JPWO2018155469A1 - Diazachlorin analogs and method for producing the same - Google Patents

Diazachlorin analogs and method for producing the same Download PDF

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JPWO2018155469A1
JPWO2018155469A1 JP2019501363A JP2019501363A JPWO2018155469A1 JP WO2018155469 A1 JPWO2018155469 A1 JP WO2018155469A1 JP 2019501363 A JP2019501363 A JP 2019501363A JP 2019501363 A JP2019501363 A JP 2019501363A JP WO2018155469 A1 JPWO2018155469 A1 JP WO2018155469A1
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洋 忍久保
洋 忍久保
文香 山路
文香 山路
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Tokai National Higher Education and Research System NUC
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Abstract

フォトルミネセンスを生起するジアザクロリン類縁体を提供することを解決すべき課題とする。一般式(B)〜(D)で表される部分構造を骨格としてもつジアザクロリン類縁体。(式中、Mは、2H、Zn、Pt、Pd、Mg、Al、Ga、又は、Auである。)It is an object of the present invention to provide a diazachlorin analog which causes photoluminescence. A diazachlorin analog having a partial structure represented by any one of formulas (B) to (D) as a skeleton. (Wherein, M is 2H, Zn, Pt, Pd, Mg, Al, Ga, or Au.)

Description

本発明は、蛍光や燐光などのフォトルミネセンスを生起するジアザクロリン類縁体及びその製造方法に関する。   The present invention relates to a diazachlorin analog that causes photoluminescence such as fluorescence and phosphorescence, and a method for producing the same.

ジアザクロリン類縁体としては金属元素としてNiを有するNi錯体が知られている(非特許文献1)。   As a diazachlorin analog, a Ni complex having Ni as a metal element is known (Non-Patent Document 1).

Ayaka Y., Hayato T., Yoshihiro M., Kazushi M., Hiroshi S., Chemo- and Regioselective Reduction of 5,15-Diazaporphyrins Providing Antiaromatic Azaporphyrinoids, Chem. Eur. J. 2016, 22 3956-3961Ayaka Y., Hayato T., Yoshihiro M., Kazushi M., Hiroshi S., Chemo- and Regioselective Reduction of 5,15-Diazaporphyrins Providing Antiaromatic Azaporphyrinoids, Chem. Eur. J. 2016, 22 3956-3961

ところで、ジアザクロリン類縁体はポルフィリンに類似する化学構造を有している。ポルフィリンの類縁体には蛍光を発する化合物が存在し、ジアザクロリン類縁体についても蛍光を発する化合物が得られると、種々の応用が期待できる。   By the way, the diazachlorin analog has a chemical structure similar to porphyrin. Compounds that emit fluorescence are present in porphyrin analogs, and if a compound that emits fluorescence can also be obtained for diazacroline analogs, various applications can be expected.

非特許文献1に開示のジアザクロリン類縁体は蛍光を発することはないため蛍光や燐光などのフォトルミネセンスを生起することができるジアザクロリン類縁体を提供することを解決すべき課題とする。   The diazachlorin analog disclosed in Non-Patent Document 1 does not emit fluorescence, and thus it is an object to be provided to provide a diazachlorin analog capable of generating photoluminescence such as fluorescence or phosphorescence.

ジアザクロリン類縁体について本願発明者らは鋭意検討を行った結果、ジアザクロリン類縁体に含有される金属元素をNiから異なる元素に変更することにより蛍光などのフォトルミネセンスを生起するようになることを見出して以下の発明を完成した。   As a result of diligent studies on diazachlorin analogs, the present inventors have found that changing the metal element contained in the diazachlorin analog from Ni to a different element causes photoluminescence such as fluorescence. The following invention was completed.

すなわち、上記課題を解決する本発明のジアザクロリン類縁体は、一般式(1)、(2)、又は、(3)で表され、測定温度25℃における発光ピークの少なくとも1つが500nm〜1200nmの範囲内に存在するフォトルミネセンスを生起する。   That is, the diazachlorin analog of the present invention that solves the above problem is represented by the general formula (1), (2), or (3), and at least one of the emission peaks at a measurement temperature of 25 ° C is in a range of 500 nm to 1200 nm. Produces photoluminescence that exists within.

Figure 2018155469
(式中、Z〜Z10はそれぞれ独立して選択される置換基で有り、H、一部乃至全部の水素がXにて置換されていても良い炭素数1〜20の炭化水素基、OH基、アミノ基、アミド基、一部乃至全部の水素がXにて置換されていても良いフェニル基、ハロゲン、一部乃至全部の水素がXにて置換されていても良い炭素数1〜20のアルコキシ基、一部乃至全部の水素がXにて置換されていても良い含窒素複素環置換基、含硫黄複素環置換基、含酸素複素環置換基、Mは、2H、Zn、Pt、Pd、Mg、Al、Ga又は、Auである。Xは炭素数1〜3の炭化水素基、アルコキシ基、OH基、アミノ基、又は、ハロゲンである。Z〜Z10から選択される任意の2以上の置換基は互いに結合して環状構造を構成することもできる。一般式(1)〜(3)で表される化合物は同一の又は異なる2つ以上が結合することができる。)
Figure 2018155469
(Wherein, Z 1 to Z 10 are independently selected substituents; H, a hydrocarbon group having 1 to 20 carbon atoms in which some or all of hydrogen may be substituted by X; An OH group, an amino group, an amide group, a phenyl group in which some or all of the hydrogens may be substituted by X, a halogen, a carbon number of 1 to 1 in which some to all of the hydrogens may be substituted by X, 20 alkoxy groups, nitrogen-containing heterocyclic substituents in which some or all of the hydrogens may be substituted by X, sulfur-containing heterocyclic substituents, oxygen-containing heterocyclic substituents, M is 2H, Zn, Pt , Pd, Mg, Al, Ga or Au, and X is a hydrocarbon group having 1 to 3 carbon atoms, an alkoxy group, an OH group, an amino group, or a halogen, and is selected from Z 1 to Z 10. Any two or more substituents may be bonded to each other to form a cyclic structure. The same or different two or more compounds represented by the formulas (1) to (3) can be bonded.)

特に、前記一般式(1)〜(3)におけるZ〜Z及びZ〜Z10は、Hであり、前記Z及びZは、下記の置換基(X)から独立して選択されることが好ましい。In particular, Z 2 to Z 5 and Z 7 to Z 10 in the general formulas (1) to (3) are H, and the Z 1 and Z 6 are independently selected from the following substituents (X) Preferably.

Figure 2018155469
(式(X)中のR〜R、及び、前記一般式(1)〜前記一般式(3)中のMは、以下の(i)〜(xii)の組み合わせのうちの何れかである。
(i)R、R、及びRはMe;R及びRはH、Mは2H、
(ii)R、R、及びRはMe;R及びRはH;MはZn、Pt、Pd、Mg、Ga、Al、又はAu、
(iii)R、R、R、R、及びRはH;Mは2H、
(iv)R、R、R、R、及びRはH;MはZn、Pt、Pd、Mg、Ga、Al、又はAu、
(v)R、R、R、R、及びRはF、Mは2H;
(vi)R、R、R、R、及びRはF;MはZn、Pt、Pd、Mg、Ga、Al、又はAu、
(vii)R、R、R、及びRはH;Rは炭素数1以上のアルキル基、ペルフルオロアルキル基、炭素数1以上のアルコキシ基、又はOH;M=2H、
(viii)R、R、R、及びRはH;Rは炭素数1以上のアルキル基、ペルフルオロアルキル基、炭素数1以上のアルコキシ基、又はOH;M=Zn、Pt、Pd、Mg、Ga、Al、又はAu、
(ix)R、R、及びRはH;R及びRは炭素数1以上のアルキル基、ペルフルオロアルキル基、炭素数1以上のアルコキシ基、又はOH;Mは2H、
(x)R、R、及びRはMe;R及びRは炭素数1以上のアルキル基、ペルフルオロアルキル基、炭素数1以上のアルコキシ基、又はOH;MはZn、Pt、Pd、Mg、Ga、Al、又はAu、
(xi)R及びRはH、R、R、及びRは炭素数1以上のアルキル基、ペルフルオロアルキル基、炭素数1以上のアルコキシ基、又はOH;Mは2H、
(xii)R及びRはMe;R、R、及びRは炭素数1以上のアルキル基、ペルフルオロアルキル基、炭素数1以上のアルコキシ基、又はOH;MはZn、Pt、Pd、Mg、Ga、Al、又はAu。)
Figure 2018155469
(R 1 to R 5 in the formula (X) and M in the general formulas (1) to (3) are any of the following combinations of (i) to (xii) is there.
(i) R 1 , R 3 and R 5 are Me; R 2 and R 4 are H, M is 2H,
(ii) R 1 , R 3 , and R 5 are Me; R 2 and R 4 are H; M is Zn, Pt, Pd, Mg, Ga, Al, or Au;
(iii) R 1 , R 2 , R 3 , R 4 , and R 5 are H; M is 2H;
(iv) R 1 , R 2 , R 3 , R 4 , and R 5 are H; M is Zn, Pt, Pd, Mg, Ga, Al, or Au;
(v) R 1 , R 2 , R 3 , R 4 and R 5 are F, M is 2H;
(vi) R 1 , R 2 , R 3 , R 4 , and R 5 are F; M is Zn, Pt, Pd, Mg, Ga, Al, or Au;
(vii) R 1 , R 2 , R 4 , and R 5 are H; R 3 is an alkyl group having 1 or more carbon atoms, a perfluoroalkyl group, an alkoxy group having 1 or more carbon atoms, or OH; M = 2H;
(viii) R 1 , R 2 , R 4 , and R 5 are H; R 3 is an alkyl group having 1 or more carbon atoms, a perfluoroalkyl group, an alkoxy group having 1 or more carbon atoms, or OH; M = Zn, Pt; Pd, Mg, Ga, Al, or Au,
(ix) R 1 , R 3 and R 5 are H; R 2 and R 4 are an alkyl group having 1 or more carbon atoms, a perfluoroalkyl group, an alkoxy group having 1 or more carbon atoms, or OH; M is 2H;
(x) R 1 , R 3 and R 5 are Me; R 2 and R 4 are an alkyl group having 1 or more carbon atoms, a perfluoroalkyl group, an alkoxy group having 1 or more carbon atoms, or OH; M is Zn, Pt; Pd, Mg, Ga, Al, or Au,
(xi) R 1 and R 5 are H, R 2 , R 3 , and R 4 are an alkyl group having 1 or more carbon atoms, a perfluoroalkyl group, an alkoxy group having 1 or more carbon atoms, or OH; M is 2H;
(xii) R 1 and R 5 are Me; R 2 , R 3 and R 4 are an alkyl group having 1 or more carbon atoms, a perfluoroalkyl group, an alkoxy group having 1 or more carbon atoms, or OH; M is Zn, Pt, Pd, Mg, Ga, Al, or Au. )

更に、フォトルミネセンスは、発光ピークが以下の範囲に1つ以上存在することが好ましい。一般式(1)の化合物から選択するときは25℃で550〜950nmの範囲内、一般式(2)の化合物から選択するときは25℃で700〜1200nmの範囲内、一般式(3)の化合物から選択するときは25℃で500〜950nmの範囲内である。   Further, the photoluminescence preferably has one or more emission peaks in the following range. When selected from the compound of the general formula (1), it is within the range of 550 to 950 nm at 25 ° C .; When selected from compounds, the range is from 500 to 950 nm at 25 ° C.

上記課題を解決するジアザクロリン類縁体の製造方法は、下記一般式(A)で表される部分構造をもつ原料化合物に対し、還元剤を作用させて下記一般式(B)、(C)、又は、(D)で表される部分構造をもつジアザクロリン類縁体に変換する方法である。   The method for producing a diazachlorin analog which solves the above-mentioned problem is characterized in that a reducing agent is allowed to act on a starting compound having a partial structure represented by the following general formula (A), and , (D) is converted into a diazachlorin analog having a partial structure.

Figure 2018155469
Figure 2018155469

Figure 2018155469
(式(A)〜(D)中、Mは、2H、Zn、Pt、Pd、Mg、Al、Ga又は、Auである。)
Figure 2018155469
(In the formulas (A) to (D), M is 2H, Zn, Pt, Pd, Mg, Al, Ga, or Au.)

特に前記還元剤はヒドラジン誘導体またはジイミドまたはヒドリド還元剤であることが好ましい。   Particularly, the reducing agent is preferably a hydrazine derivative or a diimide or hydride reducing agent.

ある化合物がフォトルミネセンスを生起するかどうかは簡単には推測できず、フォトルミネセンスを生起する上記化合物を提供できることは有意義なことである。   Whether a compound produces photoluminescence cannot be easily predicted, and it would be significant to be able to provide such compounds that do produce photoluminescence.

実施例における試料S1〜S3についての紫外・可視分光スペクトル(UV−VISスペクトル)である。It is an ultraviolet-visible spectrum (UV-VIS spectrum) about samples S1-S3 in an example. 実施例における試料S1〜S3についての蛍光スペクトルである。It is a fluorescence spectrum about samples S1-S3 in an example.

本発明のジアザクロリン類縁体及びその製造方法について以下実施形態に基づいて詳細に説明を行う。   The diazachlorin analog of the present invention and a method for producing the same will be described in detail below based on embodiments.

(ジアザクロリン類縁体)
上記一般式(1)〜(3)で表されるジアザクロリン類縁体のうち、特に一般式(2)で表されるジアザクロリン類縁体を採用することが長波長側でのフォトルミネセンス(蛍光や燐光など)を生起するようことができる可能性が高いため好ましい。一般式(1)〜(3)中のMとしては2H、Mg、Zn、Ga、Alを採用することが好ましく、2H、Mg、Znを採用することが更に好ましい。
(Diazachlorin analog)
Among the diazachlorin analogs represented by the general formulas (1) to (3), the use of the diazachlorin analog represented by the general formula (2) is particularly effective in photoluminescence (fluorescence or phosphorescence) on the long wavelength side. And so on). As M in the general formulas (1) to (3), 2H, Mg, Zn, Ga, and Al are preferably used, and 2H, Mg, and Zn are more preferably used.

フォトルミネセンスは測定温度25℃における発光ピークの少なくとも1つが500nm〜1200nmの範囲内に存在する。そして、測定温度25℃で以下の波長範囲に1つ以上の発光ピークが存在することが好ましい。一般式(1)の化合物から選択するときは550〜950nmの範囲内が好ましく、600〜930nmの範囲内がより好ましく、650〜900nmの範囲内が更に好ましい。一般式(2)の化合物から選択するときは700〜1200nmの範囲内が好ましく、720〜1150nmの範囲内がより好ましく、750〜1100nmの範囲内が更に好ましい。一般式(3)の化合物から選択するときは500〜950nmの範囲内が好ましく、530〜900nmの範囲内がより好ましく、550〜850nmの範囲内が更に好ましい。   In photoluminescence, at least one of the emission peaks at a measurement temperature of 25 ° C. exists in the range of 500 nm to 1200 nm. It is preferable that one or more emission peaks exist in the following wavelength range at a measurement temperature of 25 ° C. When selecting from the compounds of the general formula (1), the range is preferably from 550 to 950 nm, more preferably from 600 to 930 nm, even more preferably from 650 to 900 nm. When selecting from the compounds of the general formula (2), the range is preferably from 700 to 1200 nm, more preferably from 720 to 1150 nm, even more preferably from 750 to 1100 nm. When selecting from the compounds of the general formula (3), the range is preferably from 500 to 950 nm, more preferably from 530 to 900 nm, even more preferably from 550 to 850 nm.

これらの化合物において、フォトルミネセンスを生起する励起光のピーク波長としては特に限定しないが、可視光、紫外光、近赤外光であることが好ましい。特に300nm〜1200nmの範囲であることが好ましく、400nm〜1000nmの範囲であることがより好ましい。励起光としては効率が最も高い波長は存在することが通常ではあるが、コストや入手性などの観点から汎用されている405nm、532nm、650nm、800nmなどにピーク波長をもつ半導体レーザを利用することを目的としてこれらの波長にて充分に励起可能なピークをもつ化合物であることが好ましい。充分に励起可能であるかどうかは生起するフォトルミネセンスによる発光の強度が充分になるかどうかで判断できる。   In these compounds, the peak wavelength of the excitation light that causes photoluminescence is not particularly limited, but is preferably visible light, ultraviolet light, or near-infrared light. In particular, it is preferably in the range of 300 nm to 1200 nm, and more preferably in the range of 400 nm to 1000 nm. As the excitation light, there is usually a wavelength having the highest efficiency, but a semiconductor laser having a peak wavelength at 405 nm, 532 nm, 650 nm, 800 nm, or the like, which is widely used from the viewpoint of cost and availability, should be used. Preferably, the compound has a peak that can be sufficiently excited at these wavelengths for the purpose of. Whether or not excitation is sufficiently possible can be determined by whether or not the intensity of light emission due to the generated photoluminescence is sufficient.

また、本発明の一般式(1)〜(3)で表されるジアザクロリン類縁体は紫外−近赤外光の範囲に吸収ピークを有することができる。具体的には300nm〜1100nmの範囲内に1つ以上の吸収ピークをもつことができ、500nm〜900nmの範囲内に1つ以上の吸収ピークをもつことが更に好ましい。そして、一般式(1)の化合物から選択するときに有する吸収ピークとしては550〜850nmの範囲内が好ましく、580〜750nmの範囲内がより好ましく、600〜700nmの範囲内が更に好ましい。一般式(2)の化合物から選択するときに有する吸収ピークとしては600〜900nmの範囲内が好ましく、650〜850nmの範囲内がより好ましく、700〜820nmの範囲内が更に好ましい。一般式(3)の化合物から選択するときに有する吸収ピークとしては450〜700nmの範囲内が好ましく、470〜650nmの範囲内がより好ましく、500〜620nmの範囲内が更に好ましい。   Further, the diazachlorin analogs represented by the general formulas (1) to (3) of the present invention can have an absorption peak in a range from ultraviolet to near-infrared light. Specifically, it can have one or more absorption peaks in the range of 300 nm to 1100 nm, and more preferably has one or more absorption peaks in the range of 500 nm to 900 nm. The absorption peak when selected from the compounds of the general formula (1) is preferably in the range of 550 to 850 nm, more preferably in the range of 580 to 750 nm, and still more preferably in the range of 600 to 700 nm. The absorption peak when selected from the compounds of the general formula (2) is preferably in the range of 600 to 900 nm, more preferably in the range of 650 to 850 nm, and still more preferably in the range of 700 to 820 nm. The absorption peak when selected from the compounds of the general formula (3) is preferably in the range of 450 to 700 nm, more preferably in the range of 470 to 650 nm, and still more preferably in the range of 500 to 620 nm.

(ジアザクロリン類縁体の製造方法)
本実施形態のジアザクロリン類縁体の製造方法は、一般式(A)で表される部分構造をもつ原料化合物に対し、還元剤を作用させて一般式(B)、(C)、又は、(D)で表される部分構造をもつジアザクロリン類縁体に変換する方法である。一般式(A)で表される部分構造に対して還元剤が作用することによって、一般式(A)で表される部分構造が一般式(B)〜(D)で表される部分構造に変換される。還元剤としては特に限定しないが、ヒドラジン誘導体、ジイミド、ヒドリド還元剤が例示できる。反応は適正な溶媒中にて加熱するなどして行うことができる。
(Method for producing diazachlorin analog)
In the method for producing a diazachlorin analog according to the present embodiment, a reducing agent is allowed to act on a raw material compound having a partial structure represented by the general formula (A), and the compound represented by the general formula (B), (C), or (D) This is a method of converting into a diazachlorin analog having a partial structure represented by the following formula: When the reducing agent acts on the partial structure represented by the general formula (A), the partial structure represented by the general formula (A) is changed to the partial structure represented by the general formulas (B) to (D). Is converted. Although it does not specifically limit as a reducing agent, A hydrazine derivative, a diimide, and a hydride reducing agent can be illustrated. The reaction can be performed, for example, by heating in an appropriate solvent.

(合成)・試料S1:一般式(1)のジアザクロリン誘導体(式中、Z〜Z及びZ〜Z10は、Hであり、前記Z及びZは、置換基(X)である。R1=R3=R5=Me,R2=R4=H,M=2H)の調製。(Synthesis) Sample S1: diazachlorin derivative of general formula (1) (wherein Z 2 to Z 5 and Z 7 to Z 10 are H, and Z 1 and Z 6 are substituents (X) Preparation of R 1 = R 3 = R 5 = Me, R 2 = R 4 = H, M = 2H).

ガラス反応器内に、10,20-ジメシチル-5,15-ジアザポルフィリン(0.025 mmol)、p-トルエンスルホン酸ヒドラジド (0.25 mmol)、炭酸カリウム(0.625 mmol)を加え、不活性ガス置換を行ない、乾燥・脱気したピリジン(10 ml)を加えた。不活性ガス雰囲気下、光保護下100 ℃で18時間撹拌した。加熱を止め、室温まで冷却し、減圧化でピリジンを除去した。残留物に蒸留水および酢酸エチルを加えた。有機層を分離し、蒸留水で洗浄し、無水硫酸ナトリウムを通して乾燥させて、減圧下で濃縮した。得られた固体をシリカゲルに通してクロマトグラフを行なった。カラムを酢酸エチルとヘキサンの混合物(1:4)で溶出することで、試料S1(ジアザクロリン)を12%得た。   In a glass reactor, 10,20-dimesityl-5,15-diazaporphyrin (0.025 mmol), p-toluenesulfonic acid hydrazide (0.25 mmol), and potassium carbonate (0.625 mmol) were added, and inert gas replacement was performed. Then, dried and degassed pyridine (10 ml) was added. The mixture was stirred at 100 ° C. for 18 hours under an inert gas atmosphere under light protection. Heating was stopped, the mixture was cooled to room temperature, and pyridine was removed under reduced pressure. Distilled water and ethyl acetate were added to the residue. The organic layer was separated, washed with distilled water, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained solid was chromatographed through silica gel. The column was eluted with a mixture of ethyl acetate and hexane (1: 4) to give 12% of sample S1 (diazachlorin).

1H NMR (500 MHz, CDCl3): δ 8.96 (d, J = 8.5 Hz, 1H), 8.71 (d, J = 7.5 Hz, 1H), 8.64 (d, J = 9.0 Hz, 1H), 8.53 (d, J = 9.0 Hz, 1H), 8.36 (d, J = 7.0 Hz, 1H), 8.33 (d, J = 8.5 Hz, 1H), 7.26 (s, 2H), 7.23 (s, 2H), 4.54-4.59 (m, 2H), 4.00-4.05 (m, 2H), 2.59 (s, 3H), 2.56 (s, 3H), 1.89 (s, 6H), 1.88 (s, 6H), and -0.50 (s, 2H) ppm; 13C NMR (126 MHz, CDCl3): δ 175.66, 173.33, 160.41, 151.41, 145.91, 145.21, 141.80, 138.82, 138.37, 138.08, 137.99, 135.85, 135.38, 133.58, 132.68, 132.04, 131.33, 128.99, 128.02, 127.97, 127.88, 126.34, 122.38, 112.80, 35.18, 34.94, 21.38, 21.35, 21.12, and 20.88 ppm; HR-MS (ESI-MS): m/z = 551.2926, calcd for (C36H34N6)+ = 551.2918 [(M + H)+]. 1 H NMR (500 MHz, CDCl 3 ): δ 8.96 (d, J = 8.5 Hz, 1H), 8.71 (d, J = 7.5 Hz, 1H), 8.64 (d, J = 9.0 Hz, 1H), 8.53 ( d, J = 9.0 Hz, 1H), 8.36 (d, J = 7.0 Hz, 1H), 8.33 (d, J = 8.5 Hz, 1H), 7.26 (s, 2H), 7.23 (s, 2H), 4.54- 4.59 (m, 2H), 4.00-4.05 (m, 2H), 2.59 (s, 3H), 2.56 (s, 3H), 1.89 (s, 6H), 1.88 (s, 6H), and -0.50 (s, 2H) ppm; 13 C NMR (126 MHz, CDCl 3 ): δ 175.66, 173.33, 160.41, 151.41, 145.91, 145.21, 141.80, 138.82, 138.37, 138.08, 137.99, 135.85, 135.38, 133.58, 132.68, 132.04, 131.33, 128.99, 128.02, 127.97, 127.88, 126.34, 122.38, 112.80, 35.18, 34.94, 21.38, 21.35, 21.12, and 20.88 ppm; HR-MS (ESI-MS): m / z = 551.2926, calcd for (C 36 H 34 N 6 ) + = 551.2918 [(M + H) + ].

・試料S2:一般式(2)のバクテリオジアザクロリン誘導体(式中、Z2〜Z5及びZ7〜Z10は、Hであり、前記Z1及びZ6は、置換基(X)である。R1=R3=R5= Me, R2=R4=H,M=2H)の調製。Sample S2: a bacteriodiazachlorin derivative of the general formula (2) (wherein Z2 to Z5 and Z7 to Z10 are H, and Z1 and Z6 are substituents (X). R 1 = R 3 = R 5 = Me, R 2 = R 4 = H, M = 2H) preparation of.

ガラス反応器内に、10,20-ジメシチル-5,15-ジアザポルフィリン(0.025 mmol)、p-トルエンスルホン酸ヒドラジド (0.25 mmol)、炭酸カリウム(0.625 mmol)を加え、不活性ガス置換を行ない、乾燥・脱気したピリジン(10 ml)を加えた。不活性ガス雰囲気下、光保護下100 ℃で18時間撹拌した。加熱を止め、室温まで冷却し、減圧化でピリジンを除去した。残留物に蒸留水および酢酸エチルを加えた。有機層を分離し、蒸留水で洗浄し、無水硫酸ナトリウムを通して乾燥させて、減圧下で濃縮した。得られた固体をシリカゲルに通してクロマトグラフを行なった。カラムを酢酸エチルとヘキサンの混合物(1:4)で溶出することで、試料S2(バクテリオジアザクロリン)を48%得た。   In a glass reactor, 10,20-dimesityl-5,15-diazaporphyrin (0.025 mmol), p-toluenesulfonic acid hydrazide (0.25 mmol), and potassium carbonate (0.625 mmol) were added, and inert gas replacement was performed. Then, dried and degassed pyridine (10 ml) was added. The mixture was stirred at 100 ° C. for 18 hours under an inert gas atmosphere under light protection. Heating was stopped, the mixture was cooled to room temperature, and pyridine was removed under reduced pressure. Distilled water and ethyl acetate were added to the residue. The organic layer was separated, washed with distilled water, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained solid was chromatographed through silica gel. The column was eluted with a mixture of ethyl acetate and hexane (1: 4) to obtain 48% of sample S2 (bacteriodiazachlorin).

1H NMR (500 MHz, CDCl3): δ 8.53 (d, J = 4.5 Hz, 1H), 7.53 (d, J = 5.0 Hz, 1H), 8.09 (d, J = 4.5 Hz, 1H), 8.09 (d, J = 5.0 Hz, 1H), 7.22 (s, 4H), 4.42-4.45 (m, 4H), 3.85-3.88 (m, 4H), 2.54 (s, 6H), 1.89 (s, 12H), and -0.69 (s, 2H) ppm; 13C NMR (126 MHz, CDCl3): δ 169.45, 166.17, 143.91, 138.01, 137.90, 136.30, 135.58, 128.90, 123.95, 123.40, 115.96, 35.29, 33.73, 21.49, and 20.79 ppm; HR-MS (ESI-MS): m/z = 553.3057, calcd for (C36H36N6)+ = 553.3074 [(M + H)+]. 1 H NMR (500 MHz, CDCl 3 ): δ 8.53 (d, J = 4.5 Hz, 1H), 7.53 (d, J = 5.0 Hz, 1H), 8.09 (d, J = 4.5 Hz, 1H), 8.09 ( d, J = 5.0 Hz, 1H), 7.22 (s, 4H), 4.42-4.45 (m, 4H), 3.85-3.88 (m, 4H), 2.54 (s, 6H), 1.89 (s, 12H), and -0.69 (s, 2H) ppm; 13 C NMR (126 MHz, CDCl 3 ): δ 169.45, 166.17, 143.91, 138.01, 137.90, 136.30, 135.58, 128.90, 123.95, 123.40, 115.96, 35.29, 33.73, 21.49, and 20.79 ppm; HR-MS (ESI-MS): m / z = 553.3057, calcd for (C 36 H 36 N 6 ) + = 553.3074 [(M + H) + ].

・試料S3:一般式(3)のイソバクテリオジアザクロリン誘導体(式中、Z〜Z及びZ〜Z10は、Hであり、前記Z及びZは、置換基(X)である。R1=R3=R5=Me,R2=R4=H,M=2H)の調製。Sample S3: isobacterial diazachlorin derivative of the general formula (3) (wherein Z 2 to Z 5 and Z 7 to Z 10 are H, and Z 1 and Z 6 are substituents (X) Preparation of R 1 = R 3 = R 5 = Me, R 2 = R 4 = H, M = 2H).

ガラス反応器内に、10,20-ジメシチル-5,15-ジアザポルフィリン(0.025 mmol)、p-トルエンスルホン酸ヒドラジド (0.05 mmol)、水酸化カリウム(1.35 mmol)を加え、不活性ガス置換を行ない、乾燥・脱気したピリジン(10 ml)を加えた。不活性ガス雰囲気下、光保護下100 ℃で2時間撹拌した。その後、反応容器にp-トルエンスルホン酸ヒドラジド (0.25 mmol)を加え、さらに20時間撹拌した。加熱を止め、室温まで冷却し、減圧化でピリジンを除去した。残留物に蒸留水および酢酸エチルを加えた。有機層を分離し、蒸留水で洗浄し、無水硫酸ナトリウムを通して乾燥させて、減圧下で濃縮した。得られた固体をシリカゲルに通してクロマトグラフを行なった。カラムを酢酸エチルとヘキサンの混合物(2:3)で溶出することで、試料S3(イソバクテリオジアザクロリン)を25%得た。   In a glass reactor, 10,20-dimesityl-5,15-diazaporphyrin (0.025 mmol), p-toluenesulfonic acid hydrazide (0.05 mmol), potassium hydroxide (1.35 mmol) were added, and inert gas replacement was performed. This was followed by the addition of dried and degassed pyridine (10 ml). The mixture was stirred at 100 ° C. for 2 hours under an inert gas atmosphere under light protection. Thereafter, p-toluenesulfonic acid hydrazide (0.25 mmol) was added to the reaction vessel, and the mixture was further stirred for 20 hours. Heating was stopped, the mixture was cooled to room temperature, and pyridine was removed under reduced pressure. Distilled water and ethyl acetate were added to the residue. The organic layer was separated, washed with distilled water, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained solid was chromatographed through silica gel. The column was eluted with a mixture of ethyl acetate and hexane (2: 3) to give 25% of sample S3 (Isobacteriodiazachlorin).

1H NMR (300 MHz, CDCl3): δ 7.26-7.30 (m, 4H), 7.11 (s, 2H), 7.05 (s, 2H), 6.44 (s, 2H), 3.57-3.62 (m, 2H), 3.07-3.12 (m, 2H), 2.46 (s, 3H), 2.41 (s, 3H), 2.05 (s, 6H), and 2.00 (s, 6H) ppm; 13C NMR (126 MHz, CDCl3): δ 138.27, 138.02, 137.56, 137.03, 136.87, 135.30, 134.56, 132.37, 129.61, 128.68, 127.84, 119.75, 32.21, 31.51, 21.40, 21.35, 20.44, and 20.24 ppm; ESI-MS: m/z = 553.2997, calcd for (C36H34N6)+= 553.3074 [(M + H)+]. 1 H NMR (300 MHz, CDCl 3 ): δ 7.26-7.30 (m, 4H), 7.11 (s, 2H), 7.05 (s, 2H), 6.44 (s, 2H), 3.57-3.62 (m, 2H) , 3.07-3.12 (m, 2H), 2.46 (s, 3H), 2.41 (s, 3H), 2.05 (s, 6H), and 2.00 (s, 6H) ppm; 13 C NMR (126 MHz, CDCl 3 ) : δ 138.27, 138.02, 137.56, 137.03, 136.87, 135.30, 134.56, 132.37, 129.61, 128.68, 127.84, 119.75, 32.21, 31.51, 21.40, 21.35, 20.44, and 20.24 ppm; ESI-MS: m / z = 553.2997, calcd for (C 36 H 34 N 6 ) + = 553.3074 [(M + H) + ].

(UV−VISスペクトル、蛍光スペクトル測定)
試料S1〜S3についてUV−VISスペクトル及び蛍光スペクトルを測定した(溶媒:ジクロロメタン)。UV−VISスペクトルの結果を図1に示す。
(UV-VIS spectrum, fluorescence spectrum measurement)
The UV-VIS spectrum and the fluorescence spectrum of the samples S1 to S3 were measured (solvent: dichloromethane). FIG. 1 shows the results of the UV-VIS spectrum.

試料S1〜S3について、フォトルミネセンスが生起するかどうか判断するために、UV−VISスペクトルからそれぞれ長波長側の高いピークを選択(S1:665.0nm、S2:771.5nm、S3:557.0nm)し、それらを励起光として蛍光スペクトルを測定した。結果を図2に示す。   For samples S1 to S3, in order to determine whether or not photoluminescence occurs, high peaks on the long wavelength side are respectively selected from the UV-VIS spectrum (S1: 665.0 nm, S2: 771.5 nm, S3: 557. 0 nm), and the fluorescence spectrum was measured using them as excitation light. FIG. 2 shows the results.

図2より明らかなように、試料S1〜S3についてそれぞれ蛍光が観測され、最大蛍光波長は(S1:675.5nm、S2:778.0nm、S3:582.2nm)であった。   As is clear from FIG. 2, fluorescence was observed for each of the samples S1 to S3, and the maximum fluorescence wavelength was (S1: 675.5 nm, S2: 778.0 nm, S3: 582.2 nm).

(一般式(1)〜(3)におけるフォトルミネセンスの性質とMの種類との関係について)
試料S1〜S3についてMとしてZnを導入したときのフォトルミネセンスの性質を評価した。Mの導入は試料S1〜S3について対応する金属塩である酢酸亜鉛(II)をピリジン溶媒中100℃で加熱撹拌して行った。得られた化合物について評価したところ、発光波長がそれぞれ20〜50nm程度短波長シフトし、蛍光量子収率が1〜5%減少した状態で蛍光を生起することが分かった。
(Relationship between Photoluminescence Properties and Types of M in General Formulas (1) to (3))
Photoluminescence properties of samples S1 to S3 when Zn was introduced as M were evaluated. M was introduced by heating and stirring zinc acetate (II), which is the corresponding metal salt for the samples S1 to S3, in a pyridine solvent at 100 ° C. When the obtained compound was evaluated, it was found that the emission wavelength was shifted by about 20 to 50 nm, and the fluorescence was generated in a state where the fluorescence quantum yield was reduced by 1 to 5%.

MとしてMg、Ga、Alについても、それぞれの元素の塩を用いて導入した化合物を合成でき、それぞれ500nm〜1200nmの範囲内に少なくとも蛍光を生起することが実験その他の結果や、理論的な観点から予測乃至確認された。   For M, Ga, and Al as M, compounds introduced using salts of the respective elements can be synthesized, and at least fluorescence is generated in the range of 500 nm to 1200 nm. Predicted or confirmed.

また、試料S1〜S3についてMとしてPtを導入したときのフォトルミネセンスの性質を評価した。Mの導入は試料S1〜S3について対応する金属塩である塩化白金(II)をベンゾニトリル溶媒中で還流撹拌することで行った。得られた化合物についてフォトルミネセンスの性質を評価したところ、750〜950nmの範囲内に少なくとも燐光性が観測された。MとしてPd、Auについても、それぞれの元素の塩を用いて導入した化合物を合成でき、それぞれ500nm〜1200nmの範囲内に少なくとも燐光性を生起することが実験その他の結果や、理論的な観点から予測乃至確認された。   In addition, the properties of photoluminescence when Pt was introduced as M for samples S1 to S3 were evaluated. The introduction of M was performed by subjecting platinum (II) chloride, which is the corresponding metal salt of each of the samples S1 to S3, to reflux stirring in a benzonitrile solvent. When the photoluminescence property of the obtained compound was evaluated, at least phosphorescence was observed in the range of 750 to 950 nm. For Pd and Au as M, compounds introduced by using salts of the respective elements can be synthesized, and it is possible to produce at least phosphorescence within the range of 500 nm to 1200 nm from experimental and other results and theoretical viewpoints. Predicted or confirmed.

また、試料S1〜S3についてMとしてCuを導入したときのフォトルミネセンスの性質を評価した。Mの導入は試料S1〜S3について対応する金属塩である酢酸銅(II)をN,N’-ジメチルホルムアミド溶媒中で還流撹拌して行った。得られた化合物についてフォトルミネセンスの性質性を評価したところ、発光は全く観測されなかった。同様に非特許文献1に開示のMがNiの化合物、更にはMがFe、Coの化合物についても同様に合成し、フォトルミネセンスの性質を評価したところ、発光は全く観測されなかった。   In addition, the properties of photoluminescence when Cu was introduced as M for samples S1 to S3 were evaluated. The introduction of M was carried out by stirring and refluxing copper (II) acetate, which is the corresponding metal salt, in samples S1 to S3 in an N, N'-dimethylformamide solvent. When the properties of the photoluminescence of the obtained compound were evaluated, no light emission was observed. Similarly, a compound of M is Ni disclosed in Non-patent Document 1, and a compound of M is Fe and Co were synthesized in the same manner, and the properties of photoluminescence were evaluated. As a result, no light emission was observed.

Claims (5)

一般式(1)、(2)、又は、(3)で表され、
測定温度25℃における発光ピークの少なくとも1つが500nm〜1200nmの範囲内に存在するフォトルミネセンスを生起するジアザクロリン類縁体。
Figure 2018155469
(式中、Z〜Z10はそれぞれ独立して選択される置換基で有り、H、一部乃至全部の水素がXにて置換されていても良い炭素数1〜20の炭化水素基、OH基、アミノ基、アミド基、一部乃至全部の水素がXにて置換されていても良いフェニル基、ハロゲン、一部乃至全部の水素がXにて置換されていても良い炭素数1〜20のアルコキシ基、一部乃至全部の水素がXにて置換されていても良い含窒素複素環置換基、含硫黄複素環置換基、含酸素複素環置換基、Mは、2H、Zn、Pt、Pd、Mg、Ga、Al、又は、Auである。Xは炭素数1〜3の炭化水素基、アルコキシ基、OH基、アミノ基、又は、ハロゲンである。Z〜Z10から選択される任意の2以上の置換基は互いに結合して環状構造を構成することもできる。一般式(1)〜(3)で表される化合物は同一の又は異なる2つ以上が結合することができる。)
Represented by the general formula (1), (2) or (3),
A diazachlorin analog which causes photoluminescence, wherein at least one of emission peaks at a measurement temperature of 25 ° C. exists in a range of 500 nm to 1200 nm.
Figure 2018155469
(Wherein, Z 1 to Z 10 are independently selected substituents; H, a hydrocarbon group having 1 to 20 carbon atoms in which some or all of hydrogen may be substituted by X; An OH group, an amino group, an amide group, a phenyl group in which some or all of the hydrogens may be substituted by X, a halogen, a carbon number of 1 to 1 in which some to all of the hydrogens may be substituted by X, 20 alkoxy groups, nitrogen-containing heterocyclic substituents in which some or all of the hydrogens may be substituted by X, sulfur-containing heterocyclic substituents, oxygen-containing heterocyclic substituents, M is 2H, Zn, Pt , Pd, Mg, Ga, Al, or Au, and X is a hydrocarbon group having 1 to 3 carbon atoms, an alkoxy group, an OH group, an amino group, or a halogen, and is selected from Z 1 to Z 10. Any two or more substituents may be bonded to each other to form a cyclic structure. The same or different two or more compounds represented by the general formulas (1) to (3) can be bonded.)
前記一般式(1)〜(3)におけるZ〜Z及びZ〜Z10は、Hであり、
前記Z及びZは、下記の置換基(X)から独立して選択される請求項1に記載のジアザクロリン類縁体。
Figure 2018155469
(式(X)中のR〜R、及び、前記一般式(1)〜前記一般式(3)中のMは、以下の(i)〜(xii)の組み合わせのうちの何れかである。
(i)R、R、及びRはMe;R及びRはH、Mは2H、
(ii)R、R、及びRはMe;R及びRはH;MはZn、Pt、Pd、Mg、Ga、Al、又はAu、
(iii)R、R、R、R、及びRはH;Mは2H、
(iv)R、R、R、R、及びRはH;MはZn、Pt、Pd、Mg、Ga、Al、又はAu、
(v)R、R、R、R、及びRはF、Mは2H;
(vi)R、R、R、R、及びRはF;MはZn、Pt、Pd、Mg、Ga、Al、又はAu、
(vii)R、R、R、及びRはH;Rは炭素数1以上のアルキル基、ペルフルオロアルキル基、炭素数1以上のアルコキシ基、又はOH;M=2H、
(viii)R、R、R、及びRはH;Rは炭素数1以上のアルキル基、ペルフルオロアルキル基、炭素数1以上のアルコキシ基、又はOH;M=Zn、Pt、Pd、Mg、Ga、Al、又はAu、
(ix)R、R、及びRはH;R及びRは炭素数1以上のアルキル基、ペルフルオロアルキル基、炭素数1以上のアルコキシ基、又はOH;Mは2H、
(x)R、R、及びRはMe;R及びRは炭素数1以上のアルキル基、ペルフルオロアルキル基、炭素数1以上のアルコキシ基、又はOH;MはZn、Pt、Pd、Mg、Ga、Al、又はAu、
(xi)R及びRはH、R、R、及びRは炭素数1以上のアルキル基、ペルフルオロアルキル基、炭素数1以上のアルコキシ基、又はOH;Mは2H、
(xii)R及びRはMe;R、R、及びRは炭素数1以上のアルキル基、ペルフルオロアルキル基、炭素数1以上のアルコキシ基、又はOH;MはZn、Pt、Pd、Mg、Ga、Al、又はAu。)
Z 2 to Z 5 and Z 7 to Z 10 in the general formulas (1) to (3) are H,
The diazachlorin analog according to claim 1, wherein Z 1 and Z 6 are independently selected from the following substituents (X).
Figure 2018155469
(R 1 to R 5 in the formula (X) and M in the general formulas (1) to (3) are any of the following combinations of (i) to (xii) is there.
(i) R 1 , R 3 and R 5 are Me; R 2 and R 4 are H, M is 2H,
(ii) R 1 , R 3 , and R 5 are Me; R 2 and R 4 are H; M is Zn, Pt, Pd, Mg, Ga, Al, or Au;
(iii) R 1 , R 2 , R 3 , R 4 , and R 5 are H; M is 2H;
(iv) R 1 , R 2 , R 3 , R 4 , and R 5 are H; M is Zn, Pt, Pd, Mg, Ga, Al, or Au;
(v) R 1 , R 2 , R 3 , R 4 and R 5 are F, M is 2H;
(vi) R 1 , R 2 , R 3 , R 4 , and R 5 are F; M is Zn, Pt, Pd, Mg, Ga, Al, or Au;
(vii) R 1 , R 2 , R 4 , and R 5 are H; R 3 is an alkyl group having 1 or more carbon atoms, a perfluoroalkyl group, an alkoxy group having 1 or more carbon atoms, or OH; M = 2H;
(viii) R 1 , R 2 , R 4 , and R 5 are H; R 3 is an alkyl group having 1 or more carbon atoms, a perfluoroalkyl group, an alkoxy group having 1 or more carbon atoms, or OH; M = Zn, Pt; Pd, Mg, Ga, Al, or Au,
(ix) R 1 , R 3 and R 5 are H; R 2 and R 4 are an alkyl group having 1 or more carbon atoms, a perfluoroalkyl group, an alkoxy group having 1 or more carbon atoms, or OH; M is 2H;
(x) R 1 , R 3 and R 5 are Me; R 2 and R 4 are an alkyl group having 1 or more carbon atoms, a perfluoroalkyl group, an alkoxy group having 1 or more carbon atoms, or OH; M is Zn, Pt; Pd, Mg, Ga, Al, or Au,
(xi) R 1 and R 5 are H, R 2 , R 3 , and R 4 are an alkyl group having 1 or more carbon atoms, a perfluoroalkyl group, an alkoxy group having 1 or more carbon atoms, or OH; M is 2H;
(xii) R 1 and R 5 are Me; R 2 , R 3 and R 4 are an alkyl group having 1 or more carbon atoms, a perfluoroalkyl group, an alkoxy group having 1 or more carbon atoms, or OH; M is Zn, Pt, Pd, Mg, Ga, Al, or Au. )
前記発光ピークは、以下の範囲内に1つ以上存在する請求項1又は2に記載のジアザクロリン類縁体。
一般式(1)の化合物から選択するときは25℃で550〜950nmの範囲内、
一般式(2)の化合物から選択するときは25℃で700〜1200nmの範囲内、
一般式(3)の化合物から選択するときは25℃で500〜950nmの範囲内。
The diazachlorin analog according to claim 1, wherein one or more emission peaks are present in the following range.
When selecting from the compounds of the general formula (1), within the range of 550 to 950 nm at 25 ° C.,
When selecting from the compounds of the general formula (2), within the range of 700 to 1200 nm at 25 ° C.,
When selected from the compounds of the general formula (3), within the range of 500 to 950 nm at 25 ° C.
下記一般式(A)で表される部分構造をもつ原料化合物に対し、還元剤を作用させて下記一般式(B)、(C)、又は、(D)で表される部分構造をもつジアザクロリン類縁体の製造方法。
Figure 2018155469
Figure 2018155469
(式(A)〜(D)中、Mは、2H、Zn、Pt、Pd、Mg、Al、Ga又は、Auである。)
A diazachlorin having a partial structure represented by the following general formula (B), (C) or (D) by allowing a reducing agent to act on a raw material compound having a partial structure represented by the following general formula (A) Method for producing analogs.
Figure 2018155469
Figure 2018155469
(In the formulas (A) to (D), M is 2H, Zn, Pt, Pd, Mg, Al, Ga, or Au.)
前記還元剤はヒドラジン誘導体またはジイミドまたはヒドリド還元剤である請求項4に記載のジアザクロリン類縁体の製造方法。   The method for producing a diazachlorin analog according to claim 4, wherein the reducing agent is a hydrazine derivative, a diimide or a hydride reducing agent.
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