JP2911063B2 - Phthalocyanine derivative - Google Patents
Phthalocyanine derivativeInfo
- Publication number
- JP2911063B2 JP2911063B2 JP3096901A JP9690191A JP2911063B2 JP 2911063 B2 JP2911063 B2 JP 2911063B2 JP 3096901 A JP3096901 A JP 3096901A JP 9690191 A JP9690191 A JP 9690191A JP 2911063 B2 JP2911063 B2 JP 2911063B2
- Authority
- JP
- Japan
- Prior art keywords
- mol
- compound
- represented
- general formula
- reaction
- 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.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
- C09B47/062—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide having alkyl radicals linked directly to the Pc skeleton; having carboxylic groups directly linked to the skeleton, e.g. phenyl
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
- C09B47/063—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide having oxygen or sulfur atom(s) linked directly to the skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Furan Compounds (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Indole Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【０００１】[0001]
【産業上の利用分野】この発明は、顔料や機能性色素等
として有用なフタロシアニン誘導体に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phthalocyanine derivative useful as a pigment or a functional dye.
【０００２】[0002]
【従来の技術】フタロシアニン系化合物は、高い着色力
と強い色調を示すだけでなく、耐熱性、耐候性および堅
牢性等の点でも優れているので、各種の樹脂、塗料およ
びインキ等の顔料として多用されているが、フッ素系の
樹脂や塗料等に配合して使用する場合には、分散性が不
十分なために、塗布斑や染等の発生原因となっている。2. Description of the Related Art Phthalocyanine compounds not only exhibit high coloring power and strong color tone, but also have excellent heat resistance, weather resistance and fastness properties, and are therefore used as pigments for various resins, paints and inks. It is frequently used, but when it is used by mixing it with a fluorine-based resin or paint, the dispersibility is insufficient, which causes the occurrence of spots on coating and dyeing.
【０００３】[0003]
【発明の解決しようとする課題】この発明は、上記問題
を解決し、フッ素系の樹脂や塗料等に配合しても、優れ
た分散性を発揮する新規なフタロシアニン誘導体を提供
するためになされたものである。SUMMARY OF THE INVENTION The present invention has been made in order to solve the above problems and to provide a novel phthalocyanine derivative which exhibits excellent dispersibility even when blended in a fluorine-based resin or paint. Things.
【０００４】[0004]
【課題を解決するための手段】即ちこの発明は、一般式
(Ｉ):That is, the present invention provides a compound represented by the following general formula:
(I):
【化５】 (式中、Ｍは金属、金属酸化物、金属塩化物または水素
を示し、Ｘは−Ｏ−、−ＣＨ2−または−ＯＣＯ・Ｃ6Ｈ
4・Ｏ−を示し、nは３〜１２の数を示す)で表わされる
フタロシアニン誘導体に関する。Embedded image (Wherein, M represents a metal, metal oxide, metal chloride, or hydrogen, and X represents —O—, —CH 2 —, or —OCO · C 6 H
4 —O—, and n represents a number from 3 to 12).
【０００５】上記一般式(Ｉ)ににおいて、Ｍは例えばＣ
u、Ｚn、Ｃo、Ｎi、Ｆe、ＭnおよびＭg等、金属酸化
物、例えば、ＶＯ等、金属塩化物、例えば、ＡlＣl
3等、または水素を示し、Ｘは−Ｏ−、−ＣＨ2−または
−ＯＣＯ・Ｃ6Ｈ4・Ｏ−を示し、nは３〜１２、好まし
くは６〜１０の数を示す。In the above general formula (I), M is, for example, C
Metal oxides, such as u, Zn, Co, Ni, Fe, Mn and Mg, such as VO, metal chlorides, such as AlCl
3, etc., or a hydrogen, X is -O -, - CH 2 - or -OCO · C 6 H 4 · O- are shown, n represents 3 to 12, preferably is a number of 6-10.
【０００６】上記一般式(Ｉ)で表わされるフタロシアニ
ン誘導体の製造法は特に限定的ではないが、好適な製法
は、含フッ素基ＸＣnＦ2n±1(式中、Ｘおよびnは前記と
同意義である)を有するフタル酸無水物もしくは対応す
るフタルイミドと尿素もしくは対応するフタロニトリル
および金属塩、例えばＣuＣl2、ＺnＣl2、ＣoＣl2等と
加熱反応させる方法である。The method for producing the phthalocyanine derivative represented by the general formula (I) is not particularly limited, but a preferred method is a fluorinated group XCnF 2 n ± 1 (wherein X and n are as defined above) Phthalic anhydride or the corresponding phthalimide having urea or the corresponding phthalonitrile and a metal salt such as CuCl 2 , ZnCl 2 , CoCl 2 or the like.
【０００７】該含フッ素基を有するフタル酸無水物もし
くは対応するフタルイミドと尿素および金属塩は、通常
は、モル比４:４:１の割合で、反応溶媒を使用しない場
合には、２２０〜３００℃、特に２５０〜２９０℃、対
応するフタロニトリルと金属塩は通常はモル比４:１の
割合で１２０℃〜２２０℃、特に１５０℃〜２００℃、
反応溶媒、例えば、Ｎ,Ｎ−ジメチルホルムアミド、Ｎ,
Ｎ−ジメチルアセトアミド、キノリンまたはニトロベン
ゼン等の非プロトン性極性高沸点溶媒を使用する場合に
は、反応系の沸点もしくは沸点付近の温度で反応させ
る。この場合、触媒、例えば、ホウ酸、モリブデン酸ア
ンモニウムまたは塩化アルミニウム等を使用してもよ
い。The phthalic anhydride having a fluorine-containing group or the corresponding phthalimide and urea and a metal salt are usually in a molar ratio of 4: 4: 1, and when no reaction solvent is used, 220 to 300 C., in particular 250 to 290.degree. C., the corresponding phthalonitrile and metal salt are usually in a molar ratio of 4: 1 at 120.degree. C. to 220.degree.
Reaction solvents, for example, N, N-dimethylformamide, N,
When an aprotic polar high-boiling solvent such as N-dimethylacetamide, quinoline or nitrobenzene is used, the reaction is carried out at or near the boiling point of the reaction system. In this case, a catalyst such as boric acid, ammonium molybdate or aluminum chloride may be used.
【０００８】上記の含フッ素基を有するフタル酸無水物
は、対応するフタル酸を約１５０〜２５０℃、好ましく
は１９０〜２２０℃において加熱脱水することによって
得られる。The above-mentioned phthalic anhydride having a fluorinated group can be obtained by heating and dehydrating the corresponding phthalic acid at about 150 to 250 ° C., preferably 190 to 220 ° C.
【０００９】例えば、一般式(ＩＩ):For example, the general formula (II):
【化６】 で表わされる含フッ素フタル酸無水物は、ジメチルベン
ジルハロゲン化物(例えば、３,４−ジメチルベンジルク
ロライドもしくはブロマイドまたは２,３−ジメチルベ
ンジルクロライドもしくはブロマイド等)およびパーフ
ルオロ−２−メチル−２−ペンテンを、アルカリ金属の
フッ化物(例えば、ＫＦ、ＮaＦ、ＲbＦまたはＣsＦ等)
およびヨウ化物(例えば、ＫＩ、ＮaＩ、ＲbＩまたはＣs
Ｉ等)の存在下において、非プロトン性極性溶媒(例え
ば、ヘキサメチルリン酸トリアミド、ジメチルスルホキ
シド、Ｎ,Ｎ−ジメチルアセトアミドおよびＮ−メチル
ピロリドン等)中、常圧下、室温〜８０℃で反応させて
得られる下記の一般式(Ｖ)Embedded image Are dimethylbenzyl halides (e.g., 3,4-dimethylbenzyl chloride or bromide or 2,3-dimethylbenzyl chloride or bromide) and perfluoro-2-methyl-2-pentene Is converted to an alkali metal fluoride (for example, KF, NaF, RbF or CsF, etc.)
And iodide (eg, KI, NaI, RbI or Cs
I) in an aprotic polar solvent (e.g., hexamethylphosphoric acid triamide, dimethyl sulfoxide, N, N-dimethylacetamide, N-methylpyrrolidone, etc.) under normal pressure at room temperature to 80 ° C. The following general formula (V) obtained by
【化７】 で表わされる化合物を、常法に従って、過マンガン酸カ
リウム、酸化クロムまたは重クロム酸カリウム等の酸化
剤を用い、溶媒(例えば、水−ピリジン混合溶媒)中にお
いて、５０〜１００℃で酸化し、得られた含フッ素フタ
ル酸を１５０〜２２０℃で加熱脱水することによって製
造される。Embedded image In a solvent (e.g., a mixed solvent of water and pyridine), the compound represented by is oxidized at 50 to 100 ° C using an oxidizing agent such as potassium permanganate, chromium oxide, or potassium dichromate according to a conventional method, It is manufactured by heating and dehydrating the obtained fluorinated phthalic acid at 150 to 220 ° C.
【００１０】上記製法において、ジメチルベンジルハロ
ゲン化物、パーフルオロ−２−メチル−２−ペンテン、
アルカリ金属のフッ化物およびアルカリ金属のヨウ化物
の反応割合は特に限定的ではないが、通常は、ジメチル
ベンジルハロゲン化物１モルあたり、パーフルオロ−２
−ペンテン１〜２モル、アルカリ金属のフッ化物１〜２
モルおよびアルカリ金属のヨウ化物０．０１〜０．１モ
ルである。In the above process, dimethylbenzyl halide, perfluoro-2-methyl-2-pentene,
Although the reaction ratio of the alkali metal fluoride and the alkali metal iodide is not particularly limited, usually, perfluoro-2 per mole of dimethylbenzyl halide is used.
Pentene 1-2 mol, alkali metal fluoride 1-2
Mol and 0.01 to 0.1 mol of an iodide of an alkali metal.
【００１１】上記の含フッ素基ＸＣnＦ2n±1を有するフ
タルイミドは、上述のようにして得られる対応する含フ
ッ素フタル酸もしくは含フッ素フタル酸無水物を、尿
素、アンモニアもしくは炭酸アンモニウム等と共に、１
４０〜２００℃、好ましくは１６０〜１８０℃で加熱す
ることによって製造される。この場合、反応成分の割合
は、含フッ素フタル酸無水物等１モルに対して、尿素等
１〜４モルが好ましく、また、反応溶媒は通常は不要で
ある。The above-mentioned phthalimide having a fluorinated group XCnF 2 n ± 1 can be obtained by adding the corresponding fluorinated phthalic acid or phthalic anhydride obtained as described above together with urea, ammonia or ammonium carbonate to one phthalimide.
It is manufactured by heating at 40 to 200 ° C, preferably 160 to 180 ° C. In this case, the ratio of the reaction components is preferably 1 to 4 moles of urea and the like per 1 mole of the fluorinated phthalic anhydride and the like, and the reaction solvent is usually unnecessary.
【００１２】例えば、一般式(ＩＩＩ）：For example, the general formula (III):
【化８】 で表わされるパーフルオロノネニルオキシフタルイミド
は、上述の製法に準拠して得られるパーフルオロノネニ
ルオキシフタル酸無水物を尿素、炭酸アンモニウムもし
くはアンモニアと共に、１５０〜２００℃、好ましくは
１６０〜１９０℃で加熱することによって製造される。
この場合、反応成分の割合は、該含フッ素フタル酸無水
物１モルに対して、尿素等１〜５モル、特に１〜３モル
が好ましい。Embedded image Perfluorononenyloxyphthalimide represented by, perfluorononenyloxyphthalic anhydride obtained in accordance with the above-mentioned production method together with urea, ammonium carbonate or ammonia at 150 to 200 ° C, preferably at 160 to 190 ° C. Manufactured by heating.
In this case, the proportion of the reaction component is preferably 1 to 5 mol, particularly 1 to 3 mol, such as urea, per 1 mol of the fluorinated phthalic anhydride.
【００１３】また、一般式（ＩＶ):Further, the general formula (IV):
【化９】 で表わされるパーフルオロノネニル基含有フタロニトリ
ルは、パーフルオロノネニルオキシ安息香酸(特開昭５
２−８９６３０号公報)クロリドとヒドロキシフタロニ
トリルを塩基性触媒の存在下、非プロトン性溶媒中で０
〜５０℃、特に１０〜３０℃で容易に得られる。塩基性
触媒としては、トリエチルアミン、トリメチルアミン、
ピリジン、Ｎ,Ｎ−ジメチルアニリン等が表わされる。
非プロトン性溶媒は、特に限定的ではない。Embedded image Is a phthalonitrile containing a perfluorononenyl group represented by the formula:
2-89630) Chloride and hydroxyphthalonitrile were dissolved in an aprotic solvent in the presence of a basic catalyst in an aprotic solvent.
It is easily obtained at ５０50 ° C., especially at 10-30 ° C. As the basic catalyst, triethylamine, trimethylamine,
Pyridine, N, N-dimethylaniline and the like are represented.
The aprotic solvent is not particularly limited.
【００１４】上記の一般式(ＩＩ)で表わされる含フッ素
フタル酸無水物、一般式(ＩＩＩ)で表わされる含フッ素
フタルイミドおよび一般式(ＩＶ)で表わされる含フッ素
フタロニトリルは、一般式(Ｉ)で表わされるフタロシア
ニン誘導体の中間体として有用な新規化合物であり、こ
れらの化合物も本発明に包含されるものである。なお、
含フッ素フタル酸無水物(ＩＩ)は、吸水性および吸湿性
の低いエポキシ樹脂用硬化剤としても有用である。The fluorinated phthalic anhydride represented by the general formula (II), the fluorinated phthalimide represented by the general formula (III) and the fluorinated phthalonitrile represented by the general formula (IV) are represented by the general formula (I) )) Are novel compounds useful as intermediates of the phthalocyanine derivative represented by formula (1), and these compounds are also included in the present invention. In addition,
Fluorinated phthalic anhydride (II) is also useful as a curing agent for epoxy resins having low water absorption and low moisture absorption.
【００１５】[0015]
【実施例】以下、本発明を実施例によって説明する。実施例１ 撹拌器、加熱装置および温度計を備えた反応容器内に
４−パーフルオロノネニルオキシ−フタル酸無水物２．
３８g(０．００４モル)、尿素０．２４g(０．００４モ
ル)、ＣuＣl2０．１４g(０．００１モル)を入れ、２７
０℃にて撹拌反応を約２時間行なった。室温まで冷却
後、アセトン２０mlで２回洗浄し、未反応物を除去した
後、フロン１１３を用いて溶解し、不溶分を濾別し、フ
ロン１１３を留去することにより、化合物(Ｉa)を０．
４１g(収率１７％)得た。化合物(Ｉa)の物性を以下の表
１に示す。The present invention will be described below with reference to examples.Example 1 In a reaction vessel equipped with stirrer, heating device and thermometer
1. 4-perfluorononenyloxy-phthalic anhydride
38 g (0.004 mol), urea 0.24 g (0.004 mol
), CuClTwo0.14 g (0.001 mol)
The stirring reaction was performed at 0 ° C. for about 2 hours. Cool to room temperature
Thereafter, washing was performed twice with 20 ml of acetone to remove unreacted substances.
Then, it is dissolved using Freon 113, and the insoluble matter is filtered off.
Compound (Ia) was converted to 0.1 by removing the Ron 113.
41 g (17% yield) were obtained. The physical properties of compound (Ia) are shown in the following table.
It is shown in FIG.
【化１０】 Embedded image
【００１６】実施例２ (１) 撹拌器、還流器、加熱装置および温度計を備え
た反応容器内に、４−パーフルオロノネニルオキシ−フ
タル酸無水物３２g(０．０５３モル)、尿素６．４g
(０．１０モル)を入れ、撹拌下、１７０℃に加熱反応を
行なった。反応は約２時間継続し、その後、１００mlの
水中に投入し、得られた固体を濾別、乾燥した。再結晶
は水／エタノールから行ない、淡黄色結晶の４−パーフ
ルオロノネニルオキシ−フタルイミド(ＩＩＩa)２９g
(収率９１％)得た。化合物(ＩＩＩa)の物性を以下の表
２に示す。[0016]Example 2 (1) Equipped with stirrer, reflux unit, heating device and thermometer
4-perfluorononenyloxy-phenyl
Talic anhydride 32g (0.053mol), urea 6.4g
(0.10 mol) and heated to 170 ° C under stirring.
Done. The reaction lasts about 2 hours, after which 100 ml
It was poured into water, and the obtained solid was separated by filtration and dried. Recrystallization
Is performed from water / ethanol, and 4-y
29 g of fluorononenyloxy-phthalimide (IIIa)
(Yield 91%). The physical properties of compound (IIIa) are shown in the following table.
It is shown in FIG.
【化１１】 Embedded image
【００１７】(２) 撹拌器、加熱装置および温度計を備
えた反応容器内に４−パーフルオロ−フタルイミド(Ｉ
ＩＩa)５．９３g(０．０１モル)、尿素０．６g(０．０
１モル)、ＣuＣl2０．３４g(０．００２５モル)を入れ
２９０℃で１時間撹拌反応を行ない、実施例１に準拠し
た方法で、化合物(Ｉa)を０．６４g得た(収率１１％)。(2) 4-Perfluoro-phthalimide (I) is placed in a reaction vessel equipped with a stirrer, a heating device and a thermometer.
IIa) 5.93 g (0.01 mol), urea 0.6 g (0.0 mol)
1 mol) and 0.34 g (0.0025 mol) of CuCl 2 were stirred and reacted at 290 ° C. for 1 hour, and 0.64 g of compound (Ia) was obtained in the same manner as in Example 1 (yield: 11). %).
【００１８】実施例３ 撹拌器、加熱装置および温度計を備えた反応容器内に
４−パーフルオロノネニルオキシ−フタル酸無水物２．
９７g(０．００５モル)、尿素０．３０g(０．００５モ
ル)、ＣuＣl2０．１７g(０．００１２５モル)、モリブ
デン酸アンモニウム０．０３gを入れ、２８０℃で１時
間撹拌反応を行ない、実施例１に準拠した方法で化合物
(Ｉa)を１．３４g(収率４５％)得た。[0018]Example 3 In a reaction vessel equipped with stirrer, heating device and thermometer
1. 4-perfluorononenyloxy-phthalic anhydride
97 g (0.005 mol), urea 0.30 g (0.005 mol
), CuClTwo0.17 g (0.00125 mol), molybdenum
Add 0.03 g of ammonium denate, 1 hour at 280 ° C
The mixture was stirred for a while, and the compound was prepared in the same manner as in Example 1.
1.34 g (yield 45%) of (Ia) was obtained.
【００１９】実施例４ 撹拌器、加熱装置および温度計を備えた反応容器内に
４−パーフルオロノネニルオキシ−フタル酸無水物２．
９７g(０．００５モル)、尿素０．３０g(０．００５モ
ル)、ＺnＣl2０．１７g(０．００１２５モル)、モリブ
デン酸アンモニウム０．０３gを入れ、２８０℃で１時
間撹拌反応を行ない、実施例１に準拠した方法で化合物
を０．７６g(収率２６％)得た。化合物(Ｉb)の物性を以
下の表１に示す。[0019]Example 4 In a reaction vessel equipped with stirrer, heating device and thermometer
1. 4-perfluorononenyloxy-phthalic anhydride
97 g (0.005 mol), urea 0.30 g (0.005 mol
), ZnClTwo0.17 g (0.00125 mol), molybdenum
Add 0.03 g of ammonium denate, 1 hour at 280 ° C
The mixture was stirred for a while, and the compound was prepared in the same manner as in Example 1.
0.76 g (yield 26%) was obtained. The physical properties of compound (Ib)
It is shown in Table 1 below.
【化１２】 Embedded image
【００２０】実施例５ (１) 撹拌器、還流器、加熱装置および温度計を備え
た反応容器内にパーフルオロ−２−メチル−２−ペンテ
ン２２５g(０．７５モル)、３,４−ジメチルベンジルク
ロライド７７．３g(０．５０モル)およびＮ,Ｎ−ジメチ
ルアセトアミド５００mlを入れ、次いで十分に乾燥した
ＫＦ５８g(１．０モル)、ＫＩ１６g(０．１０モル)を加
え撹拌下、７０℃で４８時間反応を行なった。反応混合
物を亜硫酸ナトリウム水溶液および水を用いて洗浄した
後、パーフルオロノネンおよびメタノールを用いて分液
し、パーフルオロノネン層を濃縮、蒸留の各処理を付す
ことによって化合物(Ｖa)を１６５g(収率７９％)得た。
化合物（Ｖa)の物性を以下の表３に示す。[0020]Example 5 (1) Equipped with stirrer, reflux unit, heating device and thermometer
Perfluoro-2-methyl-2-pentene
225 g (0.75 mol), 3,4-dimethylbenzyl
77.3 g (0.50 mol) of chloride and N, N-dimethyl
Add 500 ml of lucacetamide and then dry thoroughly
58 g (1.0 mol) of KF and 16 g (0.10 mol) of KI were added.
The reaction was carried out at 70 ° C. for 48 hours with stirring. Reaction mixing
Was washed with aqueous sodium sulfite and water
Then, liquid separation using perfluorononene and methanol
And concentrate the perfluorononene layer and apply distillation
As a result, 165 g (yield 79%) of compound (Va) was obtained.
Table 3 below shows the physical properties of the compound (Va).
【化１３】 Embedded image
【００２１】(２) 撹拌器、還流器、加熱装置および温
度計を備えた反応容器内に化合物(Ｖa)６６g(０．１５
モル)、水３０ml、ピリジン５００mlを入れ、撹拌下、
８０℃にて過マンガン酸カリウム１３０g(０．８２モ
ル)を約３時間かけて徐々に加えた後、５時間、加熱撹
拌を続けた。室温まで冷却後、２Ｎ−ＨＣl水溶液１lを
加えると白色固体が析出し、この白色固体を十分に水洗
し、乾燥後、化合物(Ｖa')を６１g(収率８２％)得た。
化合物(Ｖa')の物性を以下の表３に示す。(2) In a reaction vessel equipped with a stirrer, a reflux condenser, a heating device and a thermometer, 66 g (0.15 g) of the compound (Va) was placed.
Mol), 30 ml of water and 500 ml of pyridine.
At 80 ° C., 130 g (0.82 mol) of potassium permanganate was gradually added over about 3 hours, and then the heating and stirring were continued for 5 hours. After cooling to room temperature, 1 L of a 2N-HCl aqueous solution was added to precipitate a white solid. This white solid was sufficiently washed with water and dried to obtain 61 g (yield 82%) of a compound (Va ').
The physical properties of compound (Va ') are shown in Table 3 below.
【化１４】 Embedded image
【００２２】(３) 撹拌器、還流器、加熱装置および温
度計を備えた反応容器内に化合物(Ｖa')２．０８g(０．
００４２モル)を入れ、撹拌下、１９０℃、３０分間加
熱したのち、室温まで冷却すると白色固体が得られた。
この白色固体をn−ヘキサン２０mlを用いて再結晶し、
化合物(ＩＩa)を１．６２g得た(収率８０％)。化合物
(ＩＩa)の物性を以下の表３に示す。(3) In a reaction vessel equipped with a stirrer, a reflux condenser, a heating device and a thermometer, 2.08 g of compound (Va ') (0.
0042 mol), heated under stirring at 190 ° C. for 30 minutes, and then cooled to room temperature to obtain a white solid.
This white solid was recrystallized using 20 ml of n-hexane,
1.62 g of compound (IIa) was obtained (yield: 80%). Compound
The physical properties of (IIa) are shown in Table 3 below.
【化１５】 Embedded image
【００２３】(４) 撹拌器、加熱装置および温度計を備
えた反応容器内に化合物(ＩＩa)２．４０g(０．００５
モル)、尿素０．３０g(０．００５モル)、ＣuＣl2０．
１７g(０．００１２５モル)、モリブデン酸アンモニウ
ム０．０３gを入れ、２８０℃で１時間撹拌反応を行な
い、実施例１に準拠した方法で化合物(Ｉc)を０．２７g
(収率１１％)得た。化合物(Ｉc)の物性を以下の表１に
示す。(4) 2.40 g (0.005 g) of compound (IIa) was placed in a reaction vessel equipped with a stirrer, a heating device and a thermometer.
Mol), 0.30 g (0.005 mol) of urea, CuCl 2 0.
17 g (0.00125 mol) and 0.03 g of ammonium molybdate were added and stirred at 280 ° C. for 1 hour, and 0.27 g of compound (Ic) was obtained in the same manner as in Example 1.
(11% yield). Table 1 below shows the physical properties of the compound (Ic).
【化１６】 Embedded image
【００２４】実施例６ (１) 撹拌器、冷却管、滴下ロートおよび温度計を備
えた反応容器内に４−ヒドロキシフタロニトリル７．２
g(０．０５モル)、トリエチルアミン５．０５g(０．０
５モル)およびクロロホルム２００mlを入れ、撹拌下パ
ーフルオロノネニルオキシ安息香酸クロリド２９．３３
g(０．０５モル)を約２０分間で滴下した。撹拌反応を
約３時間継続した後、析出したトリエチルアミン塩酸塩
を濾別し、濾液を水２００mlで２回洗浄し、トリエチル
アミン塩酸塩を除去した。クロロホルム層を取り出し、
無水硫酸マグネシウムを用い、乾燥後、濾別し、濾液か
らクロロホルムを留去することにより、淡黄色固体を得
た。この固体をアセトン−n−ヘキサン１:１溶液で再結
晶することにより下記の式(ＩＶa)で表わされる白色結
晶化合物を２９．６g(収率８５．３％％)得た。化合物
(ＩＶa)の物性を以下の表４に示す。[0024]Example 6 (1) Equipped with stirrer, cooling pipe, dropping funnel and thermometer
4-Hydroxyphthalonitrile 7.2 in the reaction vessel obtained above.
g (0.05 mol), triethylamine 5.05 g (0.0
5 mol) and 200 ml of chloroform.
-Fluorononenyloxybenzoic acid chloride 29.33
g (0.05 mol) was added dropwise over about 20 minutes. Stirring reaction
After continuing for about 3 hours, the precipitated triethylamine hydrochloride
, And the filtrate was washed twice with 200 ml of water, and triethyl was added.
The amine hydrochloride was removed. Take out the chloroform layer,
After drying using anhydrous magnesium sulfate, the mixture is filtered off and the filtrate is dried.
Then, chloroform was distilled off to obtain a pale yellow solid.
Was. This solid was reconstituted with a 1: 1 solution of acetone-n-hexane.
By crystallizing, a white crystal represented by the following formula (IVa) is obtained.
29.6 g (yield 85.3 %%) of a crystalline compound was obtained. Compound
Table 4 below shows the physical properties of (IVa).
【化１７】 Embedded image
【００２５】(２) 撹拌器、加熱装置および温度計を備
えた反応容器内に化合物(ＩＶＡ)６．９４g(０．０１モ
ル)、ＣuＣl2０．３４g(０．００２５モル)を入れ、２
００℃で２時間撹拌反応を行ない、実施例１に準拠した
方法で下記の式(Ｉd)で表わされる化合物を１．４５g
(収率２０．４％)得た。化合物(Ｉd)の物性を表１に示
す。(2) In a reaction vessel equipped with a stirrer, a heating device and a thermometer, 6.94 g (0.01 mol) of the compound (IVA) and 0.34 g (0.0025 mol) of CuCl 2 were placed.
A stirring reaction was carried out at 00 ° C. for 2 hours, and 1.45 g of a compound represented by the following formula (Id) was obtained in the same manner as in Example 1.
(20.4% yield). Table 1 shows the physical properties of the compound (Id).
【化１８】 Embedded image
【００２６】[0026]
【表１】 [Table 1]
【００２７】[0027]
【表２】 [Table 2]
【００２８】[0028]
【表３】 [Table 3]
【００２９】[0029]
【表４】 [Table 4]
【００３０】[0030]
【発明の効果】本発明によるフタロシアニン誘導体は、
フッ素系の樹脂、塗料およびインキ等に配合しても十分
な分散性を示すと共に、フタロシアニン系化合物特有の
高い着色力と強い色調並びに優れた耐熱性、耐候性およ
び堅牢性等を発揮するので、これらの樹脂等の顔料とし
て有用なだけでなく、反応触媒および半導体や電子材料
等に対する機能性色素等としても有用である。The phthalocyanine derivative according to the present invention comprises:
As it shows sufficient dispersibility even when blended in fluorine-based resins, paints and inks, etc., it also exhibits high coloring power and strong color tone unique to phthalocyanine compounds and excellent heat resistance, weather resistance and robustness, etc. It is useful not only as a pigment for these resins and the like, but also as a functional catalyst for a reaction catalyst and semiconductor and electronic materials.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０９Ｂ 47/14 Ｃ０７Ｄ 209/48 Ｚ (72)発明者 矢野 興二 滋賀県甲賀郡甲西町大池町１番１ 株式 会社ネオス内 (56)参考文献 特開 昭61−141443（ＪＰ，Ａ) 特開 昭62−99125（ＪＰ，Ａ) 特開 平２−212501（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C09B 47/04 - 47/32 C07C 255/55 C07D 209/48 C07D 307/89 C07D 487/22 ＣＡ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)──────────────────────────────────────────────────続 き Continuing on the front page (51) Int.Cl. 6 Identification symbol FI C09B 47/14 C07D 209/48 Z (72) Inventor Kouji Yano 1-1, Oikecho, Kosai-cho, Koka-gun, Shiga Prefecture Neos Co., Ltd. (56) reference Patent Sho 61-141443 (JP, a) JP Akira 62-99125 (JP, a) JP flat 2-212501 (JP, a) (58 ) investigated the field (Int.Cl. 6 , DB name) C09B 47/04-47/32 C07C 255/55 C07D 209/48 C07D 307/89 C07D 487/22 CA (STN) REGISTRY (STN)
Claims (4)
を示し、Ｘは−Ｏ−、−ＣＨ2−または−ＯＣＯ・Ｃ6Ｈ
4・Ｏ−を示し、nは３〜１２の数を示す)で表わされる
フタロシアニン誘導体。1. A compound of the general formula (I): (Wherein, M represents a metal, metal oxide, metal chloride, or hydrogen, and X represents —O—, —CH 2 —, or —OCO · C 6 H
Phthalocyanine derivative represented by the formula: 4 · O-, and n represents a number of 3 to 12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3096901A JP2911063B2 (en) | 1991-04-26 | 1991-04-26 | Phthalocyanine derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3096901A JP2911063B2 (en) | 1991-04-26 | 1991-04-26 | Phthalocyanine derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04325566A JPH04325566A (en) | 1992-11-13 |
| JP2911063B2 true JP2911063B2 (en) | 1999-06-23 |
Family
ID=14177278
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3096901A Expired - Fee Related JP2911063B2 (en) | 1991-04-26 | 1991-04-26 | Phthalocyanine derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2911063B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6501351B2 (en) * | 2015-03-20 | 2019-04-17 | 国立大学法人山口大学 | Fluoroalkane derivative, gelling agent, liquid crystalline compound and gel composition |
| JP7514298B2 (en) * | 2020-04-28 | 2024-07-10 | 富士フイルム株式会社 | Compound, liquid crystal composition, cured product and film |
-
1991
- 1991-04-26 JP JP3096901A patent/JP2911063B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04325566A (en) | 1992-11-13 |
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