AU449552B2 - Improvements in or relating to disinfectants derived from alkoxylated amines - Google Patents

Description

This invention zts Io 'isinfectant compositions. Work has.been done on the presentation of iodine by combination of this halogen with various materials including tertiary amines. Some of these materials are known as "iodophors". The materials are substantially charge-transfer complexes and exhibit the characteristic ultraviolet spectrum and brown colour of such complexes. They are formed by the use of low temperature conditions during mixing. This invention provides a new range of halogen- containing disinfectant materials, many of which are not charge-transfer complexes, as evidenced by the absence of charge-transfer bands in the ultraviolet spectrum. The aw materialscan be made by the reaction of a halogen with an alkoxylated primary amine or mixture of such amines having the 'formula

R N (CnH2n)pH (CnH2nO) qH where R is a monovalent hydrocarbon radical with up to 18 carbon atoms or .ahydroxyalkyl radical with from 2 to 18 carbon atoms; Q is 2, 3 or 4 and the average of the totals of p plus is not less than 1.5 nor more than/i9, preferably not less than 2.n more than 5 Where R is a monovalent hydrocarbon/it may be saturated or unsaturated, but is pre- ferably the alkyl group CH2m 1 where m is at least 3. Mixtures of alkoxylated amines will usually be used because many amines from which they are made are available commercially as mixtures and the alkoxylation may not be uniform; indeed many amines sold as having predominantly a saturated alkyl chain often contain a small proportion of unsaturated material. However, a single alkoxylated amine

4 49.552 may be used and then, A e5,oe "average" value of the total of p plus will be an integer. are In preparing the materials very good results preferably 0.8 to 1 achieved by the use of 0.5 to 1, more atom equivalents of halogen 0.4 to 0.5 mol equivalents of amine. of iodine taken as 12) to each mole equivalent at any rate when Within these proportions, it is possible, to make materials R is one of the longer hydrocarbon chains, ultraviolet which show no charge-transfer bands in the and spectrum. These materials are excellent bactericides have fungicidal properties. If predominantly fungicidal desirable to add qualities are required, it may be found of additional halogen, up to say 1.6 atom equivalents and this may well halogen to each mole equivalent of amine, complex. appear in the form of a charge-transfer absence of The new materials may be made either in the an organic solvent. solvent, or in the presence of water or materials of lower It has been found desirable to make the overheating may molecular weight in a solvent, as otherwise a given R group, occur, with undesired side reactions. For aqueous solvents the solubility of the new materials in present. However increases with the number of alkoxy groups as the molecular the activity per unit weight decreases weight increases. consist of at A disinfectant composition may suitably an aqueous medium. least 0.01% w/v of the new material in w/v may be more suitable. A stronger solution of at least 0.1% are given of The following non-limitative Examples accordance with the disinfectants and their preparation in invention.

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EXAMPLE 1. 17. 91 87 29.9 lbs (0.1 mol equivalent) of Ethomeen C/12 (the

reaction product of 2 moles of ethylene oxide with

cocoamine, commercially available from Armour Hess

Chemicals Ltd. Ethomeen is a Registered Trade Mark) were

raised to a temperature of 50-550C and 12.7 lbs of iodine

were mixed into it. The temperature of the mixture rose

to 145 0 C and after some 30 minutes, it was found that an

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17, 918/A distilled aliquot of the mixture diluted to 1% w/v with

water gave a pH in the range of 3.5 to 3.9 indicating

completion of the reaction. The product, which was a brownish-red, was soluble in water to give a disinfectant composition. are Its ultraviolet/visible and N.M.R. Spectra

highly characteristic. The ultraviolet/visible spectrum as 1 cm. cell, a 1% solution in methylene chloride, using a

gave the following peaks Wavelength Extinction Coefficient

285 295 nm 4 8 345 360 nm 505 510 nm (shoulder) 0.1 approx.

The N.M.R. spectrum using a tetramethyl silane standard gave the following results Group Type of band Shift (prm, relative to -tetramethyl silane),

CH3 resonance in 0.9 DCCL 3

aliphatic resonance in 1.27 CH2 DOC13 OH broad ca 1.8

CH2(with broad ca 3.6 vicinal N) CH2 (with broad ca 4.1 vicinal OH) The disinfectant composition is germicidal in. aqueous solution and kills both gram-positive and gram- that negative bacteria; by way of example only tests show nseudomonas aerujinsa, staphylococcus aureus and escherichi& and col, are destroyed.' The material is also fungicidal 449.552

17. 918/70 kills, for example, fungi of the genus trichophyton, fungi of the genus microsporum and aspergillus fumigatus. The material is notably resistant to organic contamination and in this respect it is as good as, for example, crude chloroxylenol whilst at the same time possessing markedly lower toxicity and irritancy. It is effective in aqueous solution at a pH of less.than 5 even in the presence of quite heavy contamination. A typical formulation is an aqueous solution con- taining 4% of the complex and 2% of hydrogen chloride. This may be diluted one part in 40 parts of distilled water for heavy contamination and one part in 400 parts of dis- tilled water for light contamination. If particularly required as a fungicide, the fungicidal properties of the material can be enhanced by formulating the material with up to 1.6 atom equivalents of iodine for every mol equivalent of the amine. This causes some of the iodine to become apparent as a charge- transfer complex, and the material becomes slightly more fungicidal at the expense of stability. If too much iodine is added, the material is liable to become an insoluble oil. EXAMPLE 2. If the same reaction is repeated using, in place of Ethomeen/C/12 the equivalent weight of a commercial amine of which each mol is condensed with 2-5 mols of ethylene oxide, a brownish opaque solid with disinfectant properties is produced.

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17 91817 EXAMPLE 3. dzJ.fI'th) 150 Grams of Ethomeen/C/12 were heated to 90C and vigorously stirred. Chlorine gas was passed in and the 0 temperature rose to 135 C. Further additions of chlorine

gas was made at a rate which was controlled to maintain the temperature at 135°C until 17.7 grams in all had been taken up. Stirring was continued for 10 minutes and the mixture allowed to cool. An aliquot diluted to 1% w/v with distilled water gave a pH in the range of 3.5 to 3.9. The product which had a brown colour had substant- qualities ially the same powerful germicidal/and resistance to organic contamination as the product of Example 1. EXAMPLE 4. 145 Grams (1 mol) of n propyl diethanolamine are dissolved in 500 ml methylene chloride, and 120 grams of iodine dissolved in 500 ml methylene chloride are added slowly at room temperature. The mixture may be left at room temperature for 24 hours when the material separates as an oil at the bottom of the vessel, whereupon the solvent can be de- canted off. Alternatively, the mixture of amine and iodine in

methylene chloride can be brought to the boil immediately after mixing and the solvent boiled off; the rise in temperature occasioned by the boiling of the solvent causes the reaction between the amine and iodine .to occur before the solvent is removed. Lower members of the hydroxyalkyl series can be made similarly. 7 4 49.552

17918/70

Although the materials of higher molecular weight can also be made similarly, getting rid of the solvent becomes more of a problem.

EXAMPLE/f.

A molar solution of triethanolamine is reacted with a 0.5 molar solution of 12 a one-atom'equivalent) at a temperature of 400 to 50°C. The triethanolamine should be relatively pure, for example with a specification as follows Molecular weight 149.2 Specific gravity t/20°C 1.128 Boiling point 760 mmHg. 2860 C Viscosity 20°C (centistokes) 900 Both this material, and the similar product using tripropanolamine, are effective, easily prepared, dis- infectants.

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17. 91 870

THE CLAIMS DEFINING THIS INVENTION ARE AS FOLLOWS:-

1. The halogen-containing material obtainable by reacting formula a halogen with an amine or mixture of amines of the

qH R N_ (C nH 2n0)

(CnH2nO) pH

where R is a monovalent hydrocarbon radical with up to 18 hydroxyalkyl radical with from 2 to 18 carbornatoms, n is 2, 3 or 4 and the average of the totals of p,plus is not less than 1.5 nor more than 2. The material of claim 1 where the average of the totals of p plus q is not less than 2. 3. The material of claim 1 or claim 2 where R is the group

CmH2 m 1, where m is at least 3. 4. The material of any one of the preceding claims where the halogen is iodine or chlorine. The material of any one of the preceding claims being the material obtained by reacting between 0.5 and 1 atom equivalents of the halogen with each mole equivalent of the amine. A material according to claim 5 characterised by the spectrum. absence of charge-transfer bands in the ultraviolet 7. A disinfectant composition comprising a fungicidally *effective-amount of a halogen-containing material obtainable by reacting up to 1.6 atomlequivalents of a halogen with a the formula mole equivalent of an amine or mixture of amines of

Q 4 49.552

17. 91 87o

(C nH 2 n0) pH

(C nH2 n0)qH

where R is a monovalent hydrocarbon radical with up to 18

carbon atoms or a hydroxyalkyl radical with from 2 to 18

17, 918/70 of the totals carbon atoms, n is 2, 3 or 4 and the average more than of p plus q is not less than 1.5 nor a bacteri- 8. A disinfectant composition comprising material cidally effective amount of a halogen-containing 1 atom equivalent of obtainable by reacting between 0.5 and an amine or mixture of a halogen with a mole equivalent of amines of the formula

R -N 2nO H radical with up to 18 where R is a monovalent hydrocarbon with from 2 to 18 carbon atoms or a hydroxyalkyl radical average of the totals carbon atoms, n is 2, 3 or 4 and the nor more than of 2 plus q is not less than 1.5 to claim 7 or 9. A disinfectant composition according of 2 plus a is not claim 8 where the average of the totals less than 2. a material A disinfectant composition including according to any one of claims 1 to 6. in aqueous 11. A disinfectant composition comprising of any one of medium at least 0.01% w/v of the material claims 1 to 6. to claim 11 12. A disinfectant composition according material. having at least 0.1% w/v of the said which comprises 13. A method of making a disinfectant an amine or mixture of the step of reacting halogen with amines of the formula

(Cn -(CH 2nO) H 0) H radical with up to 18 where R is a monovalent hydrocarbon 449.552

Claims (1)

17. 918 o carbon atoms or a hydroxyalkyl radical with from 2 to 18

carbon atoms, n is 2, 3 or 4 and the average of the totals

of p plus a is not less than 1.5 nor more than 14. A method according to claim 13 where the average

of the totals of p plus is not less than 2 nor more than

A method according to claim 13 or claim 14 wherein

up to 1.6 atom equivalents of halogen are reacted with each

mole equivalent of the amine.

16. A method according to claim 13 or claim 14 wherein

between 0.5 and 1 atom equivalents of halogen are reacted

with each mole equivalent of amine.

17. A method according to any one of claims 13 to 16

where R is the group CmH2m where m is at least 3. 18. A method according to any one of claims 13 to 17

where the halogen is iodine or chlorine.

19. A method according to any one of claims 13 to 18

wherein the halogen is added to the amine and the

temperature of the mixture allowed to rise to a temperature

in the range of about 13500 to about 14500C.

Methods according to claim 13 substantially as

herein described in the Examples.

21. A disinfectant made by the method of any one

of claims 13 to

22. A disinfectant composition according to claim

which includes the product of the method of any one of the Examples. DATED THIS 3rd DAY OF DECEMBER. 1973 GLASBY PHARMACEUTICALS LIMITED.

by their Patent Attorneys 3 2 DAVIES COLLISON

4. 49.552