FR2698347A1 - Compsn. for treating water, contg. chloro deriv. of allantoin or of glycoluril - used in prodn. of drinkable water or for industrial or domestic use. - Google Patents

Abstract

A compsn. for treatment of water contains less than 2-3% residual moisture and a disinfectant cpd. of formula (I) or (II), R1, R2 = H, Cl, 1-5C alkyl or Ph, provided that at least one = Cl; R3, r4, R5 = H, Cl, 1-5C alkyl or Ph; R6 = H, 1-5C alkyl or Ph; R1, R2, R3, R4 = H, or Cl provided that at least one = Cl. The compsn. contains active C, pref. impregnated with an ion. The compsns. are compressed into tablets, capsules, powders, suspensions or dispersion. USE/ADVANTAGE - Drinkable water is obtd. by treating with the compsn. or the water is for domestic or industrial use. The compsns. are stable in the absence of moisture.

Description

FIELD OF THE INVENTION
The present invention relates to compositions
stable which are used for water treatment
by releasing an active ion from the chlorine. The current
The invention also relates to a practical method and
advantageous for treating water to make it drinkable.

BACKGROUND OF THE INVENTION
The various derivatives of allantoin, such as
that, for example, ureido-5-hydantoin and
# dioxo-2,5-imidazolidinyl-4-urea are well known and
used for various applications. US Patent No. 32,848 discloses the reaction product of allantoin
with formaldehyde, product that has activity
bactericidal that is effective against mold and
yeasts and that can be used as an additive to
conservation for substances likely to be
contaminated by microbes. The US patent
No. 3,380,908 describes a mixture of allantoin as support
bactericidal component (silver citroallantoinate) or
fungicidal component (sulfo-hydroxy-allantoinate
zinc). This medium is described to be used for
to treat the surfaces of splints, bandages and
packaging materials to ensure their sterility. The
German Patent No. DD 158 357 discloses a protective medium
for cosmetic emulsions that contains
allantoin and ascorbic acid. The patent
English No. GB 2 108 840 discloses derivatives of
allantoin with bactericidal activity and
bacteriostatic for the treatment of diseases and
skin lesions.The anti-inflammatory activity,
anti-tumor activity, as well as activity as
disinfecting agent and bleaching agent
allantoin were respectively described by the
Japanese patent N0 59-055874, the Japanese patent
Na 57-050969 and U.S. Patent Nos. 4,654,424 and
4,560,766. Allantoin is used in medicine for
facilitate the healing of wounds. Allantoin is
also used as a component for cosmetics
made of its biocompatibility.

Halogenated derivatives of substituted hydantoins
are generally known for their disinfecting activity, bleaching property and chlorinating property, their property as a catalytic polymerization agent and their property as an industrial deodorant agent. The commercially available products are, for example, dichloro-1,3-dimethyl-5,5-hydantoin (halane).

Allantoin is known for its ability to regenerate damaged tissues of wounds and ulcers in difficult scarring.

Chlorinated derivatives of allantoin are not mentioned to date in the literature.

The glycoluryl compounds are known compounds which are used for their disinfecting and bactericidal applications, and are described by US Pat. Nos. 3,019,160 and 3,019,075, as well as British Patent No. 831,853. The chloroglycoluryl compounds are disclosed in U.S. Patent No. 2,638,434 as chlorine-releasing agents for ointments and as anti-phlyctene agents in U.S. Patent Nos. 2,649,389; 2,934,451; Other manufacturing methods for preparing halogenated glycoluryl compounds are described in US Pat. Nos. 3,147,259 and 3,345,371.

 Natural water reserves are used increasingly to cover the needs of drinking water and water for domestic and industrial use; humic substances represent a predominant proportion of organic pollution of surface natural waters.

 Depending on their physical and chemical properties, humic acids can be classified into humic acids (humic acids, fulvic acids and hymatomelanic acids), humins and humic charcoals.

(Kalavska D., Holoubek J.: Analyza v. Alfa,
Bratislava, 1989). In humic substances present in natural surface waters, only humic acids are of importance for the treatment of water because humins and humic charcoal are insoluble in water and not hydrolyzable. Since humic acids have different solubility in acidic, basic and ethanol, this property can be used to separate each group separately. For example, humic and hymatomelanic acids can be precipitated in acid solution in the form of a brown precipitate, whereas fulvic acids remain in solution.

In contrast to humic acids, hymatomelanic acids are soluble in ethanol. In practice, it is difficult to separately isolate the components of humic substances because they have no precise predefined structure, more their composition depends on the nature of the natural materials that have broken down during their formation. However, research indicates that humic substances are high molecular weight polycyclic compounds that contain aromatic and aliphatic moieties. Theoretical structures for humic and fulvic acids are given in the literature. (Kalavska D., Holoubek J.: Analyza vdd.

Alfa, Bratislva, 1989; Zacek L.: Huminove latky v prirozenych vodach to moznosti jejich odstranovani. The presence of various functional groups (carboxy, hydroxy phenol, metoxylic alcohol, quinoic) modifies their physical and chemical properties. The COOH and OH groups involve an acid behavior, a reversibility character and a weakly polar character while the presence of quinoic structures with hydroxyl groups induce oxido-reducing properties.

 Humic substances are present in natural surface waters with concentrations ranging from 10 mg / l to 120 mg / l, with extreme values that can be around 500 mg / l. (Kalavska D., Holoubek J.

Analyza vôd. Alfa, Bratislava, 1989; Sorm J., Zacek L.,
Vyuziti spektroskopichy metod k hodnoceni organickeho znecisteni pri procesech upravy vody. VUV Publication, No. 16, SZN, Prague 1987). A concentration of 100 mg / l is considered dangerous for humans. Humic substances are not directly toxic but
their presence can degrade the appearance and taste of water.

The presence of humic substances does not only affect drinking water but also water for the industry
(textile industry) or productions may be affected, affected or degraded by the presence of such substances. The increase in corrosion phenomena is directly related to the presence of such substances.

The presence of humic substances is also very harmful to the processes concerning the treatment of
the water. In most of the processes employed, a
The increase in the content of such substances can lead to many difficulties (separation of
flocculants and humic substances, corrosive property of treated water and degradation of water quality in the city network). (Vagner V., Janda V.,
Havel L., Rudovsky J.: Vodni hospodarstvi No. 12, 315 (1989)). However, the greatest danger is due to the formation of trihalogenomethane during chlorination.

 Dangerous compounds may appear in the treatment of water by the presence of humic substances; not only by the action of chlorine, but also by the action of chlorine dioxide and ozone.

(Havlik B., Hanusova J.: Vodni hospodarstvi No. 4, 85 (1989)). The reaction between humic acids and chlorine produced initially chlorloform as well as mono-, di- and tri-chloroacetonitriles of cyanobutanic acids were also demonstrated. In alkaline medium, chloropicrin was detected in the presence of nitrite. Ozonation of humic acids degrades the polymer chains to yield aliphatic acids, ketones, and aromatic compounds such as tetra, penta, and hexachlorobenzene. Ozonation also induces the release of bridged substances in humus complexes (pesticides and heavy metals).

 As a result, important research has been conducted to find an efficient and economically realistic process for the treatment of water containing humic substances. This subject has been studied in detail by Zacek. (Zacek L.: Huminove latky v prirozenych vodach a moznosti jejich odstranovani.

VUV works and studies, Prague, 1976; Sorm J., Zacek L.,
Vyuziti spektroskopichy metod k hodnoceni organickeho znecisteni pri procesech upravy vody. VUV Publication, No. 16, SZN, Prague 1987; Zacek L.: Vodni hospodarstvi No. 1,5 (1989)). He conducted a detailed study on the behavior of humic substances with water, evaluated separation methods and studied the optimization of clarification technology with iron and aluminum compounds. (Zacek L.

Huminove latky v prirozenych vodach a moznosti jejich odstranovani. VUV works and studies, Prague, 1976; SORM
J., Zacek L., Vyuziti spektroskopichy metod k hodnoceni organickeho znecisteni pri procesech upravy vody.

VUV Publication, No. 16, SZN, Prague 1987. Vagner et al (Vagner V., Janda V., Havel L., Rudovsky J.: Vodni hospodarstvi No. 12, 315 (1989)) used active charcoal for adsorption of humic substances and measured the adsorption capacity of several types of activated carbons. He measured the amount of organic substances through COD (Chemical Demand in
Oxygen) using oxidation with permanganate.

It is also mentioned the treatment of humic substances using ion exchangers, such as XAD1,
XAD7, XAD8 (Kalavka D., Holoubek J.: Analyza v. Alfa,
Bratislava, 1989) and the XAD4 ion (Havlik B., Hanusova J.

Vodni hospodarstvi No. 4, 85 (1989)) or exchange ions based on DEAE cellulose (Kalavska D.,
Holoubek J.: Blank analyza Alfa, Bratislava, 1989). Inorganic adsorbents, such as aluminum oxide, silica gel and calcium carbonates have been tested.

(Kalavska D. Holoubek J.: Analyza v. Alfa, Bratislava, 1989).

SUMMARY OF THE INVENTION
The present invention makes it possible to obtain advantageous novel compositions that can be used to transform a quantity of untreated water into drinking water or to make water intended for domestic and industrial use. The novel compositions have the particularity of releasing an active ion from chlorine in an aqueous medium and of being stable compositions until they are used. By way of nonlimiting example, examples of such compositions, such as tablets for disinfecting water, are described in the paragraph
DETAILED DESCRIPTION OF THE INVENTION

 The present invention also makes it possible to obtain advantageous compositions for the treatment of water which, in addition to releasing an active ion from chlorine in an aqueous medium, also contain active charcoal which allows the adsorption of the humic substances contained in waters treated with these new compositions.

Advantageously, the activated carbon is impregnated with a metal ion (for example iron), so as to optimize the adsorption of such humic substances.

The compositions of the invention contain one of the chlorinated derivatives of allantoin or glycoluryl respectively detailed below, according to Formulas I or II.

According to Formula I, R1 and Rz may be the same or different, being chlorine or hydrogen atoms, an alkyl group having from one to five carbon atoms or a phenyl group and / or one of the substituents is the chlorine; Ra, R *, Rs, which may be the same or different are chlorine or hydrogen atoms or an alkyl group having from one to five carbon atoms or a phenyl group; It is a hydrogen atom or an alkyl group having one to five carbon atoms or a phenyl group.

According to Formula II, R, RZ, R3 and R4 are
identical or different and are chlorine atoms or
of hydrogen provided that at least one of the atoms
referenced R1, R4 is a chlorine atom.

The compositions of the present invention
contain low amounts of residual moisture
and remain stable until they are put into
contact with the aqueous medium.

The present invention also relates to a method
to provide drinking water that includes treatment
water with one or the other of the compositions
inventive news, as well as a set of treatment
of Water to implement this method.

DETAILED DESCRIPTION OF THE INVENTION
The following detailed description does not limit this discovery. In addition the following description is given for information purposes, for those wishing to practice the present invention, describing preferred and advantageous methods, through which the present invention can be implemented. It is understood that slight variations or minor changes may be made to the inventive methods and compositions described herein without thereby departing from the spirit and scope of the present inventive discovery. As a result, such changes and variations are admitted by those who commonly practice the known art.

 The inventor's know-how in preparing the present inventive compositions for the treatment of water results from his know-how in producing compositions which contain small residual amounts of moisture (less than 2 to 3% by weight). This because the departure of an active chlorine ion compounds according to Formulas I or II requires one or two initiators. One of them is moisture or water, the other is temperature (temperatures above 60 C). Also if one of these conditions is prematurely attained, it may produce an anticipated departure of an active chlorine ion from the inventive compositions described herein.

In order to ensure that the present compositions maintain a residual moisture content of less than 2 or 3% w / w, certain procedures should be used. Firstly, each component used in the present inventive compositions will have to be tested according to its humidity (for example by gravimetric analysis), and if a humidity level is found, the same component will have to be dried if necessary in order to reach a certain level. residual humidity of less than 0.2 or 0.3% weight for weight and be placed in an environment with no relative humidity. An example of such an environment may be a desiccant containing a suitable desiccant or a controlled environment containing low levels of moisture (for example with air containing less than 1% by weight
Moreover, while preparing the present inventive compositions, it is necessary to take precautions, such as the protection of the various ingredients of the moisture contained in the breath and the breath of the preparers (we arrive at rates that can be included at 80% by weight in moisture). In this case, the present inventive compositions if prepared in good conditions will contain less than 2 to 3% by weight of moisture.

 To ensure that the present inventive compositions contain a residual moisture content of less than 2 or 3% by weight, the production of the present inventive compositions and their packaging will require very low moisture levels. In addition, the packaged compositions must be insensitive to humidity for an extended period of time; until their use. It is clear that those who practice the known art will recognize that the methods that are applicable to the preparations of the new inventive compositions are quite affordable. The use of such techniques for controlling moisture in the present inventive compositions are described below.

As noted previously, heat can destabilize the compounds described in Formulas I and
It (temperature above 60 QC). Also it is suggested that temperatures above 60 ° C are not used to prepare the present inventive compositions when the compounds described according to Formula
I or II are present because such high temperatures can cause the departure of an active chlorine ion. Also the preparation of a suitable anhydrous support which requires a high temperature is allowed, provided to cool it before combining it with the compounds described by Formula I or II.

As indicated in the paragraph BACKGROUND
Of the invention, a reduction in the level of humic substances in water treatment is highly commendable. Therefore, with the compounds described according to Formulas I and II, it will be possible to associate with the present inventive compositions, optionally, activated charcoal which will allow the adsorption of humic substances. Such active charcoal may be impregnated with a metal ion (eg Fe 3), if desired.

The inventor discovered that some ions that
impregnate activated carbons are extremely effective
and valid for removing humic substances
contained in the water samples. For example
activated carbons impregnated with an ion such as Fe'3 5 ~ in a percentage between 0.5 and 15% by weight for
weight relative to the weight of the adsorbent can
effectively and easily be used to remove the
humic substances contained in a water sample.

The active carbons and ion that permeate the 10 t activated carbons when used in
compositions described herein will be preferentially
in the form of a powder or granule. However,
Activated carbons can be separated or isolated
physically of the present inventive compositions and 15 ~ however, be associated with the inventive methods
described here. In addition, the set for water treatment
described herein may advantageously contain a
activated carbon component that will be isolated from
Other components, if desired. When an activated carbon component is isolated from the described compositions.
here it is best to put it in the form of
flake or pellet in a separate pouch (like a
tea bag). Use in this form
will treat water against humic substances 25 - by allowing to remove humic substances after
treatment. Filters containing activated carbons
can also be used if desired. In this
In this case, the sample of water to be treated will be
through the filter containing activated carbon until 30, that we obtain a water quality with a rate of
humic substances acceptable.

For example, for the preparation of a coal
active impregnated with an ion the description of the
The preparation given below makes it possible to obtain an active carbon impregnated with iron> 3% by weight.

Example of an active carbon impregnated with an ion
An activated carbon that is impregnated with iron has been
prepared by impregnation of a coal fraction
active wood of a size between 100 and 160 microns 40. by a spraying method. As a solution
of impregnation the inventor used 0.4M Fe = (SO o 9
-H # in water with a volume equivalent to that of the
sum of the pores expressed in volume (one liter per kilo) of
activated carbon used. The formed substrate has been maintained
at 30 ° C. in a closed container in an incubator.
repeated washing of the substrate with distilled water
(forty liters per kilo) until you can not detect
more ferric ion, the product was dried at 100 C.
Iron content was evaluated at 3%.

Original active charcoal and charcoal
activated with ferric hydroxide (AC / Fe) were tested
by adsorption isothermal and kinetic adsorption of
humic acids from an aqueous solution of twenty
five degrees. The test results demonstrate a
significant and substantial increase in capacity
adsorption for activated carbon impregnated with iron
compared to the original active carbon.

 The compositions of the present invention are described as being stable until used.

This stability is due to the use by the inventor
compositions that contain low levels
residual moisture.

The compositions of the present invention will be
preferably formulated in a form that can be
easily manipulated, and that allow use
advantageous for practicing the present inventive method.

By way of example, the compositions of this
invention will be used in the form of tablets,
capsule, powder, suspension or dispersion.

It is only necessary that, whatever the form of use chosen, they disinfect and treat
appropriate way the water while remaining stable until
their usage. However, it would be preferable
compositions of the present invention are manufactured
in the form of tablets.

The use of the present invention in the form of tablets is preferable because of its ease of
realization and simplicity of implementation. Indeed,
tablets can be easily prepared and
packaged in the form of a blister, if desired, which would include instructions for carrying out
methods for water treatment following the
present invention. Through the present invention
will favor use in the form of tablets, which implies, for those who practice the known art, the
possible implementation of tablets in the form of
effervescent tablets.

 If tablets are prepared according to the present invention, suitable excipients may be used. Examples of such excipients are fillers, stabilizers, dyes, lubricating agents, dispersing agents and other additives. In any case, regardless of the excipients used in a tablet formulation, a tablet will be obtained which remains stable until use and which produces the desired effects for the treatment of water. All excipients used in a tablet formulation will have to be physiologically acceptable and not affect the taste characteristics for the water that will be treated.

 In describing various inventive compositions herein, the following formulation examples are given as aids to those who practice the prior art and wish to practice the present invention. Each of the following formulations may be used to make tablet compositions according to the present invention; similar formulations may be used, if desired, to form powders or capsules, using well known techniques.

EXAMPLE OF TABLET COMPOSITION
The tablets for water treatment have been formulated to achieve the objects of the present invention, and as such are illustrative of compositions and methods for carrying out and making the present inventive compositions.

COMPRESSOR FORMULATION N0 1
FORMULA BY COMPRESS
A. Chlorinated derivative according to formula I or II 10.00 mg
Magnesium carbonate 50.00 mg
Polyvinylpyrrolidone PVP ................. 10.00 mg
Stearyl alcohol (powder) 10.00 mg
B. Baking soda ....................... 100.00 mg
Glycine 4.00 mg
Monobasic calcium phosphate 3.00 mg
TOTAL WEIGHT FOR A TABLET = 187.00 mg
Mixing instructions for the compounds of A.

1. Gently mix the first two ingredients
and sift with a fine sieve.

Leave on contact with dry air for a
time approx.

2. Add the polyvinylpyrrolidone and mix
slowly.

3. Add 1 stearyl alcohol and incorporate
intimately to the mixture.

 4. Mix thoroughly the resulting mixture.

Mixing instructions for B. compounds

 1. Mix all the ingredients of B.

2. To oven dry at 40 OC for
two or three hours, then let cool
in a dry atmosphere.

 3. Sift the mixture and mix with the mixture A.

The result of the mixture obtained with the compounds A. and
B. is then packaged as a tablet in a dry atmosphere (very low moisture content).

COMPRESSOR FORMULATION N0 2
FORMULA BY COMPRESS
A. Chlorinated derivative according to formula I or II 10.00 mg
Magnesium Carbonate 50.00 mg
Polyvinylpyrrolidone PVP ................... 10.00 mg
Magnesium Stearate ...................... 10.00 mg
Sodium lauryl sulfate .................... 10.00 mg
B. Baking Soda ....................... 100.00 mg
Glycine 4.00 mg
Monobasic Calcium Phosphate 3.00 mg
TOTAL WEIGHT PER COMPRESSED = 197.00 mg
Instructions for mixing compounds A.

1. Gently mix the first two ingredients
and sift them with a fine sieve.

 Leave on contact with dry air for one hour.

2. Add the poyvinylpyrrolidone and mix
slowly.

3. Add Magnesium Stearate and Sulfate
lauryl Sodium and incorporate thoroughly into
mixture.

4. Mix thoroughly all the compounds of the
mixture.

Instructions for mixing compounds B.

 1. Mix all the ingredients of B.

2. Leave in an oven set at 40 ° C for
two or three hours then cool to
contact with dry air.

3. Sift with a fine sieve and mix with the
mixture A
The mixture obtained with the mixture of A and B is packaged in the form of tablets in a dry atmosphere (very low moisture content).

COMPRESSOR FORMULATION N0 3
FORMULA BY COMPRESS
A. Baking Soda ...................... 100.00 mg
Mannitol powder 40.00 mg
Binding solution ........................... 46.00 mg
Polyvinylpyrrolidone PVP .................. 30.00 mg
Magnesium carbonate 30.00 mg
B. Chlorinated derivatives according to Formulas I or II 10.00 mg
Activated carbon impregnated 15.00 mg
Stearic acid 10.00 mg
Magnesium Stearate 10.00 mg
Sodium lauryl sulfate 7.00 mg
Glycine 7.00 mg
TOTAL WEIGHT PER COMPRESSED = 305.00 mg
Mixing instructions for component A.

1. Mix the ingredients of component A.
manufacturer a wet aggregate using the
binding solution.

 2. Dry in the oven at 50 ° C. for two hours.

 3. Finely sieve the dry granulate.

(Carry out a finer sieving again if
necessary).

Mixing instructions for component B.

1. Mix stearic acid, Stearate with
Magnesium, lauryl Sulfate Soda and the
glycine.

2. Add to this mixture the active charcoal
impregnated and mix well.

3. Add the chlorinated derivative according to formula I or II
to this mixture and mix properly.

4. Add the mixture B. to the mixture A. and mix
to obtain a new mixture.

Make the tablets using this mixture obtained ie A + B; make the tablets in an atmosphere with very low moisture content. Store in hermetic container.

FORMULATION FOR THE BINDER SOLUTION AS AN ADDITIVE
TWO FORMULATIONS OF PREVIOUS TABLETS
Intake per tablet
Acacia powder, USP ...................... 12,000 mg
Gelatin .................................... 34,000 mg
Distilled water ............................... 0.157mL
CONTRIBUTION BY WEIGHT PER COMPRESS = 46.0 mg
The compounds according to Formulas I and II described herein have been tested for their disinfectant property and can be prepared as will be described in the following paragraphs.

Disinfecting properties of the compounds described according to
Formula I.

The chlorinated derivatives of allantoin described by
Formula I have a high instantaneous power of disinfection by oxidation and act as a bactericide and a virocide.

The bactericidal effect of the chlorinated derivatives of allantoin was determined by inhibition method on agar gels. By way of example, the tests of 1,3-dichloroallantoin compared to the standard "LRA" which is a complex of sodium chlorite with citric acid (solution of chlorite acidified with citric acid at the time of the test) is described. right here.

TEST I - Effectiveness against Staphylococci
type aureus.

TEST II - Efficacy against Escherichia coli.

TEST III - Effect of remanence.

TEST IV - Stability in solution.

TEST V - Effectiveness in a non-aqueous medium.

TEST I
A 6 mm diameter filter paper disc is
applied on a tray of agar that is inoculated with a
Aureus Staphylococci culture and 20 UL solution
test are pipetted on the tray at a concentration of
1 mg and 0.5 mg (contained in the 20 μL). The size of the
inhibited area is determined after a day
incubation at 37 C.

concentration size of the
in mg / plateau inhibited area
expressed in
mm d @ Arb
1,3-allantoin-dichloro 1.0 28 11
0.5 26 10
LRA 1.0 36 15
0.5 26 10
Streptomycin 0.01 16 5
dd = diameter of the inhibited zone.

ar = radius of the inhibited zone - radius of the disk
filter (three millimeters)
TEST It
A 6 mm diameter filter paper disc was
applied on a tray of agar inoculated with a culture
of E. coli and 20 ML of test solution are pipetted onto the
plateau at different concentrations. The size of the areas
inhibited is determined after one day of incubation at
37 C.

concentration size of the
in mg / plateau inhibited area
expressed in
mm
da dichoro-1,3-allantoin 500 25.0 9.5
250 26.0 10.5
100 21.0 7.5
50 16.0 5.0
5 7.0 0.5
LRA 500 30.0 12.0
250 20.0 7.0
100 24.5 9.3
50 11.0 2.5 ad = diameter of the zone- inhibited.

b Ar = radius of the inhibited zone
disc radius filter paper (three milllimeters)
TEST III
A filter paper disk saturated with 10 L of the standard solution of the substance (25 mg / ml) is applied to an agar plate inoculated with an E. coli culture and is repeatedly transferred at regular intervals to a new one. agar tray.

time diameter of the area
inhibited (in cm) dichloro - 1, # - allantoin 0 4.6 +/- 0.11
2 0.8 +/- 0.0
OO
LRA O 2.8 +/- 0.05
2 0
4 0
TEST IV
10 RL of the standard solution containing the substance
(25 mg / ml) are applied to a filter paper disc
and tested at regular intervals.

The results indicate the stability of the test solution
which was stored in a sealed tube at a temperature of
laboratory for two hundred hours.

time diameter of the area
inhibited (in cm)
1,3-dichloro-allantoin 0 4.6 +/- 0.11
2 3.6 +/- 0.51
4 4.0 +/- 0.05 - 20 2.5 +/- 0.20
2.8 +/- 0.21
44 2.2 +/- 0.05
192 1.9 +/- 0.12
TEST V
100 mg of anhydrous paste (PEG, Polyethylene Glycol, alcohol
cetyl) containing 1% of the test substance are
applied to a 6 mm plastic disk and the
side that has been covered itself applied on a tray
of agar inoculated with 107 E. coli. Incubated at 37 C, the
size of the inhibited zone is determined after eighteen
incubation hours the next day.

Dichloro-1,3-allantoin - size of the area 5.5 and 6 cm
(duplicate determination)

100 mg of anhydrous paste has also been incorporated into a
sample of 1 x 1 cm2 of a porous film applied to a
agar plate inoculated with E. coli and incubated at 37 C.

After eighteen hours of incubation, the
Dichloro-1,3-allantoin inhibits the growth of E. coli
over the entire surface of the tray on a diameter of 7 cm.

Based on the tests that were conducted here, the inventor
determined from the allantoin derivatives, according to
Formula I, the best results are obtained with
1,3-dichloro-allantoin for which it has been
demonstrated that
(a) the optimal bactericidal activity is obtained with a
supply of 200 g / 6 mm disc
(b) in contact with an agar gel all the active chlorine has
been released within two hours
(c) the effectiveness is demonstrated in the form of a
ointment at a concentration of 1% (anhydrous base
polyethylene glycol molecular weight 4000,
47.5% polyethylene glycol molecular weight 400,
47.5%, cetyl alcohol 5%)
(d) the activity is even more effective when
incorporates it into a film with a lower porosity
to a micron.

Preparation of compounds according to Formula I
The preparation of various derivatives of allantoin according to
Formula I is described below.

dans laquelle R1 et R2 sont identiques ou différents et peuvent être un atome d'hydrogène, un groupe alkyl possédant de un à cinq carbones ou un groupe phényl et ou en fin de compte l'un des substituants R1 et R2 est un atome d'hydrogène ; et R3, R#, F6, Rs sont identiques ou différents et ou chacun peut être un atome d'hydrogène un groupe alkyl possédant de un a cinq atomes de carbone ou un groupe phényl.Ces composés selon la Formule IA sont réactifs dans un solvant approprié, avec le chlore en étant refroidi dans un bain à glace avec la présence éventuelle l'hydrogéno-carbonate de sodium et ou le produit de réaction est obtenu par filtration sous trompe à vide, lavage à l'eau glacée ou séchage ou par obtention du sel organique par un procédé de filtration, d'évaporation du solvant et séchage. En variant les conditions ou les matériaux de départ de façon appropriée
on obtiendra les différents composés chlorés de
l'allantoïne selon la Formule I, tels que décrits dans
les exemples ci-dessous.Generally chlorinated derivatives of allantoin according to the
Formula I in which the groups of R1 to Rs have the
designations, below, may be prepared by
additions of allantoin derivatives according to the formula
General IA:

wherein R 1 and R 2 are the same or different and may be a hydrogen atom, an alkyl group having one to five carbons or a phenyl group and, finally, one of the substituents R 1 and R 2 is an atom of hydrogen; and R3, R #, F6, Rs are the same or different and each may be a hydrogen atom an alkyl group having one to five carbon atoms or a phenyl group.These compounds according to Formula IA are reactive in a solvent with the chlorine being cooled in an ice bath with the possible presence of sodium hydrogen carbonate and or the reaction product is obtained by suction filtration, washing with ice water or drying or by obtaining organic salt by a method of filtration, evaporation of the solvent and drying. By varying the conditions or starting materials appropriately
we will obtain the different chlorinated compounds of
allantoin according to Formula I, as described in
the examples below.

Example i
Preparation of 1,3-dichloro-allantoin
(R1 = R2 = Cl, Ras Ro F6, Rs = H).

1.4 g of allantoin are mixed with 50 ml of dichloromethane with 3 g of sodium hydrogencarbonate,
the whole being cooled in an ice bath; 4 g of chlorine gas are introduced for thirty minutes.

After adding the chlorine, the reaction mixture is mixed for three hours, the product is taken out and
washed under ice-cold water to remove all traces of
chlorine. The product is dried with a water pump at 45 C.

The yield of the reaction is 70-75% relative to
theoretical yield. The product obtained contains 31.5% of chlorine, (theoretically, 31.23% is obtained). Point of
melting is at 119-120 C.

- -3352, 1750, 1691, 1329, 1235, 1177, 1100,
500 cm'f
Example 2
Preparation of chloro-3-allantoin
(R2 = Cl, R1, R3, R4, R5, R6 = H)
1.4 g of allantoin are mixed with 25 ml of water,
the whole being cooled in an ice bath, 2 g of chlorine gas are added for thirty minutes,
after adding the chlorine, the reaction mixture is mixed again for one hour, the product is
removed and washed with ice water, then dried
vacuum pump at 45 C. The yield is 55%. The
obtained product contains 18.3% of chlorine (theoretically
18.41%). The melting point is 155-157 C.

- 3440, 3340, 3320, 3244, 3067, 1790, 1739, 1655,
1538, 1328, 1275, 1187, 1103, 590, 520 cm -1.

Example 3
Preparation of chloro-1-methyl-3-allantoin
(R1 = Cl, R2 = CH3, R3, R #, R1, R3 = H)
1.5 g of methyl-3-allantoin are mixed with 50 ml of
dichloromethane with 1.5 g of hydrogen carbonate of soda, the whole being cooled by an ice bath. 2 g of chlorine gas are introduced for thirty minutes and the mixture is mixed again for three
hours, the product is removed, washed under ice water and dried at a temperature of 45 ° C in the vacuum pump. The
yield is 67%, the product contains 17.7% chlorine (theoretically 17.16%). The melting point is
located at 170-172 degrees C.

- -3308, 3232, 1716, 1544, 1473, 1305, 1094,
556 cm-1.

Example 4
Preparation of chloro-1,3-methyl-5-allantoin
(R 1 = R 2 = Cl, R 3 = CH 3, R 3, R *, F 6 = H) 0.5 g of methyl-5-allantoin are mixed with 15 ml of dichloromethane with 1 g of sodium hydrogencarbonate,
the whole being cooled with an ice bath. 2 g of
chlorine gas are added for thirty minutes and
the reaction mixture is further mixed for two and a half hours. The product is filtered, the dichloromethane is evaporated with a rotary evaporator,
the residue is dried at 45 C, by a water pump. The yield is 71%, the product contains 30.11% of
chlorine (theoretically 29.41%) The melting point is 89-91 ° C.

IRKBr -3386, 1758, 1727, 1687, 1616, 1337, 1280, 1206,
1132 cm-1.

Bactericidal properties of the compounds according to Formula II
Dichloroglycoluril was supplied by JP BRON, it is in the form of a fine white powder forming a few globules.

 A solution containing 50 mg of dichloroglycoluril per ml of water was prepared. At this concentration, a bad dissolution of the substance is observed.

The addition of ethanol (about 15%) does not affect the size of the solubility. However, the solution was pipetted, as described below, into one liter of distilled water contaminated with a known E. coli culture.

The following dilutions of dichloroglycoluril were tested 1. 50 ppm 3. 12.5 ppm 2. 25 ppm 4. 6.25 ppm
The original suspension of dichloroglycoluril, as soon as it was transferred to a liter of contaminated water, was observed forming a clear solution within one to two minutes.

100 μl samples were collected after incubation times of zero, five, ten, and fifteen minutes, placed in a sterile petri dish with an agar gel. The solution was disseminated over the entire surface of the agar. Samples were incubated for 14 hours at 37 ° C, increasing number of colonies were counted.

The results are detailed in the table below
Samples ppm CFU time
of sampling / 100> 1
(in minutes)
1 50 0 2000
5 0
10 0
15 0
2 25 0 2000
5 7
10 10
15 0
3 12.5 0 2000
5 0
10 3
1.5 0
4 6.5 0 2000
5 0
10 25
15 0
Conclusion
At 6.25 ppm final concentration of dichloroglycoluril, there is 100% mortality in five minutes.

 The substance is very effective as a bactericidal agent and does not require an activator. It is an easy to use substance. The sporadic development of E. coli after 10 minutes, with 12.5 or 6.25 ppm, of dichloroglycoluril concentration shows an external contamination of the plate by dissemination of the 100 #L beyond the agar plate.

Preparation of the compounds according to Formula II
The glycoluril derivatives according to Formula II can be prepared according to conventional methods, well known in the art, as described by US Patent Nos. 3,019,160 and 3 Olg 075, all of which are mentioned herein as as references.

 While the tablets and other compositions provided herein remain stable until introduced into an aqueous medium, it is preferred that the formulations used to prepare such compositions and more so the compositions themselves be maintained and stored under very low humidity. In the case of tablet compositions, it is preferred that the tablets are provided in a container which can maintain the composition at a very low moisture content. For example, the tablets may be provided in a sealed container or a blister pack or possibly a vial in combination with a desiccant bag, etc. The ability to produce and store tablets and similar compositions under conditions of very low humidity is well understood by those who practice the known art; also such considerations do not limit the present discovery.

Eneemb.l # -e # for water treatment
Another possibility for the present invention is that of providing a water treatment package which generally includes a water treatment composition containing less than 2 or 3% by weight of residual moisture which is a means for treating and disinfecting water according to the compounds of Formulas I or
It as described above and a container for storing the compositions for the treatment of water in a very low humidity environment. The set for the treatment of water may optionally contain an activated carbon or an active carbon impregnated with an ion.

 These elements can be physically separated from the water treatment compositions. for the purpose of combining them at a fixed time. The assembly may optionally contain instructions for producing potable water by using the compositions for water treatment.

 The invention being thus described, it is clear that it can vary in different ways. Such variations will not be considered as a drift of the spirit and scope of the invention and all modifications will occur to those who practice the art known to be within the scope of the following claims. Each publication and patent that relate to what has been described above is expressly cited in full reference.

Claims (15)

claims 1. A composition for the treatment of water containing less than 2 to 3% residual moisture and which comprises an effective content of disinfecting agent according to the compound of Formula I

 or, R1 and Ra are selected from the group consisting of a hydrogen atom, a chlorine atom, an alkyl or phenyl group having from one to five carbons and, finally, one of R1 and R2 is a chlorine atom. . Rs is selected from the group consisting of a hydrogen atom, an alkyl or phenyl group having from one to five carbons.  R>, R #, and Rs are selected from the group consisting of a hydrogen atom, a chlorine atom, an alkyl or phenyl group having one to five carbons; and 2. A water treatment composition which contains less than 2 to 3% w / w of residual moisture which comprises an effective content of disinfecting agent according to the compound of Formula II:

  or, R1, R2, R3 and Ro are selected from the group having a hydrogen or chlorine atom and, finally, one of R1, R2, RS or R4 is a chlorine atom. 3. The composition of claim 1 which comprises an activated carbon. 4. The composition of claim 2 which comprises an activated carbon. The composition of claim 1 which comprises an active carbon impregnated with an ion. The composition of claim 2 which comprises an active carbon impregnated with an ion. The composition of claim 1 in the form of a tablet. The composition of claim 2 in the form of a tablet. 9. The composition of claim 3 in the form of a tablet. The composition of claim 4 in the form of a tablet. 11. The composition of claim 5 in the form of a tablet. The composition of claim 6 in the form of a tablet. 13. A method for producing drinking water, which comprises a composition for treating water to be added to a certain amount of untreated water. R 1 and R 2 are selected from the group consisting of a hydrogen atom, a chlorine atom, an alkyl or phenyl group having from one to five carbons and, finally, one of the groups R 1 and R 2 is an atom of chlorine R #, R #, and Rs are selected from the group consisting of a hydrogen atom, a chlorine atom, an alkyl or phenyl group having from one to five carbon atoms and or Rs is selected from the group consisting of an atom hydrogen, an alkyl or phenyl group having from one to five carbon atoms.  or,

This composition comprises less than 2 to 3% w / w of residual moisture and comprises an effective content of disinfecting agent according to the compound of formula I 14. A method for producing drinking water that includes a composition for treating water to be added to a certain amount of untreated water. This composition comprises less than 2 to 3% w / w of residual moisture and comprises an effective disinfectant content of a compound of Formula II:

 or, R 1, R a, R 3 and R 4 are selected from the group having a hydrogen atom, a chlorine atom and, finally, one of the groups R 1, R 2, R 3 or Ro is a chlorine atom. 15. The method of claim 13 or the composition for treating water further comprises an activated carbon.