NL8120511A - ALFA-DIAZOACETYL DERIVATIVES OF AROMATIC, NITROGENIC, Heterocyclic Compounds, AND PHOTOSENSITIVE MATERIAL. - Google Patents

Description

81 20 5 1 1 - * N.O. 31.298 11, TR / An / pl 'α-Diazoacetyl derivatives of aromatic nitrogen-containing heterocyclic compounds and photosensitive material. j ... ··· .- · .- ·. · * «*! ï l

The Applicant mentions as inventors:] ', 24AUG1982

Nikolai Markovich Emanuel, Moscow |

Viktor Georgievich Kartsev, Moskovskaya Tamara Sergeevna Pokidova, Moskovskaya Leonid Ivanovich Kirkovsky, Moskovskaya, USSR

Field of the invention

The present invention relates to new chemical compounds n.1. on o-diazoacetyl derivatives of aromatic nitrogen-containing heterocycles and on a photosensitive material prepared on the basis of these new compounds.

Description of the prior art.

Structural analogues of the compounds of the present invention are diazoacetophenones 10 / R R = Ci, Ch3} 0ch3, Nq2

Furthermore, as structural analogues of the novel compounds of the present invention, β- and ii-diazoacetylpyridines of the formulas: 20 COCHN * 1 2 3 4 5 6 81 2 0 5 1 1 2 can be considered.

3

The structural analogs specified above do not have photosensitive properties, although some of them have previously been used to study the chemical reactivity of the diazo-carbonyl group. Among the known compounds, which have photosensitive properties, may be mentioned, for example, diazotype dyes, spiropyran, derivatives of triarylmethane dyes (see MVAlphimov, OBYakusheva, "Achievements of the Scientific Photography", "Nauka" Publishing House, 1978 , volume XIX, biz. 152).

However, the prior art photosensitive compounds have a number of drawbacks. For example, diazotype compounds, which are only sensitive to UV light, form a latent image necessitating the process of ammonia development. A colored form of spiropyranes fades over time - the longest period for half-fading of the color in the dark is about 30 hours, making it impossible to store the information recorded thereon for a long time.

Known in the art are syndone derivatives, for example, 4-bromo-3- (3-pyridyl) sydnon, used in actinometers for X-ray radiation indication (CSSR inventor certificate No. 172686, Cl.G 03 C 1/72, 15 published 1979) .

Also known is the use of a solid solution of 1,3,3-trimethyl-6'-nitrospiropyran in ethyl cellulose in UV light actinometers (EGAhalkatsi et al, "0n the use of photochrome agents as actinometers", Reports of Georgian SSR Academy of Sciences, 1969, vol. 55, pp. 81-84) The use of this compound ensures a high speed of measurements and good reproducibility, however the photometry time should not be more than 40 seconds after finishing of the irradiation of the actinometer due to a significant decolorization rate of the latter in the dark.

Among substances exhibiting photosensitive properties in polycrystalline layers with the visible image developed directly thereon during the exposure without the need for further development, salicylidene anilines (anil) are known to be used as photosensitive polycrystalline component in materials which have been adapted 30 for recording optical information by laser or any other source of UV radiation (see VABarachevsky, GILashkov, VATsekholsky "Phorochromism and lts Applications", "Khimija"

Publishing House, 1977, pp. 35-36, 116; P.S.Lo et al. Appl. Options, 1974, 13, 816-865; V.A.Barachevsky, Zhurnal vsesojuznogo khimicheskogo 35 obschestva, 1974, XIX, 4, 427).

Photosensitive materials based on the use of anil contain polycrystalline layers coated on two transparent substrates as a support (e.g. quartz glass) with a polycrystalline layer thickness of 1.8 to 2.2 µm. Registration of information is performed 40 by means of a laser beam to obtain an orange 8 1 2 0 5 1 t

V

3 image against a yellow background. The spectral photosensitivity of these anils is calculated according to the formula: 5 h 1.2 x 109 ^ ΑΒ, ελΑ'λΑ 10 where Η χ - the exposure radiation dosage necessary to obtain an image with the optical density Dg = 0.2 ;

V

Ag “is the quantum yield of the formation of the colored product; 15 - the extinction coefficient of the initial form at the wavelength of λ; λa “is the wavelength of the activation radiation.

According to known data, the spectral photosensitivity of salicylidene anilines is Ho / 0.6 J / cm 2. A significant disadvantage of these photosensitive materials lies in the reversibility of the staining process - the longest half-life of the color fading in the dark is about 30 hours and the discoloration of the colored form is significantly accelerated in the light, with the storage time and the usage time of the recorded information is significantly reduced.

The present invention is directed to the provision of new compounds, which have a photosensitive activity within both the UV and visible ranges of the spectrum, which will enable the production of silverless photosensitive materials that produce stable images. with great contrast. This object is accomplished by providing α-diazoacetyl derivatives of aromatic nitrogen containing heterocyclic compounds, which according to the present invention have the following formula:

Het - C - CHN2 40 where Het 8120511 4 R3 R6 Rg Ry Ph ^ ÎOl 10 PHOTOGRAPH or i @

5 S ^> 'Vo-'V

«B

wherein R 1, R 2, R 3, R 4 are each hydrogen or a NO 2 or COCHN 2 group; R5 and Rg may be the same or different and represent chlorine and groups such as OH, NH2 OCH3, N-piperidyl, NHNHPh, N = Ph, OPh, 8-mercaptoquinolyl, 2-mercaptoquinolyl; R7, Rg and R9 may be the same or different and each represent hydrogen or groups such as CH3 or NO2.

These new compounds of the present invention have photosensitivity. According to the present invention, it is advisable to use ordiazoacetyl derivatives of aromatic nitrogenous heterocyclic compounds of the formula: 20% Λ, COC HN & 25, wherein, when R 3 represents COCHN 2, R 1 = R2 = R 4 = H; when R ^ = R3 represent COCHN2, R2 = R4 = H; or when R 1 represents COCHN 2 and R 4 represents NO 2 R 2 = R 3 = H, sensitivity within the visible and UV regions of the spectrum is shown.

Furthermore, according to the present invention, it is advisable to use α-diazoacetyl derivatives of aromatic nitrogen-containing heterocyclic compounds of the formula: 35%

Iet ° CHNa 40 81 2 0 5 1 1 5 where when R5 represents chlorine, a chlorine atom, a group OCH3, NH-NHPh, N = Ph, OPh N-piperidyl, 8-mercaptoquinolyl and when R5 = Rg and a group OH or NH2, photosensitive properties within the visible and UV regions of the spectrum 5 are shown.

Furthermore, according to the present invention, it is advisable to use α-diazoacetyl derivatives of aromatic nitrogen-containing heterocyclic compounds of the formula:% «1 V ^ N co CHNos» wherein, where R7 * Rg = Rg represent these hydrogen atoms; when R9 represents a NO2 group, R7 = Rg and represent hydrogen, when Rg represents NO2, R7 = R9 and represent hydrogen; When R7 represents NO2 or CH3, Rg = R9 and hydrogen represent photosensitivity both within the visible and UV regions of the spectrum.

Furthermore, according to the present invention, it is recommended that 3-phenyl-4-diazoacetylsydnon having the formula:

PhX_rC0CHNa Λ <§1 30 to be used with photosensitivity both in the UV and visible areas of the spectrum, which gives a yellow color in the case of fo-35 totransformation.

To obtain a stable contrast image according to the present invention, a photosensitive material contains a substrate and a photosensitive polycrystalline layer formed by a crdiazoacetyl derivative of aromatic nitrogenous heterocycles 40 of the formula: 8120511 * 6

O

you

It - C - CHN2 5 where Het

Re 5 * «V

R "jRl (öt)) fi fi® 10 N N N where Rj_, R2, R3 and R4 each represent hydrogen or the groups NO2 or CO2CHN2, R5 and Rg may have the same or different meanings and chlorine and the groups OH , NH2, OCH3, N-piperidyl, NHNHPh, N = Ph, OPh, 8-mercaptoquinolyl, 2-mercaptoquinolyl: R7, Rg, Rg may have the same or different meanings and represent hydrogen or the groups CH3 and NO2.

In order to record information by lasers or other radiation sources and to form contrast images (blue or brown images against a light yellow background), according to the present invention, use is made of a photosensitive material whose polycrystalline layer is formed by α-diazoacetyl derivatives of aromatic nitrogen-containing heterocyclic compounds of the formula: 25 * 6 '' Tgr * · ^ TT COCHN, wherein where R 3 represents CO 2 CH 2, R 1 = R 2 - R 4 - H; when R1 88 R3 represent COCHN2, R2 = R4 = H; or when R ^ represents COCHN2 and R4 represents NO2 R2 = R3 β H.

According to the present invention, a photosensitive material, the polycrystalline layer formed by α, is used to record information by means of lasers or any other radiation source, as well as to improve the contrast and stability of the images obtained. diazoacetyl derivatives of aromatic nitrogen-containing heterocyclic compounds of the formula: 8 1 2 0 5 1 1 7 J * 5 n * cochn *.

wherein, when R5 represents chlorine, Rg represents chlorine, the OCH3 group, NH-NHPh, N = NPh, POh, N-piperidyl, 8-mercaptoquinolyl or 2-mercaptoquinolyl, and when R5 = Rg represents OH or NH2.

In order to record optical information by means of lasers, sources of UV radiation and visible (λ n »450 nm) radiation, for the purpose of producing stable contrast images according to the present invention, use is made of a photosensitive material, of which the polycrystalline layer is formed by ordiazoacetyl derivatives of aromatic nitrogenous heterocycles of the formula:

Af R7 ”(èrai COCHN *.

Ra 25 where, when R7 = Rg = R9, they each represent a hydrogen atom, when Rg represents NO2, R7 = R9 and represent hydrogen; when R7 represents NO2 or CH3, Rg = Rg and hydrogen.

To produce actinometers for indication of X-ray radiation and increasing the range of the measured doses of UV radiation, use is made of a photosensitive material, the polycrystalline layer of which is formed by 3-phenyl-4-diazoacetylsydnon of the formula : 35 _ ^ COCHNj.

N I

A © 1 ^ 0 o 40 8 1 2 0 5 1 1 8

The novel crdiazoacetyl derivatives of aromatic nitrogen-containing heterocycles of the present invention make it possible to obtain images which are stable in the dark when deposited on a substrate. As shown by experiments, no contrast drop of images in the dark is observed for 6 months. In operation with the image obtained in a scattered daylight, the main value of contrast damping is 2 to 40 days depending on the structure of the compound, allowing the use of the recorded information for a long time without any noticeable deterioration of its quality. Compared to the images generated from anil (orange images against yellow background), the materials based on the compounds of the present invention allow to produce more contrast-rich images (clear brown or dark violet images against a light yellow background), that are suitable for reading the information. The photosensitivity of the materials of the present invention is 0.1 J / cm 2 (at X = 300 nm), i.e. 6 times greater than in the case of analogs based on anil.

Therefore, comparing the data from the investigations 20 performed with the photosensitive compounds of the present invention with the data on the known silverless photosensitive materials (MVAlphimov, OBYakusheva, "Achievements of the Scientific Photography", XIX, "Nauka" Publishing House, 1978, p. 154) it may be possible to emphasize some of the advantages of the compounds of the present invention.

I. The absence of the development process as opposed to diazotype, vesicle, photopolymerization, free radical, photodeformation, photothermopolymerization and luminescence materials, as well as photosensitive polymers, physical development materials and chromium coated colloids. Only photochromic and cyanotype materials do not necessitate development, however: II. Compounds with photosensitive layer based on compounds of the present invention have a higher energy photosensitivity (up to S of 0.1 x 10 2 j / cm 2 at S of 102 J / cm) compared to photochromic and diazotype materials ^ for photochromic and even less photosensitivity in the case of cyanotype materials). In terms of energetic photosensitivity, the compounds of the present invention are superior to some blistering, photopolymerization, free radical, photodeformation, luminescent materials, photosensitive polymers, chromium-coated colloids, as well as 8120511 materials of physical development; furthermore: III. The materials based on the photosensitive materials of the present invention are better, in terms of resolving power, than some diazotype, blistering, photopolymerization, photodeformation, photoheropolymerization, luminescent materials, as well as photosensitive polymers and materials of physical development; furthermore: IV. Compared to photochromic materials, which are characterized by decolorization of the colored form with time, the images produced by the compounds of the present invention are not decolorized. Finally: V. The compounds of the present invention are better than negative photosensitive polymers, photodeformation, photothermopolymerization, cyanotype and luminescent photosensitive compounds with respect to the range of spectral sensitivity in the long wavelength region. MVAlphimov, OBYuakusheva, "Achievements of the Scientific Photography", XIX, "Nauka" Publishing House,

Moscow, 1978, biz. 157-164).

Therefore, with respect to the entire range of photographic properties, the photosensitive compounds of the present invention are better than various classes of known chemical, silverless, photosensitive systems.

The best way to practice the invention.

The compounds of the present invention are new and have hitherto not been described in the literature; as already mentioned above, these photosensitive compounds comprise α-diazoacetyl derivatives of aromatic nitrogen-containing heterocyclic compounds of the general formula:

II

It - C - CHN2 where It is 35 © R * R * P> k .__ “JOT iQl © O) or I © R 'N Rs VNr Νν.η / * Ό * 9 40, 81 205 1 1 10 where R ^, R2> R3 and R4 represent hydrogen or the groups NO2 »COCHN2, R5 and Rg may have the same or different meanings and chlorine or the groups OH, NH2, OCH3, N-piperidyl, NHNHPh, N = NPh, OPh, 8- mercaptoquinolyl and 2-mercaptoquinolyl; R7, Rg and R9 may have the same or different meanings and each represent hydrogen or the groups CH3 or NO2.

The compounds of the present invention can be prepared by known methods, for example, 2-diazoacetylquinolines of the general formula: 10 1 ^ 7.

wherein, when R7 = Rg = R9, these represent hydrogen, when Rg represents NO2, R7 = Rg and represent hydrogen; when R 8 represents NO 2, R 7 = R 9 and hydrogen; when R7 represents NO2 or CH3, Rg = R9 and hydrogen, as well as derivatives of 2-diazoacetylpyridine of the general formula: 25

kjL

Λ, - j j s co co chn chn ^ ^ ^ 2 1 2 3 4 5 6 8120511 2 where, when R 3 represents COCHN 2, R 1 = R 2 = R 4 = H; when 3 represents R ^ = R3 and COCHN2, R2 = R4 = H; or when 4 represents R 1 COCHN 2 and R 4 represents NO 2, R 2 = R 3 = H, are prepared according to the process for the preparation of α-diazoketones 6 as used for the preparation of, for example, crdiazoacetophenones (see Preparation Organics Chemistry I, Ver Chemistry Weiheim, 1944, 359). The general scheme of the procedure is as follows: 11

oc O

rt jfsGCCz n, ƒ CHiNa. o S

ft - q -M -C - ^ -C

5 X0H ^ Ct

For the synthesis of bisdiazoacetylpyridines and trisdiazoacetylpyridines as starting compounds, use is made of the corresponding bis and tris carboxylic acids, for example:. CHa.N ^ / N \ / N \ 15 HO ^ C CO ^ H cecc coce. NfcCW0C COCHN ^

The synthesis of the starting pyridyl-substituted carboxylic acids is performed by conventional methods (see 20 A.W. Sigger, S.M. Mc Elvain, J.Am.Chem.Soc., 57, 1135, (1935)).

The derivatives of 2-diazoacetylpyridine and 2-diazoacetylquinoline of the present invention differ from the known analogs not only in their structure:

In contrast to the known derivatives of diazoacetylpyridine and diazoacetophenones, they reveal a new, hitherto unknown property - photosensitivity within the visible and UV ranges of the spectrum. The compounds corresponding to formula (I), i.e. derivatives of 6-diazoacetylpyridine of the general formula: 6-6-6 ΎΓi ΎΓ COCHN ^ 35 where, when R5 = Cl, chlorine, OCH3, N-piperidyl, 8-mercap -tochinolyl or 2-mercaptoquinolyl, when when R5 = R5 and OH or NH2, may be prepared according to conventional methods (see U.S. Patent 4,025,515) by action of 2,4-dichloro-6-diazoacetylpyrimidine on nucleophilic reagents with 81 205 1 1 12 the formula RgH, wherein Rg has a meaning similar to that previously specified, in an organic solvent medium (e.g., methanol) or without, wherein a 2-5 fold excess of a nucleophilic reagent in the presence of a 2-3 fold excess of triethylamine (or without) at a temperature within the range of 0 to 80 ° C for a period of from 30 minutes to 10 hours, depending on the particular reaction, followed by isolation of the desired product according to custom calibration techniques.

2,4-Dichloro-6-diazoacetylpyrimidine is prepared by carrying out successive conversions using an easily available uracil-6-carboxylic acid according to the following reaction scheme: OH CU Cd 01 ho. cOjH ct cogH ce coed ce coc hnz 20 Furthermore, 3-phenyl-4-diazoacetylsydnon with the formula:

Ph. yC0CHMa N-

I O

be prepared according to the known method for the synthesis of sydnones with subsequent conversion to a diazoketone according to the Arndt-30 Eystert reaction: o ...... 0

Ph ll PH iCHN

\. / CCG. \ N_

33 ΡΗ-Γ0, -ΟΟΟΗ- ^ Ν01 ^ | @i NO-COOH N ^ 0 'o ^ O'O

According to the present invention, from the point of view of economic properties, it is most recommended to use the compounds §1 2 05 1 1 13 of the present invention as photosensitive components in the materials made suitable for recording optical information by means of of UV radiation sources and visible light sources (λ ^ 450 nm).

As the substrate in the photosensitive materials of the present invention, all materials suitable for these purposes may be used, such as paper, film, wood, etc.

The photosensitive materials of the present invention having a polycrystalline layer based on the novel compounds of the invention have a number of advantages over the prior art materials: 1. The novel compounds of the present invention make it stable in the dark to produce images. As shown by experimental data, no drop in the contrast of images when used with it in the dark for 6 months is observed. When used with the obtained image in scattered daylight, the half-life period of contrast attenuation is 2 to 40 days on average, allowing the use of the recorded information for a long time without any noticeable deterioration in its quality.

2. Compared to the images generated from anals, (orange images against yellow background), the materials based on the new compounds of the present invention allow to obtain more contrast-rich images - brown or blue-violet images against a light yellow background suitable for reading out information.

3. The photosensitivity of the materials based on 6-diazoacetylpyrimidines is H ^ = 0.2-0.4 J / cm ^ (at λ = 300-350 nm), i.e.

1.5-2 times greater than anil-based analogs; the photosensitivity of the materials based on 2-diazoacettylquinolines is H Ai 0.1 j / cm ^ Λ (at λ = 300 nm), ie 6 times greater in analogous analogues, the photosensitivity of the materials based on derivatives of 2 -diazo-acetylpyridine is H · ^ = 0.2-0.4 J / cm ^ (at λ = 300-350 nm), ie 1.5-2 times higher than with anil-based analogs.

It should be noted that the use of photosensitive materials on quartz substrates described in the literature limits their use for graphic information recording, for example, graph plotter, spectrum recording, and the like, which is associated with operating inconvenience therewith, as well as their storage.

40 The study of the materials based on the compounds according to 8120511 14 the present invention using other substrates such as paper, Silufol UV-254 plates has demonstrated the applicability of these materials for recording information by lasers or other sources of UV radiation, as well as visible radiation.

We have conducted some experiments proving that the most promising, with respect to technical and economic parameters, is the use of 3-phenyl-4-diazoacetylsydnon according to the present invention as a photosensitive component in UV radiation actinometers, that of be of great practical importance for the adjustment of optical instruments, the focusing of radiation from different sources, determination of the spatial distribution of the intensity of laser radiation, as well as for other cases of visualization of the UV radiation.

An essential advantage of the actinometers based on the photosensitive compound 3-phenyl-4-diazoacetylsydnon according to the present invention is a slow decolorization process, which allows an extension of the photometry period (not less than 6 months in the case of storage in the dark).

Furthermore, an important advantage of using the photosensitive properties of 3-phenyl-4-diazoacetylsydnon in actinometers is a wider range of measured doses of UV radiation: from 1.10-1 to 20 J / cm ^ The compound according to the present invention it is possible to register higher doses of UV radiation, which is impossible for the prior art actinometers based on a known compound - spiropyran.

The determination of an integral photosensitivity of the compounds of the present invention is carried out by the following method: a) composition of a photosensitive layer.

Photosensitive layers are produced by applying a solution of a corresponding diazoketone in chloroform to a barite-treated paper, followed by evaporation of the solvent.

b) exposure of the photosensitive layer.

The exposure of photosensitive layers is performed up to a full luminous flux from a lamp having an integral radiant power in the exposure plane of 1.3 x 100 w / cm 2. Attenuation of the luminous flux is performed by means of a segmented electric shutter with transmission coefficients, which forms a series of a geometric progression with the modulus 1/2. As a result, a set of seven fields is obtained.

»1 2 05 1 1 15 c) measurement of the optical density of individual fields.

This is performed using Soviet-manufactured densitometers and a densitometer RD-519 (available from a British company "MacBeth") with suitable light filters in the measurement of colored samples. The data on the effect of different radiation doses on photosensitive layers are analyzed by characteristic curves (D against log H, where H is an exposure dose of radiation, J / cm ^, equal to the product of the stream E with the corresponding exposure time τ) Since in no case 10 optical densities of the image D = 1 are reached, the criterion D = 0.2 (above the veil) is used for the evaluation of the photosensitivity. The integral photosensitivity data is given in Tables 1 to 3 below.

The spectral sensitivity determination is carried out using a spectrosensitometer FSR-9 with quartz optics and a mercury quartz lamp as a source of UV radiation. Optical densities of the images obtained have been evaluated semi-quantitatively by comparison with known density of images of the fields generated by integral sensitometry. However, intensities of individual 20 lines in the mercury lamp spectrum differ from each other, therefore the data densities of the images have been reduced to a unit power of the line radiation (the data on spectral energy distribution had previously been obtained by means of a thermocell). The spectral photosensitivity curve qualitatively corresponds to the absorbance spectrum. The spectral sensitivity data are given in the table below.

The resolving power of layers based on the diazocarbonyl compounds of the present invention was determined on a resolving power meter, followed by examination of the obtained images by microscope. R> 900 mm-l, 8120511 applies to all materials studied

Table 1 16

Photosensitivity and physicochemical properties of 5 2-diazoacetylpyridine derivatives.

Rs

Rh m lol 10 R, N ^ COtHN ^

No. R2 R3 R4 Photosensitivity S0,2 <m2 / J) 15 __ 1 Η Η Η H 0,14j <), 01xl0-5 2 COCH N2 Η Η Η 1,3 + Ο, ΙχΙΟ "5 3 Η H C0CHN2 HI, 0jj3 , lxl0-5 4 C0CHN2 H C0CHN2 H l, 4j <), lxl0-5 20 5 C0CHN2 Η H N02 l, 2jK), lxlO “5

The resolving power of all compounds of the present invention is above 900 lines / mm. In IR spectra of compounds I, intensive absorption bands of N N groups at V 2100 cm -1, as well as absorption bands of C = 0 and C = N groups at 1580-1640 cm -1, are observed.

The comparison of the data from the studies of the photosensitive materials of the present invention based on the new compounds with the data on known silverless photosensitive materials (see MVAlphimov, 0.B. Yakusheva, "Achievements of the Scientific Photography ", XIX," Nauka "Publishing House, Moscow, 1978, biz. 154) allows to specify a number of advantages of the materials of the present invention (see Tables 1 and 2). 35 8120511 17 yy e ω 0 (D ^ s omm-j-OOvocM vo i> -

t) Γ-'Ι'-ΜΟ ^ ΟΓ ^ ΙΛΙΛΟΟ 00 LTivO

P

0)

Pi p 0) p • Η Ά Ό Ή

ft QJ

0 -O

• H ÖO i ”5 sh ft m mm m vo

> 3 h m in i m in i in i m l vO I

& <U 0 I O I I O I O I O IO

H O'- 'OftOOftOftO ft O ft ^ 3 ^ ι — I ft ft ft ft X ft ft ajcMXmXXmXmx m Xm <u ooiiocMcM-d-ftcocMoo nm cm OOO ΛΛΛΛΛΛΛΛ «S es n co 4JCO ooooooo'o o oo 0 o N b co

• H

T3

vO

- 1Ü S ö cp o) rHinr ^ cN (NO <T »<r sr» η> ^ 13 oocncOf-icn ^ -mc ^ cm γ-ι, -ι (J) AAAMMAAA «S« «P ih ιτινο \ οσισιθιπρ -ι ft ft i ".

0) ω NNMNNNNN CM (Tl <f

ft PQ

CU td s 03 C.

p r <u o ω μ. p ft Φ cm ai kj O moooftstoooof σ> r>. σ \ _ / P! 3 vOftCMOftftCOft O 03 00 H 4) / \ 0 Λ Λ Λ Λ Λ Α Λ Λ «3 ·» «1 <UX / _ \> BS ΐ0ν0 \ 00303θιηρΗ ρ-1 Ονό Χ> Ο ίΟ / S \\ (U CMCMCMCMCMCMCMCM CM C <lMf * ΐ ^ Λ Ο 21 ° 1 "2 - /? S ^ ~ • Ρ CC ft ft ft

Ü C JJ 4J

»Ρ Ο -ί <f Γ- ~ 00 / -3 -ft Ρ Ρ • Η Ά« ΐ Ο in ft m · · ο ο Μ Ρ Ο ι — I ρ-1 ι — I ι — I ι— (pH ft '- ^> 3 Η ο IIIII ft ft Ή <U moOCMCMvOvDOvoCOCu-iin. θ -ίηοίΛρ ^ -ίιοιη at 00003

Ρ C0 '—I ι — I ι — I ι — I ι — I r — t ι — I pH N ^ pH V pH pH

0) o ft

I I I

ft o o 4-1 4-3

(¾ rH ft rH

id> 3 td> 3

vp · -Ρ υ H O H

pi ftftjd Mono

Cftffift, P OJ P <U P

W ftga-Cft 0ft 0 ft CM

^ υ I. E JL & <Es ι 10 ι ΛΜώ oozazogooucMuoz

ΙΛ ftftftftftftftft pH pi CM

pci UOCJCJOUUO O O a 8120511 O Oft S ftcMn-crmvor ^ oo 03 ftft

Table 3 18

Photo properties of 2-diazoacetylquinolines 5 R, R-7 (ojpl ™ COCHN? H 10 ___

No. Rg Rg Ry Photosensitivity S0,2 (“2 / J) 15 1 Η Η H 2,1 + 0,2x10“ ^ 2 N02 Η Η 1,9 + 0,2x10 “^ 3 H N02 H 1,8 + 0, 2x10 “5 4 Η H N02 1,5HHD, 15x10“ 5 5 Η H CH3 2,2 + 0,2x10 “5 20 8120511 19 I. The absence of the development process as opposed to diazotype, bubble-shaped, photopolymerization, free radical, photodefor -mation, photothermopolymerization, luminescent materials, as well as photosensitive polymers, materials with physical development and chromium-coated colloids. Only photochromic and cyanotype materials do not require development, however: II. Compounds with a photosensitive layer based on compounds of the present invention, compared to photochromic and cyanotype materials, have a photosensitivity of higher energy 10 (up to S 0, 1 x 10 2 j / cm ^ at S or 10 ^ j / cm ^ for photochromic and even less for cyanotype materials). In terms of energetic photosensitivity, the compounds of the present invention are better than certain blistering, photopolymerization, free radical, photoreformation, luminescent materials, photosensitive polymers, chromium-coated colloids, as well as physical development materials; furthermore: III. The materials based on the photosensitive materials of the present invention are better, in terms of resolving power, than certain diazotypes, blistering, photopolymerization, photodeformation, photothermopolymerization, luminescence materials, as well as photosensitive polymers and materials of physical development; furthermore: IV. Compared to photochromic materials, which are characterized by decolorization of the colored shape with time, the images produced by the compounds of the present invention are not decolorized; finally: V. The compounds of the present invention are better than negative photosensitive polymers, photodeformation, photothermopolymerization, cyanotype and luminescent photosensitive compounds with respect to the range of spectral sensitivity within the long wave region (see also MVAlphimov, OBYakusheva, opt.cit., Pp. 157-164).

Therefore, with respect to the entire range of photographic properties, the photosensitive materials of the present invention are better than various classes of known chemical, silver-less, photosensitive systems.

8120511 20

3 <D

ft 3 in 3

ft 1H

0) • H «3 ft Φ 1) O) 3 3 3

3 Ό Ό Ό T3 3 'O

ft 3 3 3 3 U-ι 3

ft ft ft ft 4Jm 4J

3 Ή · Η · Η τΗ: α) Ή Ή '—liHrH Ο Ο 3 rH · Η Ο1 ""! 00 ftftft.P4J3ftrHftft ¾ aa 0 · Η · Η 3 0 3 -Hi PS 3 3 3 O'üMH3ftO «) 3 3 cd a 3> ft oo ο 3 4J> • Η · Η ό α> <υ 3 ft Ό • Η ^ + + + + + +1+ + + £> Η 3 3 η ω 3 Ρ Η> «Ü ft ο Q) Cd Η

00 • Η rH

3 ο> 3 00 Ο Ό ft I · Η ο ο <υ Μη 3 33 & 00 3 3 · 3 γΗ> 33 Ο Ο Ο Ο Ο ΟΟΟ Ο Ο ΛΟ ιη ιΟ ιη ιη ο ΟΟΟ ΟΟ 3>> -3- <τ «ί nt m ιη ν -ί η. m

3 3 Chf I I I I I III II

ft 4J 60 o o o © o ooo oo ft o oooooommooo nr 3 33 cn cn cn co cn cn nj cm men

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8120511 22

For a better understanding of the present invention, some specific examples are given below by way of illustration. Example I

2-Diazoacetylquinoline (R7 = Rg = R9 = H) 5 To an ethereal solution of diazomethane prepared by alkaline decomposition of 12 g of nitrosomethyl urea with vigorous stirring and cooling at -15 ° C, an ethereal solution is added dropwise for 20 minutes of 4.5 g (0.024 mol) of quinaldinic anhydride. After completion of the dropwise addition, the reaction mixture is stirred for an additional 30 minutes without cooling to bring the temperature to 0 ° C. Ether is evaporated and the crystalline residue is recrystallized from hexane. The yield of 2-diazoacetylquinoline is 3.2 g (76%). Melting point 73-74 ° C.

Found,%: C 67.18, H 3.46. C ^^ HyNgO.

Calculated,%: C 67.01, H 3.55. Rf = 0.64 (system benzene-ethyl acetate 9: 1), Silufol UV-254.

Example 2 4-Methyl-2-diazoacetylquinoline (Rg "R9" H, R7 "CH3)

This compound is prepared under similar conditions as described in the previous Example 1. The return is (72%). Melting point 68 ° C.

Found,%: C 68.11, H 4.37. C12H9N3O

Calculated,%: C 68.25, H 4.27. Rf = 0.72 (benzene-ethyl acetate system 9: 1), Silufol UV-254.

Example 3 4-Ni tro-2-diazoacetylquinoline (Rg = R9 - H, R7 = NO2)

This compound is prepared as follows. A solution of 2.37 g (10 mmol) of 4-nitrochinaldic acid chloro anhydride in 40 ml of absolute ether 30 is added dropwise over 20 minutes to an ethereal solution of diazomethane cooled to -15 ° C and prepared from 20 g nitrosomethyl urea with vigorous stirring. The reaction mixture is then cooled to a temperature of -35 to 40 ° C and maintained at this temperature for 1 hour. The resulting crystal line residue is filtered and recrystallized from hexane.

The yield is 1.59 g (66%). Melting point is 105 ° C.

Found,%: C 54.40, H 2.51. Cj ^ Hg ^ Og.

Calculated,%: C 54.55, H 2.48. Rf = 0.58 (system benzene-ethyl acetate 6: 1), Silufol UV-254.

40 Example 4 8ΓΖΤ51 1 23 5-Nitro-2-diazoacetylquinoline (Ry = R9 = H, Rg = NO2)

This compound is prepared from 5-nitrochinaldinic acid-5 chloro anhydride and diazomethane under similar conditions as described in Example 3 above. The yield is (70%). Melting point is 133-134 ° C.

Found,%: C 54.38, H 2.44. GqH ^ N ^ Oj.

Calculated,%: C 54.55, H 2.48. Rf = 0.55 (system benzene-ethyl acetate 6: 1), Silufol UV-254.

Example 5 8-Nitro-2-diazoacetylquinoline (R9 = NO2, R7 = Rg = H>

This compound is prepared from 8-nitrochinaldinic acid chlorohydridide and diazomethane under similar conditions as described in Example 3. The return is 58%. Melting point 155-157 ° C (with decomposition).

Found,%: C 54.42, H 2.47. C ^^ HgN ^ Oj.

Calculated,%: C 54.55, H 2.48. Rf = 0.52 (system benzene-ethyl acetate 6: 1), Silufol UV-254.

Example 6 2-Diazoacetylpyridine (Rx = R2 = R3 - R4 = H)

Step 1. Preparation of q-picolinic anhydride 20 g of a-picolinic acid are heated under reflux with 38 g of thionyl chloride in the presence of 0.5 ml of dimethylformamide for 10 hours. The excess thionyl chloride is distilled off. The residue is extracted twice with 40 ml portions of hexane. Hexane is evaporated and the residue is distilled, collecting the fraction boiling at 76-82 ° C (10 mm Hg). The yield of chlorine-30 anhydride is 15.7 g (69%).

Step 2. Preparation of 2-diazoacetylpyridine

To an ethereal solution of diazomethane, prepared from 27 g of nitrosomethyl urea with vigorous stirring and cooling to -15 ° C, the solution of 7.1 g (0.05 mole) of a-pico-35-acyl anhydride is added dropwise in 40 ml of absolute ether were added over 30 minutes. Stirring is continued for 1 hour to bring the reaction temperature to 0 ° C. The ether is evaporated and the residue is recrystallized twice from hexane. The yield of 2-diazoacetylpyridine is 5.2 g (71%). Melting point 50 ° C.

40 Found,%: C 48.82, H 2.70. C7H5N30.

8120511 24

Calculated,%: C 48.98, H 2.72. Rf = 0.51 (system benzene-ethyl acetate 9: 1), Silufol UV-254.

Example 7 2.6- Bisdiazoacetylpyridine 5 (Rx = C0CHN2> r2 = r3 = r4 = H)

Step 1. 2,6-Pyridinedicarboxylic acid dichloro anhydride is prepared under conditions similar to those described in Example 6 above. The yield is 75%.

Step 2. 2,6-Bisdiazoacetylpyridine is prepared under conditions similar to those described in Example 6 from 8 g of 2,6-pyridinedicarboxylic anhydride and an ethereal solution of diazomethane prepared from 40 g of nitrosomethyl urea. The crystalline precipitate obtained is filtered off and recrystallized from methanol.

The yield is 7.9 g (94%). Decomposition temperature 150 ° C.

Found,%: C 50.12, H 2.24. C9H5N5O2

Calculated,%: C 50.23, H 2.32. Rf = 0.46 (benzene-ethyl acetate system 1: 1), Silufol UV-254.

Example 8 2,4-Bisdiazoacetylpyridine 20 (RX = R2 = R4 = H, R3 - COCHN2)

Steps 1 and 2 are performed under conditions similar to those described above in Examples 6 and 7. The yield of 2,4-diazoacetylpyridine is 82%. Melting point is 155 ° C (dec.).

Found,%: C 50.08, H 2.18. Cg ^ N ^.

Calculated,%: C 50.23, H 2.32. Rf = 0.33 (system benzene-ethyl acetate 1: 1), Silufol UV-254.

Example 9 2.4.6- Trisdiazoacetylpyridine 30 (R] _ = R3 = COCHN2, R2 = r4 = H)

Steps 1 and 2 are performed under conditions similar to those described in Examples 6 and 7. Diazomethane is prepared on the basis of calculations for trichloranhydride.

The yield of 2,4,6-trisdiazoacetylpyridine is 95%. Decomposition temperature is 160-165 ° C.

Found,% C 46.48, H 1.91. (41H5O3N7.

Calculated,%: C 46.64, H 1.77. Rf = 0.24 (system benzene-ethyl acetate 1: 1), Silufol UV-254.

Example 10 40 2,6-Bisdiazoacetyl-3-nitropyridine 8120511 ► 25 (R3 = COCHN2, R4 = NO2, R2 = R3 = H)

Step 1. Preparation of 3-nitro-2,6-pyridinecarboxylic acid.

83 g of potassium permanganate are dissolved in 1.4 l of water after heating and 17.6 g of 3-nitro-2,6-lutidine are added. The mixture is boiled for 2 hours, the residue is filtered and the mother liquor is evaporated to 150 ml, acidified with concentrated hydrochloric acid to a pH of 1-2, cooled and the resulting crystalline precipitate of orange color is filtered and dried, whereby 14 g (48%) is obtained.

10 Stage 2.

3-Nitro-2,6-pyridinecarboxylic acid dichloro anhydride is prepared under conditions similar to those described in step 1 of Example 7. The yield is 56%.

Stage 3.

2,6-Bisazoacetyl-3-nitropyridine is prepared under conditions similar to those described in step 2 of Example 6. The product is recrystallized from ether. The return is 58%. Melting point is 108 ° C.

Found,%: C 41.42, H 1.48. C9H4N6O4.

Calculated,%: C 41.54 Rf = 0.75 (benzene ethyl acetate system 3: 1), Silufol UV-254.

Example 11 2.4- Dichloro-6-diazoacetylpyrimidine (R5 = R6 = Cl) 25 15.6 g (0.1 mol) uracil-6-carboxylic acid with 37 g (0.22 mol) phosphorus oxychloride at a temperature of 107 ° C heated for 10 hours, phosphorus oxychloride is distilled off, 48 g of thionyl chloride and a few drops of dimethylformamide are added. The reaction mixture is heated for 2 days, the excess thionyl chloride is distilled off and the residue is distilled in vacuo to collect the fraction at the boiling temperature of 75-90 ° C / 1 mm Hg. The yield of 2.5-dl-chloro-6-pyrimidinecarboxylic acid chloranhydride is 7.7 g (43.6%). Melting point is 28-30 ° C.

To the ethereal solution of diazomethane (250 ml), dried over the solution of potassium hydroxide and prepared with decomposition of 25 g of N-nitrosomethyl urea by reacting with 140 ml of a 40% solution of potassium hydroxide (caustic potash) in water with vigorous stirring and cooling of the reaction mass at a temperature of from -10 to -15 ° C, after which a solution of 7.7 g of 2,4-dichloro-6-pyrimidinecar-40 carboxylic anhydride in 30 ml of absolute ether for 20 minutes was added dropwise 8 1 2 05 1 1 26 is added. The precipitate formed is filtered, washed with ether and dried on the filter. The yield of 2,4-dichloro-6-diazoacetylpyrimidine is 5.5 g (70%). Melting point is 145 ° C. (decomposition). Found,%: C 33.04, H 0.95. C6H2N4OCI2.5 Calculated,%: C 33.21, H 0.95.

Example 11a 2.4- Dihydroxy-6-diazoacetylpyrimidine

To a suspension of 1.08 g (6 mmol) of finely divided 2,4-dichloro-6-diazoacetylpyridine in 20 ml of water, 3 g (30 mmol) of triethylamine 10 are added and the mixture is heated under reflux to complete dissolution of the residue. The solution is evaporated to 5 ml and the precipitate formed after cooling is filtered off, washed twice with cold water (1 ml portions) and recrystallized from water. The yield is 500 ml (56%). The decomposition temperature is 185 ° C.

Found,%: C 39.62, H 2.78. CgH ^ N ^ Oj.

Calculated,%: C 39.79, H 2.78.

Example 12 2.4- Diamino-6-diazoacetylpyrimidine (R1 = K.2 = NH2) 20 1.08 g (5 mmol) 2,4-dichloro-6-diazoacetylpyrimidine are mixed with 40 ml of absolute ethanol, heated under reflux and in the boiling ethanolic solution for 2 hours, an intensive stream of ammonia is passed. After cooling the reaction mixture, the precipitate formed is filtered off, washed twice with ethanol, dried and recrystallized from tetrahydrofuran. The yield of 2,4-diamino-6-diazoacetylpyrimidine is 0.55 g (67%). Decomposition temperature is 195 ° C. Found,%: C 40.32, H 3.30. N 47.28. C6HeN60.

Calculated,%: C 40.45, H 3.40, N 47.17.

Example 13 30 2-Chloro-4-methoxy-6-diazoacetylpyrimidine (R5 - Cl, Rö - 0CH3)

To a solution of 1.08 g of sodium methanolate in 20 ml of methanol, 1.08 g (5 mmol) of 2,4-dichloro-6-diazoacetylpyrimidine are maintained at a temperature of the reaction mixture with vigorous stirring within the range of 0 to 5 ° C, added. After 4 hours, the loose residue is filtered, washed with methanol, dried on the filter and recrystallized from benzene. The yield of 2-chloro-4-methoxy-6-diazoacetylpyrimidine is 0.33 g (75%). Melting point is 138-140 ° C.

Found,%: C 39.67, H 2.29, N 47.28. C7H5N4O2CI.

40 Calculated,%: C 39.63, H 2.35.

81 2 05 1 1 27

Example 14 2-Chloro-4- (N-piperidyl) -6-diazoacetylpyrimidine (R5 = Cl, Rg, “N-piperidyl)

To a solution of 0.8 ml (5-fold excess) of piperidine in 20 ml of abs.ethanol, 760 mg (3.6 mmol) of 2,4-dichloro-6-diazoacetylpyrimidine are added and thoroughly mixed together room temperature for 6 hours, the reaction mixture is cooled to 0 ° C, the yellowish residue is filtered off, washed with cold ethanol and dried. The yield of 2-chloro-4- (N-piperidyl) -6-diazoacetylpyri-10 midine is 600 mg (65%). Melting point is 102-104 ° C.

Found,%: C 49.84, H 4.56. C ^ H ^ ^ Od.

Calculated,%: C 49.72, H 4.52.

Example 15 2-Chloro-4-phenylhydrazine-6-diazoacetylpyrimidine 15 (R5 = Cl, R $ = NHNHPh)

To a solution of 648 mg (6 mmol) phenylhydrazine and 0.5 ml triethylamine in 10 ml methanol is added 651 mg (3 mmol) 2,4-dichloro-6-diazoacetylpyrimidine (prepared as described in Example 1). The mixture is stirred at room temperature for 3 hours. The resulting bright yellow residue is filtered off, washed with cold methanol and dried. The yield of 2-chloro-4-phenylhydrazino-6-diazoacetylpyrimidine is 550 mg (64%). Melting point is 152-154 ° C.

Found,%: C 50.14, H 3.08. Cj ^ HgN ^ OCl.

Calculated,%: C 50.0, H 3.13.

Example 16 2- Chloro-4-phenylazo-6-diazoacetylpyrimidine (R5 = Cl, R $ = -N = N-Ph) 280 mg (1 mmol) 2-chloro-4-phenylhydrazo-6-diazoacetylpyrimidine, prepared as in Example 15 above, in 10 ml of benzene in the presence of activated, powdery manganese dioxide, are boiled for 6 hours with a Dean-Stark trap (to distill eluent water). A warm benzene solution is separated from the manganese dioxide residue by filtration. The solution is evaporated and a clear orange precipitate is recrystallized from benzene. The yield is 35,196 mg (70%). Melting point is 116-117 ° C.

Found,%: C 50.4, C 4 HyNgOCl.

Calculated,%: C 50.3.

Example 17 3-Phenyl-4-diazoacetylsydnon 40 2.24 g (0.01 mol) N-phenyl-N-nitroso-N-aminomalon acid and 10 ml 8120511 A-28 thionyl chloride are stirred at 50 ° C for 20 hours the excess thionyl chloride is distilled off and the residue is extracted with 20 ml of ether. The ethereal solution is added dropwise with stirring for 30 minutes to an ethereal solution of diazomethane cooled to -10 ° C and prepared by alkaline decomposition of 10 g of nitrosomethyl urea. The reaction mixture is cooled to -30 ° C and the residue obtained is filtered and dried, then crystallized from benzene. The yield of 3-phenyl-4-diazoacetylsydnon is 1.2 g (52%). Melting point is 10 183-184 ° C (dec.). Rf 0.57 (system benzene-ethyl acetate, 3: 1),

Silufol UV-254.

Found,%: C 52.31, H 2.50. C10H6N4O3.

Calculated,%: C 52.17, H 2.61.

Example 18 A polycrystalline layer of 2-diazoacetylquinoline having a thickness of 1.5-2.0 µm is formed between two quartz plates by pouring from a solution. Registration of an image on the obtained material is performed by means of a beam from an optical quantum generator (Cd-He 0QG). λ = 325 nm; E = 0.01 J, τ = 15 sec., D = 0.38. The image thus obtained has a dark brown color against a light yellow background. The image is stable when stored in the dark - no reduction in optical density for 6 months is observed. After storing the image in scattered daylight, the half-life period of the contrast drop is 2 days.

25 Example 19

Under conditions similar to those specified in Example 18 above, a photosensitive material is prepared from 5-nitro-2-diazoacetylquinoline and image recording is performed by full flow from a mercury lamp E = 1.3x10 ^ W / cm ^, 30 τ = 40 sec., D = 0.34). A brown image against a light yellow background is obtained. The image is stable when stored in the dark - no reduction in contrast is observed for 6 months. When the image is stored in scattered daylight, the half-life of the contrast reduction is 5 days.

35 Example 20

A polycrystalline layer of 8-nitro-2-diazoacetylquinoline at a concentration of 1.6 mg / cm 2 is deposited on a barite-treated paper. An exposure is performed by a master plate by means of a full current from a mercury lamp (E = 1.3x10 ”^ W / cm ^, 40 τ = 20 sec., D = 0.31). The image color and stability are similar 8120511 29 to those mentioned in the previous example 19.

Example 21

A polycrystalline layer of 4-methyl-2-diazoacetylquinoline is deposited on a plate of Silufol-UV-254 at a concentration of 2.0 mg / cm 2. Recording of the image is performed under conditions similar to those described in Example 19 (λ = 325 nm; E = 0.01 W / cm ^, τ 50 sec, D = 0.30). A brown image is thus obtained, which can be kept in the dark (no reduction of contrast is observed after 6 months of storage). In the case of storing the image in scattered daylight, the half-life period of the contrast deterioration is 4 days.

Example 22

A photosensitive layer containing 2-diazoacetylquinoline at a concentration of 3.5 mg / cm 2 is applied to a barite-treated paper. The exposure is performed by a negative by means of a lamp with a set of light filters: yellow glass - 10 (6 mm) and blue glass - 15 (3 mm) at λ = 404-436 nm, the integral irradiation energy pf E = 4.2 x 10- w / cm ^. The exposure time is 10 min. Dark violet images with an optical density of D = 0.45 are obtained. Stability and color of the images are similar to that described in Example 18 above.

Example 23

A polycrystalline layer of 2,4-bis-diazoacetylpyridine with a thickness of 1.5-2.5 µm is formed between two quartz plates by pouring from a solution. The recording of the image is performed on the material thus treated by means of a beam from a Cd-He laser (λ = 325 nm; E = 0.01 W / cm ^, τ = 10 sec., D * 0.34 ).

The images obtained are of a brown color against a light yellow background. The image is stable when stored in the dark - no deterioration of contrast is observed after 6 months. After storing the image in scattered daylight, the half-life period of the contrast deterioration is 5 days.

Example 24

Under conditions similar to that specified in Example 23 above, a photosensitive material is prepared based on 2,4,6-trisdiazoacetylpyridine and the recording of an image is performed by full flow from a mercury vapor lamp radiation (E = 1.3x10-2 w / cm ^, τ * 30 sec, D = 0.28).

A steely color image against a light yellow background is obtained. The image is tenable when stored in the dark - no stress decay was observed for 6 months. After storing in scattered daylight, the half-life period of the contrast deterioration of the image is two days.

Example 25 5 A polycrystalline layer of 2,4,6-trisdiazoacetylpyridine is applied to a concentration of 1.3 mg / cm 2 on a barite-treated paper. The exposure is performed by a master plate by means of a full current from a mercury lamp (E = 1.3x10 2 W / cm 3, x = 30 sec, D = 0.25). The stability and color of the image are similar to the values indicated in Example 24.

Example 26

A polycrystalline layer of 2,6-bis-diazoacetyl-3-nitropyridine is applied to a Silufol UV-254 plate at a concentration of 2.5 mg / cm ^ <Image registration under conditions of type-15 equal to that specified in example 23 (E = 0.01 W / cm 3, X = 5 sec, D = 0.36).

A brown image is thus obtained which is "stable in the dark (no contrast deterioration is observed after 6 months of storage). When the image is stored in scattered daylight, the half-value period of the contrast deterioration is 3 days.

Example 27

A polycrystalline layer of 2,4-dichloro-6-diazoacetylpyrimidine with a thickness of 2.0-2.7 µm is applied from a solution between two quartz plates. Registration of an image on the material thus prepared is performed by means of a beam from a Cd-He laser (λ = 325 nm; E = 0.01 W / cm ^, χ = 15 sec., D = 0 , 29). The images obtained have a bright brown color against a light yellow background. The images can be stored in the dark - no contrast deterioration is observed after storage for 6 months. When stored in scattered 30 daylight, the half-life period of the contrast deterioration of the image is 25 days.

Example 28

A photosensitive layer containing 3-phenyl-4-diazoacetylsydnon in chloroform is applied to a barite-treated paper by pouring at a concentration of 0.95 mg / cm 2 and then dried.

The sample thus prepared is used as an actinometer to measure the dose of UV radiation at λ = 365 nm (a lamp with a set of light filters: - 10 + UV glass - 2 + UV glass - 4). Dose measurement is performed by a ferric oxalate actinometer according to a known method (see J. Cavert et al., Photochemistry, MIR Publishing 8 1 2 0 5 1 1 31

House, Moscow, 1968, pp. 625-627).

The optical density of the exposed layer is measured by a densitometer R-519 (MacBeth Co., Great Britain) using a blue light filter. A straight calibration line 5 is plotted from the measurement results according to the relationship D against log H, which graph is used for further measurements. Control measurements taken at 1 day, 1, 3, and 6 months have shown similar results within the experimental phase range.

Industrial Applicability The compounds of the foregoing general formula (I) of the present invention manifest photosensitive properties and can be used for the manufacture of materials for silverless photography, information recording materials and for all other applications of photosensitive compounds: photochemical pro-15 processes of information registration, light reproduction, microfilms.

8120511

Claims (18)

1. a-Diazoacetyl derivatives of aromatic nitrogen-containing heterocyclic compounds of the general formula: 5 0 II Het - C - CHN2 (I) in which Het 10 \ ^ 2 ^ 7 Ou ^ J © (¾ Ί®ί R, N fis H represents Npx% A>, wherein R 1, R 2, R 3 and R 4 represent hydrogen or NO 2 or COCHN 2 groups, R 5 and R 9 may be the same or different and each represents 20 chlorine, OH, NH 2, OCH 3, N-piperidyl, NHNHPh, N ^ Ph, OPh, 8-mercaptoquinolyl or 2-mercaptoquinolyl and R7, Rg and Rg may be the same or different and each represent hydrogen or CH3 or NO2 groups. 2. a-Diazoacetyl derivatives of aromatic nitrogen-containing hetero-cyclic compounds according to claim 1, characterized in that they correspond to the formula: 13 30 ^ 35, where R 3 represents CO 2 CH 2 R 2 = R 2 = R 4 = H; when R1 = R3 represent COCHN2 R2 85 R4 = H or when R1 represent COCHN2 and R4 represent NO2 R2 = R3 = H. 3. α-Diazoacetyl derivatives of aromatic nitrogen-containing heterocyclic compounds according to claim 1, characterized in that they correspond to the formula : 8120511 i n N COC-HN * where when R5 represents a chlorine atom Rg represents a chlorine atom or an OCH3, NH-NHPh, N = NPh, OPh, N-piperidyl, 8-mercaptoquinolyl or 10 2-mercaptoquinolyl group and when R5 = Rg it propose an OH or NH2 group. OrDiazoacetyl derivatives of aromatic nitrogen-containing heterocyclic compounds according to claim 1, characterized in that they correspond to the formula: 15 R $, ^ 7 ml "COCHNj. 20 * S, where when R7 = Rg = R9 this hydrogen atom, when Rg is NO2 is, Ry = Rg and hydrogen, when Rg is NO2 R7 = Rg represent hydrogen and when R7 NO2 is 25 or CH3, Rg = Rg and represent hydrogen 5. α-Diazoacetyl derivative of aromatic nitrogenous heterocyclic compounds according to claim 1, characterized that this derivative has the formula: 30-COCHHT J ©. -35 and is 3-phenyl-4-diazoacetylsydnon. 6. Photosensitive material containing a substrate and a photosensitive polycrystalline layer, characterized in that the photosensitive polycrystalline layer is formed by an α-diazoacetyl derivative of 40 aromatic nitrogen-containing heterocyclic compounds of the general formula: 8120511. Het - C - CHN2 5 wherein Het represents "Ift 5 r9 O", where R 1, R 2, R 3 and R 4 each represent hydrogen or the groups NO 2 or COCHN 2, R 5 and R 9 may be the same or different and each chlorine or the groups OH, NH2, OCH3, N-piperidyl, NHNHPh, N = Ph, OPh, 8-mercaptoquinolyl or 2-mercaptoquinolyl and R7, Rg and R9 may be the same or different and each represent hydrogen or the groups CH3 or NO2. Photosensitive material according to claim 6, characterized in that the photosensitive polycrystalline layer is formed by an α-diazoacetyl derivative of aromatic nitrogen-containing heterocyclic compounds of the formula: 25 XT Rv ^ 'N ^ COchN ^ where when R3 represents COCHN2 R ^ = R2 = R4 = H; when R] ^ = R3 represent COCHN2 R2 = R4 = H or when R ^ 35 COCHN2 and R4 represent NO2 R2 = R3 = H. Photosensitive material according to claim 6, characterized in that the photosensitive polycrystalline layer is formed by ordiazoacetyl derivatives of aromatic nitrogen-containing heterocyclic compounds of the formula: 81 2 05 1 1 O% N COCH, where when R5 represents chlorine, Rg is chlorine or is an OCH3, N-pipididyl, 8-mercaptoquinolyl or 2-mercaptoquinolyl group and when R5 R5 both represent an OH or NH2 group. Photosensitive material according to claim 6, characterized in that the photosensitive polycrystalline layer is formed by cc-diazoacetyl derivatives of aromatic nitrogen-containing heterocyclic compounds of the formula: 15 Re R-7 N COCHNj. Rs 20 where when R7 * Rg = R9 represent hydrogen, when R9 represents NO2 R7 = Rg and represent hydrogen, when Rg represents NO2 R7 = R9 and represent hydrogen and when R7 represents NO2 or CH3 represent Rg = Rg and hydrogen. The photosensitive material according to claim 6, characterized in that the photosensitive polycrystalline layer is formed by 3-phenyl-4-diazoacetylsydnon having the formula: 30 1 8120511. Claims changed according to International Patent Application PCT / SU 81/0079 1. Or- Diazoacetyl derivatives of aromatic nitrogenous hetero-5 cyclic compounds of the general formula: 0 Het - C - CHN2 (I) 10 wherein Het ft, ks ft »ft-ι Ph Ή1 'iQl ί © (15 ft, R, NT ^" ^ 0 «3, wherein, R 2, R 3 and R 4 represent hydrogen or NO 2 or CO 2 CH 2 groups, R 5 and R 9 may be the same or different and each is chlorine or OH, NH 2, OCH 3, N-piperidyl, NHNHPh, N = NPh, OPh 8-mercaptochinolyl or 2-mercaptoquinolyl and R7, Rg and Rg may be the same or different and each represent hydrogen or CH3 and NO2 groups 2. CrDiazoacetyl derivatives of aromatic nitrogenous heterocyclic compounds, characterized in that they correspond to the formula: 30 o K * N COCHN ^ 35 where when R3 represents COCHN2% = R2 = R4 = H; when R1 'R3 represent COCHN2 R2 = R4 = H or when R1C0CHN2 and R4NO2 represent R2' R3 = H. 3. α-Diazoacetyl derivatives of aromatic nitrogen-containing heterocyclic compounds according to claim 1, characterized in that they correspond to the formula : 11 205 1 1 if K * ö / sf COCH where when R5 represents chlorine Rg represents chlorine or an OCH3, NH-NHPh, N - NPh, OPh, N-piperidyl, 8-mercaptoquinolyl or 2-mercapto-10 quinolyl group and when R5 = Rg these represent an OH or NH2 group. Α-Diazoacetyl derivatives of aromatic nitrogen-containing heterocyclic compounds according to claim 1, characterized in that they correspond to the formula: IQÉ j 'W C0CHNa 20 where when R7 = Rg = Rg they each represent hydrogen, when R9 represents NO2 R7 * Rg and hydrogen represent, when Rg represents NO2 R7 = R9 and hydrogen and when R7 represents NO2 or CH3, Rg = Rg and hydrogen. Α-Diazoacetyl derivative of aromatic nitrogen-containing heterocyclic compounds according to claim 1, characterized in that it has the formula: 30 has Ph ^ K / _ ^ COCHN * Ï®T ΝΥΛ> 35 and is 3-phenyl-4-diazoacetylsydnon. 6. Photosensitive material containing a substrate and a photosensitive polycrystalline layer, characterized in that the photosensitive polycrystalline layer is formed by an α-diazoacetyl derivative of 40 aromatic nitrogenous heterocyclic compounds of the general formula: 8120511 3 θ 0 II It - C - CHN2 5 where Het Rs Re Rt ^ 7 'ή.' j £ l (êtó) ot Jöi kjj 'n γττ Nv0' ^ 0 R, 15 where R], R2, R3 and R4 each represent hydrogen or NO2 or COCHN2 groups, R5 and Rg may be the same or different and each chlorine or the groups OH, NH2, OCH3, N-piperidyl, NHNHPh, N = NPh, OPh, 8-mercaptoquinolyl or 2-mercaptoquinolyl and R7, Rg and R9 may be the same or different and each hydrogen or CH3 or NO2 groups introduce. 7. Photosensitive material according to claim 6, characterized in that the photosensitive polycrystalline layer is formed by ot-diazoacetyl derivatives of aromatic nitrogen-containing heterocyclic compounds of the formula: R * ~ ifiTR "where when R 3 is COCHN 2 R] ^ = R2 = R4 = H; when R ^ = 35 R3 represents COCHN2 R2 = R4 = H or when R ^ represents COCHN2 and R4 represents NO2 R2 = R3 = H. Photosensitive material according to claim 6, characterized in that the photosensitive polycrystalline layer is formed by cr-diazoacetyl derivatives of aromatic nitrogen-containing heterocyclic compounds of the formula: 8120511 * Γ J 3 «β Μ ^^ N ^ COCHN ^ where when R5 represents chlorine, chlorine or an OCH3, N-pipididyl, 8-mercaptoquinolyl or 2-mercaptoquinolyl group, and when R5 represents Rg these represent an OH or NH2 group. Photosensitive material according to claim 6, characterized in that the photosensitive polycrystalline layer is formed by α-diazoacetyl derivatives of aromatic nitrogen-containing heterocyclic compounds of the formula: QÉ TT COCHN »Λ '20 where when R7 Rg = Rg this hydrogen when Rg represents NO2 represent Ry = Rg and represent hydrogen and when Rg represents NO2 represent R7 = Rg and represent hydrogen. 10. The photosensitive material according to claim 6, characterized in that the photosensitive polycrystalline layer is formed by 3-phenyl-4-diazoacetylsydnon having the formula: COCHN, 30 I (?) 1 1120511 -----