JP2016102074A - Novel salt - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide cyclo[n]pyrroles that is suitable as an organic coloring matter and is easy to synthesize.SOLUTION: Provided is a salt having a structure represented by formula 90.SELECTED DRAWING: None

Description

  The present invention relates to a novel salt having a cyclo [n] pyrrole ring.

  As ring-expanded porphyrins, saphyrin and hexaphyllin are known, but as ring-expanded porphyrins and their derivatives, it is thought that there are many compounds that are not yet known about the synthesis method, structure, and physical properties. The group of compounds is an attractive group of compounds.

  In 2002, Sessler et al. [30] octaphyrin (0.0.0.0.0.0.0.0) free from meso-bridged carbon by oxidative coupling reaction from 2,2′-bipyrrole with iron (III) chloride. It was reported that [8] pyrrole) can be synthesized. Since then, as reported in Non-Patent Documents 1 to 4, vigorous researches such as anion binding, liquid crystallinity, semiconductor properties, and electronic state analysis of cyclo [n] pyrroles (n = 6-8) It has been.

Seidel, D .; Lynch, V .; Sessler, J. L. Angew. Chem. Int. Ed. 2002, 41, 1422 Sessler, J. L .; Karnas, E .; Kim, S. K .; Ou, Z .; Zhanf, M .; Kadish, K. M .; Ohkubo, K .; Fukuzumi, S. J. Am. Chem. Soc. 2008, 13, 15256 Eller, L. R .; Stepien, M .; Fowler, C. J .; Lee, J. T .; Sessler, J. L .; Moyer, B. A. J. Am. Chem. Soc. 2007, 129, 11020 Stepien, M .; Donnio, B .; Sessler, J. L. Angew. Chem. Int. Ed. 2007, 46, 1431.

However, the cyclo [n] pyrroles known so far are only β-alkyl derivatives, and the reports have been limited due to the difficulty of synthesis.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide cyclo [n] pyrroles that can be easily synthesized.

  This invention is a salt which has a structure represented by following formula (1), and the said objective of this invention is achieved by this.

（式（１）中、複数あるＲ¹およびＲ²は、下記（ａ）〜（ｄ）の何れかである。
（ａ）Ｒ¹およびＲ²が水素原子である。
（ｂ）Ｒ¹およびＲ²が−ＯＣＨ₃である。
（ｃ）Ｒ¹およびＲ²が−ＣＦ₃である。
（ｄ）Ｒ¹が−ＯＣＨ₃であり、Ｒ²が−ＣＦ₃である。）

(In the formula (1), a plurality of R ¹ and R ² are any of the following (a) to (d).
(A) R ¹ and R ² are hydrogen atoms.
(B) R ¹ and R ² are —OCH ₃ .
(C) R ¹ and R ² are —CF ₃ .
(D) R ¹ is —OCH ₃ and R ² is —CF ₃ . )

  According to the present invention, it is possible to provide an easily synthesized cyclo [n] pyrrole having a cyclo [n] pyrrole ring, which has only been reported so far. Moreover, according to this invention, the salt which has a cyclo [n] pyrrole ring suitably utilized as an organic pigment | dye can be provided.

  Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and can be arbitrarily modified and implemented without departing from the scope of the invention.

  The salt of the present invention is characterized by having a structure represented by the following formula (1).

（式（１）中、複数あるＲ¹およびＲ²は、下記（ａ）〜（ｄ）の何れかである。
（ａ）Ｒ¹およびＲ²が水素原子である。
（ｂ）Ｒ¹およびＲ²が−ＯＣＨ₃である。
（ｃ）Ｒ¹およびＲ²が−ＣＦ₃である。
（ｄ）Ｒ¹が−ＯＣＨ₃であり、Ｒ²が−ＣＦ₃である。）

(In the formula (1), a plurality of R ¹ and R ² are any of the following (a) to (d).
(A) R ¹ and R ² are hydrogen atoms.
(B) R ¹ and R ² are —OCH ₃ .
(C) R ¹ and R ² are —CF ₃ .
(D) R ¹ is —OCH ₃ and R ² is —CF ₃ . )

Plural R ¹ and R ² are all preferably the same group from the viewpoint of easiness of synthesis and the like, and more preferably (b).

  The salt of the present invention can be synthesized, for example, based on the following scheme. Specifically, compound 11 obtained by a conventionally known method is halogenated by a conventionally known method to obtain compound 12, and then the amino group of the pyrrole ring is protected by a conventionally known method to obtain compound 13 Get. Using the obtained compound 13, compound 14 which is bipyrrole is obtained by a conventionally known method. Next, compound 16 which is a salt of the present invention can be obtained from compound 14 through compound 15 by a conventionally known method.

（スキーム中、Ｒ¹およびＲ²は、前記式（１）におけるＲ¹およびＲ²と同義であり、Ｘはハロゲン原子、好ましくは塩素原子、臭素原子またはヨウ素原子であり、より好ましくはヨウ素原子であり、Ｒ³は保護基であり、好ましくはｔ−ブトキシカルボニル基である。）

(In the scheme, R ¹ and R ^2, the formula (1) have the same meanings as R ¹ and R ² in, X is a halogen atom, preferably a chlorine atom, a bromine atom or an iodine atom, more preferably an iodine atom And R ³ is a protecting group, preferably a t-butoxycarbonyl group.)

  The salt of this invention is used suitably as an organic pigment | dye mix | blended with the optical filter used for an imaging device etc., for example.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, it is not limited to these Examples.

  In the following, the molecular structure and physical properties of the products obtained in the examples are as follows: melting point measurement apparatus MP500D (Anatech Yanako Co., Ltd.), nuclear magnetic resonance apparatus AL-400 (JEOL Ltd.), Fourier transform infrared spectrophotometer FT-720 (Horiba, Ltd.), High Performance Double Convergence Mass Spectrometer JMS-700 (JEOL Ltd.), CHN Coder MT-5 (Yanaco Technical Science Co., Ltd.), and UV-Vis Near-Infrared Spectrophotometer It measured using V-570 (JASCO Corporation).

（式中、「Ｍｅ」はメチル基であり、「Ｅｔ」はエチル基である。以下同様。） [Example 1]
Synthesis of 2-Ethyl-5-iodo-3,4-bis (4-methoxyphenyl) -1H-pyrrole-2-carboxylate (Compound 86)

(In the formula, “Me” is a methyl group, “Et” is an ethyl group, and so on.)

  In a 300 ml eggplant flask, compound 85 (2-Ethyl-3,4-bis (4-methoxyphenyl) -1H-pyrrole-2-carboxylate, 4.07 g, 11.6 mmol), iodine (3.28 g) and iodic acid ( 573 mg) was added, and chloroform (40 ml), acetic acid (16 ml) and water (1.6 ml) were added thereto and refluxed for 19 hours. After completion of the reaction, the reaction solution is returned to room temperature, washed successively with saturated sodium sulfite, saturated aqueous sodium bicarbonate, water and saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and washed with methanol to yield 4.78 g. Of the target compound 86 (yellow powder).

The melting point (mp), ¹ H NMR, ¹³ C NMR, IR, mass spectrometry (MS) and elemental analysis of the obtained compound 86 are shown below.
mp: 235.5-237.4 ° C.
¹ H NMR (CDCl ₃ , 400 MHz) δ 9.40 (brs, 1H, NH), 7.07 (m, 2H, 3-OMeC ₆ H ₄ ^o ), 7.02 (m, 2H, 4-OMeC ₆ H ₄ ^o ), 6.78 (m, 2H, 3-OMeC ₆ H ₄ ^m ), 6.75 (m, 2H, 4-OMeC ₆ H ₄ ^m ), 4.23 (q, 2H, J = 7.3 Hz, CO ₂ Et), 3.78 (s, 3H, 3-OMe), 3.77 (s, 3H, 4-OMe), 1.20 (t, 3H, J = 7.3 Hz, CO ₂ Et).
¹³ C NMR (CDCl ₃ , 100 MHz) δ 160.2, 158.4, 158.2, 131.6, 131.4, 130.4, 126.4, 125.6, 123.5, 113.3, 112.7, 73.8, 60.5, 55.1, 14.2.
IR (KBr) ν _max 3256, 1661, 1238, 1173, 829 cm ^-1 .
MS (FAB) m / z (%) 477 (38) [M ⁺ ].
Anal.calcd for C ₂₁ H ₂₀ INO ₄ : C, 52.84; H, 4.22; N, 2.93.
Found: C, 52.67; H, 4.41; N, 3.16.

（式中「Ｂｏｃ」はｔ−ブトキシカルボニル基である。以下同様。） Synthesis of 1-t-Butyl-2-ethyl-5-iodo-3,4-bis (4-methoxyphenyl) -1H-pyrrole-1,2-dicarboxylate (Compound 87)

(In the formula, “Boc” is a t-butoxycarbonyl group. The same shall apply hereinafter.)

Compound 86 (4.49 g, 9.41 mmol) and N, N-dimethyl-4-aminopyridine (DMAP, 53.6 mg) were placed in a 300 ml eggplant flask and purged with argon. To this was added Dry methylene chloride (65 ml) and di-t-butyl dicarbonate ((Boc) ₂ O, 2.60 ml), and the mixture was stirred at room temperature for 10 hours. After completion of the reaction, the mixture was washed successively with water and saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Furthermore, purification by silica gel chromatography (chloroform) and washing with methanol gave the target compound 87 (yellow powder) in a yield of 4.80 g.

The melting point, ¹ H NMR, ¹³ C NMR, IR, mass spectrometry and elemental analysis of the obtained compound 87 are shown below.
mp: 144.6-146.3 ° C.
¹ H NMR (CDCl ₃ , 400 MHz) δ 7.05 (m, 2H, 3-OMeC ₆ H ₄ ^o ), 7.00 (m, 2H, 4-OMeC ₆ H ₄ ^o ), 6.78 (m, 2H, 3-OMeC ₆ H ₄ ^m ), 6.72 (m, 2H, 4-OMeC ₆ H ₄ ^m ), 4.14 (q, 2H, J = 7.1 Hz, CO ₂ Et), 3.77 (s, 3H, 3-OMe), 3.76 ( s, 3H, 4-OMe), 1.67 (s, 9H, 8-t-Bu), 1.10 (t, 3H, J = 7.3 Hz, CO ₂ Et).
¹³ C NMR (CDCl ₃ , 100 MHz) δ 160.5, 158.5, 158.5, 148.8, 133.5, 132.1, 131.7, 131.7, 126.2, 125.7, 124.8, 113.3, 112.6, 86.2, 76.0, 60.9, 55.0, 27.7, 13.9.
IR (KBr) ν _max 2988, 2933, 1241, 1149, 839 cm ^-1 .
MS (FAB) m / z (%) 577 (20) [M ⁺ ], 477 (100), 351 (6).
Anal.calcd for C ₂₆ H ₂₈ INO ₆ : C, 54.08; H, 4.89; N, 2.43.
Found: C, 54.34; H, 5.06; N, 2.47.

Synthesis of Diethyl-3,3 ', 4,4'-tetrakis- (4-methoxyphenyl) -1H, 1'H-2,2'-bipyrrole-5,5'-dicarboxylate (Compound 88)

  Compound 87 (2.16 g, 3.74 mmol) and copper (1.77 g) were placed in a 50 ml eggplant flask and purged with argon. To this was added Dry dimethylformamide (DMF, 12 ml), and the mixture was stirred at 110 ° C. for 19 hours. After completion of the reaction, the temperature was returned to room temperature, insolubles were removed by celite filtration, extracted with methylene chloride, washed successively with 1M hydrochloric acid, water and saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Then, ethyl acetate (AcOEt, 32 ml) and concentrated hydrochloric acid (8 ml) were added and stirred at room temperature for 17 hours. After completion of the reaction, the mixture was washed successively with saturated aqueous sodium hydrogen carbonate, water and saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and recrystallized (chloroform / methanol) to give 619 mg of the target compound 88 (white powder). )was gotten.

The melting point, ¹ H NMR, ¹³ C NMR, IR, mass spectrometry and elemental analysis results of Compound 88 are shown below.
mp: 284.2-285.6 ° C.
¹ H NMR (CDCl ₃ , 400 MHz) δ 8.69 (brs, 2H, NH), 7.19 (m, 4H, 4-OMeC ₆ H ₄ ^o ), 7.10 (m, 4H, 3-OMeC ₆ H ₄ ^o ), 6.92 (m, 2H, 4-OMeC ₆ H ₄ ^m ), 6.73 (m, 2H, 3-OMeC ₆ H ₄ ^m ), 4.05 (q, 2H, J = 7.3 Hz, CO ₂ Et), 3.82 (s, 3H, 4-OMe), 3.75 (s, 3H, 3-OMe), 1.09 (t, 3H, J = 7.1 Hz, CO ₂ Et).
¹³ C NMR (CDCl ₃ , 100 MHz) δ 159.7, 158.9, 158.2, 131.9, 131.7, 131.2, 126.0, 125.2, 123.7, 123.5, 117.8, 114.5, 112.7, 59.9, 55.1, 55.0, 14.0.
IR (KBr) ν _max 3414, 1704, 1243, 1094, 829 cm ^-1 .
MS (FAB) m / z (%) 702 (29) [M ⁺⁺ 2].
Anal.calcd for C ₄₂ H ₄₀ N ₂ O ₈・ 1 / 4H ₂ O: C, 71.52; H, 5.79; N, 3.97.
Found: C, 71.38; H, 5.81; N, 3.89.

Synthesis of 3,3 ', 4,4'-tetrakis (4-methoxyphenyl) -1H, 1'H-2,2'-bipyrrole (Compound 89)

  A 50 ml eggplant flask was charged with compound 88 (389 mg, 0.556 mmol), sodium hydroxide (271 mg) and ethylene glycol (10 ml), purged with argon, and heated at 170 ° C. for 3 hours in the dark. After completion of the reaction, the temperature was returned to room temperature, water was added, extracted with chloroform, washed successively with water and saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and recrystallized (chloroform / hexane). 287 mg of the target compound 89 (brown powder) was obtained.

The melting point, ¹ H NMR, ¹³ C NMR, IR, and mass spectrometry results of the obtained compound 89 are shown below.
mp: 224.4-226.9 ° C.
¹ H NMR (CDCl ₃ , 400 MHz) δ 7.78 (brs, 2H, NH), 7.29 (m, 4H, 3-OMeC ₆ H ₄ ^o ), 7.03 (m, 4H, 4-OMeC ₆ H ₄ ^o ), 6.92 (m, 4H, 3-OMeC ₆ H ₄ ^m ), 6.72 (m, 4H, 4-OMeC ₆ H ₄ ^m ), 6.62 (d, 2H, J = 2.9 Hz), 3.85 (s, 6H, 3- OMe), 3.75 (s, 6H, 4-OMe).
¹³ C NMR (CDCl ₃ , 100 MHz) δ 158.4, 157.4, 132.1, 128.9, 127.9, 127.9, 124.1, 122.5, 118.3, 114.9, 114.3, 113.5, 55.2, 55.2.
IR (neat) ν _max 3675, 1242, 1028, 829 cm ^-1 .
MS (FAB) m / z (%) 557 (3) [M ⁺ +1].

Synthesis of 3,4-bis (4-methoxyphenyl) -fused cyclo [8] pyrrole (salt 90)

  Compound 89 (223.3 mg, 0.401 mm), tetrabutylammonium hydrogen sulfate (5.8 mg) and chloroform (100 ml) were added to a 300 ml eggplant flask. To this was added dropwise cerium sulfate (240 mg) suspended in concentrated sulfuric acid (0.20 ml) and water (4 ml) in an ice bath, stirred at room temperature for 2 hours, and then suspended again in water (4 ml). Cerium sulfate (238 mg) was added dropwise, and the mixture was further stirred for 2 hours. After completion of the reaction, the mixture was washed successively with water and saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. Furthermore, purification by silica gel chromatography (chloroform) and gel permeation chromatography (GPC) and recrystallization (chloroform / hexane) gave 56.7 mg of the target salt 90 (yellow powder).

The melting point, ¹ H NMR, UV-vis, mass analysis and elemental analysis results of the obtained salt 90 are shown below.
mp:> 300 ° C.
¹ H NMR (CDCl ₃ , 400 MHz) δ 6.90 (m, 32H, OMeC ₆ H ₄ ^o ), 6.57 (m, 32H, OMeC ₆ H ₄ ^m ), 3.83 (s, 48H, OMe), 1.46 (brs, 8H, NH).
UV-vis (CHCl ₃ ) λ _max , nm (logε) 472 (5.24), 908 (4.59), 1044 (5.45).
MS (MALDI-TOF) m / z (%) 2314 [M ⁺ +1].
Anal.calcd for C ₁₄₄ H ₁₂₀ N ₈ O ₂₀ S ・ 3H ₂ O: C, 71.92; H, 5.45; N, 4.66.
Found: C, 71.71; H, 5.34; N, 4.54.

Claims (1)

A salt having a structure represented by the following formula (1).

(In the formula (1), a plurality of R ¹ and R ² are any of the following (a) to (d).
(A) R ¹ and R ² are hydrogen atoms.
(B) R ¹ and R ² are —OCH ₃ .
(C) R ¹ and R ² are —CF ₃ .
(D) R ¹ is —OCH ₃ and R ² is —CF ₃ . )