JPS63222172A - Production of meso-tetraallyltetrabenzoporphyrin derivative - Google Patents
Production of meso-tetraallyltetrabenzoporphyrin derivativeInfo
- Publication number
- JPS63222172A JPS63222172A JP5615187A JP5615187A JPS63222172A JP S63222172 A JPS63222172 A JP S63222172A JP 5615187 A JP5615187 A JP 5615187A JP 5615187 A JP5615187 A JP 5615187A JP S63222172 A JPS63222172 A JP S63222172A
- Authority
- JP
- Japan
- Prior art keywords
- meso
- metal salt
- formula
- reacting
- benzoic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 9
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 7
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- 150000001340 alkali metals Chemical group 0.000 claims abstract description 4
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 3
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 3
- 125000004076 pyridyl group Chemical group 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001873 dinitrogen Inorganic materials 0.000 abstract description 3
- 239000004020 conductor Substances 0.000 abstract description 2
- 239000011261 inert gas Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- GZEFZLXJPGMRSP-UHFFFAOYSA-N 37,38,39,40-tetrazanonacyclo[28.6.1.13,10.112,19.121,28.04,9.013,18.022,27.031,36]tetraconta-1(37),2,4,6,8,10,12(39),13,15,17,19,21,23,25,27,29,31,33,35-nonadecaene Chemical group c1ccc2c3cc4[nH]c(cc5nc(cc6[nH]c(cc(n3)c2c1)c1ccccc61)c1ccccc51)c1ccccc41 GZEFZLXJPGMRSP-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 239000004246 zinc acetate Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- VHMICKWLTGFITH-UHFFFAOYSA-N 2H-isoindole Chemical compound C1=CC=CC2=CNC=C21 VHMICKWLTGFITH-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- -1 alkali metal salt Chemical class 0.000 description 2
- 150000001793 charged compounds Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 2
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- NOVIRODZMIZUPA-UHFFFAOYSA-N 2,3-dihydro-1h-isoindole;hydrochloride Chemical compound Cl.C1=CC=C2CNCC2=C1 NOVIRODZMIZUPA-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- ITIONVBQFUNVJV-UHFFFAOYSA-N Etomidoline Chemical compound C12=CC=CC=C2C(=O)N(CC)C1NC(C=C1)=CC=C1OCCN1CCCCC1 ITIONVBQFUNVJV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- AYFVYJQAPQTCCC-GBXIJSLDSA-N L-threonine Chemical compound C[C@@H](O)[C@H](N)C(O)=O AYFVYJQAPQTCCC-GBXIJSLDSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003968 arylidene group Chemical group [H]C(c)=* 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- MXHTZQSKTCCMFG-UHFFFAOYSA-N n,n-dibenzyl-1-phenylmethanamine Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)CC1=CC=CC=C1 MXHTZQSKTCCMFG-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229960003424 phenylacetic acid Drugs 0.000 description 1
- 239000003279 phenylacetic acid Substances 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000004032 porphyrins Chemical group 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- FYRHIOVKTDQVFC-UHFFFAOYSA-M potassium phthalimide Chemical compound [K+].C1=CC=C2C(=O)[N-]C(=O)C2=C1 FYRHIOVKTDQVFC-UHFFFAOYSA-M 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940006198 sodium phenylacetate Drugs 0.000 description 1
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 1
- JDLYKQWJXAQNNS-UHFFFAOYSA-L zinc;dibenzoate Chemical compound [Zn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 JDLYKQWJXAQNNS-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
- G03G5/0622—Heterocyclic compounds
- G03G5/0624—Heterocyclic compounds containing one hetero ring
- G03G5/0627—Heterocyclic compounds containing one hetero ring being five-membered
- G03G5/0629—Heterocyclic compounds containing one hetero ring being five-membered containing one hetero atom
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Photoreceptors In Electrophotography (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、可視光用増感剤、導電性材料などの充電材料
に有用なメソ−テトラアリルテトラベンゾポルフィリン
誘導体の製法に関する。更に詳しくは、３−アリリデン
フタルイミジンまたはその金属塩を安息香酸金属塩と反
応させる事を特徴とする。メソー位がすべてアリル基で
置換された構造を有するメソ−テトラアリルテトラベン
ゾポルフィリン誘導体の製法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing meso-tetraallyltetrabenzoporphyrin derivatives useful as visible light sensitizers and charging materials such as conductive materials. More specifically, it is characterized by reacting 3-allylidenephthalimidine or its metal salt with a benzoic acid metal salt. The present invention relates to a method for producing a meso-tetraallyltetrabenzoporphyrin derivative having a structure in which all meso positions are substituted with allyl groups.
メソー位がアリル基で置換されたテトラベンゾポルフィ
リンの製法として、これまでに次のような例が公知であ
る。The following examples are known as methods for producing tetrabenzoporphyrin substituted with an allyl group at the meso position.
１）３−アリリデンフタルイミジンと酢酸亜鉛とを、あ
るいは、フタルイミドカリウム塩、アリル酢酸及び酢酸
亜鉛とを加熱反応させる（Ｖ、Ｎ、フプラネンコフらｅ
Ｚｈ、０ｂｓｃｈｃｈ、 Ｋｈｉｍ−＋ ５１巻、１
１号。1) Heat reacting 3-allylidenephthalimidine with zinc acetate, or phthalimide potassium salt, allyl acetate and zinc acetate (V, N, Huplanenkov et al.
Zh, 0bschch, Khim-+ vol. 51, 1
No. 1.
２５１３ページ（１９８１年）参照）。(See page 2513 (1981)).
２）イソインドール、ベンツアルデヒド及び酢酸亜鉛を
加熱反応させる（、 Ｄ、 Ｅ、レミー、 Ｔｅｔｒａ
ｈｅｄｒｏｎＬｅｔｔ、 、 ２４巻、１４５１ページ
（１９８３年）参照）。2) Heat reaction of isoindole, benzaldehyde and zinc acetate (D, E, Remy, Tetra
Hedron Lett, vol. 24, p. 1451 (1983)).
３）イソインドリンの塩酸塩、フェニル酢酸ナトリウム
塩あるいはトリベンジルアミン及び酢酸亜鉛とを加熱反
応させる（ Ｖ、 Ｎ、コブラネンコフら。3) Heat reaction of isoindoline hydrochloride, sodium phenylacetate or tribenzylamine and zinc acetate (V, N, Kobranenkov et al.
Ｋｈｔｍ、 Ｇｅｔｅｒｏｔｓｉｋｌ、 ５ｏｅｄｔｎ
、、 ｔｏ、 １３７２（１９８５年）参照）。Khtm, Geterotsikl, 5oedtn
, to, 1372 (1985)).
４）フタルイミドあるいはそのアルカリ金属塩とアリル
酢酸金属塩とを加熱反応させる（特許出願第６１−２２
６６６４号参照）。4) Heating and reacting phthalimide or its alkali metal salt with allyl acetate metal salt (Patent Application No. 61-22)
6664).
これまでに知られているメソー位にアリル基を有スるテ
トラベンゾポルフィリンの製法のウチ。This is one of the previously known methods for producing tetrabenzoporphyrin having an allyl group at the meso position.
メソー位のすべてがアリル基で置換されたメソ−テトラ
アリルテトラベンゾポルフィリンのみを生成しうる方法
はなく、これら公知の方法によって製造されるメソ−ア
リル置換テトラベンゾポルフィリン誘導体は、メソー位
が０個から４個のアリル基で置換されたものの混合物と
して得られている。There is no method that can produce only meso-tetraallyltetrabenzoporphyrin in which all meso positions are substituted with allyl groups, and meso-allyl substituted tetrabenzoporphyrin derivatives produced by these known methods have 0 meso positions. It is obtained as a mixture of those substituted with four allyl groups.
本発明者らは２以上の問題点を十分に吟味し。The inventors have carefully examined two or more problems.
鋭意努力を重ねた結果、３−アリリデンフタルイミジン
類を安息香酸金属塩と反応させると、４つのメン位がす
べてアリル基で置換されたメソ−テトラアリルテトラベ
ンゾポルフィリン誘導体を選択的に与える事を見いだし
９本発明をなすに至った。As a result of extensive efforts, we have found that when 3-allylidenephthalimidines are reacted with metal benzoate, meso-tetraallyltetrabenzoporphyrin derivatives in which all four men's positions are substituted with allyl groups can be selectively obtained. The present invention has been completed based on the following findings.
（式中、Ｘは水素原子またはアルカリ金属原子を示し、
Ａ及びＢは水素原子、 Ｃ＋〜Ｃｓのアルキル基、シア
ノ基、またはアルコキシカルボニル基からえらばれた一
員、もしくはその両者で縮合ベンゼン環を構成するＣＨ
−ＣＨを示し、Ｒは無置換または置換フェニル、ナフチ
ル、ピリジル基を示す）で表される３−アリリデンフタ
ルイミジンまたはその金属塩を、一般式（Ｉ［）
（式中９Ｍは二価の金属原子を示す）
で表される安息香酸金属塩と反応させる事を特徴とする
メゾ−テトラアリルテトラベンゾポルフィリン誘導体の
製法を提供するものである。(In the formula, X represents a hydrogen atom or an alkali metal atom,
A and B are a hydrogen atom, a member selected from an alkyl group, a cyano group, or an alkoxycarbonyl group of C+ to Cs, or CH constituting a fused benzene ring with both of them;
-CH, R represents an unsubstituted or substituted phenyl, naphthyl, or pyridyl group) or a metal salt thereof, with the general formula (I[) (wherein 9M is a divalent The present invention provides a method for producing a meso-tetraaryltetrabenzoporphyrin derivative, which is characterized by reacting it with a benzoic acid metal salt represented by (representing a metal atom).
本発明に用いられる一般式（Ｉ）で表される３−アリリ
デンフタルイミジン類は、ベンゼン環に置換基を有して
いてもよい。従って、無置換アリリデンフタルイミジン
の他に、３−アリリデン−５−メトキシカルボニルフタ
ルイミジン、３−アリリデン−５−ｔ−ブチルフタルイ
ミジンなどが用いられる。また、アリル基も同様に置換
基を有していてよ＜、ａ−ｐ−メチルベンジリデンフタ
ルイミジン、３−ｐ−シアノベンジリデンフタルイミジ
ン、３−ｐ−メチルベンジリデンフタルイミジン、３−
ｐ−クロロベンジリデンフタルイミジ・ンなども用いら
れる。さらには、これらの７タルイミジン類の窒素原子
はナトリウムやカリウムなどのアルカリ金属で置換され
ていてもよい。一般式（ｎ）で表される安息香酸金属塩
の金属としては。The 3-allylidenephthalimidine represented by the general formula (I) used in the present invention may have a substituent on the benzene ring. Therefore, in addition to unsubstituted allylidene phthalimidine, 3-allylidene-5-methoxycarbonylphthalimidine, 3-allylidene-5-t-butylphthalimidine, etc. are used. In addition, the allyl group also has a substituent in the same way.
p-chlorobenzylidenephthalimidine and the like are also used. Furthermore, the nitrogen atom of these 7-thalimidines may be substituted with an alkali metal such as sodium or potassium. The metal of the benzoic acid metal salt represented by the general formula (n) is:
マグネシウム、亜鉛、カドミウム、銅、ニッケル。Magnesium, zinc, cadmium, copper, nickel.
コバルト、パラジウム、鉛などの二価の金属カ挙げられ
る。Examples include divalent metals such as cobalt, palladium, and lead.
一般式＋Ｉ）で表される３−７タルイミジン類と一般式
（ＩＩ）で表される安息香酸金属塩は、１：０．３から
１：５のモル比、より好ましくは１：０．５から１：３
のモル比で反応させる事がよい。The molar ratio of the 3-7 thalimidine represented by general formula +I) and the benzoic acid metal salt represented by general formula (II) is 1:0.3 to 1:5, more preferably 1:0.5. From 1:3
It is preferable to carry out the reaction at a molar ratio of
反応は溶媒を用いずに両者を混合して加熱する。The reaction is carried out by mixing and heating the two without using a solvent.
反応温度は２００°ＣからＳＯＯｏＣ，より好ましくは
２５０℃から４００℃である。反応時間は１０分から３
時間の範囲であり、より好ましくは３０分から２時間で
ある。また、この高温反応を窒素ガスなどの不活性気体
中で行うのが好ましい。The reaction temperature is 200°C to SOOoC, more preferably 250°C to 400°C. Reaction time is 10 minutes to 3
The time range is more preferably 30 minutes to 2 hours. Moreover, it is preferable to carry out this high temperature reaction in an inert gas such as nitrogen gas.
本発明で製造されるメソ−テトラアリルテトラベンゾポ
ルフィリン誘導体は、一般式画（式中、Ａ、Ｂ、Ｍ、Ｒ
は前記と同じ意味を持つ）で表される構造を持つ。The meso-tetraallyltetrabenzoporphyrin derivative produced in the present invention has a general formula (wherein A, B, M, R
has the same meaning as above).
前述の従来の方法では、メソ−テトラアリル置換体は主
生成物ではなく、主に、メソ−ジアリル及びメソ−トリ
アリル置換体が生成する。しかしながら９本発明の方法
において製造されるのは。In the conventional methods described above, meso-tetraallyl substitutions are not the main products, but meso-diallyl and meso-triallyl substitutions are mainly produced. However, 9 are produced in the method of the present invention.
メソ−テトラアリルテトラベンゾポルフィリンである事
が明らかとなった。It was revealed that it was meso-tetraallyltetrabenzoporphyrin.
本発明において、酢酸金属塩を安息香酸塩に置き換える
事により、テトラ置換体のみが製造される理由は明らか
でないが、以下の事が考えられる。In the present invention, the reason why only tetra-substituted products are produced by replacing metal acetate with benzoate is not clear, but the following may be considered.
酢酸金属塩の場合、そのカルボニルのα−位が活性なメ
チレン基であるため、加熱中に一般式（Ｉ）で表される
３−アリリデンフタルイミジン類のアリリデン基と反応
し、３−メチレンフタルイミジンを生成する可能性があ
る。これがメゾー位に無置換のポルフィリン骨格を構成
する。それに対し。In the case of acetic acid metal salt, since the α-position of its carbonyl is an active methylene group, it reacts with the arylidene group of 3-allylidenephthalimidine represented by general formula (I) during heating, and forms 3-methylene. May produce phthalimidine. This constitutes a porphyrin skeleton with no substitutions at the meso position. For it.
安息香酸塩は活性な炭素を有さず、アリリデンフタルイ
ミジンと反応しないために、メソー位に４個のアリル基
で置換された誘導体が生成するものと考えられる。Since benzoate does not have an active carbon and does not react with arylidenephthalimidine, it is thought that a derivative substituted with four allyl groups at the meso position is produced.
本発明の化合物は、約７５０ｎｍにまで至る長波長の光
を効率良（吸収するうえ、高分子やミセルなどに高濃度
で混合することができるので、レーザ光用の増感剤とし
て極めて有用である。The compound of the present invention is extremely useful as a sensitizer for laser light because it efficiently absorbs light with long wavelengths up to about 750 nm and can be mixed into polymers, micelles, etc. at high concentrations. be.
次に、実施側番こよって本発明をさらに詳しく説明する
。なお９本発明はこれらの例に限定されるものではない
。Next, the present invention will be explained in more detail based on the implementation details. Note that the present invention is not limited to these examples.
実施例
３−ベンジリデンフタルイミジン２．１２ｇ（１０ｇリ
モル）と安息香酸亜鉛２．４６ｇ（８ミリモル）を乳鉢
でよ（混合し、これを窒素ガス気流下３６０℃で１時間
加熱した。得られた生成物にベンゼン１００１！ｊを加
え２時間加熱還流した。室温まで冷却した後、このベン
ゼン溶液を吸引ろ過し、不溶物を除去した。ろ液からベ
ンゼンを減圧留去してから、残留物をベンゼンとへキサ
ンの１＝１容量比の混合溶媒に溶解し、アルミナカラム
クロマトグラフィーに供した。濃緑色の留分を分取し、
０゜０５ｇの生成物を得た。可視吸収スペクトルはジク
ロロメタン中でｅ４５５ｎｍ（ツレ−帯）、６５０ｎｍ
（Ｑ帯）にテトラベンゾポルフィリン金属錯体に特有な
吸収を示した。電界脱離イオンスペクトルはメソ−テト
ラフェニルテトラベンゾポルフィリン亜鉛錯体に相当す
る分子イオン（ｍ／Ｚ＝８７６）が検出され、その構造
が確認された。Example 3 - 2.12 g (10 g mol) of benzylidenephthalimidine and 2.46 g (8 mmol) of zinc benzoate were mixed in a mortar and heated at 360° C. for 1 hour under a stream of nitrogen gas. Benzene 1001!j was added to the resulting product and heated under reflux for 2 hours. After cooling to room temperature, this benzene solution was suction filtered to remove insoluble matter. Benzene was distilled off from the filtrate under reduced pressure, and the residue was dissolved in a mixed solvent of benzene and hexane at a volume ratio of 1=1 and subjected to alumina column chromatography.A dark green fraction was collected.
0.05 g of product was obtained. Visible absorption spectrum is e455nm (Three band) and 650nm in dichloromethane.
(Q band) showed an absorption characteristic of tetrabenzoporphyrin metal complexes. In the field desorption ion spectrum, a molecular ion (m/Z=876) corresponding to a meso-tetraphenyltetrabenzoporphyrin zinc complex was detected, and its structure was confirmed.
Ｈ，ａ、メソ−フェニルのオルソＨ）、８．１２（８Ｈ
。H, a, meso-phenyl ortho H), 8.12 (8H
.
ｔ、メソ−フェニルのメタＨ） 、 ８．２１ （４Ｈ
，ｔ、メソ−フェニルのパラＨ）。t, meso-phenyl meta H), 8.21 (4H
, t, meso-phenyl para H).
比較例１
とフェニル酢酸１．３６ｇ （１０ミ！ｊモル）及び酢
酸亜鉛２水知物０．８８ｇ（４”！ｊモル）とを実施例
と同様にして緑色の生成物０．１８ｇを得た。これは塩
化メチレン中で４４１ｎｍ（ツレ−帯）−６３４ｎｍ（
Ｑ帯）に吸収極大を持ち、実施例゛で得られた化合物の
吸収極大より約１５ｎｍ短波長であった。Comparative Example 1, 1.36 g (10 mm!j moles) of phenylacetic acid and 0.88 g (4''! j moles) of zinc acetate dihydrogen were used in the same manner as in Example to obtain 0.18 g of a green product. This was measured in methylene chloride from 441 nm (Three band) to 634 nm (
It had an absorption maximum in the Q band), which was about 15 nm shorter than the absorption maximum of the compound obtained in Example (2).
生成物の電界脱離イオンスペクトルでは８７６゜８００
．７２４，６４８，５７２の分子イオンが検出され。The field desorption ion spectrum of the product is 876°800
．． 724,648,572 molecular ions were detected.
これらはそれぞれメソー位に４．３，２．１個のフェニ
ル基が置換したテトラベンゾポルフィリン亜鉛錯体及び
無置換のテトラベンゾポルフィリン亜鉛錯体であった。These were a tetrabenzoporphyrin zinc complex substituted with 4.3 and 2.1 phenyl groups at the meso position and an unsubstituted tetrabenzoporphyrin zinc complex, respectively.
比較例２
イソインドール０．１ｇ（０，８ミリモル）、ベンツア
ルデヒド０．２２ｇ（２ミリモル）、酢酸亜鉛２水和物
０．１５ ｇ （０，７ミＩＪモル）とを実施例と同様
な条件で反応させ、緑色の生成物を得た。Comparative Example 2 0.1 g (0.8 mmol) of isoindole, 0.22 g (2 mmol) of benzaldehyde, and 0.15 g (0.7 mmol) of zinc acetate dihydrate were added in the same manner as in the example. The reaction was carried out under the following conditions to obtain a green product.
これらは塩化メチレン中でツレ−帯の吸収が４３３゜４
４２、４５５ ｎｍ ！ζ存在しており、これらの極大
波長からメソー位にフェニル基が４．３．２個置換した
テトラベンゾポルフィリン亜鉛錯体である事が分かった
。These have a Thre band absorption of 433°4 in methylene chloride.
42,455 nm! ζ, and from these maximum wavelengths, it was found that it was a tetrabenzoporphyrin zinc complex substituted with 4.3.2 phenyl groups at the meso position.
Claims (1)
Ａ及びＢは水素原子、Ｃ＿１〜Ｃ＿５のアルキル基、シ
アノ基、またはアルコキシカルボニル基から選ばれた一
員、もしくはその両者で縮合ベンゼン環を構成するＣＨ
＝ＣＨを示し、Ｒは無置換または置換フェニル、ナフチ
ル、ピリジル基を示す）で表される３−アリリデンフタ
ルイミジンまたはその金属塩を、一般式 ▲数式、化学式、表等があります▼ （式中、Ｍは二価の金属原子を示す） で表される安息香酸金属塩と反応させる事を特徴とする
メソ−テトラアリルテトラベンゾポリフィリン誘導体の
製法。[Claims] General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, X represents a hydrogen atom or an alkali metal atom,
A and B are a hydrogen atom, a member selected from C_1 to C_5 alkyl groups, cyano groups, or alkoxycarbonyl groups, or CH that constitutes a fused benzene ring with both.
=CH and R represents an unsubstituted or substituted phenyl, naphthyl, or pyridyl group) or its metal salt is expressed by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Formula 1. A method for producing a meso-tetraaryltetrabenzoporphyrin derivative, characterized by reacting it with a benzoic acid metal salt represented by (wherein, M represents a divalent metal atom).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5615187A JPS63222172A (en) | 1987-03-11 | 1987-03-11 | Production of meso-tetraallyltetrabenzoporphyrin derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5615187A JPS63222172A (en) | 1987-03-11 | 1987-03-11 | Production of meso-tetraallyltetrabenzoporphyrin derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63222172A true JPS63222172A (en) | 1988-09-16 |
| JPH0319234B2 JPH0319234B2 (en) | 1991-03-14 |
Family
ID=13019087
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5615187A Granted JPS63222172A (en) | 1987-03-11 | 1987-03-11 | Production of meso-tetraallyltetrabenzoporphyrin derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63222172A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5252730A (en) * | 1992-04-10 | 1993-10-12 | Northrop Corporation | Polymer composition having intense magnetic properties and method for preparation thereof |
| EP1798600A1 (en) * | 2005-12-19 | 2007-06-20 | Xerox Corporation | Imaging Member |
-
1987
- 1987-03-11 JP JP5615187A patent/JPS63222172A/en active Granted
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5252730A (en) * | 1992-04-10 | 1993-10-12 | Northrop Corporation | Polymer composition having intense magnetic properties and method for preparation thereof |
| US5340915A (en) * | 1992-04-10 | 1994-08-23 | Northrop Corporation | Crosslinked magnetic polymers and methods for preparation thereof |
| US5352764A (en) * | 1992-04-10 | 1994-10-04 | Northrop Corporation | Stepwise linear magnetic polymers and methods for preparation thereof |
| EP1798600A1 (en) * | 2005-12-19 | 2007-06-20 | Xerox Corporation | Imaging Member |
| US7527904B2 (en) | 2005-12-19 | 2009-05-05 | Xerox Corporation | Imaging member |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0319234B2 (en) | 1991-03-14 |
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