SU1071622A1 - Quaternary salts of 1-oxo-1,2,3,4-tetrahydroacridinium as component of photosensitive composition for obtaining luminecent lemon-yellow images - Google Patents

Abstract

Quaternary salts of 1-oxo-1,2, 3,4-tetrahydro-acridini of the general formula R4O IRS C104 - Cj Hg, Rj -Rg - H / where RR - CjH, 2 R «f ii, RS CHj, (Л R - CfiHg, Rt-R - H, RS CHs; R - CgHis, RQ and Rg - H, Ry to Hi, together - (); R4 - CgHs, RZ - H, Rg and RH - C together - (), Ri - CHj f R - n-CHjOCgH, Rj-H, RJ and together - (CHaCH), 1g, -CH3; R, - n-CH3OCeHi, Ri - H, RI And Rts together - () j, e R, - CHj, R ;, and RZ together - (CHj, Rj and R, - H, RS - C%.) As a component of the light-sensitive composition for obtaining luminescent images of lemon-yellow color. N0

Description

The invention relates to new chemical compounds of the acin of a series of the sonic series, namely to quaternary salts of 1-OXO-1,2,3,4-tetrahydroacridini of the general formula RI O Ri -RS - H / - H, RS- - cN3; RI-RA -D / .RS.- CH |; and RS is H, Rg and Ri, together - () 2; R, - CfiHg, Ri - H, Rj and R together, - () g. , BS - CHj RI - n-CHjCeHtt, HI - H, RS and RA together - () g, Rj - CH f R, -, R, i-H, -RjMR together - () 2, R - CH RI and Rj. together - (CHi), Rg and R4 H, Rpj - CH It is known the use of anthracene to obtain luminous images under the action of ultraviolet light SP. However, these images have a blue color, since the luminescence band of anthracene is located in the region of 450 nm. The purpose of the invention is new chemical compounds possessing photoluminescence in a longer wavelength region of the spectrum and having an increased sensitivity to light. This goal is achieved by the specified quaternary salts of 1-OXO-1,2,3,4-tetrahydroacridini of general formula I, which are obtained by treating a secondary aromatic amine with a mixture of) formaldehyde and cyclic 1,3-diketone in the presence of a mineral acid and an oxidizing agent. Example: A mixture of 0.1 g-mol of the corresponding aromatic aglyne 0.2-g-mol of cyclic -diketone, P, 2-g-mol of 57% perchloric acid, 0.8 g-mol of nitrobenzene was heated to, added dropwise to for 3 h 0.1 g-mol of fomaldehyde, obtained by depolymerization of paraform in 0.5 g-mol of butanol in the presence of catalytic amounts of acid. The synthesis is continued in b-30 hours. The solvents are distilled off with water pao. The product is separated from the filtrate, as well as by repeated treatment of the resinous mass in portions (200-250 ml each) of boiling water until the sample is taken separately and rescaled during the treatment with alkali of the colored precipitate. The aqueous extracts are filtered, combined and evaporated until crystallization begins. The precipitates are treated with acetone and crystallized. I The required amount of the starting compounds and the characteristics of the target products obtained on their basis are listed in Table 1. The compounds obtained are used as components for the preparation of a photosensitive composition, which is a polymer film containing these substances I. For this purpose, a transparent film made of cellulose acetobutyrate, incubated for 24 hours in a mixture of solvents of the composition, parts by weight: toluene 28, methyl ethyl ketoi 28, ethanol (95%) 54, butanol 1-0.6. It is then immersed for 48 hours in a saturated solution of compound (I) in butyl alcohol. Then the film is dried in air at room temperature. The film is stored in a dry place, protected from direct sunlight. Compounds (1) (0.1 g) are dissolved in 2 ml of dichloroethane a and the resulting solution is mixed thoroughly with 2 g of polystyrene in 2 ml of dichloroethane. The resulting mass is poured over the substrate (glass, quartz, plastic, X-ray film, NaCi single crystal, etc.) and dried at room temperature for 15 minutes; The resulting photosensitive material is stored in air at room temperature in a dark place. To obtain the latent image on the proposed photosensitive film, an installation consisting of a light source (DRSh250) and two lenses of the projected object and the photosensitive film holder are used. The image of the object when the lamp is turned on is projected onto the photosensitive film for 5 WH. In the illuminated areas, a strong weakening occurs (in some cases, the disappearance) of luminescence. As a result of the exposure, without any further processing, an image of the subject is formed. Upon subsequent excitation of the luminescence of the film, as with the first exposure of its ultraviolet light to light, an image of the object is observed against the luminescent background. This practically inertialess development allows the use of a carrier when speedy reading of information and rapid pattern recognition is required. Resolution is at the molecular level. The sensitivity of the carrier is several times higher than the sensitivity of a known carrier; they are close in image contrast. The luminescence light and the position of the maximum of the luminescence band depend on the structure of the substance (see table 2). Figure 1 shows the photoluminescence spectra of compounds (1) at room temperature while the DRSh-250 lamp is excited by UV radiation (the numbers of the curves correspond to the compounds in Table 1); figure 2 - spectrum of photol minescence anthracene; Fig. 3 is a curve reflecting the process of quenching the luminescence of the proposed PM-5 carrier during exposure to radiation with a wavelength of L. 365 nm. The photoluminescence spectra were measured on a device with photoelectric recording of spectra, collected on the basis of an SPM-2 monochromator. The obtained substances are used only as solid solutions in the polymer matrix, prepared by embedding the substance in the film under curing, (pre-softened) film in a saturated solution of the substance, or by watering a liquid polymer solution and substance on any substrate. In both cases, the physicist, the mechanical properties of photosensitive materials are determined by the properties of the polymers. The adhesion of the polymers is much higher than that of the brittle crystalline films of anthracene. However, this particular application of adhesion of substances and polymers is insignificant, since the substrate can be used only at the moment of preparation of the material, and then the polymer film Ci with the substance embedded in it is used independently of the substrate (and even better without a substrate — it is easier and can be rolled up) . Physical and mechanical properties (strength and plasticity) of cellulose acetobutyrate film. Threats after substance I is introduced into it (by keeping the substance in a saturated solution) do not deteriorate. The amount of substance on the polymer film is insignificant and can be specifically removed, since it does not affect the image quality. The resolution of the materials is determined using the same worlds as acetylene - at 400 lines / mm. In both cases, the resolution is not worse than 400 mm. However, the material is a combination of isolated from each other substance molecules in a polymer matrix, therefore the resolution should be at the level of the size of molecules (5-10 A). Due to the absence of luchgchih the world can still guarantee that it is not worse than 400 mm. The contrast and photosensitivity of these materials is higher than that of anthracene. Some comparative data are given in table 3. Thus, the obtained new compounds, oxotetrahydroacridini salts, have intense photoluminescence with a peak in the 483–575 nm region. When illuminating polymer films containing the substances under study, the substance luminesces weakly in the irradiated areas through negative photochemical transformations. Therefore, the subsequent uniform (i.e., without negative) illumination of the sample with UV light. Makes it possible to observe the recorded images. The obtained substances can be used to obtain photographic images, which, unlike anthracene, have an increased sensitivity to light and a wide range of bluish-white to yellow T colors. whether c a 1

Continuation of table 1,

H NN H1,25215-217 N H GHj, 8,624.3 N H N H H, 1230261-262 C "NbN () t H 16.95 40 SvN, H () CHj 9,222 QffHijCHg-rtH () j СН 5.55 15 Ceaj dCHj-nH (), CH, 10.5 24 -aij.-CHj-CHt - H H CH., 13.1 35.9

Optical properties of compounds (1) and light-sensitive films obtained from them

1a yellowish white

16 Greenish White

1Y Greenish White

1g Yellowish white

(alcohol water) 3.89 (alcohol water) (alcohol).

Table 2

520 500

500

464, 520 (pl) 3.95 C, H, COHQr 3.75 278-280 4.06 С NCO COHOs- 3.96 4.10 3.60 Сц, HJQ C8HC) s 3.49 3.59 230- 232 dj H "CQ HOs 3.30 (alcohol) 3.52 293-295 3, 88 C" Hj CfiHOs 3.10 (butanol) 3, OB 273-275 3.12 SONMO MLE 3.01 (butanol) 3, 15 257-258 2.95 Cju H SOMOG 2.90 (butanol) 3.58 263-265 3.78 CAgH oCONCfe 3.82 (alcohol) 3.72

I Color luminescence | L

one,

Blue

IsGreen white 520

1 "Green Ato 506

1ft Yellowish520

Indicator

(Fine-crystalline layer of a brittle, mechanically fragile substance on the surface of a solid substrate

cooking

Required vacuum unit for thermal spraying. Most of the substance disappears due to precipitation on parts of the plant.

During thermal spraying in vacuum, films are always polycrystalline; crystal size depends on evaporation temperature and substrate

Contrast ratio

Photosensitivity, units. GOST

Not less than 400

Resolution, mm

Continued table. 2

.J

I

nk

n “cef

458, 520 (pl)

. ; T faces 3

Compounds obtained

Anthracene

The solid solution of the substance in the polymer matrix, which can be coiled up, compressed between the drawn rollers of the apparatus. Not afraid of bumps and blows.

When mass production of material can be used conventional packers, producing polyethylene film. Under laboratory conditions, it is also easy to obtain a solution without any equipment and with absolutely no loss.

No grain

1.2. This material better conveys the image of dashed images (text, graphics) and at the same time all semitones are saved.

1.0

3.0-3.5

Not less than 400 (experimentally established), but - the structure of the photosensitive material lack of grains - will allow resolving smaller images up to the size of the molecule

Anthracene Blue

400-470

Continued, 3

I Compounds obtained

Lemon Yellow

420-680

Claims (1)

<claim-text> <table border = "1"> <tbody> <tr> <td> 9 </ td> <td> 1071622 </ td> <td> ten four Continued tabl ,, 3 </ td> </ tr> <tr> <td> Indicator] </ td> <td> Anthracene | </ td> <td> ί Compounds Obtained </ td> </ tr> <tr> <td> The color of the luminous image </ td> <td> Blue - </ td> <td> Lemon Yellow </ td> </ tr> <tr> <td> Spectral region. luminescence (wavelength), km </ td> <td> 400-470 </ td> <td> 420-680 </ td> </ tr> </ tbody> </ table> <claim-text> o Μ ~ Μ I Μ 150 1, with Fig.Z </ claim-text>