1,2,3-tris-[(ammonio)methylcarbonyloxypoly(alkyleneoxy)]-propane trichlorides possessing bactericidal and fungicide activity and demulsifying property of petroleum emulsion and method for their preparing

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to novel 1,2,3-tris-[(ammonio)methylcarbonyloxypoly(alkyleneoxy)]-propane trichlorides of the general formula:

wherein at -X+ as -N+R1RR, R1 = R2 mean hydrogen atom (H), R3 means aliphatic hydrocarbon radical comprising 10-16 carbon atoms, a + c + e (the general degree of oxypropylation) = 49,b + d + f (the general degree of oxyethylation) = 0; at -X+ as -N+R1R2R3, R1 = R2 mean H, R3 means aliphatic hydrocarbon radical comprising 10-16 carbon atoms, a + c + e = 55, b + d + f = 0; at -X+ as -N+R1R2R3, R1 = R2 mean H, R3 means aliphatic hydrocarbon radical comprising 10-16 carbon atoms, a + c + e = 80, b + d + f = 24; at -X+ as -N+R1R2R3, R1 = R2 mean H, R3 means aliphatic hydrocarbon radical comprising 10-16 carbon atoms, a + c + e = 90, b + d + f = 27; at -X+ as -N+R1R2R3, R1 = R2 means H, R3 means phenyl, a + c + e = 80, b + d + f = 24; at -X+ as -N+R1R2R3, R1 = R2 mean H, R3 means phenyl, a + c + e = 90, b + d + f = 27; at -X+ as , a + c + e = 80, b + d + f = 24; at -X+ as , a + c + e = 90, b + d + f =27. Also, invention relates to a method for synthesis of these compounds. Method involves interaction of 1,2,3-tris-[hydroxypoly(alkyleneoxy)]-propane of the formula:

wherein a + c + e = 49-90, b + d + f = 0-27 with monochloroacetic acid in the presence of acidic catalyst, in boiling organic solvent medium with azeotropic removal of water formed and the following treatment of synthesized reaction product in polar solvent medium at heating with amino-compounds of the formula: NR1R2R3 wherein R1 = R2 mean H, R3 means aliphatic hydrocarbon radical comprising 10-16 carbon atoms, phenyl, or morpholine of the formula:

in the following mole ratios of reagents - propane hydroxyl derivative : monochloroacetic acid : amino-compound or morpholine = 1:(3.0-3.2):(3.0-3.2), respectively. New compounds show the bactericidal and fungicide activity and properties of demulsifying agents for petroleum emulsions.

EFFECT: improved method of synthesis, valuable properties of compounds.

7 cl, 3 tbl, 8 ex

 

The invention relates to organic chemistry, namely the synthesis of previously unknown 1,2,3-Tris[(ammonia)methylcarbazole(alkylene)]propane of trichlorides with bactericidal and fungicidal activity, which can be used to combat fungal and bacterial lesions in medicine, veterinary medicine and agriculture, as well as the properties of the emulsion oil emulsions, which can be used for breaking oil emulsions in the preparation processes in the oil industry.

Connection of the proposed series are distinguished by the fact that in its structure simultaneously contain three ammonium center with:

as well as ester and poly(oxyalkylene) group.

Known compounds, in the structure contain both ammonium centers and ester groups and which is N,N-dimethyl-N-alkyl-N-ethoxycarbonylmethylene chlorides, of General formula:

[Shelton R.S., M.J. Van Campen, Tilport C.H. et all. Quaternary Ammonium Salts as Germicides. II Acetoxy and at Carbethoxy Derivates of Aliphatic Quaternary Ammonium Salts // j. Chem. Soc., 1946, v.68, No. 5, P.755-757].

Also known Quaternary ammonium compound comprising the structure of the ammonium center one or more polyoxyethylene fragments. Such are the Quaternary and monavie connection with three polyoxyethylene fragments, General formula:

[M. Pletnev Cosmetics and hygienic detergents. - M.: Chemistry, 1990, 272 S.; Kroke H. // Cosmet. Perfum. 1975. V.90. No. 11. R. 31-34].

The most similar structure to the proposed compounds are N-[isononylphenol(ethylenoxy)carbonylmethyl]ammonium chlorides, of General formula:

[Patent 1531416 of the Russian Federation. IPC C 07 C 87/30. Publ. 10.04.1995. Fakhretdinov PS, Novels, GV, etc. a Method of producing corrosion inhibitors for carbon steel in hydrogen sulfide-containing saline water environments, showing fungistatic, bacteriostatic and disinfectant action].

The disadvantage of this solution is relatively low bactericidal activity of the claimed compounds against gram-positive and gram-negative bacteria, as well as lack of fungicidal activity against various species of fungi, for example, pathogen Ashteroth (brood disease of bees).

The technical result of the present invention is the synthesis of novel 1,2,3-Tris[(ammonia)methylcarbazole(alkylene)]propane of trichlorides with bactericidal and fungicidal activity and properties of the emulsion oil emulsion, and the way they are received.

Offers 1,2,3-Tris[(ammonia)methylcarbazole(alkylene)]propane trichloride provided the three ammonium center, ester groups and polyoxyalkylene fragments of General formula:

where:

R1=R2=H;

R3= aliphatic hydrocarbon radical containing 10 to 16 carbon atoms;

a+C+e = total oxypropylation, equal to 49;

b+d+f = total degree of oksietilirovannye 0;

in:

R1=R2=H;

R3= aliphatic hydrocarbon radical containing 10 to 16 carbon atoms;

a+C+e = total oxypropylation equal to 55;

b+d+f = total degree of oksietilirovannye 0;

in:

R1=R2=H;

R3= aliphatic hydrocarbon radical containing 10 to 16 carbon atoms;

a+C+e = total oxypropylation, 80;

b+d+f = total degree of oksietilirovannye equal to 24;

in:

R1=R2=H;

R3= aliphatic hydrocarbon radical containing 10 to 16 carbon atoms;

a+C+e = total oxypropylation, 90;

b+d+f = total degree of oksietilirovannye equal to 27;

in:

R1=R2=H;

R3= phenyl;

a+C+e = total oxypropylation, 80;

b+d+f = total degree of oksietilirovannye, RA is Naya 24;

in:

R1=R2=H;

R3= phenyl;

a+C+e = total oxypropylation, 90;

b+d+f = total degree of oksietilirovannye equal to 27;

in:

a+C+e = total oxypropylation, 80;

b+d+f = total degree of oksietilirovannye equal to 24;

in:

a+C+e = total oxypropylation, 90;

b+d+f = total degree of oksietilirovannye equal to 27.

Declare 1,2,3-Tris[(ammonia)methylcarbazole(alkylene)]propane trichloride are new, not previously known compounds having bactericidal and fungicidal activity and properties of the emulsion oil emulsion.

A method of obtaining Quaternary ammonium compounds containing ester and polyoxyethylene groups, for example, N-[isononylphenol(ethylenoxy)carbonylmethyl]ammonium chloride, the General formula:

where:

R1=R2=CH3, alkyl fraction C7-C9;

R3= alkyl fraction7-C9, alkyl fraction10-C16, alkyl fraction C15-C18;

n=3, 10;

by interacting monochloracetic acid with an alcohol component, which are economicpolitical the Lee, General formula:

where:

n=3, 10;

and subsequent treatment of the amines, the General formula:

where:

R1=R2=CH3, alkyl fraction7-C9;

R3= alkyl fraction C7-C9, alkyl fraction10-C16, alkyl fraction C15-C18

[Patent 1531416 of the Russian Federation. IPC C 07 C 87/30. Publ. 10.04.1995. Fakhretdinov PS, Novels, GV, etc. a Method of producing corrosion inhibitors for carbon steel in hydrogen sulfide-containing saline water environments, showing fungistatic, bacteriostatic and disinfectant action].

To declare us 1,2,3-Tris[(ammonia)methylcarbazole(alkylene)]propane of trichloride features the way they are received by reacting 1,2,3-Tris[hydroxypoly(alkylene)]propanol, of the formula:

where:

a+C+e = total oxypropylation equal 49-90;

b+d+f = total degree of oksietilirovannye equal 0-27;

with monochloracetic acid in the presence of an acid catalyst, in an environment of boiling organic solvent, with azeotropic removal of water formed and the subsequent processing of the obtained reaction product, in the environment of the polar solvent by heating, the amino compounds of the formula:

where:

R1=R2=H;

R3= aliphatic hydrocarbon radical containing 10 to 16 carbon atoms; phenyl;

or morpholine of the formula:

when the molar ratios of reagents - hydroxyl derivative of propane : monochloracetic acid : aminosidine or morpholine=1 : 3,0-3,2 : 3,0-3,2 respectively.

As the source of 1,2,3-Tris[hydroxypoly(alkylene)]propanol along with individual connections, you can use the produced petrochemical industry, various ethoxylated and/or oxypropylene glycerine, including:

Laprol 3003 (TU 2226-022-10488057-95) with a total degree of oxypropylation equal 49-55 and the total degree of oksietilirovannye equal to 0.

Laprol 6003-2-18 (TU 2226-020-10488057-94) with a total degree of oxypropylation equal to 80-90 and the total degree of oksietilirovannye equal 24-27.

Monochloracetic acid is used in the form of individual compounds or technical product beyond 2431-288-05763441-99.

As the acid catalyst used N+-form cation-exchange resin KU-2-8, which is a solid, partially swellable macromolecular polysulphonate copolymer of styrene with divinylbenzene General formula:

and is available in various modificati the x, different amount of divinylbenzene in the copolymer. For example, the brand of the cation exchange resin KU-2-8 and KU-2-10 contain 8% and 10% divinylbenzene, respectively. [Saldadze K.M., Pashkov A.B., Titov, V.S. Ion-exchange high-molecular compounds edited Saldadze K.M. Moscow: GOS. ).technology. ed. chem. lit., 1960, S.112-114]. Cation-exchange resin KU-2-8 produced according to GOST 20298-74.

As the organic solvent in the interaction of hydroxyl derivative of propane with monochloracetic acid using an aromatic hydrocarbon solvent, for example toluene, xylene, nefras-120/200.

Under the symbol Nefras-120/200 petrochemical industry produces heavy oil solvent on THE 38-101809-90 obtained from the products of catalytic reforming, and contains a mixture of aromatic hydrocarbons, C8-C9(xylenes, propylbenzene, methylethylbenzene, mesitylene, pseudotumor and others)

Processing of the reaction product of hydroxyl derivative of propane with monochloracetic acid with amino compounds or morpholine are in medium polar solvents, which use low molecular weight alcohols, such as isopropanol, ethanol at a temperature of 60-85°C.

The proposed method of obtaining new, not previously known compounds of type 1,2,3-Tris[(ammonia)methylcarbazole(alkylene)]propantriol has some similarities with the way other series of Quaternary ammonium compounds, for example, N-[isononylphenol(ethylenoxy)carbonylmethyl]ammonium chloride [U.S. Pat. 1531416 of the Russian Federation. Publ. 10.04.1995]. But the differences between these two methods are significant. In a known way as alcohol components use economicpolitical, of General formula:

,

but as amino compounds - long-chain aliphatic tertiary amines of the type N,N,N-dialkylamino fraction7-C9N,N-dimethyl-N-alkylamines followed fraction10-C16or fraction C15-C18.

In the proposed method as alcohol components use 1,2,3-Tris[hydroxypoly(alkylene)]propane, of General formula:

where:

a+C+e = total oxypropylation equal 49-90;

b+d+f = total degree of oksietilirovannye equal 0-27, referred to in the present application is a hydroxyl derivative of propane. The resulting reaction product is then treated with amino compounds of the formula:

where:

R1=R2=H;

R3= aliphatic hydrocarbon radical containing 10 to 16 carbon atoms; phenyl;

or morpholine of the formula:

In the proposed method uses a molar ratio of reagents - hydroxyl derivative of propane : monochloracetic to the slot : aminosidine or morpholine= 1 : 3,0-3,2 : 3,0-3,2 respectively.

Thus, the proposed method using as initial products 1,2,3-Tris[hydroxypoly(alkylene)]propanol and amino compounds of the above formula or research differs from existing methods of obtaining well-known series of Quaternary ammonium compounds and allows to obtain previously unknown 1,2,3-Tris[(ammonia)methylcarbazole(alkylene)]propane trichloride with bactericidal and fungicidal activity and properties of the emulsion oil emulsion.

The proposed method for 1,2,3-Tris[(ammonia)methylcarbazole(alkylene)]propane of trichloride is simple, does not require special conditions and special equipment and can be performed on virtually any chemical production.

Declare 1,2,3-Tris[(ammonia)methylcarbazole(alkylene)]propane trichloride are new, and the retrieval method is new.

Cited specific examples of carrying out the invention.

Example 1

1,2,3-Tris{[(N-alkylammonium)methylcarbonate(2 mutilati-Lenox)]}propane trichloride fraction C10-C16with a total degree of oxypropylation, equal to 49.

A mixture of 52.9 g (1,8·10-2g-mol) of 1,2,3-Tris[hydroxypoly(2 methylethylidene)]propane with a total degree of oxypropylation, equal to 49; 5,1 g (5,4·10-2GMOs) monochloracetic acid and 120 ml of toluene, 1.8 g (3.4 percent by weight of hydroxyl derivative of propane) H+form kationoobmennuyu acid KU-2-8 (as acid catalyst) is boiled with trap Dean - stark and reflux until complete cessation of water excretion and reducing the acid number of the reaction mass to values less than or equal to 2 mg KOH/g acid Value of the number in the sample is determined by titration with alcoholic KOH solution. The reaction time of 14 hours. The catalyst is filtered off from the reaction mixture and the water-jet pump vacuum to remove the organic solvent (toluene) and unreacted monochloracetic acid.

The resulting reaction product is mixed with a solution of 10.8 g (5,4·10-2g·mol) alkylamines followed fraction C10-C16in 82 ml of isopropanol and heated under stirring and the temperature of 60-85°C for 10 hours. Control reactions are titrimetrically, determining the content of free amines potentiometric titration with alcoholic solution of hydrochloric acid. The reaction is stopped at a residual content of free amines less than 0.3%. The solvent is removed in vacuum. Output 67,0 g (99,0% of theoretical.) viscous liquid light yellow color.

IR-spectrum: ν(C=O)=1748 cm-1; ν(C-O)acicl=1110 cm-1; ν(C-O)acetate=1256 cm-1.

Example 2.

1,2,3-Tris[(N-alkylammonium)metolcarb yloksypoli(2-methylethyl-noxy)]propane trichloride fraction C 10-C16with a total degree of oxypropylation equal to 55.

Is obtained analogously to example 1 from 66,2 g (2,0·10-2g·mol) of 1,2,3-Tris[hydroxypoly(ethylenoxy)poly(2-methylethylidene)]propane with a total degree of oxypropylation equal to 55; 6,1 g (6,4·10-2g·mol of monochloracetic acid and 150 ml of xylene, 3.8 g (5,7% by weight of the hydroxyl derivative of propane) H+-form cation-exchange acid KU-2-8 (as acid catalyst); 12.8 g (6,4·10-2g·mol) alkylamines followed fraction10-C16and 100 ml of ethanol. Output and 82.2 g (99.9% of theory.) viscous liquid light yellow color.

IR-spectrum: ν(C=O)=1748 cm-1; ν(C-O)acicl=1111 cm-1; ν(C-O)acetate=1255 cm-1.

Example 3.

1,2,3 Tris[(N-alkylammonium)methylcarbazole(etileno-C)poly(2-methylethylidene)]propane trichloride fraction C10-C16with a total degree of oxypropylation equal to 80, and the total degree of oksietilirovannye equal to 24.

Is obtained analogously to example 1, from 65,0 (1,1·10-2g·mol) of 1,2,3-Tris[hydroxypoly(ethylenoxy)poly(2-methylethylidene)]propane with a total degree of oxypropylation equal to 80, and the total degree of oksietilirovannye equal to 24; 3.2 g (3,4-10-2 g·mol of monochloracetic acid and 130 ml of nefras And-120/200, 2.0 g (3.0 percent by weight of hydroxyl derivative of propane) H+-form cation-exchange acid KU-2-8 (as acid catalyst); 6.7 g (3,4·10-2g·mol) alkylamines followed fraction C10-C16and 86 ml of ISO-propanol. The output of 73.8 g (99.8% of theoretical.) viscous liquid light yellow color.

IR-spectrum: ν(C=O)=1749 cm-1; ν(C-O)acicl=1110 cm-1; ν(C-O)acetate=1252 cm-1.

Example 4.

1,2,3 Tris[(N-alkylammonium)methylcarbazole(etileno-C)poly(2-methylethylidene)]propane trichloride fraction C10-C16with a total degree of oxypropylation equal to 90, and the total degree of oksietilirovannye equal to 27.

Is obtained analogously to example 1, from 68,0 g (1,0·10-2g·mol) of 1,2,3-Tris[hydroxypoly(ethylenoxy)poly(2-methylethylidene)]propane with a total degree of oxypropylation equal to 90, and the total degree of oksietilirovannye equal to 27; 3,2 g (3.5·10-2g·mol of monochloracetic acid and 136 ml of toluene, 3.4 g (5.0 percent by weight of hydroxyl derivative of propane) N+-form cation-exchange acid KU-2-8 (as acid catalyst); 6.3 g (3,1·10-2g·mol) alkylamines followed fraction C10-C16and 90 ml of ethanol. The yield of 76.3 g (99.6% of theory.) viscous liquid light yellow color.

IR-spectrum: ν(C=O)=1748 cm-1; ν(C-O)acicl=1108 cm-1; ν(C-O)acetate=1254 cm-1.

Example 5.

1,2,3-Tris[(N-phenylamino)methylcarbazole(ethylenoxy)poly(2-methylethylidene)]is Roman trichloride with a total degree of oxypropylation, equal to 80, and the total degree of oksietilirovannye equal to 24.

Is obtained analogously to example 1, from 72,0 (1,2·10-2g·mol) of 1,2,3-Tris[hydroxypoly(ethylenoxy)poly(2-methylethylidene)]propane with a total degree of oxypropylation equal to 80, and the total degree of oksietilirovannye equal to 24; 3.5 g (3,7·10-2g·mol of monochloracetic acid and 144 ml of xylene, 2.2 g (3,1% by weight of the hydroxyl derivative of propane) N+-form cation-exchange acid KU-2-8 (as acid catalyst); 3.5 g (3,7·10-2g·mol) of aniline and 100 ml of isopropanol. Output to 78.3 g (99.7% of theory.) viscous liquid light yellow color.

IR-spectrum: ν(C=O)=1748 cm-1; ν(C-O)acicl=1109 cm-1; ν(C-O)acetate=1243 cm-1.

Example 6.

1,2,3 Tris[(N-phenylamino)methylcarbazole(ethylenoxy)POI(2 methylethylidene)]propane trichloride with a total degree of oxypropylation equal to 90, and the total degree of oksietilirovannye equal to 27.

Is obtained analogously to example 1, from 74,0 (1,1·10-2g·mol) of 1,2,3-Tris[hydroxypoly(ethylenoxy)poly(2-methylethylidene)]propane with a total degree of oxypropylation equal to 90, and the total degree of oksietilirovannye equal to 27; 3.4 g (3,6·10-2g·mol of monochloracetic acid and 150 ml of nefras And-120/200, 3.7 g (5.0 percent by weight of hydroxyl derivative of propane) H+forms Katie is Normanni acid KU-2-8 (as acid catalyst); 3.4 g (3,6·10-2g·mol) of aniline and 100 ml of isopropanol. The output of 79.8 g (99,4% of theoretical.) viscous liquid light yellow color.

IR-spectrum: ν(C=O)=1747 cm-1; ν(C-O)acicl=1109 cm-1; ν(C-O)acetate=1245 cm-1.

Example 7.

1,2,3 Tris[(morpholino)methylcarbazole(ethylenoxy)poly(2-methylethylidene)]propane trichloride with a total degree of oxypropylation equal to 80, and the total degree of oksietilirovannye equal to 24.

Is obtained analogously to example 1, from 73,0 (1,3·10-2g·mol) of 1,2,3-Tris[hydroxypoly(ethylenoxy)poly(2-methylethylidene)]propane with a total degree of oxypropylation equal to 80, and the total degree of oksietilirovannye equal to 24; 3.6 g (3,8·10-2g·mol of monochloracetic acid and 150 ml of toluene, 2.2 g (3.0 percent by weight of hydroxyl derivative of propane) N+-form cation-exchange acid KU-2-8 (as acid catalyst); and 3.3 g (3,8·10-2g·mol) of the research and 100 ml of ethanol. The output of 78.1 g (99.9% of theory.) viscous liquid light yellow color.

IR-spectrum: ν(C=O)=1749 cm-1; ν(C-O)acicl=1109 cm-1; ν(C-O)acetate=1254 cm-1.

Example 8.

1,2,3 Tris[(N-morpholino)methylcarbazole(ethylenoxy)poly(2-methylethylidene)]propane trichloride with a total degree of oxypropylation equal to 90, and the total degree oxyethylene the project, equal to 27.

Is obtained analogously to example 1, from 76,0 g (1,2·10-2g·mol) of 1,2,3-Tris[hydroxypoly(ethylenoxy)poly(2-methylethylidene)]propane with a total degree of oxypropylation equal to 90, and the total degree of oksietilirovannye equal to 27; 3,3 g (3,7·10-2g·mol of monochloracetic acid and 155 ml of xylene, 3.8 g (5.0 percent by weight of hydroxyl derivative of propane) N+-form cation-exchange acid KU-2-8 (as acid catalyst); 3,26 g (3,7·10-2g·mol) of the research and 100 ml of isopropanol. The output of 79.6 g (99.7% of theory.) viscous liquid light yellow color.

IR-spectrum: ν(C=O)=1750 cm-1; ν(C-O)acicl=1110 cm-1; ν(C-O)acetate=1255 cm-1.

Determination of the bactericidal activity of compounds (drugs) against gram-positive and gram-negative bacteria.

The bactericidal activity of the proposed compounds were studied against representative gram-positive group of bacteria - Staphylococcus aureus Staphylococcus aureus strain R-209 and gram-negative groups Escherichia coli Escherichia coli strain 7904 is logged on generally accepted in bacteriology methods [Methods of experimental chemotherapy / Edited. edit Pershin G.N., M.: Medicine, 1973, S-320; witches E.A., purer NM Guide for Microbiology, clinic and epidemiology, clinical picture and epidemiology of infectious disease is. M.: Medicine, 1964, S-610]. Using the optical method of the turbidity standard was prepared a suspension of microorganisms in saline solution with bacterial load 500 000 microbial cells in 1 ml of Bacterial suspension was poured in test tubes containing certain concentrations of the studied drugs. Control tubes contained the same amount of sterile saline. Exposure at this amounted to 0,5; 1,0; 1,5; 2,0 and 3,0 hours. Upon expiry of the exposure experienced and control materials were sown on elective nutritional environment: gene - environment Endo; St.aureus - salt agar. Incubation was performed in a thermostat at 37°C. monitoring the crops were carried out over 7 days.

The bactericidal activity of the proposed compounds against highly resistant to disinfectants bacteria was studied on the example of Mycobacterium tuberculosis Micobacteriura bovis strain 14 method cambric test [Methods of experimental chemotherapy / edited by Pershina G.N., M.: Medicine, 1973]. Sterile cambric test size 1 cm2inspired suspension culture at a concentration of 2 mltm/ml. Then in bottles with a water solution of the investigated compounds were made by two cambric test. Exposure time in all cases was 2 hours. Upon expiry of the exposure experienced and control materials were subjected to three washing is of sterile distilled water from the test preparation by centrifugation at 5 Tyson/min for 30 minutes. Then spent sowing on Lowenstein-Jensen medium. Incubation was carried out in a thermostat at 37°C for one month. Analysis conducted in the presence or absence of growth of colonies in the experimental tubes compared to control.

The bactericidal activity of the proposed compounds against highly resistant to disinfectants bacteria was studied on the example of M. tuberculosis Micobacterium bovis strain 14 method cambric test [Methods of experimental chemotherapy / edited by Pershina G.N., M.: Medicine, 1973]. Sterile cambric test size 1 cm2inspired suspension culture at a concentration of 2 mltm/ml. Then in bottles with a water solution of the investigated compounds were made by two cambric test. Exposure time in all cases was 2 hours. Upon expiry of the exposure experienced and control materials were subjected to three washing with sterile distilled water from the test preparation by centrifugation at 5 Tyson/min for 30 minutes. Then spent sowing on Lowenstein-Jensen medium. Incubation was carried out in a thermostat at 37°C for one month. Analysis conducted in the presence or absence of growth of colonies in the experimental tubes compared to the control. The results are given in table 1.

As a reference sravanabelagola activity used structural similar - "The drug f-761", which is a N,N-dimethyl-N-alkyl-N-[isononylphenol(ethylenoxy)carbonylmethyl]ammonium chloride fraction C10-C16formula:

where:

R1=R2=CH3;

R3- aliphatic hydrocarbon radical containing 10 to 16 carbon atoms;

n=10

[Patent 1531416 of the Russian Federation. IPC C 07 C 87/30. Publ. 1995.04.10. Fakhretdinov P.S. CENTURY Novels and other Method of obtaining corrosion inhibitors for carbon steel in hydrogen sulfide-containing saline water environments, showing fungistatic, bacteriostatic and disinfectant action].

"The drug f-761" along with the fact that is a structural analogue of the proposed in the present invention compounds, possesses the same activity (antibacterial and antifungal action).

The data in table 1 indicate bacterial activity claimed 1,2,3-Tris[(ammonia)methylcarbazole(alkylene)]propane of trichloride against gram-positive and gram-negative bacteria at about the level of structural analogue of the Drug f-761". At the same time, the data in table 1 show that the inventive compounds exhibit high antibacterial activity against resistant to disinfectants M. tuberculosis Micobacterium bovis, MBC which is 0.25 to 1.0%. Structures of the first analog to the f-761" bactericidal activity against .bovis is not.

The results of the test show that the claimed 1,2,3-Tris[(ammonia)methylcarbazole(alkylene)]propane trichloride on the bactericidal activity of superior structural analogue of the Drug f-761" and can be used for preventive and disinfection treatment in the foci of infection with TB agents in veterinary medicine and agriculture.

Determination of the fungicidal activity.

The fungicidal activity of the proposed compounds were investigated on the example of the pathogen ascosphaerosis (brood disease of bees) - Ascosphaera apis, the strain VG-8. The tests were carried out on generally accepted in Microbiology methods of serial dilutions [Methods of experimental chemotherapy / edited by Pershina G.N., M.: Medicine, 1973. S-320; witches E.A., purer NM Guide for Microbiology, clinic and epidemiology, clinical picture and epidemiology of infectious diseases. M.: Medicine, 1964. S-610].

For the experiments used a suspension of fungi the fungal load 200000 fungal bodies in 1 ml of physiological solution. Fungal suspension was poured in test tubes containing certain concentrations of the studied drugs in the proportion of 1 part of a fungal suspension of 1 part of solution of the drug. As the standard of comparison used a structural analogue of "Drug f-761", which is a N,N-dimethyl-N-alkyl-N-[isononylphenol(ethylenoxy)is carbonylmethyl]ammonium chloride and possessing antibacterial and antifungal activity. As control using the same amount of sterile saline. Exposure is 5, 10, 30, 60 and 120 minutes After exposure carry out sowing of the test and control materials on selective nutrient medium - wort-agar. Incubation is carried out in a thermostat at a temperature of 37°and observation are within 14 days.

Research results fungicidal activity proposed compounds and benchmark comparisons are presented in table 2

The data of table 2 show that the claimed compounds exhibit fungicidal activity against the pathogen of ascosphaerosis bees Ascosphaera apis. Minimum fungicidal concentrations of these compounds are 1,0-2,0% at exposure of 2 hours, while a structural analogue of the Drug f-761", showing fungistatic action, the fungicidal activity is not.

The presented data confirm the advantages of the proposed 1,2,3-Tris[(ammonia)methylcarbazole(alkylene)]propane of trichloride before structural analogue for fungicidal activity.

The definition of a demulsifying activity of compounds against water and oil emulsions.

The compound obtained in example 1-8, the original Laprol 3003 and 6003-2-18 and industrial demulsifier REKOD-758 tested as demulsifiers for water-in-oil emulsions. The definition of a demulsifying is aktivnosti based on a comparison of the dynamics of sludge water from oil in the presence of compounds according to example 1-8 and standards of comparison - industrial used demulsifiers REKOD-758, Lapola 3003 and Lapola 6003-2-18.

The studies were conducted according to the standard technique "bottle test". For emulgirovanija used artificial and natural emulsion. Natural emulsion taken with SLE. 9267 (JSC "Nurlat-oil"). Artificial emulsion was prepared at a temperature of 20°With a six-bladed turbine stirrer immediately before testing demulsifying activity. Mode settings were as follows: engine speed 1300 rpm, mixing time 5 minutes

The volume of the sample was 20 ml in a specially graduated test tubes. Subjects demulsifiers (connection according to claim 1 to 8, REKOD 758, Laprol 3003 and 6003-2-18) were dosed out in the form of a 20% spirit-toluene solutions. The experiment was conducted at dose levels of 30, 60, 90, 120 g/T. the Sample destructible emulsion was treated with a solution of demulsifier, which was mixed for 30 seconds a six-bladed turbine stirrer at 500 rpm after which the samples were placed on static sucks at temperatures of 20 and 50°with fixation of the dynamics of water separation. The amount of separated water was recorded after 1 and 2 hours of sludge. In the settling process was carried out periodic turning tubes to simulate the actual movement of production wells (according to RD 153-39.0-313-03).

The obtained data are given in Alice 3.

As can be seen from table 3, the compounds 1-8 have a higher demulsifying activity than industrial demulsifiers used REKOD 758, Laprol 3003 and Laprol 6003-2-18.

Thus, the proposed 1,2,3-Tris[(ammonia)methylcarbazole(alkylene)]propane trichloride are new compounds having bactericidal and fungicidal activity and properties of the emulsion oil emulsion, and can be used to combat fungal and bacterial lesions in medicine and veterinary medicine and agriculture, as well as the properties of the emulsion oil emulsions, which can be used for breaking oil emulsions in the preparation processes in the oil industry.

The proposed method for obtaining the claimed compounds is simple, does not require special conditions and special equipment and can be performed on virtually any chemical production.

td align="center"> 1
Table 1.

The results of the study of bactericidal activity of drugs.
ConnectionExposure time, hoursThe minimum bactericidal concentration %
St.aurerusE.coliM. bovis
21,02,01,0
221,02,01,0
321,02,00,25
421,02,00,25
521,02,01,0
621,02,01,0
723,02,01,0
823,02,01,0
Structural analog20,51,0Activity is not

td align="center"> 2
Table 2

The results of the study fungicidal activity.
ConnectionExposure time, hMinimum fungicidal concentration %
122,0
222,0
322,0
422,0
522,0
62,0
721,0
821,0
A structural analogue of the Drug f-761" Pat. Of the Russian Federation No. 1531416Does not possess fungicidal activity

1. 1,2,3-Tris[(ammonia)methylcarbazole(alkylene)]propane trichloride General formula

where

R1=R2=H;

R3= aliphatic hydrocarbon radical containing 10 to 16 carbon atoms;

a+C+e = total oxypropylation, equal to 49;

b+d+f = total degree of oksietilirovannye 0;

when

R1=R2=H;

R3= aliphatic hydrocarbon radical containing 10 to 16 carbon atoms;

a+C+e = total oxypropylation equal to 55;

b+d+f = total degree of oksietilirovannye 0;

when

R1=R2=H;

R3= aliphatic hydrocarbon radical containing 10 to 16 carbon atoms;

a+C+e = total oxypropylation, RA is owned 80;

b+d+f = total degree of oksietilirovannye equal to 24;

when

R1=R2=H;

R3= aliphatic hydrocarbon radical containing 10 to 16 carbon atoms;

a+C+e = total oxypropylation, 90;

b+d+f = total degree of oksietilirovannye equal to 27;

when

R1=R2=H;

R3= phenyl;

a+C+e = total oxypropylation, 80;

b+d+f = total degree of oksietilirovannye equal to 24;

when

R1=R2=H;

R3= phenyl;

a+C+e = total oxypropylation, 90;

b+d+f = total degree of oksietilirovannye equal to 27;

when

a+C+e = total oxypropylation, 80;

b+d+f = total degree of oksietilirovannye equal to 24;

when

a+C+e = total oxypropylation, 90;

b+d+f = total degree of oksietilirovannye equal to 27.

2. Compounds according to claim 1, having bactericidal and fungicidal activity and properties of the emulsion oil emulsion.

3. Method of preparing compounds according to claim 1 which consists in the interaction of 1,2,3-Tris[hydroxypoly(alkylene)]propanol formula

where a+C+e = total oxypropylation equal 49-90;

b+d+f = total degree of oksietilirovannye equal 0-27,

with monochloracetic acid in the presence of acid catalyst in the medium boiling organic solvent azeotropic removal of water formed and the subsequent processing of the obtained reaction product in the environment of the polar solvent by heating the amino compounds of the formula

where R1=R2=H;

R3= aliphatic hydrocarbon radical containing 10 to 16 carbon atoms; phenyl,

or morpholine of the formula

in molar ratios of reagents - hydroxyl derivative of propane: monochloracetic acid: aminosidine or morpholine= 1:3,0-3,2:3,0-3,2 respectively.

4. The method according to claim 3, namely, that as the acid catalyst used N+-form cation-exchange resin KU-2-8, taken in an amount of 3.0 to 5.7% of the weight of the original hydroxyl derivative of propane.

5. The method according to claim 3, which consists in the fact that as an organic solvent in the interaction of hydroxyl derivative of propane with maharasnadi acid using an aromatic hydrocarbon solvent is, for example, toluene, xylene, nefras-120/200.

6. The method according to claim 3, which consists in the fact that during the processing of a reaction product of hydroxyl derivative of propane with monochloracetic acid with amino compounds or morpholine as polar solvents use of low molecular weight alcohols, such as isopropanol, ethanol.

7. The method according to claim 3, which consists in the fact that the processing aminoguanidinium or morpholine reaction product of hydroxyl derivative of propane with monochloracetic acid is conducted at a temperature of 60-85°C.



 

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