JPH0794423B2 - Phthalonitrile compound - Google Patents
Phthalonitrile compoundInfo
- Publication number
- JPH0794423B2 JPH0794423B2 JP134988A JP134988A JPH0794423B2 JP H0794423 B2 JPH0794423 B2 JP H0794423B2 JP 134988 A JP134988 A JP 134988A JP 134988 A JP134988 A JP 134988A JP H0794423 B2 JPH0794423 B2 JP H0794423B2
- Authority
- JP
- Japan
- Prior art keywords
- tert
- compound
- group
- cyclohexylidene
- butylcyclohexylidene
- 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 - Lifetime
Links
- -1 Phthalonitrile compound Chemical class 0.000 title claims description 16
- 229920006391 phthalonitrile polymer Polymers 0.000 title claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 9
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- FNIATMYXUPOJRW-UHFFFAOYSA-N cyclohexylidene Chemical group [C]1CCCCC1 FNIATMYXUPOJRW-UHFFFAOYSA-N 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- YIAIHKYSUCSBQA-UHFFFAOYSA-N 10-amino-1,2,3,4,5,6,7,8-octahydrophenanthrene-9-carbonitrile Chemical compound C1CCCC2=C(C#N)C(N)=C(CCCC3)C3=C21 YIAIHKYSUCSBQA-UHFFFAOYSA-N 0.000 description 2
- TYDSIOSLHQWFOU-UHFFFAOYSA-N 2-cyclohexylidenecyclohexan-1-one Chemical compound O=C1CCCCC1=C1CCCCC1 TYDSIOSLHQWFOU-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- 150000001989 diazonium salts Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- YSZLFGZFQTTZIQ-UHFFFAOYSA-N 1,2,3,4,5,6,7,8-octahydrophenanthrene Chemical compound C1CCCC2=C1C=CC1=C2CCCC1 YSZLFGZFQTTZIQ-UHFFFAOYSA-N 0.000 description 1
- UOMVIPGXCMPOMH-UHFFFAOYSA-N 1,2,3,4,5,6,7,8-octahydrophenanthrene-9,10-dicarbonitrile Chemical compound C1CCCC2=C(C#N)C(C#N)=C(CCCC3)C3=C21 UOMVIPGXCMPOMH-UHFFFAOYSA-N 0.000 description 1
- FQIMAWQQOPBDEC-UHFFFAOYSA-N 2,6-ditert-butyl-1,2,3,4,5,6,7,8-octahydrophenanthrene-9,10-dicarbonitrile Chemical compound C1CC(C(C)(C)C)CC(C(C#N)=C2C#N)=C1C1=C2CCC(C(C)(C)C)C1 FQIMAWQQOPBDEC-UHFFFAOYSA-N 0.000 description 1
- AATFVEWYPSIRAT-UHFFFAOYSA-N 4-(4-pentylphenyl)cyclohexan-1-one Chemical compound C1=CC(CCCCC)=CC=C1C1CCC(=O)CC1 AATFVEWYPSIRAT-UHFFFAOYSA-N 0.000 description 1
- USJQDUXDFHRUMC-UHFFFAOYSA-N 4-tert-butylcyclohexan-1-one Chemical compound C(C)(C)(C)C1CCC(CC1)=O.C(C)(C)(C)C1CCC(CC1)=O USJQDUXDFHRUMC-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 239000003054 catalyst Substances 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
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- SXOZDDAFVJANJP-UHFFFAOYSA-N cyclodecanone Chemical compound O=C1CCCCCCCCC1 SXOZDDAFVJANJP-UHFFFAOYSA-N 0.000 description 1
- CGZZMOTZOONQIA-UHFFFAOYSA-N cycloheptanone Chemical compound O=C1CCCCCC1 CGZZMOTZOONQIA-UHFFFAOYSA-N 0.000 description 1
- YKFKEYKJGVSEIX-UHFFFAOYSA-N cyclohexanone, 4-(1,1-dimethylethyl)- Chemical compound CC(C)(C)C1CCC(=O)CC1 YKFKEYKJGVSEIX-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000006193 diazotization reaction Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002265 electronic spectrum Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical class N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XTVMZZBLCLWBPM-UHFFFAOYSA-N tert-butylcyclohexane Chemical compound CC(C)(C)C1CCCCC1 XTVMZZBLCLWBPM-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000005389 trialkylsiloxy group Chemical group 0.000 description 1
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
- C09B47/067—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile
- C09B47/0673—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile having alkyl radicals linked directly to the Pc skeleton; having carbocyclic groups linked directly to the skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は新規なフタロニトリル化合物に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel phthalonitrile compound.
さらに詳しくは新規なフタロシアニン化合物の製造中間
体として有用なフタロニトリル化合物に関する。More specifically, it relates to a phthalonitrile compound useful as an intermediate for the production of a novel phthalocyanine compound.
フタロニトリル化合物は古くから染料、顔料の中間体と
して有用な化合物であることが知られており、特に顔料
として非常に有用なフタロシアニン化合物の製造中間体
として重要な化合物である。It has long been known that a phthalonitrile compound is a compound useful as an intermediate for dyes and pigments, and in particular, it is an important compound as an intermediate for producing a phthalocyanine compound which is very useful as a pigment.
フタロシアニン化合物は、電導材料、光電導材料、酸化
触媒材料、エレクトロクロミズム材料等の機能性材料と
して注目を集めている。さらに、フタロシアニン化合物
は近赤外領域に吸収を有しており、半導体レーザーと組
み合わせた各種電気光学素子としての応用が期待されて
いる。Phthalocyanine compounds have been attracting attention as functional materials such as conductive materials, photoconductive materials, oxidation catalyst materials, and electrochromic materials. Furthermore, the phthalocyanine compound has absorption in the near infrared region, and is expected to be applied as various electro-optical elements combined with a semiconductor laser.
このように各種の機能材料として非常に注目を集めてい
るフタロシアニン化合物ではあるが、従来知られている
フタロシアニン化合物は、各種有機溶剤に対し、非常に
難溶であり、各種機能素子として成形することが困難で
あった。Although it is a phthalocyanine compound that has received a great deal of attention as various functional materials in this way, conventionally known phthalocyanine compounds are extremely insoluble in various organic solvents and must be molded as various functional elements. Was difficult.
本発明の課題は、光化学的、化学的に非常に安定であ
り、半導体レーザー域に吸収を有し、しかも有機溶剤、
液晶等に対し、非常に高い溶解性を有し、塗布加工やLB
（Langmuir−Blodgett）膜による薄膜加工が容易なフタ
ロシアニン化合物の製造中間体として非常に有用なフタ
ロニトリル化合物を提供することである。The subject of the present invention is photochemically, chemically very stable, has absorption in the semiconductor laser region, and an organic solvent,
It has a very high solubility in liquid crystal, etc.
It is to provide a phthalonitrile compound which is very useful as an intermediate for producing a phthalocyanine compound which can be easily processed into a thin film by a (Langmuir-Blodgett) film.
本発明者らは、前記の問題点を解決するため種々の化合
物を合成し、その特性を検討した結果、本発明に到達し
た。The present inventors arrived at the present invention as a result of synthesizing various compounds in order to solve the above problems and examining the properties thereof.
すなわち、本発明は一般式（Ｉ） （式中、R1およびR2は水素原子、アルキル基またはアリ
ール基を示し、ｍおよびｎは３〜10の整数である）で表
わされるフタロニトリル化合物である。That is, the invention has the general formula (I) (In the formula, R 1 and R 2 represent a hydrogen atom, an alkyl group or an aryl group, and m and n are integers of 3 to 10).
（Ｉ）式の化合物は種々の方法で製造できるが、代表的
には下記合成経路により製造できる。The compound of formula (I) can be produced by various methods, but typically, it can be produced by the following synthetic route.
（R1、R2、ｍおよびｎは前記に同じ） すなわち（ａ）の構造で表わされるカルボニル化合物と
マロノニトリルとを縮合させ（ｂ）の化合物とし、その
後さらに酸性条件下（たとえば、濃硫酸、濃塩酸等の存
在下）環化を行い（ｃ）とする。（ｃ）をまずジアゾ化
を行ない、ジアゾニウム塩（ｄ）とした後、このジアゾ
ニウム塩を適当なシアン化合物（例えば、シアン化銅、
シアン化銅と硫酸銅の錯体等）と反応させ（Ｉ）の化合
物を製造することができる。 (R 1 , R 2 , m and n are the same as described above) That is, the carbonyl compound represented by the structure of (a) and malononitrile are condensed to form the compound of (b), and then under acidic conditions (for example, concentrated sulfuric acid, Cyclization is carried out in the presence of concentrated hydrochloric acid or the like to obtain (c). (C) is first subjected to diazotization to form a diazonium salt (d), and this diazonium salt is then converted into a suitable cyanide compound (for example, copper cyanide,
The compound (I) can be produced by reacting with a complex of copper cyanide and copper sulfate.
一般式（Ｉ）においてR1およびR2は水素原子、アルキル
基、アリール基であり、アルキル基の場合、炭素数１〜
20の直鎖状あるいは分岐状のアルキル基が好ましく、特
に炭素数１〜10の直鎖状あるいは分岐状のアルキル基が
好ましく、具体例としては、メチル基、エチル基、プロ
ピル基、イソプロピル基、ブチル基、tert−ブチル基、
ペンチル基、ヘキシル基、ヘプチル基、オクチル基、te
rt−オクチル基、ノニル基、デシル基等が挙げられる。
アリール基としてはフェニル基、ナフチル基、ビフェニ
ル基や複素環基やそれらのアルキル置換誘導体等を挙げ
ることができる。In the general formula (I), R 1 and R 2 are a hydrogen atom, an alkyl group or an aryl group.
20 linear or branched alkyl groups are preferable, and particularly linear or branched alkyl groups having 1 to 10 carbon atoms are preferable, and specific examples include methyl group, ethyl group, propyl group, isopropyl group, Butyl group, tert-butyl group,
Pentyl group, hexyl group, heptyl group, octyl group, te
Examples include rt-octyl group, nonyl group and decyl group.
Examples of the aryl group include a phenyl group, a naphthyl group, a biphenyl group, a heterocyclic group, and their alkyl-substituted derivatives.
またｍ及びｎは３〜10の整数であるが、好ましくは３〜
８の整数である。Further, m and n are integers of 3 to 10, but preferably 3 to
It is an integer of 8.
以下に本発明の代表的化合物を例示する。The representative compounds of the present invention are exemplified below.
例えば、本発明の化合物（Ｉ）の中で（II）の構造 （式中、R3及びR4は水素原子、アルキル基、またはアリ
ール基を示す） で表わされる化合物より、たとえばF.H.Moser and A.L.
Thomas「ザ・フタロシアニンズ」（The Phthalocyanine
s）vol.II,Chapter II,CRC Press（1983）記載の方法に
準じて製造される一般式（III） （式中、R5〜R12は水素原子、アルキル基またはアリー
ル基を示し、Ｍは２個の水素原子、金属原子、金属酸化
物、金属ハロゲン化物、金属水酸化物、ジアルキル金
属、ジアリール金属、ビスアルキルオキシ金属、ビス
（トリアルキルシリルオキシ）金属を表わす）で示され
るフタロシアニン化合物の内、いくつかの化合物の電子
スペクトルの最大吸収波長を第１表に示した。 For example, in the compound (I) of the present invention, the structure of (II) (Wherein R 3 and R 4 represent a hydrogen atom, an alkyl group, or an aryl group), for example, FHMoser and AL
Thomas "The Phthalocyanine"
s) General formula (III) produced according to the method described in vol.II, Chapter II, CRC Press (1983). (In the formula, R 5 to R 12 each represent a hydrogen atom, an alkyl group or an aryl group, and M represents two hydrogen atoms, a metal atom, a metal oxide, a metal halide, a metal hydroxide, a dialkyl metal or a diaryl metal. , Bisalkyloxy metal, bis (trialkylsilyloxy) metal), the maximum absorption wavelengths of the electronic spectra of some compounds are shown in Table 1.
第１表に示したように一般式（III）で表わされる化合
物は近赤外域に吸収を有しており、また具体例１で表わ
される化合物はｎ−ヘキサンに対し室温で30g/以上の
溶解度を有していることが判明した。 As shown in Table 1, the compound represented by the general formula (III) has absorption in the near infrared region, and the compound represented by Example 1 has a solubility in n-hexane at room temperature of 30 g / or more. Was found to have.
以下実施例により本発明を具体的に説明するが、勿論、
本発明の主旨と適用範囲はこれらの実施例によって限定
されるものではない。The present invention will be specifically described below with reference to examples, but of course,
The spirit and scope of application of the present invention is not limited by these examples.
実施例１ 9,10−ジシアノ−1,2,4,5,6,8−ヘキサヒドロ−3,7−ジ
−tert−ブチルフェナントレン（例示化合物No.8）の製
造 （ｉ）２−（４′−tert−ブチルシクロヘキシリデン）
−４−tert−ブチルシクロヘキサノンの製造４−tert−
ブチルシクロヘキサノン500gを700mlのキシレン中、15g
の無水ホウ酸存在下、副生する水を留去しながら10時間
加熱還流を行なった。反応混合物を濾過した後、濾液よ
りキシレンおよび未反応の４−tert−ブチルシクロヘキ
サンを減圧下で留去し、残渣として淡黄色の粘い油状物
として目的とする２−（４′−tert−ブチルシクロヘキ
シリデン）−４−tert−ブチルシクロヘキサノン430g得
た。（収率91％） このものは、さらに精製することなく次の反応に用い
た。Example 1 Production of 9,10-dicyano-1,2,4,5,6,8-hexahydro-3,7-di-tert-butylphenanthrene (Exemplified Compound No. 8) (i) 2- (4 ' -Tert-butylcyclohexylidene)
Preparation of 4-tert-butylcyclohexanone 4-tert-
Butylcyclohexanone 500g in 700ml xylene 15g
In the presence of boric anhydride, the mixture was heated under reflux for 10 hours while distilling off water as a by-product. After filtering the reaction mixture, xylene and unreacted 4-tert-butylcyclohexane were distilled off from the filtrate under reduced pressure, and the residue of the desired 2- (4'-tert-butyl) was obtained as a pale yellow viscous oil. 430 g of cyclohexylidene) -4-tert-butylcyclohexanone was obtained. (Yield 91%) This was used for the next reaction without further purification.
（ii）〔２−（４′−tert−ブチルシクロヘキシリデ
ン）−４−tert−ブチルシクロヘキシリデン〕マロノジ
ニトリルの製造 （ｉ）で製造した２−（４′−tert−ブチルシクロヘキ
シリデン）−４−tert−ブチルシクロヘキサノン220g、
マロノニトリル60g、酢酸12mlおよび酢酸アンモニウム3
7gを350mlのベンゼン中、副生する水を留去しながら８
時間加熱還流した。(Ii) Preparation of [2- (4'-tert-butylcyclohexylidene) -4-tert-butylcyclohexylidene] malonodinitrile 2- (4'-tert-butylcyclohexylidene) -prepared in (i) 220 g of 4-tert-butylcyclohexanone,
Malononitrile 60g, acetic acid 12ml and ammonium acetate 3
7g in 350ml benzene while distilling off the by-product water 8
Heated to reflux for hours.
冷却後、有機層を飽和炭酸水素ナトリウム水溶液および
水で洗浄後、ベンゼンを留去し、残渣として淡黄色の粘
い油状物として目的とする〔２−（４′−tert−ブチル
シクロヘキシリデン）−４−tert−ブチルシクロヘキシ
リデン〕マロノジニトリル250gを得た。（収率97％） このものはさらに精製することなく次の反応に用いた。After cooling, the organic layer was washed with a saturated aqueous solution of sodium hydrogencarbonate and water, benzene was distilled off, and the residue was obtained as a pale yellow viscous oil [2- (4'-tert-butylcyclohexylidene)]. 250 g of -4-tert-butylcyclohexylidene] malonodinitrile was obtained. (Yield 97%) This was used for the next reaction without further purification.
（iii）９−アミノ−10−シアノ−1,2,4,5,6,8−ヘキサ
ヒドロ−3,7−ジ−tert−ブチルフェナントレンの製造 （ii）で製造した〔２−（４′−tert−ブチルシクロヘ
キシリデン）−４−tert−ブチルシクロヘキシリデン〕
マロノジニトリル200gを０℃に冷却した１の濃硫酸に
徐々に加えた。反応液はさらに０℃で２時間撹拌した
後、さらに室温で８時間撹拌した。反応液を５の氷水
に注いだ後、析出した結晶を濾別した。この結晶をさら
に１の水に分散後、５％水酸化ナトリウム水溶液にて
中和し再び濾過、水洗を行なった。(Iii) Preparation of 9-amino-10-cyano-1,2,4,5,6,8-hexahydro-3,7-di-tert-butylphenanthrene Prepared in (ii) [2- (4'- tert-butylcyclohexylidene) -4-tert-butylcyclohexylidene]
200 g of malonodinitrile was slowly added to 1 concentrated sulfuric acid cooled to 0 ° C. The reaction solution was further stirred at 0 ° C. for 2 hours and then at room temperature for 8 hours. After pouring the reaction solution into ice water (5), the precipitated crystals were separated by filtration. The crystals were further dispersed in 1 part of water, neutralized with 5% aqueous sodium hydroxide solution, filtered again and washed with water.
この粗生物をベンゼン/n−ヘキサンより再結晶し無色板
状結晶として目的とする９−アミノ−10−シアノ−1,2,
4,5,6,8−ヘキサヒドロ−3,7−ジ−tert−ブチルフェナ
ントレンを156g得た。（収率78％） 融点 212〜214℃ IR（KBr） ν＝3470、3380、3270、2200cm-1 1 H−NMR（CDCl3） δ＝1.0（s,18H）、1.3〜3.0（m,14
H）、4.2ppm（s,2H） 元素分析値 計算値（C23H34N2として） 分析値 C:81.60％ C:81.71％ H:10.12％ H:10.10％ N: 8.28％ N: 8.31％ （iv）（iii）で製造した９−アミノ−10−シアノ−1,
2,4,5,6,8−ヘキサヒドロ−3,7−ジ−tert−ブチルフェ
ナントレン30gを酢酸250mlに溶かし、40mlの濃塩酸を加
え、０℃に冷却した。この溶液に亜硝酸ナトリウム8.6g
の水（15ml）溶液を５分間で滴下後、さらに０℃で10分
間撹拌を行なった。この溶液を硫酸銅５水和物100gとシ
アン化ナトリウム52gを用い文献（Org.Synth.Coll.Vol.
I,p170およびp514）に記載されている方法に従い調整し
たシアン化銅水溶液（500ml）、および500gの炭酸水素
ナトリウムと300mlのベンゼンよりなる溶液に撹拌下、2
0分間で０℃にて加えた。The crude product was recrystallized from benzene / n-hexane to give 9-amino-10-cyano-1,2
156 g of 4,5,6,8-hexahydro-3,7-di-tert-butylphenanthrene was obtained. (78% yield) mp 212~214 ℃ IR (KBr) ν = 3470,3380,3270,2200cm -1 1 H-NMR (CDCl 3) δ = 1.0 (s, 18H), 1.3~3.0 (m, 14
H), 4.2ppm (s, 2H ) Elemental analysis Calculated (C 23 H 34 N 2) analysis C: 81.60% C: 81.71% H: 10.12% H: 10.10% N: 8.28% N: 8.31% (Iv) 9-amino-10-cyano-1, prepared in (iii),
30 g of 2,4,5,6,8-hexahydro-3,7-di-tert-butylphenanthrene was dissolved in 250 ml of acetic acid, 40 ml of concentrated hydrochloric acid was added, and the mixture was cooled to 0 ° C. 8.6g of sodium nitrite in this solution
A water (15 ml) solution of was added dropwise over 5 minutes, and the mixture was further stirred at 0 ° C. for 10 minutes. This solution was prepared using 100 g of copper sulfate pentahydrate and 52 g of sodium cyanide as a reference (Org.Synth.Coll.Vol.
I, p170 and p514) and a solution of copper cyanide aqueous solution (500 ml) prepared according to the method described in I, p170 and p514), and a solution of 500 g of sodium hydrogen carbonate and 300 ml of benzene under stirring.
Add at 0 ° C. for 0 minutes.
この反応混合物をさらに室温で５時間撹拌した後、ベン
ゼン層を分離し、ベンゼンを減圧下留去し残渣をベンゼ
ンを溶出液としシリカゲルカラムクロマトを用い精製し
た。After the reaction mixture was further stirred at room temperature for 5 hours, the benzene layer was separated, benzene was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography using benzene as an eluent.
粗生成物はエタノールより再結晶し、ほとんど無色の板
状結晶として目的とする9,10−ジシアノ−1,2,4,5,6,8
−ヘキサヒドロ−3,7−ジ−tert−ブチルフェナントレ
ンを8g得た。（収率26％） 融点 164〜165℃ IR（KBr） ν＝2200cm-1 1 H−NMR（CDCl3） δ＝1.0（s,18H）、 1.3〜3.0ppm（m,14H） 元素分析値 計算値（C24H32N2として） 分析値 C:82.71％ C:82.67％ H: 9.26％ H: 9.25％ N: 8.04％ N: 8.00％ 実施例２ 9,10−ジシアノ−1,2,3,4,5,6,7,8−オクタヒドロフェ
ナントレン（例示化合物No.3）の製造（ｉ）２−（シク
ロヘキシリデン）シクロヘキサノンの製造 実施例１の（ｉ）おいて４−tert−ブチルシクロヘキサ
ノンの代りにシクロヘキサノンを使用した以外は実施例
１の（ｉ）に記載の方法に従い反応を行ない、２−（シ
クロヘキシリデン）シクロヘキサノンを製造した。The crude product was recrystallized from ethanol to give the target 9,10-dicyano-1,2,4,5,6,8 as almost colorless plate crystals.
8 g of hexahydro-3,7-di-tert-butylphenanthrene were obtained. (26% yield) mp 164~165 ℃ IR (KBr) ν = 2200cm -1 1 H-NMR (CDCl 3) δ = 1.0 (s, 18H), 1.3~3.0ppm (m, 14H) Elemental analysis calculated Value (as C 24 H 32 N 2 ) Analytical value C: 82.71% C: 82.67% H: 9.26% H: 9.25% N: 8.04% N: 8.00% Example 2 9,10-dicyano-1,2,3 Preparation of 1,4,5,6,7,8-octahydrophenanthrene (Exemplified Compound No. 3) (i) Preparation of 2- (cyclohexylidene) cyclohexanone 4-tert-butyl in (i) of Example 1 2- (Cyclohexylidene) cyclohexanone was produced by carrying out the reaction according to the method described in (i) of Example 1 except that cyclohexanone was used instead of cyclohexanone.
（ii）〔２−（シクロヘキシリデン）シクロヘキシリデ
ン〕マロノジニトリルの製造 実施例１の（ii）において２−（４′−tert−ブチルシ
クロヘキシリデン）−４−tert−ブチルシクロヘキサノ
ンの代りに２−（シクロヘキシリデン）シクロヘキサノ
ンを使用した以外は実施例１の（ii）に記載の方法に従
い反応を行ない、〔２−（シクロヘキシリデン）シクロ
ヘキシリデン〕マロノジニトリルを製造した。(Ii) Production of [2- (cyclohexylidene) cyclohexylidene] malonodinitrile In place of 2- (4'-tert-butylcyclohexylidene) -4-tert-butylcyclohexanone in (ii) of Example 1, 2 was used. [2- (Cyclohexylidene) cyclohexylidene] malonodinitrile was produced by carrying out the reaction according to the method described in (ii) of Example 1 except that-(cyclohexylidene) cyclohexanone was used.
（iii）９−アミノ−10−シアノ−1,2,3,4,5,6,7,8−オ
クタヒドロフェナントレンの製造 実施例１の（iii）において〔２−（４′−tert−ブチ
ルシクロヘキシリデン）−４−tert−ブチルシクロヘキ
シリデン〕マロノジニトリルの代りに〔２−（シクロヘ
キシリデン）シクロヘキシリデン〕マロノジニトリルを
使用した以外は実施例１の（iii）の記載の方法に従い
反応を行ない、９−アミノ−10−シアノ−1,2,3,4,5,6,
7,8−オクタヒドロフェナントレンを製造した。(Iii) Preparation of 9-amino-10-cyano-1,2,3,4,5,6,7,8-octahydrophenanthrene In (iii) of Example 1, [2- (4'-tert-butyl Cyclohexylidene) -4-tert-butylcyclohexylidene] malonodinitrile was used instead of [2- (cyclohexylidene) cyclohexylidene] malonodinitrile to carry out the reaction according to the method described in (iii) of Example 1. 9-amino-10-cyano-1,2,3,4,5,6,
7,8-Octahydrophenanthrene was produced.
融点 157〜158℃ （iv）実施例１の（iv）において９−アミノ−10−シア
ノ−1,2,4,5,6,8−ヘキサヒドロ−3,7−ジ−tert−ブチ
ルフェナントレンの代わりに９−アミノ−10−シアノ−
1,2,3,4,5,6,7,8−オクタヒドロフェナントレンを使用
した以外は実施例１の（iv）に記載の方法に従い反応を
行ない、目的とする9,10−ジシアノ−1,2,3,4,5,6,7,8
−オクタヒドロフェナントレンを製造した。Melting point 157-158 ° C (iv) In place of 9-amino-10-cyano-1,2,4,5,6,8-hexahydro-3,7-di-tert-butylphenanthrene in (iv) of Example 1. 9-amino-10-cyano-
The reaction was carried out according to the method described in (iv) of Example 1 except that 1,2,3,4,5,6,7,8-octahydrophenanthrene was used to obtain the desired 9,10-dicyano-1 , 2,3,4,5,6,7,8
-Octahydrophenanthrene was prepared.
融点 249.5〜252.0℃ IR（KBr） ν＝2220cm-1 1 H−NMR（CDCl3） δ＝1.78（m,8H）、2.48ppm（m,8
H） 元素分析値 計算値（C16H16N2として） 分析値 C:81.32％ C:81.47％ H: 6.83％ H: 6.77％ N:11.86％ N:11.90％ 実施例３−６ 例示化合物No.1,9,11,13の製造 出発原料にシクロヘンタノンあるいは４−（４′−ペン
チルフェニル）シクロヘキサノンあるいはシクロヘプタ
ノンあるいはシクロデカノンを使用し、実施例１に記載
した方法に従い反応を順次行ない、各種のフタロニトリ
ル誘導体を製造した。Mp 249.5~252.0 ℃ IR (KBr) ν = 2220cm -1 1 H-NMR (CDCl 3) δ = 1.78 (m, 8H), 2.48ppm (m, 8
H) Elemental analysis value Calculated value (as C 16 H 16 N 2 ) Analysis value C: 81.32% C: 81.47% H: 6.83% H: 6.77% N: 11.86% N: 11.90% Example 3-6 Exemplified compound No. Preparation of 1,9,11,13 Cyclohentanone or 4- (4'-pentylphenyl) cyclohexanone, cycloheptanone or cyclodecanone was used as a starting material and the reaction was sequentially performed according to the method described in Example 1, Various phthalonitrile derivatives were produced.
第２表に元素分析値を示した。Table 2 shows the elemental analysis values.
〔発明の効果〕 本発明の化合物を用い製造したフタロシアニンは近赤外
域に吸収を有し、さらに有機溶剤に対し非常に大きい溶
解性を有しており、各種の機能素子を構成するにあたり
有用な化合物である。 [Effect of the Invention] The phthalocyanine produced by using the compound of the present invention has absorption in the near infrared region and has a very large solubility in an organic solvent, and is useful in forming various functional devices. It is a compound.
Claims (1)
ール基を示し、ｍおよびｎは３〜10の整数である）で表
わされるフタロニトリル化合物。1. A general formula (I) (In the formula, R 1 and R 2 represent a hydrogen atom, an alkyl group or an aryl group, and m and n are integers of 3 to 10.) A phthalonitrile compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP134988A JPH0794423B2 (en) | 1988-01-08 | 1988-01-08 | Phthalonitrile compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP134988A JPH0794423B2 (en) | 1988-01-08 | 1988-01-08 | Phthalonitrile compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01180865A JPH01180865A (en) | 1989-07-18 |
| JPH0794423B2 true JPH0794423B2 (en) | 1995-10-11 |
Family
ID=11499012
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP134988A Expired - Lifetime JPH0794423B2 (en) | 1988-01-08 | 1988-01-08 | Phthalonitrile compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0794423B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015118296A (en) * | 2013-12-19 | 2015-06-25 | 山本化成株式会社 | Filter comprising phthalocyanine compound |
-
1988
- 1988-01-08 JP JP134988A patent/JPH0794423B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01180865A (en) | 1989-07-18 |
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