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
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Application Number | Title | Priority Date | Filing Date |
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JP3096901A Expired - Fee Related JP2911063B2 (en) | 1991-04-26 | 1991-04-26 | Phthalocyanine derivative |
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JP (1) | JP2911063B2 (en) |
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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 |
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1991
- 1991-04-26 JP JP3096901A patent/JP2911063B2/en not_active Expired - Fee Related
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JPH04325566A (en) | 1992-11-13 |
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