JPH02250883A - Fluorine-substituted porphyrin compound - Google Patents

Abstract

NEW MATERIAL:A compound expressed by the formula {R<1> to R<8> represent H or F and at least one is F; Z consists of n-valent cation [M<n+>(n is 1-5)] of an element in I A-VI A, I B-VII B and VIII groups, O and anion (X<->) of F<->, Cl<->, Br<->, I<->, O<->, OH<->, CH3O<->, C6H5O<->, SCN<->, etc., and takes the form of any one of 2M<+>, H<+>M<+>, M<2+>, M<3+>X<->, M<4+>X, O=M<4+> and O=M<5+>X<->}. EXAMPLE:2,3,7,8,12,13,17,18-Octafluoro-5,10,15,20-tetrakis(pentafluoro phenyl) porphyrinato.zinc. USE:An oxidizing catalyst for organic compound. PREPARATION:For example, 5,10,15,20-tetrakis(pentafluorophenyl)-21H,23H- porphyrin is dissolved in a solvent, mixed with a methanol solution of zinc acetic anhydride and heated while being stirred to afford 5,10,15,20-tetrakis(pentafluorophenyl)porphyrinato.zinc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to fluorine-substituted porphyrin compounds and a method for oxidizing organic compounds using them as catalysts.

[Conventional technology]

The fluorine-substituted porphyrin compound of the present invention is a novel substance that has not been previously known. Note that the term "fluorine-substituted porphyrin compound" as used herein refers to a general term for a porphyrin ligand in which Z is 2H' in -saccharide (1) and porphyrin complexes other than that.

Porphyrin compounds are attracting attention not only in the field of bio-related chemistry, including heme, but also as oxidation catalysts.

However, common porphyrin compounds tend to be easily destroyed in the presence of oxidizing agents such as hydrogen peroxide, hypochlorite, or iodosylbenzene.

As a method of increasing resistance to oxidizing agents, it is known to replace hydrogen atoms bonded to carbon in porphyrin compounds with halogen atoms, which are electron-withdrawing groups. For example, in the compound of the following formula, A-H, B-FS C-F, Z=Fe
”C1-(J,C,S, ,Chem,Com5u
n, 4fijll+ 778) A=HS B=CI, C
-H,Z-Mn” C1(J,C,S,,Chem,
Com5un,, dish+888), and A=Br, B
-CI, C-H, Z-Fe” Cl4-(rnorg
, Chem, 1338 (1987)).

However, both substances are easily destroyed by oxidizing agents and have residual double bonded carbon bonded to hydrogen, so their stability is insufficient. Therefore, among the industrial uses of these porphyrin compounds, their use as oxidation catalysts is considered to be impractical.

If all the hydrogen atoms in a porphyrin compound are replaced with fluorine atoms, which are the most electronegative among halogen atoms, it is thought that it is possible to provide an unprecedentedly stable porphyrin compound. 3.7
．． Conventionally, there is no known method for directly introducing fluorine into positions 8, 12, 13, 17, and 18.

(Problems to be Solved by the Invention) The problems to be solved by the present invention are as follows: 2.3.7.8.1
The object of the present invention is to develop a method for directly introducing fluorine into positions 2, 13, 17, and 18, and to provide a fluorine-substituted porphyrin compound that is expected to be used in a wide variety of fields.

[Means to solve the problem]

The present inventors synthesized a porphyrin compound having no carbon-hydrogen bond by fluorine substitution, found that the compound was effective as an oxidation catalyst, and completed the present invention.

That is, the present invention provides the following methods: An n-valent cation of one type of element selected from among (M", where n is an integer of 1 to 5), oxygen (0), and F-1CI-
1Br-1I-1O-011-, Cl11G-, Cs1
lzG-, n-CJJ-i-CsHvO-, t-CJ,
O-, CJsO-, ^cO-CN-, 5CN-, CIO
, one type of anion (X゛) selected from -, 2M"H"M・, M鵞・, M3・X−1M”X
-, 0=M" and 0-M"X-) is a fluorine-substituted porphyrin compound represented by This is a method of oxidizing organic compounds using peroxides.

The fluorine-substituted porphyrin compound of the present invention refers to a tetraphenylporphyrin compound in which some or all of the carbon-hydrogen bonds are replaced with carbon-fluorine bonds.

For example, a fluorine-substituted porphyrin complex with zinc as the central metal is prepared as follows. 5.10.15.20-tetrakis(pentafluorophenyl)-218,23H-porphyrin manufactured by Aldrich is dissolved in a halogenated hydrocarbon and mixed with a methanol solution of anhydrous zinc acetate of 20 to 150 equivalents. By heating and stirring at °C, 5.10.15.20-tetrakis (
Zinc pentafluorophenyl)porphyrinato is obtained. This compound is mixed with 0.1 to 200 equivalents of cobalt trifluoride and a halogenated hydrocarbon and a nitrogen-containing aromatic compound as a solvent in an inert gas such as nitrogen or argon, and the mixture is heated at 20 to 200°C. Heat and stir. Examples of halogenated hydrocarbons include methylene chloride, chloroform, carbon tetrachloride, 1,1.2.2-tetrachloroethane, and chlorobenzene. Examples of the nitrogen-containing aromatic compound include pyridine, 2,4-dimethylpyridine, collidine, and quinoline.

The desired porphyrin compound can be obtained by washing the contents with water, concentrating them, and then purifying them using a silica gel column. If the amount of cobalt trifluoride used is large, 2.3.7.8.
12.13.17.18-octafluoro-5,10,
Zinc 15,20-tetrakis(pentafluorophenyl)porphyrinato (hereinafter abbreviated as (Zn(OPP))) is obtained. This compound has a frequency of 270MHz, 'HNMR spectrum shows that it has no hydrogen atoms, and mass spectrometry shows that it has no hydrogen atoms.
It is identified as the desired porphyrin complex because it has a parent peak at /e and shows Soret absorption at the 4411 end from ultraviolet-visible absorption measurements.

In addition, the elemental analysis values are: C44,65; HO,00; N 4.80 (theoretical value Cn4FtsN*Zn ・1181.84C44,7
2; Ho, oo; N 4.74).

If the central metal is other than that of porphyrin complexes, zinc is removed from this zinc porphyrin complex by acid treatment in the same manner as in the case of other conventionally known porphyrin complexes, and then zinc is removed with 1 to 20 equivalents of the desired metal salt, such as pyridine. in the presence or absence of a base, in a solvent that dissolves both, such as tetrahydrofuran or dimethylformamide, from 30 to 200
It can be easily obtained by heating at C for 0.5 to 50 hours, washing with water, condensing, and purifying using a silica gel column.

Table 1 Position of 5-oret absorption in the ultraviolet-visible spectrum of fluorine-substituted porphyrin compounds When the porphyrin compound of the present invention is used in an oxidation reaction, the central metal is T
I, V%MnsFe, C0%Cu.

Complexes of Zr, Nb, Mo, Pd, Rus and - are preferably used. Oxidizing agents include hydrogen peroxide, peracids (such as peracetic acid), alkyl peroxides (such as t-butyl hydroperoxide), alkylidene peroxides (such as methyl isobutino and reketone peroxide), and hypochlorites ( Although sodium hypochlorite, etc.), iodosylbenzene, and molecular oxygen are used, hydrogen peroxide is preferably used from the viewpoint of reactivity and economy. The oxidation reaction can be carried out without a solvent, but a solvent may also be used. Examples of solvents include halogenated hydrocarbons (methylene chloride, etc.),
Water, alcohols (such as methanol), ketones (such as acetone), and nitriles (such as acetonitrile) can be used. These can be used alone or in combination of two or more.

The reaction temperature is -78~150°C, preferably 10~a
o'c. As the reaction pressure, normal pressure is preferably used, but reduced pressure or increased pressure may be used.

〔Example〕

Example 1 2, 3, 7, 8, 12, 13, 17
．． 18-octafluoro-5. 10, 15. 2
Preparation of zinc 0-tetrakis(pentafluorophenyl)porphyrinato (abbreviated as (Zn(OPP))) manufactured by Aldrich 5, 10, 15. 20-tetrakis(pentafluorophenyl)-21) 1,231(-porphyrin 10-1) was dissolved in 200af of chloroform.To this was added 200d of a methanol solution of 100swol of anhydrous zinc acetate, and the mixture was stirred under reflux for 2 hours. The obtained solution was washed with water, concentrated, and purified using a silica gel column to obtain 3v of 5, 10, 15.20-tetrakis(pentafluorophenyl)porphyrinatozinc.
++ol got it. 5. 10. 15. 20-tetrakis(pentafluorophenyl)porphyrinato zinc (
5 g+sol) to anhydrous cobalt trifluoride (5 0
(1+m@l) was dissolved in a mixed solvent of methylene chloride (100d) and pyridine (100d), and the mixture was stirred under reflux under an argon atmosphere. After confirming the completion of the reaction by UV, the resulting solution was washed with water, concentrated, and purified using a silica gel column to obtain 3.5 seals of (Zn (OPP)).

Example 2 2, 3, 7, 8, 12. 13. 17
．． 18-octafluoro-5. 10, 15. 2
9-tetrakis(pentafluorophenyl)-21H,
Preparation of 23H-porphyrin (abbreviated as (2H (OPP))) (Zn (OPP) ) (5+uao
Trifluoroacetic acid (10 mmol) was added to a solution of 1) in methylene chloride (100 affi). After stirring for 5 hours, the contents were poured into ice water.

The organic layer was washed with water and then with an aqueous sodium bicarbonate solution. A solution? 4.4-mol of (2H (OPP)) was obtained by condensation and purification using an alumina column.

Example 3 2, 3, 7, 8, 12. 13, 17
．． 18-octafluoro-5. 10, 15. 2
Preparation of 0-tetrakis(pentafluorophenyl)porphyrinatoiron(III) chloride (abbreviated as (Fe (OPP)Cj) (2H (OPP) ) (1 mm
ol) was dissolved in dimethylformamide m) together with iron chloride (Ill) (10 liters), and the mixture was stirred under reflux for 5 hours.
The obtained solution was washed with water, concentrated, and purified using a silica gel column to obtain (Fe (OPP)Cj'l of 0.7
I got msol.

Example 4 Oxidation of benzene (Fe (OPP) C1 (IXIO-' mo
l/j methylene chloride solution (0,1d) and benzene (
Table 2 shows the results of the 0 reaction in which a 35% aqueous hydrogen peroxide solution (0, 1d) was dropped into a mixed solvent consisting of 3id) and stirred in air at 25°C for 2 hours.

Furthermore, it was confirmed by examining the peak intensity of the ultraviolet-visible spectrum that the catalyst was not decomposed after the reaction.

Example 5 Oxidation of Benzene The reaction was carried out in the same manner as in Example 4 except that the amount of catalyst was changed to 17,100. The reaction results are shown in Table 2.

Comparative Example 1 In Example 4, 5.1G and 15.20-
The same operation was carried out except that tetraphenylporphyrinato iron (m) chloride (Aldrich) was used. No production of phenol was observed. Furthermore, complete decomposition of the catalyst after the reaction was confirmed by examining the peak intensity of the ultraviolet-visible spectrum.

Comparative Example 2 The same operation as in Example 4 was performed except that 5.10.15.20-tetrakis(pentafluorophenyl)polyphyllinate iron (In) chloride (Aldrich) was used as the catalyst. No formation of phenol was observed. Furthermore, it was confirmed that 60% of the catalyst was decomposed after the reaction by examining the peak intensity of the ultraviolet-visible spectrum.

Comparative Example 3 In Example 4, 2, 3, 7, 8°12, 1
3.17.18-octabromo-5,10,15,20
-tetrakis(2,6-dichlorophenyl)porphyrinatoiron(III) chloride (Inorg, Chew,
The same procedure was carried out except that the following procedure was used: Furthermore, it was confirmed by examining the peak intensity of the ultraviolet-visible spectrum that 30% of the catalyst had decomposed after the reaction.

Example 6 Oxidation of Phenol The same operation as in Example 4 was performed except that phenol was used instead of benzene and methanol (0,1d) was added. Further, it was confirmed that the catalyst had not decomposed after the reaction by checking the peak intensity of the ultraviolet-visible spectrum.

The reaction results are shown in Table 2.

Example 7 Oxidation of cyclooctene Cyclooctene (1 mol/l), (Fe (O
PP) CIri (JXIO-”sol/Jri
, methylene chloride (0,2d) and methanol (0,
A 35% aqueous hydrogen peroxide solution (0,625 sol/j!) was gradually added dropwise to the mixture consisting of 2-) and stirred five times at room temperature. The yield of cyclooctyne is 0.58 mol/J! The yield was 93% based on the added hydrogen peroxide. Furthermore, it was confirmed by examining the peak intensity of the ultraviolet-visible spectrum that the catalyst was not decomposed after the reaction.

Example 8 The same operation as in Example 7 was performed except that cyclohexane was used instead of cyclooctene. Cyclohexanol was produced with the same results as in Example 7. In addition, ultraviolet light can be used to confirm that the catalyst has not decomposed after the reaction.
1i1 by examining the peak intensity of the visible spectrum
1 approved.

Identification and quantification of the product were both done by gas chromatography.

〔Effect of the invention〕

The fluorine-substituted porphyrin compound of the present invention is considered to be a useful material in a wide range of fields, including biological fields such as medicine and agricultural chemicals, and electronic materials.

Furthermore, the porphyrin compound of the present invention is much more stable in a system in which hydrogen peroxide coexists than other porphyrin compounds conventionally known.

As shown in Example 4 and Comparative Examples, the porphyrin compound of the present invention exhibits good catalytic activity even in the reaction to obtain phenol from benzene, which was not possible with other conventionally known porphyrin compounds. Therefore, the porphyrin compound of the present invention is an extremely suitable catalyst for the oxidation reaction of organic substances with peroxides.

Patent applicant: Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] (1) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (However, in the formula, R^1 to R^8 each represent a hydrogen atom or a fluorine atom, and at least One is a fluorine atom, and Z is an n-valent cation (M^n) of one type of element selected from groups IA to VIA, IB to VIIB, and VIII.
^+where n is an integer from 1 to 5), oxygen (O), and F^-
, Cl^-, Br^-, I^-, O^-, OH^-, C
H_3O^-, C_2H_5O^-, n-C_3H_7
O^-, i-C_3H_7O^-, t-C_4H_9O
^-, C_4H_5O^-, AcO^-, CN^-, S
Consists of one type of anion (X^-) selected from CN^-, CIO_4^-, 2M^+, H^+M^
+, M^2^+, M^3^+X^-, M^4^+X^-
A fluorine-substituted porphyrin compound represented by _2, O=M^4^+ and O=M^5^+X^-. (2) The fluorine-substituted porphyrin compound according to claim 1, wherein R^1 to R^8 are all fluorine atoms. (3) A method for oxidizing an organic compound with a peroxide, which is carried out in the presence of the perfluorinated porphyrin compound according to claim 1. (4) The method according to claim 3, wherein the organic compound is an aromatic compound. (5) The method according to claim 4, wherein the aromatic compound is benzene, toluene, xylene, cymene, phenol, cresol, anisole, acetanilide, or naphthalene. (6) The method according to claim 3, wherein the organic compound is an olefin. (7) The olefin is propylene, 1-butene, 2-butene, butadiene, isoprene, cyclopentene, cyclohexene, cyclooctene, 1,4-cyclooctadiene, styrene, α-methylstyrene, stilbene, allyl chloride, allyl bromide , allyl alcohol, oleic acid and its ester, or soybean oil. (8) The method according to claim 3, wherein the organic compound is paraffin. (9) Paraffin is butane, isobutane, hexane,
9. The method according to claim 8, which is any one of octane, cyclopentane, cyclohexane, or methylcyclohexane.