Method of production of surfactant alkoxy-(alkyl-substituted) methylpyridin chlorides

FIELD: production of alkoxy-(alkyl-substituted) methylpyridin chlorides of branched structure used as emulsifying agents, solubilizing agents, detergents, disinfectants, auxiliary textile products.

SUBSTANCE: proposed method includes alkylation of pyridin by alkyl-substituted chloromethyl ethers which are obtained through interaction of three starting components: higher alcohols or their fractions, carbonyl compound which is just aldehyde or ketone and chlorinating agent containing sodium chloride and sulfuric acid.

EFFECT: facilitated technology; enhanced economical efficiency and safety.

4 cl, 7 ex

The invention relates to a method for producing Quaternary ammonium salts with alkoxymethyl radicals at the nitrogen atom in the heterocyclic ring, which are used in various industries as emulsifiers, solubilization, detergent-disinfectants, textile auxiliaries (Asarc, Jiri, Jer. Surfactants and detergents. M: Statenot, 1960), in particular to a method for producing alkoxy-(alkyl substituted)methylpyridine chloride branched structure.

A method of obtaining Quaternary salts with long chain desoximetasone radical at the nitrogen of the General formula:

where

or nitrogenous heterocycle. The method consists in the fact that tertiary amines alkiliruyutza chlorotoluene ethers, which in turn is produced by interaction of higher alcohols with paraformaldehyde and hydrogen chloride at a temperature of from -5 to 0°With a yield of about 80%. The reaction is carried out in benzene. The obtained Quaternary salt is washed with ether (Ipocol, Vaincre. Surface-active salts of Quaternary ammonium bases with alkoxymethyl radicals at the nitrogen // Russian journal of applied chemistry. 1966. 39, No. 8, s-1860).

The disadvantage of this method is the use of explosive and flammable solvents (Ben is Ola, ether) and toxic gaseous hydrogen chloride.

The closest technical solution is a method of obtaining a surface-active alkoxystyrene chlorides (EN 2141949, 11.03.98, prototype) alkylation of pyridine chlorotoluene esters (HMA), which is obtained by the interaction of the higher alcohols, paraformaldehyde and chloride tiomila in carbon tetrachloride:

To a solution of alcohol or faction synthetic higher alcohols C₁₂-C₁₄with stirring, add paraformaldehyde, and then added dropwise SOCl₂so that the temperature did not exceed 35°C. After removal of the solvent, HMA subjected to interaction with pyridine under stirring, keeping the temperature no higher than 45°

in the environment of carbon tetrachloride. Precipitated salt is filtered off, washed CCl₄and dried. The output is 82-83%.

The disadvantages of this method are the use of expensive reagents - paraformaldehyde, which is unstable during storage, toxic chloride tonila, and the need for disposal of gaseous waste SO₂and HCl.

The objective of the invention is to simplify the technology, increasing its safety, efficiency, and extensibility asso the end of the target products.

This object is achieved by alkylation of pyridine, alkyl substituted chlorotoluene esters, which are produced by interaction of three primary components: higher alcohols or their fractions, carbonyl compounds, representing an aldehyde or ketone, and gloriouse agent consisting of sodium chloride and sulphuric acid.

The process consists of two stages, and each stage is performed in the same reactor without isolation of the intermediate product, unless there is another purpose, namely to obtain alkyl substituted hlorofilovykh esters. In this case, the filtered reaction mass (after removal of Na₂SO₄) is distilled in vacuum and get an individual connection.

Synthesis is carried out as individual alcohols and industrial factions synthetic higher alcohols (SHS). Usually in the syntheses use alcohols and fractions of alcohols C₁₂-C₁₄. In the present invention expands the range of alcohols from C₈to C₁₄that became possible due to the use of carbonyl compounds with longer chain than paraformaldehyde.

When using carbonyl compounds with C>1 can receive alkyl substituted chlormadinone esters of ISO-structure, which when interacting with pyridine to form the alkoxy-(alkyl substituted)methylpyridine chlorite is s branched structures with improved surface-active properties.

where R=C_8-14H_17-29OH, R₁, R₂=H, CH₃With₂H₅, (CH₃)₃and other

Carbonyl compounds are selected from a range of ketones and aldehydes, which at the reaction temperature are liquids, such as 2-methylpropanal, acetic aldehyde, 2,2-dimethyl-propanal, acetone, methyl ethyl ketone, diethylketone and other

The use of liquid carbonyl compounds does not require the introduction of another solvent to obtain a reaction medium, as well as for washing and recrystallization of the salt obtained, which greatly simplifies the process.

Reagents take in equimolar amounts, in addition to carbonyl compounds, which is added in excess, mainly from three - to fivefold. The synthesis is carried out at a temperature not exceeding 35°C, preferably at room temperature.

The process is carried out in a reactor made of glass or stainless steel, which is poured ketone or aldehyde, an alcohol (C_8-14H_17-29IT), then under stirring load table salt (NaCl) and dosed sulfuric acid so that the reaction temperature did not exceed 35°and stavke with reactor was not observed breakthrough of hydrogen chloride. After addition of the entire quantity of sulfuric acid, the reaction mass is stirred at ControlTemplate within one hour. Unreacted sulfuric acid is neutralized with soda or alkali, and the resulting reaction mass is filtered. The resulting solid precipitate - Na₂SO₄dried and used as a commodity product. Filtered the reaction mass is treated with pyridine under stirring, keeping the temperature not above 35°and unreacted ketone or aldehyde is distilled and used in the following synthesis. The obtained Sol is dried and identified by NMR.

Thus, the developed method allows to significantly expand the resource base through the use of higher alcohols With₈-C₁₄, aldehydes and ketones, to eliminate the expensive and toxic raw materials, to improve the technology, eliminating the stage of disposal of gaseous waste and the introduction of the solvent, and also to make it more economical. Replacement of toxic and expensive glorieuses agent SOCl₂on NaCl and H₂SO₄allows you to make the process safe.

The big advantage of this method is the possibility of obtaining surface-active alkoxy-(alkyl substituted)methylpyridine chloride branched structure, wetting ability is higher (Chemical encyclopedia. V.3. M. 1992, s).

The following examples illustrate the invention but do not restrict it.

Example 1.

In to the forehead, equipped with stirrer, reflux condenser and addition funnel, pour 290 grams (5 moles) of acetone, 130 g (1 mol) of 2-ethylhexanol (C₈H₁₇OH) and under stirring load 58 g (1 mol) of NaCl. Then dispense 98 g (1 mol) of H₂SO₄so that no leakage of hydrogen chloride in the bubbler after the return of cooler (sauvca with the back of the refrigerator passes through the bubbler with concentrated H₂SO₄and directed into the flask with an alkaline solution to absorb the possible breakthrough of HCl). The temperature of the reaction mass support 30°C. After addition of the total number of H₂SO₄the reaction mass was stirred at room temperature for 1 hour, add 20 g of baking soda (to the disappearance of the expansion), filtered and obtain 142 g of a solid residue, Na₂SO₄. Filtered the reaction mass with stirring 79 g (1 mol) of pyridine and stir the resulting mass is within 15 minutes of Precipitated salt is filtered off and dried in a vacuum desiccator. The result is 218 g of 2-ethylhexoxy-(dimethyl)methylpyridinium chloride. Yield 76%. The remaining liquid phase fraction is distilled and obtain 242 g of acetone, 29 g of 2-ethylhexanol, 17 g of pyridine.

Example 2.

Synthesis is carried out analogously to example 1.

Into the flask was placed 50 g (1.1 mol) of acetaldehyde, 36 g (0.23 mol) of decanol (C₁₀H_{21/sub> OH), 14 g (0.24 mol) of NaCl and stirring dose of 24 g (0.24 mol) of H2SO4. The reaction temperature 35°C. After separation of 34 g of Na2SO4to the reaction mass is added 18 g (0.23 mol) of pyridine and obtain 46 g detoxi(methyl)methylpyridinium chloride and allocate 39 g of acetic aldehyde, 5.7 g of pyridine, and 10.5 g of decanol. The yield of the desired product in 68%.}

Example 3.

Synthesis is carried out analogously to example 1.

The flask 40 g (0.46 mol) of 2,2-DIMETHYLPROPANE, 12 g (0.09 mol) of 2-ethylhexanol (C₈H₁₇OH), 6 g (0.1 mol) of NaCl and stirring dose of 10 g (0.1 mol) of N₂SO₄. The reaction temperature 24°C. After separation of 14.2 g of Na₂SO₄to the reaction mass is added to 7.3 g (0.09 mol) of pyridine and receive a 20 g 2-ethylhexoxy-(tert-butyl)methylpyridinium chloride, and there are 33 g of 2,2-DIMETHYLPROPANE, 2 g of pyridine, 3.4 g of 2-ethylhexanol. The yield of the desired product in 71%.

Example 4.

Synthesis is carried out analogously to example 1.

Into the flask was placed 20 g (0.28 mol) of methyl ethyl ketone, 7.2 g (by 0.055 mol) of 2-ethylhexanol (C₈H₁₇OH), 4 g (0.07 mol) of NaCl and stirring dose of 7 g (0.07 mol) of H₂SO₄. The reaction temperature is 20°C. After separation of 10 g of Na₂SO₄to the reaction mass is added 4.4 g (0.55 mol) of pyridine and obtain 11.2 g of 2-ethylhexoxy-(methyl) (ethyl)methylpyridinium chloride and allocate 16 g methylethylketon is a, 1.2 g of pyridine, 2 g of 2-ethylhexanol. The yield of the desired product in 68%.

Example 5.

Synthesis is carried out analogously to example 1.

The flask 29 g (0.5 mol) of acetone, 16 g (0.1 mol) of decanol (C₁₀H₂₁OH), 7 g (0.12 mol) of NaCl and stirring dose of 12 g (0.12 mol) of H₂SO₄. The reaction temperature is 20°C. After separation of 17 g of Na₂SO₄to the reaction mass is added 7.9 g (0.1 mol) of pyridine and obtain 22.1 g of detoxi-(dimethyl)methylpyridinium chloride and allocate 24 g of acetone, 2.1 g of pyridine, 4.5 g of decanol. The yield of the desired product in 71%.

Example 6.

Synthesis is carried out analogously to example 1.

The flask 24 g (0.28 mol) of diethylketone, 10.4 g (0.06 mol) of dodecanol (C₁₂H₂₅OH), 3.9 g (0.06 mol) of NaCl and stirring dose of 6.6 g (0.06 mol) of H₂SO₄. The reaction temperature 15°C. After separation of 9.5 g of Na₂SO₄to the reaction mass is added 4.4 g (0.06 mol) of pyridine and obtain 16.2 g of dodecane-(diethyl)methylpyridinium chloride and produce a 20.2 g diethylketone, 0.9 g of pyridine, 2.2 g of dodecanol. The yield of the desired product in 79%.

Example 7.

Synthesis is carried out analogously to example 1.

The flask of 18.4 g (0.26 mol) of 2-methylpropanal, 10,9 g (0.51 mol) tetradecanol alcohol (C₁₄H₂₉OH), 3.6 g (0.06 mol) of NaCl and stirring dose of 6 g (0.06 mol) of H₂SO₄. The reaction temperature is 5°C. After separation of 8.7 is Na ₂SO₄to the reaction mass is added 4 g (0,051 mol) of pyridine and 15 g tetradeoxy-(isopropyl)methylpyridinium chloride and allocate 15.6 g of 2-methylpropanal, 0.9 g of pyridine, 2.5 g tetradecanol alcohol. The yield of the desired product 77%.

1. A method of obtaining a surface-active alkoxy-(alkyl substituted)methylpyridine chlorides by alkylation of pyridine, alkyl substituted chlorotoluene esters obtained by the interaction of the higher alcohols, carbonyl compounds, and gloriouse agent, which is used as sodium chloride and sulphuric acid.

2. The method according to claim 1, in which the carbonyl compounds used aldehydes, for example, 2-methylpropanal, acetic aldehyde, 2,2-dimethylpropyl and other

3. The method according to claim 1, in which the carbonyl compounds using ketones, such as acetone, methyl ethyl ketone, diethylketone and other

4. The method according to claim 1, in which the carbonyl compounds are in the liquid state.