2)
〔式中、Ｒ１およびＲ２はそれぞれ独立に水素原子、アルキル基、アラルキル基、アルコキシ基、アルキルチオ基、アリール基、ヘテロアリール基、アリールオキシ基、アリールチオ基を表す〕で表される化合物を反応させる、一般式（３） [Wherein R1 and R2 each independently represent a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group, an alkylthio group, an aryl group, a heteroaryl group, an aryloxy group, or an arylthio group] And general formula (3)
〔式中Ｒ３〜１０は、それぞれ独立に水素原子、アルキル基、アラルキル基、アルコキシ基、アルキルチオ基、アリール基、ヘテロアリール基、アリールオキシ基、アリールチオ基を表し、Ｍは２価の金属原子、３価または４価の置換金属原子、あるいはオキシ金属を表す〕で表される化合物の製造方法に関するものである。 [Wherein R3 to 10 each independently represents a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group, an alkylthio group, an aryl group, a heteroaryl group, an aryloxy group, or an arylthio group, and M represents a divalent metal atom, Represents a trivalent or tetravalent substituted metal atom or an oxy metal].
本発明によれば、高純度なテトラアザポルフィリン化合物を収率良く製造する方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the method of manufacturing a highly purified tetraazaporphyrin compound with a sufficient yield can be provided.
本発明の製造方法は、一般式（１）で表される化合物と一般式（２）で表される化合物を反応させて一般式（３）で表される化合物を製造することを特徴とする。 The production method of the present invention is characterized in that a compound represented by the general formula (3) is produced by reacting a compound represented by the general formula (1) with a compound represented by the general formula (2). .
一般式（１）中のＭは１価〜５価の金属原子表し、Ｒはヒドロキシ基、アルキル基、フェニル基、−ＯＳｉ（ＣＨ３）３又は酸素原子を表し、Ｘはハロゲン原子を表し、ａは０〜４の整数、ｂ及びｃは各々１〜６の整数、ｄは０〜６の整数を表す。 M in the general formula (1) represents a monovalent to pentavalent metal atom, R represents a hydroxy group, an alkyl group, a phenyl group, —OSi (CH 3) 3 or an oxygen atom, X represents a halogen atom, a Represents an integer of 0 to 4, b and c each represents an integer of 1 to 6, and d represents an integer of 0 to 6.
一般式（１）中のＭとしては、Ｃｒ、Ｓｉ、Ｚｒ、Ａｌ、Ｇａ、Ｉｎ、Ｔｌ、Ｃｕ、Ｚｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｒｕ、Ｐｄ、Ｐｔ、Ｍｎ、Ｍｇ、Ｔｉ、Ｂｅ、Ｃａ、Ｂａ、Ｃｄ、Ｈｇ、Ｐｂ、Ｓｎ、Ｇｅ等の１〜５価の金属原子が挙げられる。 As M in the general formula (1), Cr, Si, Zr, Al, Ga, In, Tl, Cu, Zn, Fe, Co, Ni, Ru, Pd, Pt, Mn, Mg, Ti, Be, Ca , Ba, Cd, Hg, Pb, Sn, Ge, etc. 1-5 pentavalent metal atoms.
一般式（１）中、Ｒのアルキル基としては特に制限はないが、炭素数1〜８のアルキル基が好ましいものとして挙げられる。 In general formula (1), the alkyl group for R is not particularly limited, but an alkyl group having 1 to 8 carbon atoms is preferable.
一般式（２）中のＲ１およびＲ２はそれぞれ独立に水素原子、アルキル基、アラルキル基、アルコキシ基、アルキルチオ基、アリール基、ヘテロアリール基、アリールオキシ基又はアリールチオ基を表す。 R 1 and R 2 in the general formula (2) each independently represent a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group, an alkylthio group, an aryl group, a heteroaryl group, an aryloxy group or an arylthio group.
一般式（２）中、Ｒ１およびＲ２のアルキル基としては特に限定されないが、炭素数１〜２０のアルキル基が好ましいものとして挙げられる。 In general formula (2), the alkyl group of R1 and R2 is not particularly limited, but an alkyl group having 1 to 20 carbon atoms is preferable.
なお、アルキル基は、アルコキシ基、シクロ炭化水素基等の置換基で置換されていてもよい。 The alkyl group may be substituted with a substituent such as an alkoxy group or a cyclohydrocarbon group.
一般式（２）中、Ｒ１およびＲ２のアラルキル基としては特に限定されないが、炭素数７〜２０のアラルキル基が好ましいものとして挙げられる。 In the general formula (2), the aralkyl group of R1 and R2 is not particularly limited, but an aralkyl group having 7 to 20 carbon atoms is preferable.
なお、アラルキル基はアルキル基、ニトロ基、シアノ基、ヒドロキシ基、ハロゲノ基、ハロゲン化炭素基で置換されていてもよい。 The aralkyl group may be substituted with an alkyl group, a nitro group, a cyano group, a hydroxy group, a halogeno group, or a halogenated carbon group.
一般式（２）中、Ｒ１およびＲ２のアルコキシ基としては炭素数１〜２０のアルコキシ基が好ましいものとして挙げられる。 In the general formula (2), the alkoxy group of R1 and R2 is preferably an alkoxy group having 1 to 20 carbon atoms.
一般式（２）中、Ｒ１およびＲ２のアルキルチオ基としては炭素数１〜２０のアルキルチオ基が好ましいものとして挙げられる。 In general formula (2), the alkylthio group of R1 and R2 is preferably an alkylthio group having 1 to 20 carbon atoms.
一般式（２）中、Ｒ１およびＲ２のアリール基としては炭素数６〜２０のアリール基が好ましいものとして挙げられる。 In general formula (2), the aryl group of R1 and R2 is preferably an aryl group having 6 to 20 carbon atoms.
なお、アリール基はアルコキシ基、アミノ基、アルキル基、ニトロ基、シアノ基、ヒドロキシ基、ハロゲノ基、ハロゲン化炭素基で置換されていてもよい。 The aryl group may be substituted with an alkoxy group, amino group, alkyl group, nitro group, cyano group, hydroxy group, halogeno group, or halogenated carbon group.
一般式（２）中、Ｒ１およびＲ２のヘテロアリール基としては炭素数４〜２０のヘテロアリール基が好ましいものとして挙げられる。 In general formula (2), the heteroaryl group of R1 and R2 is preferably a heteroaryl group having 4 to 20 carbon atoms.
一般式（２）中、Ｒ１およびＲ２のアリールオキシ基としては炭素数６〜２０のアリールオキシ基が好ましいものとして挙げられる。 In general formula (2), the aryloxy group of R1 and R2 is preferably an aryloxy group having 6 to 20 carbon atoms.
なお、アリールオキシ基はアルキル基および／またはアルコキシ基で置換されていてもよい。 The aryloxy group may be substituted with an alkyl group and / or an alkoxy group.
一般式（２）中、Ｒ１およびＲ２のアリールチオ基としては炭素数６〜２０のアリールチオ基が好ましいものとして挙げられる。 In general formula (2), the arylthio group of R1 and R2 is preferably an arylthio group having 6 to 20 carbon atoms.
なお、アリールチオ基はアルキル基および／またはアルコキシ基で置換されていてもよい。 The arylthio group may be substituted with an alkyl group and / or an alkoxy group.
一般式（３）中、Ｒ３〜Ｒ１０は、それぞれ独立に水素原子、置換または無置換のアルキル基、アラルキル基、アルコキシ基、アルキルチオ基、アリール基、ヘテロアリール基、アリールオキシ基、アリールチオ基を表し、Ｍは２価の金属原子あるいはオキシ金属を表す。 In general formula (3), R 3 to R 10 are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, an aralkyl group, an alkoxy group, an alkylthio group, an aryl group, a heteroaryl group, an aryloxy group, and an arylthio group. the stands, M is a divalent metal source core Rui represents an oxy metal.
一般式（３）中、Ｒ３〜Ｒ１０の置換または無置換のアルキル基、アラルキル基、アルコキシ基、アルキルチオ基、アリール基、ヘテロアリール基、アリールオキシ基、アリールチオ基は、前記の一般式（２）中の各基の定義と同義である。 In general formula (3), the substituted or unsubstituted alkyl group, aralkyl group, alkoxy group, alkylthio group, aryl group, heteroaryl group, aryloxy group, and arylthio group of R 3 to R 10 are represented by the above general formula ( It is synonymous with the definition of each group in 2).
一般式（３）中、Ｍの２価の金属原子としては、Cu（II）、Zn（II）、Fe（II）、Co（II）、Ni（II）、Ru（II）、Rh（II）、Pd（II）、Pt（II）、Mn（II）、Mg（II）、Ti（II）、Be（II）、Ca（II）、Ba（II）、Cd（II）、Hg（II）、Pb（II）、Sn（II）等が挙げられる。 In the general formula (3), as the divalent metal atom of M, Cu (II), Zn (II), Fe (II), Co (II), Ni (II), Ru (II), Rh (II ), Pd (II), Pt (II), Mn (II), Mg (II), Ti (II), Be (II), Ca (II), Ba (II), Cd (II), Hg (II ), Pb (II), Sn (II) and the like.
一般式（３）中、Ｍのオキシ金属としては、VO、MnO、TiO等が挙げられる。 In one general formula (3), as the oxy metal M, VO, MnO, TiO, and the like.
一般式（１）で表される化合物と一般式（２）で表される化合物との反応には反応溶媒を必ずしも必要としないが、温度制御および/または攪拌効率を考慮すれば、反応溶媒を用いるのが好ましい。 A reaction solvent is not necessarily required for the reaction between the compound represented by the general formula (1) and the compound represented by the general formula (2). However, if temperature control and / or stirring efficiency are taken into consideration, the reaction solvent is not used. It is preferable to use it.
反応溶媒は一般式（３）で表される化合物の生成を妨げるものでなければ特に限定されない。このような反応溶媒としては、例えば、トルエン、キシレン等の炭化水素類、ペンタノール、ブタノール、オクタノール等のアルコール類、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルスルホキシド、Ｎ−メチルピロリドン、１，３−ジメチルイミダゾリジノン等の高沸点親水性溶媒等が挙げられる。これらの中でも、一般式（２）で表される化合物及び一般式（３）で表される化合物の溶解性が高いアルコール類は好ましい。 The reaction solvent is not particularly limited as long as it does not prevent the formation of the compound represented by the general formula (3). Examples of such a reaction solvent include hydrocarbons such as toluene and xylene, alcohols such as pentanol, butanol and octanol, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, and 1,3-dimethyl. And high boiling hydrophilic solvents such as imidazolidinone. Among these, alcohols having high solubility of the compound represented by the general formula (2) and the compound represented by the general formula (3) are preferable.
一般式（１）で表される化合物と一般式（２）で表される化合物との反応の反応条件としては、通常、温度は０〜１００℃、圧力は０.０１〜１ＭＰａ、雰囲気は空気または窒素やヘリウム、アルゴン等の不活性ガス雰囲気である。 As reaction conditions for the reaction of the compound represented by the general formula (1) and the compound represented by the general formula (2), the temperature is usually 0 to 100 ° C., the pressure is 0.01 to 1 MPa, and the atmosphere is air. Or an inert gas atmosphere such as nitrogen, helium, or argon.
一般式（１）で表される化合物は市販品として入手できるものもあるが、一般式（４） Some of the compounds represented by the general formula (1) are commercially available, but the general formula (4)
［式中、Ｍは１価〜５価の金属原子を表し、Ｒはヒドロキシ基、アルキル基、フェニル基、−ＯＳｉ（ＣＨ３）３又は酸素原子を表し、Ｘはハロゲン原子を表し、ａは０〜４の整数、ｃは１〜６の整数、ｄは０〜６の整数を表す。］で表される化合物とアンモニアを反応させて製造することができる。例えば、一般式（１）で表される化合物は新実験化学講座（昭和52年6月20日発行、8巻1294ページ）に記載された方法に準じて製造することができる。具体的には塩化ニッケルに濃アンモニア水を加え、1時間ほど空気を通じて製造する。 [Wherein, M represents a monovalent to pentavalent metal atom, R represents a hydroxy group, an alkyl group, a phenyl group, —OSi (CH 3) 3 or an oxygen atom, X represents a halogen atom, and a represents 0 -4, c represents an integer of 1-6, d represents an integer of 0-6. It can be produced by reacting a compound represented by For example, the compound represented by the general formula (1) can be produced according to the method described in the New Experimental Chemistry Course (issued June 20, 1977, Vol. 8, page 1294). Specifically, concentrated ammonia water is added to nickel chloride, and it is produced through air for about 1 hour.
一般式（２）で表される化合物は市販品として入手できるものもあるが、例えば、下記一般式（５） Some of the compounds represented by the general formula (2) are available as commercial products. For example, the following general formula (5)
［式中のＲ１およびＲ２は一般式（２）のＲ１およびＲ２と同義である。］で表される１,２−ジブロモエタン化合物をシアン化ナトリウムやシアン化銅と反応させて得ることもできる。 [Wherein R1 and R2 have the same meanings as R1 and R2 in formula (2). It can also be obtained by reacting a 1,2-dibromoethane compound represented by the formula with sodium cyanide or copper cyanide.
一般式（４）で表される化合物とアンモニアを反応させて形成された一般式（１）で表される化合物と一般式（２）で表される化合物とを反応させることにより一般式（３）で表される化合物を製造することもできる。 By reacting the compound represented by the general formula (1) formed by reacting the compound represented by the general formula (4) with ammonia, the compound represented by the general formula (2) is reacted with the compound represented by the general formula (3). ) Can also be produced.
一般式（４）で表される化合物とアンモニアを反応させて形成された一般式（１）で表される化合物と一般式（２）で表される化合物とを反応させて一般式（３）で表される化合物を製造する方法に特に制限はないが、例えば、前記の反応溶媒に溶解させた一般式（４）で表される化合物の溶液にアンモニアを添加した後、この反応混合物に一般式（２）で表される化合物を添加する方法及び一般式（４）で表される化合物と一般式（２）で表される化合物の混合物にアンモニアを添加して反応させる方法等が挙げられる。これらの方法のうち、前者の方法は反応収率及び純度の点で好ましい。 The compound represented by the general formula (1) formed by reacting the compound represented by the general formula (4) with ammonia is reacted with the compound represented by the general formula (2) to obtain the general formula (3). There is no particular limitation on the method for producing the compound represented by general formula (4). For example, after adding ammonia to the solution of the compound represented by the general formula (4) dissolved in the reaction solvent, The method of adding the compound represented by Formula (2), the method of adding ammonia to the mixture of the compound represented by General Formula (4), and the compound represented by General Formula (2), etc. are mentioned. . Among these methods, the former method is preferable in terms of reaction yield and purity.
例えば、一般式（４）中のＭがＣｕである化合物とアンモニアを反応させ（１）中のＭがＣｕである化合物を単離することなく一般式（２）で表される化合物と反応させることにより一般式（３）中のＭがＣｕである化合物を製造することができる。また、一般式（４）中のＭがＶである化合物とアンモニアを反応させた後、一般式（１）中のＭがＶである化合物を単離することなく一般式（２）で表される化合物と反応させることにより一般式（３）中のＭがＶＯである化合物を製造することができる。 For example, a compound in which M in general formula (4) is Cu and ammonia are reacted, and a compound in which M in Cu is (1) is reacted with a compound represented by general formula (2) without isolation. Thus, a compound in which M in the general formula (3) is Cu can be produced. In addition, after reacting ammonia in the general formula (4) with a compound in which M is V, the compound in which the M in the general formula (1) is V is represented by the general formula (2) without isolation. A compound in which M in the general formula (3) is VO can be produced by reacting with the compound.
一般式（４）で表される化合物とアンモニアとの反応に使用するアンモニアガスの量は、一般式（４）で表される化合物中のハロゲン原子１モルに対して１乃至３モル、好ましくは１．５乃至２．５モル、より好ましくは１．８乃至２．２モルである。 The amount of ammonia gas used for the reaction between the compound represented by the general formula (4) and ammonia is 1 to 3 mol, preferably 1 mol per 1 mol of the halogen atom in the compound represented by the general formula (4). The amount is 1.5 to 2.5 mol, more preferably 1.8 to 2.2 mol.
一般式（４）で表される化合物とアンモニアとの反応の反応温度は、通常、１００℃以下であるが、０乃至４０℃の範囲で行うのが好ましい。 The reaction temperature of the reaction between the compound represented by the general formula (4) and ammonia is usually 100 ° C. or lower, but it is preferably performed in the range of 0 to 40 ° C.
一般式（３）で表される化合物の反応混合物からの分離は、通常、反応混合物から反応溶媒の大部分を蒸留により除去した後、一般式（３）で表される化合物の溶解度が低い溶媒を添加し、析出した一般式（３）で表される化合物の固体を濾過して分離することができる。 The separation of the compound represented by the general formula (3) from the reaction mixture is usually performed by removing most of the reaction solvent from the reaction mixture by distillation, and then the solvent represented by the general formula (3) having a low solubility. And the precipitated solid of the compound represented by the general formula (3) can be separated by filtration.
一般式（３）で表される化合物の溶解度が低い溶媒としては、例えば、メタノール、エタノール、水、ヘキサン等が挙げられる。 これらの溶媒は２種以上を混合して使用することができるが、含水メタノールを好ましいものとして挙げることができる。 As a solvent with low solubility of the compound represented by General formula (3), methanol, ethanol, water, hexane etc. are mentioned, for example. These solvents can be used as a mixture of two or more thereof, and water-containing methanol can be mentioned as a preferable one.
以下に本発明を実施例により具体的に説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.
なお、以下の各実施例中の純度が記載された化合物の純度の測定は、高速液体クロマトグラフィー（以下、「ＨＰＬＣ」と略記する。）に依った。 In addition, the measurement of the purity of the compound in which the purity in each following Example was described was based on the high performance liquid chromatography (henceforth "HPLC").
ＨＰＬＣ分析の条件は次のとおりである。
カラム： 株式会社ワイエムシィ製 ＹＭＣ−Ｐａｃｋ ＯＤＳ−Ａ Ａ−３１２
カラムオーブン温度： ４０℃
溶離液： ＴＨＦ：メタノール比＝１：６の混合溶媒
検出波長： ２５４ｎｍ
The conditions for HPLC analysis are as follows.
Column: YMC-Pack ODS-A A-312 manufactured by YMC Co., Ltd.
Column oven temperature: 40 ° C
Eluent: THF: methanol ratio = 1: 6 mixed solvent Detection wavelength: 254 nm
１−ペンタノール５０ｇに三塩化バナジウム１．５７ｇを装入し、２０℃でアンモニアガス１．０２ｇを１時間かけて導入した。アンモニアガスは反応液中へ導入した。アンモニア導入中は発熱を伴った。２０乃至３０℃で１時間攪拌を行った後、下記式（６）で表される化合物（市販品）５．３８ｇを装入し、１２５℃に昇温した。昇温終了後１２５℃で６時間攪拌を続けた。次いで、反応混合物から１−ペンタノール約４０ｇを蒸留により除去し、メタノール水（メタノールと水の重量比は１：１）を装入して無定形の下記式（７）で表される化合物を析出させた。析出した式（７）で表される化合物を濾過して回収し、乾燥させて式（７）で表される化合物５．４６ｇを得た。乾燥後の式（７）で表される化合物をＨＰＬＣ分析した結果、その純度は９４％、収率は８５％であった。式（７）で表される化合物の元素分析結果およびＦＤ−ＭＳ測定結果は次のとおりであった。 50 g of 1-pentanol was charged with 1.57 g of vanadium trichloride, and 1.02 g of ammonia gas was introduced at 20 ° C. over 1 hour. Ammonia gas was introduced into the reaction solution. There was an exotherm during the introduction of ammonia. After stirring at 20 to 30 ° C. for 1 hour, 5.38 g of a compound (commercial product) represented by the following formula (6) was charged, and the temperature was raised to 125 ° C. After completion of the temperature increase, stirring was continued at 125 ° C. for 6 hours. Next, about 40 g of 1-pentanol was removed from the reaction mixture by distillation, and methanol water (the weight ratio of methanol to water was 1: 1) was charged to obtain an amorphous compound represented by the following formula (7). Precipitated. The precipitated compound represented by the formula (7) was collected by filtration and dried to obtain 5.46 g of a compound represented by the formula (7). As a result of HPLC analysis of the compound represented by the formula (7) after drying, the purity was 94% and the yield was 85%. The elemental analysis results and FD-MS measurement results of the compound represented by formula (7) were as follows.
元素分析結果 Ｃ Ｈ Ｎ ＦＤ−ＭＳ
（ｍ／ｚ）
化合物（７） ６３．７０ ６．７１ １８．５５ ６０３
理論値（％） ６３．６７ ６．６８ １８．５６ ６０３
Elemental analysis results C H N FD-MS
(M / z)
Compound (7) 63.70 6.71 18.55 603
Theoretical value (%) 63.67 6.68 18.56 603
化合物（７）の合成
１−ペンタノール５０ｇに三塩化バナジウム１．５７ｇ、前記式（６）で表される化合物５．３８ｇを装入し、２０℃でアンモニアガス１．０２ｇを１時間かけて導入した。アンモニアガスは反応液中へ導入した。アンモニア導入中は発熱を伴った。２０乃至３０℃で１時間攪拌を行った後、１２５℃に昇温した。昇温終了後１２５℃で６時間攪拌を続けた。次いで、反応混合物から１−ペンタノール約４０ｇを蒸留により除去し、重量比１：１のメタノール水を装入して無定形の前記式（７）で表される化合物を析出させた。析出した前記式（７）で表される化合物を濾過して回収し、乾燥させて式（７）で表される化合物５．００ｇを得た。乾燥後の式（７）で表される化合物をＨＰＬＣ分析した結果、その純度は９４％、収率は７８％であった。式（７）で表される化合物の元素分析結果およびＦＤ−ＭＳ測定結果は次のとおりであった。
Synthesis of Compound (7) 50 g of 1-pentanol was charged with 1.57 g of vanadium trichloride and 5.38 g of the compound represented by the formula (6), and 1.02 g of ammonia gas was added at 20 ° C. over 1 hour. Introduced. Ammonia gas was introduced into the reaction solution. There was an exotherm during the introduction of ammonia. After stirring for 1 hour at 20 to 30 ° C, the temperature was raised to 125 ° C. After completion of the temperature increase, stirring was continued at 125 ° C. for 6 hours. Next, about 40 g of 1-pentanol was removed from the reaction mixture by distillation, and methanol water having a weight ratio of 1: 1 was charged to precipitate an amorphous compound represented by the formula (7). The precipitated compound represented by the formula (7) was collected by filtration and dried to obtain 5.00 g of a compound represented by the formula (7). As a result of HPLC analysis of the compound represented by the formula (7) after drying, the purity was 94% and the yield was 78%. The elemental analysis results and FD-MS measurement results of the compound represented by formula (7) were as follows.
元素分析結果 Ｃ Ｈ Ｎ ＦＤ−ＭＳ
（ｍ／ｚ）
化合物（７） ６３．７１ ６．７０ １８．５５ ６０３
理論値（％） ６３．６７ ６．６８ １８．５６ ６０３
Elemental analysis results C H N FD-MS
(M / z)
Compound (7) 63.71 6.70 18.55 603
Theoretical value (%) 63.67 6.68 18.56 603
化合物（８）の合成
１−ペンタノール５０ｇに無水塩化銅（II）１．３４ｇを装入し、２０℃でアンモニアガス０．６８ｇを１時間かけて導入した。アンモニアガスは反応液中へ導入した。アンモニア導入中は発熱を伴った。２０乃至３０℃で１時間攪拌を行った後、前記式（６）で表される化合物５．３８ｇを装入し、１２５℃に昇温した。昇温終了後１２５℃で６時間攪拌を続けた。次いで、反応混合物から１−ペンタノール約４０ｇを蒸留により除去し、重量比１：１のメタノール水を装入して無定形の式（８）で表される化合物を析出させた。式（８）で表される化合物を濾過して回収し、乾燥させて式（８）で表される化合物５．５６ｇを得た。乾燥後の式（８）で表される化合物をＨＰＬＣ分析した結果、その純度は９５％、収率は８８％であった。式（８）で表される化合物の元素分析結果およびＦＤ−ＭＳ測定結果は次のとおりであった。
Synthesis of Compound (8) 1.34 g of anhydrous copper (II) chloride was charged into 50 g of 1-pentanol, and 0.68 g of ammonia gas was introduced at 20 ° C. over 1 hour. Ammonia gas was introduced into the reaction solution. There was an exotherm during the introduction of ammonia. After stirring at 20 to 30 ° C. for 1 hour, 5.38 g of the compound represented by the formula (6) was charged, and the temperature was raised to 125 ° C. After completion of the temperature increase, stirring was continued at 125 ° C. for 6 hours. Next, about 40 g of 1-pentanol was removed from the reaction mixture by distillation, and methanol water having a weight ratio of 1: 1 was charged to precipitate an amorphous compound represented by the formula (8). The compound represented by formula (8) was collected by filtration and dried to obtain 5.56 g of compound represented by formula (8). As a result of HPLC analysis of the compound represented by the formula (8) after drying, the purity was 95% and the yield was 88%. The elemental analysis results and FD-MS measurement results of the compound represented by formula (8) were as follows.
元素分析結果 Ｃ Ｈ Ｎ ＦＤ−ＭＳ
（ｍ／ｚ）
化合物（８） ６４．０５ ６．７１ １８．６６ ６００
理論値（％） ６４．０３ ６．７２ １８．６７ ６００
Elemental analysis results C H N FD-MS
(M / z)
Compound (8) 64.05 6.71 18.66 600
Theoretical value (%) 64.03 6.72 18.67 600
化合物（１０）の合成
１−ペンタノール５０ｇに塩化パラジウム（II）１．７７ｇを装入し、２０℃でアンモニアガス０．６８ｇを１時間かけて導入した。アンモニアガスは反応液中へ導入した。アンモニア導入中は発熱を伴った。２０乃至３０℃で１時間攪拌を行った後、下記式（９）で表されるル化合物（市販品）９．２１ｇを装入し、１２５℃に昇温した。昇温終了後１２５℃で６時間攪拌を続けた。次いで、反応混合物から１−ペンタノール約４０ｇを蒸留により除去し、重量比１：１のメタノール水を装入して無定形の下記式（１０）で表される化合物を析出させた。析出した式（１０）で表される化合物を濾過して回収し、乾燥させて式（１０）で表される化合物９．４１ｇを得た。乾燥後の式（１０）で表される化合物をＨＰＬＣ分析した結果、その純度は９５％、収率は８７％であった。式（１０）で表される化合物の元素分析結果及びＦＤ−ＭＳ測定結果は次にとおりであった。
Synthesis of Compound (10) 1.77 g of palladium chloride (II) was charged into 50 g of 1-pentanol, and 0.68 g of ammonia gas was introduced at 20 ° C. over 1 hour. Ammonia gas was introduced into the reaction solution. There was an exotherm during the introduction of ammonia. After stirring at 20 to 30 ° C. for 1 hour, 9.21 g of a ru compound (commercial product) represented by the following formula (9) was charged, and the temperature was raised to 125 ° C. After completion of the temperature increase, stirring was continued at 125 ° C. for 6 hours. Subsequently, about 40 g of 1-pentanol was removed from the reaction mixture by distillation, and methanol water having a weight ratio of 1: 1 was charged to precipitate an amorphous compound represented by the following formula (10). The precipitated compound represented by the formula (10) was collected by filtration and dried to obtain 9.41 g of a compound represented by the formula (10). As a result of HPLC analysis of the compound represented by the formula (10) after drying, the purity was 95% and the yield was 87%. The results of elemental analysis and FD-MS measurement of the compound represented by formula (10) were as follows.
元素分析結果 Ｃ Ｈ Ｎ ＦＤ−ＭＳ
（ｍ／ｚ）
化合物（１０） ７４．７８ ３．９３ １０．８９ １０２６
理論値（％） ７４．８１ ３．９２ １０．９１ １０２６
Elemental analysis results C H N FD-MS
(M / z)
Compound (10) 74.78 3.93 10.89 1026
Theoretical value (%) 74.81 3.92 10.91 1026
化合物（１１）の合成
１−ペンタノール５０ｇに塩化ニッケル（II）１．３０ｇを装入し、２０℃でアンモニアガス０．６８ｇを１時間かけて導入した。アンモニアガスは反応液中へ導入した。アンモニア導入中は発熱を伴った。２０乃至３０℃で１時間攪拌を行った後、前記式（９）で表される化合物９．２１ｇを装入し、１２５℃に昇温した。昇温終了後１２５℃で６時間攪拌を続けた。次いで、反応混合物から１−ペンタノール約４０ｇを蒸留により除去し、重量比１：１のメタノール水を装入して無定形の下記式（１１）で表される化合物を析出させた。式（１１）で表される化合物を濾過して回収し、乾燥させて式（１１）で表される化合物９．０８ｇを得た。乾燥後の式（１１）で表される化合物をＨＰＬＣ分析した結果、その純度は９６％、収率は８９％であった。式（１１）で表される化合物の元素分析結果及びＦＤ−ＭＳ測定結果は次のとおりであった。
Synthesis of Compound (11) 1.30 g of nickel chloride (II) was charged into 50 g of 1-pentanol, and 0.68 g of ammonia gas was introduced at 20 ° C. over 1 hour. Ammonia gas was introduced into the reaction solution. There was an exotherm during the introduction of ammonia. After stirring for 1 hour at 20 to 30 ° C., 9.21 g of the compound represented by the formula (9) was charged, and the temperature was raised to 125 ° C. After completion of the temperature increase, stirring was continued at 125 ° C. for 6 hours. Next, about 40 g of 1-pentanol was removed from the reaction mixture by distillation, and methanol water having a weight ratio of 1: 1 was charged to precipitate an amorphous compound represented by the following formula (11). The compound represented by the formula (11) was collected by filtration and dried to obtain 9.08 g of the compound represented by the formula (11). As a result of HPLC analysis of the compound represented by the formula (11) after drying, the purity was 96% and the yield was 89%. The elemental analysis results and FD-MS measurement results of the compound represented by formula (11) were as follows.
元素分析結果 Ｃ Ｈ Ｎ ＦＤ−ＭＳ
（ｍ／ｚ）
化合物（１１） ７８．４４ ４．１１ １１．４７ ９７８
理論値（％） ７８．４６ ４．１２ １１．４４ ９７８
Elemental analysis results C H N FD-MS
(M / z)
Compound (11) 78.44 4.11 11.47 978
Theoretical value (%) 78.46 4.12 11.44 978
［比較例１］
化合物（７）の合成
１−ペンタノール５０ｇに前記式（６）で表される化合物５．３８ｇを装入して約７０℃に昇温した。約７０℃昇温後、ジアザビシクロウンデセン１．２２ｇを加え、さらに温度を上昇させた。９０℃になった時点で三塩化バナジウム１．５７ｇを装入し、温度１２０乃至１２５℃で２０時間攪拌を続けた。次いで、反応混合物から１−ペンタノール約４０ｇを蒸留により除去し、重量比１：１のメタノール水を装入して無定形の前記式（７）で表される化合物を析出させた。式（７）で表される化合物を濾過して回収し、乾燥させて式（７）で表される化合物４．４１ｇを得た。乾燥後の式（７）で表される化合物をＨＰＬＣ分析した結果、その純度は８９％、収率は６５％であった。
[Comparative Example 1]
Synthesis of Compound (7) 5.38 g of the compound represented by the formula (6) was charged into 50 g of 1-pentanol, and the temperature was raised to about 70 ° C. After raising the temperature at about 70 ° C., 1.22 g of diazabicycloundecene was added, and the temperature was further raised. When the temperature reached 90 ° C., 1.57 g of vanadium trichloride was charged, and stirring was continued at a temperature of 120 to 125 ° C. for 20 hours. Next, about 40 g of 1-pentanol was removed from the reaction mixture by distillation, and methanol water having a weight ratio of 1: 1 was charged to precipitate an amorphous compound represented by the formula (7). The compound represented by the formula (7) was collected by filtration and dried to obtain 4.41 g of the compound represented by the formula (7). As a result of HPLC analysis of the compound represented by the formula (7) after drying, the purity was 89% and the yield was 65%.
本発明の製造方法は、高純度のテトラアザポルフィリン化合物を収率良く製造するのに有用である。 The production method of the present invention is useful for producing a high-purity tetraazaporphyrin compound with high yield.
Claims (4)
一般式（４）中、Ｍは１価〜５価の金属原子を表し、Ｒはヒドロキシ基、アルキル基、フェニル基、−ＯＳｉ（ＣＨ ３ ） ３ 又は酸素原子を表し、Ｘはハロゲン原子を表し、ａは０〜４の整数、ｃは１〜６の整数、ｄは０〜６の整数を表す。
一般式（１）中、Ｍは１価〜５価の金属原子を表し、Ｒはヒドロキシ基、アルキル基、フェニル基、−ＯＳｉ（ＣＨ３）３又は酸素原子を表し、Ｘはハロゲン原子を表し、ａは０〜４の整数、ｂ及びｃは各々１〜６の整数、ｄは０〜６の整数を表す。
一般式（２）中、Ｒ１およびＲ２はそれぞれ独立に水素原子、アルキル基、アラルキル基、アルコキシ基、アルキルチオ基、アリール基、ヘテロアリール基、アリールオキシ基又はアリールチオ基を表す。
一般式（３）中、Ｒ３〜Ｒ １０は、それぞれ独立に水素原子、アルキル基、アラルキル基、アルコキシ基、アルキルチオ基、アリール基、ヘテロアリール基、アリールオキシ基、アリールチオ基を表し、Ｍは２価の金属原子あるいはオキシ金属を表す。 A step of obtaining a compound represented by the following general formula (1) by reacting a compound represented by the following general formula (4) with ammonia at a temperature of 0 to 40 degrees; was following by the general formula (1) and a compound represented by the following general formula and a compound represented by (2) reacting, a manufacturing method including a step of obtaining a compound represented by the following general formula (3).
In general formula (4), M represents a monovalent to pentavalent metal atom, R represents a hydroxy group, an alkyl group, a phenyl group, —OSi (CH 3 ) 3 or an oxygen atom, and X represents a halogen atom. A represents an integer of 0 to 4, c represents an integer of 1 to 6, and d represents an integer of 0 to 6.
In general formula (1), M represents a monovalent to pentavalent metal atom, R represents a hydroxy group, an alkyl group, a phenyl group, —OSi (CH 3 ) 3 or an oxygen atom, and X represents a halogen atom. , A represents an integer of 0 to 4, b and c each represents an integer of 1 to 6, and d represents an integer of 0 to 6.
In general formula (2), R 1 and R 2 each independently represent a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group, an alkylthio group, an aryl group, a heteroaryl group, an aryloxy group, or an arylthio group.
In general formula (3), R 3 to R 10 each independently represent a hydrogen atom, an alkyl group, an aralkyl group, an alkoxy group, an alkylthio group, an aryl group, a heteroaryl group, an aryloxy group, or an arylthio group, and M is divalent metal original core Rui represents an oxy metal.
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