PL209149B1 - Alkoxy methyl trihexyl phosphonium acesulphamates, saccharinates, methylsulphates, bis (trifluor methylsulphonyl) imides as well as method for the manufacture of alkoxy methyl trihexyl phosphonium acesulphamates, saccharinates, methylsulphates, bis (trifl - Google Patents

Description

The present invention relates to alkoxymethyltrihexylphosphonium salts and a process for their preparation.

Molecules containing one or more phosphorus-carbon bonds belong to the group of organophosphorus compounds. The phosphorus atom can exist in these molecules in many oxidation states and have different coordination numbers, therefore many organophosphorus compounds are known. The most common representatives of these compounds are phosphines - phosphine derivatives PH3, in the molecule of which subsequent hydrogen atoms have been replaced with an alkyl or aryl group. They are mostly malodorous liquids, toxic, weaker bases than amines. They are used, among others as polymerization catalysts.

Important organophosphorus compounds are phosphonium salts of formula R4P ⁺ X ^- , classified as cationic surfactants. They are composed of a cation containing a quaternary phosphorus atom to which four alkyl groups are attached. The positive charge is neutralized by the most common anion of an inorganic nature, e.g. Cl, Br, I, NO3, CIO4. Phosphonium salts are effective against bacteria and fungi and at the same time have the lowest toxicity towards warm-blooded organisms. Both acesulfame K and saccharin were used to exchange the anion in phosphonium halides - sweeteners commonly used in foodstuffs replacing sugar, as well as sodium methyl sulfate and lithium bis (trifluoromethylsulfonyl) imide.

Acesulfame occurs in the form of acesulfame potassium salt {systematic name - 5,6-dimethyl-1,2,3-oxathiazine-4 (3H) -one [2,2-dioxide] potassium salt}. It has the form of a white, pure crystalline powder, with a strongly sweet taste exceeding the sweetness of sugar by about 130-200 times. Acesulfame-K is well soluble in water, has a high resistance to high temperature (the decomposition temperature is 498K) and does not change during thermal treatment, therefore it is widely used mainly in the food industry. It is used in dietary and diabetic foods, in desserts, fruit preserves, confectionery products and bread, in chewing gums and as an ingredient in table-top sweeteners.

Saccharin is chemically an o-sulfobenzoic acid imide. It is the oldest known sweetener discovered by man, with a sweetness much higher than sucrose. The perception of sweetness depends on its concentration and varies, according to various sources, from 300-600 times. This compound is in the form of a white, crystalline powder, odorless, the melting point is 491-493K, in the acid form it is poorly soluble in water, therefore it is used in the form of sodium, potassium or calcium salts, which are much more soluble. This sweetener is characterized by high thermal stability and high resistance to hydrolysis.

The sodium salt of methyl sulphate is a commercial reagent, it is in the form of a white, hygroscopic powder with a melting point of 364-367K.

Lithium bis (trifluoromethylsulfonyl) imide is a commercial reagent, available as a white, highly hygroscopic powder, mp 507-511K. It is used in electrolytes of lithium batteries and as a catalyst.

The object of the invention is the synthesis of salts with the acesulfame, saccharin, methylsulfate, bis (trifluoromethylsulfonyl) imide anions and the alkoxymethyltrihexylphosphonium cation of the general formula 1.

The structures of the cited anions are presented in the following formulas:

PL 209 149 B1

saccharin

CH3OSO3 methyl sulfate (CF3SO2) 2N bis (trifluoromethylsulfonyl) imide

The invention relates to the alkoxymethyltrihexylphosphonium salts of the general formula I, in which R is a straight-chain alkyl group containing from 1 to 18 carbon atoms, and A ^- is acesulfame or saccharin, or methylsulfate, or bis (trifluoromethylsulfonyl) imides, and the method of their preparation is in that an alkoxymethyltrihexylphosphonium chloride of general formula II, in which R is a straight chain alkyl group containing from 1 to 18 carbon atoms, is reacted with acesulfame-K or a saccharinate or methyl sulfate or bis (trifluoromethylsulfonyl) imide at a molar ratio of 0, 5: 3.0 in an anhydrous organic solvent at a temperature from 273 K to the boiling point of the organic solvent, then the anhydrous organic solvent is evaporated, and then anhydrous acetone is added, the by-product of the reaction, which is an inorganic salt, potassium chloride, is separated, and from the filtrate the solvent is completely evaporated off in a vacuum evaporator, for example The obtained product is dried under reduced pressure at the temperature of 293-373K.

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

new acesulfamates, saccharinates, methylsulfates and bis (trifluoromethylsulfonyl) imides belonging to the group of quaternary phosphonium salts were obtained. The synthesized acesulfamates, saccharinates, methylsulfates and bis (trifluoromethylsulfonyl) alkoxymethyltrihexylphosphonium imides are not soluble in water, but they dissolve in organic solvents (chloroform, DMSO, methanol, acetone), they are thermally stable, antielectrostatic and have antielectrostatic activity surfactants.

The following examples illustrate the invention:

P r z k ł a d I

Acesulfame pentoxymethyltrihexylphosphonium ₃

In a round bottomed reaction flask of 100 cm ³ provided 0.01 mol pentoksymetylotriheksylofosfoniowego chloride dissolved in 40 cm ³ of anhydrous acetone and added the stoichiometric amount of acesulfame-K. The mixture was vigorously stirred for 24 hours. The resulting precipitate was separated, and acetone was distilled off from the filtrate. The residue was dried at 323 K under reduced pressure. The obtained liquid was 97% efficient, with a density of 1.030 g / cm ³ and a viscosity of 88 mPas, thermally stable up to the temperature of 573 K. The structure of the compound was confirmed by performing proton, carbon and phosphorus nuclear magnetic resonance spectra:

(DMSO-d6) ¹ H NMR cation: 4.39 (ds, JH-P = 6 Hz, 2H), 3.53 (t, JH-H = 5 Hz, 2H), 2.22 (m, 6H) , 1.52 (m, 8H), 1.35 (m, 22H), 0.89 (t, JH-H = 6Hz, 4CH3); anion: 5.34, 1.93 (3H);

¹³ C NMR cation: 74.7 (d, JC-P = 15 Hz, OCH 2), 59.8 (d, JC-P = 62 Hz, P ⁺ CH2), 30.3 (3CH2), 29.5 ( d, JC-P = 13Hz, 2CH2), 28.2 (d, JC-P = 14Hz, 3CH2), 22, 21.3 (3CH2), 20.7 (d, JC-P = 6Hz, 3CH2), 16.5 (d, JC-P = 46Hz, 3CH2), 13.8 (4CH3); anion: 167.7, 160.4, 101.3, 19.4;

³¹ P NMR 32.4;

Elemental analysis for C28H56NO5PS (549.78) calculated (%): C 61.17, H 10.27, N 2.55; Measured: C 61.49, H 10.55, N 2.37;

P r z x l a d II

Decyloxymethyltrihexylphosphonium saccharin

An accurately weighed amount decyloksymetylotriheksylofosfoniowego chloride (0.01 mol) was dissolved in 40 cm ³ of anhydrous acetone. Sodium saccharinate was then added in a 25% excess. Reak4

The exchanges were carried out at room temperature for 24 hours. Sodium chloride precipitated from the reaction mixture which was separated and acetone was evaporated from the filtrate in a vacuum evaporator.

The obtained liquid was 94% efficient, with a density of 0.995 g / cm ³ and a viscosity of 588 mPa · s, thermally stable up to the temperature of 608K. The structure of the compound was confirmed by performing proton, carbon and phosphorus nuclear magnetic resonance spectra:

(DMSO-d6) ¹ NMR cation: 4.4 (ds, JH-P = 5 Hz, 2H), 3.53 (t, JH-H = 6 Hz, 2H), 2.23 (m, 6H), 1.53 (m, 8H), 1.29 (m, 32H), 0.88 (t, JH-H = 7Hz, 4CH3); anion: 7.64 (m, 4H);

¹³ C NMR cation 73.5 (d, JC-P = 12 Hz, OCH 2), 59.9 (d, JC-P = 63 Hz, P ⁺ CH2), 31.3, 30.8, 30.4 (3CH2), 29.7 (d, JC-P = 15Hz, 3CH2), 29.1, 28.7 (d, JC-P = 12Hz, 3CH2), 25.5, 22.1, 21, 8 (3CH2), 20.6 (d, JC-P = 5Hz, 3CH2), 16.6 (d, JC-P = 46Hz, 3CH2), 13.8 (4CH3); anion: 167.5, 145.1, 134.7, 131.2, 130.7, 122.2, 118.8;

³¹ P NMR 32.5;

Elemental analysis for C36H66NO4PS (639.95) calculated (%): C 67.57, H 10.40, N 2.19; measured: C 67.81, H 10.61, N 2.13;

Example III

Pentadecyloxymethyltrihexylphosphonium methyl sulfate

0.01 mol of pentadecyloxymethyltrihexylphosphonium chloride was dissolved in anhydrous acetone at the temperature of 293K. Then 0.015 mol of sodium methyl sulfate was added with continued stirring. The reaction mixture was vigorously stirred for 24 hours. After this time, the precipitate was filtered off, and acetone was distilled off from the filtrate in a vacuum evaporator. The residue was dried at the temperature of 333K under reduced pressure.

The liquid was obtained with a yield of 98%. The structure of the compound was confirmed by proton, carbon and phosphorus nuclear magnetic resonance spectra: Elemental analysis C34H73O4PS (608.98) calculated (%): C 67.06, H 12.08; measured: C 67.77, H 12.62

P r x l a d IV

Dodecyloxymethyltrihexylphosphonium bis (trifluoromethylsulfonyl) imide

In a round bottomed reaction flask of 100 cm ³ provided 0.01 mol dodecyloksymetylotriheksylofosfoniowego chloride dissolved in 50 cm ³ of anhydrous acetone and added bis (trifluoromethylsulfonyl) imidide in a molar ratio of 1: 1.5. The mixture was vigorously stirred for 24 hours. The resulting precipitate was separated, and acetone was distilled off from the filtrate. The residue was dried at the temperature of 323K under reduced pressure. A liquid was obtained with a yield of 95%, ₃ with a density of 1.044 g / cm and a viscosity of 128 mPas, thermally stable up to the temperature of 703K. The structure of the compound was confirmed by performing proton, carbon and phosphorus nuclear magnetic resonance spectra:

(DMSO-d6) ¹ NMR 4.37 (ds, JH-P = 7Hz, 2H), 3.51 (t, JH-H = 6Hz, 2H), 2.21 (m, 6H), 1, 51 (m, 8H), 1.28 (m, 36H), 0.88 (t, JH-H = 6Hz, 4CH3);

¹³ C NMR cation 73.4 (d, JC-P = 13 Hz, OCH 2), 59.7 (d, JC-P = 63 Hz, P ⁺ CHZ), 31.1 (3CH2), 30.6, 30 , 2 (3CH2), 29.7 (d, JC-P = 15Hz, 3CH2), 29.1, 28.6 (d, JC-P = 14Hz, 3CH2), 25.6, 22.1, 21.6 (3CH2), 20.4 (d, JC-P = 6Hz, 3CH2), 16.5 (d, JC-P = 46Hz, 3CH2), 13.7 (4CH3); anion: 125.6, 121.6, 117.2, 113.5;

³¹ P NMR 32.5;

Elemental analysis for C33H66F6NO5PS2 (765.97) calculated (%): C 51.74, H 8.68, N 1.83; Measured: C 52.12, H 8.96, N 1.68;

Claims (2)

CLAIMS 1. Alkoxymethyltrihexylphosphonium salts of general formula I wherein R is a straight chain alkyl group containing from 1 to 18 carbon atoms and A is acesulfame or saccharin or methyl sulfate or bis (trifluoromethylsulfonyl) imide. 2. A method for producing a salt as defined in claim 1 Wherein R is a straight chain alkyl group containing from 1 to 18 carbon atoms, characterized in that an alkoxymethyltrihexylphosphonium chloride of general formula II in which R is a straight chain alkyl group containing from 1 to 18 carbon atoms is subjected to reaction with acesulfame-K, or saccharinate, or methylsulfate, or bis (trifluoromethylsulfonyl) imide at a molar ratio of 0.5: 3.0 in an anhydrous organic solvent at a temperature from 273K to the boiling point of the organic solvent, and then evaporation anhydrous organic solvent, and then anhydrous acetone is added, the by-product of the reaction, which is an inorganic salt, potassium chloride, is separated, and the solvent is completely evaporated from the filtrate in a vacuum evaporator, while the obtained product is dried under reduced pressure at a temperature