The method of obtaining compounds distributionally

 

(57) Abstract:

Describes a new method of obtaining distributionally compounds, which are optical brighteners, textile material, paper and detergents. The difference method is that the condensation of substituted or unsubstituted 4,4'-bis(dialkoxybenzene)-diphenylene compounds with substituted or unsubstituted benzaldehyde is carried out in liquid ammonia in the presence of strongly alkaline substances. The technical result is easy otdelimosti product from by-products. 16 C.p. f-crystals.

The invention relates to a new method of obtaining distributionally connections.

Methods of obtaining distributionally compounds by the reaction of the Wittig-Horner is known, for example, from the Federal Republic of Germany patent DE-A-1793482. Proposed there the reaction solvent has proven to be suitable only dimethylformamide and dimethylsulfoxide (European patent A-364403), and of the proposed grounds today finds application mainly only sodium methylate.

The use of dimethylformamide as the reaction solvent, however, is associated with large faults. So, for example, on what conditions a small part of its shades of dimethylformamide with sodium methylate. The resulting diethylamin cause not only environmental problems, but also gives selected distributorname connection unpleasant, difficult to remove the smell of dimethylamine. Additionally, the base /sodium methylate/ poorly soluble in dimethylformamide, so that in practice the base used in the form of a 30% methanolic solution of sodium methylate. This way of working is associated with the disadvantage that it is necessary to regenerate two solvent /dimethylformamide and methanol/. As a dipolar aprotic solvent with a high boiling point (154oC) in practice, dimethylformamide is used, which can be regenerated only with the loss of 5-10%.

The use of dimethyl sulfoxide as a reaction solvent associated with such disadvantages. Dimethyl sulfoxide, however, in contrast to dimethylformamide in the presence of bases, stable and applied to the base (sodium methylate) soluble in dimethyl sulfoxide. However, dimethylsulfoxide unstable against oxidation-reduction reactions, and the formed dimethyl sulfide, dimethyl disulfide, and especially with a very unpleasant mercaptan odor. Further, dimethylsulfoxid the eat in this case, losses are greater due to twice as high cost compared with dimethylformamide.

Carrying out the above reaction using the above-mentioned solvents and sodium methylate the processing associated with large faults. According to the subsequent regeneration of the used solvent in order to highlight the condensation product in a sufficiently pure state by crystallization, the product of condensation must first be dissolved in water and then filter to lighten. As in the case of the reaction of the Wittig-Horner produces not only the desired product of the condensation, but also formed equimolecular number corresponding salt dialkylamide ester of phosphoric acid, the above operations because of the strong effect of vysalivaniya this salt of phosphoric acid must be carried out at a strong dilution. After selecting distributiing connection, therefore, it is necessary to remove large amounts of severely diluted and containing dialkyl ethers of phosphoric acid mother solutions.

Currently, it is found that distributionally the compounds of formula (1)

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can be obtained by condensing compounds of the formula (2)

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with a compound of the formula (3)

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where R1denotes hydrogen, C1- C5-BR> n = 2 or 4;

m = 0 or 2 and

p = 0 or 1 provided that m + p = 2 or 4;

if the condensation is carried out in liquid ammonia and in the presence of reacting as strongly alkaline substances.

As residue R1consider, for example, hydrogen, methyl, ethyl, propyl, butyl, tert.-butyl, propyl, chlorine or bromine, preferably hydrogen, methyl, ethyl and chlorine. As residue R2usually used methyl, ethyl, propyl, butyl, hexyl or octyl, preferably methyl, ethyl, propyl and butyl.

As cations M take into account, for example, cations of alkali metals as sodium and potassium; the cations of alkaline-earth metals such as calcium and magnesium, and ammonium cations.

As components of the condensation is preferably introduced compounds of the formulas (4) and (5)

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where R1denotes hydrogen, C1-C5-alkyl or halogen;

R2represents C1-C8-alkyl,

M denotes a salt-forming colorless cation.

In a particularly preferred method condense the compounds of formulas (4) and (6)

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where R1denotes hydrogen, C1-C5-alkyl or chlorine; R2represents C1-C8-Leimer, from the patent Germany And 1793482 and in General can be obtained by the method Arbuzov by reacting 4,4'-bis-(chloromethyl)-diphenyl-derivative with alkylphosphine as trimethylphosphite.

The compounds of formula (3) can be obtained, for example, by reacting chlorinated benzaldehyde with sodium sulfate in water and under pressure.

According to the proposed invention method in particular, one can obtain compounds of the formulas (7)-(12)

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According to the invention the condensation is carried out in liquid ammonia, for example, at temperatures from -40oC to 25oC, preferably at 0-25oC and particularly preferably at 10-20oC, in the presence of strong bases. From the boiling point of ammonia, equal -33,35oC /760 Torr/, it follows that we need to work with the overlying temperatures under high pressure.

As suitable for the condensation reaction, reacting as strongly alkaline substances are suitable, for example, alkali or alkaline-earth metals as lithium, sodium, potassium, magnesium and calcium, as well as their strongly basic compounds, such as hydroxides, amides or alcoholate, as well as strongly basic ion exchangers. As alcoholate prementioned alcohols with 1 to 8 C-atoms, preferably 1-4-two C-atoms as methanol, ethanol, propanol, butanol, isopropanol and tert.-butanol. These alcoholate are used preferably in the form of the corresponding alcohol solution. Primarily as reacting as strongly alkaline substances are used alkali metals or their strongly basic compounds, preferably amides, hydrides or alkali metal alcoholate, or a mixture thereof, in particular the alcoholate or amides of sodium and primarily sodium amide.

Preferably used sodium or potassium compounds, and practical importance of their hydroxides, alcoholate and amides. Of particular importance is the use of their sodium amide. For this purpose, for example, sodium make available in liquid ammonia, preferably in the presence of a suitable catalyst, as iron chloride(III) or nitrate iron(II).

These reacting as strongly alkaline substance is used preferably in an anhydrous condition, either individually or in a mixture. A small amount of water such that there is some strong technical grounds, however, does not prevent condensation. Strong bases have very different solubility in the liquid ampicillinum the solubilities. Depending on the kind of the used base sometimes has the advantage of the use of small quantities of proton solvent as an auxiliary solvent. As the proton of the water or solvent used is preferably an open-chain, branched or cyclic low molecular weight aliphatic alcohols with 1 to 8 C-atoms. Special practical importance, however, is the use of methanol as an auxiliary solvent, as used most frequently hydroxide is very soluble in methanol.

Enter the number of bases may vary within wide limits. However, it is preferable to use at least 2-3 equivalents of base per one equivalent of the compound of the formula (2). To implement the condensation of the base can gradually add in the reaction vessel to the compound of formula (2) during or after addition of the compounds of formula (3). Preferably the base is gradually added to a reaction vessel compounds of the formula (2) and (3).

Excess base after the condensation reaction can be neutralized by adding acidic compounds. Examples of the acidic compounds are, for example, chloride is entrusted is 1:2 - 1:2.5 and particularly preferably 1:2.1 to 1:2,2.

A special advantage of the invention method is easy otdelimosti product from by-products. Thus, the condensation product of formula (1) is in the form of insoluble components and can be separated by filtration. Formed as a by-product of a complex phosphate ester, and other side reaction products, in contrast, remain dissolved in the liquid ammonia. Used as solvent liquid ammonia can then be cleaned from all impurities by evaporation and condensation and re-use.

Thus, the obtained distributionally connection is usually used for optical bleaching of textile material such as cotton, polyamide and wool, or optical bleaching of paper. For this purpose they can be made in solid or liquid detergents, dye baths or solutions for coating.

For this, in General, they are diluted to the optimum for the respective application concentration by the addition of other auxiliaries or water.

Thus, the formulations may additionally contain usual auxiliary materials is, preservatives, pigments, enzymes, perfumes, and passivator.

As the dispersant preferably used nonionic dispersing agents, such as fatty alcohols, ethoxylated products of fatty alcohols or fatty acids or anionic dispersing agents, as condensation products of aromatic sulphonic acids with formaldehyde, for example, those based on detailbug (simple) esters of sulfonic acids or naphthalenesulfonic, or ligninsulfonate.

As builders or protective colloids take into account, for example, modified polysaccharides, which are produced from cellulose, or heteropolysaccharides as xanthan gum, carboxymethyl cellulose, and silicates of aluminum or magnesium.

As other AIDS to stabilize, you can add, for example, ethylene glycol, propylene glycol, as well as other dispersers.

As preservatives are used, for example, compounds such as 1,2-benzisothiazolin-3-one, formaldehyde or chloracetamide.

The following examples explain the invention without limiting its scope.

Example 1. Installed in a number of equipment is specified in n the th for cooling/heating pressure gauge (0,10 bar) and pressure regulator TESCOM(0-7 bar), stirrer with permanent magnetic drive, a cartridge for a thermometer, inlet pipe for ammonia and suction inlet for sodium and podavlivaya washer [Berstscheibe] (10 bar);

from the second glass autoclave BUECHIwith a capacity of 1.5 liters, equipped with a jacket for cooling /heating, pressure gauge (0-10 bar) and pressure regulator TESCOM(0-7 bar), stirrer with permanent magnetic drive, a cartridge for a thermometer, inlet nozzles for liquid ammonia and suspension of sodium amide in ammonia, the exhaust valve in the bottom and podavlivaya washer (10 bar), and

of the pressure suction filter high pressure LIGACONwith a capacity of 2 l, equipped with a jacket for cooling/heating, pressure gauge (0-10 bar) and pressure regulator TESCOM(0-7 bar), stirrer with permanent magnetic drive, a cartridge for a thermometer, inlet pipes for the suspension of the reaction product, a plate of metal alloy with a pore size of 10 μm and covered with a substance filter SEITZKoo, discharge valve in the bottom, in connection with the second glass autoclave and podavlivaya washer 10 bar.

oC /4.2 bar/. The autoclave is cooled to -40oC and the pressure reduced to atmospheric, at this temperature now and with stirring, after the addition of one piece weighing approximately 0.5 g of sodium and 0.5 g of nonahydrate nitrate iron (III) within 20 minutes, add small pieces in General, 15.5 g (0,676 mol) of sodium, and stands out from the reaction mixture a stream of hydrogen. The autoclave after about 10 minutes after the addition of sodium closed and the resulting gray-black suspension of sodium amide are stirred further at the 11oC (5,8 bar) for 30 minutes.

The second glass autoclave at atmospheric pressure placed 105,7 g of 4,4'-bis-/dimethoxyphosphoryl/-diphenyl (98% active substance; 0.26 mol) and 148, 8 persons g of sodium salt of benzaldehyde-2-sulfonic acids (80% active substance; 0,572 mol). The autoclave is closed, cooled to 12oC and at this temperature under stirring for 5 minutes dose of 210 g of liquid ammonia, forming a pale yellow suspension. The suspension is cooled to 6oC (4.3 bar) and under stirring for 10 minutes dispense a suspension of sodium amide from the first glass autoclave, and the reaction temperature increases from 6oC to 14oC and formed yellow Kim ammonia, using each time in 50 g of liquid ammonia, the solution after rinsing enter the second glass autoclave and the reaction mixture is finally stirred for one hour at the 11oC (5,8 bar). Excess sodium amide is then neutralized by adding 6 g (0,156 mol) of gaseous hydrogen chloride, the reaction mixture is cooled to 6oC and 6oC injected into the autoclave suction filter high pressure. The second glass autoclave rinse twice with 50 g of liquid ammonia, and the solution after rinsing injected into the autoclave suction filter high pressure.

The reaction mixture is initially homogeneous mix and then without stirring at a 6oC (5,6 bar) is filtered by suction under high pressure 1.5 bar, and the filtrate is directed to the second glass autoclave. The precipitate with suction at the 6oC double-Usacheva (suspended) while mixing in liquid ammonia, using each time in 100 g of liquid ammonia, and without stirring sucked off by suction, and the filtrate is directed to the second autoclave.

The pressure in the autoclave suction high pressure filter and the second glass autoclave was reduced to atmospheric by partial evaporation of the ammonia and then the precipitate with suction>. Both unload the autoclave, and the precipitate with suction, and filtrate the residue is heated under vacuum at 100oC and dried to constant weight.

Get 153,7 g disodium salt of 4,4'-bis-/2-colfosceril/-diphenyl in the form of a pale yellow crystalline powder with so pl. 300oC, which is the content of the active substance ( the UV-spectrophotometric) of 88.6%. The output of the disodium salt of 4,4'-bis-/2-colfosceril/-diphenyl is 93.1% of theory. Filtrate balance (123 g of light yellow crystalline hygroscopic product) consists mainly of the sodium salt of dimethyl ester of phosphoric acid.

Analogously to example 1 from the appropriate starting materials have the following distillerie compounds of the formulas (8) - (12)

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Example 2. Repeat example 1, and instead of 10% excess of sodium salt of benzaldehyde-2-sulfonic use only 7% excess, i.e., 144,8 g (80% active substance; 0,556 mol).

Get 154,8 g disodium salt of 4,4'-bis-/2-colfosceril/-diphenyl in the form of a light yellow crystalline powder with so pl. above 300oC, which contains 88.5% of the active substance (the UV-spectrophotometric). Output Dina crystalline hygroscopic product) consists mainly of the sodium salt of dimethyl ester of phosphoric acid.

Example 3. Repeat example 1, and instead of 10% excess of sodium salt of benzaldehyde-2-sulfonic use only 5% excess, i.e., to 142.1 g (80% active substance; 0,546 mol).

Get 148, 8 persons g disodium salt of 4,4'-bis-/2-colfosceril/-diphenyl in the form of a light yellow crystalline powder with so pl. above 300oC, which contains 89,0% of the active substance (the UV-spectrophotometric). The output of the disodium salt of 4,4'-bis-/2-colfosceril/-diphenyl is 90.5% of theory. Filtrate balance (110,9 g of light yellow crystalline hygroscopic product) consists mainly of the sodium salt of dimethyl ester of phosphoric acid.

Example 4. Installed in the form of a cascade equipment consisting of the sequence:

the first reaction vessel with a capacity of 0.75 liters, equipped with a jacket for cooling /heating, stirrer, thermometer and a valve in the bottom;

the second reaction vessel with a capacity of 1 l, equipped with a jacket for cooling /heating, stirrer, thermometer and a valve in the bottom;

the suction pressure SEITZwith a capacity of 2 l, equipped with a jacket for cooling/heating, thermometer, pressure gauge and a valve in the bottom,

the third reaction with
cooled to -40oC.

In the first reaction vessel is placed 140 g of liquid ammonia at -40oC. At this temperature, now with stirring after the addition of one piece weighing approximately 0.5 g of sodium and 0.4 g of nonahydrate nitrate iron (III) within 20 minutes, add small pieces in General, 8.6 g (0,374 mol) of sodium from the reaction vessel is allocated a stream of hydrogen. The resulting gray-black suspension of sodium amide further stirred at -40oC for 30 minutes.

In the second reaction vessel is placed in the sequence: to 67.9 g of 4,4'-bis-/dimethoxyphosphoryl/-diphenyl (88% active substance; 0.15 mol);

by 89.8 g of sodium salt of benzaldehyde-2-sulfonic acids (80% active substance; 0,345 mol) and

280 g of liquid ammonia and stirred.

To this yellow suspension over 5 minutes with stirring suspension of amide from the first reaction vessel, and the reaction temperature increases from -40oC to -34oC and formed a red suspension. The reaction mixture is now stirred further for 5 hours at -40oC, and after about 2 hours formed a yellow suspension. Excess sodium amide is neutralized by the add is UP>C is sucked off using high pressure 1.5 bar of nitrogen through the overlapped substance filter SEITZTo 3. The precipitate with suction, washed twice with 100 g of liquid ammonia and then freed from ammonia by passing a weak current of nitrogen while raising the temperature of the jacket for cooling/heating from -40oC up to +26oC.

The filtrate in the third reaction vessel is then freed from ammonia by increasing the temperature of the jacket for cooling/heating from -40oC up to +26oC. the Precipitate with suction and filtrate the residue is finally heated in vacuum at 100oC and dried to constant weight.

Get to 105.3 g of disodium salt of 4,4'-bis-/2-colfosceril/-diphenyl in the form of a light yellow crystalline powder with so pl. above 300oC, which contains 75.8% of the active substance (the UV-spectrophotometric). The output of the disodium salt of 4,4'-bis-/colfosceril/-diphenyl is a 94.6% of theory. Filtrate balance (of 57.8 g of a light brown crystalline hygroscopic product) consists mainly of the sodium salt of dimethyl ester of phosphoric acid.

Example 5. Repeat example 4, and instead of the 15% excess of sodium salt Benza Get to 104.8 g of disodium salt of 4,4'-bis-/2-colfosceril/-diphenyl in the form of a light yellow crystalline powder with so pl. above 300oC, which contains 76,2% of the active substance (the UV-spectrophotometric). The output of the disodium salt of 4,4'-bis-/2-colfosceril/-diphenyl is 94.5% of theory. Filtrate balance (of 53.7 g of light yellow crystalline hygroscopic product) consists mainly of the sodium salt of dimethyl ester of phosphoric acid.

Example 6. Installed in a number of equipment consisting of the sequence:

the first glass autoclave BUECHIwith a capacity of 1 l, equipped with a jacket for cooling /heating, pressure gauge (0,10 bar) and pressure regulator TESCOM(0-7 bar), stirrer with permanent magnetic drive, a cartridge for a thermometer, inlet nozzles for liquid ammonia and sodium, as well as podavlivaya washer (10 bar) and the second glass autoclave BUECHIwith a capacity of 1.6 liters, equipped with a jacket for cooling/heating, pressure gauge (0-10 bar) and pressure regulator TESCOM(0-7 bar), stirrer with permanent magnetic actuator, the inlet pipe for liquid ammonia and suspension of sodium amide in ammonia and podavlivaya washer (10 bar), operates as follows.

In the first glass autoclave is placed 130 g is ri this temperature and with stirring, after the addition of one piece weighing approximately 0.5 g of sodium and 0.7 nonahydrate nitrate iron (III) for 20 minutes, add small pieces in the whole of 14.4 g (of 0.625 mol) of sodium, and stands out from the reaction mixture a stream of hydrogen. The autoclave after about 10 minutes after the addition of sodium closed and the resulting gray-black suspension of sodium amide are stirred further for 12oC (6,1 bar) for 30 minutes.

The second glass autoclave at atmospheric pressure place of 113.2 g of 4,4'-bis -/dimethoxyphosphoryl/-diphenyl (88% active substance; 0.25 mol) and 142,4 g of sodium salt of benzaldehyde-2-sulfonic acids (80,4% of active substance; 0.55 mol). The autoclave is closed, cooled to 0oC and at this temperature under stirring dose of 210 g of liquid ammonia, forming a yellow suspension. To this suspension within 15 minutes, add with stirring a suspension of sodium amide from the first glass autoclave, and the reaction temperature is increased from 0oC [4.1 bar] up to 9oC [5,7 bar] and forms a yellow, crystalline suspension of the reaction product. The first autoclave rinse once with 50 g of liquid ammonia and the solution after rinsing enter the second glass autoclave. The reaction mixture is now stirred further for one hour at 10oC and huts which I was handling the pressure in the second glass autoclave decrease from 6.4 bar to atmospheric by partial evaporation of the ammonia, moreover, the internal temperature drops from +10oC to -30oC, the reaction mixture is diluted with 500 ml of water and the resulting suspension next release from ammonia by slow heating up to +20oC. the Stirrer is stopped and the autoclave is emptied. The reaction mixture is concentrated to dryness on a rotary evaporator under vacuum, at about the 90oC is treated with a solution of 81 g of sodium chloride in 375 ml of water and cooled to room temperature. The reaction product is sucked off by suction, washed with 250 ml of 7.5% aqueous solution of sodium chloride, is heated under vacuum at 100oC and dried to constant weight.

Get 141,7 g disodium salt of 4,4'-bis-/2-colfosceril/-diphenyl in the form of a light yellow crystalline powder with so pl. above 300oC, which contains 93,2% of the active substance (the UV-spectrophotometric). The output of the disodium salt of 4,4'-bis-/2-colfosceril/-diphenyl is 93.9% of theory.

Example 7. Repeat example 6, and instead of 10% excess of sodium salt of benzaldehyde-2-sulfonic use only 7% excess, i.e., on 138.5 g (80,4% of active substance; 0,535 mol).

Get of 148.4 g of disodium salt of 4,4'-bis-/2-colfosceril/-diphenyl in the form of light yellow is antropologicheskii). The output of the disodium salt of 4,4'-bis-/2-colfosceril/-diphenyl is 95.9%.

Example 8. Repeat example 6, both the original product is 4,4'-bis-/dimethoxyphosphoryl/-diphenyl and the sodium salt of benzaldehyde-2-sulfonic - handle 260 g of liquid ammonia instead of 210,

Get 147,1 g disodium salt of 4,4'-bis-/2-colfosceril/-diphenyl in the form of a light yellow crystalline powder with so pl. above 300oC, which contains 91,4% of the active substance /the UV-spectrophotometric/. The output of the disodium salt of 4, 4'-bis-/2-colfosceril/-diphenyl is 95.6% of theory.

Example 9. Apparatus consisting of a glass autoclave BUECHIwith a capacity of 1 l, equipped with a jacket for cooling/heating, monometr (0-10 bar) and pressure regulator TESCOM(0-7 bar), stirrer with permanent magnetic drive, a cartridge for a thermometer, inlet nozzles and podavlivaya washer (10 bar), cooled to -45oC.

In this glass autoclave is placed 320 g of liquid ammonia at -45oC and with stirring, after the addition of one piece weighing approximately 0.5 g of sodium and 0.3 g of nonahydrate nitrate iron (III), for 20 minutes, add small pieces in General, 5.8 g ( amide sodium further stirred at -45oC for 30 minutes.

To this suspension of sodium amide at -45oC - -38oC for 5 minutes add up 40.7 g of 4,4'-bis-/dimethoxyphosphoryl/-diphenyl (98% active substance; 0.12 mol) with stirring using a funnel for dispensing powders, forming a dark red suspension, which was stirred further for 30 minutes at -45oC. To this dark-red suspension is now over 5 minutes with stirring and at -45oC - -33oC add a 50.5 g of sodium salt of benzaldehyde-2-sulfonic acids (99% active substance; 0.24 mol) using a funnel for dispensing powders.

A glass autoclave was closed and dark-red suspension is stirred further at -10oC (2 bar) for 4 hours, and the dark red color disappears and forms a crystalline light yellow suspension of the reaction product. Excess sodium amide is neutralized by adding 2 g (0.05 mol) of gaseous hydrogen chloride.

To handle pressure in a glass autoclave reduce from 2 bar to atmospheric by partial evaporation of the ammonia, and the internal temperature decreases from -10oC to -33oC. the Reaction mixture is diluted with 300 ml of water and the resulting suspen unload. The reaction mixture is finally concentrated to dryness on a rotary evaporator under vacuum, at about the 90oC is treated with a solution of 30 g of sodium chloride in 150 ml of water and cooled to room temperature. The reaction product is sucked off by suction, washed with 100 ml of 7.5% sodium chloride solution and dried in vacuum at 100oC to constant weight.

Get 52,5 g disodium salt of 4,4'-bis-/2-colfosceril/-diphenyl in the form of a light yellow crystalline powder with so pl. above 300oC, which contains 91,4% of the active substance (the UV-spectrophotometric). The output of the disodium salt of 4,4'-bis-/2-colfosceril/-diphenyl is 85.3% of theory.

Example 10. Repeat example 9, and the condensation is carried out at -35oC and at atmospheric pressure.

Get to 54.1 g of disodium salt of 4,4'-bis-/2-colfosceril/-diphenyl water light yellow crystalline powder with so pl. above 300oC, which contains 89.2% of the active substance (the UV-spectrophotometric). The output of the disodium salt of 4,4'-bis-/2-colfosceril/-diphenyl is 95.8% of theory.

Example 11. As described in example 9, the apparatus is placed in the sequence:

and 67.8 g of 4.4'-bis-/Dimitar what the notes (79,3% of active substance; 0,345 mol) and

230 g of liquid ammonia and stirred at the 9oC (6 bar).

This blen-ojeloi the suspension for 10 minutes and with stirring, add 81,0 g of methanol and 30% aqueous solution of sodium methylate (0.45 mol), and the reaction temperature increased from 9oC (6 bar) up to 20oC (6,6 bar) and a yellow crystalline suspension of the reaction product.

The reaction mixture was stirred further for one hour at 20oC and an excess of sodium methylate is neutralized by adding 6 g (0.15 mol) of gaseous hydrogen chloride.

To reduce the processing pressure in a glass autoclave with 6.6 bar to atmospheric by partial evaporation of the ammonia, and the internal temperature is reduced from the 20oC to -19oC. the Reaction mixture is diluted with 300 ml of water and the resulting suspension is then freed from ammonia by slow heating up to +20oC. the Stirrer is stopped and the autoclave is emptied. The reaction mixture is finally evaporated to dryness on a rotary evaporator under vacuum, at about the 90oC is treated with a solution of 45 g of sodium chloride in 225 ml of water and cooled to room temperature. The reaction product is sucked off by suction, washed with 150 ml of 7.5% of the

Get of 83.6 g of disodium salt of 4,4'-bis-/2-colfosceril/-diphenyl in the form of a light yellow crystalline powder with so pl. above 300oC, which contains 94,0% of active substance /the UV-spectrophotometric/. The output of the disodium salt of 4,4'-bis-/2-colfosceril/-diphenyl is 93.1% of theory.

Example 12. Repeat example 11, and instead of the 15% excess of sodium salt of benzaldehyde-2-sulfonic use only 10% excess, i.e. 86,6 g (79.3 percent of the active substance; 0.33 mol).

Get 83,2 g disodium salt of 4,4'-bis-/2-colfosceril/-diphenyl in the form of a light yellow crystalline powder with so pl. above 300oC, which contains 94.7% of active substance /the UV-spectrophotometric/. The output of the disodium salt of 4,4'-bis-/2-colfosceril/-diphenyl accounts for 93.4% of theory.

1. The method of obtaining distributionally compounds of the formula I

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the condensation of the compounds of formula 2

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with the compound of the formula 3

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where R1denotes hydrogen, C1- C5-alkyl or halogen;

R2- represents C1- C8-alkyl;

M denotes a salt-forming colorless cation;

n is 2 or 4;

m is 0 or 2;

p is 0 or 1, provided that m + p = 2 Isetta.

2. The method according to p. 1, characterized in that the compound of formula 4

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condensed with the compound of the formula (5):

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where R1denotes hydrogen, C1- C5-alkyl or halogen;

R2- represents C1- C8-alkyl, and M denotes a salt-forming colorless cation.

3. The method according to p. 2, characterized in that the compound of formula 4 condensed with the compound of the formula 6:

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where R1denotes hydrogen, C1- C5-alkyl or chlorine, R2- represents C1- C8-alkyl, and M denotes a salt-forming colorless cation.

4. The method according to PP.1 to 3, characterized in that as a strongly alkaline substance use alkali metals or their strongly basic compounds.

5. The method according to PP.1 to 4, characterized in that as a strongly basic compounds used amides, hydrides or alkali metal alcoholate, or a mixture thereof.

6. The method according to PP.1 to 5, characterized in that as a strongly basic compounds used alcoholate or amides of sodium.

7. The method according to PP.1 - 6, characterized in that as a strongly basic compound using sodium amide.

8. The method according to PP.1 to 7, characterized in that use the/P> 9. The method according to PP.1 to 8, characterized in that the condensation is carried out at temperatures from - 40oC to 25oC.

10. The method according to PP.1 to 9, characterized in that the condensation is carried out at temperatures of 0 - 25oC.

11. The method according to PP.1 to 10, characterized in that the condensation is carried out at temperatures of 10 - 20oC.

12. The method according to PP.1 - 11, characterized in that the compound of formula 1 is separated from by-products by filtration of liquid ammonia.

13. The method according to PP.1 - 12, characterized in that the ammonia recyclery.

14. The method according to PP.1 - 13, characterized in that the ratio of the compounds of formulas 2 and 3 is 1 : 2 to 1 : 2,5.

15. The method according to PP.1 to 14, characterized in that the ratio of the compounds of formulas 2 and 3 is 1 : 2.1 to 1 : 2,2.

16. The method according to PP.1, 7 and 8, characterized in that for producing compounds of formula 7

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carry out the condensation of the compounds of formula 4

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with the compound of the formula 8

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where R2represents C1- C8-alkyl and M is an ion of sodium, potassium or ammonium, and sodium, and add catalyst in liquid ammonia, the resulting suspension of sodium amide is added to a suspension of compounds of formula 4 and formula 8 in the liquid is jut by evaporation and condensation.

17. The method of obtaining distributionally compounds, PP.1 - 16, having the properties of optical bleaching of textile material, paper and liquid detergents.

 

Same patents:

FIELD: paper-and-pulp industry.

SUBSTANCE: formulation includes optic bleacher and low-viscosity water-soluble nonionic polysaccharide derivative, whose 5% aqueous solution exhibits at ambient temperature Brookfield viscosity below about 1500 cP.

EFFECT: increased brightness of coated paper.

34 cl, 9 tbl, 2 ex

FIELD: organic chemistry, paper industry.

SUBSTANCE: invention relates to compositions used for coating paper covers. Invention describes a composition for coating paper cover comprising whitening pigment comprising: (a) product of melamine formaldehyde or phenol-formaldehyde polycondensation, and (b) water-soluble fluorescent whitening agent of the formula:

wherein R1 and R2 represent independently of one another -OH, -Cl, -NH2, -O-(C1-C4)-alkyl, -O-aryl, -NH-(C1-C4)-alkyl, -N-(C1-C4-alkyl)2, -N-(C1-C4)-alkyl-(C1-C4-hydroxyalkyl)- -N-(C1-C4-hydroxyalkyl)2 or -NH-aryl, for example, anilino-, anilinemono- or disulfonic acid or aniline sulfone amide, morpholino-, -S-(C1-C4)-alkyl(aryl) or radical of amino acid, for example, aspartic acid or iminoacetic acid that is replaced with radical in amino-group; M means hydrogen, sodium, potassium, calcium, magnesium atom or ammonium, mono-, di-, tri- or tetra-(C1-C4)-alkylammonium, mono-, di- or tri-(C1-C4)-hydroxyalkylammonium, or ammonium di- or tri-substituted with a mixture of (C1-C4)-alkyl and (C1-C4)-hydroxyalkyl groups. Covers prepared on coating paper elicit high photostability and enhanced whiteness degree.

EFFECT: improved method for preparing, improved properties of covers.

7 cl, 1 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention concerns fluorescent bleach containing a mix of two asymmetrically substituted and one symmetrically substituted triazinylaminostilbene disulfone acid, a new symmetrically substituted derivative, method of their obtaining, and application of the mix in synthetic or natural organic material (especially paper) bleaching and in fluorescent bleaching and sun resistance boost of textile.

EFFECT: high substantivity and light resistance of the claimed fluorescent bleaches and their mixes, and better water solubility of the claimed mixes in comparison to the solubility of each individual bleach.

15 cl, 2 tbl, 12 ex

FIELD: chemistry, textiles, paper.

SUBSTANCE: present invention relates to new amphoteric bis-triazinylaminostilbene fluorescent whitening agents for fluorescent whitening of organic materials, particularly paper. Description is given of use of compounds with formula (5) for fluorescent whitening of paper.

EFFECT: compounds have high bleaching power; fluorescence is not prevented by cation-active polymers or anion-active fluorescent whitening agents contained in the paper.

2 cl, 2 tbl, 48 ex

FIELD: chemistry.

SUBSTANCE: described is a composition, containing (A) 2 to 30 wt % composition of amino alcohol - 2-amino-2-methyl-1-propanol with formula (1), and (B) 70 to 98 wt % composition of fluorescent optical bleaching agent with formula (2) , where X - is hydrogen, ion of alkali metal or ammonium, or hydroxyalkylammonium radical, derived from amino alcohol (1); R7, R8, R9 and R10 - -OR11, -NR11R12 or , where R11 and R12 - is hydrogen, alkyl, hydroxyalkyl, alkoxyalkyl, carboxyalkyl, dicarboxyalkyl, H2N-CO-alkyl or alkylthio group.

EFFECT: high solubility in water and increased stability when storing its aqueous solutions.

4 cl, 3 tbl, 3 ex

FIELD: textile fabrics, paper.

SUBSTANCE: aqueous solutions are related to toluylene optical bleaches and may be used in production of chalk overlay paper of high whiteness. Aqueous solutions contain at least one optical bleach, polyvinyl alcohol, having extent of hydrolysis over 75% and Brookfield viscosity of 2-40 mPa·s, and water. This composition may be used for paper coating. It may be applied on paper after its moulding to produce chalk overlay paper.

EFFECT: provision of stability in storage of aqueous solutions of toluylene optical bleaches and simplified method for production of chalk overlay paper.

9 cl, 3 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to concentrated aqueous solutions of hexa-sulfonated stilbene used optical brighteners. Description is given of an aqueous solution of hexa-sulfonated stilbene optical brightener which is stable during storage with over 0.214 mol/kg content thereof in the solution. The solution does not contain a soluble agent, for example urea. By removing salts formed during synthesis of the optical brightener, its concentration of up to 0.35 mol/kg can be achieved without losing stability during storage. Also described is a method of preparing an aqueous solution of the said optical brightener and its use for bleaching paper or cellulose materials.

EFFECT: high concentration solutions of the said optical brightener do not show crystallisation signs after 2 weeks at 5°C and enables formation of coating compositions with low water content, which reduces energy consumption on drying and reduces penetration of water and adhesive into the paper layer.

10 cl, 1 dwg, 1 tbl, 3 ex

FIELD: textile, paper.

SUBSTANCE: procedure refers to production of wood pulp and can be implemented in pulp-and-paper industry. The procedure consists in whitening fibres of sulphate pulp with a whitening agent on base of chlorine and in washing whitened fibres of sulphate pulp. Upon washing fibres of sulphate pulp are subject to interaction with at least one optic whitener before mixing ponds. Interacting is carried out in solution at pH from 3.5 to 8.0 and temperature from 60 to 80°C during 0.5-6 hours. The invention also refers to wood pulp produced by the said procedure.

EFFECT: increased whiteness and optic brightness of paper at decreased utilisation of optic whitener.

22 cl, 11 dwg, 11 tbl, 7 ex

FIELD: paper industry.

SUBSTANCE: methods refer to manufacturing of bleached cellulose material, prevention of yellowing and loss of whiteness in bleached craft-cellulose, and manufacturing of paper goods. In process of bleached cellulose material manufacturing, bleached craft-cellulose is produced and exposed to contact with sufficient amount of more or several reducing agents. Additionally bleached craft-cellulose is exposed to contact with one or several optical bleach, with one or more chelating agent. Method for prevention of yellowing and loss of whiteness of bleached craft-cellulose in storage includes addition of efficient amount of one or more reducing agent into bleached cellulose and possibly one or more chelating agent, one or more polycarboxylate or their combinations. Method for production of paper goods includes production of bleached craft-cellulose, formation of initial water suspension from it, water drainage with formation of sheet and sheet drying. Besides efficient amount of one or more reducing agent is added into bleached craft-cellulose, initial suspension or sheet. Additionally one or more chelating agent is added there, one or more optical bleach, one or more polycarboxylate, or their combination.

EFFECT: improved quality of paper goods, increased stabilisation of whiteness and increased resistance to yellowing in process of paper production and to thermal yellowing, improved colour pattern.

17 cl, 33 tbl

FIELD: chemistry.

SUBSTANCE: invention describes an aqueous dispersion of an optical bleaching agent which is stable during storage, does not contain dispersants and stabilisers and contains 20-40% active substance in form of one or more optical bleaching agents obtained through successive reaction of cyanuric chloride with 4,4'-diamino-2,2'- stilbene sulphonic acid, amine and a product of reacting monoethanol amine with acrylamide.

EFFECT: disclosed dispersion of optical bleaching agent does not require dispersants or other stabilising additives to prevent settling during storage and has excellent properties for bleaching paper and other cellulose materials.

8 cl, 2 tbl, 4 ex

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