JP2014051451A - Non-aromatic macrocyclic compound having heteroelement and methods of producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide expanded porphyrin having a thiophene ring and a method of producing the same.SOLUTION: For example, an expanded porphyrin compound is obtained by subjecting 2,5-bis(4-propyl-2-pyrrolyl)thiophene and an aromatic aldehyde represented by the general formula ArCOH (Ar represents a substituted or unsubstituted phenyl group) to a cyclization reaction under acidic conditions and subsequently oxidizing the product.

Description

  The present invention relates to a non-aromatic macrocycle containing a hetero element and a method for producing the same.

  Porphyrin compounds are pigments that generate charge separation by excitation with light energy, as represented by chlorophyll used in plants that carry out photosynthesis, and a photoelectric conversion system for converting light energy into electrical energy or chemical energy It is a compound used in. Ring-extended porphyrins, like these porphyrin compounds, are dyes that cause charge separation by excitation with light energy, but their specific structure and novel physical properties associated with the expansion of π-conjugated systems have been reported (Non-patent Document 1). Oil. For example, it is known that a molecule is twisted by macrocyclization, and a new chiral compound derived from a twisted structure has been reported. It has also been reported that compounds with 4n π electrons that originally do not satisfy the Huekel rule become aromatic compounds. For this reason, there is great interest not only as a new optical property accompanying macrocyclization but also as a new functional material such as ion recognition.

  There are various types of extended porphyrins, and a synthetic example of extended porphyrins containing a thiophene ring was reported in 1992 by J. A. Ibers (Non-patent Document 2) and others.

A. Osuka, et al., Angew. Chem. Int. Ed. 2011, 50, 4342-4373 J. A. Ibers, et al., J. Org. Chem., 1992, 57, 4414-4417

  An object of the present invention is to provide an extended porphyrin including a new type of thiophene ring having a novel physical property that has not been reported in Non-Patent Document 2.

  When 2,5-bis (4-propyl-2-pyrrolyl) thiophene was cyclized with various aromatic aldehydes under acidic conditions, it was clarified that compounds with completely new structures could be synthesized. Furthermore, it was clarified that it is a non-aromatic compound from the spectral characteristics and single crystal X-ray analysis structure analysis of the compound. Based on these facts, the present invention has been completed.

  The present invention relates to an extended porphyrin compound represented by any one of general formulas (1) to (3).

  In the formula, Ar represents a substituted or unsubstituted phenyl group, and in the case of a substituted phenyl group, the position of the substituent is 2-position, 3-position or 4-position, and the substituent is an alkyl group having 1 to 6 carbon atoms, carbon It is a C1-C6 alkoxyl group, an amide group, a C1-C6 alkylamide group, or a nitro group.

  Furthermore, the present invention provides a method for producing an extended porphyrin compound represented by any one of the above general formulas (1) to (3), comprising 2,5-bis (4-propyl-2-pyrrolyl) thiophene and the general formula An aromatic aldehyde represented by ArCOH (Ar is as defined above) is subjected to a cyclization reaction under acidic conditions, and then the product is oxidized to be represented by any one of the general formulas (1) to (3). To at least one of the extended porphyrin compounds produced.

  According to the present invention, a non-aromatic extended porphyrin having a completely new structure can be provided. These compounds have unique structural and spectral characteristics.

¹ shows the ¹ H NMR spectrum of compound 1-1 (Ar = Ph). The bottom is the spectrum for very low concentrations. ¹ shows the ¹ H NMR spectrum of Compound 1-2 (Ar = Ph). ¹ shows the ¹ H NMR spectrum of compound 1-3 (Ar = Ph). 1 shows an X-ray single crystal structure of Compound 1-1. The upper row shows the structure only, and the lower row shows the element. 2 shows an X-ray single crystal structure of Compound 1-2. The upper row shows the structure only, and the lower row shows the element. 1 shows an X-ray single crystal structure of Compound 1-3. The upper row shows the structure only, and the lower row shows the element. 1 shows a UV-vis absorption spectrum of Compound 1-1. Blue line (-H ⁺ ): No acid added, Red line (+ H ⁺ ): A small amount of trifluoroacetic acid added The UV-vis absorption spectrum of compound 1-2 is shown. Blue line (-H ⁺ ): No acid added, Red line (+ H ⁺ ): A small amount of trifluoroacetic acid added 1 shows a UV-vis absorption spectrum of Compound 1-3. Blue line (-H ⁺ ): No acid added, Red line (+ H ⁺ ): A small amount of trifluoroacetic acid added 2 shows TOF-MS spectra of compounds 1-1 and 1-2. ¹ H NMR spectrum of compound 2-2 (Ar = Ph-OMe) is shown. 1 shows a TOF-MS spectrum of Compound 3-1 (Ar = C ₆ H ₄ —NHCOCH ₃ ). 1 shows a TOF-MS spectrum of compound 3-2 (Ar = C ₆ H ₄ —NHCOCH ₃ ). 1 shows a TOF-MS spectrum of compound 3-3 (Ar = C ₆ H ₄ —NHCOCH ₃ ). ¹ H NMR spectrum of compound 4-1 (Ar = Ph-NO ₂ ) is shown. ¹ H NMR spectrum of compound 4-2 (Ar = Ph-NO ₂ ) is shown. ¹ H NMR spectrum of compound 4-3 (Ar = Ph-NO ₂ ) is shown. 1 shows an X-ray single crystal structure of Compound 4-2 (Ar = Ph-NO ₂ ). The upper row shows the structure only, and the lower row shows the element.

  Any of the expanded porphyrin compounds containing the thiophene ring of the present invention is a novel compound. The compound of the present invention can be synthesized according to the following scheme.

The starting compound 2,5-bis (4-propyl-2-pyrrolyl) thiophene (10) is a known compound, and according to the method described in Non-Patent Document 2, ethyl 3-oxohexanoate and 3-oxobutanesanethyl And can be synthesized.
The phenylaldehyde represented by the general formula ArCOH is available as a commercial product, or can be appropriately synthesized using a commercial product as a raw material. A compound.

  The condensation reaction between the compound (10) and phenylaldehyde is suitably performed in an organic solvent under acidic conditions. The molar ratio of compound (10) to phenylaldehyde is, for example, from 1 to 10 moles of phenylaldehyde per mole of compound (10), which means that the compounds of general formulas (1) to (3) are synthesized. It is appropriate from the viewpoint. The condensation reaction is suitably performed in an organic solvent capable of dissolving the compound (10) and phenylaldehyde, and such an organic solvent is not particularly limited, and examples thereof include dichloromethane shown in the above scheme. In addition to dichloromethane, chloroform, tetrahydrofuran and the like can be mentioned. An acidic substance that dissolves in an organic solvent is used to achieve acidic conditions. Although there is no restriction | limiting in particular in an acidic substance, For example, the trifluoroacetic acid (TFA) shown to the said scheme can be mentioned, p-toluenesulfonic acid, a trichloroacetic acid etc. can be mentioned besides TFA. The acidic condition can be a condition in which the acidic substance is present in the range of 0.001 to 1 mol, preferably 0.01 to 0.1 mol, per 1 mol of the compound (10). The condensation reaction can be performed, for example, at room temperature (for example, 0 to 50 ° C.) for 0.5 to 24 hours, and the solution can be stirred during the reaction.

  After completion of the condensation reaction, the condensation reaction product is oxidized to obtain compounds of general formulas (1) to (3). For oxidation of the condensation reaction product, an oxidizing agent can be used, and examples of the oxidizing agent include p-chloranil. In addition to p-chloranil, examples include 2,3-dichloro-5,6-dicyano-p-benzoquinone. After the oxidation reaction, the compounds of the general formulas (1) to (3) can be separated and produced from the solution containing the product by a conventional method. The oxidation reaction can be performed, for example, at room temperature (for example, 0 to 50 ° C.) for 0.5 to 24 hours, and the solution can be stirred during the reaction. After completion of the reaction, the product can be separated and purified by conventional methods.

  When general formula (1)-(3) is a substituted phenyl group, the position of a substituent can be either 2-position, 3-position, or 4-position, and the number of substituents can be either 1-3. As for the substituent, the alkyl group having 1 to 6 carbon atoms is, for example, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, tert-butyl group, n-pentyl group, n- It can be a hexyl group. Examples of the alkyl group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, a tert-butoxy group, an n-pentyloxy group, and an n-hexyloxy group. Can be. Examples of the alkyl group having 1 to 6 carbon atoms in the alkylamide group having 1 to 6 carbon atoms include, for example, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, tert-butyl group, n- It can be a pentyl group or an n-hexyl group.

  Specific examples of the compounds represented by the general formulas (1) to (3) of the present invention include Ar, for example, a phenyl group, a nitrophenyl group, a methoxyphenyl group, an amidophenyl group, and the like.

  The compounds represented by the general formulas (1) to (3) of the present invention may be used for low molecular organic electronic functional materials, ion recognition dyes, selective interphase compounds, and chiral catalysts depending on the spectral characteristics and structure. it can. In particular, the compounds represented by the general formulas (1) and (3) can be used for low molecular organic electronic functional materials, ion recognition dyes, selective interphase compounds, and chiral catalysts, and are represented by the general formula (2). Can be used for low molecular organic electronic functional materials and ion recognition dyes.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not intended to be limited to these examples.

Example 1

Compound 10 (50.0 mg, 1.68 × 10 ⁻⁴ mol, 1 eq.) And a stirrer bar were placed in a two-necked eggplant type flask, and purged with argon. Methylene chloride was added to it and stirred until completely dissolved, then benzaldehyde (Ar = Ph) (17.1μl, 1.78 × 10 ^-4 mol, 1 eq.) And trifluoroacetic acid (TFA) (40.0μl) were added. Stir for 3 hours at room temperature. Thereafter, p-chloranil (136 mg, 3 eq.) Was added as an oxidizing agent, and the mixture was stirred overnight at room temperature under argon. After the reaction, the solvent was distilled off with an evaporator. Each fraction was specially prepared using alumina column chromatography and silica gel column chromatography with methylene chloride as a developing solvent. Then, by recrystallization from methylene chloride / hexane, compound (1) (Ar = Ph, compound 1-1), compound (2) (Ar = Ph, compound 1-2), compound (3) (Ar = Ph and compound 1-3) were obtained respectively. The yields of Compound 1-1 were trace amounts, Compound 1-2 was 3.2%, and Compound 1-3 were trace amounts. Traces and traces mean that the structure of the compound could be determined, but not so high as to yield.

For each compound, ¹ H NMR spectrum, X-ray single crystal structure (Bruker AXS, CCD crystal structure analyzer (SMART APEX II)), UV-vis absorption spectrum and TOF-MS spectrum (Bruker AXS) A time-of-flight mass spectrometer (Autoflex III) manufactured by S. Co., Ltd. was obtained, and the results are shown in FIGS. Similar devices were used in Examples 2-4.

Examples 2-4
Compounds 2-1, 2-2, and 2-3 corresponding to compounds (1) to (3) in the same manner as in Example 1 except that each compound shown in Table 1 was used as a raw material compound (Example 2) Compound 3-1, 3-2, 3-3 (Example 3) and Compound 4-1, 4-2, 4-3 (Example 4) were obtained. Table 1 used in Examples 2 to 4, amount of compound 10, type and amount of aromatic aldehyde, amount of TFA, amount of p-chloranil, yield of compounds (1) to (3) and structure determination data Indicates.

The columns of the compounds (1) to (3) show the compound number, yield (when obtained), confirmation method and result (number in the figure).

  INDUSTRIAL APPLICABILITY According to the present invention, a non-aromatic extended porphyrin having a specific structure and spectral characteristics can be provided, which is useful in the field using a material having a novel function.

Claims (2)

An extended porphyrin compound represented by any one of the general formulas (1) to (3).

In the formula, Ar represents a substituted or unsubstituted phenyl group, and in the case of a substituted phenyl group, the position of the substituent is 2-position, 3-position or 4-position, and the substituent is an alkyl group having 1 to 6 carbon atoms, carbon It is a C1-C6 alkoxyl group, an amide group, a C1-C6 alkylamide group, or a nitro group. A method for producing an extended porphyrin compound represented by any one of the general formulas (1) to (3) according to claim 1,
2,5-bis (4-propyl-2-pyrrolyl) thiophene and an aromatic aldehyde represented by the general formula ArCOH (Ar is as defined in claim 1) are cyclized under acidic conditions; The said method of oxidizing a product and obtaining at least 1 sort (s) of the extended porphyrin compound represented by either of General formula (1)-(3).