IL44561A - Salts of 2,6-dioxocyclohexane thiocarboxylic acid 4'-halo-anilides and pharmaceutical compositions thereof - Google Patents

Salts of 2,6-dioxocyclohexane thiocarboxylic acid 4'-halo-anilides and pharmaceutical compositions thereof

Info

Publication number
IL44561A
IL44561A IL44561A IL4456174A IL44561A IL 44561 A IL44561 A IL 44561A IL 44561 A IL44561 A IL 44561A IL 4456174 A IL4456174 A IL 4456174A IL 44561 A IL44561 A IL 44561A
Authority
IL
Israel
Prior art keywords
dioxocyclohexane
compound
thiocarboxylic acid
chloroanilide
salt
Prior art date
Application number
IL44561A
Other versions
IL44561A0 (en
Original Assignee
Hoechst Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hoechst Ag filed Critical Hoechst Ag
Publication of IL44561A0 publication Critical patent/IL44561A0/en
Publication of IL44561A publication Critical patent/IL44561A/en

Links

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Description

π^κ *m nvnsnn imnyni SALTS OF 2,6-DIOXOCYCLOHEXANE THIOCARBOXYLIC ACID »-HALO-ANILIDES AND PHARMACEUTICAL COMPOSITIONS THEREOF (HOE 73/F 097) The present invention relates to salts of 2,6-dioxocyclo-hexane thiocarboxylic acid ' -halo-anilides and to pharmaceutical compositions thereof.
Over the recent 10 to 15 years, diseases caused by cutaneous fungi in domestic and commercially reared animals have been gaining significance in the economic field. Infested animals are a source of infection not only for other animals but - since man and animal are living closely together nowadays - also, to a considerable extent, for human beings.
This risk of infection is generally even increased by the fact that large numbers of animals are kept on a narrow space which intensifies the contacts between the animals.
Moreover, even in non-agricultural households, the keeping of dogs, cats or other pet animals has had a considerable boom. Just these animals, however, are frequently infested by cutaneous fungi, and demand for adequate compositions for the treatment of small animals has become urgent in veterinary medicine. Whereas commercially reared animals are mainly infested by trichophyton species, the cutaneous fungi infesting small domestic animals are, above all, microsporum species, in addition to the trichophytons.
In recent years, attempts have therefore been made to develop a composition against cutaneous fungi, which can be domesti cally used for all dome-stitr and commercially reared animals and which, in its activity spectrum, comprises the most important cutaneous fungi occurring in the veterinary medicine.
For application purposes, those compositions are especially useful which can be sprayed locally. In addition to a good compatibility with the skin and a good adhesive power, these compositions must be able to penetrate the keratin of the skin and hair in order to reach the seat of the infectants. In spite of the good antimycotic effect evidenced in vitro, many of the medicaments do therefore not assure a satisfactory cure.
The sparingly water-soluble dioxocyclohexane carboxylic acid anilides disclosed in German Offenlegungsschrift No. 2 039 466 have excellent antimycotic properties. For example, 2,6-dioxo-cyclohexane carboxylic acid '-bromoanilide was used as a 1 % solution in diethyl arbonate to treat six fattened bulls infested by a medium strong to heavy trichophytosis. The animals were treated by applying the solution of the composition to the infected sections of the skin by means of a cotton swab twice at a time interval of 3 days.
It appeared that the trichophytosis infestation in all six treated bulls was completely cured within 20 to 25 days after beginning of the treatment. In a following observation period of more than 6 weeks, there was no relapse. The infestation with the cutaneous fungi in an animal, which had been treated with diethyl carbonate only, as well as in the four untreated control animals did not show any clinical change during this time.
In spite of their good activity, these compounds are not very l ee suitable for an application in the veterinary medicine, for they have a solubility which is sufficient for therapeutical purposes only in organic solvents and the handling of those solutions usually involves a certain risk (explosion and fire) .
Drugs used in the veterinary medicine, especially if they are not administered by a veterinarian, require a simple mode of administration. As a composition form for a veterinary composition against cutaneous fungi, there is especially suitable a dry composition which is readily soluble in tap water.
The solubility in water of the alkali metal and alkaline earth metal salts of 2 , 6-dioxocyclohexane carboxylic acid 4'-halo-anilide is, however, not sufficient for therapeutical purposes and, moreover, aqueous solutions of these salts are stable only at a pH-value of more than 12.
It has now been found that odorless solutions which are stable in water can be obtained by dissolving an alkali metal or alkaline earth metal salt of a 2,6-dioxocyclohexane thio- carboxylic acid 4'-halo-anilide of the general formula I in which X stands for a halogen atom and Me for an alkali metal or alkaline earth metal.
The present invention therefore provides physiologically acceptable alkali metal and alkaline earth metal salts of a 2,6-dioxocyclohexane thiocarboxylic acid 4'-halo-anilide of the formula I, a process for the manufacture thereof as well as compositions containing them as active ingredients.
Compounds in which X stands for a chlorine atom are especially preferred.
The above salts are prepared by reacting a 2, 6-dioxocyclohexane thiocarboxylic acid 4'-halo-anilide with an alkali metal or alkaline earth metal hydroxide or a water-soluble carbonate or alcoholate thereof.
The reaction is preferably carried out using equivalent amounts of the two starting compounds. An excess amount of an acid results in an impure product, since the unreacted acid precipitates with the salt. An excess amount of a base, however, has no adverse effect since it remains in solution in the mother liquor after separation of the salt.
When alkali metal and alkaline earth metal hydroxides or carbonates are used, the solvents chosen may be water, lower alcohols (of 1 to 6 carbon atoms), aqueous lower alcohols (of 1 to 6 carbon atoms), aqueous tetrahydrofuran, aqueous dioxan, or aqueous acetone. When alkali metal or alkaline earth metal alcoholates are chosen, anhydrous lower alcohols (of 1 to 6 carbon atoms) or anhydrous inert solvents are used. A solution of an alkali metal or alkaline earth metal hydroxide or a solution or suspension of an alkali metal or alkaline earth metal alcoholate is prepared and reacted with a 2,6-dioxo-cyclohexane thio-carboxylic acid -'-halo-anilide. The salts of the 2 , 6-dioxo-cyclohexane thiocarboxylic acid A-'-halo-anilide have been obtained from their solutions by crystallization, concentration until crystallization or precipitation by addition of suitable solvents, for example acetone.
The acids mentioned as starting compounds are obtained, for example according to German Offenlegungsschrift No. 2,039,466.
The compositions of the invention are preferably dry compositions which are dissolved in tap water to yield a solution suitable for therapeutical application. The active ingredient content of these solutions is preferably about 1 %.
Since the alkaline earth metal salts of a 2,6-dioxocyclo-hexane thiocarboxylic acid 4'-halo-anilide are not so readily soluble in water, it is convenient to add a complexing agent to this dry composition in order to assure a therapeutically effective concentration of the active ingredient in the aqueous solution. The addition of a complexing agent is also required for a dry composition which contains an alkali metal salt, since alkaline earth metal ions which may be present in tap water produce sparingly water-soluble alkaline earth metal salts during the preparation of the aqueous solution, and these salts would then precipitate.
Owing to the poor rheological properties of the salts, the dry compositions contain water-soluble excipients, for example polyglycols, in addition to the active ingredient and the complexing agent.
Subjected to in-vitro tests the compounds of the invention show a very good inhibiting effect on Trichophyton and Micro-sporon species.
This result was also confirmed in the veterinary practice.
The therapeutic tests were performed using the alkali metal and alkaline earth metal salts of 2,6-dioxocyclohexane thio-carboxylic acid 4'-chloroanilide in the form of a dry composition soluble in tap water, to which potassium carbonate, polyglycol 4000 and tetrasodium salt of acetic acid as excipients had been added. The composition was used in a 1 % solution, calculated on active ingredient.
The treatment of a total number of 187 cattle naturally infested by trichophytosis showed the following result: Total of cured upon ... slightly not cattle treatments improved improved cured treated 1Qy 1x 2x 3x 4x 6x ^ 2^ ^ 1^ 84 39 12 5 *) 21 cattle were observed for only 17 days upon the second treatment Successful treatment of dogs and cats demonstrated that the salts of the invention can also be used for the treatment of Microsporon canis as well as trichophytosis diseases in these kinds of animals.
The following Examples serve to illustrate the invention.
E X A M P L E 1; Sodium salt of 2,6-dioxocyclohexane thiocarboxylic acid 4'-chloro-anilide 60 Grams of 2,6-dioxocyclohexane thiocarboxylic acid 4'-chloroanilide were introduced while stirring into a solution of 9.0 g of pure sodium hydroxide in 680 ml of water. Stirring was continued for 15 minutes, the solution was filtered and evaporated at 50°C in vacuo to a small volume. After cooling, off the separated crystals were suction-filtered,/ washed with 35 ml of acetone and dried at 60°C until their weight remained constant. 49.5 Grams of sodium salt of 2,6-dioxocyclohexane thiocarboxylic acid 4'-chloroanilide of the composition C^^H^-Cl aO S were obtained.
E X A M P L E 2; Potassium salt of 2,6-dioxocyclohexane thiocarboxylic acid '-chloroanilide 6.6 g of potassium hydroxide (85 9 were dissolved in 200 ml of water and 28 g of 2,6-dioxocyclohexane thiocarboxylic acid 4'-chloranilide were introduced while stirring into this solution. Stirring was continued for minutes, the solution was filtered and evaporated at 50°C in vacuo to a small volume After cooling, the separated crystals were suction-filtered, off washed with 30 ml of acetone and dried at room temperature. 25 g of potassium salt of 2,6-dioxocyclohexane thiocarboxylic acid 4'-chloroanilide of the composition C^^H^ ^CIKM^S · 1^0 were obtained.
E X A M P L E 3: Calcium salt of 2,6-dioxocyclohexane thiocarboxylic acid 41-chloroanilide 2.8 g of pure calcium oxide were stirred for 1 hour in 200 ml of water, 28 g of 2,6-dioxocyclohexane thiocarboxylic acid 4'-chloroanilide were added and stirring was continued for 1 hour. The solution was filtered and evaporated at 50°C in vacuo to a small volume. After cooling, the separated off crystals were suction-filtered,/ washed with 40 ml of acetone and dried over P2°5 * 15 g of calcium salt of 2,6-dioxocyclohexane thiocarboxylic acid 4'-chloroanilide of the composition (C^H-] ^Cl ^S^Ca were obtained.
E X A M P L E 4; Lithium salt of 2,6-dioxocyclohexane thiocarboxylic acid 4' -chloroanilide 28 Grams of 2,6-dioxocyclohexane thiocarboxylic acid 4'-chloroanilide were introduced while stirring into a solution of 2#4 g of pure lithium hydroxide in 400 ml of water. The solution was then treated further as disclosed in Example 1. 15.8 g of lithium salt of 2,6-dioxocyclohexane thiocarboxylic acid 4,-chloro-anilide of the composition ClLil^^S were obtained.
E X A M P L E 5: Sodium salt of 2,6-dioxocyclohexane thiocarboxylic acid 4' -chloroanilide 2.3 Grams of sodium were reacted in 80 ml of anhydrous ethanol. To the sodium ethylate solution, 28 g of 2,6-dioxocyclohexane thiocarboxylic acid '-chloroanilide were added and the mixture was refluxed for 5 minutes. The hot solution was filtered, cooled, the crystals were suction-filtered^ off washed with 10 ml of ethanol and dried until their weight remained constant. 22 Grams of sodium salt of 2,6-dioxocyclohexane thiocarboxylic acid 4'-chloroanilide of the composition C, ^H-j ClNNa02S were obtained.
E X A M P L E 6: Sodium salt of 2,6-dioxocyclohexane thiocarboxylic acid 41-bromoanilide 33 Grams of 2,6-dioxocyclohexane thiocarboxylic acid 4'-bromoanilide were introduced while stirring into a solution of 4.1 g of sodium hydroxide (98 %) in 300 ml of water. Stirring was continued for 30 minutes, the solution was filtered and evaporated at 50°C in vacuo until the crystals began to separate. After addition of 60 ml of acetone, the solution was cooled, the separated crystals were suction-filtered^off washed with 30 ml of acetone and dried at 70°C until their weight remained constant. 23 Grams of sodium salt of 2,6-di cyclohexane thiocarboxylic acid ' -bromoanilide of the composition C1 -^H11Br Na02S were obtained.
E X A M P L E 7; Preparation of a dry composition soluble in tap water The following substances were mixed with each other: potassium salt of 2,6-dioxocyclohexane thiocarboxylic acid 4'-chloroanilide 10.000 g polyglycol 4000 0.500 g potassium carbonate 0.515 g tetrasodium salt of ethylene-diamine- 1.485 g tetraacetic acid 12.500 g In order to improve the rheological properties, the compacted mixture was -ma e--e-empe-et. on a mill and then passed through a granulating device having a mesh width of 1.5 mm.
The granules obtained could be dissolved in tap water within 2 minutes to give a 2 % solution. !

Claims (6)

♦ HOE 75/F 097 We claim:
1. . An alkali metal and alkaline earth metal salt of a compound of the formula in which X stands for a halogen atom.
2. A compound of claim 1 which is the lithium salt of 2,6-dioxocyclohexane thiocarboxylic acid 4'-chloroanilide.
3. A compound of claim 1 which is the sodium salt of 2,6-dioxocyclohexane thiocarboxylic acid 4f-chloroanilide
4. A compound of claim 1 which is the potassium salt of 2,6-dioxocyclohexane thiocarboxyl acid 4'-chloroanilide.
5. A compound of claim 1 which is the calcium salt of 2,6-dioxocyclohexane thiocarboxylic acid 4'-chloroanilide.
6. A compound of claim 1 which is the sodium salt of 2,6-dioxocyclohexane thiocarboxylic acid 4'-bromoanilide. HOE 73/F 097 » A composition which is active against cutaneous fungi and which contains at least one compound as claimed in claim 1 and, where required a complexing agent and/or further excipients. A composition which is active against cutaneous fungi and which contains at least one compound as claimed in claims 2 to 6 and, where required a complexing agent and/or further excipients. A process for the manufacture of a compound as claimed in claim 1, which comprises reacting a 2 , 6-dioxocyclohexane thiocarboxylic acid 4'-halo-anilide with an alkali metal or alkaline earth metal hydroxide or a water-soluble carbonate or alcoholate thereof. An - -e f---fch e--com owi d--a-s--ciainred-irr-cla±m s--an antimycotic ^ge&t, composition of matter containing as active ingredient a compound P. O. Box 33116 Tel-Aviv Attorneys for Applicant - 41, -
IL44561A 1973-04-07 1974-04-03 Salts of 2,6-dioxocyclohexane thiocarboxylic acid 4'-halo-anilides and pharmaceutical compositions thereof IL44561A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19732317579 DE2317579A1 (en) 1973-04-07 1973-04-07 SALTS OF 2,6-DIOXOCYCLOHEXANTHIOCARBONIC ACID 4'-HALOGENANILIDES AND THEIR PHARMACEUTICAL PREPARATIONS

Publications (2)

Publication Number Publication Date
IL44561A0 IL44561A0 (en) 1974-06-30
IL44561A true IL44561A (en) 1977-01-31

Family

ID=5877353

Family Applications (1)

Application Number Title Priority Date Filing Date
IL44561A IL44561A (en) 1973-04-07 1974-04-03 Salts of 2,6-dioxocyclohexane thiocarboxylic acid 4'-halo-anilides and pharmaceutical compositions thereof

Country Status (20)

Country Link
JP (1) JPS49126810A (en)
AT (1) AT338231B (en)
BE (1) BE813430A (en)
CA (1) CA1019765A (en)
CH (1) CH599146A5 (en)
CS (1) CS191911B2 (en)
DD (1) DD112994A5 (en)
DE (1) DE2317579A1 (en)
DK (1) DK136154C (en)
ES (1) ES424848A1 (en)
FR (1) FR2224161B1 (en)
GB (1) GB1464878A (en)
HU (1) HU168937B (en)
IE (1) IE39358B1 (en)
IL (1) IL44561A (en)
IT (1) IT1043914B (en)
KE (1) KE2802A (en)
NL (1) NL7404495A (en)
ZA (1) ZA742190B (en)
ZM (1) ZM6274A1 (en)

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS551724B2 (en) * 1974-03-16 1980-01-16

Also Published As

Publication number Publication date
DK136154B (en) 1977-08-22
ATA287774A (en) 1976-12-15
BE813430A (en) 1974-10-08
ZM6274A1 (en) 1975-01-21
HU168937B (en) 1976-08-28
GB1464878A (en) 1977-02-16
IT1043914B (en) 1980-02-29
DK136154C (en) 1978-01-23
IL44561A0 (en) 1974-06-30
FR2224161B1 (en) 1977-11-04
IE39358L (en) 1974-10-07
ZA742190B (en) 1975-04-30
IE39358B1 (en) 1978-09-27
NL7404495A (en) 1974-10-09
DD112994A5 (en) 1975-05-12
JPS49126810A (en) 1974-12-04
CA1019765A (en) 1977-10-25
CS191911B2 (en) 1979-07-31
ES424848A1 (en) 1976-11-16
FR2224161A1 (en) 1974-10-31
AT338231B (en) 1977-08-10
AU6756774A (en) 1975-10-09
DE2317579A1 (en) 1974-10-24
CH599146A5 (en) 1978-05-12
KE2802A (en) 1978-01-06

Similar Documents

Publication Publication Date Title
JPS62161728A (en) Antibacterial
DE1815452A1 (en) Aryl and heteroaryl methylthiopropionic acids and processes for their preparation
US3830824A (en) Physiological organic acid silver allantoinates
CH650504A5 (en) PIPERAZINE DERIVATIVES, METHOD FOR THEIR PRODUCTION AND MEDICINAL PRODUCTS CONTAINING THE SAME.
US4151188A (en) Arsenamide compound
FR2476071A1 (en) NOVEL 2-AMINO-3- (A-HYDROXYBENZYL) -PHENYLACETIC ACIDS AND THEIR ESTERS AND AMIDES, PARTICULARLY USEFUL AS ANTI-INFLAMMATORY AGENTS, AND PHARMACEUTICAL COMPOSITIONS CONTAINING SAME
RU2439063C1 (en) Method of obtaining medication
JPS6119620B2 (en)
DE2920861A1 (en) PHENYLAMINOTHIOPHENIC ACIDS, THE METHOD OF MANUFACTURING AND MEDICINAL PRODUCTS CONTAINING THEM
JPS60166645A (en) Benzoic acid derivative, manufacture and use drug, fungicideor antiseptic
NL8200607A (en) 2-AMINO-3 (HALOGENBENZOYL) METHYLPHENYL ACETIC ACIDS, AND THEIR SALTS.
DE3219605A1 (en) SOLUBLE CONNECTION WITH ANALGETIC EFFECT
CS210659B2 (en) Method of preparation of amidobenzoic acid derivatives
DE2706841C2 (en)
DE69519581T2 (en) GUANIDYLMETHYL CYCLOHEXANCARBONIC ACID ESTER DERIVATIVES
US2891943A (en) Novel antibiotically active products
JPS62294616A (en) Fungicidal drug, manufacture and therapy
US4364928A (en) Novel salts of ion exchange resins of the acid type
JPS597151A (en) Amidine derivative, manufacture and pharmaceutic composition
DE1931466C3 (en) Copper (II) complexes of 6-lower alkoxy-1-phenazinol-5,10-dioxides
DE2412388A1 (en) DIBENZOTHIOPHEN DERIVATIVES, PROCESS FOR THEIR PRODUCTION AND MEDICINAL PRODUCTS CONTAINING THEM
US2608506A (en) Arylsulfamyl benzoic acids
RU2818489C1 (en) Complex compound of 5-aminosalicylic acid with oxidised pectin, exhibiting antiulcer activity, and method for production thereof
US4016272A (en) Anthelmintic thiodiphenylamine cupric chloride complex salt
US4510147A (en) Compositions for and medical use of water-soluble derivatives of 6,6-methylene-bis-(2,2,4-trimethyl-1,2-dihydroquinoline)