A method of manufacturing dispersions of coupler component
(57) Abstract:Usage: chemical-photographic industry. The inventive solutions color-forming component in the solvent mixture of tributyl phosphate, dibutyl phthalate, triphenyl, acetoacetic ester containing polymer, f-crystals 1, where X and Y are the mass part (X 5,0 - 7,0, Y 0,2 - 0,7) is subjected to dispersion in an aqueous solution of ionic surfactants containing Aerosil, retropositional apparatus in the gap between the stator and the rotating rotor when the value of the velocity gradient from 3.5 to 106to 6.8 106m/s m 3 PL., 1 Il. The invention relates to methods for producing dispersions of hydrophobic color-forming component and can be used in the technology of color films in chemical-photographic industry.A known method of manufacturing dispersions of coupler component for color films by dissolving the color-forming components, for example, derivatives of pyrazolone-5 or derivatives oximately acid in a high boiling organic solvent dibutyl phthalate, introducing into the resulting solution of nonionic surface-acaho surfactants of dodecylbenzenesulfonate sodium 
The disadvantage of this method is that it get rough dispersion of color-forming component with an average particle diameter of > 0.2 μm, resulting in poor structural redkostnym properties of the films.The closest to the invention is a method of manufacturing dispersions of coupler component (derivatives of pyrazolone-5 or oximately acid) by dissolving the components in a mixture of high-boiling organic solvent dibutyl phthalate and triphenyl, introducing into the resulting solution of nonionic surfactants of isooctylmercaptoacetate and dispersing the resulting solution in an aqueous gelatin solution in the presence of ionic surfactants of dodecylbenzenesulfonate sodium (prototype)
This method allows to obtain a dispersion of coupler component with an average particle diameter of 0.1 ám.However, the dispersion obtained by the above method are unsatisfactory stable. The shelf life of these dispersions at 3-5aboutWith less than 7 days, and at 10-12aboutWith less than 1 day, which makes their practical use in the production of the ne stability in the presence of irrigation additives (alcohols, sensitizers, tannins, etc). This leads to coalescence of the droplets of the dispersion, the formation of drops with a diameter of 20-100 mm, which does not allow to obtain materials with high consumer properties. However, upon receipt of the dispersions according to the method of the prior art by treating the colloidal system containing gelatin, in the dispersing device (colloid mill, rotary pulsation apparatus, ultrasonic dispersers) processes gelation, koatservatsii and destruction of gelatin, which results in significant difficulties in filtering dispersions and silver halide emulsions containing dispersion.The aim of the invention is to improve the stability of dispersions of hydrophobic coupler component.This is achieved in that in the method of manufacturing dispersions of hydrophobic color-forming component by dissolving each component in a separate container in a mixture of high-boiling organic solvent dibutyl phthalate and tributyl phosphate and dispersing the resulting solution in an aqueous solution of ionic surfactants using a mixture of high-boiling organic solvent, optionally containing a tribe is phat 0.5 to 1 Acetoacetic ether is from 0.01 to 0.4 and to dissolve the color-forming components in the specified solvent mixture additionally dissolve the copolymer, the General formula
where X and Y mass parts, X 5,0-7,0, Y 0,2-0,7 c specific viscosity of 0.5% solution in acetone of 0.1-0.5 in the amount of 0.3-7.0 wt. by weight of a mixture of organic solvents, using an aqueous solution of ionic surfactants, which further dispersed Aerosil with a specific surface area 300-380 m2in an amount of 0.1-2.0 wt. by weight of the specified solution, and the dispersion of Aerosil, acetoacetic ester and a dispersion solution of a color-forming component in an aqueous solution of surface-active substances containing Aerosil, is carried out in a rotary pulsation apparatus, the gap between the stator and the rotating rotor when the value of the velocity gradient from 3,0106to 8,8106m/SECM.The drawing shows the element of the gap between the stator and the rotor 1 rotor 2 stator, the gap between the rotor and stator, the angular speed of rotation of the rotor, while R WPAbout plot of the velocity of the fluid in the gap between rotor and stator.The gradient of velocity (W) is determined by the calculation formula
W where Wpthe linear speed of rotation of the rotor;
Wc0 the speed of rotation of the stator (stationary);
- the gap between rotorura (from 6.5 to 9.5 thousand rpm), gap (0.01 mm) and diameters (90 mm and 178 mm) rotor and stator, which are coaxial cylinders of the rotor and stator, get the value of the minimum (Wmin) and maximum ( Wmax) velocity gradients
Wmin3,0106< / BR>Wmax8,8106< / BR>The implementation process of the proposed method with the stated values of velocity gradients from 3,0106to 8,8106m/cm allows significantly intensify the process of dispersion, to obtain a dispersion containing no gelatin with an average diameter of particles of the dispersed phase to 0.05 μm, to increase the stability of dispersions of hydrophobic color-forming component in the process of their storage at 10-12aboutWith up to 18 months, and also increase the stability of the dispersions in the presence of additives watering, which results in lack of large droplets of the dispersed phase in the dispersion.The following examples illustrate the manufacture of dispersions of hydrophobic color-forming component in the prototype method and the proposed method.As a hydrophobic coupler component was used, for example:
blue color-forming components
-(2,4-diretamente)-butylamide-1-hydroxy-2-naphthoic acid (3 G-97)
--(2,4-di is omponent:
I(2I,4I,6I-trichlorophenyl)-[3II-/2III,4IIIdi (tratamientocialis)benzoyl-Mino]pyrazolone-5 (3P-24),
I(2I, 4I,6I-trichlorophenyl-3-[2II-chloro-5-octadecyltrimethylammonium] pyrazolone-5 (M-651),
yellow color-forming component:
-[/(2I, 4I-diretamente)propiona - methanolic -(3-hydantoin)]-pivaloyloxy acid (U-488);
as ionogenic surface-active substances, for example,
dodecylbenzenesulfonate sodium (SV-81)
diethyl ether-N--dellarciprete-(-carboxylphenyl)-asparagi new acid (SV-1147).The copolymer of the above formula is a white powder, the copolymer is non-toxic, readily available, soluble in organic solvents (acetone, benzene, and others)
P R I m e R 1 (the prototype). A portion 280g color-forming components of the CW-24 dissolved in a mixture solvent of dibutyl phthalate (500 g) and triphenyl (250 g) ( 2 1) at the 90aboutC, the resulting solution is injected 80 ml of nonionic surfactants of isooctylmercaptoacetate and the resulting solution is dispersed in 3000 ml of 10% aqueous solution of gelatin containing 600 ml of 4% of the Torah DGK-04B for 6 min at a rotor speed of 6.7 thousand rpm, when values of the velocity gradient between the rotor and stator 3,8106m/seeThe particle size of the dispersion and the stability of the dispersions are shown in table. 2.P R I m m e R 2 (the proposed method). a) Preparation of solution of color-forming components:
In the apparatus of stainless steel with a capacity of 10 l, equipped with a lid, stirrer, thermometer, input device and a jacket for heating load, 3.3 kg of tributyl phosphate, 1.8 kg of dibutyl phthalate, 0.9 kg of triphenyl, 0.3 kg of acetoacetic ester. The mixture is heated with stirring at 60-70aboutWith, then enter the copolymer, the General formula
where X is 5, Y is 0.2, with a specific viscosity of 0.5% solution in acetone in the amount of 0.1 0.46 kg (7% by weight of solvent). The contents of the apparatus are heated at a temperature of 70-90aboutWith up to complete dissolution of the copolymer.In the obtained solution at 40-50aboutTo download 3.2 kg yellow color-forming components U-488, the mixture was stirred at 70-90aboutWith up to complete dissolution of the components.b) Preparation of an aqueous surfactant solution containing Aerosil:
In the apparatus of stainless steel, of a capacity of 100 liters, equipped with a jacket for cooling a bottom valve, thermometer and vivanta sodium content of the basic substance is 21.3%) and 0.6 kg of Aerosil with a specific surface area of 300 m2(2% by weight aqueous solution of ST-81). The mixture is treated in the mode of circulation in the RPA in the gap between the stator and the rotating rotor when the value of the velocity gradient 3,0106m/cm (the number of revolutions of the rotor 6.5 thousand rpm) at a temperature of 40-70aboutC for 2 minutesC) Preparation of dispersion-488.In the apparatus containing an aqueous solution of wetting agent and Aerosil (under item (b) of this example) at a temperature of 70-80aboutTo enter solution components U-488 (prepared according to p. (a) of this example). The contents of the process apparatus in the mode of circulation of the liquid through the RPA DGK-04B, when values of the velocity gradient 8,8106m/cm (the number of revolutions of the rotor 9.5 thousand rpm) at a temperature of 75-80aboutC for 5 min to Obtain a dispersion of a yellow color-forming components, the characteristics of which are given in table. 2.Similarly prepare the dispersions of the individual Magenta and cyan color-forming component or a mixture thereof.P R I m e R 3. a) Preparation of solution of color-forming components.According to the method of example 1 in 4.5 kg of tributyl phosphate, 1.5 kg of dibutyl phthalate, 0.5 kg of triphenyl and 0.015 kg of acetoacetic ester (mass ratio 3 1 0, 5 0,01) dissolve the copolymer of the criminal code of the ssy solvents). The resulting solution was dissolved 3.2 kg Magenta components-213 or RFP-24.b) Preparation of an aqueous surfactant solution containing Aerosil:
According to the method of example 1 to prepare a dispersion medium consisting of 30,0 l of water, and 0.9 kg DM-81, 0.06 kg of Aerosil with a specific surface area of 380 m2(0.1 to by weight of the environment).C) Preparation of dispersion C-213 or RFP-24:
According to the method of example 1 a solution of color-forming components is dispersed in the dispersion medium in the circulation in DGK-04-B when the value of the velocity gradient 3,8106m/cm for 8 minutesA measure of dispersion are given in table. 2.P R I m e R 4. According to the method of example 1 to obtain a dispersion of a cyan color-forming component 3G-97 or mixtures thereof.Used:
a) preparation of a solution component 4.0 kg of tributyl phosphate, 2.0 kg of dibutyl phthalate, 1.0 kg of triphenyl, 0.4 kg of acetoacetic ester, a copolymer of the above formula (where X is 7, Y is 0.7), 3.7 kg blue components;
b) for the preparation of an aqueous solution of wetting agent containing Aerosil use 30,0 l of water, and 0.9 kg DM-1147, of € 0.195 kg of Aerosil with a specific surface area of 300 m2(to 0.6 by weight of solution);
C) preparation of dispersion of the blue component is when the value of the velocity gradient between the rotor and stator 6,8106m/seeA measure of dispersion are given in table. 1.Similarly receive the dispersion of cyan color-forming components-213.To establish the stability of the dispersions of coupler component used the following method.In a 100.0 ml of 6% aqueous solution of gelatin containing 8.0 ml of 0.1% alcohol solution of sensitizer pyridine salt of 3,3-di--sulfopropyl-9-ethyl-4,5,4I, 5I-dibenzothiophene - betaine (3912), 10.0 ml of 1% aqueous solution of the stabilizer 5-methyl-7-hydroxy-1,3,4-triazinetrione (f-1), 1.3 ml of 4% aqueous solution of wetting agent SV-1147, 0.7 ml of 3%-aqueous solution of a tanning agent monosodium salt of 2,4-dichloro-6-exitreason-1,3,5 (DD-679), 0.25 ml of ethylene glycol (irrigation additives used in the manufacture of color please film co-100M (TU 6-44-959. P-89) in the same quantities) was administered to 20.0 g of a dispersion of cyan components-213 (example 4). The composition was stirred for 2 h at 40aboutWith under stirring, and then estimated the change in the mean diameter of the particles of the dispersions, using the technique of electron-microscopic examination of specimens by the author. St. USSR N 1405540.Similarly, we determined the stability of dispersions of Magenta svetaobrazI-diphenyl-9I-ecologicalpotential (4063).The research results are summarized in table. 2.As can be seen from the above data, the variance of the color-forming component obtained by the proposed method are characterized by a significantly higher stability both at rest and in the presence of additives irrigation compared to the dispersions obtained according to the method prototype, and can be used in the production of color papers, color negative, and please positive chinafotopress.In table. 1 shows an example of manufacturing a color photo paper "Votive-P (TU 6-17-1429-57), in which instead of the aqueous-alkaline solutions of hydrophilic color-forming component in the emulsion layers of blue-, green - and krasnodonvuhillya layers are introduced dispersion of color-forming component obtained in examples 2-4, in quantities of from 280 to 67 g per 1 kg of the emulsion, depending on the layer.Used silver halide emulsions have the following characteristics.After watering emulsions and auxiliary layers, the samples were subjected to chemical-photographic processing process intended for photo paper "Votive-11".Photographic p. the paper "Votive-11" are shown in table. 3.As shown, the dispersion of hydrophobic color-forming component obtained by the proposed method can be used in the technology of colored papers with improved photographic properties, namely, lower values of the veil (Lmin), higher values of the maximum optical density (Dmax) and increased sensitivity. A METHOD of MANUFACTURING dispersions of COUPLER COMPONENT by dissolving each component in a separate container in a mixture of organic solvents, dibutyl phthalate and triphenyl and dispersing the resulting solution in an aqueous solution of ionic surfactants, characterized in that a mixture of organic solvents, optionally containing tributyl phosphate and acetoacetic ester, in the following ratio, wt.h.:
Tributyl phosphate - 3 - 4
Dibutyl - 1 - 2
Triphenyl - 0,5 - 1
Acetoacetic ether - 0,01 - 0,4,
to dissolve the color-forming components in the specified solvent mixture additionally dissolve the copolymer of General formula
< / BR>where X and Y are the mass part; X = 5,0 - 7,0; Y = 0.2 to 0.7 with specific watconsult aqueous solution of ionic surfactants, in which optionally dispersed Aerosil with a specific surface area of 300 to 380 m2in the amount of 0.1 - 2.0 wt.% by weight aqueous solution of ionic surfactants, the dispersion of Aerosil and the dispersion solution of a color-forming components in aqueous solution of surfactant containing Aerosil, is carried out in a rotary pulsation apparatus in the gap between the stator and the rotating rotor when the value of the velocity gradient from 3.0 106to 8.8 106m/s m
FIELD: organic chemistry, chemical technology.
SUBSTANCE: invention relates to a method for preparing 3,4-diaryl(hetaryl)maleimides of the formula (I): wherein R means (C1-C4)-alkyl or benzyl, or phenyl; R1 means bromine atom (Br) or aryl, such as phenyl or naphthyl substituted with alkyl, alkoxy-group or halogen atom; unsubstituted hetaryl or substituted, such as thienyl-, benzothienyl-, furyl-, benzofuryl-, pyrrolyl or indolyl- wherein substitutes represent alkyl, alkoxy-, alkylthio-group, halogen atom or trifluoromethyl group; Ar means aryl, such as phenyl or naphthyl substituted with alkyl, alkoxy-group or halogen atom; unsubstituted hetaryl or substituted, such as thienyl-, benzothienyl-, furyl-, benzofuryl-, pyrrolyl or indolyl- wherein substitutes represent alkyl, alkoxy-, alkylthio-group, halogen atom or trifluoromethyl group with exception for 3,4-di-(2,5-dimethyl-3-thienyl)-1-butylmaleimide. Method involves interaction of aryl(hetaryl)boronic acid of the formula: ArB(OH)2 wherein Ar has abovementioned values with N-substituted 3,4-dibromomaleimide of the formula (III): or N-substituted 3-bromo-4-aryl(hetaryl)maleimide of the formula (IV) wherein R and Ar have abovementioned values and with using palladium catalyst in the presence of base in organic solvent medium. Also, invention to some new derivatives of 3,4-diaryl(hetaryl)maleimides that show photochrome properties.
EFFECT: improved preparing method.
7 cl, 2 dwg, 14 ex
SUBSTANCE: present invention relates to new compounds, and more specifically to 5-formyl-substituted indoline spirobenzopyrans with general formula 1 where R1, R2 - Alk or c-Alk; R3 -CHO or NO2 group (electron-acceptor substitute), with photochromic properties. The invention also relates to the method of producing 5-formyl substituted derivatives of indoline spirobenzopyrans with formula 1. Spirobenzopyrans, which have electron-acceptor substitutes in the pyran part of the molecule, are subjected to direct selective formylation in position 5 in a trifluoroacetic acid medium with urotropine (hexamethylenetetramine) at boiling point of the mixture in an inert atmosphere for 1-1.5 hours. The obtained 5-formyl-substituted spirobenzopyrans are photochromic compounds are photochromic and can be used for making new photochromic materials (recording devices or information storage; photo-switching activity of biological objects and polymer matrices, complex formation; information security media, maps, special document protection equipment) or as advanced initial compounds for further synthesis of a large number of new photochromic objects.
EFFECT: wider field of application of the compounds.
2 cl, 1 tbl, 3 ex
SUBSTANCE: invention relates to novel compounds, specifically to 4-substituted-3-(1-alkyl-2-chloro-1H-indol-3-yl)furan-2,5-diones of general formula I , where R1=H, C1-C6 alkyl; R2=H, C1-C6 alkyl, C1-C6 alkoxy; R3=phenyl, naphthyl, 2-phenyl-1-ethenyl, thienyl, furyl, pyrrolyl, benzothiophenyl, benzofuranyl, indolyl, synthesis method thereof and use as compounds capable of photochemical generation of stable fluorophores of formula II, which can be used, for instance in information storage systems, particularly as photosensitive components of material for three-dimensional recording and storage of information. The invention also relates to novel 4,5-substituted-6-alkyl-1H-furo[3,4-c]carbazole-1,3(6H)diones of general formula II , where R1=H, C1-C6 alkyl; R2=H, C1-C6 alkyl, C1-C6 alkoxy; R4=H, R5=phenyl, R4, R5=benzo, naphtho, thieno, furo, pyrrolo, benzothieno, benzofuro, indolo, method for synthesis of said compounds and use as fluorophores.
EFFECT: obtaining novel compounds and possibility of using said compounds as fluorophores.
14 cl, 2 tbl, 8 ex
SUBSTANCE: present invention relates to novel derivatives of 5'-vinyl-6-nitro-spirobenzopyran of formula 1 , where R1=R2=H (SP2); R1=CN, R2=H (SP3); R1=CHO, R2=H(SP4); R1=NC2, R2=H(SP5); R1=CN, R2=CN(SP6); R1=CO2CH3, R2-CN(SP7); R1,R2=-C(O)-O-C(CH3)2-O-(O)C-(SP8), which have photochromic properties, as well as production methods thereof. Disclosed are methods for directed modification on the 5'-position of a photochrome molecule using well-known and simple experimental procedures of organic synthesis (Wittig and Horner-Emmons olefination, nucleophilic bonding on the carbonyl group of reactants containing active methyl or methylene groups: nitromethane, malonodinitrile, cyanoacetic acid and esters thereof, Meldrum acid).
EFFECT: method of producing substituted 5'-vinyl-indoline spirobenzopyrans is characterised by that the starting 5'-formyl derivative in the solution undergoes olefination with different CH-acids in the presence of corresponding bases in an argon atmosphere at high temperature of the reaction mixture.