Quaternary ammonium compounds based on resin acids and colophony eliciting fungicide, bactericidal and surface-active properties

FIELD: organic chemistry.

SUBSTANCE: invention relates to compounds of the general formula: wherein R means ethyl or benzyl; X means chlorine atom (Cl) or bromine atom (Br). Invention provides preparing quaternary ammonium compounds eliciting fungicide, bactericidal and surface-active properties.

EFFECT: valuable properties of compounds.

2 tbl, 4 ex

 

The present invention relates to new biological and surface-active chemical compounds of General formula

where R is ethyl or benzyl, X Is CL or Br.

These new compounds have fungicidal, bactericidal and surface activity and can be used in various branches of industry, agriculture and medicine.

Known compounds of similar structure,

where R is the radical of carboxylic acids [ARS, Lpitem, Shippingand. Surfactants. L.: Chemistry, 1988. P.51]. However, for these compounds, there are no data on their biological activity.

The aim of the invention is the creation on the basis of environmentally sound virtually inexhaustible natural plant materials - diterpene (resin) acids and rosin - new compounds with fungicidal, bactericidal and surface activity that will expand the Arsenal of clean compounds with the specified properties.

The method of obtaining compounds of formula (1) based on known reactions, and it is carried out according to the scheme: getting anhydrides of organic acids by reacting organic acids with Halogens [Buger K., Miron D. Organic syntheses, ch. II. M.: Mir, 1973. the.348-351]; obtaining the amino esters of the acids by reacting acid chlorides of the acids with low molecular weight aminoalcohols and subsequent quaternization of the amino esters [ARS, Lpitem, Shippingand. Surfactants. L.: Chemistry, 1988. P.51-52].

To obtain the proposed Quaternary ammonium compounds based on rosin and resin (diterpene) acids, proceed as follows.

At the first stage receives the acid chloride dehydroabietic acid [Kushnir S.R., Borisova NB, Radbill A.B., etc. the Synthesis of the acid chloride dehydroabietic acid. ZH. 2003. T. No. 11. S-1847], or similarly, the rosin acid chlorides or crystalline mixture of resin acids, selected from rosin. Further, by reacting the corresponding acid chloride with dimethylethanolamine get aminoether dehydroabietic acid, rosin or crystalline mixture of resin acids (depending on feedstock), which is then quaternized in a known manner by an excess of methyl ethyl or benzyl chloride in the solvent (acetonitrile).

Quaternary ammonium compounds on the basis of resin acids or rosin are slightly coloured resinous mass or light powder depending on the source of raw materials. They are soluble in water, ethanol, toluene, dioxane, acetone, ACE is onitrile, carbon tetrachloride. Stable in air at ambient temperature.

Example 1. Getting Quaternary ammonium compounds on the basis of dehydroabietic acid (dehydroabietyl-4-carbonyldiimidazole bromide).

In triggerlevel flask equipped with a stirrer, jacket heating and reflux condenser, load 85 g dimethylethanolamine on THE 6-02-1086-91 and 85 g of toluene according to GOST 9980-76 with changes 1-5. The mixture was thoroughly stirred and slowly portions in order to avoid overheating add 200 g of a 50%aqueous solution of the acid chloride dehydroabietic acid in toluene. After that, the temperature of the reaction mixture increased to 97°and maintain the reaction mass at this temperature and stirring for 4 hours the reaction mass is filtered off, the filtrate is washed with water to neutral reaction in water extract is dried and distilled from it the solvent under reduced pressure. Get aminoether dehydroabietic acid with the release of 86-87% of theoretical. The IR spectrum of the product is the characteristic absorption band in the region 1720 cm-1

To obtain the claimed compounds of formula (1) in the apparatus, equipped with a stirrer, reflux condenser and jacket for heating, load 100 g dimethylethanolamine EF the RA dehydroabietic acid. There, with constant stirring portions 450 g of methyl ethyl. The mixture was thoroughly stirred for 5 hours at a temperature of 30°C. Upon completion of the reaction the excess of methyl ethyl distilled off under reduced pressure. Received 128.8 g of product (yield is almost quantitative) with TPL 175-178°C.

According to elemental composition, UV, IR, PMR and mass spectra of this substance is a Quaternary ammonium compound of the formula (1) based on dehydroabietic acid, where R is ethyl, X is bromine.

Found, %: C 65.05; N, 8.68; N, 3.40; VG 15.60.

[C26H42O2N]+Br-

Calculated, %: C 64.99; N, 8.81; N, 3.49; VG 16.63.

Qualitative reaction on the Quaternary ammonium compound - positive.

Ammonia nitrogen, %: 2.73 found; calculated 2.91.

In the UV spectrum appear three absorption bands 259, 267 and 276 nm, characteristic fragments dehydroabietic acid.

The IR spectrum revealed three characteristic absorption bands in the region of 3400 cm-1(-N-C bond), a triplet in the region 3000-2800 cm-1(-C-H bond), and in 1727 cm-1(C=0 bond fragment). Strip 1460 and 1380 cm-1refer to the vibrations of CH2and CH3ethyl group.

In the PMR spectrum clearly shows the characteristic signals: 6.7-7.3 ppm (protons of aromatic nuclei); 1.14 ppm, 1.17 and 1.22 ppm (protons of the sawn and 2CH 3groups); broadened signal 4.5 ppm (protons of CH2in the ether of the C-O-CH2-); 3.7 ppm (protons 2CH2associated with nitrogen); 3.4 ppm (protons 2CH3associated with nitrogen, intensity 6N); 2.7 ppm (multiplets, the intensity at 2CH2each).

Brutha formula was confirmed by mass spectrometrically on fragmentation ion m/z 385.299.

Example 2. Getting dehydroabietyl-carbonyldiimidazole chloride.

In the apparatus, equipped with a stirrer, reflux condenser and jacket for heating, download 10.3 g dimethylethanolamine ether dehydroabietic acid obtained in example 1, 50 ml of acetonitrile and the mixture is stirred at a temperature of 45°C to obtain a clear homogeneous solution. The resulting solution was cooled to ambient temperature and to it with constant stirring portions add a solution of 3.85 g of benzylchloride in 10 ml of acetonitrile. The resulting reaction mass is maintained at ambient temperature for 1 h, then heated to a temperature of 80°C and maintained at this temperature and stirring for 5 hours At the end of the process from the reaction mixture the solvent is distilled off at a temperature of 50°and reduced pressure.

Obtained 13.5 g of product (yield is almost quantitative) as a light powder is ka with TPL 51.5-52.5°C. Soluble in water, toluene, acetone, acetonitrile, alcohol.

According to elemental composition, UV, IR, PMR and mass spectra of the product is a Quaternary ammonium compound of the formula (1) based on dehydroabietic acid, where R is benzyl, X is chlorine.

Found, %: C 74.93; N, 8.67; N, 2.98; Cl 7.88.

[C31H44O2N]+Cl-

Calculated, %: C 74.74; N, 8.90; N, 2.81; Cl 7.12.

Qualitative reaction on the Quaternary ammonium compound - positive.

Ammonia nitrogen, %: found 2.89; calculated 3.02.

In the UV spectrum showed a slight extension of example 1 absorption bands in the region 250-285 nm, caused by the absorption of benzyl radical.

The IR spectrum is almost identical to the compound of example 1 and has the same characteristic absorption bands in the region of 3400 cm-1, 3000-2800 cm-1and 1730 cm-1. Is a band in the area, characteristic of the C-H benzyl radical.

PMR-spectrum is almost identical to the compound of example 1.

Example 3. The mixture abieto-8,11,13-triene-4-carbonyldiimidazole bromides.

All as in example 1, but as feedstock take a mixture of resin acids with TPL 169°and acid number 184 mg KOH per 1 g of the product isolated from rosin conventional method (purified rosin), of the following composition (wt. % by GLC): daydream Minova acid 70.5, dihydroabietic acid - 18.1, the amount of acid pimaric series - 10.3, the amount of acids with conjugated double bonds (abietic acid) - 0.8.

The yield is practically quantitative.

According to elemental composition, UV, IR, PMR and mass spectra of the product is a Quaternary ammonium compound of General formula (1) based on the mixture of the resin (diterpene) acids, where R is ethyl, X is bromine.

Found, %: C 65.30; N, 9.10; N, 3.65; Br 15.90.

[C26H42O2N]+VG-

Calculated, %: C 65.00; N, 8.80; N, 3.52; Br 16.60.

Qualitative reaction on the Quaternary ammonium compound - positive.

Ammonia nitrogen, %: found 2.69; calculated 2.91.

UV, IR, PMR and mass spectra are almost identical spectra of the product of example 1 and confirm the structure of matter of the formula (1).

Example 4. The mixture abieto-8,11,13-triene-4-carbonyldiimidazole bromides based on rosin.

All, as in example 1, but as raw material take rosin tall disproportionately on THE 13-00281074-265-95 with the changes with the following physico-chemical properties characteristics: appearance - glassy, partially crystallized mass; an acid number of 164 mg KOH/g; the mass fraction of acids with conjugated double bonds - 0.8%.

Get with quantitative yield resinous product is light yellow CEE is and. Soluble in water, acetonitrile, dioxane, toluene, alcohol.

Qualitative reaction on the Quaternary ammonium compound - positive.

Ammonia nitrogen, found %: 2.58.

The elemental composition found %: C 65.20; N, 8.70; N, 3.20; Br 14.80.

UV, IR and PMR spectra are similar to spectra of the compounds in example 1, and there are characteristic absorption bands for the substance (1), namely: in the UV spectrum absorption bands in the region 250-280 nm; IR spectrum absorption bands in the region 3400, 3000-2800 and 1740-1710 cm-1.

Evaluation of biocidal activity (bactericidal and fungicidal) stated Quaternary ammonium compounds according to examples 1-4 were performed by standard test-cultural method. As the test cultures used:

bacteria: Escherichia coli; Proteus vulgaris; Staphylococus aureus; Bacillus B. megaterium; Pseudomonas aeruginosa; Streptococcus salivarius.

fungi: Aspergillus oryzae; Aspergillus niger; Aspergillus terreus; Chaetomium globosum; Paecilomyces variotii; Penicillium funiculosum; Penicillium chrysogenum; Penicillium cyclopium; Trichoderma viride.

In wells akaraserani nutrient medium make the test substance at a given concentration in water. When using aqueous solutions of the following concentrations (wt. %): 0.05; 0.1; 0.5; 1 (or more if necessary). Each preset concentration tested in three sequences. About the presence of bactericidal and fungicidal activity is judged by the size of zone of inhibition (R, mm), the growth of the test cultures, which occurs around the holes with a test connection.

For comparison studied in similar conditions fungicidal and bactericidal activity are widely used in the Russian Federation and abroad drug Irgasan DP300 (manufacturer : Ciba Speciality Chemicals, Bazel', Switzerland) - triclosan (2,4,4’-trichloro-2’-hydroxydiphenyl ether).

The data obtained are shown in table 1.

Surface-active properties of the proposed Quaternary ammonium compounds of the formula (1) define common in the classical way by measuring surface tension by the method of maximum pressure education bubble and the method records Wilhelmi. As the reference liquid used bidistilled water, which is at a temperature of 18°C has a surface tension of at 73.05 mn/m Measurement of surface tension of each solution of a given concentration are at least 4 times. Surface-active properties of the proposed compounds according to examples 1-4, namely the minimum surface tension (σminmn/m) and the critical micellization concentration (CMC, %) are shown in table 2.

The proposed compounds have effective bactericidal, fungicidal and surface activity, and thus find application in various fields of technology, agriculture, and copper is ine. It is important that they receive from the available environmentally friendly renewable vegetable and therefore virtually inexhaustible raw materials.

Table 2
Surface-active properties
The Quaternary ammonium compoundThe minimum surface tension, σminmn/mThe critical micellization concentration, CMC, %
Example 1350.2
Example 2380.2
Example 3420.2
Example 4420.2

The Quaternary ammonium compound-based resin acids and rosin General formula

where R is ethyl or benzyl, X Is CL or Br, with bactericidal, fungicidal and surface activity.



 

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