DE3152651T - α-Diazoacetyl derivatives of aromatic nitrogen-containing heterocycles and a light-sensitive material - Google Patents

Description

37 339 u / va

θ (- DIAZOACETYL DERIVATIVES OF THE AROMATIC STICKSTOPPIC HETEROCYCLES AND A LIGHT SENSITIVE

MATERIAL

Field of technology

The present invention relates to new chemical compounds, specifically to o ^ - diazoacetyl derivatives of the aromatic nitrogen-containing heterocycles and to a photosensitive material prepared on the basis of said new compounds.

Prior art

As structural analogues to the compounds of the invention can Diazoazetophenone 0 R - / Q \ - CCHSl _z R = Ct, CH _3, OCU _3, ATOF

be considered.

In addition, as structural analogues to the novel compounds according to the invention, Ib- and Ϋ- diazoaze tylpyridines of the formula:

COCHAk ■ COCNN _Z

(Qf

N '

be considered.

The structural analogues listed have no light-sensitive properties. Some of them were previously used to study the chemical reactivity of the diazo carbonyl group.

Of the known substances that are sensitive to light, diazotype compounds may be mentioned, for example, Spiropyrans, derivatives of triarymethane dyes (M.W.Alfimov, O.B. Jakuschewa "Advances der scientific photography ", Moscow, 1978, Verlag Nauka, see Volume XIX, page 125, in Russian).

The known photosensitive compounds

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however, have a number of disadvantages. So are For example, the diazotype compounds are only sensitive to the ultraviolet light and form a picture latent image that requires the process of ammonia evolution. The colored picture of the spiropyrans discolored over time; so is the largest Half-life of discoloration in the dark is about 30 hours, which means that it can be kept on its for longer Based on recorded information makes impossible.

Sidnon derivatives are known, for example 4-bromo-3- (3-pyridyl) -sidnon, which are used in Aktiometers for Indication of X-ray radiation (CSSR copyright certificate 172686, class G03C 1/72, published in 1979),

3,3-trimethyl-6 is known to use a solid solution of I, ^{r-nitro-spiropyran} in Xthylzellulose in Aktinometera of UV radiation (EC Achalkazi al ".At the use of photochromic materials as an actinometer" et _f release of the Academy of Sciences of the Russian SSR, 1969, vol. 55, pages 81-84).

The use of said connection ensures a high speed of measurements and good reproducibility. However, time may Photometry after the end of the exposure of the actinometer due to the significant speed of dark discoloration in the latter 40 seconds exceed.

'Among the substances that have light-sensitive properties show in polycrystalline layers on which the visible image is directly in the exposure process developed without requiring subsequent development is the use of Salicylidenanilinen (anilene) as a light-sensitive polycrystalline component in the materials for

Recording of the optical information with HiITe a laser or another source of UV radiation (W.A. Bartschewskij, G.I. Laechkow, W.A. Zecholekij "Photochromism and its application", Chimija Publishing House, Moscow 1977, pages 35-36, 116; P.S. do et Appl. Optics, 1974, 13, 816-865; V.A. Bartschewekij, Journal of the Chemical Society of the USSR 1974, XIX, 4, 427).

The photosensitive materials using anilene are polycrystalline layers, matrixed by two transparent substrates (for example, quartz glasses) with a polycrystalline layer thickness of 1.8 to 2.2 μm . The information is recorded with a laser beam and is obtained an orange picture on a yellow background. The spectral light sensitivity is calculated using the following formula:

u -

where Hj \ is the exposure dose of the radiation

means that for the generation of a

Image with an optical density Dg »0.2 is necessary;

Qßj> the quantum yield of the formation of a

colored product is; the extinction coefficient of the Aus

represents the waveform at the wavelength;

£. ^. activating radiation means.

According to the known data, the spectral j is 0 photosensitivity of salicylidene anilines

H ^ 0.6 J / cm. A major disadvantage of the above light-sensitive materials is the reversibility of the coloring process (the longest half-life of the

Discoloration in the dark takes about 30 hours), the discoloration of the color image in light is significantly accelerated, which significantly limits the time of storage and utilization of the recorded information.

The present invention is based on the object of developing new compounds which are light-sensitive both in the ultraviolet and in the visible spectral range, on the basis of which it is possible to develop silver-free light-sensitive materials which allow stable, high-contrast images to be produced.

The above object is solved by the development of egg Diazoazetylderivaten of the aromatic nitrogen-containing Reterozyklen, in the present invention has the general formula

Hei-C-ChlN _z

in which Rj, Rp »R ^, R. are hydrogen or the groups KOp, COCHK ₂ ; Rr and R ^ can be identical or different and represent a chlorine atom, the groups OH, NH ₂ , OCH ₃ , K - piperidyl, NHNHPh, N = NPh, OPh, 8 - ifierkaptoquinolyl, 2 - mercaptoquinolyl; R ₇ , Rq and Rq can be the same or different and y / ater off atom, the groups CH ^, NO ₂ , have.

The new compounds mentioned have light

sensitivity. According to the invention, it is expedient to use oC-diazoacetyl derivatives of the aromatic nitrogen-containing heterocycles of the formula

where for R ₃ "COHN ₂ Rj - R ₂ · R ₄ " H, for R ^ ■ R. "COCHN ₂ R ₂ - R ₄ * H or for R ₁ * COCHN ₂ and R ₄ "

R ₂ = R ₃ = H, which have sensitivity in the visible and ultraviolet spectral regions.

In addition, one uses appropriately according to the invention c / - Diazoacetyl derivatives of the aromatic nitrogen-containing heterocycles of the formula

in which where R ₁ - = chlorine atom Rg for chlorine atom, the group OCH ₃ , N-piperidine, 8-mercaptoquinollyl, 2 -

/] ^ Is mercaptoquinolyl and when Rr = Rg the radicals R. and Rg denotes the OH or NH group, the light-sensitive Properties in the visible and ultraviolet spectral range own.

Furthermore, according to the invention, weckmassi used diazoacetyl derivatives of the aromatic nitrogen-containing heterocycles of the formula

COCHNp

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in which R ₇ = R _Q = R _g = H, for R ₉ = IiO ₂ - group R ₇ = R ₈ = H, for R _Q = KO ₂ - group R ₇ = R _g = H; with R ₇ = NO ₂ - or CH ₃ - group R ₃ = R _g = H, the photosensitivity both in the Ultravio] ctt- a If? also have in the visible spectral range.

In addition, according to the invention is used advantageously 3 - phenyl -A- diazoazetylsidnon of formula

^ O the sensitivity to light in both the ultraviolet light also has in the visible spectral range and at. the photo-conversion a yellow colored one Image generated.

In order to produce a stable, high-contrast '05 image, a light-sensitive one was used in accordance with the invention IvIaterial developed from a base and consists of a photosensitive polycrystalline layer, which is tylclerivat by an oi-Diaz.oaze aromatic nitrogenous ileterocycles of the

■ 3 3pm

general formula

in which Het for

-X

stands in which

Hydrogen or the

^l 2 »^ 3» ^Λ 4
Groups NO ₂ , COCHN ₂ mean} R, - and Rg can be the same or different and for chlorine atom, the groups OH, NH ₂ , OCH ₃ , N - piperidyl, NHNHPh, N = NPh, OPh, 8 - mercaptoquinolyl, 2 - Mercaptoquinolyl; Bthening; Ry, Rg and R "can be identical or different and hydrogen atoms, which represent groups CH ₃ , NOg, are formed.

To record the information with the help of lasers or another radiation source and generate

In order to produce contrast images (blue or brown images on a pale yellow background), a photosensitive material is used according to the invention, the polycrystalline photosensitive layer of which is composed of cL-diazoacetyl derivatives of the aromatic nitrogen

^ u containing heterocycles of the formula

Rs

in the at
* COCHN ₂ R

COCHN,

H; at I 2 » ^R 4

-R ₃ ■> 2 "

R ₃ = COCHN ₂ Rj s E ₂ = E = R. β.H or when R _x = group Rp »R,« H, is formed.

To record the information with the help of lasers or another radiation source as well as for Increase in contrast and stability of the

According to the invention, a photosensitive material is used, the photosensitive polycrystalline layer of which is formed by d- diasoasetyl derivatives of the aromatic nitrogen-containing heterocycles of the formula

CDCHN,

in which with R ₁ - «chlorine atom, Rg chlorine atom, OCH., group, N - piperidyl, 8 - mercaptoquinolyl, 2 - mercaptoquinolyl and with R, -« = R ^ the radicals R _c and R _c OH or NH ₂ - Group mean, is formed.

To record the optical information with the help of lasers, sources of UV radiation and of visible radiation (Jl ~ 450 nm) with generation stable, high-contrast images are used according to the invention a photosensitive material, its light-sensitive polycrystalline layer by c / -diazoacetyl derivatives of the aromatic nitrogen-containing heterocycles of the formula

* 7

in which R- * R _Q = R _g «H, with R _g = NO ₂ - group R- = Rq = H, with R" * NO ₂ - or CH ^ - group R _ß = = Rn = H, is formed .

For the manufacture of actinometers for indication the X-ray radiation and expansion of the range of the measured doses of UV radiation are used a photosensitive material whose photosensitive polycrystalline layer is represented by 3 phenyl - 4 diazoacetylsidnone the formula

is formed.

The novel of ~ diazoacetyl derivatives according to the invention of aromatic nitrogen-containing heterocycles it, applied to a base, to obtain stable images in the dark. Like the experimental Data showed no decrease in image contrast is observed in the dark within 6 months. At the Working with the image obtained in daytime scattered light, the half-life of the contrast reduction is 2 up to 40 days depending on the structure of the compound, which makes it possible to keep the recorded Exploiting information for a long time without noticeably reducing its quality. Compared to the Base of the images obtained from anile (orange Images on a yellow background) permit those obtained on the basis of the compounds according to the invention Materials, high-contrast images (bright brown or dark purple images on pale yellow Background) that are more suitable for reading the information. The sensitivity to light of the materials according to the invention is Η ^ · ~ Ο, Ι J / cm (at Λ »300 nm), that is to say is 6 times higher than the analogs based on

^ Anilen. '

Thus, it allows a comparison of the details of the investigations carried out with those according to the invention light-sensitive compounds with the information on the known silver-free light-sensitive materials

O lien (MW Alfimow, OBJakuschewa "Port Steps of Scientific Photographic · ¹ , XIX, Verlag Nauka, Koskau 1978, page 154), a number of advantages

- ier-

to recognize the compounds according to the invention.

I. Absence of the process of development in contrast to the diazotype, vesicular, photopolymerization, free radical, photo deformation, photothermopolymerization, Luminescent materials as well as the photosensitive polymers, the materials with physical development and the chromized colloids. It doesn't require any development photochromic and cyanotype materials only.

II. The materials with a light-sensitive layer based on the compounds according to the invention have a greater energetic light compared to photochroine and diazotype materials «

-? ?

sensitivity to (up to S 0.1 · IO J / cm to

- »2 2

S IO J / cm for the photochromic and even less for the cyantype materials). In the energetic - Photosensitivity surpass that according to the invention Connections some vesicular, photopolymerization, free radical, photo-forming, luminescent materials, photosensitive polymers, chromed Colloids and materials with physical development.

III. The materials based on the invention photosensitive compounds surpass some diazotype, vesicular, Photopolymerization, photo deformation, Photothermopolymerization, luminescent materials as well as the photosensitive polymers and materials with physical development.

IV. Compared to the photochromic materials, characteristic of the discoloration of the colored light over time is, the images obtained with the aid of the compounds according to the invention discolor not.

V. Exceed the compounds according to the invention in the spectral sensitivity in the long-wave

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tl

in the field of negative photosensitive polymers, the photo-molding, photothermopolymerization, Cyanotype and Xumineezenz compounds (see also M.V.Alfimov, O.B. Jakusheva "Advances in Scientific Photographic ", XIX, Bauka Verlag, Moscow 1978, pages 157-164).

Thus, the photosensitive ones of the present invention are superior Compounds according to the complex of photographic characteristics of various classes of known chemical silver-free photosensitive systems. Best way to carry out the invention The compounds proposed in the present invention are new and not described in the literature. As noted above, these represent photosensitivity Compounds containing o £ - dyazoacetyl derivatives of the aromatic nitrogen-containing heterocycles of the general formula

M-C-CHN _Z where Het is

15 2 6 51

■ j

in which Rj, R ₂ , R ₃ and H are hydrogen or the groups BO ₂ , COCHH ₂ ; R ₅ and R ^ can be identical or different and represent the chlorine atom, the groups OH, HH ₂ , OCH ₃ , H-piperidyl, HHNHPh, H «= NPh, OPh, 8-mercaptoquinolyl, 2-mercaptoquinolyl; R ", Rq, Rq can be identical or different and represent hydrogen atoms which represent groups CH ₁ , NO 2. The compounds proposed in the present invention can be obtained by known processes. For example, 2-diazoacetylquinolines of the general formula:

Rs

R ₉

in which R- = R _ß »R = H; when R _g = NO ₂ R ₇ = Rg ■ H; when R ₈ = NO ₂ R ₇ * R _g * H; with R ₇ = NO ₂ - or CH ₃ group Rg = Rg χ H, as well as 2 - diazoacetylpyridine derivatives of the general formula:

COCHNg

in which at R ₃ «COCHN ₂ R ₃ -« R ₂ = R ^ = H; when R ₁ = R ₃ = «COCHN ₂ R ₂ = R = H; or when R ₁ = COCHN, R ₄ = NO _2, group R ₂ = R ₃ = H, can be obtained by the process for the preparation of o £ - diazoketones, which is used, for example, in the preparation of oL diazoazetophenones (see preparation of the organic Chemie I, Ver. Chemie Weinheim, 1944, 359).

The general scheme of the procedure is as follows:

-, ar--

In the synthesis of Bisdiazoazetylpyridinen and Trisdiazoazetylpyridinen one starts from the corresponding the bis- and tri-carboxylic acids, e.g .:

CtOC ^N COCf NJHOC N COCHN ₁

The synthesis of the pyridyl-substituted carboxylic acids used as the starting product is carried out according to known methods Methods (see A.W. Sigger, S.M. Elvain, J.Am.Chem.Soc. 57, II35 (1935).

The 2-diazoacetylpyridine derivatives according to the invention and 2-diazoacetylquinolines differ from the known analogues not only in construction. The difference of the well-known diazoacetylpyridine and diazoazetophenone derivatives, they have a new one for analogous compounds previously unknown property, light sensitivity in the visible and ultraviolet spectral range, on.

Compounds which correspond to the general formula (I), namely 6-diazoacetylpyrimidine derivatives the general formula

COCHN ₁

in which at R ₁ - «= Cl * Rg ^ u ** chlorine atom, the group OCH-, H-piperidyl, 8-mercaptoquinolyl, 2-mercaptoquinolyl , and at R, -» Rg the radicals R, - and Rg die Group OH or NHp can also be prepared by known methods (see US-PS 4,025,515, class 260-256.4, published in 1977) by reacting 2,4-dichloro-6-diazoacetylpyrimidine with nucleophilic reagents of the general formula:

in which Rg has the above meaning, in the medium of an organic solvent (for example of methanol) or without this in a 2 to 5-fold excess of the nucleophilic reagent in the presence of a 2 to 3-fold excess of triethylamine (or without this) at a temperature of 0 to 80 ^° C. can be obtained within 30 minutes to 10 hours, depending on the specific reaction, and the subsequent separation of the end product by known methods. The 2 _f ^ -Dichlor-e-diazoazetylpyrimidine is obtained from accessible orotic acid by carrying out the following reactions in stages: OH Ct 9 ^£

Furthermore, the proposed in the present invention ^ -phenyl-A-diazoazetylsidnon of the formula

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according to the known process for the synthesis of sidnones with subsequent conversion into diazoketone the Arndt-Eistert reaction:

Ph-N-CH-COOH ^soee \ NO COOH

5 can be obtained.

According to the invention, it is for technical and economic reasons Reasons particularly useful to use the proposed new substances as light-sensitive components in Materials for recording optical information with the help of sources of UV radiation and the visible Radiation (JIi: 450 nm) to be used.

Any of these can be used as the base in the photosensitive materials according to the invention Commonly used materials such as paper, film, wood, etc. can be used for the purposes of this.

The photosensitive materials of the present invention with a polycrystalline layer based on the novel compounds according to the invention a number of advantages over the known on:

I. The new compounds according to the invention make it possible to generate images that are stable in the dark are. As the experimental data showed, no decrease in image contrast is observed within 6 months. When working with the received The half-life of the reduction in contrast is on average 2 to 40 days, which makes it possible to use the recorded optical To use information for a long time without noticeably lowering its quality.

2. In comparison with the images obtained on the basis of anilene (orange images on yellow Background) allow the materials on the

3 \ 52651

Basis of the connections according to the invention, rich in contrast Images (brown or blue-violet images on a pale yellow background to obtain readable are more appropriate to the information.

3. The photosensitivity of the materials based on the 6-diazoacetylpyrimidines is Hj \ = 0.2 to 0.4 J / cm ² (at λ * 300 to 350 mn), that is 1.5 to 2 times higher than that of the Analogs based on anilene. The photosensitivity of the materials based on the 2-diazoacetylquinolines is H ^ 0.1J / cm (at g = 300 nm), that is to say

6 times higher than the analogs based on anilene. The photosensitivity of the materials the basis of the 2-diazoacetylpyridine derivatives is

H ^ = 0.2 to .0.4 J / cm ² (at JU 300 to 350 nm), i.e. 1.5 to 2 times higher than with the analogs based on anilene.

It should be noted that the use of photosensitive materials is limited to what is described in the literature quartz documents described their use for recording the graphic information, for example The recording of spectra, etc. in the grapho encoders is limited, which limits working with these and makes it difficult to keep them.

The study of the materials based on the compounds of the invention using others Documents, for example of paper, of the Silufol UV-254 sheets, showed that these materials are suitable for the recording of information with the help of lasers or other sources of UV radiation as well as visible ones Radiation are suitable.

The tests we carried out proved that it was for technical and economic reasons It is particularly expedient to use the 3-phenyl-4-diazoazetylsidnone according to the invention as light-sensitive Component to be used in actinometers of UV radiation

J i S

those who are of great practical interest to the Adjustment of optical devices, focusing of the radiation from different sources, determination of the spatial ones Distribution of the radiation intensity of the laser as well as for other cases of the visualization of the UV radiation are.

An essential advantage of the actinometer based on the light-sensitive according to the invention 3-pkenyl-4-diazoazetylsidnons is the slow speed the process of discoloration, which makes it possible to increase the duration of photometry enlarge (at least 6 months in storage in the dark).

In addition, an important advantage of utilizing the light-sensitive properties of 3-phenyl-4-diazoacetylsidnone in actinometers is the broader range of measured doses of UV radiation (from 10 to 20 J / cra ² ). The substance according to the invention makes it possible to register significantly larger doses of UV radiation, which the airtinometer based on the known spyropyran does not guarantee.

The determination of the integral light sensitivity the substances according to the invention were made according to the following 5 methodology carried out:

a) Creation of a photosensitive layer

The light-sensitive layers were obtained by applying a solution of the respective diazoketone in Chloroform on baryta paper with subsequent evaporation of the solvent.

b) exposure of the photosensitive layer The exposure of the photosensitive layers

took place with the total current of the quartz mercury lamp, the integral power of which in the exposure level was 1.3 '· 10 ~ ² w / cm ² .

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/ 9

The 8th transmission factors form a geometric series with the module 1/2. As a result one a series of seven areas.

c) Measurement of the optical density of the individual areas

The measurement of the optical thickness of the individual areas was carried out on Soviet deneitometers and the densitometer RD-519 (Macbeth, England) using appropriate color filters when measuring colored samples. The information on the effect of the action of different doses of radiation on the light-sensitive layers was analyzed according to the characteristic curves (dependence of D on log H, where H is the exposure radiation dose in J / cm, which is the product of the luminous flux output E and the respective exposure time t ) . Since the optical densities of the image D = I were not achieved in any of the cases, the criterion D = 0.2 (above the fog) was used to estimate the photosensitivity. The data on the integral photosensitivity are given in Tables 1-3.

The determination of the spectral sensitivity was carried out on the SpectroBensitometer FCP-9 with quartz optics and Quartz mercury lamp carried out as a UV radiation source. The optical densities of the images obtained were semi-quantitative by comparison with the known densities of the images of the areas obtained at integral sensitometry. However, differ the intensities of the individual lines in the spectrum of the quartz-mercury lamp, which is why the information on the densities of the images on the individual radiation power the line were reduced (the information on the spectral distribution of the energy were previously obtained with the help of a thermocouple). the The curve of the spectral light sensitivity corresponds qualitatively to the absorption spectrum. The information on the

Spectral sensitivity are shown in the table. The resolving power of the layers based on the diazocarbony compounds according to the invention was determined on a resolver meter with subsequent examination of the images obtained under the microscope. For all the materials investigated, R> 900 mm * " ¹ .

Table I. Photosensitivity and physicochemical characteristics of the 2-diazoacetylpyridine derivatives

No.

Photosensitivity / _2

I. H H H H 0 , 14 * 0 , 01 χ 10 "* ⁵ 2 " COGHN ₂ H H H I. , 3 * 0, I χ ΙΟ " ⁵ 3. H H COGHN ₂ H I. , 0 * 0, I χ ΙΟ " ⁵ 4th COGHN ₂ H COCHN ₂ H I. , 4 * 0, I χ ΙΟ " ⁵ 5. COCHN ₂ H H NO ₂ I. , 2 * 0, I χ ΙΟ " ⁵

The resolving power of all compounds according to the invention is> 900 lines / mm. In the IR spectra of the compounds I, intense absorption bands of the N = N groups at 0 2100 cm "and absorption bands of the C = O and C = N groups at 1580-1640 cm ^{-1 are} observed.

Table 2. Photo- and physico-chemical properties of 6-diazoacetylpyrimidines

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- -str-

No.

R,

M.p.

⁰ C

Found,% Ber.,% Light Sensitivity Detection te,%

Cl Cl 145 Decomp.
185 25.65 25.81 ^S 0.2 (m ² / J) 70 I. Cl OCH ₃ 138-140 Decomp.
195 26.18 26.35 Ο, 5 · ΙΟ " ⁵ 75 2. Cl N-Pyp IO2-IO4 3. Photo parameters 26.20 26.37 0.25 · ΙΟ " ⁵ 65 3. Cl HHNHPh 152-154 29.01 29.12 Ο, 2 · ΙΟ " ⁵ 64 4th Cl K = MPh II6-II7 29.14 29.32 0.4 · ΙΟ " ⁵ 70 5. Cl OPh. 146 20.18 20.40 Ο, Ι5 · ΙΟ " ⁵ 50 6th Cl NHPh - 160 25.38 25.59 ο, 3 · ΐθ " ⁵ 56 7th Cl 8-Merkap- 156-
tochino- 158
tyl 21.11 21.24 Ο, 25 · ΙΟ ~ ⁵ 82 8th. Cl 2-Merkap- dec.
tochino- 150
lyi 21.09 21.24 Ο.3ΊΟ " ⁵ 87 9. OH OH 30.97 31.11 56 ΙΟ. H ₂ KH ₂ 46.89 47.19 0.5 «ΙΟ" ⁵ 67 II. table Ο, 25 · ΙΟ "" ⁵ the 2-diazoacetylquinolines

Nr.i Rg: R ₈ : R-: Light sensitivity

(m / y)

I.

2.1 i 0.2-10

-j

1 2. HO ₂ r 3 : 4 r 1.9 5 ΙΟ " ⁵ 3. H H H 1.8 ± 0.2 10 " ⁵ 4th H HO ₀ H 1.5 ± 0.2 ΙΟ ' ⁵ 5. H d
H NO ₂ 2.2 ± 0.15 ΙΟ " ⁵ H CH ₃ ± 0.2.

A comparison of the information on the according to the invention light-sensitive materials on the basis Investigations carried out on the compounds according to the invention with the information on the known silver-free photosensitive materials (Ii .- '. V. Alfimov /, 0.B.Jnkuschewn "Advances in scientific riioLev; raphie ", XlX, Verlag iJuukti, Loaküu 197U, page 154) reveals a number of advantages of the materials according to the invention (see Tables I and 2).

I. Absence of the process of development in contrast to the diazotype, vesicular, photopolymerization, free radical, photo deformation, photothermopolymerization, Luminescent materials so.vie the light-sensitive polymers, the .Materials with physical development and the chromized colloids. It doesn't require development just photochromic and cyanotype materials.

II. The materials with a photosensitive Layer based on the compounds according to the invention point towards the photochromic and diazotype materials a greater energetic light sensitivity (up to S 0.1 «10 J / cm compared to

—2 2
S 10 J / cm for the photochromic and even less for the cyanotype materials). In terms of energetic photosensitivity, the compounds according to the invention surpass some vesicular, photopolymerization, free radical, photoforming, luminescent materials, photosensitive polymers,

52651

Zl

chromed colloids as well as materials with physical Development.

III. The materials based on the invention photosensitive compounds surpass some diazotype, vesicular, Photopolymerization, photo deformation, photothermopolymerization, Luminescent materials as well as the photosensitive polymers and materials with physical Development.

IV. Compared to photochromic materials, characteristic of the discoloration of the color image over time is, the images obtained with the aid of the compounds according to the invention do not discolor.

V. The compounds according to the invention surpass in the spectral sensitivity in the long-wave range the negative light-sensitive polymers, the photosensitive photo deformation, photo thermopolymerization B-, Cyanotype and luminescence compounds (see also M.W.Alfimow, O.B. Jakuschewa "Advances of scientific photography ", XIX, Verlag Kauka, Moscow 1978, pages 157-164).

Thus surpass the light-sensitive ones according to the invention Compounds according to the complex of photographic characteristics of various classes of known chemical silver-free photosensitive systems. Table 4. Photographic characteristics of the photosensitive links

Mr. Photosensitive Development Area Stock Regi-

fabrics of diness

Spectrum of the

ralemp color image type sensitive speed

I. 2-diazoacetyl- none 300-450 + ampli-

quinoline tuden

(inventive. type according to)

I. 2. 2 3 4th 5 6 3. 2-diazoacetyl
pyridines
(inventive
according to) none 300-450 + Ampli
do
Type 4th 2-diazoacetyl
pyrimidines
(inventive
according to) none 300-450 + Ampli
do
Type 5. 3-phenyl-4-
diazoacetyl
sidnon
(inventive
according to) none 300-450 + Ampli
do
Type 6th Diazotype
fabrics treatment
with ammo
niak 300-500 + Ampli-
tude
Type 7th Vesicular
Fabrics through
warmth 300-500 + Phases
Type 8th. Photochromic
Fabrics none 250-700 - Ampli
do
Type,
Phases
Type 9. Photosensitive
liche poly
mere Laundry in
correspond
better
solution 250-400 + Relief.
Phases *
Type ΙΟ. Photopolymer
risky
fabrics Laundry in
correspond
better
solution 280-700 + Relief
Phase
Type II. Free radical
cal substances optical 300-500 + Ampli
do
Type 12th Chromed
Colloids 7 / ash in
water 250-580 + Relief.
Phases «
Type 13th Photoverfor
mung substances through
warmth 250-400 + Relief
Phases
Type Photothermal
polymerisa-
tion substances through
warmth 220-260 + Relief
Phases
Type

IS

ο μ; ο c 5 1

3 i b26

14th Cyanotype
fabrics none 280-400 + Ampli
do
Type 15th Luminescence
Btoffe optical 250-380 Ampli-
tude
Type

In order that the present invention may be better understood, the following examples are given of how it is actually carried out cited.

Example I. 2-diazoacetylcholine (R ₇ = R ₈ «= Rq = H)

An ethereal solution of diazomethane, obtained by alkaline decomposition of 12 g of nitrosomethylurea with intensive stirring and cooling to a temperature of from - 15 ⁰ C, is added dropwise to an ethereal solution of 4.5 g (0.024 mol) Chinaldinsäurechlorid within 20 minutes. After the completion of Zutrupfens stirring the reaction mixture for another 30 minutes without cooling, by bringing the temperature to 0 ⁰ C. The ether is evaporated and the crystalline precipitate is recrystallized from hexane. The yield of 2-Diaziazetylchinolin is 3.2 g (76%), melting point 73-74 ⁰ C.

Found, %: C, 67.18; H 3.46. C ₁₁ H ₇ N ₃ O. Calculated,%: C, 67.01; H 3.55. R _f = 0.64 (benzene / xethyl acetate system, 9: 1), Silufol UV-254.

Example 2 . 4-Kethyl-2-diazoacetylquinoline (Rg ^s Rq = H, R ~ = CHo),

This compound is obtained under the conditions analogous to those described in Example I. The yield is 72 %, the melting point 68 ^° C.

Found 'C 68, II; .H 4.37. CjjHqN ^ O. Calculated, %% C 68.25; H 4.27. R _f = 0.72 (benzene / ithylazetat-Syetem, 9: 1), Silufol UV-254.

O ■> r λ ρ γ / ι

ο \ ο Aod I

Example 3. 4-Nitro-2-diazoacetylquinoline

_{7 2}

A solution of 2.37 g (IO mol) of 4-Nitrochinaldinßäurechlorid in 40 ml of absolute ether is added dropwise within 20 minutes to a to a temperature of - 15 ⁰ C cooled ethereal solution of diazomethane, obtained from 20 g of nitrosomethylurea, with vigorous stirring to . The reaction mixture is then cooled to a temperature of from -35 to -40 ^° C. and is kept at this temperature for 1 hour. The precipitated crystalline precipitate is filtered and recrystallized from hexane. The yield is I _f 59 g (66%), the melting point 105 ^° C.

Found, %: C, 54.40; H 2.51. ⁰ H ¹¹ A ^ - Calculated,%: C 54.55; H 2.48. R _f = 0.53 (benzene / ethyl acetate system, 6: 1), Silufol UV-254.

Example 4. S-nitro ^ -diazoacetylquinoline (R ₇ = Rg = H ₁ R _8. N0 ₂₎

This compound is obtained under the conditions analogous to those described in Example 3 from 5-nitroquinaldinic acid chloride and diazomethane. The yield is 70%, melting point 133-134 ⁰ C. Found,%: C 54.38; H 2.44. C ₁₁ H ₆ N ₄ O ₃ . Calculated, £: C, 54.38; H 2.44. ^c n ^H 6 ^N 4 ° 3 «Calculated,%: C 54.55; H 2.48. R _f * 0.55 (benzene / ethyl acetate system, 6il), Silufol UV-254.

Example 5 . 8-nitro-2-diazoacetylquinoline (R ^ = UO ₂ , R ₇ = R ₈ = H)

This compound is obtained under the conditions analogous to those described in Example 3 from e-nitroquinaldic acid chloride and diazomethane. The yield is 58%, melting point 155-157 ⁰ C (decomposition). '

Found,%: C, 54.42; H 2.47. ^c n ^H 6 ^R 4 ^O 3 • ^Bereclinet »# ^: C, 54.55; H 2.48. R _f «= 0.52 (benzene / ethyl acetate system, 6: 1), Sulufol UV-254.

i ~ o .eel

ύ _t : OJ ¹ I.

Example 6. 2-Diazoacetylpyridine (Rj = R ^ * Ro ^β Rj »H) Stage Ij Preparation of af-picolinic acid chloride 20 g of 0 (-picolinic acid are boiled with 38 g of thionyl chloride in the presence of 0.5 ml of dimethylformamide within 10 hours. the excess thionyl is distilled off, the residue is extracted twice, each with 40 ml of hexane, the hexane evaporated to and distilled to residue by the fraction of boiling point 76 -... 82 ⁰ C (IO Torr) collects the yield of ssure chloride is 15.7 g (69 %) .

Step 2: Preparation of 2-Diazoazetylpyrldin One ethereal solution of diazomethane, obtained from 27 g Hitrosomethylharnstoff, is added dropwise with thorough stirring and cooling to a temperature door from - 15 ⁰ C a solution of 7.1 g (0.05 mol) tf Picolinic acid chloride in 40 ml of absolute ether within 30 minutes. The mixture is stirred for a further hour by bringing the temperature to 0 ^° C. ' Man "the ether evaporated and the residue is crystallized twice from hexane. The yield of 2-Diazoazetylpyridin is 5.2 g (71%), the melting point of 50 ⁰ C.

Found,%: C, 48.82; H 2.70. C ₇ H ₅ K ^ O. Calculated C, 48.98; H 2.72. R = 0.51 (benzene / ethyl acetate system, 9: 1), Silufol UV-254.

Example 7 . 2.6-bisdiazoacetylpyridine (R ₁ * COCHN ₂ , R ₂ = R ₃ = R ₄ = H)

Stage I: The 2,6-pyridinedicarboxylic acid dichloride is obtained under the analogous conditions described in Example 6 from 8 g of 2,6-pyridinedicarboxylic acid dichloride and an ethereal solution of diazomethane, obtained from 40 g of nitrosomethylurea. The deposited precipitate is filtered and recrystallized from methanol. The yield is 7.9 g (94 %) , the decomposition temperature 150 C.

Found, % i C 50.12; H 2.24. CgH ₅ N ₅ O ₂ . Calculated,%:

18 '

- -27 -

C 50.23; H 2.32. R _f * 0.46 (benzene / ethyl acetate system, 1: 1), Silufol UV-254.

Example 8 . 2,4-bisdiazoacetylpyridine (R- «COCHN ₂ )

Stages I and 2 are carried out under the conditions analogous to those described in Examples 6 and 7. The yield of 2,4-bisdiazoacetylpyridine is 82%, the melting point 155 ^° C. (decomposition).

Found,%: C 50.08; H 2.18. C ₉ H ₅ NcO ₂ . Calculated, ¹ %: C, 50.23; H 2.32. R _f - 0.33 (benzene / ethyl acetate system, 1: 1), Silufol UV-254.

Example 9 . 2,4,6-trisdiazoacetylpyridine (R

₁₃ R ₂ «R.« H)

Steps I and 2 are carried out under the conditions analogous to those described in Examples 6 and 7. The diazomethane is obtained when using tris acid chloride. The yield of 2,4,6-Trisdiazoazetylpyridin is 95% _t the decomposition temperature I6O-I65 ⁰ C.

Found, %: C, 46.48; H 1.91. ^c n ^H 6 ° 3 ^K 7 · Calculated C 46.64; H 1.77. R _f = 0.24 (benzene / ethyl acetate system, 1: 1), Silufol UV-254.

Example IO . 2,6-bisdiazoacetyl-3-nitropyridine (R - COCHN ₂ , R ₂ »R ₃ « H)

Stage I: Production of S-nitro ^^ - pyridine carboxylic acid 83 g of potassium permanganate are dissolved in 1.4 liters Water with heating and gives 17.6 g of 3-nitro-2,6-lutidine to. The mixture is boiled for 2 hours, the precipitate is filtered off and the mother liquor is evaporated 150 ml, acidified with concentrated hydrochloric acid

a pH of I to 2, cools, the orange-colored crystalline precipitate which has precipitated is filtered off and dried. The yield is 14 g (48 %). Stage 2: 3-Nitro-2,6-pyridinkarbon-βäuredichlorid is obtained under the analogous conditions mentioned in Stage I of Example 7. The yield

.-- .: ■ 315.2851

ti

- ^ erbe carries 56%.

Step 3: 2 _f 6-Bi8diazoacetyl-3-nitropyridine are obtained among the . in Step 2 Example 6 dee analogous conditions described. It is recrystallized from Ither. The yield is 58%, the melting point 108 ^° C.

Found, %: C, 41.42; H 1.48. C ₉ H ₄ N ₆ O ₄ . Calculated,%: C 41.54. R _f «0.75 (benzene / ethyl acetate system, 3: 1), Silufol UV-254.

Example II. 2,4-dichloro-6-dia5D-acetylpyrimidine (R ₅ = R ₆ = Cl)

15.6 g (0.1 mol) of orotic acid is heated with 37 g (0.22 mol) of phosphorus (Y) oxychloride at a temperature of 107 ⁰ C within IO hours, the phosphor (Y) oxychloride is distilled off, add 48 g of thionyl chloride and a few drops of dimethylformamide. Heating the Reaktinsgemisch within 48 hours, the excess thionyl chloride is distilled off and the residue is distilled in vacuo by C / collect the fraction of boiling point 75-90 ⁰ I Torr. The yield of 2,4-dichloro-6-pyrimidinkarbonsäurechlorid is 7.7 g (43.6%), melting point 28-30 ⁰ C.

An ethereal solution of diazomethane (250 ml) dried over the solution of potassium hydroxide, obtained in the decomposition of 25 g of N-Mtroazomethylurea by the action of 140 ml of 40% aqueous solution of caustic potash, is added dropwise with vigorous stirring and cooling of the reaction mixture temperature of (-10) to (-15 ⁰ C) a solution of 7.7 g of 2,4-dichloro-6-pyrimidin-carboxylic acid to 30 ml of absolute ether in the course of 20 minutes. The precipitate formed is filtered off, washed with ether and dried on the filter.

The yield of 2,4-dichloro-6-diazoacetylpyridimine is 5.5 g (70 %) , the melting point 145 ° C. (decomposition).

Found, %: C, 33.04; H 0.95. C ^ H ₂ K.OCI ₂ . Calculated, % i C 33.21? H 0.95.

Example Ha . 2,4-Dioxy-6-diazoacetylpyrimidine To a suspension of 1.08 g (6 × nmol) of finely ground 2,4-dichloro-6-diazoacetylpyrimidine in 20 ml of water is added 3 g (30 × nmol) of triethylamine and boiled until it is completely dissolved dee precipitation. The solution is evaporated to 5 ml, the precipitate which has separated out after cooling is filtered, washed twice with cold water (1 ml each time) and recrystallized from water. The yield is 500 ml (56 %) , the decomposition temperature 185 C.

Found, %: C 39.62; H 2.70. CgHcN ₄ O ₃ . Calculated, %: C 39.79; H 2.78.

Example 12. 2,4-Diamino-6-diazoacetylpyrimidine (R

₁ * R ₂ =

1.08 g (5 mUol) of 2,4-dichloro-6-diazoacetylpyrimidine are mixed with 40 ml of absolute ethanol, heated to boiling, and an intensive stream of ammonia is introduced into the boiling ethanol solution within 2 hours. After the reaction mixture has cooled, the precipitate which has separated out 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 %) , the decomposition temperature 195 ° C.

Found, %: C 40.32; H 3.30; N 47.28. CgH ^ NgO. Calculated, %. C 40.45; H 3.40; N 47.17.

Example 13 . 2-chloro-4-methoxy-6-diazoacetylpyrimidine (R ₅ = Cl, R ^ = OCH ₃ )

A solution of 1.08 g of sodium methylate in 20 ml Methanol is added with vigorous stirring 1.08 g (5 mmol) of 2,4-dichloro-6-diazoacetylpyrimidine at a Temperature of the reaction mixture from 0 to 5 ° C to. After 4 hours, the fluffy precipitate is filtered off, washed with methanol and dried on the filter

: ■! 52651 3 /?

and recrystallized from benzene. The yield of 2-chloro-4-methoxy-6-diazoazetylpyrimidin amounts to 0.33 g (75%), melting point 138-140 ⁰ C.

Found, %: C 39.67; H 2.29. C ₇ HeN ₄ O ₂ Cl. Calculated,%: C 39.53; H 2.35.

Example 14, 2-chloro-4- (H-piperidyl) -6-diazoacetylpyrimidine (R ₅ «Cl; Rg« N-piperidyl)

760 mg (3 »5 mmol) of 2,4-dichloro-6-diazoacetylpyrimidine are added to a solution of 0.8 ml (5-fold excess) of piperidine in 20 ml of absolute ethanol, and the mixture is stirred intimately at room temperature over the course of 6 hours. The reaction mixture cools down to a temperature of 0 ^° C., the yellowish precipitate is filtered off, washed with cold ethanol and dried. The yield of 2-chloro-4- (N-piperidyl) -6-diazoazetylpyrimidin is 600 mg (65%), melting point 102-104 ⁰ C.

Found, %: C 49.84; H 4.56. C ₁₁ H ₁₂ NcOCl. Calculated, #: C, 49.72; H 4.52.

Bai play JS . 2-chloro-4-phenylhydΓazo-6-diazoazetylpyrimidine (R ₅ = Cl; R ₆ * NHNHPh)

65I mg (3 mmol) of 2,4-dichloro-6-diazoacetylpyrimidine (obtained analogously to Example I) are added to a solution of 648 mg (6 mmol) of phenylhydrazine and 0.5 ml of triethylamine in 10 ml of methanol. The mixture is stirred at room temperature within 3 hours. The bright yellow precipitate which has separated out is filtered off, washed with cold methanol and dried. The yield of 2-chloro-4-phenylhydΓazo-6-diazoazetylpyrimidin is 550 mg (64%), melting point 152-154 ⁰ C.

Found, %: C, 50.14; H 3.08. C ₁₂ H ₉ N ₆ OCl, Calculated, #: C, 50.0; H 3.13.

Example 16 . 2-chloro-4-phenylazo-6-diazoacetylpyrimidine (R ₅ - Cl, Rg - - N «N - Ph) 280 mg (1 mmol) 2-chloro-4-phenylhydrazo-6-diazo-

. · -..-. /..--. 3 15265 T. 32

Acetylpyrimidine, obtained in Example 15, is boiled in 10 ml of benzene in the presence of activated pulverulent manganese dioxide within 6 hours with a Dien-Stark attachment (by distilling off the water which separates out). The hot benzene solution is separated from the manganese dioxide precipitate by filtration. The solution is evaporated and the bright orange precipitate is recrystallized from benzene. The yield is 196 mg (70%), melting point II6-II7 ⁰ C.

Found, #: C 50.4. Cj ₂ H NgOCl. Calculated C 50.3.

Example 17 . 3-phenyl-4-diazoazetylsidnon 2.24 g (0.01 mol) of N-Fhenyl-N-nitroso-N-aminomalonic and IO ml of thionyl chloride is heated within 20 hours at a temperature of 50 ⁰ C, the excess thionyl chloride distilled and extracted the residue with 20 ml of ether. The ethereal solution is added dropwise within 30 minutes with stirring to a to a temperature of ⁰ C-IO cooled ethereal solution of diazomethane, obtained by alkaline decomposition of IO mg of N-nitrosomethylurea, too. The reaction mixture is cooled to a temperature of - 30 ⁰ C and filtered and dried the precipitate. It is recrystallized from benzene. The yield of 3-phenyl-4-diazoazetylsidnon is 1.2 g (52%), melting point 183-184 ⁰ C (decomposition). H _f · 0.57 (benzene / ethyl acetate system, 3: 1), Silufol UV-254. · Found, % \ C 52.31; H 2.50. C ₁₀ H ₆ N ₄ O-. Calculated _t % \ C 52.17; H 2.61.

Example 18 . A polycrystalline layer of 2-diazoacetylquinoline 1.5 to 2.0 m thick is applied from the solution between two parallel quartz plates. The image is recorded on the material obtained with a beam of the laser (Cd - He

2 1b 2 6

La8er). λ «325 mn; E * 0.0IJ; T * 15 β; D ■ 0.3β.

The images obtained are dark brown in color on a pale yellow background. The image is stable when stored in the dark (no drop in optical density was observed within 6 months). When the image is stored in daytime scattered light, the half-life of the contrast drop is 2 days.

Example 19 . A photosensitive material based on 5-nitro-2-dlazoacetylquinoline is prepared under the analogous conditions described in Example 18 and the image is recorded with the total current of the radiation from the quartz-mercury lamp (E «1.3 IO" ² W / cm ² , T MO 8, D _s 0.34).

Images of brown color on a pale yellow background are obtained. The picture is in the Persistent in the dark (no drop in contrast was observed within 6 months). When storing In the daily scattered light, the half-life of the decrease in contrast is 5 days.

Example 20 . A polycrystalline layer of 8-nitro-2-diazoacetylquinoline is applied to baryta paper

2 at a concentration of 1.6 mg / cm. Through a stencil one takes exposure with the total

—2 current of the quartz-mercury lamp (E «1.3» 10 W / cm; C = 20 b; D = 0.31). The constancy and the The colors of the image are analogous to those mentioned in Example 19.

Example 21 . A polycrystalline layer of 4-methyl- - ^ diazoacetylquinoline is applied to a Silufol UV-254 plate at a concentration of 2.0 mg / cm. The image is recorded under the analogous conditions mentioned in Example 19 (λ = 325 nm; E «0.01 W / cm; Έ = 50 s; D - 0.30). An image is obtained which is brown in color because it persists in the dark (it was made within 6

Months no decrease in contrast was observed). When storing the picture in the daily scattered light is the half-life of the drop in contrast is 4 days.

Example 22 . A light-sensitive layer is applied to baryta paper, which 2-diazoacetylchino-

2 lin at a concentration of 3.5 mg / cm.

The exposure is through a negative with a quartz mercury lamp with a set of filters (yellow glass-IO of 6 mm thick and blue glass-15 of 3 mm thick) at A = 404 to 436 nm, an integral beam

■ s 2 power output E = 4.2 · IO ^ W / cm. the Exposure time is 10 minutes. An image of dark purple color is obtained with an optical Density D = 0.45. The durability and the color of the picture are analogous to those mentioned in example ΙΘ.

Example 23 . A 1.5 to 2.5 µm thick polycrystalline layer of 2,4-bis-diazoacetylpyridine is applied between two quartz plates. The image is recorded on the material obtained with the beam of the Cd-He laser {λ * 325 nm; E = 0.01 W / cm ² ; T = IO s; D «s 0.34).

Images of brown color on a pale yellow background are obtained. The picture is in storage stable in the dark (no drop in optical density was observed within 6 months). at If the image is stored in the daily scattered light, the half-life of the decrease in contrast is 5 days.

Example 24. , Sub. . A photosensitive material based on 2,4,6-trisdiazoacetylpyridine is prepared under the analogous conditions mentioned in Example 23 and the image is recorded with the total current of the radiation from the quartz-mercury lamp (E = 1.3 * 10 " ² W / cm ² ; t = 30 s; D «= 0.28). An image of steel blue color on a pale yellow background is obtained. The image is stable when stored in the dark (no contrast

15 2

-M-

decline observed within 6 lionates). In the Storage of the image in the daily scattered light is the half-life of the contrast abiall s 2 days.

Example 25 “A polycrystalline layer of 2,4,6-tris-diazoacetylpyridine is applied to baryta paper at a concentration of 1 mg / cm. Exposure to the total luminous flux of the quartz mercury lamp (E = 1.3 * 10 Y / cm; £ "= 5 3; D = .0.36) is carried out through a stencil mentioned analog.

Example 26 . A polycrystalline layer of 2,6-bisdiazoacetyl-3-nitropyridine at a concentration of 2.5 mg / cm is applied to a Silufol UV-254 plate. The image is recorded under the analogous conditions mentioned in Example 23 (E = 0, OI V. '/ Cm ² ; T = 5 s; D = 0.36).

Juan receives a picture of brown Parbe, dar; is stable in the dark (it was found within 6 hours Decrease in contrast observed). When storing in daytime scattered light is the half-life of the decrease in contrast 10 days.

Example 27 . A 2.0 to 2.7 / wm thick polycrystalline layer of 2,4-dichloro-6-diazoacetylpyrininine is applied between two quartz plates. The image is recorded on the material obtained with the beam of the Cd-He laser ( λ = 325 nm; E = 0.01 "// cm ² ; Z = 15 s; D = 0.29). LIan Obtains images of bright brown color on a pale yellow background. The image is persistent when stored in the dark (no decrease in control was observed within 6 months). When the image is kept in daily scattered light, the half-life of the decrease in contrast is 25 days.

Example 28 . A light-sensitive layer is applied to baryta paper by pouring it, the 3-phenyl-diazoazetylsidnon in chloroform for a

- 35 "-

Contains concentration of 0.95 mg / cm. The applied layer is dried. The sample obtained is used as an actinometer to measure the dose of UV radiation at λ * 365 mn (quartz mercury lamp with a set of light filters: white Ultraviolet Glass - IO + Ultraviolet Glass - 2 + Ultraviolet Glass - 4). The measuring of the dose was taken with a Ferrioxalataktinometer made according to a known method (see for example J..Kavert et al. Photochemie, Verlag Mir, Moscow 1968, pages 625-627).

The measurement of the optical density of the exposed layer was carried out with the densitometer R-519 (from the company Macbeth, England) using a blue one Light filter made. According to the measurement results a calibration line of the dependence of D on log H was constructed, which can be used for further measurements used. The control measurements carried out after 24 hours, after 1, 3 and 6 months showed the same The results are within the limits of the experimental error.

Industrial applicability

The compounds of the above general formula proposed in the present invention (I) have photosensitive properties and can be the production of materials for silver-free photographic, of substances for the registration of information and in all other cases of Use of light-sensitive substances, such as photochemical processes for registering the information,

Blueprints, microfilming, may be used.

Claims (1)

PATENTAIJ CLAIMS 1. o (-Diazoacetyl derivatives of the aromatic nitrogen containing heterocycles of the general formula; Het- in which Het for in which Rj, R ₂ , R ₃ , R. are hydrogen or the groups COCHN ₂ mean; c and Rr can be identical or different and represent the chlorine atom, the groups OH, NH ₂ , OCH-, N-piperidyl, NHIiHPh, N = NpH, OPh, 8-mercaptoquinolyl, 2-mercaptoquinolyl; stand; R ₇ , R 1 and Rq can be identical or different and represent a hydrogen atom, the groups CH ₃ , IiO ₂ . 2. OC -diazoacetyl derivatives of the aromatic nitrogen-containing heterocycles according to claim I, characterized in that they have the pormeI: COCHNp in which at R ₃ = COCHN = R = H; at = R ₃ = COCHN ₂ R ₂ = R ₄ = = COCHW ₂ and H; or in the case of: R. = NO ₂ - group R ₂ = R ₃ = H. 3. c * c -diazoacetyl derivatives of the aromatic nitrogen-containing ones Heterocycles according to claim I, there- IB characterized by that they are the Formula: in the at R ^ «chlorine atom Rg Chloratoxn, OCH- - group, N-piperidyl, 8-mercaptoquinolyl, 2-mercaptoquinolyl means and with R, - «Rg the radicals Rc and Rg for the OH or NHp group, have. A.oC diazoacetyl derivatives of the aromatic nitrogen-containing heterocycles according to claim!, Characterized in that they have the formula: COCHN, Si. in which for R- «NO ₂ - group R ₇ denotes» R «and hydrogen atom; at R _ß »NO ₂ group R ₇ = R _Q and stand for hydrogen atom; at R ₇ «NO ₂ - or CH - group Rg.« represent Rq and hydrogen atom. 5.0C- diazoacetyl derivative of the aromatic nitrogen-containing heterocycles according to claim I, characterized in that it has the formula: COCHN, ί 5 5 7 6 5 and represents 3-phenyl-4-diazoazetylsidnone. 6. Photosensitive material, which consists of a base and a photosensitive polycrystalline layer, characterized in that the photosensitive polycrystalline layer, by an o (- Diazoacetylderivat of the aromatic nitrogen-containing heterocycles of the general formular • 0 Het —C-CHN ₃₁ Rg -in which Rj, Rp, R · ,, R. hydrogen or the groups ₂ , COCHN ₂ 'mean; R ₅ and R ^ can be the same or different and for chlorine atom, the groups OH, OCH ₃ , N-piperidyl, NHNHPh, N = NPh, OPh, 8-Mer- ₃
kaptoquinolyl, 2-mercaptoquinolyl; stand; R. ₇ , J {"and may be the same or different and hydrogen atom, the groups CH ^, NO ₂ mean, is formed. 7. Photosensitive material according to claim 6, characterized in that the photosensitive polycrystalline layer is formed by oC diazoacetyl derivatives of the aromatic polycrystalline heterocycles of the formula: COCHN ₂ in the at COCHH COCHH and; R. = HO ₂ group Hj at H or at R COCHH, R- «H, is formed. θ. Photosensitive material according to Claim 6, characterized in that the photosensitive polycrystalline layer is formed by CC diazoacetyl derivatives of the aromatic polycrystalline heterocycles of the formula: in which at R _{5 is} chlorine atom, OCH ₃ - group, H-piperidyl, 8-mercaptoquinolyl, 2-mercaptoquinolyl and at R the radicals R ₅ and Rg the OH or Represents group is formed. 9.Lichtempfindliches material according to claim 6 _t characterized in that the photosensitive layer is formed by polycrystalline oA Diazoazetylderlvate the aromatic polycrystalline heterocycles of the formula: 20 in the R ₇ «R ₉ XOCNN, - = uj ucj. Rq = HO ₂ group _ - «g - H? for Rg <= HO ₂ group R ₇ «R- = H and for R ₇ m HO ₂ - or CH-- group R _g χ = R ^« = H. 10. Photosensitive material according to claim 6, characterized in that the photosensitive polycrystalline layer through · ■ ι s :> 6 51 ΨΙ 3-Phenyl-4-diazoazetylsidnone of the formula: Ph, COCHNi, is formed. - 42 Reformulated patent claim according to the international Registration PCT / SÜ 8I / 00P79 (- Dlazoacetyl derivatives of the aromatic nitrogen-containing heterocycles of the general formula: ■ Hei-C-CHNi in which Het for in which Rj, R ₂ , R ₃ , R / are hydrogen or the groups NO ₂ , COCHN ₂ ; Rc and Rg can be identical or different and represent chlorine atoms, the groups OH, NH ₂ , OCH ₃ , N-piperidyl, NHNHPh, N = NPh, OPh, 8- mercaptoquinolyl, 2-mercaptoquinolyl; R ~, Rg and R "may be the same or different and are hydrogen atom, the radicals CH ,, NO _2, eteht. 2, OC- diazoacetyl derivatives of the aromatic nitrogen-containing heterocycles according to claim I, characterized in that they have the formula: COCHNj, in the at R B ₁ =: and R 3 COCHN COCHN ₂ R ₁ 2 ^R 2 ^{β R} 4 * : R ₀ * R. ■ H; at 2 4 H; or if Rj> COCHN, R-, = H have. ■ - NO ₂ - group R ₂ - * ·. -3. oC- diazoacetyl derivatives of the aromatic stick- 5 2 651 substance-containing heterocycles according to claim!, characterized in that they have the formula: η COCHN, c in the at R ^ * chlorine atom, Rg chlorine atom, OCHy group, NH-NHPh, N «NPh, OPh, N-piperidyl, 8-lttercaptoquinolyl, Means 2-mercaptoquinolyl and in R, - * Rg the radicals Rc and Rg stand for the OH or NHg group. 4, cC- diazoacetyl derivatives of the aromatic nitrogen-containing heterocycles according to claim I, characterized in that they have the formula: ■ ■ ft COCHNo Λ5 in the row Kj «« Q = Rq and for hydrogen atom Btehen, for Rq * NO ₂ - group R- »Rq and hydrogen atom mean; when Rg = NO ₂ - group R- = Rg and represent hydrogen atom; at R- «NO ₂ - or CH ^ - group R _ß « Rq and represent hydrogen atom. 5. OC diazoacetyl derivative of the aromatic nitrogen-containing heterocycles according to claim I, characterized in that it has the formula: COCHN _A. - 44 - has and is 3-phenyl-4-diazoazetylsidnone. 6. Light-sensitive material consisting of a base and a light-sensitive polycrystalline Layer consists, characterized in that the photosensitive polycrystalline Layer by an of-diazoacetyl derivative of the aromatic nitrogen-containing heterocycles of the general Formula: 0 Hei-C-CHN ₂ 10 in which Het for in which R _T , R ₀ , R 1, R. are hydrogen or the groups NO ₂ , COCHN ₂ ; R ₁ - and Rg can be identical or different and represent a chlorine atom, the groups OH, NH ₂ , OCH-, N-piperidyl, NHNHPh, N «NPh, OPh, 8-mercaptoquinolyl, 2-mercaptoquinolyl; Ry, Rg and Rq can be the same or different and hydrogen atoms, the groups CH ,, NO ₂ mean, is formed. 7. Photosensitive material according to claim 6, characterized in that the light-sensitive polycrystalline layer - by oi-diazoacetyl derivatives of the aromatic nitrogen-containing heterocycles of the formula: in which at R- ■ COCHN ₂ Rj «R ₂ » R, «H; at R ₁ . «R-« COCHH ₀ R ₀ ■ R. * H or for R _x ■ COCHN ₀ J- 3 ά ά Df Xc and R. * NO ₂ group R ₂ ■ R ~ ■ H, is formed. 8, the light-sensitive material according to claim 6, characterized in that the photosensitive _f polycrystalline layer by o (- Dia "zoazetylderiyate of the aromatic nitrogen-containing heterocycles of the formula: N ' in which at R, - is chlorine atom, Rg is chlorine atom, OCH, - group, H-piperidyl, 8-mercaptoquinolyl, 2-mercaptoquinolyl and at Rr «Rg is the radicals Rr and Rg represents the OH or NH ₂ group is. 9. Photosensitive material according to claim 6, characterized in that the photosensitive polycrystalline layer by 0 (- diazoacetyl derivatives of the aromatic nitrogen-containing heterocycles of the formula: in which R- = R «= Rg * H; at R _q «NO ₂ - group R_ * Rq.« H; with Rg * NO ₂ - group R ₇ = R _q «H and with R- e NO ₂ - or CH-- group R _ß « R _q = H. 10. Photosensitive material according to claim 6, characterized in that the photosensitive polycrystalline layer through 3-phenyl-4-diazoacetylsidnone of the formula; COCHN ₀ is formed.