JPH0749531B2 - Method for producing phthalocyanine compound - Google Patents
Method for producing phthalocyanine compoundInfo
- Publication number
- JPH0749531B2 JPH0749531B2 JP2118574A JP11857490A JPH0749531B2 JP H0749531 B2 JPH0749531 B2 JP H0749531B2 JP 2118574 A JP2118574 A JP 2118574A JP 11857490 A JP11857490 A JP 11857490A JP H0749531 B2 JPH0749531 B2 JP H0749531B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- formula
- phthalocyanine compound
- amount
- bromine
- 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 phthalocyanine compound Chemical class 0.000 title claims description 39
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 14
- 229910052794 bromium Inorganic materials 0.000 claims description 14
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 125000004429 atom Chemical group 0.000 claims description 6
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 230000002140 halogenating effect Effects 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 15
- 239000013078 crystal Substances 0.000 description 12
- 238000000921 elemental analysis Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 125000001246 bromo group Chemical group Br* 0.000 description 9
- 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 9
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 8
- 238000006467 substitution reaction Methods 0.000 description 6
- 230000026030 halogenation Effects 0.000 description 5
- 238000005658 halogenation reaction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 4
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- SCZNXLWKYFICFV-UHFFFAOYSA-N 1,2,3,4,5,7,8,9-octahydropyrido[1,2-b]diazepine Chemical compound C1CCCNN2CCCC=C21 SCZNXLWKYFICFV-UHFFFAOYSA-N 0.000 description 1
- 125000000453 2,2,2-trichloroethyl group Chemical group [H]C([H])(*)C(Cl)(Cl)Cl 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910018085 Al-F Inorganic materials 0.000 description 1
- 229910018179 Al—F Inorganic materials 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- QZRGKCOWNLSUDK-UHFFFAOYSA-N Iodochlorine Chemical compound ICl QZRGKCOWNLSUDK-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 229910003691 SiBr Inorganic materials 0.000 description 1
- 229910008449 SnF 2 Inorganic materials 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 229940107816 ammonium iodide Drugs 0.000 description 1
- 125000006226 butoxyethyl 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
- 239000003054 catalyst Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- BUMGIEFFCMBQDG-UHFFFAOYSA-N dichlorosilicon Chemical compound Cl[Si]Cl BUMGIEFFCMBQDG-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl 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])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- CMJCEVKJYRZMIA-UHFFFAOYSA-M thallium(i) iodide Chemical compound [Tl]I CMJCEVKJYRZMIA-UHFFFAOYSA-M 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000004665 trialkylsilyl group Chemical group 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Nitrogen Condensed Heterocyclic Rings (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、近赤外線吸収剤として有用なハロゲン化アル
コキシフタロシアニンの製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a halogenated alkoxyphthalocyanine useful as a near infrared absorber.
〔従来の技術〕 ハロゲン化アルコキシフタロシアニンあるいはハロゲン
化アリールオキシフタロシアニンの製造方法としては、
特開昭61−197280号公報やJournal of Chemical Societ
y Perkin Transition I,2453〜2458頁（1988年）に既に
開示されており、前者はハロゲン化フタロシアニンを脂
肪族アルコールのアルカリ金属塩あるいは芳香族アルコ
ールのアルカリ金属塩等で置換して目的とするハロゲン
化アルコキシフタロシアニンあるいはハロゲン化アリー
ルオキシフタロシアニンを製造する方法であり、後者
は、ジアルコキシジハロゲノフタロニトリルを閉環して
目的とするハロゲン化アルコキシフタロシアニンを製造
する方法である。[Prior Art] As a method for producing a halogenated alkoxyphthalocyanine or a halogenated aryloxyphthalocyanine,
JP-A-61-197280 and the Journal of Chemical Societ
y Perkin Transition I, 2453 to 2458 (1988), the former is the target halogen by replacing the halogenated phthalocyanine with an alkali metal salt of an aliphatic alcohol or an aromatic alcohol. The present invention is a method for producing a halogenated alkoxyphthalocyanine or a halogenated aryloxyphthalocyanine. The latter is a method for producing a desired halogenated alkoxyphthalocyanine by ring-closing a dialkoxydihalogenophthalonitrile.
近赤外線吸収剤、特に、追記型CD（CD−WO）の780nm用
の記録材料として有用なハロゲン化アルコキシフタロシ
アニンとしては、そのハロゲン化率が１〜４の範囲のも
のが好ましい。ハロゲン化率が５以上になると屈折率、
反射率の規格を満たすことができなくなる。上述の方法
では、ハロゲン原子の導入量を制御することができず、
CD−WO用の近赤外線吸収剤としては未だ十分であるとは
言えなかった。As the near-infrared absorbing agent, particularly as a halogenated alkoxyphthalocyanine useful as a recording material for write-once type CD (CD-WO) for 780 nm, one having a halogenation ratio of 1 to 4 is preferable. When the halogenation rate is 5 or more, the refractive index,
The reflectance standard cannot be met. In the above method, the amount of halogen atoms introduced cannot be controlled,
It could not be said to be sufficient as a near-infrared absorber for CD-WO.
〔課題を解決するための手段〕 本発明者らは、前項の課題を解決すべく鋭意検討の結
果、ハロゲン化溶媒中で、反応温度、溶媒量をコントロ
ールすることにより、アルコキシフタロシアニンよりハ
ロゲン化率の制御されたハロゲン化アルコキシフタロシ
アニンが得られることを見いだし、本発明に到達した。[Means for Solving the Problems] As a result of intensive studies to solve the problems of the preceding paragraph, the present inventors have found that the halogenation rate is higher than that of alkoxyphthalocyanine by controlling the reaction temperature and the amount of the solvent in a halogenated solvent. It was found that the controlled halogenated alkoxy phthalocyanine of the above was obtained, and the present invention was accomplished.
即ち本発明は、下記一般式（Ｉ） 〔式（Ｉ）中、Ｒは、置換または未置換のアルキル基を
あらわし、Metは２個の水素原子、２価の金属原子、置
換３価金属原子、２置換４価金属原子を表わす。〕で示
されるフタロシアニン化合物をハロゲン化溶媒中、20〜
90℃でハロゲン化剤と反応させることを特徴とする、下
式（II） 〔式（II）中、Ｒ及びMetは式（Ｉ）と同一の意味を表
し、Ｘは、塩素、臭素、またはヨウ素を表し、ｎは１≦
ｎ≦４である。〕で示されるフタロシアニン化合物の製
造方法である。That is, the present invention provides the following general formula (I) [In the formula (I), R represents a substituted or unsubstituted alkyl group, and Met represents two hydrogen atoms, a divalent metal atom, a substituted trivalent metal atom or a disubstituted tetravalent metal atom. A phthalocyanine compound represented by
The following formula (II) characterized by reacting with a halogenating agent at 90 ° C [In the formula (II), R and Met have the same meanings as in the formula (I), X represents chlorine, bromine, or iodine, and n is 1 ≦
n ≦ 4. ] It is a manufacturing method of the phthalocyanine compound shown by these.
一般式（Ｉ）及び式（II）中、Ｒで示される置換または
未置換のアルキル基のとしては、メチル基、エチル基、
ｎ−プロピル基、iso−プロピル基、ｎ−ブチル基、iso
−ブチル基、sec−ブチル基、tert−ブチル基、ｎ−ペ
ンチル基、iso−ペンチル基、neo−ペンチル基、1,2−
ジメチルプロピル基、ｎ−ヘキシル基、1,3−ジメチル
ブチル基、シクロヘキシル基、ｎ−ヘプチル基、1,4−
ジメチルペンチル基、２−メチル−１−iso−プロピル
プロピル基、１−エチル−３−メチルブチル基、ｎ−オ
クチル基、２−エチルヘキシル基、３−メチル−１−is
o−プロピルブチル基、ｎ−ノニル基、3,5,5−トリメチ
ルヘキシル基、３−メチル−１−iso−ブチルブチル
基、ｎ−デシル基などの炭化水素基、メトキシメチル
基、エトキシメチル基、メトキシエチル基、エトキシエ
チル基、ブトキシエチル基、メトキシエトキシエチル
基、エトキシエトキシエチル基、２−メトキシプロピル
基、２−エトキシプロピル基、2,3−ジメトキシプロピ
ル基、2,2−ジメトキシエチル基、２−メトキシブチル
基、１−メチル−２−メトキシエチル基、１−エチル−
２−エトキシエチル基、エトキシブチル基などのアルコ
キシアルキル基、２−ヒドロキシエチル基、２−ヒドロ
キシプロピル基、４−ヒドロキシブチル基、６−ヒドロ
キシヘキシル基などのヒドロキシアルキル基、トリフル
オロメチル基、2,2,2−トリクロロエチル基、ヘキサフ
ルオロ−iso−プロピル基、ペンタフルオロエチル基な
どのハロゲン化アルキル基などが挙げられる。In the general formulas (I) and (II), examples of the substituted or unsubstituted alkyl group represented by R include a methyl group, an ethyl group,
n-propyl group, iso-propyl group, n-butyl group, iso
-Butyl group, sec-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, neo-pentyl group, 1,2-
Dimethylpropyl group, n-hexyl group, 1,3-dimethylbutyl group, cyclohexyl group, n-heptyl group, 1,4-
Dimethylpentyl group, 2-methyl-1-iso-propylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group, 3-methyl-1-is
Hydrocarbon groups such as o-propylbutyl group, n-nonyl group, 3,5,5-trimethylhexyl group, 3-methyl-1-iso-butylbutyl group, n-decyl group, methoxymethyl group, ethoxymethyl group, Methoxyethyl group, ethoxyethyl group, butoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, 2-methoxypropyl group, 2-ethoxypropyl group, 2,3-dimethoxypropyl group, 2,2-dimethoxyethyl group, 2-methoxybutyl group, 1-methyl-2-methoxyethyl group, 1-ethyl-
2-ethoxyethyl group, alkoxyalkyl group such as ethoxybutyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 4-hydroxybutyl group, hydroxyalkyl group such as 6-hydroxyhexyl group, trifluoromethyl group, 2 Examples thereof include halogenated alkyl groups such as a 2,2,2-trichloroethyl group, a hexafluoro-iso-propyl group and a pentafluoroethyl group.
又、Metで表わされる２価金属の例としては、Cu(II),Zn
(II),Fe(II),Co(II),Ni(II),Ru(II),Rh(II),Pd(II),Pt
(II),Mn(II),Mg(II),Be(II),Ca(II),Ba(II),Cd(II),Hg
(II),Sn(II)など、１置換３価金属の例としては、Al−C
l,Al−Br,Al−F,Al−I,Ga−Cl,Ga−F,Ga−I,Ga−Br,In
−Cl,In−Br,In−I,In−F,Tl−Cl,Tl−Br,Tl−I,Tl−F,
Al−C6H5,Al−C6H4CH3,In−C6H5,In−C6H4CH3,In−C10H
7,Mn（OH）などが挙げられる。Further, as an example of the divalent metal represented by Met, Cu (II) , Zn
(II) , Fe (II) , Co (II) , Ni (II) , Ru (II) , Rh (II) , Pd (II) , Pt
(II) , Mn (II) , Mg (II) , Be (II) , Ca (II) , Ba (II) , Cd (II) , Hg
Examples of monosubstituted trivalent metals such as (II) and Sn (II) include Al-C
l, Al-Br, Al-F, Al-I, Ga-Cl, Ga-F, Ga-I, Ga-Br, In
-Cl, In-Br, In-I, In-F, Tl-Cl, Tl-Br, Tl-I, Tl-F,
Al-C 6 H 5, Al -C 6 H 4 CH 3, In-C 6 H 5, In-C 6 H 4 CH 3, In-C 10 H
7 , Mn (OH), etc.
２置換の４価金属の例としては、CrCl2,SiCl2,SiBr2,Si
F2,SiI2,ZrCl2,GeCl2,GeBr2,GeI2,GeF2,SnCl2,SnBr2,Sn
I2,SnF2,TiCl2,TiBr2,TiF2,Si（OH）2,Ge（OH）2,Zr（O
H）2,Mn（OH）2,Sn（OH）2,TiR2,CrR2,SiR2,SnR2,GeR2
［Ｒはアルキル基、フェニル基、ナフチル基及びその誘
導体を表わす］、Si（OR′）2,Sn（OR′）2,Ge（OR′）
2,Ti（OR′）2,Cr（OR′）２［Ｒ′はアルキル基、フェ
ニル基、ナフチル基、トリアルキルシリル基、ジアルキ
ルアルコキシシリル基の誘導体を表わす］、Sn（SR″）
2,Ge（SR″）２［Ｒ″はアルキル基、フェニル基、ナフ
チル基及びその誘導体を表わす］などが挙げられる。Examples of disubstituted tetravalent metals include CrCl 2 , SiCl 2 , SiBr 2 and Si.
F 2 , SiI 2 , ZrCl 2 , GeCl 2 , GeBr 2 , GeI 2 , GeF 2 , SnCl 2 , SnBr 2 , Sn
I 2 , SnF 2 , TiCl 2 , TiBr 2 , TiF 2 , Si (OH) 2 , Ge (OH) 2 , Zr (O
H) 2 , Mn (OH) 2 , Sn (OH) 2 , TiR 2 , CrR 2 , SiR 2 , SnR 2 , GeR 2
[R represents an alkyl group, a phenyl group, a naphthyl group and its derivatives], Si (OR ') 2 , Sn (OR') 2 , Ge (OR ')
2 , Ti (OR ′) 2 , Cr (OR ′) 2 [R ′ represents a derivative of an alkyl group, a phenyl group, a naphthyl group, a trialkylsilyl group or a dialkylalkoxysilyl group], Sn (SR ″)
2 , Ge (SR ″) 2 [R ″ represents an alkyl group, a phenyl group, a naphthyl group or a derivative thereof] and the like.
オキシ金属の例としては、VO,MnO,TiOなどが挙げられ
る。Examples of oxymetals include VO, MnO, TiO and the like.
式（Ｉ）で示されるアルコキシフタロシアニン化合物の
合成法としては、下式（III）又は（IV） で示される化合物の１〜４種を混合して、例えば1,8−
ジアザビシクロ［5.4.0］−７−ウンデセン（DBU）の存
在下にブタノール中で加熱下反応することにより得るこ
とができる。The method for synthesizing the alkoxyphthalocyanine compound represented by the formula (I) includes the following formula (III) or (IV) 1 to 4 of the compounds represented by
It can be obtained by reacting with heating in butanol in the presence of diazabicyclo [5.4.0] -7-undecene (DBU) under heating.
本発明に使用できるハロゲン化剤としては、塩素、臭
素、ヨウ素、塩化スルフリル、塩化チオニル、一塩化ヨ
ウ素、４級アンモニウムクロリド、４級アンモニウムブ
ロミド、４級アンモニウムヨウダイド、次亜塩素酸ｔ−
ブチル、３ヨウ化カリウムなどが好ましい、また、必要
に応じて酸化剤、鉄粉などの触媒を用いても良い。ハロ
ゲン化剤の量としては、原料である式（Ｉ）のフタロシ
アニンに対して、１〜６モル比が好ましい。Examples of the halogenating agent usable in the present invention include chlorine, bromine, iodine, sulfuryl chloride, thionyl chloride, iodine monochloride, quaternary ammonium chloride, quaternary ammonium bromide, quaternary ammonium iodide, and t-hypochlorous acid.
Butyl, potassium iodide and the like are preferable, and a catalyst such as an oxidizing agent and iron powder may be used if necessary. The amount of the halogenating agent is preferably 1 to 6 molar ratio with respect to the raw material phthalocyanine of the formula (I).
本発明に用いられるハロゲン化溶媒としては、四塩化炭
素、クロロホルム、ジクロロメタン、1,1,1−トリクロ
ロエタン、1,1,2−トリクロロエタン、テトラクロロエ
チレン、1,1,2,2−テトラクロロエタンなどが挙げられ
る。溶媒の量としては、原料のフタロシアニンに対して
５〜500重量倍、好ましくは10〜200重量倍であり、その
量は必要とするハロゲン化率（式（II）中のｎが１〜
４）により適宜調整される。Examples of the halogenated solvent used in the present invention include carbon tetrachloride, chloroform, dichloromethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, tetrachloroethylene, 1,1,2,2-tetrachloroethane and the like. To be The amount of the solvent is 5 to 500 times by weight, preferably 10 to 200 times by weight with respect to the phthalocyanine as a raw material, and the amount is the required halogenation rate (n in the formula (II) is 1 to 1 times).
It is appropriately adjusted by 4).
反応温度としては、20〜90℃、好ましくは40〜70℃であ
る。反応温度が20℃よりも低いと反応がうまく進行せ
ず、また90℃を越えるとハロゲン化率を制御することが
困難となる。The reaction temperature is 20 to 90 ° C, preferably 40 to 70 ° C. If the reaction temperature is lower than 20 ° C, the reaction does not proceed well, and if it exceeds 90 ° C, it becomes difficult to control the halogenation rate.
本発明においては、反応温度、溶媒量を調節し、生成す
るハロゲン化アルコキシフタロシアニンを反応系より反
応・析出せしめるものである。In the present invention, the reaction temperature and the amount of solvent are adjusted so that the resulting halogenated alkoxyphthalocyanine is reacted and precipitated from the reaction system.
以下、実施例により本発明を具体的に説明するが、本発
明の実施の態様はこれにより限定されるものではない。Hereinafter, the present invention will be described specifically with reference to Examples, but the embodiments of the present invention are not limited thereto.
実施例１ パラジウム テトラα−（1,3−ジメチルブチルオキ
シ）フタロシアニン15gを四塩化炭素375mlに装入し、45
℃に昇温して溶解させた。次に臭素19gを滴下し、50℃
で１時間攪拌した。反応液を40℃に降温し、析出した結
晶をろ別した。得られた結晶をメタノール200mlで３回
スラッジし、減圧乾燥した。収量は17.7gであった。Example 1 Palladium tetra α- (1,3-dimethylbutyloxy) phthalocyanine (15 g) was charged in carbon tetrachloride (375 ml) and charged with 45
The temperature was raised to 0 ° C. to dissolve. Next, add 19 g of bromine dropwise to 50 ° C.
It was stirred for 1 hour. The reaction liquid was cooled to 40 ° C., and the precipitated crystals were separated by filtration. The obtained crystals were sludged with 200 ml of methanol three times and dried under reduced pressure. The yield was 17.7 g.
元素分析により、臭素の置換数は３個であることが判明
した。Elemental analysis revealed that the number of bromine substitutions was three.
元素分析:C56H61N8O4Br3Pd Ｃ Ｈ Ｎ Br 理論値(%) 53.54 4.89 8.92 19.08 分析値(%) 52.86 4.67 8.68 19.41 実施例２ パラジウム テトラα−（1,3−ジメチルブチルオキ
シ）フタロシアニン10gを四塩化炭素150mlに装入し、40
℃に昇温して溶解させた。次に臭素6gを滴下し、40℃で
30分間攪拌した。そのままの温度で析出した結晶をろ別
した。得られた結晶をメタノール100mlで３回スラッジ
し、減圧乾燥した。収量は11gであった。Elemental analysis: C 56 H 61 N 8 O 4 Br 3 Pd C H N Br Theoretical value (%) 53.54 4.89 8.92 19.08 Analytical value (%) 52.86 4.67 8.68 19.41 Example 2 Palladium tetra α- (1,3-dimethylbutyl) Oxy) phthalocyanine 10g is charged into carbon tetrachloride 150ml, and 40
The temperature was raised to 0 ° C. to dissolve. Then add 6 g of bromine dropwise at 40 ° C.
Stir for 30 minutes. Crystals precipitated at the same temperature were filtered off. The obtained crystals were sludged three times with 100 ml of methanol and dried under reduced pressure. The yield was 11g.
元素分析により、臭素の置換数は２個であることが判明
した。Elemental analysis revealed that the number of bromine substitutions was two.
元素分析:C56H62N8O4Br2Pd Ｃ Ｈ Ｎ Br 理論値(%) 57.13 5.31 9.52 13.57 分析値(%) 56.76 5.59 9.28 13.83 実施例３ パラジウム テトラα−（１−iso−プロピル−２−メ
チルブチルオキシ）フタロシアニン10gを1,1,2−トリク
ロロエタン400mlに装入し、40℃に昇温して溶解させ
た。次に臭素16gを滴下し、70℃で５時間攪拌した。反
応液を40℃に降温し析出した結晶をろ別した。得られた
結晶をメタノール100mlで３回スラッジし、減圧乾燥し
た。収量は12.3gであった。Elemental analysis: C 56 H 62 N 8 O 4 Br 2 Pd C H N Br theoretical value (%) 57.13 5.31 9.52 13.57 analytical value (%) 56.76 5.59 9.28 13.83 Example 3 Palladium tetra α- (1-iso-propyl- 10 g of 2-methylbutyloxy) phthalocyanine was charged into 400 ml of 1,1,2-trichloroethane, and the temperature was raised to 40 ° C. to dissolve it. Next, 16 g of bromine was added dropwise, and the mixture was stirred at 70 ° C for 5 hours. The reaction solution was cooled to 40 ° C. and the precipitated crystals were filtered off. The obtained crystals were sludged three times with 100 ml of methanol and dried under reduced pressure. The yield was 12.3g.
元素分析により、臭素の置換数は４個であることが判明
した。Elemental analysis revealed that the number of bromine substitutions was four.
元素分析:C60H68N8O4Br4Pd Ｃ Ｈ Ｎ Br 理論値(%) 51.80 4.93 8.05 23.97 分析値(%) 51.56 5.20 8.21 23.33 実施例４ パラジウム テトラα−（２−エチルヘキシルオキシ）
フタロシアニン2gを1,1,2,2−テトラクロロエタン400ml
に装入し、40℃に昇温して溶解させた。次に臭素5gを滴
下し、50℃で１時間攪拌した。反応液を40℃に降温し析
出した結晶をろ別した。得られた結晶をメタノール30ml
で３回スラッジし、減圧乾燥した。収量は2.2gであっ
た。Elemental analysis: C 60 H 68 N 8 O 4 Br 4 Pd C H N Br theoretical value (%) 51.80 4.93 8.05 23.97 analytical value (%) 51.56 5.20 8.21 23.33 Example 4 Palladium tetra α- (2-ethylhexyloxy)
Phthalocyanine 2g 1,1,2,2-tetrachloroethane 400ml
It was charged into a vessel and heated to 40 ° C. to dissolve it. Next, 5 g of bromine was added dropwise, and the mixture was stirred at 50 ° C for 1 hour. The reaction solution was cooled to 40 ° C. and the precipitated crystals were filtered off. 30 ml of the obtained crystals
Was sludged 3 times and dried under reduced pressure. The yield was 2.2 g.
元素分析の結果、得られたものは臭素置換数２個と３個
の中間の値を示し、臭素２個置換と３個置換のフタロシ
アニンの混合物であることが判明した。As a result of elemental analysis, it was found that the obtained product had an intermediate value between 2 and 3 in bromine substitution, and was a mixture of 2- and 3-substituted bromine phthalocyanines.
元素分析： Ｃ Ｈ Ｎ Br 理論値(%)ｎ＝２ 59.60 6.10 8.69 12.39 理論値(%)ｎ＝３ 56.17 5.67 8.19 17.52 分析値(%) 57.91 5.86 8.47 14.94 実施例５ ジクロロシリコン テトラα−（２−エチルヘキシルオ
キシ）フタロシアニン5gを1,1,1−トリクロロエタン100
mlに装入し、40℃に昇温して溶解させた。次に臭素5gを
滴下し、50℃で１時間攪拌した。反応液を40℃に降温し
析出した結晶をろ別した。得られた結晶をメタノール10
0mlで３回スラッジし、減圧乾燥した。収量は5.2gであ
った。Elemental analysis: C H N Br theoretical value (%) n = 2 59.60 6.10 8.69 12.39 theoretical value (%) n = 3 56.17 5.67 8.19 17.52 analytical value (%) 57.91 5.86 8.47 14.94 Example 5 dichlorosilicon tetra α- (2 -Ethylhexyloxy) phthalocyanine 5 g was added to 1,1,1-trichloroethane 100
It was charged in ml and the temperature was raised to 40 ° C. to dissolve it. Next, 5 g of bromine was added dropwise, and the mixture was stirred at 50 ° C for 1 hour. The reaction solution was cooled to 40 ° C. and the precipitated crystals were filtered off. The obtained crystals are methanol 10
It was sludged three times with 0 ml and dried under reduced pressure. The yield was 5.2g.
元素分析により、臭素の置換数は３個であることが判明
した。Elemental analysis revealed that the number of bromine substitutions was three.
元素分析:C64H77N8O4Br3Cl2Si Ｃ Ｈ Ｎ Br Cl 理論値(%) 56.48 5.70 8.23 17.61 5.21 分析値(%) 57.05 5.85 8.33 17.01 5.38 実施例６ パラジウム テトラα−（1,3−ジメチルブチルオキ
シ）フタロシアニン2gを四塩化炭素40mlに装入し、35℃
に昇温して溶解させた。次に塩化スルフリル2gを滴下
し、50℃で1.5時間攪拌した。反応液を35℃に降温し、
析出した結晶をろ別した。得られた結晶を水50mlで２回
洗浄し、メタノール50mlで３回スラッジし、減圧乾燥し
た。収量は2.2gであった。Elemental analysis: C 64 H 77 N 8 O 4 Br 3 Cl 2 Si C H N Br Cl Theoretical value (%) 56.48 5.70 8.23 17.61 5.21 Analytical value (%) 57.05 5.85 8.33 17.01 5.38 Example 6 Palladium tetra α- (1 Charge 2 g of (3-dimethylbutyloxy) phthalocyanine into 40 ml of carbon tetrachloride at 35 ° C.
It was heated to and dissolved. Next, 2 g of sulfuryl chloride was added dropwise, and the mixture was stirred at 50 ° C. for 1.5 hours. The reaction solution is cooled to 35 ° C,
The precipitated crystals were filtered off. The obtained crystals were washed twice with 50 ml of water, sludged with 50 ml of methanol three times, and dried under reduced pressure. The yield was 2.2 g.
元素分析により、塩素の置換数は４個であることが判明
した。Elemental analysis revealed that the number of chlorine substitutions was four.
元素分析:C56H60N8O4Cl4Pd Ｃ Ｈ Ｎ Cl 理論値(%) 58.11 5.23 9.68 12.25 分析値(%) 57.73 5.10 9.58 12.65 〔発明の効果〕 本発明により、アルコキシフタロシアニンにハロゲン原
子の導入量を制御して置換することが可能となった。Elemental analysis: C 56 H 60 N 8 O 4 Cl 4 Pd C H N Cl Theoretical value (%) 58.11 5.23 9.68 12.25 Analytical value (%) 57.73 5.10 9.58 12.65 [Effect of the invention] According to the present invention, alkoxyphthalocyanine has halogen It became possible to replace by controlling the introduction amount of.
Claims (3)
あらわし、Metは２個の水素原子、２価の金属原子、置
換３価金属原子、２置換４価金属原子を表わす。〕で示
されるフタロシアニン化合物をハロゲン化溶媒中、20〜
90℃でハロゲン化剤と反応させることを特徴とする、下
式（II） 〔式（II）中、Ｒ及びMetは式（Ｉ）と同一の意味を表
し、Ｘは、塩素、臭素、またはヨウ素を表し、ｎは１≦
ｎ≦４である。〕で示されるフタロシアニン化合物の製
造方法。1. The following general formula (I): [In the formula (I), R represents a substituted or unsubstituted alkyl group, and Met represents two hydrogen atoms, a divalent metal atom, a substituted trivalent metal atom or a disubstituted tetravalent metal atom. A phthalocyanine compound represented by
The following formula (II) characterized by reacting with a halogenating agent at 90 ° C [In the formula (II), R and Met have the same meanings as in the formula (I), X represents chlorine, bromine, or iodine, and n is 1 ≦
n ≦ 4. ] The manufacturing method of the phthalocyanine compound shown by these.
ロシアニン化合物に対して10〜200重量倍である請求項
１記載の製造方法。2. The process according to claim 1, wherein the amount of the halogenated solvent used is 10 to 200 times by weight the amount of the phthalocyanine compound of the formula (I).
シアニン化合物に対して１〜６モル比である請求項２記
載の製造方法。3. The method according to claim 2, wherein the amount of the halogenating agent used is 1 to 6 molar ratio with respect to the phthalocyanine compound of formula (I).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2118574A JPH0749531B2 (en) | 1990-05-10 | 1990-05-10 | Method for producing phthalocyanine compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2118574A JPH0749531B2 (en) | 1990-05-10 | 1990-05-10 | Method for producing phthalocyanine compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0415264A JPH0415264A (en) | 1992-01-20 |
| JPH0749531B2 true JPH0749531B2 (en) | 1995-05-31 |
Family
ID=14739966
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2118574A Expired - Lifetime JPH0749531B2 (en) | 1990-05-10 | 1990-05-10 | Method for producing phthalocyanine compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0749531B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0703281B1 (en) * | 1994-09-23 | 2000-03-01 | Ciba SC Holding AG | Process for the manufacture of brominated, alkoxy substituted metal phthalocyanine |
-
1990
- 1990-05-10 JP JP2118574A patent/JPH0749531B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0415264A (en) | 1992-01-20 |
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