DE1035148B - Process for the production of stable, practically odorless germicidal quaternary ammonium halides - Google Patents

Description

GERMAN

The invention relates to an improved method of making germicidal, persistent quaternaries Ammonium halides in increased yields that do not react acidic and practically free from the unpleasant Smell are.

The process according to the invention is characterized in that an alkylbenzyl halide of the general formula

R ₁ - s ^

■ CH, X

R,

where R _{1 is} an alkyl radical, R _{2 is} an alkyl radical or hydrogen and X is a halogen atom, with a tertiary amine in the presence of - based on the total weight of the alkylbenzyl halide and tertiary amine present - 0.25 to 15 percent by weight of an alkali salt of boric acid or acetic acid in Condenses water, an alcohol or a water-alcohol mixture.

Quaternary ammonium halides of this type are known. They are usually caused by condensation of an alkylbenzyl halide with a tertiary amine in the presence of water and correspond mostly the formula

for the production of resistant,
practically odorless germicidal
quaternary ammonium halides

Applicant:

Continental Oil Company,
Ponca, OkIa. (V. St. A.)

Representative: Dr.-Ing. H. Ruschke, Berlin-Friedenau,

and Dipl.-Ing. K. Grentzenberg, Munich 27,

Pienzenauerstr. 2, patent attorneys

Claimed priority:
V. St. v. America 10 October 1955

Edsel Leo Miller, Ponca, OkIa. (V. St. A.),
has been named as the inventor

R ₁ .

LR ₂

In this formula, R ₁ , R ₂ , R ₃ and R _{4 are} identical or different alkyl, aryl or substituted alkyl or aryl radicals and X is a halogen atom. In order that such compounds can develop an adequate germicidal effect, at least one of the radicals R ₁ , R ₂ , R ₃ and R _{4 must be} strongly hydrophobic.

Since the germicidal effect is a quaternary ammonium halide in the p _H range from 7 to 8.5 at best, it is necessary to treat the condensation product with an alkali in general in order to give it the desired _pH value. If the condensation product has now been made alkaline, considerable amounts of the tertiary amine are released, which can be recognized by the characteristic and unpleasant fish-like odor. This unpleasant odor has hitherto prevented general use of these quaternary ammonium halides as germicides. In addition, the released tertiary amines are practically non-germicidal and represent impurities.

In order to remedy the disadvantage shown, it has already been proposed that the alkylaryl halide and the to condense tertiary amine in the presence of water, in the presence of about 0.1 to 10 percent by weight of an alkali bicarbonate, on the total amount of the organic halide and the tertiary amine based. The quaternary ammonium halide obtained in the latter process is essentially free from unpleasant odor when it is freshly made; but if it is stored for a longer period of time, especially in the presence of warm water, a certain amount of tertiary amine is also released here gives the product an unpleasant, fishy odor.

The invention relates to a process for the production of germicidal quaternary ammonium halides, which are stable even after long periods of storage, do not react acidic and are practically free from unpleasant effects Smells are. It has been found that quaternary ammonium halides meet these conditions sufficient, even if they are stored in the presence of water, can be produced, if you an alkylbenzyl halide with a tertiary amine in the presence of water, an alcohol or Mixtures thereof and, based on the total weight of alkylbenzyl halide and tertiary amine present based, about 0.25 to 15 percent by weight of an alkali salt of boric or acetic acid condensed.

809 579/484

3 4

Although almost every tertiary amine can be used as mentioned, the condensation of the alkylbenzyl

can, those are preferred, the no more than total halide with the tertiary amine in the presence of a

including 12 carbon atoms; specific examples carried out solvent. Suitable as a solvent

are trimethylamine, triethylamine, triethanolamine, di-alcohols are monohydric aliphatic alcohols with not

methylbenzylamine, diethylethanolamine, pyridine, methyl 5 more than 4 carbon atoms, also hexylene glycol,

morpholine, ethyl morpholine. Suitable alkylbenzylhalo-ethylene glycol and glycerin.

Genide are those that could theoretically be the reaction of the halide with the following general formula

correspond to: the amine are carried out in a molar ratio of 1: 1,

However, R ^^ "^ \, Qjj χ is preferred for best results

^{1 2} »ίο a slight excess of amine is used.

J ^ The reaction temperature is not critical and

^ \ ^^ can be between 30 and 70 ⁰ C. The implementation time

In this formula, R _{1 is} alkyl, R _{2 is} alkyl or can be 0.25 to 3.5 hours.

Hydrogen and X halogen. Alkylbenzylhalogenide that the products of the invention are able to find neutral or erfindungsgemiß use can be prepared in 15 weakly alkaline and have p _H values are from 7 to 8.5 and with respect to their content of carbon atoms very under- of germicidal action, without being a be different. So is z. B. the carbon content must also be subjected to further treatment. An alkylbenzyl halide to some extent further advantage of the process lies in the fact that, depending on the particular tertiary amine used. the tertiary amine in the process according to the invention. If a tertiary amine with a relatively low 20 is almost completely utilized, so that compared to molecular weight such as trimethylamine, the yield of quaternary is used compared to previous processes, it is advantageous that the alkylbenzyl halide 12 to ammonium halide is significantly improved and contains 18 carbon atoms, so that it can give the quaternary this, both with regard to its germicidal ammonium halide, the required strong hydro-effect, its odor and its storage-phobic properties. If, on the other hand, a high molecular weight tertiary amine is used, the resistance of the known products is lower.

may be an alkylbenzyl halide of a smaller number. The following examples are intended to further illustrate the invention

of carbon atoms can be applied. Alkylbenzyl- explain. Parts are parts by weight,
halides, which are particularly effective according to the invention,

are those made from dodecylbenzene, dodecyltoluene and 3 ° Example 1
Polydodecylbenzene have been produced.

Dodecylbenzene, from Continental Oil Company 200 parts of dodecylbenzyl chloride was made with 110 parts

available under the trade name "Neolene 400", water and 20 parts of sodium tetraborate (borax) in one

has the following physical properties: reaction vessel thoroughly mixed, the mixture to approx

Specific weight at 16 ° C 0.8742 ³⁵ ^ ^bi ? ⁶⁰ ° J? 5 ™ * ™? ^and ^ ¹⁹² . ^{Teüe, 1} J, ^b ^? ° ^{/ oi} P

Average molecular weight 232 ^aq . Methylamine slowly within 30 minutes

Boiling range added according to ASTM-Ver. The mixture was at a temperature

tu ^ ni: a / τγ ,, ^ ι ^, λ stirred from 70 to 80 C for a further 30 minutes, then

drive D-l3ö (Jingler). , .. ,,,,., _r _ ", ·. · ^{,,, ... ö} ,". ·. · ,,.

Cooled at boiling point 279 ° C and diluted with 50% ethanol. The ethanol

285 ° r + ° water solution was extracted three times with pentane;

JiQ 288 ⁰ C ^ ^{e s0} S ^ereui igt ^e aqueous phase was then by a

CQ 293 ° C evaporate to 20 to 30 ° / ₀ concentrated. The end product

OQ 303 ⁰ C ^was P ^ra ktisch odorless. A dilution of this pro-

gj 311 ⁰ C product with distilled water in a ratio of 1: 1 resulted

Final boiling point 317 ° C ^{45 s} * ^ne solution having a _pH value of 8.4.

Refractive index at 20 ⁰ C 1.4885 Example 2

Viscosity at 20 ° C 14 cP ^ _{ΛΓ,,, D.} ..., - · ,,,.

Bromine number 0 16 ^s "learned according to Example 1 was repeated, only

'That instead of sodium tetraborate, 20 parts of sodium acetate

Polydodecylbenzene is made up of monoalkylbenzenes and 50 were used.
Dialkylbenzenes in an approximate ratio of 2: 3. His

typical physical properties are as follows: Example 3

Specific weight at 38 ° C 0.8649 200 parts of dodecylbenzyl chloride, 110 parts of methanol

Average molecular weight 365 and 20 parts of sodium tetraborate were added to the reaction

Sulphonizability introduced into ₀ 88 55 vessel. The mixture was stirred up

Boiling range according to ASTM 50 to 60 ⁰ C heated and then 192 parts 18 to 20 ° / ₀ iges

drive D-158 (Engler) methanolic trimethylamine slowly over the course of

The start of boiling 342 ° C. was added for about 30 minutes. The mixture became wider

5361 ⁰ C stirred for 30 minutes at a temperature of 70 to 8O ⁰ C,

10 379 ⁰ C 60 then cooled and diluted with 50% ethanol. the

90 404 ⁰ C ethanol-water solution was three times with pentane extra-

95 413 ° C hiert and the aqueous phase concentrated to 20 to 30%,

Boiling end 415 ° C whereby a product was obtained which is practically odorless

Refractive index at 23 ° C was 1.4900. If this product with an equal amount

Viscosity at - 10 ⁰ C 2800 cP was diluted 65 distilled water was added a solution

20 ° C 280 cP obtained with a _pH value of 8.4.

40 ° C 78 cP _. . . .

8O ⁰ C 18 cP Example 4

Aniline point 69 ° C The procedure of Example 1 was repeated, only

Pour point 4 ⁰ C 70 were instead of the 18 to 20 ° / ₀ igen aqueous trimethyl

amines 192 parts of 18 to 20% methanolic trimethylamine are used.

Example 5

The procedure of Example 1 was repeated, except that 210 parts of methyldodecylbenzyl chloride were used in place of 200 parts of dodecylbenzyl chloride used.

Example 6

The procedure of Example 1 was repeated, except that 306 parts of polydodecylbenzyl chloride were used in place of the 200 parts of dodecylbenzyl chloride are used.

Example 7

A number of experiments were carried out according to Example 1, except that triethylamine, triethanolamine and pyridine were used instead of the trimethylamine used there. All were in Examples 1 to 7 manufactured products, resistant than a week even when diluted with hot water at 8O ⁰ C for storage periods longer.

Example 8

100 parts of dodecylbenzyl chloride were placed in a glass flask equipped with a reflux condenser, brought in. 25 parts of methanol were added, followed by 5 parts of water and 1 part of sodium bicarbonate. On that 24 parts of a 25% strength solution of trimethylamine in methanol were slowly added to this reaction mixture while stirring added. The mixture was refluxed for about 1 hour. The yield at quaternary ammonium chloride was quantitative and all of the dodecylbenzyl chloride was converted. the cooled solution was then diluted with an approximately equal amount of water and three times with Petroleum ether extracted. The aqueous phase was concentrated by evaporation, followed by the concentrate enough distilled water was added to ultimately result in a 10% solution. This product Developed a strong fishy odor when diluted with hot water after one week of storage after trimethylamine.

Claims (3)

Patent claims: 1. Process for making persistent, practically odorless, germicidal quaternaries Ammonium halides, characterized in that an alkylbenzyl halide of the general formula --CH, X wherein R _{1 is} an alkyl radical, R _{2 is} an alkyl radical or a hydrogen atom and X is a halogen atom, with a tertiary amine in the presence of - based on the total weight of alkylbenzyl halide and tertiary amine - 0.25 to 15 percent by weight of an alkali salt of boric or acetic acid condensed in water, an alcohol or a water-alcohol mixture. 2. The method according to claim 1, characterized in that the alkylbenzyl halide is dodecylbenzyl chloride, Methyldodecylbenzyl chloride or polydodecylbenzyl chloride is used. 3. The method according to claim 1 or 2, characterized in that the tertiary amine is trimethylamine, Triethylamine, triethanolamine or pyridine are used. © 809 579/484 7.58