Photochromic polymers for three dimensional optical random access memory

FIELD: chemistry.

SUBSTANCE: present invention pertains to new photochromic monomers and new polymers based on such monomers, intended for use in making two-photon photochromic recording media for three dimensional optical memory and photoswitches of optical signals. Description is given of monomers

Q=; ; ;

Alk=CH3-C10H21 X=Cl, Br, I, F, NH2, CH2OH, CH2Cl, CH2Br, CHO, CO2H and X=CH2, O, S, NAlk; Y=O, S, NAlk; n=0-6; Q=; ; ; ; ;

Alk=CH3-C10H21, methods of obtaining them, photochromic polymers based on them, method of obtaining photochromic monomers and their application. The proposed materials exhibit thermal irreversibility of photochromic transformations and properties, making it possible to use photochromic polymers in two-photon random access optical memory.

EFFECT: obtaining materials with thermal irreversibility of photochromic transformations and properties, making it possible to use photochromic polymers in two-photon random access optical memory.

15 cl, 46 dwg, 31 ex

 

(1) the Area of technology

The present invention relates to novel photochromic polymers and methods for their preparation with the aim of creating a two-photon photochromic recording media for three-dimensional optical random-access memory with bit-wise registration of the optical information.

(2) the Level of technology

Currently an urgent task in the field of information technology is the creation of a database for telecommunication systems. In this regard, we are actively developing optical memory very large information capacity due to the transition from two-dimensional media for registering three-dimensional environments to achieve the highest possible density of information recording (up to 1 Tbit/cm3). Create an operational three-dimensional optical memory requires the creation of two-photon recording media (I.Cokgor, F.B.McCormick, A.S.Dvornikov, M.Wang, N.Kim, .Koblentz, S.C.Esener, P.M.Rentzepis. Proc. SPIE, vol.3109, pp.182-186, 1997; S.Kawata, Y.Kawata. Chem. Rev., vol.100, pp.1777-1791, 2000). These environments are developed mainly in the USA (firm Call/Recall Corporation, Irvine and San Diego Universities of California) and Japan Science and Technology Corporation, Kyushu, Osaka and Shizuoka Universities). These developments are polymer solutions of thermally irreversible photochromic compounds of various classes: diarylethenes, fulgides, polymides, phenoxypropionic Phenoxyethanol and others (A.S.Dvornikov, I.Cokgor, M.Wang, F.BMcCormick, S.C.Esener, P.M.Rentzepis. IEEE Transaction. Part A, vol.20, No.2, pp.203-212, 1997). It is known that compounds of this type provide two-photon excitation and, therefore, the recording optical information medium volume.

The drawback of such recording media is that the photochromic layer is prepared from Monomeric photochromic compounds of one of the above classes and a polymeric binder. Essentially, this environment represents a molecular solution of the photochromic compound in a polymer matrix. This leads to the fact that the concentration of photochromic molecules, and hence the number of photosensitive centers is determined by the marginal solubility of the compounds in the polymer, which is typically less than 10% by weight of dry polymer binder. In such environments are the crystallization of photochromic substances, phase separation, aggregation of photochromic molecules and the formation of gradients of concentration of the photochromic compound in the bulk and on the surface layer (D.M.Buland, R.D.Miller, C.A.Walsh. Chem. Rev., vol.94, p.31, 1994). As a result of this information capacity and cyclic record-overwrite information in such a photochromic medium is significantly reduced. In addition, the quantum yield of photochromic transformations of some of the most acceptable photochromic compounds, namely radial diarylethenes, due to the randomness of their distribution in the amount by which the iMER does not exceed ϕ =0,5 (MGE. In: Organic Photochromic and Thermochromic Compounds. Eds. J..Crano and R.J.Guglielmetti, N.Y. and L., Plenum Press. 1999. V.1. p.207), and therefore, the sensitivity of the photochromic medium does not reach the maximum values.

In this regard, the greatest interest for use as two-photon recording media are photochromic polymers containing valence associated photochromic molecules either in the main polymer chain or in the side pieces. In photochromic polymers covalently linked photochromic molecules are more stable over time during storage due to the difficulties of travel volume environment. These photochromic recording media include, for example, photochromic polymers with diarylethene fragments based on the monomers styrene and butyl methacrylate (ECM, Y.-K.Choi, M.-H.Lee, Macromolecules, vol.32, pp.4855-4860, 1999; S.Y.Cho, H.-W.Shin, K.H.Ahn, Y.R.Kim, Kim. Optical Materials, vol.21, pp.279-284, 2002). Environments of this type compared to polymer solutions allow you to obtain layers with a thickness of 0.05-0.1 μm high quality. Developed environment provides the optical information recording by the radiation from a helium-cadmium laser (325 nm), and erasing using lasers emitting in the visible region of the spectrum (663 and 532 nm). Nondestructive readout of the recorded information is achieved due to the photoinduced change of the refractive index (Δn=0,008) at the emission wavelength of a semiconductor laser (830 nm).

The closest analogue of the present invention are photochromic polymers based on 1,2-bis(3-thienyl)cyclopentenone monomer (publication of the patent application U.S. No. 20040030078 of 12 February 2004).

The lack of such photochromic polymers is that they use the definite structure of the photochromic monomer and homopolymers based on them.

This disadvantage is due to the limited choice of the starting substances for the synthesis of photochromic polymers.

(3) Disclosure of inventions

The aim of the present invention is the synthesis of novel photochromic copolymers and polymers on the basis of new photochromic functional compounds from the class of diarylethenes excellent from the nearest similar structure, but with thermal irreversible photochromic transformations and other properties, providing the possibility of using photochromic polymers in two-photon optical random-access memory.

This goal is achieved by the fact that as photochromic monomers used the following functional compounds from the class of digitalisation I-III (figure 1).

Photochromism of diarylethene (DAE) is reversible photocyclization, i.e. in the photoinduced transition from the open form And in a circular form (figure 2).

A method of obtaining a photochromic monomers class I includes acelerou is the derivative benzothiophene, and peroration, thienothiophene or pornotopia dichlorohydrin glutaric acid in methylene chloride in the presence of aluminum chloride and subsequent reductive cyclization of the obtained diketones under the action of TiCl4, Zn in THF in the presence of pyridine, with further formirovanie reaction products dichlormethane ether in nitrobenzene in the presence of aluminum chloride.

A method of obtaining a photochromic monomers class II includes the processing of derivatives of 1,3-oxazolin-2-she and thiophene, and benzothiophene, peroration, thienothiophene or pornotopia allylamines and further processing of the reaction products triperoxonane acid.

A method of obtaining a photochromic monomers class III includes processing tetrahydropyranyl derived bromothiophene butyllithium and subsequent interaction with perversionen further gidrolizom product of reaction under the action of hydrochloric acid.

A method of obtaining a photochromic oligomer of the monomer class I involves reacting 2,2-bis[4-(3-aminophenoxy)phenyl]geksaftorpropena with dialdehydes derived 1,2-cyclopentene at elevated temperatures with concurrent distillation of the water azeotrope.

A method of obtaining a photochromic polymers from monomers class II involves the interaction of allyl derivative of 1,3-oxaze the it-2-it is derived from acrylic acid at an elevated temperature in the presence of the initiator.

A method of obtaining a photochromic polymers from monomer class III includes the interaction of 1,2-bis(5-hydroxymethyl-2-methylthiophene-3-yl)hexabenzocoronene with dichlorohydrin acid at an elevated temperature in the presence of pyridine.

The novelty of the claimed indication is used as a photochromic functional fragments of digitalisation I-III, other than the nearest equivalent. The use of these photochromic compounds allows photochromic polymers based on them to exercise two-photon optical registration information in the device is a three-dimensional optical random-access memory.

Study and analysis of known scientific-technical and patent literature showed that the full set of features that characterize these technical solutions, which previously was not known, i.e. the proposed solutions meet the patentability criteria of "novelty".

(4) a Brief description of the drawings

The essence of the present invention is illustrated further by means of examples and drawings.

Figure 1 shows the structural formulas of photochromic monomers I-III, used to obtain a photochromic copolymers and polymers.

Figure 2 illustrates the design of photochromic transformations of digitalisation.

Figure 3 shows a diagram of a method of obtaining a photochromic monomer 5 from class I.

Figure 4 shows with entry absorption of the original open form A (curve 1) and photoinduced form through a glass filter UFS-2 (curves 2-7) with increasing exposure to UV light, photochromic compounds 5 in a solution of toluene (C=2· 10-4M).

Figure 5 shows the kinetic curves of photocreative UV light through the optical filter UFS-6 (curve 1) and photobleaching visible light through the filter LGL-12 (curve 2) solution of the photochromic compound 5 in toluene at the wavelength of maximum absorption band of the cyclic forms of the Century

Figure 6 shows the scheme of obtaining photochromic monomer 10 from class I.

Figure 7 shows the scheme for photochromic monomer 12 from class I.

On Fig the scheme for obtaining photochromic monomer 13 from class I.

Figure 9 shows a scheme for photochromic monomer 14 of class II.

Figure 10 shows a scheme for photochromic monomer 21 from class I.

Figure 11 shows the scheme of obtaining photochromic monomer 24 from class I.

On Fig the scheme for obtaining photochromic monomer 30 from class I.

On Fig the scheme for obtaining photochromic monomer 35 from class I.

On Fig the scheme for obtaining photochromic monomer 38 of class II.

On Fig shows absorption spectra of the original open form A (curve 1) and photoinduced forms with increasing exposure to UV light through a filter UFS-2 (curves 2-6) for the photochromic compound 38 of class II in the toluene.

On Fig shows kinetic curves of photocreative UV light through a glass filter UFS-2 (cu is the first 1) and photobleaching visible light through the filter LGL-12 (curve 2) solution of the photochromic compound 38 of class II in the toluene at the wavelength of maximum absorption band of the cyclic forms of the Century

On Fig the scheme for obtaining photochromic monomer 41 of class II.

On Fig the scheme for obtaining photochromic monomer 44 from class II.

On Fig the scheme for obtaining photochromic monomer 47 of class II.

On Fig the scheme for obtaining photochromic monomer 50 from class II.

On Fig the scheme for obtaining photochromic monomer 53 of class II.

On Fig the scheme for obtaining photochromic monomer 56 of class II.

On Fig the scheme for obtaining photochromic compounds of 60 class III.

On Fig shows absorption spectra of the original open form A (curve 1) and photoinduced forms with increasing exposure to UV light through a filter UFS-2 (curves 2-5) for the photochromic compounds of 60 class III in toluene.

On Fig shows kinetic curves of photocreative UV light through a glass filter UFS-2 (curve 1) and photobleaching visible light through the filter LGL-12 (curve 2) solution of the photochromic compound 60 of class III in toluene at the wavelength of maximum absorption band of the cyclic forms of the Century

On Fig the scheme for obtaining photochromic oligomer IV.

On Fig shows absorption spectra of the original open form A (curve 1) and photoinduced In shape (curve 2) for films of photochromic oligomer IV in polimetilmetakrilat is the (10 wt.% by weight of dry polymer) before and after exposure to UV light, respectively.

On Fig shows kinetic curves of photocreative UV light (curve 1) and photobleaching visible light (curve 2) film photochromic oligomer IV in polymethyl methacrylate (10 wt.% by weight of dry polymer) at the wavelength of maximum absorption band of the cyclic forms of the Century

On Fig shows the curves consistent photocreative and photobleaching during periodic change filters UFS-8 and FP-7 + LS-18 for film photochromic oligomer IV in polymethyl methacrylate (10 wt.% by weight of dry polymer) at the wavelength of maximum absorption band of the cyclic forms of the Century

On Fig the scheme for obtaining photochromic oligomer IVa.

On Fig the scheme for obtaining photochromic oligomer IVb.

On Fig the scheme for obtaining photochromic oligomer IVc.

On Fig is a diagram of the synthesis of the photochromic polymer V.

On Fig shows absorption spectra of the original open form A (curve 1) and photoinduced form (curve 2) film photochromic polymer V polycarbonate (10% by weight of dry polymer) before and after exposure to UV light, respectively.

On Fig shows kinetic curves of photocreative UV light (curve 1) and photobleaching visible light (curve 2) film photochromic polymer V polycarbonate (10% by weight of dry polymer) at the wavelength of maximum Polo is s absorption cyclic form Century.

On Fig the structure of the photochromic polymer Va.

On Fig the structure of the photochromic polymer Vb.

On Fig the structure of the photochromic polymer Vc.

On Fig the structure of the photochromic polymer Vd.

On Fig is a diagram of the synthesis of the photochromic polymer VII.

On Fig shows absorption spectra of the original open form A (curve 1) and photoinduced form after exposure to UV light through the optical filter UFS-2 (curve 2) and subsequent irradiation with visible light through the filter LGL-12 (curve 3) for films of photochromic polymer VII polycarbonate (4 wt.% by weight of dry polymer) before and after exposure to UV light, respectively.

On Fig shows kinetic curves of photocreative UV light (curve 1) and photobleaching visible light (curve 2) film photochromic polymer VII polycarbonate (4 wt.% by weight of dry polymer) at the wavelength of maximum absorption band of the cyclic forms of the Century

On Fig the structure of the photochromic polymer VIIa.

On Fig the structure of the photochromic polymer VIIb.

On Fig the structure of the photochromic polymer VIIc.

On Fig the structure of the photochromic polymer VIId.

(5) Information confirming the possibility of carrying out the invention

Example 1

Photochromic monomers 1,2-bis(2-methyl-6-formyl-1-b is stiofan-3-yl)cyclopentene 5A-e class used photochromic monomers, containing benzothiophene fragments associated cyclopentenone bridge, was synthesized on the basis of benzothiophenes 2A-e according to the scheme shown in figure 3.

Source benzothiophene 2A-e were obtained by the described methods: 2-methylbenzoate (2A) (Synthesis of sulfides, teofanov and thiol type compounds found in crude oil. Edited Enterology, Izd-vo "Nauka", 1988, s), 2,4-dimethylbenzamide and 2.7-dimethylbenzamide (2b and 2C) (Monatsh. Chem. 1960, 91, 1070), 2,4-dimethylbenzamide and 2,6-dimethylbenzamide (2d and 2E) (J. Chem. Soc, Chem. Com. 1974, 5, 174).

Synthesis of 1,2-bis(2-methyl-6-formyl-1-benzothiophen-3-yl)Cyclopentanol 5A-e included acylation of benzothiophenes 2A-e dichlorohydrin glutaric acid in methylene chloride in the presence of aluminum chloride and subsequent reductive cyclization of the obtained diketones 3A-e, which is distinguished by the fact that compounds 4A-e were obtained from 60-73% yield by cyclization of diketones 3A-e under the action of TiCl4, Zn in THF in the presence of pyridine, while the literature describes the connection is obtained by cyclization of 4A diketone 3A under the action of TiCl4, Zn in THF to yield 54% (Synthesis 1998, 1092-1094). Subsequent formirovanie products 4A-e dichlormethane ether in nitrobenzene in the presence of aluminum chloride led to the formation of 1,2-bis(2-methyl-6-formyl-1-benzothiophen-3-yl)Cyclopentanol 5A-E.

The General synthetic scheme is as 1,5-bis-(methyl-1-benzothiophen-3-yl)pentane-1,5-diones 3A-e

To a well stirred mixture of 20.2 mmol of methylbenzamide 2A-e and 10.1 mmol of dichlorohydrin glutaric acid in 50 ml of methylene chloride was added at 0°From 42.5 mmol of anhydrous aluminum chloride. The reaction mass was stirred at room temperature for 3-6 hours. Poured into ice water, was extracted with methylene chloride (3×100 ml), the collected organic layers were washed in an aqueous solution of NaHCO3, dried over magnesium sulfate, the solvent was evaporated under vacuum. The residue was recrystallized from hexane.

1,5-Bis-(2-methyl-1-benzothiophen-3-yl)pentane-1,5-dione 3A: Received 3.25 g of product 3A (82%), TPL=165-167°With (hexane: chloroform, 6:1, by vol.). Mass spectrum, m/z: 392, [M]+. An NMR spectrum1H (DMSO-d6, δ, ppm, J/Hz): 2,0-2,2 (m, 2H, CH2), 2,62 (s, 6N, 2×CH3), 3,1-3,2 (USM, 4H, 2×CH2), 7,3-7,5 (USM, 4H, 4×CHarene.), a 7.85-8,2 (USM, 4H, 4×CHarene.). Found (Percent): C - 70,42; N - 5,16; S - 16,29. C23H20O2S2. Calculated (Percent): C - 70,37; N - 5,14; S - 16,34.

1,5-Bis-(2,5-dimethyl-1-benzothiophen-3-yl)pentane-1,5-dione 3b: Received 3.57 g of product (3b) (84%), TPL=171-173°With (hexane: chloroform, 6:1, by vol.). Mass spectrum, m/z: 420, [M]+. An NMR spectrum1H (DMSO-d6, δ, ppm, J/Hz): 2,0-2,3 (m, 2H, CH2), is 2.40 (s, 6N, 2×CH3), 2,62 (s, 6N, 2×CH3), a 2.75-3,2 (USM, 4H, 2×CH2), 7,4-8,1 (USM, 6N, 6×CHarene.). Found The (%): - 71,45; N - 5,77; S - 15,20. C25H24O2S2. Calculated (Percent): C - 71,39; N - 5,75; S - 15,25.

1,5-Bis-(2,7-dimethyl-1-benzothiophen-3-yl)pentane-1,5-dione 3C: Received 3,61 g of the product (3C) (85%), TPL=159-161°With (hexane: chloroform, 6:1, by vol.). Mass spectrum, m/z: 420, [M]+. An NMR spectrum1H (DMSO-d6, δ, ppm, J/Hz): of 2.1-2.4 (m, 2H, CH2), of 2.56 (s, 6N, 2×CH3), to 2.66 (s, 6N, 2×CH3), 2,8-3,2 (USM, 4H, 2×CH2)and 7.1-7.5 (USM, 4H, 4×CHarene), an 8.0-8.3 (USM, 2H, 2×CHarene.). Found (Percent): C - 71,43; N - 5,73; S - 15,29. C25H24O2S2. Calculated (Percent): C - 71,39; N - 5,75; S - 15,25.

1,5-Bis-(2,4-dimethyl-1-benzothiophen-3-yl)pentane-1,5-dione 3d: Received of 3.32 g of the product (3d) (78%), TPL=156-158°With (hexane: chloroform, 6:1, by vol.). Mass spectrum, m/z: 420, [M]+. An NMR spectrum1N DMSO-d6, δ, ppm, J/Hz): 2,0-2,3 (m, 2H, CH2), 2,62 (s, 6N, 2×CH3), of 2.64 (s, 6N, 2×CH3), 2,9-3,2 (USM, 4H, 2×CH2), 7,2-8,0 (USM, 6N, 6×CHarene.). Found (Percent): C - 71,35; N - 5,77; S - 15,30. C25H24O2S2. Calculated (Percent): C - 71,39; N - 5,75; S - 15,25.

1,5-Bis-(2,6-dimethyl-1-benzothiophen-3-W)pentane-1,5-dione 3E: Received 3,66 g of the product (3E) (86%), TPL=171-173°With (hexane: chloroform, 6:1, by vol.). Mass spectrum, m/z: 420, [M]+. An NMR spectrum1H (DMSO-d6, δ, ppm, J/Hz): 2,05-of 2.25 (m, 2H, CH2), 2,44 (s, 6N, 2×CH3), 2,62 (s, 6N, 2×CH3), a 2.9-3.15 in (USM, 4H, 2×CH2), 7,25 to 7.4 (USM, 2H, 2�D7; CHarene), 7,7-7,9 (USM, 4H, 2×CHarene). Found (Percent): C - 71,47; N - 5,73; S - 15,31. C25H24O2S2. Calculated (Percent): C - 71,39; N - 5,75; S - 15,25.

General methods of synthesis of 1,2-bis(2-methyl-1-benzothiophen-3-sh)cyclopentene 4

To a well stirred suspension of 7.93 mmol of zinc in fresh anhydrous THF (50 ml) at -10°C under argon was added dropwise 2.8 ml of TiCl4. After the addition, the reaction mixture was heated under argon for 1 hour. Was cooled to 20°and added 12.8 mmol diketone 3A-e and anhydrous pyridine (5 ml). Was heated under argon for another 20 hours. Was poured into 10%2CO3(150 ml) and the aqueous layer was extracted with Et2O (5×100 ml). The collected organic extracts were dried MgSO4and kept under vacuum. The residue was cleaned using flash chromatography on silica gel (Merck, 0,063-0,1), eluent - petroleum ether (40/70) - AcOEt (10:1, by vol.).

1,2-bis(2-methyl-1-benzothiophen-3-yl)cyclopentan 4A: Received 2.76 g of the product 4A (60%) with TPL=186,5-187,5°S, TPL(liter.)=187-188°With (Synthesis 1998, 1092-1094).

1,2-bis(2,5-dimethyl-1-benzothiophen-3-yl)cyclopentan 4b: Received 3,19 g of the product (4b) (69%), TPL=165-167°With (hexane: chloroform, 6:1, by vol.). Mass spectrum, m/z: 388, [M]+. An NMR spectrum1H (DMSO-d6, δ, ppm, J/Hz): 2,08-2,23 (USM, 2H, CH2), is 2.40 (s, 6N, 2×CH3), 2,52 (s, 6N, 2×CH3), 3,09-3,24 (USM, 4H, 2×CH2), 7,16 (m, 2H, Har is m ) 7,31 (m, 2H, Harene) of 7.55 (m, 2H, Harene). Found (Percent): C - 77,30; N - 6,21; S - 16,43. C25H24S2. Calculated (Percent): C - 77,35; N - 6,23; S - 16,38.

1,2-bis(2,7-dimethyl-1-benzothiophen-3-yl)cyclopentene 4C: Received 3,37 g of the product (4C) (73%), TPL=174-176°With (hexane: chloroform, 6:1, by vol.). Mass spectrum, m/z: 388, [M]+. An NMR spectrum1H (DMSO-d6, δ, ppm, J/Hz): 2,08-2,23 (USM, 2H, CH2), 2,50 (s, 6N, 2×CH3), 2,52 (s, 6N, 2×CH3), 3,09-3,24 (USM, 4H, 2×CH2), 7,02 (m, 2H, Harene), 7,12 (m, 2H, Harene), 7,21 (m, 2H, Harene). Found (Percent): C - 77,32; N - 6,24; S - 16,45. C25H24S2. Calculated (percent): C - 77,25; N - 6,26; S - 16,50,

1,2-bis(2,4-dimethyl-1-benzothiophen-3-yl)cyclopentene 4d: Received 2,82 g of the product (4d) (61%), TPL=171-173°With (hexane: chloroform, 6:1, by vol.). Mass spectrum, m/z: 388, [M]+. An NMR spectrum1H (DMSO-d6, δ, ppm,/Hz): 2,08-2,23 (USM, 2H, CH2), 2,52 (s, 6N, 2×CH3), 2,69 (s, 6N, 2×CH3), 3,09-3,24 (USM, 4H, 2×CH2), 7,00 (m, 2H, Harene), 7,20 (m, 2H, Harene), 7,52 (m, 2H, Harene). Found (Percent): C - 77,33; N - 6,24; S - 16,48. C25H24S2. Calculated (Percent): C - 77,26; N - 6,23; S - 16,52.

1,2-bis(2,6-dimethyl-1-benzothiophen-3-yl)cyclopentene 4E: Received 3.0 g of product (4E) (65%), TPL=184-186°With (Mass spectrum, m/z: 388, [M]+. An NMR spectrum1H (DMSO-d6, δ, ppm, J/Hz): 2,21-2,23 (USM, 2H, CH2), 2,44 (s, 6N, 2×CH3), 2,52 (s, 6N, 2×CH ), 3,09-3,24 (USM, 4H, 2×CH2), 7,18 (m, 2H, Harene), 7,38 (m, 2H, Harene), 7,53 (m, 2H, Harene). Found (Percent): C - 77,30; N - 6,24; S - 16,44. C25H24S2. Calculated (Percent): C - 77,41; N - 6,22; S - 16,50.

General methods of synthesis of 1,2-bis(formyl-1-benzothiophen-3-yl)Cyclopentanol 5A-e

To a stirred solution of 3.33 mmol of 1,2-bis(dimethyl-1-benzothiophen-3-yl)cyclopentene 4A-e in nitrobenzene (25 ml) at 0°With added 50 mmol dichlorodifluoro ether and 13,35 mmol of anhydrous aluminum chloride, was stirred 30 min at 0°and 20 hours at room temperature. The reaction mixture was poured into ice water and the product was extracted with ethyl acetate, washed with water, dried with magnesium sulfate. After distillation of nitrobenzene under vacuum the product was purified by column chromatography (Silica Gel, 0,063-0,1), eluent - petroleum ether (40/70): ethyl acetate (6:1, by vol.).

1,2-bis(2-methyl-6-formyl-1-benzothiophen-3-yl)cyclopentan 5A: Received 0.56 g of the dialdehyde (5A) (40%), TPL=196-197°With (hexane: chloroform, 6:1, by vol.). Mass spectrum, m/z: 416, [M]+. An NMR spectrum1H (DMSO-d6, δ, ppm, J/Hz): 2,25 (m, 6N, 2×CH3), 2,97 (USS, 6N, 3×CH2), a 7.6-8.5 in (USM, 6N, CHarene), 9,98 (USS, 2H, 2×CHO). Found (Percent): C - 72,16; N - 4,86; S - 15,34. C25H20O2S2. Calculated (Percent): C - 72,08; N - 4,84; S - 15,40.

The obtained compound 5A was dissolved in toluene at a concentration of C=2·10-4M absorption Spectra of forms a and b were measured on the spectrophotometer Saga 50 (Varian) immediately after dissolution (figure 4, curve 1) and after exposure to UV light mercury lamps DRSH-250 through a glass filter UFS-2 of the standard set of optical glass filters (figure 4, curves 2-7). Photochromic monomer is characterized by a high reversibility (cycles) photochromic transformations, as evidenced by the presence isometrically point on the curves of absorption (figure 4). Then measured the change in optical density (kinetics) of the solution at the maximum of the absorption band of the cyclic form under the action of the same UV light (a process photocreative) (figure 5, curve 1) and after reaching the state of equilibrium under the action of visible light of the same light source, passed through a glass filter LGL-12 (the process of photobleaching) (figure 5, curve 2). From the spectral-kinetic data shows that the connection has acceptable for practical use photochromic properties.

1,2-bis(2,5-dimethyl-6-formyl-1-benzothiophen-3-yl)cyclopentan 5b: Received 0.71 g of the dialdehyde (5b) (48%), TPL=181-183°With (hexane: chloroform, 6:1, by vol.). Mass spectrum, m/z: AAA, [M]+. An NMR spectrum1H (DMSO-d6, δ, ppm, J/Hz): 2,0-2,4 (m, 2H, CH2), to 2.55 (s, 6N, 2×CH3), 2,86 (s, 6N, 2×CH3), 2,95-of 3.25 (m, 4H, 2×CH2), 7,40 (USS, 2H, 2×CHarene.), 8,24 (USS, 2H, 2×CHarene.), to 10.09 (USS, 2H, 2×SNO). Found (%): 73,03; N - 5,43; S - 14,37. C27 H24O2S2. Calculated (%): 72,94; N - 5,44; S - 14,42.

1,2-bis(2,7-dimethyl-6-formyl-1-benzothiophen-3-yl)cyclopentan 5C: Received 0.96 g of the dialdehyde (5C) (65%), TPL=163-165°With (hexane: chloroform, 6:1, by vol.). Mass spectrum, m/z: AAA, [M]+. An NMR spectrum1H (DMSO-d6, δ, ppm, J/Hz): of 2.05 to 2.35 (m, 2H, CH2), 2,50 (s, 6N, 2×CH3), only 2.91 (s, 6N, 2×CH3), a 3.0 to 3.25 (m, 4H, 2×CH2), 7,32 (USD, 2H, 2×CHarene.), 7,79 (USD, 2H, 2×CHarene.), 10,10 (USS, 2H, 2×SNO). Found (Percent): C - 72,90; N - 5,43; S - 14, 48mm. C27H24O2S2. Calculated (%): 72,94; N - 5,44; S - 14,42.

1,2-bis(2,4-dimethyl-5-formyl-1-benzothiophen-3-yl)cyclopentan 5d: Received of 1.05 g of the dialdehyde (5d) (68%), TPL=187-189°With (hexane: chloroform, 6:1, by vol.). Mass spectrum, m/z: AAA, [M]+. An NMR spectrum1H (DMSO-d6, δ, ppm, J/Hz): 2,0 to 2.35 (m, 2H, CH2), to 2.54 (s, 6N, 2×CH3), 2,97 (s, 6N, 2×CH3), 3,1-3,3 (m, 4H, 2×CH2), 7,47 (USD, 2H, 2×CHarene), of 7.90 (USD, 2H, 2×CHarene.), 10,31 (USS, 2H, 2×SNO). Found (Percent): C - 72,99; N - The 5.45; S - 14,38. C27H24O2S2. Calculated (%): 72,94; N - 5,46; S - 14,42.

1,2-bis(2,6-dimethyl-5-formyl-1-benzothiophen-3-yl)cyclopentan 5e: Received of 0.77 g of the dialdehyde (5e) (52%), TPL=201-203°With (hexane: chloroform, 6:1, by vol.). Mass spectrum, m/z: AAA, [M]+. An NMR spectrum1H (DMSO-d6, δ, ppm, J/Hz): 2,0-2,4 (m, 2H, CH2), 2,52 (s, 6N, 2×CH3), and 85 (s, 6N, 2×CH3), a 3.0 to 3.35 (m, 4H, 2×CH2), 7,31 (USS, 2H, 2×CHarene), 8,42 (USS, 2H, 2×CHarene), 10,28 (USS, 2H, 2×SNO). Found (Percent): C - 73,01; N - 5,46; S - 14,35. C27H24O2S2. Calculated (%): 72,94; N - 5,44; S - 14,42.

Example 2

1,2-bis(2-decyl-6-formyl-1-benzothiophen-3-yl)cyclopentan 10 received similarly 1,2-bis(2-methyl-6-formyl-1-benzothiophen-3-yl)cyclopentene 5A (see Example 1 in the main application materials) according to the scheme shown in Fig.6, using as starting compound 2-deliberative 6.

The target 1,2-bis(2-decyl-6-formyl-1-benzothiophen-3-yl)cyclopentan 10 was obtained as amorphous powder.

Mass spectrum, m/z: 668, [M]+. An NMR spectrum1H (DMSO-d6, δ, ppm, J/Hz): 0,88 (Tr, 6N, 2×CH3,); 1,40-1,8 (m N, 8×CH2) 2,97 (USS, 6N, 3×CH2), 3,20 (m, 4H, 2×CH2); 7,6-8,5 (USM, 6N, CHarene.), 9.98 (USS, 2H, 2×SNO). Found (Percent): C - 77,16; N - 8,86; S 9,34. C43H56O2S2. Calculated (Percent): C - 77,25; N Is 8.38; S - 9,58.

Example 3

Synthesis of 1,2-bis(2-methyl-6-carboxy-1-benzothiophen-3-yl)cyclopentene 12 was carried out according to the scheme shown in Fig.7.

Synthesis of dictaphone 11

To a solution of 0.75 g (2.1 mmol) of compound 4 in 15 ml of CH2Cl2added 0.75 g (5.6 mmol) AlCl3the reaction mixture was cooled to a temperature of 5°and then pricipal 5.5 mmol of acid chloride VI. Mixed CME is ü at a temperature of 5-15° C for 3 hours, then added 50 ml of water and was extracted with 3×50 ml of ethyl acetate. The organic layer was dried over MgSO4and then was evaporated. The residue was cleaned through column chromatography (4:1 petroleum ether - ethyl acetate). The output connection 11 0.45 g (39%). TPL=158-162°C.

Synthesis of decollate 12

To a solution of 0.09 g (0.16 mmol) of compound (11) in 3 ml dioxane was added 0.035 g (0.8 mmol) of NaOH in 3 ml of water and 0.5 ml of N2About2(30% solution in N2About). The reaction mixture was stirred for 10 hours, then added 10 ml of water and was acidified solution to pH 4 with diluted sulfuric acid. Precipitated amorphous precipitate was filtered and possil. The output connection 12 of 72%.

Mass spectrum, m/z: 448, [M]+. An NMR spectrum1H (DMSO-d6, δ, ppm, J/Hz): of 2.26 (m, 6N, 2×CH3), 2,93 (USS, 6N, 3×CH2), a 7.6-8.5 in (USM, 6N, CHarene.). Found (Percent): C - 66,46; N - 4,86; S - 14,34. C25H20O4S2. Calculated (Percent): C - 66,70; N - 4,46; S Of 14.28.

Example 4

Synthesis of 1,2-bis(2-methyl-6-metiloksi-1-benzothiophen-3-yl)cyclopentene 13 was carried out according to the scheme shown in Fig.

Recovery dialdehyde 5 was performed by standard methods NaBH4in methanol. Output connection 13 52%.

Mass spectrum, m/z: 420, [M]+. An NMR spectrum1H (DMSO-d6, δ, ppm, J/Hz): 2,28 (m, 6N, 2×CH3), 2,87 (USS, 6N, 3×CH2), 4,56 (USS, 4H, 2×CH2), a 7.6-8.5 in (USM, 6N, CHarene. ). Found (Percent): C - 71,76; N - 5,86; S - 15,34. C25H20O4S2. Calculated (Percent): C - 71,43; N - 5,71; S - 15,23.

Example 5

Synthesis of 1,2-bis(2-methyl-6-chloromethyl-1-benzothiophen-3-yl)cyclopentene 14 was carried out according to the scheme shown in Fig.9.

Getting dichloride 14 was performed by standard methods in the two-phase system of chloroform - 32% hydrochloric acid. Yield 67%.

An NMR spectrum1H (DMSO-d6, δ, ppm, J/Hz): 2,25 (m, 6N, 2×CH3), 2,97 (USS, 6N, 3×CH2), of 4.45 (s, 4H, 2×CH2), a 7.6-8.5 in (USM, 6N, CHarene.). Found (Percent): C - 65,76; N - 4,96; Cl - 15,92; S - 14,34. C25H20Cl2S2. Calculated (Percent): C - 65,79; N - 4,82; Cl -15,35; S - 14,03.

Example 6

Photochromic 1,2-bis(2-methyl-5-formyl-4H-thieno[3,2-b]pyrrol-3-yl)cyclopentan 21 of the class used photochromic monomers were synthesized according to the scheme shown in figure 10.

Methyl ester 2-azido-3-(5'-methyl-2'-thienyl)acrylic acid 16.

To a mixture of sodium methylate prepared from 1.8 g (to 78.3 mmol) of sodium and 30 ml of abs. methanol and 22.8 g (0.2 mol) methyl ester etidocaine acid with stirring and the temperature-5-0°With added 30 mmol of methylthiophenethylamine 15 [Methylthiocarbamate 15 was synthesized according to the method described in Organic Syntheses, Coll. Vol.4, p.915 (1963); Vol.31, p.108 (1951)]. The mixture was stirred at 0°With 30 minutes and 2 hours at room temperature. Was added an aqueous solution nasusunog the NH 4CI and stirred for 10 minutes. The precipitation is filtered off and dried. The output connection 16 76%, TPL=51°C (With decomp.). Mass spectrum, m/z: 223, [M]+. An NMR spectrum1H (CDCl3that δ, ppm): to 2.55 (s, 3H, CH3), of 3.80 (s, 3H, CH3O)6,74 (s, 1H, CH), 7,10 (s, 1H, CHarene.), to 7.15 (s, 1H, CHarene.). IR-spectrum (KBr tablet with), ν/cm-1: 2120 OCS(N3). Found (%): 48,52; N - 4,20; N - 19,02; S - 14,81. C9H9N3O2S. Calculated (%): 48,42; N - 4,06; N - 18,82; S - 14,36.

Methyl ester 2-Matt-4H-thieno[3,2-b]pyrrole-5-carboxylic acid 17.

A solution of 30 mmol of methyl ether 2-azido-3-(thienyl-2')-acrylic acid 16 in 50 ml of toluene was boiled for 3 hours. The precipitation is filtered off, the mother liquor was evaporated under vacuum and recrystallized from toluene. Precipitation unite. The output connection 17 of 95%, TPL=189-190°C (from toluene). Mass spectrum, m/z: 195, [M]+. An NMR spectrum1H (CDCl3that δ, ppm): to 2.54 (s, 3H, CH3), 3,82 (C., 3H, CH3O)of 6.65 (s, 1H, CHarene.), 7,06 (s, 1H, CHarene.), 9,25 (USS, 1H, NH). Found (%): 55,40; N With 4.65; N - 7.23 Percent; The S - 16,53. C9H9NO2S. Calculated (%): 55,37; N With 4.65; N - 7,17; S - 16,42.

1,5-bis-(2-methyl-5-methoxycarbonyl-4H-thieno[3,2-b]pyrrol-3-yl)pentane-1,5-dione 18.

To a well stirred mixture of 20.2 mmol of thienopyrrole 17 and 10.1 mmol of dichlorohydrin glutaric acid in 50 ml of methylene chloride was added PR is 0° From 42.5 mmol of anhydrous aluminum chloride. The reaction mass was stirred at room temperature for 6 hours. Poured into ice water, was extracted with methylene chloride (3×100 ml), the collected organic layers were washed in an aqueous solution of NaHCO3, dried over magnesium sulfate, the solvent was evaporated under vacuum. The residue was recrystallized from hexane. The output connection 18 82%, TPL=175-177°With (hexane: chloroform, 6:1, by vol.). Mass spectrum, m/z: 486, [M]+. An NMR spectrum1H (DMSO-d6, δ, ppm, J/Hz): 2,0-2,2 (m, 2H, CH2), 2,62 (s, 6N, 2×CH3), 3,1-3,2 (USM, 4H, 2×CH2), 3,82 (s, 6N, 2×CH3O)6,84 (s, 2H, 2×CHarene.), 9,25 (USS, 2H, 2×NH). Found (%): 56,64; N Was 4.42; N - Of 5.82. C23H22N2O6S2. Calculated (%): 56.78 Has; N - 4,56; N - 5,76.

1,2-bis(2-methyl-5-methoxycarbonyl-4H-thieno[3,2-b]pyrrol-3-yl)cyclopentan 19.

To a well stirred suspension of 7.93 mmol of zinc in fresh anhydrous THF (50 ml) at -10°C under argon was added dropwise 2.8 ml of TiCl4. After the addition, the reaction mixture was heated under argon for 1 hour. Was cooled to 20°and added 12.8 mmol diketone 18 and anhydrous pyridine (5 ml). Was heated under argon for another 20 hours. Was poured into 10%2CO3(150 ml) and the aqueous layer was extracted with Et2About (5×100 ml). The collected organic extracts were dried MgSO4and drove the under vacuum. The residue was cleaned using flash chromatography on silica gel (Merck, 0,063-0,1), eluent - petroleum ether (40/70) - AcOEt (10:1, by vol.). The output connection 19 60%, TPL=196,5-197,5°C. Mass spectrum, m/z: 454, [M]+. An NMR spectrum1H (DMSO-d6, δ, ppm, J/Hz): 1,9-2,1 (m, 2H, CH2), 2,42 (s, 6N, 2×CH3), 3,0-3,1 (USM, 4H, 2×CH2), 3,71 (s, 6N, 2×CH3O)6,63 (s, 2H, 2×CHarene.), 9,12 (USS, 2H, 2×NH). Found (Percent): C - 60,64; N - 4,72; N - 6,22. C23H22N2O4S2. Calculated (Percent): C - 60,77; N - 4,88; N - 6,16.

1,2-bis(2-methyl-5-oximeter-4H-thieno[3,2-b]pyrrol-3-yl)cyclopentan 20.

To a well stirred solution of compound 19 (12 mmol) in 5 ml of ether was added LiAlH4(10 mmol) and the reaction mixture was stirred for 1 hour. When cooled, added water, and the separated ether layer. The solvent was distilled, the resulting product was cleaned using flash chromatography on silica gel (Merck, 0,063-0,1), eluent - petroleum ether (40/70) - AcOEt (10:1, by vol.). The output connection 19 59%, TPL=KZT 166.5-167,5°C. Mass spectrum, m/z: 398, [M]+. An NMR spectrum1H (DMSO-d6, δ, ppm, J/Hz): 1,9-2,1 (m, 2H, CH2), 2,42 (s, 6N, 2×CH3), 3,0-3,1 (USM, 4H, 2×CH2), 4,82 (s, 4H, 2×CH2), is 6.61 (s, 2H, 2×CHarene.), 9,11 (USS, 2H, 2×NH). Found (%): 63,34; N - 5,62; N - 7,12. C21H22N2O2S2. Calculated (Percent): C - 63,29; N - 5,56; N - 7,03.

1,2-bis(2-methyl-5-formyl-4H-thieno[32-b]pyrrol-3-yl)cyclopentan 21.

To a well stirred solution of compound 20 (12 mmol) in 20 ml of methylene chloride was added to the complex of chromium trioxide with two molecules of pyridine (72 mmol) and the reaction mixture was stirred for 30 minutes at room temperature. The solvent was distilled, the resulting product was cleaned using flash chromatography on silica gel (Merck, 0,063-0,1), eluent - petroleum ether (40/70) - AcOEt (10:1, by vol.). Output connection 21 28% in the form of a viscous oil. Mass spectrum, m/z: 394, [M]+. An NMR spectrum1H (DMSO-d6, δ, ppm, J/Hz): 1,9-2,0 (m, 2H, CH2), is 2.40 (s, 6N, 2×CH3), 3,0-3,1 (USM, 4H, 2×CH2), to 6.58 (s, 2H, 2×CHarene.), 9,18 (USS, 2H, 2×NH), 10,02 (USS, 2H SNO). Found (Percent): C - 63,66; N - To 4.62; N - 7,15. C21Hl8N2O2S2. Calculated (Percent): C - 63,96; N - Of 4.57; N - 7,11.

Example 7

1,2-bis[N-methyl(2-methyl-5-formyl-4H-thieno[3,2-b]pyrrol-3-yl)]cyclopenten 24 was synthesized according to the scheme given on 11.

1,2-bis[N-methyl(2-methyl-5-methoxycarbonyl-4H-thieno[3,2-b]pyrrol-3-yl)]cyclopenten 22 obtained by the standard technique of methylation of the connection 19 iodide stands.

Mass spectrum, m/z: 482, [M]+. An NMR spectrum1H (DMSO-d6, δ, ppm, J/Hz): 1,9-2,1 (m, 2H, CH2), 2,42 (s, 6N, 2×CH3), 2,92 (s, 6N, 2×CH3), 3,0-3,1 (USM, 4H, 2×CH2), 3,71 (s, 6N, 2×CH3O)6,63 (s, 2H, 2×CHarene.). Found (Percent): C - 62,64; N - 5,72; N - 5,22. C25H6 N2O4S2. Calculated (Percent): C - 62,24; N. Of 5.39; N - 5,80.

1,2-bis(2-methyl-5-oximeter-4H-thieno[3,2-b]pyrrol-3-yl)cyclopentan 23.

To a well stirred solution of compound 22 (12 mmol) in 5 ml of ether was added LiAlH4(10 mmol) and the reaction mixture was stirred for 1 hour. When cooled, added water, and the separated ether layer. The solvent was distilled, the resulting product was cleaned using flash chromatography on silica gel (Merck, 0,063-0,1), eluent - petroleum ether (40/70) - AcOEt (10:1, by vol.). Output connection 23 43% with TPL=155-157,5°C.

Mass spectrum, m/z: 426, [M]+. An NMR spectrum1H (DMSO-d6, δ, ppm, J/Hz): 1,9-2,1 (m, 2H, CH2), 2,42 (s, 6N, 2×CH3), 2,92 (s, 6N, 2×CH3), 3,0-3,1 (USM, 4H, 2×CH2), 4,82 (s, 4H, 2×CH2), is 6.61 (s, 2H, 2×CHarene.). Found (Percent): C - 64,34; N - 6,32; N - 6,12. C23H26N2O2S2. Calculated (Percent): C - 64,79; N - 6,10; N - 6,57.

1,2-bis(2-methyl-5-formyl-4H-thieno[3,2-b]pyrrol-3-yl)cyclopentan 24.

To a well stirred solution of compound 23 (12 mmol) in 20 ml of methylene chloride was added to the complex of chromium trioxide with two molecules of pyridine (72 mmol) and the reaction mixture was stirred for 30 minutes at room temperature. The solvent was distilled, the resulting product was cleaned using flash chromatography on silica gel (Merck, 0,063-0,1), eluent - petroleum ether (40/70) - AcOEt (10:1, about). The output connection 24 32% in the form of a viscous oil.

Mass spectrum, m/z 422, [M]+. An NMR spectrum1H (DMSO-d6, δ, ppm, J/Hz): 1,9-2,0 (m, 2H, CH2), is 2.40 (s, 6N, 2×CH3), 2,92 (s, 6N, 2×CH3), 3,0-3,1 (USM, 4H, 2×CH2), to 6.58 (s, 2H, 2×CHarene.), 10,02 (USS, 2H SNO). Found (%): 65,66; H - 7,62; N - 10,45. C23H22N2O2S2. Calculated (%): 65,40; N - Of 7.97; N - 10,14.

Example 8

Photochromic 1,2-bis(2-methyl-5-formestane[3,2-b]thiophene-3-yl)cyclopentan 29 of the class I used photochromic monomers were synthesized according to the scheme shown in Fig.

1,5-bis-(2-methyl-5-methoxycarbonyl-4H-thieno[3,2-b]thiophene-3-yl)pentane-1,5-dione 26

To a well stirred mixture of 20.2 mmol 2-methyl-5-methoxycarbonyl-4H-thieno[3,2-b]thiophene 25 and 10.1 mmol of dichlorohydrin glutaric acid in 50 ml of methylene chloride was added at 0°From 42.5 mmol of anhydrous aluminum chloride. The reaction mass was stirred at room temperature for 6 hours. Poured into ice water, was extracted with methylene chloride (3×100 ml), the collected organic layers were washed in an aqueous solution of NaHCO3, dried over magnesium sulfate, the solvent was evaporated under vacuum. The residue was recrystallized from hexane. The output connection 26 82%, TPL=165-167°With (hexane: chloroform, 6:1, by vol.). Mass spectrum, m/z 520, [M]+. An NMR spectrum1H (DMSO-d6, δ, ppm, J/G is): 2,0-2,2 (m, 2H, CH2), 2,62 (s, 6N, 2×CH3), 3,1-3,2 (USM, 4H, 2×CH2), 3,82 (s, 6N, 2×CH30), at 6.84 (s, 2H, 2×CHareneFound (%): 53,28; N - 3,65. C23H20O6S4. Calculated (%): 53,08; N - A 3.87.

1,2-bis(2-methyl-5-methoxycarbonyl-4H-thieno[3,2-b]thiophene-3-yl)cyclopentan 27

To a well stirred suspension of 7.93 mmol of zinc in fresh anhydrous THF (50 ml) at -10°C under argon was added dropwise 2.8 ml of TiCl4. After the addition, the reaction mixture was heated under argon for 1 hour. Was cooled to 20°and added 12.8 mmol diketone 26 and anhydrous pyridine (5 ml). Was heated under argon for another 20 hours. Was poured into 10%2CO3(150 ml) and the aqueous layer was extracted with Et2O (5×100 ml). The collected organic extracts were dried MgSO4and kept under vacuum. The residue was cleaned using flash chromatography on silica gel (Merck, 0,063-0,1), eluent - petroleum ether (40/70) - AcOEt (10:1, by vol.). Output connection 27 60%, TPL=177,5-176,5°C. Mass spectrum, m/z 488, [M]+. An NMR spectrum1H (DMSO-d6, δ, ppm, J/Hz): 1,9-2,1 (m, 2H, CH2), 2,42 (s, 6N, 2×CH3), 3,0-3,1 (USM, 4H, 2×CH2), 3,71 (s, 6N, 2×CH3O)6,63 (s, 2H, 2×CHarene.). Found (%): 56,83; N - 4,22. C23H20O4S4. Calculated (%): 56,55; N - 4,10.

1,2-bis(2-methyl-5-oximeter-4H-thieno[3,2-b]thiophene-3-yl)cyclopentan 28

Well peremeshivaemogo to a solution of compound 27 (12 mmol) in 5 ml of ether was added LiAlH 4(10 mmol) and the reaction mixture was stirred for 1 hour. When cooled, added water, and the separated ether layer. The solvent was distilled, the resulting product was cleaned using flash chromatography on silica gel (Merck, 0,063-0,1), eluent - petroleum ether (40/70) - AcOEt (10:1, by vol.). Output connection 28 of 59% in the form of a viscous oil. Mass spectrum, m/z 432, [M]+. An NMR spectrum1H (DMSO-d6, δ, ppm, J/Hz): 1,9-2,1 (m, 2H, CH2), 2,42 (s, 6N, 2×CH3), 3,0-3,1 (USM, 4H, 2×CH2), 4,82 (s, 4H, 2×CH2), is 6.61 (s, 2H, 2×CHarene.). Found (%): 63,34; N - To 4.52. C21H20O2S4. Calculated (Percent): C - 63,89; N - 4,63.

1,2-bis(2-methyl-5-formyl-4H-thieno[3,2-b]thiophene-3-yl)cyclopentan 29

To a well stirred solution of compound 28 (12 mmol) in 20 ml of methylene chloride was added to the complex of chromium trioxide with two molecules of pyridine (72 mmol) and the reaction mixture was stirred for 30 minutes at room temperature. The solvent was distilled, the resulting product was cleaned using flash chromatography on silica gel (Merck, 0,063-0,1), eluent - petroleum ether (40/70) - AcOEt (10:1, by vol.). Output connections 29 28% in the form of a viscous oil. Mass spectrum, m/z 428, [M]+. An NMR spectrum1H (DMSO-d6, δ, ppm, J/Hz): 1,9-2,1 (m, 2H, CH2), 2,42 (s, 6N, 2×CH3), 3,0-3,1 (USM, 4H, 2×CH2), 4,82 (s, 4H, 2×CH2), is 6.61 (s, 2H, 2×CHarene.), 9,11 (USS, 2H, Cho)Nagano (%): - 64,34; N - 3,62. C21H16S4. Calculated (Percent): C - 64,49; N - 3,74.

Example 9

Photochromic 1,2-bis(3,5-dimethyl-2-formestane[3,2-b]furan-6-yl)cyclopentan 35 of the class used photochromic monomers were synthesized according to the scheme shown in Fig.

Ethyl 3,5-dimethylthieno[3,2-b]furan-2-carboxylate 31

3 Hydroaxe-5-methylthiophene 30 was obtained from 2-methyl-4-bromo-thiophene according to the method described in Organic Syntheses, Coll. Vol.5, p.642 (1973); Vol.43, p.55 (1963). To a solution of hydroxythiophene 18 (1.5 mmol) in 5 ml of benzene was added 1 mmol of NaH and heated to the boiling point of the reaction mixture were added 1.5 mmol of ethylchlorothioformate. The mixture is boiled for 4 hours, cooled, washed with water, the organic layer was dried over MgSO4. The solvent was distilled, the resulting substance was added with stirring for 1 hour to 3 ml of concentrated sulfuric acid at a temperature of 5°C. the Mixture was stirred for another 1 hour. Then added a mixture of water and ice and was extracted with 2 times 5 ml of benzene. The organic layer was washed with water, sodium carbonate solution, dried over MgSO4and removed, the product was isolated on a column of silica gel (eluent CHCl3). Output connection 31 48%, TPL=120-121°C. Mass spectrum, m/z: 224, [M]+. An NMR spectrum1H (DMSO-d6, δ, ppm, J/Hz): an NMR Spectrum1H (DMSO-d6, δ, ppm): 1,31 (m, 3H, CH3), of 1.93 (s, 3H, CH3), 2,43 (s, 3H, CH3), or 4.31 (m, 2H, CH2), 6,76 (C, H, Narene). Found (%): 58,83; N - 5,22; S - 14,18. C11H12O3S. Calculated (%): 58,91; N - 5,39; S - 14,30.

1,5-bis(3,5-dimethyl-2-ethoxycarbonylethyl[3,2-b]furan-6-yl)pentane-1,5-dione 32

To a well stirred mixture of 20.2 mmol of taeniura 31 and 10.1 mmol of dichlorohydrin glutaric acid in 50 ml of methylene chloride was added at 0°From 42.5 mmol of anhydrous aluminum chloride. The reaction mass was stirred at room temperature for 6 hours. Poured into ice water, was extracted with methylene chloride (3×100 ml), the collected organic layers were washed in an aqueous solution of NaHCO3, dried over magnesium sulfate, the solvent was evaporated under vacuum. The residue was recrystallized from hexane. Output connection 32 82%, TPL=169-170°With (hexane: chloroform, 6:1, by vol.). Mass spectrum, m/z: 544, [M]+. An NMR spectrum1H (DMSO-d6, δ, ppm, J/Hz): an NMR Spectrum1H (DMSO-d6, δ, ppm): 1,34 (m 6N, 2×CH3), a 1.96 (m, 2H, CH2), to 1.98 (s, 6N, 2×CH3), is 2.40 (m, 4H, 2×CH2), 2,43 (s, 6N, 2×CH3), or 4.31 (m, 4H, 2×CH2). Found (Percent): C - 59,64; N - 5,22; S - 11,82. C27H28O8S2. Calculated (%): 59,54; N - 5,18; S - 11,77.

1,2-bis(3,5-dimethyl-2-ethoxycarbonylethyl[3,2-b]furan-6-yl)cyclopentan 33

To a well stirred suspension of 7.93 mmol of zinc in fresh anhydrous THF (50 ml) at -10°C under argon was added what about the drops to 2.8 ml of TiCl 4. After the addition, the reaction mixture was heated under argon for 1 hour. Was cooled to 20°and added 12.8 mmol diketone 32 and anhydrous pyridine (5 ml). Was heated under argon for another 20 hours. Was poured into 10%2CO3(150 ml) and the aqueous layer was extracted with Et2O (5×100 ml). The collected organic extracts were dried MgSO4and kept under vacuum. The residue was cleaned using flash chromatography on silica gel (Merck, 0,063-0,1), eluent - petroleum ether (40/70) - AcOEt (10:1, by vol.). Output connections 33 62%, TPL=198,5-199,5°C. Mass spectrum, m/z: 512, [M]+. An NMR spectrum1H (DMSO-d6, δ, ppm, J/Hz): an NMR Spectrum1H (DMSO-d6, δ, ppm): 1,34 (m 6N, 2×CH3), was 1.94 (m, 2H, CH2), to 1.98 (s, 6N, 2×CH3), 2,31 (m, 4H, 2×CH2), is 2.40 (m, 4H, 2×CH2), 2,42 (s, 6N, 2×CH3). Found (%): 63,34; N - 5,62; N - 12,36. C27H28O6S2. Calculated (Percent): C - 63,26; N - 5,51; S - 12,51.

1,2-bis(3,5-dimethyl-2-oxymethylene[3,2-b] furan-6-yl)cyclopentan 34

To a well stirred solution of compound 33 (12 mmol) in 5 ml of ether was added LiAlH4(10 mmol) and the reaction mixture was stirred for 1 hour. When cooled, added water, and the separated ether layer. The solvent was distilled, the resulting product was cleaned using flash chromatography on silica gel (Merck, 0,063-0,1), eluent - petroleum ether (40/70) - AcOEt (10:1, by vol.). Output connection 34 59%, sub> PL=168,5-169, 5mm°C. Mass spectrum, m/z: 428, [M]+. An NMR spectrum1H (DMSO-d6, δ, ppm): 1,94 (m, 2H, CH2), to 1.98 (s, 6N, 2×CH3), 2,31 (m, 4H, 2×CH2), 2,42 (s, 6N, 2×CH3) to 4.62 (s, 4H, 2×CH2). Found (Percent): C - 64,34; N - 5,52. C23H24O4S2. Calculated (%): 64,48; N - 5,64; S - 14,96.

1,2-bis(3,5-dimethyl-2-formestane[3,2-b]furan-6-yl)cyclopentan 35

To a well stirred solution of compound 34 (12 mmol) in 20 ml of methylene chloride was added to the complex of chromium trioxide with two molecules of pyridine (72 mmol) and the reaction mixture was stirred for 30 minutes at room temperature. The solvent was distilled, the resulting product was cleaned using flash chromatography on silica gel (Merck, 0,063-0,1), eluent - petroleum ether (40/70) - AcOEt (10:1, by vol.). Output connection 35 28% in the form of a viscous oil. Mass spectrum, m/z: 424, [M]+. An NMR spectrum1H (DMSO-d6, δ, ppm, J/Hz): 1,9-2,1 (m, 2H, CH2), 2,42 (s, 6N, 2×CH3), 3,0-3,1 (USM, 4H, 2×CH2), 4,82 (s, 4H, 2×CH2), 6,78 (s, 2H, 2×CHarene), 9,34 (USS, 2H, Cho). Found (Percent): C - 65,24; N - 4,56. C23H20O4S2. Calculated (Percent): C - 65,09; N - 4.72 In.

Example 10

Photochromic monomer 3-allyl-4,5-bis(2,5-dimethyl-3-thienyl)-1,3-oxazol-2-it 38 from class II received by the scheme shown in Fig.

The technique of synthesis of 3-allyl-4,5-bis(2,5-dimethyl-3-thienyl)-4-hydroxy-1,3-oxazolin-it 37

To a solution of 1.0 g (of 3.27 mmol) carbonate 10 in 10 ml of ethanol was added 0.3 g (5.00 mmol) of allylamine and stirred under ˜25°1-1,5 hours. The precipitation was filtered and was led product from ethanol. Received 1.1 g oxazoline 37 (93%), TPL=181-182°C. Found (%): 59,54; N - 5,71; S - 17,55. C18H21NO3S2. Calculated (%): 59,48; N - Of 5.82; S - 17,64.

An NMR spectrum1H (DMSO-d6that δ, ppm): 1,79 (s, 3H, CH3); to 2.13 (s, 3H, CH3); to 2.29 (s, 3H, CH3); a 2.36 (s, 3H, CH3); the 3.65 (d, 2H, CH2, J=6 Hz); of 5.05 (d, 1H, CH, J=10 Hz); 5,11 (d, 1H, CH, J=17 Hz); to 5.35 (s, 1H, CH); of 5.83 (m, 1H, CH); 6.42 per (s, 1H, HE); is 6.61 (s, 1H, CH); to 6.80 (s, 1H, CH).

The technique of synthesis of 3-allyl-4,5-bis(2,5-dimethyl-3-thienyl)-1,3-oxazol-2-it 38

A solution of 0.9 g (2.5 mmol) of 1,3-oxazolin-2-it 37 25 ml (0,325 mol) CF3COOH was stirred under ˜25°With 3-3,5 hours. Has evaporated the solvent in vacuo and has led the residue from ethanol. Got 0,63 g oxazole 38 (73%), TPL=103-104°C. Found (%) : - 62,43; N - 5,62; S - 18,78. C18H19NO2S2. Calculated (Percent): C - 62,58; N Is 5.54; S - 18,56. An NMR spectrum1H (DMSO-d6, δ, ppm): 1,99 (s, 3H, CH3); a 2.12 (s, 3H, CH3); and 2.27 (s, 3H, CH3); 2,32 (s, 3H, CH3); a 4.03 (d, 2H, CH2, J=6 Hz); is 4.93 (d, 1H, CH, J=17 Hz); 5,09 (d, 1H, CH, J=10 Hz); 5,73 (m, 1H, CH); 6,37 (s, 1H, CH); 6,74 (s, 1H, CH).

According to the method described in example 1, was measured similar spectral (Fig) and kinetic (Fig) har is cteristic, showing photochromic properties of the photochromic monomer.

Example 11

According to the method described in example 10, from carbonate 39 received oxazol 41 (Fig).

Example 12

According to the method described in example 10, from carbonate 42 received oxazol 44 (Fig).

Example 13

According to the method described in example 10, from carbonate 45 received oxazol 47 (Fig).

Example 14

According to the method described in example 10, from carbonate 48 received oxazol 50 (Fig).

Example 15

According to the method described in example 10, from thiocarbonate 51 received oxazol 53 (Fig).

Example 16

According to the method described in example 10, from thiocarbonate 54 received oxazol 56 (Fig).

Example 17

Photochromic monomer 1,2-bis(5-hydroxymethyl-2-metallian-3-yl)hexafluoropentane 60 was synthesized according to the scheme shown in Fig.

This method differs in that in the synthesis of 1,2-bis(5-hydroxymethyl-2-alkylthio-3-yl)hexafluoropentane 60 as a protective group used more available 1,2-dihydropyran, whereas in the literature were applied hard-tert-butyldimethylsilyl protection (Chem. Letters, 1998, p.1093-1094).

The method of synthesis of 2-[(4-bromo-5-methylthiophene-2-yl)methoxy]tetrahydro-2H-Piran 58

To 5,4 g of 4-bromo-2-hydroxymethyl-5-methylthiophene 57 in 40 ml of methanol was added to 2.6 ml of 1,2-dihydropyran and 0.2 g of p-toluenesulfonic acid. The reaction mixture was stirred at room the th temperature for 24 hours. Methanol drove under vacuum, the residue was distilled in an oil pump. Received 6,82 g of the product 58 (90%) with TKip=125-130°C (5 mm Hg), nd16'5=1,5610. Mass spectrum, m/z: 291, [M]+. An NMR spectrum1H (CDCl3that δ, ppm, J/Hz): 1,45-of 1.95 (m, 6N, 3×CH2), is 2.37 (s, 3H, CH3), 3,50-the 3.65 (m, 1H, CH), of 3.80 to 4.0 (m, 1H), 4,55-4,85 (m, 3H), PC 6.82 (s, 1H, CH). Found (%): 45,43; N - 5,20; S - 10,92. C11H15BrO2S. Calculated (%): 45,37; N - 5,19; S - Br11.01.

The technique of synthesis of 1,2-bis{5-methoxy(tetrahydro-2H-peril-2)-2-metallian-3-yl}hexafluoropentane 59

To 5.3g 2-[(4-bromo-5-methylthiophene-2-yl)methoxy]tetrahydro-2H-Piran in 30 ml of anhydrous THF at -78°and under argon was added 14 ml of a 1.6 M solution of utility in hexane, the reaction mixture was stirred at -78°With 10 minutes and was added 1,93 g octafluorocyclopentene. The reaction mixture was stirred at a temperature of -78°1 h and left overnight at room temperature. Was poured into ice water, extracted with ether, dried over magnesium sulfate. The solvent is kept under vacuum, the resulting oil was chromatographically. Received 3,37 g of oily product 59 (62%). Mass spectrum, m/z: 596, [M]+. An NMR spectrum1H (CDCl3that δ, ppm, J/Hz): 1,45-2,0 (m, N, 6×CH2, 2×CH3), 3,45-of 3.60 (m, 2H, 2×SN), 3,80-3,95 (m, 2H, 2×SN), 4,60-4,85 (m, 6N), 6,93 (s, 2H, CH). Found (%): 54,42; N - 5,08; S - To 10.62. C27H30F6 O4S2. Calculated (%): 54,35; N Is 5.07; S - 10,75.

The technique of synthesis of 1,2-bis(5-hydroxymethyl-2-metallian-3-yl)hexafluoropentane 60

To 3 g of 1,2-bis{5-methoxy(tetrahydro-2H-peril-2)-2-metallian-3-yl}hexafluoropentane 59 in 30 ml of methanol was added 3 ml of concentrated hydrochloric acid. The reaction mixture was stirred at room temperature for 20 hours. The excess methanol is kept under vacuum, the residue was recrystallized from hexane. Received of 1.62 g of the product 60 (75%) with TPL=129-133° (TPL(liter.)=125-128°). Mass spectrum, m/z: 428, [M]+. An NMR spectrum1H (CDCl3that δ, ppm, J/Hz): 1,83 (s, 2H, 2×HE), 1,89 (s, 6N, 2×CH3), and 4.75 (s, 4H, 2×CH2), 6,94 (s, 2H, CH). Found (%): 47,72; N - 3,30; S - 14,02. C17H14F6O2S2. Calculated (%): 47,66; N - 3,29; S - 14,97.

According to the method described in example 1, was measured similar spectral (Fig) and kinetic (Fig) characteristics indicating photochromic properties of the photochromic monomer.

Example 18

Photochromic oligomer - oligo(Chippewa) base IV was obtained according to the scheme presented on Fig. In a two-neck conical flask, equipped with a system for input and output of argon, trap Dean-stark, addition funnel, magnetic stirrer and reflux condenser, was placed 103,7 mg (0.2 mmol) of 2,2-bis[4-(3-aminophenoxy)phenyl]geksaftorpropena, and 83.3 mg (0.2 IMO the b monomer 5A, 2 ml DMF and 2 ml of toluene. Under stirring and a strong current of argon, the flask was heated to 140°C. the Reaction mixture was stirred at this temperature for 4 hours, periodically prokopeva a total of 2 ml of toluene, while trapped in a Dean-stark condenses azeotrop toluene with water. Then the oligomer precipitated with ethanol, filtered on the filter SCHOTT, washed with ethanol, and dried. The output amounted to 0.14 g (70%).

Sample photochromic polymer was prepared by co-dissolving the obtained oligomer and polymethyl methacrylate (10 wt.% by weight of dry polymer) in chloroform. Then measured the spectral and kinetic characteristics of the obtained sample according to the method described in example 1. Spectral (Fig) and kinetic (Fig) characteristics indicate photochromic properties of the synthesized photochromic oligomer. On Fig shows the cyclic coloring of UV light through the optical filter UFS-8 and discoloration through the combination of two filters PS-7 and HC-18 (periodic change of filters). From Fig follows that the photochromic polymer has a high recurrence without loss of photochromic properties.

Example 19

Analogously to example 18 from monomer 21 the polymer obtained IVa (Fig).

Example 20

Analogously to example 18 from monomer 29 the polymer obtained IVb (Fig).

Example 21

Analogously to example 18 and the monomer 35 the polymer obtained IVc (Fig).

Example 22

Photochromic copolymer V synthesized from 3-allyl-4,5-bis-(2,5-dimethyl-3-thienyl)-1,3-oxazol-2-she (compound 38) of class II and methyl methacrylate according to the scheme shown in Fig. The solution 0,173 g (0.5 mmol) of 3-allyl-4,5-bis-(2,5-dimethyl-3-thienyl)-1,3-oxazol-2-she (compound 38) 1 g (10 mmol) of methyl methacrylate were placed in a vial with 0,0017 g (0.1 wt.% from the amount of monomers) initiator - azoisobutyronitrile. The ampoule was filled with argon and was heated at 60°C for 20 hours. Received the vitreous copolymerisation V Mw=80000. The copolymer is soluble in chloroform.

Sample photochromic polymer for measuring the spectral-kinetic characteristics were prepared by co-dissolving the photochromic polymer and polycarbonate, which was used as a polymeric binder, in chloroform. Then the solution was applied on a quartz substrate by centrifuging. The result was obtained photochromic film, which were measured by the method of example 1 absorption spectra of form a (Fig, curve 1) and form (Fig, curve 2), and kinetic curves photocreative (Fig, curve 1) and photobleaching (Fig, curve 2). The spectral and kinetic data indicate photochromism samples photochromic film.

Example 23

Photochromic copolymer Va (Fig) was obtained from compound 8 and butylmethacrylate analogously to example 22. Mw=87000. The polymer is soluble in chloroform.

Spectral-kinetic characteristics of the sample photochromic polymer made according to methods described in example 22, indicate practically acceptable photochromism.

Example 24

Photochromic copolymer Vb (Fig) was obtained from compound 41 and butylmethacrylate analogously to example 22. Mw=72000. The polymer is soluble in chloroform.

Spectral-kinetic characteristics of the sample photochromic polymer made according to methods described in example 22, indicate practically acceptable photochromism.

Example 25

Photochromic copolymer Vc (Fig) was obtained from compound 47 and butylmethacrylate analogously to example 22. Mw=85000. The polymer is soluble in chloroform.

Spectral-kinetic characteristics of the sample photochromic polymer made according to methods described in example 22, indicate practically acceptable photochromism.

Example 26

Photochromic copolymer Vd (Fig) was obtained from compound 53 and butylmethacrylate analogously to example 15. Mw=76000. The polymer is soluble in chloroform.

Spectral-kinetic characteristics of the sample photochromic polymer made according to methods described in example 22, indicate practically acceptable photochromism.

Example 27

Complex polyester VII of 1,2-bis(5-hydroxymethyl-2-methylthiophene-3-yl)hexafluoropentane (compound 60) and dichlorohydrin terephthalic acid according to the scheme, presented at Fig. In a three-neck flask with a capacity of 25 ml and equipped with a stirrer, reflux condenser and input for argon, was placed 0.27 g (0,63 mmol) 1,2-bis(5-hydroxymethyl-2-methylthiophene-3-yl)hexafluoropentane (compound 61), 0,128 g (0,63 mmol) dichlorohydrin terephthalic acid (compound VI), 3.2 ml of dichloroethane. The temperature of the reaction mixture was brought to 40°and slowly, within a few minutes the reaction mixture was bury 0,154 ml of pyridine. Duration of response was 2 hours. Then the reaction mixture was poured into methanol, the precipitate was dried under vacuum for 24 hours at 40°C. the Yield of polymer VIII was 98%. IR (KBr, cm-1): C=O 1710. Mn=35000. The polymer is soluble in tetrahydrofuran, dimethylformamide, ethanol, acetone, when heated in chloroform, insoluble in toluene.

Sample photochromic polymer for measuring the spectral-kinetic characteristics were prepared by co-dissolving the photochromic polymer and polycarbonate, which was used as a polymeric binder, in chloroform. Then the solution was applied on a quartz substrate by centrifuging. The result was obtained photochromic film, which were measured by the method of example 1 absorption spectra of form a (Fig, curve 1) and form (Fig, curve 2), and kinetic curves photocreative (Fig, to the of IVA 1) and photobleaching (Fig, curve (2). The spectral and kinetic data indicate photochromism samples photochromic film.

Example 28

Complex polyester VIIa (Fig) was obtained from compound V and dichlorohydrin isophthalic acid analogously to example 22. The yield was 93%. Mn=28000. The polymer is soluble in chloroform, tetrahydrofuran, dimethylformamide, toluene, ethanol and acetone.

Spectral-kinetic characteristics of the sample photochromic polymer made according to methods described in example 22, indicate practically acceptable photochromism.

Example 29

Complex polyester VIIb (Fig) was obtained from compound 61 and dichlorohydrin 4,4'-diphenyl dikanbai acid analogously to example 22. The yield was 89%. Mn=22000. The polymer is soluble in chloroform, tetrahydrofuran, dimethylformamide, not soluble in toluene, ethanol and acetone.

Spectral-kinetic characteristics of the sample photochromic polymer made according to methods described in example 5 indicate practically acceptable photochromism.

Example 30

Complex polyester VIIc (Fig) was obtained from compound V and dichlorohydrin 4,4'-diphenil-oxide dikanbai acid analogously to example 22. The yield was 91%. Mn=24000. The polymer is soluble in chloroform, tetrahydrofuran, dimethylformamide, toluene, ethanol and acetone.

With ertraline-kinetic characteristics of the sample photochromic polymer, manufactured according to methods described in example 22, indicate practically acceptable photochromism.

Example 31

Complex polyester VIId (Fig) was obtained from compound 61 and dichlorohydrin 4,4'-difenilmetana dikanbai acid analogously to example 22. The yield was 96%. Mn=30000. The polymer is soluble in chloroform, tetrahydrofuran, dimethylformamide, toluene, ethanol and acetone.

Spectral-kinetic characteristics of the sample photochromic polymer made according to methods described in example 22, indicate practically acceptable photochromism.

1. Photochromic monomers of General formula

Q=;;;

Alk=CH3-C10H21;

X=Cl, Br, I, F, NH2CH2OH, CH2Cl, CH2Br, CHO, CO2H.

2. A method of obtaining a photochromic monomers according to claim 1, comprising the acylation derivative benzothiophene and peroration, thienothiophene or pornotopia dichlorohydrin glutaric acid in methylene chloride in the presence of aluminum chloride and subsequent reductive cyclization of the obtained diketones under the action of TiCl4, Zn in THF in the presence of pyridine, with a further formirovanie the m reaction products dichlormethane ether in nitrobenzene in the presence of aluminum chloride.

3. Photochromic monomers of General formula

X=CH2, O, S, NAlk; Y=O, S, NAlk; n=0-6;

Q=;;;;;

Alk=CH3-C10H21.

4. A method of obtaining a photochromic monomers according to claim 3, including the processing of derivatives of 1,3-oxazolin-2-she and thiophene, and benzothiophene, peroration, thienothiophene or pornotopia allylamines and further processing of the reaction products triperoxonane acid.

5. Photochromic monomers of General formula

Alk=CH3-C10H21.

6. A method of obtaining a photochromic monomers according to claim 5, comprising processing tetrahydropyranyl derived bromothiophene politician and subsequent interaction with perversionen further gidrolizom product of reaction under the action of hydrochloric acid.

7. Photochromic copolymer-oligo(Chippewa) the basis on the basis of the photochromic monomer according to claim 1

8. A method of obtaining a photochromic oligomer according to claim 7, including the interaction of 2,2-bis[4-(3-aminophenoxy)phenyl]geksaftorpropena with dialdehydes derived 1,2-Cyclops is tena at elevated temperatures with concurrent distillation of the water azeotrope.

9. Condensation and polymerization complex photochromic polyesters based on photochromic monomers according to claim 3.

10. A method of obtaining a photochromic polymer according to claim 9, including the interaction of allyl derivative of 1,3-oxazolin-2-it is derived from acrylic acid at an elevated temperature in the presence of the initiator.

11. Condensation and polymerization complex photochromic polyesters based on photochromic monomers according to claim 5.

12. A method of obtaining a photochromic polymer according to claim 11, including the interaction of 1,2-bis(5-hydroxymethyl-2-methylthiophene-3-yl)hexabenzocoronene with dichlorohydrin acid at an elevated temperature in the presence of pyridine.

13. The use of photochromic oligomer according to claim 7 in a polymeric binder as two-photon recording medium for three-dimensional optical memory and photoperiodically optical signals.

14. The use of photochromic polymer according to claim 9 in a polymeric binder as two-photon recording medium for three-dimensional optical memory and photoperiodically optical signals.

15. The use of photochromic polymer according to claim 11 in a polymeric binder as two-photon recording medium for three-dimensional optical memory and photoperiodically optical signals.



 

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FIELD: information technologies.

SUBSTANCE: invention refers to information medium, to record and reproduction modes and devices. Information medium includes record material "L-H" ("low to high"). And record wavelength is shorter than 620 nanometers. Channel bit length is less than 105 nm. Track pitch is shorter than 600 nm. Minimum number of series channel bits of value "0" after modulation is equal 1.

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FIELD: information technologies.

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12 cl, 7 dwg

FIELD: chemistry.

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3 cl, 2 tbl, 4 ex

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FIELD: optical recording technologies, namely, engineering of two-layered optical disks with high recording density, and of devices for recording/reproducing from them.

SUBSTANCE: two-layered optical disk with high recording density contains first recording layer and second recording layer, positioned on one side of central plane, dividing the disk in half along thickness, close to surface, onto which light falls. First thickness of substrate from surface, onto which light falls, to first recording layer has minimal value over 68,5 micrometers, second thickness of substrate from surface, onto which light falls, to second recording layer has maximal value less than 110,5 micrometers, while refraction coefficient is within range 1,45-1,70.

EFFECT: minimization of distortion of wave front, provision of possibility of more precise recording of signals onto optical disk or reproduction of signals from optical disk.

8 cl, 10 dwg

FIELD: technological processes.

SUBSTANCE: method of object protection against forgery includes application of information identifying mark to the surface of protected object by means of glue layer, in composition of which light-sensitive protein bacteriorhodopsin is introduced. Information identifying mark or its part is made transparent, and corresponding portion of protected object surface is made transparent or with mirror reflecting coating. During monitoring of object authenticity light-sensitive element that contains bacteriorhodopsin is illuminated, by means of two sources of light with lengths of waves, accordingly, in band of main and intermediate conditions of bacteriorhodopsin absorption.

EFFECT: invention allows to increase reliability of protection against forgery and monitoring of valuable documents and items.

3 cl, 4 dwg

FIELD: physics, photographic material.

SUBSTANCE: invention pertains to polymer cholesteric photoactive compounds, which can independently generate laser emission when irradiated with laser light. Such a compound can be used, for example, in photonics, optoelectronics and telecommunication systems. The cholesteric photoactive compound for generating laser emission consists of cholesteric liquid crystal, photoactive additive and laser dye. The liquid crystal used contains conjoint polymer n-(6-acrylyl oxycapril hydroxyphenyl)-n-methoxy benzoate with cholesterine-11-acrylyl undecanoate, containing molar quantities between 30% and 25% of the cholesterine-11-acrylyl undecanoate links. Photoactive additive used is 2.5-bis(4-methoxy cynnamoyl)-1.4;3.6-dianhydro-B-sorbitol, while the laser dye used is 4-(dicyano methylene)-2-methyl-6-(4-dimethyl amino styryl)-4H-pyran. The invention improves the temporal and thermal stability of the compound, and allows for its use at room temperatures and at lower temperatures as well. Sensitivity of the compound to external effects is also lowered.

EFFECT: increased thermal stability of photoactive compounds and lower sensitivity to external effects.

2 ex, 1 dwg

FIELD: polymer materials.

SUBSTANCE: invention relates to technology of manufacturing transparent profiled articles, for example, containers and bottles. Transparent article comprises continuous polyester matrix containing at least one incompatible filler dispersed therein. Incompatible filler provides domains in polyester matrix, each of them having particular size thereby forming a size range for domains contained in an article. To create turbidity, domain sizes lie within the range between about 400 nm and about 700 nm. Once size range is determined, a light absorbing substance can be selected to absorb light within a wavelength range, which at least essentially overlaps the preliminarily found domain size range.

EFFECT: facilitated finding substance masking turbidity of a polymer article.

20 cl, 12 dwg, 3 tbl

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to novel oxazine compounds of the formula (I): wherein X means carbon atom; R1 and R2 mean hydrogen atom; n = 0; A and A' mean independently of one another: (a) linear or branched (C1-C12)-alkyl, (C3-C12)-cycloalkyl; (b) unsubstituted or monosubstituted aryl groups. Also, invention relates to a method for synthesis of photochrome oxazine compounds of the formula (I). Invention provides synthesis of novel compounds and a method for their synthesis used as photochrome compounds.

EFFECT: improved method of synthesis.

10 cl, 1 tbl, 9 ex

FIELD: optical materials.

SUBSTANCE: invention relates to radiation-sensitive compositions with variable refraction coefficients allowing novel model with refraction coefficient distribution to be obtained, in particular optical material used in optical electronics and information representation devices. Invention discloses emission-sensitive composition with variable dielectric permittivity containing decomposable compound (A), non-decomposable component (B) including inorganic oxide particles resistant to acid or base originated from acid or base source (C), and radiation-sensitive degradable substance (C), wherein refraction coefficient nA of decomposable compound A and refraction coefficient nB of non-decomposable compound B lie in one of following relationships: nB-nA ≥ 0.05 (1) and nA-nB ≥ 0.05 (2), amount of component B ranges from 10 to 90 wt parts based on 100 wt parts of summary amount of components A and B, and amount of component C ranges from 0.01 to 30 wt parts based on 100 wt parts of summary amount of components A and B. Model obtained from indicated composition allows one to vary in a simple way refraction coefficients thereby achieving sufficiently large difference between them and their stability irrespective of application conditions.

EFFECT: expanded possibilities in optical representation of information.

12 cl, 3 tbl, 7 ex

FIELD: optical data carriers.

SUBSTANCE: device has cation dye or mixture of cation dyes with optical characteristics, changed by means of recording beam, an at least one substance with functions of damper and phenol or substituted phenol with one hydroxide group or more, while it additionally contains phenol or substituted phenol in form of phenolate ion, forming a portion of anions for dye cations, as a stabilizer. Data carrier can contain anionic metal-organic thyolene complex as damper, which forms other portion of anions for dye cations.

EFFECT: higher stability, higher durability, lower costs.

5 cl, 1 tbl, 3 ex

FIELD: color-forming compositions and recording material.

SUBSTANCE: claimed composition includes developer containing urea-urethane compound and colorless or light colored leuco dye. Recording material based on this composition also is proposed.

EFFECT: color-forming compositions with improved image conservation ability and increased image intensity.

21 cl, 14 tbl, 153 ex

The invention relates to a method for ensuring the authenticity of the subject by applying to a photochromic ink

The invention relates to the field of devices that change color under the influence of electric current, namely, the electrochromic device and method of its manufacture

The polarizer // 2199571
The invention relates to a light polarizers and can be used in flat panel LCD displays, lighting, optical modulators, matrix systems light modulation, etc

FIELD: chemistry.

SUBSTANCE: invention relates to method of producing higher-thermal stability polyester resins. This invention proposes the method of producing higher-thermal stability polyester resins via interaction of terephthalic acid dimethyl ether with 1,4-butylene glycol in melt at 150 to 220°C in the presence of organically modified clays in the amount of 1 to 10 wt % polyether. In compliance with the proposed invention, spatially unfavourable phenol (0.1 wt % polymer), tri-nonyl phenyl phosphite or three(2,4-di-tretbutylphenyl)phosphite (0.35) and calcium hypophosphite (0.05) are used as thermally stabilising system with synergistic properties, while boric acid, boric anhydride, sodium borate or their mix with tetrabutoxititanate (0.05 to 0.1% of the of polymer weight) are used as a catalyst. The formed product is subjected to polycondensation at residual pressure of 0.1 mm Hg. and at temperatures of 220 to 250°C.

EFFECT: method of producing complex high thermal stability aliphatic-aromatic polyethers.

1 cl, 2 tbl, 10 ex

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