JPH03188083A - Porphyrin polymer and production thereof - Google Patents
Porphyrin polymer and production thereofInfo
- Publication number
- JPH03188083A JPH03188083A JP32644089A JP32644089A JPH03188083A JP H03188083 A JPH03188083 A JP H03188083A JP 32644089 A JP32644089 A JP 32644089A JP 32644089 A JP32644089 A JP 32644089A JP H03188083 A JPH03188083 A JP H03188083A
- Authority
- JP
- Japan
- Prior art keywords
- porphyrin
- formula
- skeleton
- group
- tables
- 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
- 150000004032 porphyrins Chemical class 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229920000642 polymer Polymers 0.000 title abstract 2
- -1 porphyrin compounds Chemical class 0.000 claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims abstract 2
- 239000000126 substance Substances 0.000 claims description 11
- 230000003009 desulfurizing effect Effects 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 150000003457 sulfones Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 4
- 102000018832 Cytochromes Human genes 0.000 abstract description 2
- 108010052832 Cytochromes Proteins 0.000 abstract description 2
- 102000001554 Hemoglobins Human genes 0.000 abstract description 2
- 108010054147 Hemoglobins Proteins 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 229930002875 chlorophyll Natural products 0.000 abstract description 2
- 235000019804 chlorophyll Nutrition 0.000 abstract description 2
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 230000029553 photosynthesis Effects 0.000 abstract description 2
- 238000010672 photosynthesis Methods 0.000 abstract description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract 1
- 125000005843 halogen group Chemical group 0.000 abstract 1
- 239000011368 organic material Substances 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 230000027756 respiratory electron transport chain Effects 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 125000003944 tolyl group Chemical group 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 210000000988 bone and bone Anatomy 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 108091006149 Electron carriers Proteins 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、ポルフィリン化合物同志が共役二重結合によ
って連結されたポルフィリン多量体及びその製造法に関
するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a porphyrin multimer in which porphyrin compounds are linked together by conjugated double bonds, and a method for producing the same.
ポルフィリン化合物は、自然界のクロロフィル、ヘモグ
ロビン、チトクローム等の光合成、酸素担体、電子伝達
体として重要な機能を有しており、工業的にも有機感光
材料、有機導電材料として重要である。Porphyrin compounds have important functions in the photosynthesis of chlorophyll, hemoglobin, cytochrome, etc. in nature, as oxygen carriers, and electron carriers, and are also important industrially as organic photosensitive materials and organic conductive materials.
ポルフィリン化合物の上記機能が同化合物の共役構造に
起因するものであることは疑問のないところであり、こ
の意味で、共役二重結合によって連結されたポルフィリ
ン多量体は既存のポルフィリン化合物と同様の分野への
利用が期待されるものである。There is no doubt that the above-mentioned functions of porphyrin compounds are due to the conjugated structure of the same compounds, and in this sense, porphyrin multimers linked by conjugated double bonds can be applied to the same field as existing porphyrin compounds. It is expected that it will be used.
〔従来の技術と発明が解決しようとする課題〕従来は、
ポルフィリン化合物同志を共役二重結合で連結させる優
れた一般的な方法はなかった。理論的には、ポルフィリ
ン化合物のアルデヒドとポルフィリン化合物のリンイリ
ドとを反応させれば良い考えられるが、ポルフィリン化
合物のアルデドやリンイリドの調製は非常に困難である
。[Problems to be solved by conventional technology and inventions] Conventionally,
There was no good general method for linking porphyrin compounds with conjugated double bonds. Theoretically, it would be possible to react the aldehyde of the porphyrin compound with the phosphorus ylide of the porphyrin compound, but it is extremely difficult to prepare the aldehyde and phosphorus ylide of the porphyrin compound.
〔課題を解決するための手段と作用〕
上記の実情に鑑み本発明者は、ポルフィリン化合物同志
を共役二重結合で連結させる優れた一般的な方法を提供
するべく研究の結果、本発明に到達したものである。[Means and effects for solving the problem] In view of the above-mentioned circumstances, the present inventor has arrived at the present invention as a result of research to provide an excellent general method for connecting porphyrin compounds with each other through conjugated double bonds. This is what I did.
即ち本発明は、次のポルフィリン多量体とその製法に係
るものである。That is, the present invention relates to the following porphyrin multimer and its production method.
（骨格中の数字及びギリシア文字は位置を示す符号であ
る。以下、上記骨格を■で表し、この骨格をそのα。β
、γ、δ位のいずれかに直結する結合と共に示す場合は
、■−で表す。）を有するポルフィリン化合物同志が、
α。β、γδ位のいずれかの間で
（叉ＣＨ＝ ＣＩ −ＣＩ ＝ ＣＨ＜ヅ及び０ＣＩ＝
ＣＨ−Ｃ１（＝ＣＩ−ＣＩ＝ＣＩ＋−＠〆の群からから
選ばれる共役二重結合によって互いに連結されているポ
ルフィリン多量体。(Numbers and Greek letters in the skeleton are symbols indicating positions.Hereinafter, the above skeleton will be represented by ■, and this skeleton will be referred to as its α, β
When shown together with a bond directly connected to either the , γ or δ position, it is represented by ■-. ), the porphyrin compounds having
α. Between either β or γδ position (CH= CI −CI = CH<ㅅ and 0CI=
Porphyrin multimers interconnected by conjugated double bonds selected from the group CH-C1 (=CI-CI=CI+-@〆.
■骨ｍＥ）を有するポルフィリン化合物同志を、各ポル
フィリン化合物のα。β、Ｔ、δ位のいずれかに導入し
たー ＣＨｚＸ （式中Ｘはハロゲンを意味する。■ Porphyrin compounds with bone mE), α of each porphyrin compound. Introduced into any of the β, T, and δ positions - CHzX (wherein, X means halogen.
）と
ＣＩ、ＣＯ３−ＣＨ２＜防ＣＨｚ ５ＣＯＣＨｚ−ＣＩ
ＩｚＣＯ５ＣＨ２ＣＨ２５ＣＯＣＨｚ−及びＣＨ３ＣＤ
５ Ｃ）１２ ＣＨ＝ Ｃａｌ ＣＨ２５ＣＯＣ
１１ｙ−の群から選ばれるチオアセチル化合物との間の
求核置換反応により連結させてスルフィド型のポルフィ
リン多量体となす第一の工程；このスルフィド型のポル
フィリン多量体を酸化して対応するスルホン型のポルフ
ィリン多量体となす第二の工程；このスルホン型のポル
フィリン多量体を脱硫黄する第三の工程；の３工程から
なることを特徴とする、■記載のポルフィリン多量体の
製造法。) and CI, CO3-CH2 < protection CHZ 5COCHz-CI
IzCO5CH2CH25COCHz- and CH3CD
5 C) 12 CH= Cal CH25COC
The first step is to form a sulfide-type porphyrin multimer by linking it with a thioacetyl compound selected from the group of 11y-; The method for producing a porphyrin multimer according to (1), which is characterized by comprising three steps: a second step of forming a porphyrin multimer; a third step of desulfurizing the sulfone-type porphyrin multimer;
ポルフィリン化合物としては、前記した骨格■のα、β
、γ、δ位や１乃至８位に各種置換基を導入したものが
知られている。As porphyrin compounds, α and β of the above-mentioned skeleton
, γ, δ and 1 to 8 positions are known to have various substituents introduced therein.
ポルフィリン骨ネツのα。β、γ、δ位への置換基の導
入は、同骨格の１乃至８位への導入よりも容易であり、
前述■の本発明方法の出発原料に容易に変換することの
可能なポルフィリン化合物（α。β、γ、δ位のいずれ
かにトリル基を導入したもの）に限っても各種のものが
知られている。α of porphyrin bones. The introduction of substituents into the β, γ, and δ positions is easier than the introduction into the 1st to 8th positions of the same skeleton,
Various types of porphyrin compounds (those having a tolyl group introduced at any of the α, β, γ, or δ positions) that can be easily converted into starting materials for the method of the present invention described in (2) above are known. ing.
後記実施例の１乃至３は、ポルフィリン骨格■のα。β
、Ｔ、δ位のそれぞれにトリル基を導入したポルフィリ
ン化合物をハロゲン化して出発原料としたものである。Examples 1 to 3 described below are α of the porphyrin skeleton (■). β
A porphyrin compound having tolyl groups introduced into each of the , T, and δ positions was halogenated and used as a starting material.
但し、後記実施例では、本発明の機構や生成物の構造を
精確に確認するため、上記ポルフィリン化合物のハロゲ
ン化によって得られる各種ハロゲン化ポルフィリンの内
から、ポルフィリン骨＋Ｓのα、β。However, in the Examples described later, in order to accurately confirm the mechanism of the present invention and the structure of the product, α and β of porphyrin bone+S were selected from various halogenated porphyrins obtained by halogenating the above-mentioned porphyrin compounds.
ｒ、δ位に位置する４個のトリル基の内、一つのトリル
基のみがハロゲン化されたポルフィリン化合物のみを分
離し、これを第一工程においてチオアセチル化合物と反
応させ、引き続き第二第三の工程を実施してポルフィリ
ン化合物の二つを共役二重結合によって連結したポルフ
ィリンニ量体を製造したものである。A porphyrin compound in which only one tolyl group is halogenated among the four tolyl groups located at the r and δ positions is separated, and this is reacted with a thioacetyl compound in the first step, followed by a second and third step. The process was carried out to produce a porphyrin dimer in which two porphyrin compounds were linked by a conjugated double bond.
上述したとごろから明らかなように、ハロゲン化ポルフ
ィリンとして同一分子内にハロゲンかされたトリル基を
２個以上含むものを使用して本発明方法を実施すれば、
各種のポルフィリン多量体を製造することが可能である
。As is clear from the above, if the method of the present invention is carried out using a halogenated porphyrin containing two or more halogenated tolyl groups in the same molecule,
It is possible to produce various porphyrin multimers.
以下、実施例により本発明を更に具体的に説明する。尚
、以下においてＲはトリル基を意味する
実施例工
（４）
（５ｂ）
上記の第一の工程を実施する為、 ポルフィリンプロミ
ド（４） １．５ｇと１，４−アセチルチオキシレン０
．３ｇをＴＨＦ １０ｄに溶かし、Ｎａ０Ｈ（０，１ｇ
）を２１ｄのＭｅＯＨに溶かした溶液を加えて２０℃
で１２時間かきまぜた。反応液に２０−の水をそそぎ、
塩化メチレンで抽出した。抽出液を硫酸マグネシウムで
乾燥後、溶媒を留去した。このようにして得られた青色
の結晶をＣＩ。Hereinafter, the present invention will be explained in more detail with reference to Examples. In addition, in the following, R means a tolyl group. Example (4) (5b) In order to carry out the above first step, 1.5 g of porphyrin bromide (4) and 1,4-acetylthioxylene 0
．． Dissolve 3g in THF 10d and add NaOH (0.1g
) dissolved in 21d of MeOH and heated to 20°C.
I stirred it for 12 hours. Pour 20ml of water into the reaction solution,
Extracted with methylene chloride. After drying the extract over magnesium sulfate, the solvent was distilled off. The blue crystals thus obtained were designated as CI.
Ｃ１２−ＣＨ，０）１から再結晶して、０．９ｇ （６
１％）の（５ｂ）を得た。Recrystallized from C12-CH,0)1 to give 0.9 g (6
1%) of (5b) was obtained.
この物質の物性を次に示す。The physical properties of this substance are shown below.
耶計算値Ｃ＋ｏａＨｍｚＮｓＳｚ ｍ／ｅ１５０６
実測値ａ＋／ｅ１５０９ＵＶＪ、、、 （ＣＨ，Ｃｌ２
）４１９．５，５１５．５，５５４．０，５９２．０，
６４７．０’ ＩＩＮＭＲ（ＣＤＣＩ 、）δ８．８３
（ｓ、 １６Ｈ） 、δ８．１４（ｄ、Ｊ＝７．８ｔｌ
ｚ。Calculated value C+oaHmzNsSz m/e1506
Actual measurement value a+/e1509UVJ, (CH, Cl2
)419.5,515.5,554.0,592.0,
647.0' IINMR (CDCI,) δ8.83
(s, 16H), δ8.14(d, J=7.8tl
z.
４Ｈ）、６８．０７（ｄ、Ｊ＝９．３Ｈｚ、４Ｈ） 、
δ８．０５（ｄ、Ｊ＝７．８１１ｚ。4H), 68.07 (d, J=9.3Hz, 4H),
δ8.05(d, J=7.811z.
８Ｈ）、δ７．６５（ｄ、Ｊ＝７．８Ｈｚ、４Ｈ）、
δ７．５３ （ｄ 、 Ｊ＝７．８１１ｚ 。8H), δ7.65 (d, J=7.8Hz, 4H),
δ7.53 (d, J=7.811z.
４Ｈ）、δ７．５０（ｓ、４８） 、 ６７．４９（
ｄ、Ｊ＝８．８Ｈｚ、８Ｈ） 。4H), δ7.50(s, 48), 67.49(
d, J=8.8Hz, 8H).
６３．９８（ｓ、４ｌ−１） 、 ６３．９２（ｓ、
４Ｈ）、 ６２．６９（ｓ、６Ｈ） 。63.98(s, 4l-1), 63.92(s,
4H), 62.69(s, 6H).
δ２．６５（ｓ、 １２Ｈ） 、δ−２，７８（ｓ、４
Ｈ）（５ｂ）
（６ｂ）
上記の第二の工程を実施する為、スルフィド型のポルフ
ィリン化合物（５ｂ） ０． ７５ ｇとメタパーベン
ゾイックアシッド０．３ｇとを１０ｍ１の塩化メチレン
に溶かし、２５°Ｃで１２時間かき混ぜた。反応液をＩ
Ｎの炭酸水素ナトリウムＩＯＩＭ１に注ぎ、塩化メチレ
ンで抽出した。δ2.65 (s, 12H), δ-2,78 (s, 4
H) (5b) (6b) In order to carry out the above second step, a sulfide type porphyrin compound (5b) 0. 75 g and 0.3 g of metaperbenzoic acid were dissolved in 10 ml of methylene chloride and stirred at 25°C for 12 hours. The reaction solution is
Pour into N sodium bicarbonate IOIM1 and extract with methylene chloride.
抽出液を硫酸マグネシウムで乾燥後、溶媒を留去した。After drying the extract over magnesium sulfate, the solvent was distilled off.
このようにして得られた青色の結晶を再結晶して（６ｂ
） ０．７ｇ （８９％）を得た。The blue crystals thus obtained were recrystallized (6b
) 0.7g (89%) was obtained.
この物質の物性を次ぎに示す。The physical properties of this substance are shown below.
耶計算値Ｃ＋ｏ４）１ｓｚＯＪｓｓｚ ｍ／ｅ１５７０
実測値ｍ／ｅ５７１
ＵＶλ、、、 （ＣＩＩＣｈ）４１９．０，５１７．０
，５５１．５，５９２．０，６４６．５’ＩＮＭＲ（Ｃ
ＤＣＩ３）６８．８５（ｍ、 １２Ｈ） 、δ８．７８
（ｄ、Ｊ＝４．９Ｈｚ。Calculated value C+o4)1szOJssz m/e1570
Actual value m/e571 UVλ,, (CIICh)419.0,517.0
,551.5,592.0,646.5'INMR(C
DCI3) 68.85 (m, 12H), δ8.78
(d, J=4.9Hz.
４１）、６８．２５（ｄ、Ｊ＝７．８Ｈｚ、４Ｈ） 、
６８．０６（ｍ、 １２Ｈ） 。41), 68.25 (d, J=7.8Hz, 4H),
68.06 (m, 12H).
６７．７７（ｄ、Ｊ＝８．３Ｈｚ、４Ｈ） 、 ６７
．６８（ｓ、４Ｈ）、 δ７．５２（■、 ｌ５ＩＩ
） 、δ４．５２（ｓ、４Ｈ）、 δ４．４４（ｓ、
４Ｈ）、 δ２．６９（ｓ、６Ｈ）、 δ２．６６
（ｓ、 １２８） 、δ−２，７９（ｓ、４Ｈ）（６ｂ
）
（７ｂ）
上記の第三の工程を実施する為、スルホン型のポルフィ
リンニ量体（６ｂ） ０．７６ｇをテトラヒドロフラン
２０ｄに溶かし、続いてｔ −Ｃ，ＨｑＯＫｏ、１ｇ、
ＣＣＬ ０．１ｇを加え、２５°Ｃで２時間かき混ぜた
。反応液を水１０．ｄに注ぎ、塩化メチレンで抽出した
。抽出液を硫酸マグネシウムで乾燥後、溶媒を留去して
、青色結晶（７ｂ）０．４ ｇ（５４％）を得た。67.77 (d, J=8.3Hz, 4H), 67
．． 68 (s, 4H), δ7.52 (■, l5II
), δ4.52(s, 4H), δ4.44(s,
4H), δ2.69 (s, 6H), δ2.66
(s, 128), δ-2,79(s, 4H) (6b
) (7b) To carry out the third step above, 0.76 g of sulfone-type porphyrin dimer (6b) was dissolved in 20 d of tetrahydrofuran, followed by 1 g of t -C,HqOKo,
0.1 g of CCL was added and stirred at 25°C for 2 hours. Add 10% of the reaction solution to water. d and extracted with methylene chloride. After drying the extract over magnesium sulfate, the solvent was distilled off to obtain 0.4 g (54%) of blue crystals (7b).
この物質の物性を次に示す。The physical properties of this substance are shown below.
ＭＳ計算値Ｃ＋ａ４１１ｔｓＮｓ ｍ／ｅ １４３Ｂ、
実測値ａｌｅ １４３８ＵＶλ、、、 （ＣＨ，Ｃｈ）
４２１．０．５１Ｂ、５，５５４．５，５９１．５，６
４７．５’ＩＩＮＭＲ（ＣＤＣ１，）６８．９０（＋＊
、８Ｈ）、 δ８．８６（ｍ、８Ｈ） 。MS calculation value C+a411tsNs m/e 143B,
Actual measurement value ale 1438UVλ, (CH, Ch)
421.0.51B, 5,554.5,591.5,6
47.5'IINMR (CDC1,) 68.90 (+*
, 8H), δ8.86(m, 8H).
６８．２４（ｄ、ｌ） 、 ６８．１０（ｄ、１２８
）、δ７．９４（ｄ、４■）。68.24 (d, l), 68.10 (d, 128
), δ7.94 (d, 4■).
６７．７５（ｓ、４Ｈ） 、 δ７．５６（ｄ、 １
２）１） 、δ７．５１（＋ａ、４Ｈ） 。67.75 (s, 4H), δ7.56 (d, 1
2) 1) , δ7.51 (+a, 4H).
δ２．７Ｈｓ、１２１（）、δ２．６Ｂ（ｓ、６Ｈ）、
δ−２，７５（ｓ、４Ｈ）実施例２
実施例１と同様にして得た各工程での物質とその物性を
以下順に示す。δ2.7Hs, 121(), δ2.6B(s, 6H),
δ-2,75(s,4H) Example 2 The substances obtained in each step in the same manner as in Example 1 and their physical properties are shown below in order.
第一の工程で得た物質とその物性 耶計算値 Ｃ＋ｏｏＨｇｏＮ＊Ｓｚ ｍ／ｅ１４５６ 実測値園／ｅ１４５６Substance obtained in the first step and its physical properties Calculated value C+ooHgoN*Sz m/e1456 Actual value garden/e1456
Claims (1)
る。）を有するポルフィリン化合物同志が、α、β、γ
、δ位のいずれかの間で ▲数式、化学式、表等があります▼、 ▲数式、化学式、表等があります▼及び ▲数式、化学式、表等があります▼の群から 選ばれる共役二重結合によって互いに連結されているポ
ルフィリン多量体。 ［２］骨格 ▲数式、化学式、表等があります▼ （骨格中の数字及びギリシア文字は位置を示す符号であ
る、）を有するポルフィリン化合物同志を、各ポルフィ
リン化合物のα、β、γ、δ位のいずれかに導入した−
−ＣＨ＿２Ｘ（式中Ｘはハロゲンを意味する。）と ▲数式、化学式、表等があります▼、 −ＣＨ＿３ＣＯＳ−ＣＨ＿２−ＣＨ＿２−ＳＣＯＣＨ＿
３−及び−ＣＨ＿３ＣＯＳ−ＣＨ＿２−ＣＨ＝ＣＨ−Ｃ
Ｈ＿２−ＳＣＯＣＨ＿３−の群から選ばれるチオアセチ
ル化合物との間の求核置換反応により連結させてスルフ
ィド型のポルフィリン多量体となす第一の工程；このス
ルフィド型のポルフィリン多量体を酸化して対応するス
ルホン型のポルフィリン多量体となす第二の工程；この
スルホン型のポルフィリン多量体を脱硫黄する第三の工
程；の３工程からなることを特徴とする、請求項１記載
のポルフィリン多量体の製造法。[Scope of Claims] [1] Porphyrin compounds having a skeleton ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (The numbers and Greek letters in the skeleton are symbols indicating positions.)
, a conjugated double bond selected from the group of ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Porphyrin multimers connected to each other by. [2] Porphyrin compounds that have a skeleton ▲ There are mathematical formulas, chemical formulas, tables, etc. -
-CH_2X (X in the formula means halogen) and ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -CH_3COS-CH_2-CH_2-SCOCH_
3-and-CH_3COS-CH_2-CH=CH-C
The first step is to form a sulfide-type porphyrin multimer by linking with a thioacetyl compound selected from the group H_2-SCOCH_3- by a nucleophilic substitution reaction; oxidize this sulfide-type porphyrin multimer to form the corresponding sulfone The method for producing a porphyrin multimer according to claim 1, characterized in that it consists of three steps: a second step of forming a sulfone-type porphyrin multimer; a third step of desulfurizing the sulfone-type porphyrin multimer; .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32644089A JPH07113031B2 (en) | 1989-12-15 | 1989-12-15 | Porphyrin multimer and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32644089A JPH07113031B2 (en) | 1989-12-15 | 1989-12-15 | Porphyrin multimer and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03188083A true JPH03188083A (en) | 1991-08-16 |
| JPH07113031B2 JPH07113031B2 (en) | 1995-12-06 |
Family
ID=18187829
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32644089A Expired - Lifetime JPH07113031B2 (en) | 1989-12-15 | 1989-12-15 | Porphyrin multimer and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07113031B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1308481A3 (en) * | 1992-08-14 | 2004-04-28 | The Trustees Of The University Of Pennsylvania | Metal-mediated cross-coupling with ring-metalated porphyrins |
| JP2007221168A (en) * | 2001-02-26 | 2007-08-30 | Univ Pennsylvania | Luminescent multicolor chromophore system |
-
1989
- 1989-12-15 JP JP32644089A patent/JPH07113031B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1308481A3 (en) * | 1992-08-14 | 2004-04-28 | The Trustees Of The University Of Pennsylvania | Metal-mediated cross-coupling with ring-metalated porphyrins |
| JP2007221168A (en) * | 2001-02-26 | 2007-08-30 | Univ Pennsylvania | Luminescent multicolor chromophore system |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07113031B2 (en) | 1995-12-06 |
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