SU1604733A1 - Method of producing nitrozonium salts - Google Patents

Abstract

The invention relates to methods for producing nitrosone salts of the general formula (NO _N A ^N- , where A ^N- - BF ₄ , CLO ₄ , SO ₃ F, SIF ₆

N = 1-2, which can be used in organic syntheses as active nitrosating and oxidizing reagents, as well as initiators of electrophilic reactions. The purpose of the invention is to expand the nomenclature and increase the yield of nitrozone salts produced while maintaining their high purity. To do this, at 0-15 ° C in the presence of a solvent, the reaction is carried out between nitrogen tetroxide and tertiary ammonium salts of the general formula [ALK ₃ NH] _N A ^N- , where ALK is methyl, ethyl, n-butyl

A ^N- - BF ₄ , CLO ₄ , SO ₃ F ^- , SIF ₆ , N = 1-2. The solvent is selected from the group methylene chloride, chloroform, concentrated nitric acid, or a mixture thereof. The ammonium salts necessary for the synthesis are obtained by reacting tertiary amines with the corresponding acids. The purity of the nitrosone salts obtained reaches 99.85-99.9%, and the practical yield as compared with the prototype increases by 6-11%. 1 hp f-ly.

Description

This invention relates to the chemistry of nitrogen-containing compounds, and specifically to a process for the preparation of nitrosone salts of the general formula

(L / 0 +), where, Сюг,, or 2, which are used in organic syntheses as active nitrosating and oxidizing reagents, as well as initiators of electrophilic reactions.

The purpose of the invention is to expand the range and increase the yield of nitrozone salts obtained while maintaining their high frequency.

In the presence of a solvent, the reaction is carried out between nitrogen tetroxide and tertiary ammonium salts of the general formula

Alk NH A

ftr

SiP, -:

where Alk is methyl, ethyl, n-butyl

, -, syug, SO, Fp or 2.

The reaction temperature is about -15 ° C. The solvent is selected from the group: methylene chloride, chloroform, concentrated nitric acid (99%) or a mixture of them. The resulting reaction, eating nitrozone, is separated on a funnel with a porous glass filter, washed with two portions of hardened methylene chloride and dried under vacuum. The obtained nitrosone salts do not require additional purification. Their structure is confirmed by the data of IR spectroscopy and the results of elemental analysis. The reaction proceeds with a yield close to quantitative, due to the high solubility in these solvents of the reaction products — salts of nitroO5 O 4.

00

with

zones. with decreasing temperature, the solubility of nitrozonium salts in the solvents used decreases, and their yield slightly increases. The desired temperature is maintained using a thermostat. Nitrosonium salts are formed in good yield in any of the suggested solvents. Synthesis of nitrozonium salts proceeds according to the nNONO scheme, +

The mother liquor remaining after separation of the desired product is regenerated. To this end, the solvent is stripped off from the mother liquor and the required amount of strong acid or its aqueous solution is added. Then, in the vacuum of a water jet pump, the resulting nitric acid or its aqueous solution is distilled off. Substitution reaction proceeds to subcircuit

4Л / яз / Я Л / Оз - + Я „Л --4Л // гзЛ Я« + nHN03.

Salts of trikylamines and strong acids thus obtained are dried in vacuum at 50-70 ° C to constant weight and used to make a nitrozonium salt, i.e. Ecologically clean, waste-free production is realized.

The nitrozone tertiary salts used for the synthesis of ammonium salts are easily obtained by the reaction of tertiary amines with the corresponding acids by the reaction

t35

ABOUT

where ASH is methyl, ethyl, n-butyl;

, СЮ4-,, or 2.

The reaction is carried out with cooling and stirring; the tides according to the scheme are the required amount of tertiary amine to an aqueous 30-65% acid solution. After the completion of the reaction, the water is distilled off and the salt formed is dried in a water jet pump vacuum at 50-7U C. 45 With the use of pure reagents, the salts thus obtained do not need to be purified. Trialkylammonium fluorosulfate is synthesized in methylene chloride or chloroform, tide with stirring and cooling trialkylamine to a 30-45% 50 solution of fluorosulfonic acid in methylene chloride or chloroform. The resulting solution of trialkylammonium fluorosulfate is introduced directly into the synthesis reaction of nitrosone fluorosulfate, not separating the salt from the solvent.

The purity of the nitrozone salts obtained is determined by IR spectroscopy and liquid chromatography. IR spectra taken on a spectrometer in vaseline, bee

the resulting salts are spectrally pure. IR spectroscopic data indicate the presence of a nitrosonium ion (bands and 2240 cm). Absorption bands corresponding to vibrations of the nitronium ion (bands 570 and 2360 cm) and nitric acid (bands 925, 1300 and 1050) were not detected. The sensitivity of the method to nitrozonium ions and nitric acid is about 0.05%.

Chromatographic analysis was performed on a liquid chromatograph using a UV detector. The solutions of the nitrosonium salts obtained in trimethyl phosphate and sulfolane are analyzed.

According to liquid chromatography data, the obtained nitrozonium salts contain 008-012% of the tertiary ammonium salt and about 0.01-0.03% I in the form of hydroxonium salts. NZO ul. In cases when nitric acid or its the mixture in the test samples contains 0.02-0.05% nitric acid. No impurities of nitronium salts were detected in nitrozonium salts. The content of the main product according to the data of liquid chromatography is 9E, 8H-UU, U / O5.

0

five

45 50

Example 1. Preparation of nitrosone boron fluoride (NO + BF, -).

293.6 g (2.0 mol) of trimethyl-ammonium borfluoride are dissolved in 1 liter of Lena chloride and 184 g (2 mol) of nitrogen tetroxide are poured into the solution while stirring at 15 ° C. The desired product is isolated while cooling the mixture. The boron fluoride nitrozonium precipitate is separated on a funnel with a porous glass filter, washed with two 100 ml portions of absolute methylene chloride and dried in a water jet pump vacuum at 50 ° C. Yield 224.3 g, which corresponds to 96% of the theoretically calculated.

Found,%: L / 11.51; B 8.83; f 65.19. Calculated,%: L / 11.99; S 9.25; f 65.06. IR spectrum V, cm ±: 1815,2240 (L / 0 +); Example 2. Getting nitrosone perchlorate (yvo + c / or).

Analogously to example 1, starting with 184 g of nitrogen tetroxide and 403 g of triethylammonium perchlorate in a mixture of methylene chloride and nitric acid, taken in a volume ratio of 3: 5, at 0 ° C, 259 g of this nitrozonium salt is obtained. Output

97%

Found,%: N 10.66; C / 27.62. Calculated,%: N 10.82; C / 27.38. IR spectrum V, cm-: 1815,2240 (L / 0 +);

625,1100 ().

Example 3. Preparation of nitrosone fluorosulfate (NO + SO, F-).

Analogously to example 1, starting from 402 g of triethylammonium fluorosulfate and 184 g of nitrogen tetroxide in chloroform, with

the specified connection 24,68; S 24.84;

five

10 ° C get 258 g. Yield 93%.

Found,%: L 10.44; F 14.39.

Calculated,%: jV 10,85; F 14.72.

IR spectrum V, cm-: 1815.2240 (); 1083 (OGD-).

Example 4. Preparations of nitrosone fluorosilicate ((NO JzSiFu -).

257.4 g (0.5 mol) of tri-n-butylammonium fluorosilicate is dissolved in 1 l of nitric acid (99%) and 92 g (1 mol) of nitric oxide is added to the solution while stirring at 5 ° C. The precipitated nitrosone fluorosilicate is separated, washed with two portions of 100 ml of "absolute methylene chloride." Output 93 g, which corresponds to 92% of the theoretically calculated. Found,%: YY 14.28; Si 13.47;

F 56 03 Calculated,%:, 86; Si 13.89;

F 56,40.

IR spectrum V, 1815,240 ().

As can be seen from the examples, the invention

in comparison with the known method, it allows to expand the range of nitrosonium obtained for salads and to increase their practical output by 6-11%. At the same time, the purity of the salts of nitrosone reaches 99.85-99.9%.

Claims (2)

1. A method of producing nitrosis salts. It includes reacting in the presence of a nitrogen tetroxide solvent with a reagent 10, which is characterized by the fact that tertiary salts are used as a reagent to expand the nomenclature and increase the yield of the nitroson salts obtained while maintaining their high purity. ammonium of the general formula Alk.H L. L 0 where Alk is methyl, ethyl; n-butyl; L --VL-, SOiF-, Sifu 2-.  OR 2, and the process is carried out at O-15 ° C. 2. A method according to claim 1, characterized in that the solvent is selected from the group: methylene chloride, chloroform, nitric acid with a concentration of 99% or lx mixture.