SU910618A1 - Macrocyclic chelates /1,10,11,20-tetrahydro-1,11-/dialkyl(diphenyl-3,13-dimethyldibenzo-1,2-c-1',2'-j)-diphyrazolo-3,4-f:3',4'-m/-1,2,5,8,9-12-hexaazocyclotetradecinato (2)-n ,n ,n ,n ,/-transitional metal as photoconductor material and method for preparing the same - Google Patents

Description

39

Vidicon-type tube with a photoconductive layer from FCSi 2.

However, the lack of photoconductive material based on FCsI is a relatively low increase in the photocurrent (K 7 at illumination L 1 lx) when measured in the Vidicon mode of operation. With large illumination x L-1000 lux and above) and relatively high fields x (10 V / cm and above) the multiplicity reaches saboy larger magnitude: K. The spectral range of the photosensitivity of FCSsi is also not wide enough - the ultraviolet region and part of the visible region (MiW nm). The spectral distribution of photocurrent for FTsCo has a discontinuity from 530 to 395 nm and a relatively weak photosensitivity in the near-IR spectral region.

In addition, the relatively low solubility of FCsI in most solvents is associated with the difficulty of its purification and, as a result, with a significant variation of parameters and working photoelectric characteristics, poor reproducibility of properties, which leads to a decrease in the processability of production of devices based on FCCH1.

Closest to the proposed method is a method based on the condensation reaction of an amino halide compound of the general formula

rr-w

.

NHc

where X is C1, Br and J;

R is alkyl or aryl.

According to this method, the said compound, for example, 2-bromobenzene-1-azo-} -5-acm-2-isopropyl-3 methylpyrazole, is subjected to condensation in the presence of a transition metal salt in an environment of a suitable organic solvent, for example dimethylformamide, with heating. the target product with known techniques with a maximum yield of the target product of 9-31%. The maximum yield of the target product is obtained if the process is carried out at 130-160 ° C.

However, the mechanism of this reaction has not been studied. In particular, it turned out that the target condensation reaction product 6184

2-Bromobenzene-11-azo-41-5-amino-1-isopropyl-Zmethylpyrazole is obtained as a mixture of isomeric macrocyclic chelates.

5 The purpose of the invention is the synthesis of macrocyclic transition metal coat as a photoconductive material, the relative expansion of the spectral range of photosensitivity in the long wavelength region of the spectrum while maintaining a relatively high dark resistance and relatively low inertia, increasing the solubility in

15 widely available organic solvents (e.g., benzene, toluene, m-xylene, chloroform, carbon tetrachloride, sulfuric ether, DMF, acetic acid, and other solvents).

New macrocyclic chelates {l, 10,11,20-tetrahydro-1, 11-dialkyl (diphenyl) -3,13 dim825 tyldibenz-ll, 2: 1,2-3-dipyrazo-3 are proposed as photoconductive materials. , -f: 3,, 2,5,8,9.12i-reKcases aclotetradecinato (2), N, a transition metal of the general formula

R

R is methyl, ethyl, propyl or phenyl

M - Ni, Cd, Co, Pd Pt .. or Pb.

The method for preparing macrocyclic chelates of formula 1 consists in the fact that

2-bromine (or chlorine, or iodine) benzene-1-azo-3-5-amino-1-alkyl (or aryl) -3-methylpyrazole is subjected to cyclization in the presence of active copper as a catalyst, a transition metal salt, potassium carbonate in azeotropic medium of a polar organic solvent with its boiling point followed by chromatographic isolation of the target product

from the resulting mixture of isomers using alumina or silica gel with sorbent with the addition of 3,5,8,10-tetranitropyrene as a sorbent. 3,5,8,10-Tetranitropyrene as an additive is more convenient to use in the amount of 1-7 wD. In order to increase the yield of the target product, the cyclization process is better carried out in an inert gas, such as nitrogen or argon. In the graph shown in the drawing, curve 1 is the electronic absorption spectrum of the FCsi film (prototype); curve 2 is the spectral distribution of the photocurrent for FCC (measurements in a Sandwich cell); curve 3 the electron absorption spectrum of a 9 8 new macrocyclic chelate {1,10,11,20-tetrahydro-1,11-diisopropyl-3, 1 3 Dimethyldibenzo-1,2-c: 11,2-L-dipyrazolo-13,: 3, 2,5,8,9,1 21-hexaazacyclotetradecinate (2) N, N, nickel (11) and curve k is the spectral distribution of the photocurrent for this hepate (measured in a Sandwich cell). The table presents summary physicochemical, spectral, and photoelectric data for macrocyclic chelates of formula 1. 11 The resulting macrocyclic chelates of formula 1 have a relatively wide continuous spectral range of photosensitivity and absorb from the ultraviolet region. spectrum up to 960-1070 nm, i.e. right up to the middle of the near infrared region of specure, inclusive. In the region from W to-StO nm, where FCIF (prototype) does not have photosensitivity, the photosensitivity of macrocyclic chelates of formula 1 is maximum K 4: iOTO Toi-io with a reality L of 0.015 W / cm in a field of 100 V / s. The quantum luminescence yield reaches 25-33. The dark resistance of macrocyclic chelates of formula 1 is relatively high (f 10 100 m-cm, depending on R and M). Their thermal stability (so pl. Samples. 290-400 C, depending on R and M) is high, extremely sensitive to the action of acids and alkalis, they are not soluble in water and alcohols. Macrocyclic chelates of formula 1 have relatively good adhesion, are well soluble in most organic solvents (in xylene, chloroform, benzene, toluene, SCC, DMF, acetic acid, and others); easily sublimated and sublimated under vacuum, i.e. have relatively good processability. The half-way of these chelates is relatively simple and convenient, it allows to obtain the target product of high purity with a relatively high yield (from theoretical). Example 1. In a three-neck round-bottom flask equipped with a stirrer, thermometer and reflux condenser, l80 ml of anhydrous solvent mixture: acetonitrile-benzene in a ratio of 1: 3; 11.06 g (0.08 mol) of potassium carbonate, 12.5 g (0.0 mol) of 2-bromobenzene-1-aa-l-5 amino-1-isopropyl-3 methylpyrazole; 0.00001 g of active copper as a catalyst; , 92 g (0.02 mol) of nickel acetate (II) tetrahydrate. While stirring, the contents of the flask are brought to a boil and boiled for 2.5 hours. The progress of the reaction is monitored by thin layer chromatography (after the disappearance of the azo compound). After cooling, the precipitated precipitate is filtered off, washed with absolute alcohol, dried and recrystallized from benzene-dimethylformamide U: l). The resulting dry product is a solution of S1T in 150 ml of benzene-dimethylformamide () and passed through a chromatographic column with aluminum oxide II degree of activity Brockman containing 12 wt.% In. as an additive 3,5,8,10-tetranite f5-pyrene, uniformly distributed throughout the column volume (eluent-benzene-dimethylformamide, 1: 4). When illuminated, five zones are detected that are collected. The second zone is a nickel macrocyclic chelate 1,10,1-1,20-tetrahydro-1, 11-diisopropyl-3, 13-di-methyldibenzo-1,2-e: 1, 2-j-dipyrazolo-GZ, 4- G, 3.4% 11,2,5,8,9,1. - hexaazacyclotetradecinato (2) S ,, N, nickel (fl). The crystals are green in color; 295 ° C. . Found,%: C 58.06, 57.84; H 5.3, 5.17; N 26.05, 25.84; Ni 10.76, 11.02. Calculated: C 57.91; H 5.23; N 25.98; Ni 10.88. Elemental and X-ray phase analyzes show that the composition of the chelate corresponds to the formula. The long-wave maximums of the film are 659 and 466 nm. K - 2.7-10 1g “at L 0.01.5 W / cm — in a field of 100 V / cm. The output of 1.46 g (27% of theory). Example 2. The interaction of 2-brbenzene-G1-azo-4 -5-amino-1-isopropyl-3 methylpyrazole with nickel (II) acetate is carried out analogously to example 1, however, the crude product is subjected to chromatographic separation using a roller sorbent with the addition of 1 wt. 3,5,8,10-tetranitropyrene (eluent-benzene-dimethylformamide, 4: 1). Crystals of bright green color with so-called 293 ° C show K. 3,,, 2. 10 ohm cm The relaxation time of the IT photo response is 10 s. The output of chelate 2.0 g (37 from theoretical). Example 3. A raw product was prepared as in Example 1 and separated on a column using Ali2.0 1 as an sorbent, with the addition of 7 wt.% 3,5,8,10-tetranitropyrene.

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The yield of crystalline bright green I.Sg (36% of the theoretical). . 3.8-10 at

tvmn

L 0,015 W / cm in the field of 100 V / cm-, Phemn 1.13-10 Om.cm; photoresponse relaxation time is 10 ° C.

Example k. The raw product was prepared as in Example 1 and was separated by column chromatography, using 2.3 wt. D = 3.5 | 8.10-tetranitropyrene as a sorbent. The output of bright green crystals with so pl. 293 ° C is 2.11 g (39% of theoretical).

To t- 3., Rtem "- L2-1o m. Cm

1temn

(compressed tablet) nm.

Example 5. A raw product was prepared as in Example 1, separated on a chromatographic column, using silica gel as a sorbent with the addition of 2.5 wt. D 3.5 | 8,10-tetranitropyrene. Bright green crystals of the target macrocyclic chelate 1,10,1 G, 20-tetrahydro-1, 11-diisopropyL-3.13-dimethyldibenzo-1,2-e: 1, 2-j-dipyrazolo-SZ, 4-: 3 are obtained , Vm - 1,2,5,8.9,12-hexaazacyclotetradeiinato (2) S,, Nickel (P) of formula I with a yield of 2.11 g (39% of the theoretical). They detect: To 3.8-10, the photoresponse relaxation time t, dark 1.2-10 ohm cm (pressed tablet), d1C (.. b59 nm.

Example 6, Download 220 ml of a mixture of anhydrous solvents toluene-pyridine (in the ratio 3: 1); 11.06 g (0.08 mol) of potassium carbonate 1.7 g (0.0 mol) of 2-iodobenzene-1-azo-5-amino-1-isopropyl-3-methyl pyrazole; 0,00001 grams of active copper; 5.69 g (0.02 mol) of cadmium (II) acetate trihydrate and mix thoroughly. While stirring, the contents of the flask are brought to a boil and boil for 3 hours at the boiling point of the azeotropic mixture formed: toluene-pyridine-water (110 ° C). The progress of the reaction is monitored by thin layer chromatography (after the disappearance of the azo compound). After cooling, the precipitate is filtered, washed water, then absolute alcohol, dried and recrystallized from a mixture of toluene-pyridine. The dry crude product is dissolved in 200 ml of a mixture of pyridintoluene (1: 3) and passed through

181

chromatographic column, where silica gel with the addition of 2 wt.% 3,5,8,10-tetranitropyrene is used as a sorbent. Get dark gray powder with T.pl. above 300 ° C. Found,%: .C 52.60, 52.75;

H 4.75, 4.75; N 23.78, 23.55; Cd 18.85, 19.10.

.. Calculated,%: C 52.66; H, 7b; N 23.62; Cd 18.96.

Elemental and X-ray phase analyzes show that the composition of the complex corresponds to the formula C H-, N K 2, cm (pressed tablet); relaxation time of the photoresponse i 10 with 490 nm (in the film).

Example 7. Download 270 ml of a mixture of anhydrous benzene-dimethylformamide (in the ratio 4: 1); 11.06 g (0.08 mol) of potassium carbonate; 0,00001 grams of active copper; 16.20 g (0.04 mol) of 2-bromobenzene-1-azo-4j-5-amino-1-naphthyl-3 methylpyrazole;

4.92 g (0.02 mol) of nickel acetate tetrahydrate and with stirring boil the contents of the flask until the starting azo compound disappears (determined by thin layer chromatography) for 4 hours.

The separation of the raw product is carried out according to the method of Example 4. A black crystalline powder with mp. above 400 ° C, it shows K 5.4–10 i. The relaxation time of the photoresponse is G с s. Rhemn 5.2 –10 ohm-cm (compressed tablet).

Example 8. Macrocyclic chelate}, 10,11,20-tetrahydro-1,11-diphenyl-3, 13 dimethyldibenzo-1,2-c and 2-L-Dipirazolo-3 ,, 2,5,8,9,12 α-hexaazy and cyclotetradicinato (2) LY, N; N ° cobalt (Formula 1 is prepared and isolated as in Example 4, except that the interaction is carried out in a nitrogen atmosphere. The yield of the pure desired product is 2.25 g (37% of theoretical ).

Found,%: C 63.24, 63.27;

H 3.91, 3.97; N 23.16, 23.09; From 9.75, 9.80.

Calculated,%: C 63.26, H 3.98; N 23.06; From 9.70.

Elemental and X-ray phase analyzes show that the composition of the macrocyclic chelate is 15

1 PHOTO

em formula (

oh k 41g8 ln

 2.0–10; photoresponse relaxation time t 10 s. Absorption Maximum -MaiJSS nm, 502 nm.

Example 9. In contrast to Example 8, the process of interaction is carried out in an argon atmosphere.

Found: K 2, j-10 with L 0,015 W / cm in the field of 100 V / cm; photoresponse relaxation time T 10 s.

Example 10. Download 180 ml of a mixture of acetonitrile-benzene in the ratio of 1: 3 ill, About g (0.08 mol) of potassium carbonate; 12.5 g (0, mol) 2-bromobenzene-1 -Azo-4 -5-amino-1-isopropyl-3-methylpyrazole 0.00001 active copper; 4.92 g (0.02 mol) of nickel acetate tetrahydrate, with continuous stirring, dry argon is passed through until air is displaced, the contents of the flask are brought to a boil and boiled for 1 hour. The reaction is monitored by thin layer chromatography (after the disappearance of the starting azo compound ). After cooling, the precipitated precipitate is filtered, washed with water and then with absolute alcohol, dried and recrystallized from benzene dimethylformamide (4: 1). Next, the raw product is separated as in Example 1. The yield of the pure target macrocyclic chelate of formula I is 2.33 g (43 from theoretical) K 4,5-10, relaxation time t of the photo response.

Thus, from the above examples, it is seen that due to the reaction, 2-bromo or chloro-, or iodobenzene-G1-azo-4 -5-amino-1-alkyl (or aryl) -3-methyl-pyrazole in the presence of α-active copper as a catalyst, a transition metal salt, potassium carbonate in an azeotropic medium of a polar organic solvent, for example acetonitrile-benzene-water, at its boiling point (b.p.66 C), followed by chromatographic isolation of the target product from the resulting mixture of isomers using as oxide sorbent Luminy silica gel or with an additive 3,5,8,10-tetranitropirena 1-7 vesD udaets receive macrocyclic chelates of formula I.

Formation of a triple azeotropic mixture of polar organic matter 1816

a solvent, for example acetonitrile-benzene-water, during the condensation reaction (cyclization) in the presence of active copper as a catalyst, facilitates the formation of ViaKpocyclic chelates of formula I, leads to an increase in the yield of the target product (by a factor of 2-3) and to a relative lowering of the optimum temperature reaction (in 2-2,5), which leads to a significant economic effect (the cost price of the target product is reduced several times) due to the simplification of technology, saving

time and energy costs and

relative increase in the yield of the target product.

The use of a specific sorbent - alumina or silica gel with the addition of 1-7 wt.% 3,5,8,10-tetranitropyrene allowed for the first time to separate specific isomeric macrocyclic chelates and isolate the pure target product - macrocyclic chelates of formula 1.

Carrying out the cyclization reaction in an inert gas, such as argon or nitrogen, leads to an increase in the yield of the purity of the target product

(i.e., cleanliness for electronics and optoelectronics materials: defect-free, uniform in layers, chemical individuality).

As the test data shows,

(see table) macrocyclic chelates of formula I have relatively high photosensitivity, K

}, 4-10 at L 0,015 W / cm

in a field of 100 V / cm in a relatively wide spectral range from the UV region up to the middle of the infrared region of the spectrum, have a relatively high dark resistance (Rtein -10 Ω cm depending on R and M), have a relatively low inertia of the photo effect BHytpeHHero (time photoresponse relaxation time t 10 s), a sufficiently high thermal stability (since the samples are in the range of 290-400 ° C depending on R and M). The macrocyclic chelates of the formula 1 possess relatively good adhesion, are technologically advanced (they are well sublimated under high vacuum, they easily dissolve in most organic solvents, and

Resistant to acids and alkalis).

Claims (3)

1. Macrocyclic chelates 1,10, 11,20-tetrahydro-1,11-dialkyl (diphenyl) -3,1ЗDimethyldibenzo -1,2-e:: 1,2-L-dipyrazolo-f3 ,, 1,2,5 , 8,9,12 -hexaazazacyclotetradecinate (2), NЧN ° J, the leading metal of the general formula -N Bn  / W v ii SI where R is methyl, ethyl, propyl or phenyl; M - Ni, Cd, Co, Pd, Pt, -Cu, Mn or Pb, as a photoconductive material 2. A method of producing compounds POP.1, characterized in that 2-halobenzene-l-aao-i 61818 -5-amino-1-alkyl-3-methylpyrazole is subjected to cyclization in the presence of active copper as a 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 with using alumina or silica gel as a sorbent with addition of 3,5,8,10-tetranitropyrene. 3. A method of pop, 2, cast J5 and using the sorbent containing -1% by weight 3,5,8, 10-tetranitropyrene. k. A method according to claim 2, characterized in that, in order to increase the yield and purity of the target product, the cyclization process is conducted in an inert gas medium, for example nitrogen or argon. Information sources, 25 taken into account in the examination 1. US Patent W 3009981, cl.136-89, published 1962. 2. The patent of England No. 80 + 911, cl. 37, published. 1958. 30 3. USSR Author's Certificate No. i 508l6, cl. C 07 F 1/08, 15/04, 15/06, 1973 (prototype). goo 25C 00 500 BOO 700 WOO) 3SO tOO "I 11 I I I I1- I I V / g j X to X X- /-five § .. i Si . yy H111 It 0.99 (e8} / ofc