The method of obtaining single-ended porphyrazines

 

(57) Abstract:

The invention relates to the production of unbalanced porphyrazines, combining in the molecule two diphenylpyraline or two isoindoline fragment. The essence of the invention is a method for unbalanced porphyrazines by interaction porphyrinogens, which as porphyrinogens use 2-imino-5-amino-3,4-diphenyl-2H-pyrrole and chlorhidrate 1,1-dichloro-3-amino-1H-isoindole General formula (I), where X = H, CL, Br, and interaction is carried out in acetone at room temperature in the presence of triethylamine, then under conditions of boiling acetone in the presence of copper chloride and/or hydroquinone and sodium methylate. The described method allows to obtain asymmetric piperazinone the metal complexes and their corresponding bezmetallny of the connection conditions, reducing or eliminating the formation of products of side reactions which reduce the yield of the target products. 2 Il.

The invention relates to the production of unbalanced porphyrazines, combining in the molecule two diphenylpyraline and two isoindoline fragment.

A method of obtaining asymmetric porphyrinoid complexes, which is Konami Hideo//Jnorg. Chem. - 1994. - Vol. 33, N 9. - P. 1735-1740]. As porphyrinogens use diphenylacetonitrile and 2,3-dicyano-1,4-defininately. The interaction is carried out at a temperature of 250 - 260oC in an atmosphere of dry argon according to the following scheme:

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High temperature synthesis in this case causes the formation of significant amounts of impurities. The output of the target product is 2% for zinc complex and 2.5% for the cobalt complex.

The closest analogue of the claimed method is a method of condensation of diphenylacetonitrile from 3.6-diphenylvaleronitrile in the presence of zinc salts at a temperature of 250 - 260oC. [Kobagashi Nagao, Ashido Tohru, Hiroyakou, Osa Tutsuo//Chem. Lett. - 1992. - N 8. - P. 1576-1570].

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The output of the complex of zinc with asymmetrical piperazinonyl ligand in this way does not exceed 6%. The resulting admixture, in addition to reduced output, complicate the process of isolation and purification of the target product. A sufficiently high temperature synthesis requires significant energy costs. In addition, according to this method, it is impossible to obtain the relevant bezmetallny connection.

Thus, it is not a method of obtaining asymmetric porphyrinoid metal complex is mswb adverse reactions, which reduce the yield of the target products.

Inventive task was to find a way to get unbalanced porphyrinoid complexes and Bezmaternykh compounds, combining in the molecule two diphenylpyraline and two isoindoline fragment, which would reduce the number of forming impurities, energy costs, improve the yield of the target product and would allow us to get not only the metal complexes, and their corresponding bezmetallny connection.

The problem is solved by a method of obtaining single-ended porphyrazines by interaction porphyrinogens, which as porphyrinogens use 2-imino-5-amino-3,4-diphenyl-2H-pyrrole and chlorhidrate 1,1-dichloro-3-amino-1H-isoindole and interaction is carried out in acetone at room temperature in the presence of triethylamine, then under conditions of boiling acetone in the presence of copper chloride and/or hydroquinone and sodium methylate.

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Distinctive features of the process are the use of new initial substances and the conditions of interaction between them.

The combination of these distinctive features is allowed to obtain the following advantages:

it will increase the performance as unbalanced porphyrazine complexes (IV-VI), and the corresponding bezmetallny compounds (I-III).

Necessary for the implementation of method 2-imino-5-amino - 3,4-diphenyl-2H-pyrrole obtained by processing diphenylacetonitrile ammonia in the environment methanolic solution of sodium methylate according to methods analogous to the methods of obtaining aminobenzoylamino [F. Bauman , B. Bienert , G Rosch u. a//Angew. Chem. - 1956. - Bd. 68, No. 4. - s. 133-149].

In triggerlevel flask equipped with stirrer, reflux condenser, thermometer, and bubbler, pour a methanol solution of sodium methylate obtained from 0.26 g in (11.2 mmol) of sodium and 80 ml of methanol. Added 1.84 g (8 mmol) of diphenylacetonitrile and the resulting mixture was cooled to 0oC. With stirring, the reaction mixture is passed drained ammonia. After 20 to 30 minutes the temperature is increased up to 20 - 25oC, it forms a yellow solution. At this temperature, continue to ignore the ammonia for three hours. After this part of the methanol is removed by evaporation at room temperature before the formation of a yellow precipitate, which is filtered off and dried in a vacuum desiccator over calcium chloride. Yield: 1.82 g (92%).

2-imino-5-amino-3,4-diphenyl-2H-pyrrol - yellow powder, insoluble in water, soluble in Matey decomposes with evolution of ammonia.

Found, %: C 77,5; H 5,0; N 17,1.

C16H13N3< / BR>
Calculated, %: C To 77.7; H 5,3; N 17,0.

IR range: 3000 - 3500 cm-1( NH).

Chlorhydrate 1,1-dichloro-3-amino-1H-isoindole and halogensubstituted obtained from the relevant phthalodinitrile by well-known methods by treatment of the dried hydrogen chloride in anhydrous chloroform. [Bartlett R. K., Renny Z. V., Chnn K. K.//J. Chem. Soc. - 1969. - P. 129].

1,1-dichloro-3-amino-1H-isoindole hydrochloride

In triggerlevel flask equipped with a stirrer with trap, reflux condenser and bubbler placed 12.8 g (0.1 mol) of phthalodinitrile dissolved in 150 ml of anhydrous chloroform. Through this solution with constant stirring bubbled dry hydrogen chloride for 12 hours. After this time you roll a white precipitate, which is filtered off, washed with a small amount of cooling to 5oC chloroform, press on the filter and dried at room temperature in a desiccator over pjatiokisi phosphorus.

The yield of 7.24 g (30,5%).

Found, %: C 40,7; H 2,9; N 11,6; Cl 44,5.

C8H7N2Cl3< / BR>
Calculated, %: C, 40,4; H 2,9; N 11,9; Cl 44,8.

IR-spectrum: 2900 - 3100 cm-1( In NH RNH3+); 800 - 850 ( C-Cl)

Found, %: C 35,2; H 2,0; N 10,8; Cl 49,0.

C8H6N2Cl4< / BR>
Calculated, %: C 35,3; H 2,2; N 10,3; Cl 50,2.

IR-spectrum: 2900 - 3100 ( NH in RNH3+) 800 - 850 ( C-Cl).

1,1-dichloro-3-amino-5/6-bromo-1H-isoindole hydrochloride

Receive the above method for producing 1,1-dichloro-3-amino-1H-isoindole hydrochloride of using 20.7 g (0.1 mol) 4/5-bramptontopical. The output of 6.49 g (20,5%).

Found, %: C 30,3; H 1,7; N 8,3; (Cl + Br) 57,1.

C8H6N2Cl3Br

Calculated. %: C 30,4; H 1,9; N 8,8; Cl 33,7; Br 25,3.

IR-spectrum: 2900 - 3100 cm-1( In NH RNH3+); 800 - 850 cm-1( C-Cl); 600 - 680 cm-1( C-Br).

The method of obtaining single-ended porphyrazines using as porphyrinogens 2-imino-5-amino-3,4-diphenyl-2H-pyrrole and clorhidrato 1,1-dichloro-3-amino-1H-isoindole carried out by the interaction of the parent compounds in several stages: first at room temperature in an environment of dry acetone followed by the addition of triethylamine. After the precipitate of triethylamine hydrochloride in the reaction mixture to obtain Bezmaternykh compounds (I-III) add hydroquinone and methylate n the (I-VI) occurs in boiling acetone at a temperature of 56oC.

Getting Bezmaternykh compounds (I-III)

General methods

In triggerlevel flask equipped with addition funnel, thermometer and a water seal is placed a suspension of 2 mmol of hydrochloride 1,1-dichloro-3-amino-1H-isoindole or halogensubstituted in 50 ml of dry acetone, to which then for 20 minutes was added dropwise a suspension of 0.49 g (2 mmol) of 2-imino-5-amino-3,4-diphenyl-2H-pyrrole in 10 ml of dry acetone. The mixture was incubated 1 hour at room temperature, stirring constantly. Then added 1.01 g (10 mmol) of triethylamine and incubated for another 1 hour. The precipitation of triethylamine hydrochloride is filtered off, the filtrate is returned to the reaction flask, added 0.32 g (6 mmol) of sodium methylate and 0.23 g (2,35 mmol) of hydroquinone. The mixture was incubated for 4 hours in boiling acetone (56oC). Hot reaction mass is transferred into vapaatalo Cup and the acetone is removed by evaporation. The dry residue is successively washed first with hot water, then with 10% hydrochloric acid to colorless filtrates and again with water until neutral environment and absence of leachate chloride ions. Target products (I-III) is extracted with benzene in to conventional Soxhlet extractions. The benzene removed from the extract by evaporation in the as eluent a mixture of benzene: ethanol in a ratio of 10:1 and subsequent thermal treatment (residual pressure of 10-3PA) at a temperature of 200 - 250oC for two hours.

Identification of the compounds (I-III) is conducted using the data of elemental analysis, electronic, and vibrational spectroscopy.

Compounds (I-III) are powders dark purple color, insoluble in water, soluble in benzene, chloroform and other organic solvents. In concentrated sulfuric acid even at room temperature there is their destruction with the formation of colorless solutions.

Dibenzoyltartaric (I)

Get a General methodology using of 0.48 g (2 mmol) of the hydrochloride 1,1-dichloro-3-amino-1H-isoindole. Output 0,215 g (30.1 per cent).

Found, %: C 79,7; H 4,0; N 15,1.

C48H30N8< / BR>
Calculated, %: C An 80.2; H 4.2; N 15,6.

ESP, nm: benzene 695 FF., 670, 630 FF., 608, 575 FF.

Di(garbanzo)tetraphenylporphin (II).

Get a General methodology using 0,544 g (2 mmol) of the hydrochloride 1,1-dichloro-3-amino-5/6-chloro-1H-isoindole.

Yield 0.12 g (15.2 per cent).

Found,%: C 73,0; H 3,5, N, 14,0, Cl 8,3.

C48H28N8Cl2< / BR>
Calculated, %: C 73,2; H 3,6; N 14,2; Cl 9,0.

ESP,maxnm: in benzene 696 square, 675, 630 FF., 615, 581 0,633 g (2 mmol) of the hydrochloride 1,1-dichloro-3-amino-5/6-bromo-1H-isoindole.

Output 0,128 g (14.6 percent).

Found, %: C 65,2; H 3,0; N 12,3; Br 17,5.

C48H28N8Br2< / BR>
Calculated, %: C 65,8; H 3.2; N 12,8; Br 18,2.

ESP,maxnm: in benzene 696 FF., 675, 630 square, 615, 583 FF.

Complexes of copper (IV-VI)

General methods

To the stage of separation of the precipitated precipitate of triethylamine hydrochloride, the process is conducted as and when receiving Bezmaternykh compounds (I-III).

In the filtrate after separation of the precipitate of triethylamine hydrochloride add 0,199 g (2 mmol) of copper chloride, allowed to stand for 1 hour at room temperature, then add 0,216 g (4 mmol) of sodium methylate and 0,248 g (2.25 mmol) of hydroquinone and incubated for 4 hours in boiling acetone (56oC). Hot reaction mass is transferred into vapaatalo Cup and the acetone is removed by evaporation. The dry residue is successively washed first with hot water, then with 10% hydrochloric acid to colorless filtrates, again with water until neutral environment and absence of leachate chloride ions. Target products (IV-VI) is extracted with benzene in to conventional Soxhlet extractions. The benzene extract is removed by evaporation on a water bath. Further purification perform column chromatography on silica gel L 40/100 using as eluent the PA) at a temperature of 200 250oC for two hours.

Identification of complexes (IV-VI) is conducted using the data of elemental analysis, electronic, and vibrational spectroscopy.

Complexes (IV-VI) are powders dark purple color, insoluble in water, soluble in benzene, chloroform and other organic solvents. Dissolve without decomposition in concentrated sulfuric acid.

Dibenzoyltartaric copper (IV)

Get a shared approach using value (0.475) g (2 mmol) of the hydrochloride 1,1-dichloro-3-amino-1H-isoindole. Output 0,094 g (12,1%).

Found, %: C 73,6; H 3,8; N 14,2; Cu 7,7.

C48H28N8Cu

Calculated, %: C 73,7; H 3,9; N 14,3; Cu 8,1.

ESP,maxnm: in benzene 688 FF., 648 18 M H2SO4748, 684 square

Di(garbanzo)tetraphenylporphin copper (V)

Get a General methodology using 0,544 g (2 mmol) of the hydrochloride 1,1-dichloro-3-amino-5/6-chloro-1H-isoindole.

Output 0,160 g (18.8 per cent).

Found, %: C 67,8; H 3,0; N 12,8; Cl 7,9; Cu 7,0.

C48H26N8Cu

Calculated, %: C 67,9; H 3,1; N 13,1; Cl 8,4; 7,5 Cu.

ESP,maxnm: in benzene 685 FF., 652; 18 M H2SO4750.

Di(Brabant)tetraphenyltin-isoindole.

Output 0,419 g (44.8 percent).

Found, %: C To 61.4; H, 2.7; The N 11,3; Br 16,4; Cu 6,0.

C48H26N8Br2Cu

Calculated, %: C 61,5; H 2,8; N 11,8; Br 17,1; Cu 6,8.

ESP,maxnm: in benzene 685 FF., 653; 18 M H2SO4759.

In the IR spectra (Fig. 1, the IR spectra of: 1 - di(garbanzo) tetraphenylporphin, 2 - di(garbanzo) tetraphenylporphin copper) asymmetric porphyrazines (I-VI), it is possible to identify a number of characteristic absorption bands. So in the field of 1350-1500 cm-1there is absorption related to skeletal vibrations of pyrrole rings porphyrinogen of the macrocycle. More intensive absorption in the range of 1700-1800 cm-1refers to the stretching vibrations due to C-C in the benzene rings. In addition, the IR spectra of halogen-substituted compounds (II, III, V, VI), there are additional band in the range of 800 - 850 cm-1(II, V) and 500 - 600 cm-1(III, VI), which is characteristic of stretching vibrations of C-Cl bond and the C-Br, respectively [Porphyrins: structure, properties, synthesis//K. A. Askarov, B. D. Berezin, R. P. Evstigneeva and others - M.: Nauka, 1985. - S. 85 - 87. Dyer D. R. Application of absorption spectroscopy of organic compounds. M.: Chemistry. 1970. - S. 31-65].

In the IR spectra Bezmaternykh compounds (I-III) OTS is., Kotlyar, I. P. Optics and spectroscopy. - 1961. - T. II, N 2. - S. 175-184], which indicates the absence of impurities that connection.

In the electronic absorption spectra of Bezmaternykh compounds (I-III) in benzene (Fig. 2, the electronic absorption spectra: 1 - dibenzo tetraphenylporphin, 2 - dibenzo tetraphenylporphin copper) in the long wavelength region has a greater number of bands compared to the symmetric derivative of piperazine, in particular with phthalocyanine and octaphenyltetraazaporphine. In addition, the first wavelength band in the spectrum of compound (I), for example, shifted hypsochromic compared with the first band in the spectrum of the tert.-butylamino phthalocyanine, soluble in benzene [Electronic spectra of phthalocyanines and related compounds. Directory/ Bondina N. And., Halpern M. G., and others, Ed. by E. A. Lucianna. - Cherkassy: 1989. - 93 S.] and Bathrobe compared with the corresponding band in the spectrum of octaphenyltetraazaporphine [Porphyrins: structure, properties, synthesis//Askarov K. A., Berezin B. D., Astagneau R. P. and others - M. : Science: - 1985. - 333 S.]. There are also differences in the position and relative intensity of other bands. The halogen-substituted Bezmaternykh compounds (II, III) the nature of the spectrum similar to the spectrum soedinen (IV-VI), as well as in a series of phthalocyanines and octaphenyltetraazaporphine [Berezin B. D. Coordination compounds of porphyrins and phthalocyanine. - M.: Nauka, - 1978. - 280 S. Porphyrins: structure, properties, synthesis//Askarov K. A., Berezin B. D., Evstigneeva, R. P. and others - M.: Nauka. - 1985. - 333 S.] there has been a significant change in the spectrum, however, the nature of this change does not repeat the spectral manifestations in kompleksoobrazovanii with symmetrical condensed porphyrazine complexes which in the long wavelength region have one intense band. Spectra of the asymmetric porphyrinoid complexes of copper (IV-VI) are characterized by two bands, one of which (longer wavelengths) has a weak intensity (Fig. 2).

The marked feature of ESP is a consequence of the lowering of the symmetry of distribution of electronic density in porfirinova macroalga in the asymmetric substitution of the hydrogen atoms of pyrrole rings and is a convincing confirmation of the proposed structure of the synthesized compounds, as this feature is characteristic for other derivative porphyrazine asymmetric structure [Kulinich B. N., Shaposhnikov, P., Maizlish C. E. and others Journal of General chemistry. - 1996. - T. 66, No. 9. - S. 1560-Appendix intense long-wavelength bands in comparison with symmetrically substituted and symmetrical condensed porphyrazine complexes. For example, in the spectrum of complex IV in benzene marked bathochromic shift of the position of the long wavelength band at 23 nm compared with octaphenyltetraazaporphine copper and hypsochromic offset of 27 nm in comparison with Tetra(tert.-butyl)copper phthalocyanine, having a solubility in benzene.

The method of obtaining single-ended porphyrazines by interaction porphyrinogens, characterized in that as porphyrinogens use 2-imino-5-amino-3,4-diphenyl-2H-pyrrole and chlorhidrate 1,1-dichloro-3-amino-1H-isoindole General formula

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where X Is H, CL, Br,

and interaction is carried out in acetone at room temperature in the presence of triethylamine, then under conditions of boiling acetone in the presence of copper chloride and/or hydroquinone and sodium methylate.

 

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