JP2007099744A - Method for producing tetraazaporphyrin compound - Google Patents
Method for producing tetraazaporphyrin compound Download PDFInfo
- Publication number
- JP2007099744A JP2007099744A JP2005322814A JP2005322814A JP2007099744A JP 2007099744 A JP2007099744 A JP 2007099744A JP 2005322814 A JP2005322814 A JP 2005322814A JP 2005322814 A JP2005322814 A JP 2005322814A JP 2007099744 A JP2007099744 A JP 2007099744A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- producing
- mixture
- cis isomer
- mol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- NPBLQPWAISGYEU-UHFFFAOYSA-N CC(C)(C)C(C#N)=O Chemical compound CC(C)(C)C(C#N)=O NPBLQPWAISGYEU-UHFFFAOYSA-N 0.000 description 2
- FSDIPBHENFUQPP-QXMHVHEDSA-N CC(C)(C)/C(/C#N)=C(\c1ccccc1F)/C#N Chemical compound CC(C)(C)/C(/C#N)=C(\c1ccccc1F)/C#N FSDIPBHENFUQPP-QXMHVHEDSA-N 0.000 description 1
- 0 CC(C)(C)C(C#N)=C(*)C#N Chemical compound CC(C)(C)C(C#N)=C(*)C#N 0.000 description 1
- JVHQQQZBFWIDOV-OUKQBFOZSA-N CC(C)/C(/C#N)=C(/C1=CC=CCC1)\C#N Chemical compound CC(C)/C(/C#N)=C(/C1=CC=CCC1)\C#N JVHQQQZBFWIDOV-OUKQBFOZSA-N 0.000 description 1
- UFEZOQXKLJQFJU-SEYXRHQNSA-N CC(C)/C(/C#N)=C(\c1ccccc1)/C#N Chemical compound CC(C)/C(/C#N)=C(\c1ccccc1)/C#N UFEZOQXKLJQFJU-SEYXRHQNSA-N 0.000 description 1
Landscapes
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
本発明は、光記録用色素、光学フィルター用色素などとして有用なテトラアザポルフィリン化合物の製造法に関するものである。 The present invention relates to a method for producing a tetraazaporphyrin compound useful as a dye for optical recording, a dye for optical filters, and the like.
光記録用色素、光学フィルター用色素などとして有用なテトラアザポルフィリン化合物化合物は、下記の文献に開示されている。
本発明は、１，２−ジシアノエチレン化合物の２つの異性体のうちシス体の生成比率の高い製法を探求し、ひいてはテトラアザポルフィリン化合物の収率よい製法を提供せんとするものである。 The present invention seeks a process for producing a high cis isomer among the two isomers of 1,2-dicyanoethylene compound, and therefore provides a process for producing a tetraazaporphyrin compound with high yield.
即ち本発明は、一般式（１）で示されるアシルシアニドと一般式（２）で示される１置換アセトニトリル誘導体とを、酸性触媒及び塩基性触媒の存在下に脱水反応させることにより一般式（３）で示される１，２−ジシアノエチレン化合物のシス体を製造し、次いでこの１，２−ジシアノエチレン化合物のシス体を環化してテトラアザポルフィリン化合物を製造する方法において、酸性触媒として前記したアシルシアニドの１〜２．５倍当量に相当する四塩化チタンを用いると共に、塩基性触媒として前記したアシルシアニドの２．５〜４．５倍当量に相当するＮ−メチルモルホリンを使用することを特徴とするテトラアザポルフィリン化合物の製造法に係るものである。
以下の構造式において、Ｒはオルト位にハロゲンが置換したフェニル基又は無置換のナフチル基を意味する。That is, in the present invention, the acyl cyanide represented by the general formula (1) and the 1-substituted acetonitrile derivative represented by the general formula (2) are subjected to a dehydration reaction in the presence of an acidic catalyst and a basic catalyst, whereby the general formula (3) In the method of producing a tetraazaporphyrin compound by cyclization of the cis isomer of 1,2-dicyanoethylene compound represented by the following formula, and then cyclizing the cis isomer of 1,2-dicyanoethylene compound, Tetratetrachloride corresponding to 1 to 2.5 times equivalent is used, and N-methylmorpholine corresponding to 2.5 to 4.5 times equivalent of the above-mentioned acyl cyanide is used as a basic catalyst. The present invention relates to a method for producing an azaporphyrin compound.
In the following structural formulas, R means a phenyl group substituted with a halogen at the ortho position or an unsubstituted naphthyl group.
一般式（３）で示される１，２−ジシアノエチレン化合物のシス体は、塩化亜鉛、塩化アルミニウムなどでは得られない。シス体を収率よく得るために、本発明では、酸性触媒として四塩化チタンを用い、塩基性触媒としてＮ−メチルモルホリンを用いる。
A cis isomer of the 1,2-dicyanoethylene compound represented by the general formula (3) cannot be obtained with zinc chloride, aluminum chloride or the like. In order to obtain a cis isomer with good yield, in the present invention, titanium tetrachloride is used as an acidic catalyst and N-methylmorpholine is used as a basic catalyst.
「特許文献２」の実施例では、いずれの場合もアシルアニドの３倍当量に相当する酸性触媒と、６倍当量に相当する塩基性触媒を使用している。
一般式（３）で示される１，２−ジシアノエチレン化合物のシス体の生成比率を高めるに、本発明ではアシルシアニドの１〜２．５倍当量に相当する量の四塩化チタンを使用し、アシルアニドの２．５〜４．５倍当量に相当する量Ｎ−メチルモルホリンを使用する。
因みに、アシルシアニド誘導体とモノハロゲノアセトニトリルとの脱水縮合反応により下記の様な１，２−ジシアノエチレン化合物のシス体を得ようとする場合には、四塩化チタンやＮ−メチルモルホリンの使用量を変えてもシス体、トランス体の生成比率は殆ど変わらず、テトラアザポルフィリン化合物の製造に有効なシス体の生成比率は極めて低い。In the examples of “Patent Document 2”, in each case, an acidic catalyst corresponding to 3 times equivalent of an acyl anide and a basic catalyst corresponding to 6 times equivalent are used.
In order to increase the production ratio of the cis isomer of the 1,2-dicyanoethylene compound represented by the general formula (3), in the present invention, an amount of titanium tetrachloride corresponding to 1 to 2.5 times equivalent of acyl cyanide is used. N-methylmorpholine is used in an amount corresponding to 2.5 to 4.5 times the equivalent of.
By the way, when trying to obtain a cis isomer of 1,2-dicyanoethylene compound as shown below by dehydration condensation reaction of acyl cyanide derivative and monohalogenoacetonitrile, the amount of titanium tetrachloride or N-methylmorpholine used is changed. However, the production ratio of the cis isomer and the trans isomer is hardly changed, and the production ratio of the cis isomer effective for the production of the tetraazaporphyrin compound is extremely low.
目的とするテトラアザポルフィリン化合物は、前記シス体、又はシス体／トランス体混合物と金属又は金属誘導体とをアルコール系溶媒中で有機塩基共存下で加熱反応することにより得ることが出来る。
上記の反応により得られるテトラアザポルフイリン化合物には、理論的に次の（４−１）〜（４−４）式で示される４種の異性体が存在する。
The target tetraazaporphyrin compound can be obtained by subjecting the cis isomer or cis isomer / trans isomer mixture and a metal or metal derivative to a heat reaction in the presence of an organic base in an alcohol solvent.
In the tetraazaporphyrin compound obtained by the above reaction, there are theoretically four kinds of isomers represented by the following formulas (4-1) to (4-4).
本発明によれば、１，２−ジシアノエチレン化合物に占めるシス体の比率を格段に大きくすることができ、ひいては最終目的物であるテトラアザポルフィリン化合物を収率よく得ることができる。 According to the present invention, the ratio of the cis isomer to the 1,2-dicyanoethylene compound can be remarkably increased, and as a result, the tetraazaporphyrin compound, which is the final target product, can be obtained with high yield.
１，２−ジシアノエチレン化合物に占めるシス体の比率は、前記したアシルシアニドに対する四塩化チタンの使用量とＮ−メチルモルホリンの使用量が少なければ少ないほど大きくなる傾向にある。しかしながら、これらの使用量が少なくなると反応が進まず、未反応物が増加してくるため、ひいては最終目的物の収率が悪くなる。
四塩化チタンの更に望ましい使用量は、前記したアシルシアニドの１．５〜２倍当量に相当する量であり、Ｎ−メチルモルホリン更に望ましい使用量は、前記したアシルシアニドの２．８〜４倍当量に相当する量である。The ratio of the cis form in the 1,2-dicyanoethylene compound tends to increase as the amount of titanium tetrachloride and the amount of N-methylmorpholine used relative to the acyl cyanide decreases. However, when the amount of these used decreases, the reaction does not proceed and unreacted substances increase, resulting in a poor yield of the final target product.
The more desirable use amount of titanium tetrachloride is an amount corresponding to 1.5 to 2 equivalents of the above-described acyl cyanide, and the more desirable use amount of N-methylmorpholine is 2.8 to 4 equivalents of the aforementioned acyl cyanide. The corresponding amount.
撹拌機、冷却管、温度計、及び滴下ロートを取り付けた四ツ口反応フラスコにジクロロメタン３００ｍｌと四塩化チタン２８．４ｇ（０．１５０ｍｏｌ）を仕込み、この混合物を氷／メタノール／食塩浴中で０℃以下に冷却した。ここに、ピバロイルシアニド１１．１ｇ（０．１００ｍｏｌ）を０℃以下で滴下し、続いて２−フルオロベンジルシアニド１３．５ｇ（０．１００ｍｏｌ）を０℃以下で滴下した。次いで、Ｎ−メチルモルホリン３０．３ｇ（０．３００ｍｏｌ）を発熱に注意しながら０℃以下で滴下した。滴下終了後、冷却浴を取り去り、混合物の温度を室温に戻して１５時間撹拌した。反応混合物を氷水３５０ｍｌで希釈して、この希釈液を３０分撹拌した。しばらく静置後、ジクロロメタン層を分取してこれを水洗、無水硫酸マグネシウムで脱水乾燥後、ヘキサン１００ｍｌと活性白土４５ｇを加えて３０分撹拌し、ろ過、ろ液より溶媒を減圧留去して粗製の化合物（ａ）をそのトランス体との混合物として２１．７ｇ得た。 A four-necked reaction flask equipped with a stirrer, a condenser, a thermometer, and a dropping funnel was charged with 300 ml of dichloromethane and 28.4 g (0.150 mol) of titanium tetrachloride, and this mixture was washed in an ice / methanol / saline bath. Cooled below ℃. Here, 11.1 g (0.100 mol) of pivaloyl cyanide was added dropwise at 0 ° C. or less, and then 13.5 g (0.100 mol) of 2-fluorobenzyl cyanide was added dropwise at 0 ° C. or less. Next, 30.3 g (0.300 mol) of N-methylmorpholine was added dropwise at 0 ° C. or less while paying attention to heat generation. After completion of the dropwise addition, the cooling bath was removed, and the temperature of the mixture was returned to room temperature and stirred for 15 hours. The reaction mixture was diluted with 350 ml of ice water and the diluted solution was stirred for 30 minutes. After standing for a while, the dichloromethane layer was separated, washed with water, dehydrated and dried over anhydrous magnesium sulfate, 100 ml of hexane and 45 g of activated clay were added and stirred for 30 minutes, filtered, and the solvent was distilled off from the filtrate under reduced pressure. 21.7 g of crude compound (a) was obtained as a mixture with its trans isomer.
得られた粗生成物をＧＣ測定した結果、それぞれの異性体の占めるクロマトグラフ上のピーク面積比はシス体７３．８％、トランス体１５．３％であった。これをトルエン／ヘキサン＝１／１を溶離液としたシリカゲルカラムクロマトグラフィーにより精製を行い化合物（ａ）を１６．０ｇ（収率７０．２％）得た。ｍｐ：１０１〜１０２℃。ＭＳ：Ｍ＋＝２２８（分子イオン）。１Ｈ−ＮＭＲ（３００ＭＨｚ，ＣＤＣｌ３）：δ１．１５ｐｐｍ（ｓ，９Ｈ），δ７．１４〜７．２９（ｍ，３Ｈ），δ７．４４〜７．５３（ｍ，１Ｈ）。As a result of GC measurement of the obtained crude product, the peak area ratio on the chromatograph occupied by each isomer was 73.8% cis isomer and 15.3% trans isomer. This was purified by silica gel column chromatography using toluene / hexane = 1/1 as an eluent to obtain 16.0 g of compound (a) (yield: 70.2%). mp: 101-102 ° C. MS: M <+> = 228 (molecular ion). 1 H-NMR (300 MHz, CDCl 3 ): δ 1.15 ppm (s, 9H), δ 7.14-7.29 (m, 3H), δ 7.44-7.53 (m, 1H).
反応条件、及び後処理条件を全て実施例１と同様に行い、粗製の化合物（ａ）をそのトランス体との混合物として２１．８ｇ得た。得られた粗生成物をＧＣ測定した結果、それぞれの異性体の占めるクロマトグラフ上のピーク面積比はシス体７３．５％、トランス体１５．５％であった。これをエタノール２７ｍｌに加熱溶解し、この溶液を徐々に０℃まで冷却して、この温度で３０分撹拌した。晶析物をろ集し、冷エタノールで洗浄、５０℃で乾燥して化合物（ａ）を１２．５ｇ（収率５５．０％）得た。ＧＣ測定の結果、クロマトグラフ上で占める面積比は９８％であった。 Reaction conditions and post-treatment conditions were all carried out in the same manner as in Example 1 to obtain 21.8 g of the crude compound (a) as a mixture with its trans isomer. As a result of GC measurement of the obtained crude product, the peak area ratio on the chromatograph occupied by each isomer was 73.5% cis isomer and 15.5% trans isomer. This was dissolved by heating in 27 ml of ethanol, and the solution was gradually cooled to 0 ° C. and stirred at this temperature for 30 minutes. The crystallized product was collected by filtration, washed with cold ethanol, and dried at 50 ° C. to obtain 12.5 g (yield 55.0%) of compound (a). As a result of GC measurement, the area ratio occupied on the chromatograph was 98%.
撹拌機、冷却管、温度計、及び滴下ロートを取り付けた四ツ口反応フラスコにジクロロメタン３００ｍｌと四塩化チタン３７．９ｇ（０．２００ｍｏｌ）を仕込み、この混合物を氷／メタノール／食塩浴中で０℃以下に冷却した。ここに、ピバロイルシアニド１１．１ｇ（０．１００ｍｏｌ）を０℃以下で滴下し、続いて２−フルオロベンジルシアニド１３．５ｇ（０．１００ｍｏｌ）を０℃以下で滴下した。次いで、Ｎ−メチルモルホリン４０．４ｇ（０．４００ｍｏｌ）を発熱に注意しながら０℃以下で滴下した。滴下終了後、実施例１と同様の操作を施して粗製の化合物（ａ）をそのトランス体との混合物として２１．８ｇ得た。 A four-necked reaction flask equipped with a stirrer, a condenser, a thermometer, and a dropping funnel was charged with 300 ml of dichloromethane and 37.9 g (0.200 mol) of titanium tetrachloride, and this mixture was washed in an ice / methanol / saline bath. Cooled below ℃. Here, 11.1 g (0.100 mol) of pivaloyl cyanide was added dropwise at 0 ° C. or less, and then 13.5 g (0.100 mol) of 2-fluorobenzyl cyanide was added dropwise at 0 ° C. or less. Next, 40.4 g (0.400 mol) of N-methylmorpholine was added dropwise at 0 ° C. or less while paying attention to heat generation. After completion of the dropwise addition, the same operation as in Example 1 was performed to obtain 21.8 g of a crude compound (a) as a mixture with its trans isomer.
得られた粗生成物をＧＣ測定した結果、それぞれの異性体の占めるクロマトグラフ上のピーク面積比はシス体７２．５％、トランス体１７．６％であった。トルエン／ヘキサン＝１／１を溶離液としたシリカゲルカラムクロマトグラフィーにより精製を行い化合物（ａ）を１４．９ｇ（収率６５．３％）得た。 As a result of GC measurement of the obtained crude product, the peak area ratio on the chromatograph occupied by each isomer was cis isomer 72.5% and trans isomer 17.6%. Purification was performed by silica gel column chromatography using toluene / hexane = 1/1 as an eluent to obtain 14.9 g (yield: 65.3%) of compound (a).
撹拌機、冷却管、温度計、及び滴下ロートを取り付けた四ツ口反応フラスコにジクロロメタン３００ｍｌと四塩化チタン２８．４ｇ（０．１５０ｍｏｌ）を仕込み、この混合物を氷／メタノール／食塩浴中で０℃以下に冷却した。ここに、ピバロイルシアニド１１．１ｇ（０．１００ｍｏｌ）を０℃以下で滴下し、続いて２−クロロベンジルシアニド１５．２ｇ（０．１００ｍｏｌ）を０℃以下で滴下した。次いで、Ｎ−メチルモルホリン３０．３ｇ（０．３００ｍｏｌ）を発熱に注意しながら０℃以下で滴下した。滴下終了後、冷却浴を取り去り、混合物の温度を室温に戻して１２時間撹拌した。反応混合物を氷水３５ｏｍｌで希釈して、この希釈液を３０分撹拌した。しばらく静置後、ジクロロメタン層を分取してこれを水洗、無水硫酸マグネシウムで脱水乾燥後、ヘキサン１００ｍｌと活性白土４５ｇを加えて３０分撹拌し、ろ過、ろ液より溶媒を減圧留去して化合物（ｂ）をそのトランス体との混合物として２２．０ｇ得た。 A four-necked reaction flask equipped with a stirrer, a condenser, a thermometer, and a dropping funnel was charged with 300 ml of dichloromethane and 28.4 g (0.150 mol) of titanium tetrachloride, and this mixture was washed in an ice / methanol / saline bath. Cooled below ℃. Here, 11.1 g (0.100 mol) of pivaloyl cyanide was added dropwise at 0 ° C. or less, and then 15.2 g (0.100 mol) of 2-chlorobenzyl cyanide was added dropwise at 0 ° C. or less. Next, 30.3 g (0.300 mol) of N-methylmorpholine was added dropwise at 0 ° C. or less while paying attention to heat generation. After completion of the dropwise addition, the cooling bath was removed, and the temperature of the mixture was returned to room temperature and stirred for 12 hours. The reaction mixture was diluted with 35 ml of ice water and the dilution was stirred for 30 minutes. After standing for a while, the dichloromethane layer was separated, washed with water, dehydrated and dried over anhydrous magnesium sulfate, 100 ml of hexane and 45 g of activated clay were added and stirred for 30 minutes, filtered, and the solvent was distilled off from the filtrate under reduced pressure. 22.0 g of compound (b) was obtained as a mixture with its trans isomer.
得られた粗生成物をＧＣ測定した結果、それぞれの異性体の占めるクロマトグラフ上のピーク面積比はシス体７７．２％、トランス体１８．３％であった。これをトルエン／ヘキサン＝１／１を溶離液としたシリカゲルカラムクロマトグラフィーにより精製を行い化合物（ａ）を１７．６ｇ（収率７２．０％）得た。ＭＳ：Ｍ＋＝２４４（分子イオン）。As a result of GC measurement of the obtained crude product, the peak area ratio on the chromatograph occupied by each isomer was 77.2% cis isomer and 18.3% trans isomer. This was purified by silica gel column chromatography using toluene / hexane = 1/1 as an eluent to obtain 17.6 g of compound (a) (yield 72.0%). MS: M + = 244 (molecular ion).
撹拌機、冷却管、温度計、及び滴下ロートを取り付けた四ツ口反応フラスコにジクロロメタン３００ｍｌと四塩化チタン２８．４ｇ（０．１５０ｍｏｌ）を仕込み、この混合物を氷／メタノール／食塩浴中で０℃以下に冷却した。ここに、ピバロイルシアニド１１．１ｇ（０．１００ｍｏｌ）を０℃以下で滴下し、続いて１−ナフチルアセトニトリル１６．７ｇ（０．１００ｍｏｌ）を０℃以下で滴下した。次いで、Ｎ−メチルモルホリン３０．３ｇ（０．３００ｍｏｌ）を発熱に注意しながら０℃以下で滴下した。滴下終了後、冷却浴を取り去り、混合物の温度を室温に戻して１４時間撹拌した。反応混合物を氷水３５０ｍｌで希釈して、この希釈液を３０分撹拌した。しばらく静置後、ジクロロメタン層を分取してこれを水洗、無水硫酸マグネシウムで脱水乾燥後、トルエン１００ｍｌと活性白土４５ｇを加えて３０分撹拌し、ろ過、ろ液より溶媒を減圧留去して粗製の化合物（ｃ）をそのトランス体との混合物として２４．７ｇ得た。 A four-necked reaction flask equipped with a stirrer, a condenser, a thermometer, and a dropping funnel was charged with 300 ml of dichloromethane and 28.4 g (0.150 mol) of titanium tetrachloride, and this mixture was washed in an ice / methanol / saline bath. Cooled below ℃. Here, 11.1 g (0.100 mol) of pivaloyl cyanide was added dropwise at 0 ° C. or lower, and then 16.7 g (0.100 mol) of 1-naphthylacetonitrile was added dropwise at 0 ° C. or lower. Next, 30.3 g (0.300 mol) of N-methylmorpholine was added dropwise at 0 ° C. or less while paying attention to heat generation. After completion of the dropwise addition, the cooling bath was removed, and the temperature of the mixture was returned to room temperature and stirred for 14 hours. The reaction mixture was diluted with 350 ml of ice water and the diluted solution was stirred for 30 minutes. After standing for a while, the dichloromethane layer was separated, washed with water, dehydrated and dried over anhydrous magnesium sulfate, 100 ml of toluene and 45 g of activated clay were added, stirred for 30 minutes, filtered, and the solvent was distilled off from the filtrate under reduced pressure. 24.7 g of crude compound (c) was obtained as a mixture with its trans isomer.
得られた粗生成物をＧＣ測定した結果、それぞれの異性体の占めるクロマトグラフ上のピーク面積比はシス体７０．０％、トランス体１３．３％であった。これをトルエン／ヘキサン＝１／１を溶離液としたシリカゲルカラムクロマトグラフィーにより精製を行い化合物（ｃ）を１８．７ｇ（収率７２．０％）得た。ＭＳ：Ｍ＋＝２６０（分子イオン）。As a result of GC measurement of the obtained crude product, the peak area ratio on the chromatograph occupied by each isomer was 70.0% cis isomer and 13.3% trans isomer. This was purified by silica gel column chromatography using toluene / hexane = 1/1 as an eluent to obtain 18.7 g (yield 72.0%) of compound (c). MS: M + = 260 (molecular ion).
撹拌機、冷却管、温度計を取り付けた四ツ口反応フラスコに化合物（ａ）２．２８ｇ（０．０１００ｍｏｌ）、塩化銅（Ｉ）０．３３ｇ（０．００３３ｍｏｌ）、及び１−ペンタノール３０ｍｌを仕込み、この混合物を窒素気流下で１００℃に昇温し、この温度でＤＢＵ１．５２ｇ（０．０１００ｍｏｌ）を３０分かけて滴下した。滴下終了後、この混合物を１２５℃に昇温して、この温度で窒素気流下８時間撹拌した。放冷後、反応混合物をメタノール１００ｍｌで希釈して、この希釈液に撹拌下で水５０ｍｌを滴下して色素を晶析させた。これをろ集、メタノール／水＝２／１で洗浄後、１００℃で乾燥して２．０１ｇの青紫色結晶を得た。これをヘキサン／トルエン＝１０／１〜１／１を溶離液としたシリカゲルカラムクロマトグラフィーにより精製して色素（ａ）−１〜（ａ）−４の混合物を１．４６ｇ（収率６０．０％）得た。この４種の異性体混合物のクロロホルム中でのλｍａｘは５９３．５ｎｍ、モル吸光係数εは１３５０００であった。 In a four-necked reaction flask equipped with a stirrer, a condenser, and a thermometer, compound (a) 2.28 g (0.0100 mol), copper (I) chloride 0.33 g (0.0033 mol), and 1-pentanol 30 ml The mixture was heated to 100 ° C. under a nitrogen stream, and 1.52 g (0.0100 mol) of DBU was added dropwise at this temperature over 30 minutes. After completion of dropping, the mixture was heated to 125 ° C. and stirred at this temperature for 8 hours under a nitrogen stream. After allowing to cool, the reaction mixture was diluted with 100 ml of methanol, and 50 ml of water was added dropwise to the diluted solution with stirring to crystallize the dye. This was collected by filtration, washed with methanol / water = 2/1, and dried at 100 ° C. to obtain 2.01 g of blue-violet crystals. This was purified by silica gel column chromatography using hexane / toluene = 10/1 to 1/1 as an eluent to obtain 1.46 g (yield 60.0) of a mixture of dyes (a) -1 to (a) -4. %)Obtained. Λmax of these four isomer mixtures in chloroform was 593.5 nm, and molar extinction coefficient ε was 135000.
撹拌機、冷却管、温度計を取り付けた四ツ口反応フラスコに化合物（ｂ）２．４４ｇ（０．０１００ｍｏｌ）、塩化銅（Ｉ）０．３３ｇ（０．００３３ｍｏｌ）、及び１−ペンタノール３０ｍｌを仕込み、この混合物を窒素気流下で１００℃に昇温し、この温度でＤＢＵ１．５２ｇ（０．０１００ｍｏｌ）を３０分かけて滴下した。滴下終了後、この混合物を１２５℃に昇温して、この温度で窒素気流下７時間撹拌した。放冷後、反応混合物をメタノール１００ｍｌで希釈して、この希釈液に撹拌下で水３０ｍｌを滴下して色素を晶析させた。これをろ集、メタノール／水＝３／１で洗浄後、１００℃で乾燥して２．０３ｇの青紫色結晶を得た。これをヘキサン／トルエン＝１０／１〜１／１を溶離液としたシリカゲルカラムクロマトグラフィーにより精製して色素（ｂ）−１〜（ｂ）−４の混合物を１．５１ｇ（収率５８．０％）得た。この４種の異性体混合物のクロロホルム中でのλｍａｘは５９３．５ｎｍ、モル吸光係数εは１２４０００であった。 In a four-necked reaction flask equipped with a stirrer, a condenser, and a thermometer, 2.44 g (0.0100 mol) of compound (b), 0.33 g (0.0033 mol) of copper (I) chloride, and 30 ml of 1-pentanol. The mixture was heated to 100 ° C. under a nitrogen stream, and 1.52 g (0.0100 mol) of DBU was added dropwise at this temperature over 30 minutes. After completion of the dropwise addition, the mixture was heated to 125 ° C. and stirred at this temperature for 7 hours under a nitrogen stream. After allowing to cool, the reaction mixture was diluted with 100 ml of methanol, and 30 ml of water was added dropwise to the diluted solution with stirring to crystallize the dye. This was collected by filtration, washed with methanol / water = 3/1, and dried at 100 ° C. to obtain 2.03 g of blue-violet crystals. This was purified by silica gel column chromatography using hexane / toluene = 10/1 to 1/1 as an eluent to obtain 1.51 g of a mixture of dyes (b) -1 to (b) -4 (yield 58.0). %)Obtained. Λmax in chloroform of this mixture of four isomers was 593.5 nm, and the molar extinction coefficient ε was 124000.
撹拌機、冷却管、温度計を取り付けた四ツ口反応フラスコに化合物（ｃ）３．００ｇ（０．０１１５ｍｏｌ）、ホルムアミド１．０４ｇ（０．０２３０ｍｏｌ）、三塩化バナジウム０．７２ｇ（０．００４６ｍｏｌ）、及び１−ペンタノール２５ｍｌを仕込み、この混合物を窒素気流下で７５℃に昇温し、この温度でＤＢＵ１．４０ｇ（０．００９２０ｍｏｌ）を４５分かけて滴下した。滴下終了後、この混合物を１２０℃に昇温して、この温度で窒素気流下１８時間撹拌した。放冷後、反応混合物をメタノール１００ｍｌで希釈して、この希釈液に撹拌下で水１５ｍｌを滴下して色素を晶析させた。これをろ集、メタノール／水＝３／１で洗浄後、１００℃で乾燥して２．４０ｇの青色結晶を得た。これをヘキサン／トルエン＝５／１〜１／１を溶離液としたシリカゲルカラムクロマトグラフィーにより精製して色素（ｃ）−１〜（ｃ）−４の混合物を１．９３ｇ（収率６０．６％）得た。この４種の異性体混合物のクロロホルム中でのλｍａｘは６０９．０ｎｍ、モル吸光係数εは１３１０００であった。 Compound (c) 3.00 g (0.0115 mol), formamide 1.04 g (0.0230 mol), vanadium trichloride 0.72 g (0.0046 mol) in a four-necked reaction flask equipped with a stirrer, condenser, and thermometer ) And 25 ml of 1-pentanol, the mixture was heated to 75 ° C. under a nitrogen stream, and 1.40 g (0.00920 mol) of DBU was added dropwise at this temperature over 45 minutes. After completion of the dropwise addition, the mixture was heated to 120 ° C. and stirred at this temperature for 18 hours under a nitrogen stream. After allowing to cool, the reaction mixture was diluted with 100 ml of methanol, and 15 ml of water was added dropwise to the diluted solution with stirring to crystallize the dye. This was collected by filtration, washed with methanol / water = 3/1, and then dried at 100 ° C. to obtain 2.40 g of blue crystals. This was purified by silica gel column chromatography using hexane / toluene = 5/1 to 1/1 as an eluent to obtain 1.93 g of a mixture of dyes (c) -1 to (c) -4 (yield 60.6). %)Obtained. Λmax of this four isomer mixture in chloroform was 609.0 nm, and the molar extinction coefficient ε was 131000.
撹拌機、冷却管、温度計、及び滴下ロートを取り付けた四ツ口反応フラスコにジクロロメタン３００ｍｌと四塩化チタン５６．９ｇ（０．３００ｍｏｌ）を仕込み、この混合物を氷／メタノール／食塩浴中で０℃以下に冷却した。ここに、ピバロイルシアニド１１．１ｇ（０．１００ｍｏｌ）を０℃以下で滴下し、続いて２−フルオロベンジルシアニド１３．５ｇ（０．１００ｍｏｌ）を０℃以下で滴下した。次いで、Ｎ−メチルモルホリン６０．７ｇ（０．６００ｍｏｌ）を発熱に注意しながら０℃以下で滴下した。滴下終了後、冷却浴を取り去り、混合物の温度を室温に戻して１６時間撹拌した。反応混合物を氷水３５０ｍｌで希釈して、この希釈液を３０分撹拌した。しばらく静置後、ジクロロメタン層を分取してこれを水洗、無水硫酸マグネシウムで脱水乾燥後、ヘキサン１００ｍｌと活性白土４５ｇを加えて３０分撹拌し、ろ過、ろ液より溶媒を減圧留去して粗製の化合物（ａ）をそのトランス体との混合物として２１．１ｇ得た。 A four-necked reaction flask equipped with a stirrer, a condenser, a thermometer, and a dropping funnel was charged with 300 ml of dichloromethane and 56.9 g (0.300 mol) of titanium tetrachloride, and this mixture was charged in an ice / methanol / saline bath. Cooled below ℃. Here, 11.1 g (0.100 mol) of pivaloyl cyanide was added dropwise at 0 ° C. or less, and then 13.5 g (0.100 mol) of 2-fluorobenzyl cyanide was added dropwise at 0 ° C. or less. Next, 60.7 g (0.600 mol) of N-methylmorpholine was added dropwise at 0 ° C. or less while paying attention to heat generation. After completion of the dropwise addition, the cooling bath was removed, and the temperature of the mixture was returned to room temperature and stirred for 16 hours. The reaction mixture was diluted with 350 ml of ice water and the diluted solution was stirred for 30 minutes. After standing for a while, the dichloromethane layer was separated, washed with water, dehydrated and dried over anhydrous magnesium sulfate, 100 ml of hexane and 45 g of activated clay were added, and the mixture was stirred for 30 minutes, filtered, and the solvent was distilled off from the filtrate under reduced pressure. 21.1 g of crude compound (a) was obtained as a mixture with its trans isomer.
得られた粗生成物をＧＣ測定した結果、それぞれの異性体の占めるクロマトグラフ上のピーク面積比はシス体４５．０％、トランス体３５．３％であった。これをトルエン／ヘキサン＝１／１を溶離液としたシリカゲルカラムクロマトグラフィーにより精製を行い化合物（ａ）を９．７１ｇ（収率４２．６％）得た。 As a result of GC measurement of the obtained crude product, the peak area ratio on the chromatograph occupied by each isomer was cis isomer 45.0% and trans isomer 35.3%. This was purified by silica gel column chromatography using toluene / hexane = 1/1 as an eluent to obtain 9.71 g (yield 42.6%) of compound (a).
Claims (2)
以下の構造式において、Ｒはオルト位にハロゲンが置換したフェニル基又は無置換のナフチル基を意味する。
In the following structural formulas, R means a phenyl group substituted with a halogen at the ortho position or an unsubstituted naphthyl group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005322814A JP5097928B2 (en) | 2005-10-07 | 2005-10-07 | Method for producing tetraazaporphyrin compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005322814A JP5097928B2 (en) | 2005-10-07 | 2005-10-07 | Method for producing tetraazaporphyrin compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2007099744A true JP2007099744A (en) | 2007-04-19 |
| JP5097928B2 JP5097928B2 (en) | 2012-12-12 |
Family
ID=38027024
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005322814A Active JP5097928B2 (en) | 2005-10-07 | 2005-10-07 | Method for producing tetraazaporphyrin compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5097928B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1977958A2 (en) | 2007-04-05 | 2008-10-08 | Nissan Motor Co., Ltd. | Vehicle body structure |
| WO2012020570A1 (en) | 2010-08-12 | 2012-02-16 | 三井化学株式会社 | Plastic polarizing lens, method for producing same, and polarizing film |
| JP2014130249A (en) * | 2012-12-28 | 2014-07-10 | Yamada Chem Co Ltd | Color correction filter, illumination device and display device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1111015A (en) * | 1997-06-20 | 1999-01-19 | Mitsui Chem Inc | Optical recording medium |
| JPH1143619A (en) * | 1997-07-25 | 1999-02-16 | Ricoh Co Ltd | Tetraazaporphyrin compound, its precursor and their production |
-
2005
- 2005-10-07 JP JP2005322814A patent/JP5097928B2/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1111015A (en) * | 1997-06-20 | 1999-01-19 | Mitsui Chem Inc | Optical recording medium |
| JPH1143619A (en) * | 1997-07-25 | 1999-02-16 | Ricoh Co Ltd | Tetraazaporphyrin compound, its precursor and their production |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1977958A2 (en) | 2007-04-05 | 2008-10-08 | Nissan Motor Co., Ltd. | Vehicle body structure |
| WO2012020570A1 (en) | 2010-08-12 | 2012-02-16 | 三井化学株式会社 | Plastic polarizing lens, method for producing same, and polarizing film |
| JP2014130249A (en) * | 2012-12-28 | 2014-07-10 | Yamada Chem Co Ltd | Color correction filter, illumination device and display device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5097928B2 (en) | 2012-12-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3202607B2 (en) | Method for producing 2- (4-alkoxy-3-cyanophenyl) thiazole derivative | |
| JP5208239B2 (en) | Novel production method of anticancer active tricyclic compounds by alkyne coupling | |
| CN111201212A (en) | Synthesis method of feloxicib and intermediate thereof | |
| JP5097928B2 (en) | Method for producing tetraazaporphyrin compound | |
| HU178354B (en) | Process for preparing 5-substituted 1,2-dihydro-3h-pyrrolo/1,2-a/-pyrrol-1-carboxylic acid derivatives from the corresponding nitriles | |
| WO2015097850A1 (en) | Method for producing benzyl ester 2-aminonicotinate derivative | |
| JP5288779B2 (en) | 2,3-dicyanonaphthalene derivative | |
| WO2004005276A1 (en) | Process for preparation of 1,3-benzodioxole-2-spiro- cycloalkane derivatives | |
| HU198200B (en) | Process for production of derivatives of quinoline carbonic acid | |
| JP2009132623A (en) | Method for producing 2,3-dicyanonaphthalene derivative | |
| CA3036642C (en) | Method for producing (r)-5-(3,4-difluorophenyl)-5-[(3-methyl-2-oxopyridin-1(2h)-yl)methyl]imidazolidin-2,4-dione and intermediate for producing same | |
| EP4006018B1 (en) | Method for synthesizing 2-((6-(hydroxymethyl)chromene-5-yl)oxy)-1-phenylethanone derivative | |
| CN113861121B (en) | Novel method for generating 2, 3-dihydroxyquinoxaline and derivatives thereof through direct oxidation | |
| JPH0525162A (en) | Quinolone derivative and its production | |
| JP3952670B2 (en) | Process for producing 2- (5-halogeno-2-nitrophenyl) -2-substituted acetate derivatives | |
| JPH02255673A (en) | 4-aryloxy-1,3-benzodioxoles and production thereof | |
| JP2004244362A (en) | Method for producing 1,2-disubstituted-1,4-dihydro-oxoquinoline derivative | |
| CN116947636A (en) | Preparation method of 2-acyl-4-oxo-butyrate derivative | |
| JP4449211B2 (en) | 6- (1-fluoroethyl) -5-iodo-4-pyrimidone and process for producing the same | |
| KR20230146461A (en) | METHOD FOR SYNTHESIZING 3-PHENYL-2,3,4,8,9,10-HEXAHYDROPYRANO[2,3-f]CHROMENE DERIVATIVES | |
| JP2001158774A (en) | Method for producing 6-trifluoromethylnicotinic acids | |
| JP2992033B2 (en) | Production intermediate of oxoquinoline carboxylic acid derivative | |
| WO1994006767A1 (en) | Optically active 1-phenylpyrrolidone derivative, intermediate for producing the same, and process for producing both | |
| JP6084569B2 (en) | Process for producing 3,4-dihydroisoquinoline derivatives and production intermediates thereof | |
| JP2021528440A (en) | Its use in the synthesis of compounds and intermediates and APIs of Brivaracetam |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20080326 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20081006 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120228 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120420 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20120807 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120821 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20151005 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5097928 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |