SU910619A1 - Macrocyclic chelates /1,8,9,14-tetrahydro-3,6-dimethyl-1,8-(dialkyl)diphenyldibenzo-/b,m/-dipyrazolo-[4,5-f:4',5- -1,2,5,8,9,12/-hexaazacyclotetradecinato (2)-n , n , n , n transitional metal as photoconductor material and method for producing the same - Google Patents

Description

The photosensitivity of FCsI is also not wide enough - the UV region and part of the visible region (. 1 of them. The spectral distribution of the photocurrent for FCsC has a discontinuity from 530 to 395 nm and relatively low photosensitivity in the near IR region of the spectrum. In addition, the solubility of FCSV is relatively low. most solvents are difficult to clean and, as a result, with a significant variation in the parameters and working photoelectric characteristics, poor reproducibility of properties, which leads to a decrease in processability The production of devices based on FCsI, makes it necessary to search for new, more efficient photoconductive materials from this class of compounds. The closest to the proposed method is a method based on the condensation reaction in the synthesis of {dihydro (1,2,5,8,9, 12) -hexazatetradecin system-9,2.0-dihydro-3,6 dimethyl-1, 8-diphenylbenzo-f; j-dipyrazolo-4, 5-s: 4, 5 -t - 1, 2, 5, 8.9, 12 hexaazacyclotetradecinato (2) N, N, N, nickel (P) by reacting 5,5-dichloro-3,3-dimethyl-1, l diphenyl-4, 4 -azopyrazole with 2,2-diaminazabenzene in the presence of acetate nickel (ii) and carbon potassium in dimethylformamide. The yield of the target product is 29% 4. However, the target product, despite chromatographic purification on a silica gel column (hemapol) L 100160 microns, eluent chloroform, is contaminated with isomeric macrocyclic products. The overall yield of the product is relatively low: (only 29% of theory. A slight temperature increase of 5-10 ° C leads to a significant decrease in the yield of the target product (twice) and to the formation of by-products. Macroclic chelates 1 are offered as photoconductive material , 8,9,14-tetrahydro-3,6-dimethyl-1, 8- (dialkyl) -diphenyldibenzo in, t1-dipyrazolo- 4, 5-f: 4, 2,5,8,9,12 -hexaazacyclotetradecinate (2), N5, No., N, ti is a transition metal of formula I. The method for preparing macrocyclic chelates of formula I is that 5.5-dihalo-3.3-dimethyl -1, l (dialkyl) -diphenyl-4,4 -azopyrazole is reacted with 2,2-diaminoazobenzene in the presence of an active copper catalyst, a transition metal salt, potassium carbonate in an azeotropic medium of a polar organic solvent at its boiling point, followed by chromatographic isolation of the target product from the resulting mixture of isomers and resin using alumina with the addition of 3,5,8,10-tetranitropyrene as a sorbent,. In the quality of the sorbent, it is better to use a mixture of aluminum with the addition of 1-7 wt.% 3, 5, -B, 10-tetranitropyrene. To obtain the optimum yield of the target product, the process of interaction is conducted in an inert gas, for example nitrogen or argon. The drawing shows a graph, where curve 1 is the electronic absorption spectrum of the FCsI film; curve 2 is the spectral distribution of the photocurrent for FCsi (measured in Sandwich-type cells); curve 3 — electron absorption spectrum of a new macrocyclic chelate (1,8,9,14-tetrahydro-3, 6-dimethyl-1,8- (dialkyl) diphenyldibenzo-in tni-dipirazolo 4, 5-f: 4, 5, 2 , 5,8,9,12 -reKsaazacyclotetradecinato (2) N, N, jjIS jjIOJ nickel (II); curve 4 -, the spectral distribution of the photocurrent for this macrocyclic chelate (measured in the Sandwich cell), the following table summarizes the physical chemical, spectral and photoelectric data for macrocyclic chelates of formula 1.

As can be seen from the table, both the electronic absorption spectrum and the spectral distribution of the photocurrent for macrocyclic chelates of formula I do not have a discontinuity from the UV spectral region up to 1250 nm, i.e. to the near infrared region of the spectrum, inclusive. At X 470 nm, where the photosensitivity of FCsi (prototype) is absent, the photosensitivity of macrocyclic chelates of formula 1 is relatively high

(K g- 15-: 2-10 -4.2-10 with TSwrt lit

L 0,015 W / cm in a field of 100 V / cm | dark resistance is also high (Pte1ch n I0 i-10 Ohm.cm). Macrocyclic chelates of the formula I are relatively well soluble in benzene, toluene, xylene, DMF, chloroform, acetic acid, practically insoluble in alcohols and water.

Example 1. In a three-necked round-bottomed flask equipped with a stirrer, a thermometer and a reflux condenser, 180 ml of a mixture of anhydrous solvents benzene-dimethylformamide (in the ratio 4: 1), 11.06 g (0.08 mol) of potassium carbonate, 4.25 g (0.02 mol) 2,2-diaminoazobenzene, 0.00001 g of catalyst - active copper, 4.98 g (0.02 mol) of cobalt acetate tetrahydrate, 9.76 g (0.02 mol) 5.5 dibromo- 3, 3-dimethyl-1,1-diisopropyl 4, 4-azo pyrazole and with stirring bring the contents of the flask to a boil and boil for 2 hours at the boiling point of the azeotropic formed

mixes. The progress of the reaction is controlled by thin layer chromatography. After cooling, the precipitated precipitate is filtered off, washed with cold water until a negative reaction to halogen ions, dried and recrystallized from a mixture of benzene-di-, methylformamide (4: 1). The filtrate is distilled to 1/4 of the original volume, the same amount of water is added with stirring, brought to a boil, and then cooled. The resulting slurry is filtered, washed 2-3 times with a small amount of dimethylformamide-water (1J1) solution and dried in an oven. The total yield of raw product 4.60 g (43% of theory).

The obtained dry product (4.60 g) is dissolved in 200 ml of a mixture of benzenemethylformamide (4: 1) and this solution is passed through a chromatography column with aluminum oxide P to heat Brockman activity, containing 10% by weight 3.5, a, 10- tetranitopyrene, which is uniformly distributed throughout the alumina (eluent benzene: dimethylformamide (4: 1).

Five zones are detected on the column. The first zone is a macrocyclic chelate {l, 8,9,1 4 - strahydro-3, 6-dimethyl-1,8-diisopropyldibenzene, t-dipyrazo-4,, 4, 5 G1,2 , 5,8,9,12 -hexase cyclotetradecinato (2) M, YaZ, N, cobalt (P). The residue after distillation of the eluent is dissolved in 30 ml of a mixture of benzene-dimethylformamide (4: 1), the solution is brought to a boil and cooled, transferring the contents of the flask to ice. The precipitated crystals are separated, dried and examined. Chelate yield 2.05 g (19% of theory).

Found% 5 C 57.87; 57.98; 15 H 5.13, 5.23; N 25.87, 26.02; Co 10.87, 11.03.

Calculated,%; C 57.90; H 5.19; N 25.98; From 10.93.

Elemental analysis and X-ray diffraction analysis show that the composition of the complex corresponds to the formula C | (, Hf (mol. Weight. 539.29; ebulioscopy gives mol. Weight. 529.50);

5 g, Aaiy77 nm; 2.4-10; B

so "

0,015 W / cm in the field of 100 V / cm. The set of data on the electronic absorption spectra / IR spectroscopy, magnetic susceptibility and X-ray phase analysis allows us to attribute the obtained macrocyclic chelate to the above structural formula G.

5 examples. Macrocyclic chelate 1,8,9,14-tetrahydro-3, 6-dimethyl-1, 8-diisoprpylbenzo, t dipyrazolo-4, 2.5, 8,9,121-hexaazocyclotetradecinate (2) N, No., N , cobalt (P) is obtained and isolated as in Example 1. However, the separation process is carried out using alumina with the addition of 6 wt.% 3,5,8, 10-tetraitropyrene as a sorbent. Chelate yield 2.27 g (23% of theory); K ff

5 2.7-10 at, 015 W / cm in the field of 100 V / cm.

Example 3. Macrocyclic chelate {l, 8,9,14-tetrahydro-3, 6-di0 methyl-1,8-diisopropyldibenzo-in L1 dipiraeolo-4, 5, 2,5,8, 9,121-hexag1 zcyclotetradicinato (2) N,, cobalt (P) is obtained and isolated as in Example 1. However, when isolating, alumina with 1 wt.% 3,5,8,10-tetranitropyrene is used as a sorbent. The output of pure chelate is 2.35 g (23% of theory).

0

I Found% j C 57.84, 57.95; H 5.15, 5.22; N 25.90, 25.85; From 10.66, 10.85.

You,%: C 57.90; H 5.19;

N 25.98; From 10.93. )

.. -. 26-lo-- with I, 0.01j Nt / cm

those in the field. 100 V / cm.

Example4. In the flask of example 1, load 200 ml of a mixture of anhydrous solvents m-xylene-chlorobenzene (5: 4), 11.06 g (0.08 mol) of potassium carbonate, 4.25 g (.0.02 mol) 2, 2-diaminoazobenzene, 0.00001 g of active copper catalyst, 8.23 g (0.02 mol of 5.5-dichloro 3, 3-dimethyl-1,1-diethyl-4,4 -azopyrazole, 4.98 g ( 0.02 mol of cobalt acetate tetrahydrate and then with stirring bring the contents of the cobalt to a boil and boil for 2 hours at the boiling point of the m-xylene-chlorobenzene-water azeotropic solvent mixture (t, boiling point, 130134 ° C). control method thin layer chromatography. After cooling the reaction mixture, the precipitate is filtered, washed with cold water until a negative reaction to halogen ions, dried, recrystallized twice from solvent mixtures xylene-chlorobenzene (5: 4) and dried in a drying cabinet at 100 ° C. The filtrate is distilled off up to 1/3 of the original volume, pour the same amount of water and bring it to a boil with stirring, then cool.The resulting suspension is filtered, washed 2-3 times with a small amount of m-xy.lol-chlorobenzene mixture (5: 4) and dried in an oven at 1 00 ° C. The yield of raw product is 6.08 g (50% of theory). The obtained dry product is dissolved in 180 m of anhydrous solvent m-xylene-chlorobenzene (5: 4) and the solution is passed through a chromatography column with aluminum oxide (P) of Brockman activity, containing 4 wt., 3, 5,8,10-tetranitropyrene which is uniformly distributed throughout the alumina (elglent xylene - chlorobenzene). Five zones are detected on the column. The first zone is a macrocyclic chelate complex {l, 8,9,14-tetrahydro-3, 6-dimethyl-1,3-dienyldibenzene, Tfi-dipyrazolo G4, 5-f: 4, 5 - J tl, 2 , 5,8,9,12 -hexaazacyclotetradecinato (2) N, n, n5,) cobalt (P). The isolation was carried out as in Example 1. A chelate yield of 2.4 g (23% of theory).

Found,%: C 63.33; 63.25; iH 3.91, 4.01; 23.11, 23, 05; Co 9.1 3

Calculated,%: C 63.28; H 3.95; N 23.07; From 9.70.

Elemental chemical and X-ray phase analyzes show that the composition of the complex corresponds to the formula Cj H, j N (5 Co (mol. Weight. 607.35, ebulioscope gives mol. Weight, 609.7);

XfAdnc 693 nm; K --- °° 2,7-10 when

Nemts

). 470 them, L (1,015 W / cm (3 100 V / cm.

Try, MacrocyclicPhelate {1,8,9, l -TcrTparnnpo-T, fi-dimethyl-1, 8-diphenyldibenzene, tnl-dipyrazolo- 4, 5-f: 4, 5 - jj- 1,2, 5, 121 -hexaazacyclotetradecinato (2) N, S, M, cobalt (P) are prepared and prepared as in example 4. However, the reaction process is carried out in a nitrogen atmosphere. The yield of the heleta is 2.92 g (25% of theory).

Found,%: C 63.25, 63.34; H 40.00, 3.89; N 23.13, 23.04; From 9.80, 9.75.

Calculated,%: C 63.28; H 3.95; N 23.07; From 9.70.

Elemental chemical analysis and

photosensitivity K. 7.2-10

ITS mi

at L0.015 W / cm in a field of 100-V / cm, they demonstrate sufficient purity of the chelate thus obtained.

Analogously to example 4, macrocyclic chelates of formula I are obtained with manganese, zinc, cadmium and other metals. The optimal composition of the sorbent in the chelate, which allows to obtain the target product with the maximum yield: alumina and 1-7 weight,% 3,5,8,10-tetranitropyrene,

Example 6 Into the flask of Example 1, 180 ml of a mixture of anhydrous solvents m-xylene-chlorobenzene (5: 4), 11.06 g (0.08 mol. Of potassium carbonate, 4.25 g (0.02 mol. 2.2 -diaminoazobenzene, 0.0001 g of catalyst - active copper, 8.08 g (0.02 mol), 5,5-dibrom-3, 3 -dimethyl-1, 1-diethyl-4,4 -azopyrazole, 4.9 g (0.02 mol) of manganese (II) acetate tetrahydrate and subjected to interaction and isolation as in Example 4. The yield of chelate {1,8,9,14 tetrahydro-3, 6-dimethyl-1,8-diethylbenzo-Gv, tpz- dipyrazolo- 4, 5- {: 4, 5 1,2,, 9,12 -hexaazacyclotetralecinato (2) No., No., M, M manganese (P) 2.03 g (20% of theory).

Found,%: C 56.89, 56.75; H 4.80, 4.69; N 27.65, 27.59; MP 10.90, 10.85.

Calculated,%: C, 56.82; N., 73; N 27.62; MP 10.83,

Elemental chemical and X-ray phase analyzes show that the composition of the chelate corresponds to the formula (mol. Weight 507.28; ebulioscopy gives mol. Weight 507.7);

 681 nm; , 3 10 when -Chem

, 015 W / cm in the field of 100 V / cm.

Example 7, 180 ml of a mixture of anhydrous solvents toluene-pyridine 3: 1, 11.06 g (0.08 mol) of carbonate

potassium, 4.24 g (0.02 mol), 2,2-diaminoazobenzene, 0.00001 g of active copper catalyst, 5.69 g (0.02 mol) of cadmium acetate trihydrate and 7.43 g (0.02 mole) 5,5-dichloro 3, 3-dimethyl-1,1-diisopropyl 4, 4 -azopyrazole and subjected to interaction and allocation as in example 4. The output of the robe f1,8,9,14 tetrahydro-3, 6.-dimethyl-1, 8-diisopropyldibenzene gp dipirazolo 4; 5-Е: 4, 5-П-и, 2,5,8,9,12-hexaazacyclotetradecinato (.2) M, N °, N cadmium (I) 2.49 g (21% of theory).

C 52.75, 52.63;

Found,%: N 23.07, 23.61; sa H 4.75, 4.68; IP., 91, 19.03.

Calculated ii: C 52.68; H 4.72; N 23.64; Ca 18.96.

Elemental chemical and X-ray phase analyzes show that the composition of the chelate corresponds to the formula, Sm.ves. 592.76, ebulioscope gives mol.ves. 593); Хцдакс

Choto

you

 4.2

704 nm;

tvmn 0.015 W / cm in a field of 100 V / cm.

Example8. 180 ml of a mixture of anhydrous solvents benzene-dimethylformamide (4: 1), 11.06 g (0.08 mol) of potassium carbonate, 4.25 g (0.02 mol) of 2.2-diaminoazobenzene, 4 , 39 g (0.02 mol) of zinc acetate dihydrate, 0.00001 g of active copper catalyst, 11.88 g of 5.5-diode-3,3-dimethyl-1, 1-diphenyl-4, 4 -azopyrazole and subjected to interaction and separation as in Example 4. The yield of chelate is 1,8,9,14-tetrahydro-3, 6-dimethyl-1, 8-diphenyldibenzo-Gu, t-dipyrazo-4, 5 - j - b, 2, 5, 8, 9 .1hexaazacyclotetradecinato (2) N, No., ts15, zinc W) 2.7 g (22% of theory).

Found,%: C 62.55, 62.69; H 3.99; N 22.85, 22.79; Zn 10.68, 10.60.

Calculated,%: C 62.60; H 3.94; N 22.81; 2p 10.66 (mol. Weight. 613.99; ebulioscopy gives mol. Weight. 614.2J;

lAnTO4

XvAQKc 705 nm; K, - 4.2 -10 when

U 0,015 W / cm in the field of 100 V / cm.

Thus, from the above examples, it is clear that due to the reaction of 5,5-dihalo-3, 3-dimethyl-1,1 - (dialkyl diphenyl-4, 4 -azopyrazole with 2,2-diaminoazobenzene in the presence of active copper catalyst, transition metal salt, potassium carbonate in an azeotropic organic solvent, for example benzene dimethylformamide-water, at its boiling point followed by chromatographic isolation of the target product from a mixture of isomers using alumina or silica gel as a sorbent An amount of 1-7% by weight of 3,5,8,10-tetranitropyrene can be used to prepare macrocyclic chelates of formula I.

The formation of a benzene-dimethylformamide-water ternary azeotropic mixture during the condensation reaction in the presence of active copper as a catalyst facilitates the formation of a macrocyclic chelate of formula I, leads to an increase in the yield of the target product (by 7-10%, to a relative decrease in the optimal reaction temperature (. at 30-50 ° C.

The use of alumina or silica gel as a sorbent with the addition of 1-7 wt.% 3,5,8, U-tetranitropyrene allowed us to separate the specific isomeric macrocyclic chelates and isolate the pure target product - the macrocyclic chelate of formula 1.

Carrying out the reaction in an inert gas medium leads to an increase in the yield and purity of the target product.

As shown by test data (see table), the macrocyclic chelate of formula 1 is relatively high photosensitive

Choto

2-1-4,

with L.

to

0,015 W / cm in a field of 100 V / cm), has a relatively high temperature, resistance (Rtemn-10 cm-cm, low-inertia photo-response relaxation time C, relatively soluble in a variety of widely available, relatively inexpensive organic solvents.

Claims (1)

1. Macrocyclic chelates {1,8,9 / 14-tetrahydro-3,6-dimethyl1, 8- (. Dialkyl) -diAenyldibenzo-, t dipyrazolo- 4, 5-t: 4, 5-j - 1,2, 5, 8,9,12 -hexaazazacyclotetradecinate .2) №, N3, N transition metal of general-formula 55 60 where and - ethyl, propyl, isopropyl, fe65il.