PL231631B1 - New sweet bis-ammonium salts with alkyl-1,X-bis(decyldimethylammonium) cation and saccharinate anions, method for obtaining them and application as food deterrents - Google Patents

Description

Description of the invention

The subject of the invention is a new sweet bisammonium salt with an alkyl-1, X-bis (decyldimethylammonium) cation and saccharin anions, a method of their preparation and use as food detersants.

Ionic liquids (ILs.) Are chemical compounds with an ionic structure in which the cation is organic and the anion is organic or inorganic. By definition, these compounds have a melting point that does not exceed the boiling point of water.

Ionic liquids are widely researched as solvents, in chemical power sources, extractants, surfactants, wood preservatives, anti-electrostatic substances, disinfectants and as anti-caking agents.

Food detectors are substances that act on the taste organs of insects. They can scare off insects or make food unattractive for them. Antifidants also work by discouraging the insect from continuing to feed after the insect has analyzed the agent applied to the food.

The saccharin anion was used to obtain bisammonium ionic liquids with detecting activity. The detecting activity of said anion is presented, inter alia, in patents PL 206 172, PL 212 597, PL 212 598, PL 224 279, PL 224 280.

Examples of bisammonium salts with alkyl-1, X-bis (decyldimethylammonium) cation:

• 1,4-butane-bis (decyldimethylammonium) disaccharinate, • hexane-1,6-bis (decyldimethylammonium) disaccharinate, • octane-1,8-bis (decyldimethylammonium) disaccharinate, • decane-1,10-bis (decyldimethylammonium) disaccharinate ), • dodecane-1,12-bis (decyldimethylammonium) disaccharinate.

The essence of Wynalak are the new sweet bisammonium salts with the alkyl-1, X-bis (decyldimethylammonium) cation and the saccharin anion of the general formula 1, where R is an alkyl linker from four to twelve carbon atoms, A is the saccharin anion of the general formula 3.

The method of their preparation is that the alkyl-1, X-bis (decyldimethylammonium) dibromide, of the general formula 2, is reacted with sodium saccharin in the molar ratio of salt to bisammonium dibromide 2: 1 at a temperature of 25 to 40 ° C C, preferably 25 ° C, in solvents such as isopropanol or butanol or ethanol, then the inorganic salt by-product is filtered off and the solvent is evaporated, and the final product is dried at 70 ° C.

The second method of preparation is that the alkyl-1, X-bis (decyldimethylammonium) dibromide of the general formula 2 is exchanged with sodium saccharin in a molar ratio of salt to bisammonium dibromide 2: 1 at a temperature of 20 to 25 ° C C, preferably 20 ° C, in water, then it is extracted with chloroform, the chloroform extract is washed three times with water, then the solvent is evaporated, and the salt obtained is purified by dissolving it in acetone, further cooling, and then filtering the precipitated inorganic salt then the solvent of the filtrate was evaporated and the final product was dried at 70 ° C.

The use of bisammonium salts with the alkyl-1, X-bis (decyldimethylammonium) cation and the saccharin anion as food additives.

It is preferred that the bisammonium salts with the alkyl-1, X-bis (decyldimethylammonium) cation and the saccharin anion are used neat or in the form of a water-methanol or water-ethanol solution with a concentration of at least 0.05% or in the form of a solution water-isopropanol with a concentration of at least 0.05%.

Thanks to the solution according to the invention, the following technical and economic effects were obtained:

• a method of obtaining a new group of bisammonium salts with the alkyl-1, X-bis (decyldimethylammonium) cation and with saccharin anions was developed, • the obtained salts have a sweet taste, therefore they can be classified as sweet bisammonium salts, • some of the obtained salts have a melting point below 100 ° C, according to the definition of ionic liquids, these are bisammonium sweet ionic liquids, • the obtained salts and ionic liquids show thermal stability over a wide temperature range, • the synthesized ionic liquids show an immeasurable vapor pressure above their surface, • the obtained salts and liquids are effective detectors post-office,

The possibility of using it in the protection of warehouses and field crops against pests.

The following examples illustrate the invention:

P r z k ł a d 1

Method of synthesis of 1,4-bis (decyldimethylammonium) butane disaccharinate, [C4C10] [Sacha] 2

To a reactor equipped with a magnetic stir bar was added sodium saccharine 4.10 g (0.02 mol) together with 30 cm ³ of ethanol and then added bisamoniowy dibromide in an amount of 5.87 g (0.01 mol). The anion exchange reaction was carried out for 20 minutes at 40 ° C, then the solvent was evaporated. The product obtained is dissolved in 30 cm ³ of acetone to isolate the product. The inorganic salt was filtered off under vacuum and the filtrate's solvent was evaporated and dried in a vacuum oven at 70 ° C. The reaction yield was 90%.

The proton and carbon nuclear magnetic resonance spectra for butane-1,4-bis (decyldimethylammonium) disaccharinate confirmed the salt structure:

¹ H NMR (CDCl 3) δ [ppm] = 0.80 (m, J = 6.6 Hz, 6H); 1.20 (m, 28H); 1.67 (m, 8H); 3.25 (m, 8H); 3.31 (s, 12H); 7.57 (m, 4H); 7.72 (m, 2H); 7.76 (m, 2H);

¹³ C NMR (CDCl 3) δ [ppm] = 13.90 [2C]; 19.55 [2C]; 22.44 [2C]; 25.42 [2C]; 26.11 [2C]; 29.06 [4C]; 29.25 [4C]; 31.66 [2C]; 50.64 [4C]; 63.30 [2C]; 64.80 [2C]; 119.45 [2C]; 123.12 [2C]; 131.41 [2C]; 132.05 [2C]; 134.26 [2C]; 144.29 [2C]; 169.84 [2C].

Elemental CHN analysis for C42H70N4O6S2 (Mmol = 791.16 g / mol): calculated values (%): C = 63.76; H = 8.92; N = 7.08; measured values (%): C = 63.36; H = 8.61; N = 7.41.

P r z k ł a d 2

Synthesis method of hexane-1,6-bis (decyldimethylammonium) disaccharin, [C6C10] [Sakha] 2

6.15 g (0.01 mol) dibraomu 1,6-bis (Decyldimethylammonio) was dissolved in 40 cm ^{3 of} butanol. 4.10 g (0.02 mol) of sodium saccharin was introduced into the solution obtained at a temperature of 35 ° C. In the course of the exchange reaction, an inorganic salt of potassium bromide precipitated from the mixture and was filtered off by gravity. Then acetone was evaporated from the filtrate and the final product was dried in a vacuum oven at 70 ° C. The reaction yield was 89%.

The product structure was confirmed by analyzing the proton and carbon spectra of nuclear magnetic resonance:

¹ H NMR (CDCl 3) δ [ppm] = 0.81 (m, J = 6.6 Hz, 6H); 1.24 (m, 32H); 1.67 (m, 8H); 3.22 (m, 8H); 3.35 (s, 12H); 7.58 (m, 4H); 7.73 (m, 2H); 7.76 (m, 2H);

¹³ C NMR (CDCl 3) δ [ppm] = 13.99 [2C]; 22.49 [2C]; 25.46 [4C]; 26.13 [4C]; 29.08 [4C]; 29.25 [4C]; 31.62 [2C]; 50.67 [4C]; 63.34 [2C]; 64.81 [2C]; 119.40 [2C]; 123.14 [2C]; 131.47 [2C]; 132.01 [2C]; 134.29 [2C]; 144.23 [2C]; 169.86 [2C].

Elemental analysis of CHN for C44H74N4O6S2 (Mmol = 819.22 g / mol): calculated values (%): C = 64.51; H = 9.11; N = 6.84; measured values (%): C = 64.13; H = 9.55; N = 7.15.

P r z k ł a d 3

Synthesis method of octane-1,8-bis (decyldimethylammonium) disaccharin, [C8C10] [Sacha] 2

In 30 cm ^{3 of} isopropanol, octane-1,8-bis (decyldimethylammonium) dibromide was dissolved in the amount of 6.43 g (0.01 mol), then a stoichiometric amount of sodium saccharin was added. The reaction was carried out at a temperature of 25 ° C. The solvent of the resulting product was removed on a rotary vacuum evaporator, and then acetone was added. The prepared mixture was cooled and the inorganic salt by-product was filtered off. The acetone was evaporated and the final product was dried at 50 ° C for 7 days. The reaction yield was 91%.

The structure of the compound was confirmed by performing proton and carbon nuclear magnetic resonance spectra:

¹ H NMR (CDCl 3) δ [ppm] = 0.88 (m, J = 6.6 Hz, 6H); 1.22 (m, 36H); 1.67 (m, 8H); 3.28 (m, 8H); 3.40 (s, 12H); 7.57 (m, 4H); 7.70 (m, 2H); 7.75 (m, 2H);

¹³ C NMR (CDCl 3) δ [ppm] = 13.81 [2C]; 22.33 [2C]; 25.19 [4C]; 25.95 [4C]; 28.9 [6C]; 29.09 [4C]; 31.52 [2C]; 50.54 [4C]; 63.96 [2C]; 64.04 [2C]; 119.12 [2C]; 122.80 [2C]; 130.96 [2C]; 131.59 [2C]; 134.61 [2C]; 144.61 [2C]; 169.49 [2C],

Elemental analysis of CHN for C46H78N4O6S2 (Mmol = 847.27 g / mol): calculated values (%): C = 65.21; H = 9.28; N = 6.61; measured values (%): C = 65.52; H = 9.60; N = 6.25.

P r z k ł a d 4

Synthesis method of decane-1,10-bis (decyldimethylammonium) disaccharin, [C10C10] [Sakha] 2

4.10 g (0.02 mol) of sodium saccharin was dissolved in 150 cm ^{3 of} water, and then 6.71 g (0.01 mol) of bisammonium dibromide was added with constant stirring. Stirring was continued for

The reaction time was extended to 20 ° C. The product was extracted from the mixture with chloroform. The chloroform extract was washed three times with water, and then the solvent was evaporated under reduced pressure to obtain the bisammonium salt. It was then dissolved in acetone, filtered and then subjected to vacuum drying at 70 ° C. The reaction yield was 96%.

The structure of the compound was confirmed by analyzing the proton and carbon spectra of nuclear magnetic resonance:

¹ H NMR (CDCla) δ [ppm] = 0.85 (m, J = 6.6 Hz, 6H); 1.23 (m, 40H); 1.69 (m, 8H); 3.24 (m, 8H); 3.31 (s, 12H); 7.58 (m, 4H); 7.76 (m, 2H); 7.72 (m, 2H);

¹³ C NMR (CDCl 3) δ [ppm] = 13.59 [2C]; 22.32 [2C]; 25.36 [4C]; 26.11 [4C]; 28.84 [6C]; 29.69 [6C]; 31.42 [2C]; 50.85 [4C]; 63.29 [2C]; 63.93 [2C]; 119.73 [2C]; 122.50 [2C]; 131.36 [2C]; 131.16 [2C]; 134.09 [2C]; 144.85 [2C]; 169.69 [2C],

Elemental CHN analysis for C48H82N4O6S2 (Mmol = 875.33 g / mol): calculated values (%): C = 65.86; H = 9.44; N = 6.40; measured values (%): C = 65.40; H = 9.10; N = 6.00.

P r z k ł a d 5

Synthesis method of dodecane-1,12-bis (decyldimethylammonium) disaccharinate, [C12C10] [Sakha] 2

In a flask was dissolved 6.99 g (0.01 mol) dibromide dodecane-1,12-bis (Decyldimethylammonio) in 30 cm ³ of chloroform at 25 ° C. Then a stoichiometric amount of sodium saccharin salt was added, the exchange reaction was carried out at 20 ° C for 40 minutes. The product was purified by extraction with water. The chloroform extract was washed three times with water, and then the solvent was evaporated under reduced pressure to obtain the bisammonium salt. The product was then dried at 70 ° C. The yield of the performed reaction was 92%.

The structure of the compound was confirmed by performing proton and carbon nuclear magnetic resonance spectra:

¹ H NMR (CDCl 3) δ [ppm] = 0.81 (m, J = 6.6 Hz, 6H); 1.23 (m, 44H); 1.65 (m, 8H); 3.27 (m, 8H); 3.39 (s, 12H); 7.52 (m, 4H); 7.74 (m, 2H); 7.76 (m, 2H);

¹³ C NMR (CDCl 3) δ [ppm] = 13.51 [2C]; 22.35 [2C]; 25.39 [4C]; 26.13 [4C]; 28.85 [6C]; 29.67 [8C]; 31.48 [2C]; 50.84 [4C]; 63.22 [2C]; 63.96 [2C]; 119.71 [2C]; 122.55 [2C]; 131.39 [2C]; 131.13 [2C]; 134.05 [2C]; 144.87 [2C]; 169.68 [2C],

Elemental analysis of CHN for C50H86N4O6S2 (Mmol = 903.38 g / mol): calculated values (%): C = 66.48; H = 9.60; N = 6.20; measured values (%): C = 66.03; H = 9.25; N = 6.54.

The obtained salts with saccharin anions did not lose the sweet taste of the substrates. Two of the obtained bisammonium salts were clear liquids at ambient temperature, three of the salts with a saccharin anion had a melting point below 100 ° C.

Application example

Retailing activity is determined according to two tests: the no-choice test and the choice test. For the test, discs with the following dimensions were cut: diameter 1 cm and thickness 1 mm. Subsequently, it was soaked with the pure substance or with 1% methanol or ethanolic or isporopanol solution of the tested salt or with methanol alone. The solvent was then evaporated, and the discs were weighed, the assumed number of insects was placed in them and placed in a cultivator under controlled conditions. In the selection test, one wheat wafer was saturated with methanol or ethanol or isopropanol, the other with a solution of the tested compound, while in the test without selection, both wafers were saturated with the solution of the tested salt. Tests were performed on beetles representing three families: weevils (Curculionidae), dermestids (Dermestidae) and niggers (Tenebrionidae). The experiment was carried out on three adults of grain weevil (Sitophilus granarius), ten larvae of grain peel (Trogoderma granarium) as well as ten larvae and twenty adult individuals of Trogoderma ulca (Tribolium confusum). Five days after starting the test, the disks were weighed to determine the weight loss. Each test was performed in five replicates and the results were averaged. Based on the weight loss, the relative factor (R), the absolute factor (A) and the total factor (T) were determined.

Relative coefficient of retail activity:

K-E K = E and the absolute factor:

KK-EE KK + EE * 100, * 100,

PL 231 631 Β1 the letter abbreviations used in the formulas mean respectively:

K - weight loss from selection discs,

KK - weight loss from control discs without selection,

E - weight loss from discs with the tested compound with the selection,

EE - weight loss from discs with test compound without choice.

The summary factor was determined from the formula:

T = A + R

The detecting properties are determined on the following scale:

very good add factor 200-151, good add factor 150-101, average add factor 100-51, poor add factor 50-0.

Tables 1-4 show the results obtained for the detecting properties of the bisammonium ionic liquids with saccharin anions. For comparison, the data of a known natural antifidant - azadirachtin are presented.

Table 1

Deterential activity towards adults of the grain weevil

salt AND R T. Retail properties [CsCio] [Sachab 52.5 81.2 133.7 Okay [C4C10] [Sachaj? 58.3 88.9 147.2 Okay [Ci2Cw] [Sacha] 2 86.9 100.0 186.9 Very good azadirachtin 99.0 93.1 190.3 Very good

Table 2

Deterential activity towards adults of the Troika ulca

salt AND R T. Retail properties [C _b Ci ₀ ] [Sacha] 2 64.0 93.8 157.9 Very good [C., CioJ [Sachab 55.5 85.7 141.2 Okay [Ci ₂ Cio] lSacha] ₂ 76.7 100.0 176.7 Very good azadirachtin 100.0 85.0 185.0 Very good

Table 3

Deterential activity against the larvae of the Troika ulca

salt AND R T. Retail properties [CeCiol [Sacha] 2 90.5 84.7 175.2 Very good [C ₄ Cio] [Sachah 92.8 100.0 192.8 Very good [Ci2Cio] [Sacha] 2 100.0 100.0 200.0 Very good azadirachtin 100.0 92.4 192.4 Very good

PL 231 631 Β1

Table 4

Deterential activity against grain peel larvae

salt AND R T. Retail properties [CsCiJISachah 90.0 96.2 186.2 Very good [CąCio] [Sachah 99.1 96.7 195.7 Very good [CuC: o] [Sacha] z 100.0 100.0 200.0 Very good azadirachtin 100.0 94.2 194.2 Very good

The obtained bisammonium salts were in most cases very effective. A large group of these compounds was characterized by higher activity than the reference substance (azadirachtin). The liquid [Ci2Cio] [Sacha] 2 showed the highest activity against all pests.

Claims (7)

Patent claims 1. New sweet bisammonium salts with an alkyl-1, X-bis (decyldimethylammonium) cation and a saccharin anion of the general formula 1, where R is an alkyl linker of four to twelve carbon atoms, A is a saccharin anion of general formula 3. 2. A method for the preparation of bisammonium salts with an alkyl-1, X-bis (decyldimethylammonium) cation and a saccharin anion as defined in claim A process according to claim 1, characterized in that the alkyl-1, X-bis (decyldimethylammonium) dibromide of general formula 2 is reacted with sodium saccharin in a molar ratio of salt to bisammonium dibromide 2: 1 at a temperature of 25 to 40 ° C, preferably 25 ° C, in solvents such as isopropanol or butanol or ethanol then the inorganic salt by-product is filtered off and the solvent is evaporated, and the end product is dried at 70 ° C. A method for the preparation of bisammonium salts with an alkyl-1, X-bis (decyldimethylammonium) cation and a saccharin or acesulfamate anion as defined in claim 1. A process according to claim 1, characterized in that the alkyl-1, X-bis (decyldimethylammonium) dibromide of general formula 2 is reacted with sodium saccharin in a molar ratio of salt to bisammonium dibromide 2: 1 at a temperature of 20 to 25 ° C, preferably 20 ° C, in water, then it is extracted with chloroform, the chloroform extract is washed three times with water, then the solvent is evaporated, and the salt obtained is purified by dissolving in acetone, further cooling, and then filtering the precipitated inorganic salt, then the filtrate's solvent is evaporated off and the end product is dried at 70 ° C. 4. The use of bisammonium salts with the alkyl-1, X-bis (decyldimethylammonium) cation and the saccharin anion as food additives. 5. Use according to claim 1 The process of claim 4, wherein the bisammonium salts with the alkyl-1, X-bis (decyldimethylammonium) cation and the saccharin anion are used in pure form. 6. Use according to claim 1 4. A process as claimed in claim 4, characterized in that the bisammonium salts with the alkyl-1, X-bis (decyldimethylammonium) cation and the saccharin anion are used in the form of a water-methanol or water-ethanol solution with a concentration of at least 0.05%. 7. Use according to claim 1 4. The process of claim 4, wherein the new bisammonium salts with the alkyl-1, X-bis (decyldimethylammonium) cation and the saccharin anion are used in the form of a water-isopropanol solution with a concentration of at least 0.05%.