Drug – bio-affecting and body treating compositions – Designated organic active ingredient containing – Having -c- – wherein x is chalcogen – bonded directly to...
Reexamination Certificate
1999-09-07
2002-02-19
Pryor, Alton (Department: 1616)
Drug, bio-affecting and body treating compositions
Designated organic active ingredient containing
Having -c-, wherein x is chalcogen, bonded directly to...
Reexamination Certificate
active
06348483
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to the use of methylenebisoxazolidine derivatives for increasing the solubility of derivatives of 1H-benzimidazol-2-ylcarbamic acid in liquid preparations or preservatives for use in industrial products.
BACKGROUND OF THE INVENTION
Methyl 1H-benzimidazol-2-ylcarbamate (carbendazim) is known in the prior art as a fungicide. The active compound has no bactericidal action and is virtually insoluble in water and in most organic solvents. Thus, only via salt formation, for example using strong acids such as HCl, H
2
SO
4
, Malon AS 3 acid (4-C
10-13
-sec-alkyl derivative of benzenesulphonic acid), is it possible to improve the solubility of carbendazim in preparations to such an extent that use in liquid concentrates, for example, is possible. However, in some cases salt formation requires a considerable reaction expense. Thus, for example for preparing carbendasulf (salt of carbendazim and mono-C
10-14
-alkylbenzenesulphonic acid) requires heating carbendazim with Malon AS 3 acid in propylene glycol for 4 hours. Moreover, by-products are formed in this reaction, resulting in losses of activity. Although the concentration of carbendazim in the liquid concentrates described is below 4% by weight, precipitation frequently occurs after some time. Carbendazim and carbendasulf are virtually insoluble in aqueous systems.
Aqueous dispersions based on carbendazim, such as the commercial product Parmetol DF 19 Forte (aqueous dispersion based on carbendazim (fungicide) and diuron (1,1-dimethyl-3-(3,4-dichlorophenyl)urea) (algicide)) are known. However, such preparations are not water-soluble. Stable carbendasulf-comprising concentrates having a limited content of carbendasulf (for example the commercial product Parmetol DF 18) are likewise known from the prior art. However, they have an unsatifactory stability towards low temperatures, and they do not form any clear solutions in water.
Hitherto, the preparation of an aqueous preparation comprising carbendazim or carbendasulf as fungicidal active compound did not seem to be possible or economical.
Derivatives of methylenebisoxazolidine, such as 3,3′-methylenebis-(5-methyloxazolidind) (trade name: Mar 71) are used as water-soluble bactericides; however, in practice they frequently only have low fungicidal activity.
Liquid preparations of Mar 71 and the fungicide Kathon 893 (preparation of N-octylisothiazolone in 1,2-propylene glycol), for example, are known. However, these products are not sufficiently stable towards alkali, and in particular the fungicide decomposes at a pH above about 9.5 and is furthermore subject to degradation by nucleophilic agents.
OBJECT OF THE INVENTION
It was therefore an object of the present invention to increase the solubility of derivatives of 1H-benzimidazol-2-ylcarbamic acid in liquid preparations and to provide compositions which, in addition to good fungicidal or algicidal activity, also have satisfactory bactericidal and, if appropriate, virucidal activity. With a view to possible applications in cooling lubricants (concentrates and emulsions), in the fungicidal, algicidal, bactericidal and/or virucidal finishing of products or coatings such as paints, renders and sealing materials, the substances used should have satisfactory stability towards alkali.
This object is achieved by using derivatives of methylenebisoxazolidine to increase the solubility of derivatives of 1H-benzimidazol-2-ylcarbamic acid in liquid preparations.
The invention accordingly also provides stable microbicidal compositions which are characterized in that they comprise derivatives of methylenebisoxazolidine and 1H-benzimidazol-2-ylcarbamic acid. Here, microbicidal compositions are to be understood as meaning algicidal, bactericidal, fungicidal and/or virucidal compositions.
The present invention furthermore provides the use of such compositions.
Preferred embodiments are the subject of the subclaims.
Surprisingly, it has been found that homogeneous clear solutions of derivatives of 1H-benzimidazol-2-ylcarbamic acid (carbendazim) can be prepared in the presence of derivatives of methylenebisoxazolidine.
Furthermore, it has been found that by using derivatives of methylenebisoxazolidine and, if appropriate, other active compounds, additives and/or auxiliaries, it is possible to obtain clear homogeneous concentrates whose content of carbendazim can be above 10% by weight.
These concentrates can be employed to preparer by dilution with water, ready-to-use solutions which are likewise clear and homogeneous. In addition to good bactericidal action, these ready-to-use dilutions have excellent fungicidal and algicidal action and/or virucidal activity.
Advantageously, the odour and the emission of formaldehyde of the resulting preparations are simultaneously, in particular at high contents of carbendazim, strongly reduced.
The preparations furthermore have, by comparison, excellent stability towards alkali and low temperatures. Moreover, they have a sufficiently high buffer capacity to maintain an alkaline medium.
The emission of formaldehyde or formaldehyde depot compounds from these preparations according to the invention is considerably lower than that of the preparations based on the individual components, for example Mar 71. Furthermore, the use according to the invention of methylenebisoxazolidine together with carbendazim results in synergistic action.
The compositions according to the invention generally have a pH of up to 12, in particular up to 11 and preferably up to 10.
For preparing the compositions according to the invention, use is preferably made of 3,3′-methylenebis-(5-methyloxazolidine) (trade name Mar 71).
Preferred carbamic acid derivatives are selected from methyl 1H-benzimidazol-2-ylcarbamate or its salts, for example the monohydrochloride, the monohydrobromide or the salt of Malon AS 3 acid, and methyl 1-(butylcarbamoyl)benzimidazol-2-ylcarbamate.
The compositions may comprise further active compounds, in particular N-formals and/or O-formals, additives and/or auxiliaries. It is possible to add, for example, the following substances:
further microbicidally active compounds, such as N-formals (for example Grotan BK, alpha, alpha′, alpha″-trimethyl-1,3,5-triazine-1,3,5-(2H,4H,6H)-triethanol, 4,4-dimethyloxazolidine, dimethylolurea, 5-ethyl-3,7-dioxa-l-azabicyclo[3.3.0]octane, 2-(hydroxymethylamino)ethanol, methylenebistetrahydro-1,3-bisoxazine, N-methylolchloroacetamide, bis(hydroxymethyl)-5,5-dimethylhydantoin, diazolidinylurea, Na-hydroxymethylglycinate, 3,4,4-trimethyloxazolidine), O-formals (for example propylene glycol hemiformal, propylene glycol bishemiformal, ethylene glycol bishemiformal, benzyl alcohol hemiformal, butyl diglycol hemiformal), heterocycles (for example 1,2-benzisothiazolin-3-one, 5-chloro-2-methylisothiazolin-3-one, 2-methylisothiazolin-3-one, N-octylisothiazolin-3-one, 2-mercaptopyridine N-oxide or its salts, such as Na or zinc salt, pyrion disulphide, thiabenzazole, N-cyclohexylbenzo(b)thiophene-2-carboxamide 1,1-dioxide), halogenated organic compounds (for example 3-iodopropinyl butylcarbamate, 2-bromo-2-nitropropane-1,3-diol, dibromodicyanobutane)
other active compounds, such as N-cyclohexyl-N-nitrosohydroxylamine or its salts, such as Na, K or Al salts
algicides, such as diuron (1,1-dimethyl-3-(3,4-dichlorophenyl)urea), Irgarol 1051 (2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine), terbutryn (2-methylthio-4-tert-butylamino-6-ethylamino-s-triazine)
insecticides, acaricides, nematocides
substances for regulating or adjusting the pH (for example amines or alkanolamines, in particular primary and tertiary amines or alkanolamines, acids, carboxylic acids, salts, buffers)
odour-masking substances, odour modifiers, perfume
colorants
additives for protection against corrosion
stabilizers
solvents, such as water, alcohols, glycols, glycol ethers, etc. (for example ethanol, propanols, 1,2-propylene glycol, triethylene glycol, 1-methoxypropan-2-ol, butyl diglycol, phenoxyethanol, phenoxypropanols)
The comp
Beilfuss Wolfgang
Gradtke Ralf
Air Liquide Sante ( International)
Pryor Alton
Young & Thompson
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