Zinc and aliphatic halogen-carboxylic acid salts for treatment of skin neoplasm and visible mucosa tissues

FIELD: organic chemistry, medicine, dermatology.

SUBSTANCE: invention relates to zinc and aliphatic halogen-carboxylic acid salts that can be used in treatment of benign neoplasms of skin and visible mucosa tissues. Invention proposes the following formula of zinc and aliphatic halogen-carboxylic acid salts: (1): wherein R means -CHal3, -CHHal2, -CH2Hal and (2): wherein R' means Alk, hydrogen atom (H); R'' means Hal; R' means Alk; R'' means H, Alk wherein in these formulae halogen atom can be represented by fluorine atom (F), chlorine atom (Cl), bromine atom (Br) or iodine atom (J). Invention provides the development of original preparation used in treatment of benign neoplasms of skin and visible mucosa tissues with low toxicity, rapid effect, expressed therapeutic effect and eliciting good tolerance, absence of complications in treatment, healing without formation of scar tissue. The development of the preparation provides expanding assortment of agents used in treatment of such diseases.

EFFECT: enhanced and valuable properties of agents.

13 ex

 

The invention relates to medicine, namely to dermatology, namely to new salts of zinc and haloalkaliphilic acids of the aliphatic series, which can be used for the treatment of benign lesions of skin and visible mucous membranes of the skin.

Known selenium compound with kaloxylos acid or its anhydride (EP 1293498, 30.08.2001). The connection is used for the treatment of benign skin tumors of different nature, including the mucous membranes of the skin.

Known also use for the treatment of papillomatosis mucous membranes and upper respiratory tract propionovoi ointment with low toxicity (″Properidine antitumor agent″ VNIIOFI, issue 3, M, 1973, s-138). The percentage of effectiveness of treatment in this case is equal to 70-75%. Prospidin most effective in the treatment of precancerous diseases.

Given the pronounced deep tissue damage, prospidin impractical to use for the treatment of benign lesions of skin and mucous coats.

The closest technical solution to the claimed nature and the achieved effect is the product for local treatment of superficial lesions of the skin and mucous membranes on the basis of the reaction of interaction between the solution of 1-5,5 M nitric acid with 45-170 the primary mmol C1-C5-alkanol on 1 l of nitric acid(RU 2118160, 23.06.1993). The drug, in particular, is indicated for the local treatment of superficial benign skin changes, such as Verrucae (for example, Verrucae vutgares and Verrucae plantares), seborrheic and actinic keratoses and Condylomata, and superficial benign mucosal changes, such as benign lesions in the cervical area, such as erosion, Ovula Nabothi polyps in the area of the cervical canal, Condylomata.

However, when use of the drug recurrence is 30-40%, incomplete healing - 45%. The drug is a danger to personnel and requires precaution.

The aim of the invention is the creation of an original low-toxic stable highly effective drug for the treatment of benign tumors of the skin and visible mucous membranes of the skin, with good tolerability, lack of treatment complications, healing without scar formation changes.

Proposed chemical formula zinc salts and haloalkaliphilic acids of the aliphatic series having the form

where in the formula the halogen atom may be Fluorine (F), Chlorine (Cl), Bromine (Br) or Iodine (J).

Source materials can be of various chemical products containing zinc and solutions aliphatic haloalkaliphilic acids.

The final product before the hat is a solution of zinc salts and haloalkaliphilic acids. It is brown in color, with a pH of 2.2-3.0, LD50 1100 mg/kg of the Drug is practically non-toxic, does not penetrate into the body, has no system, teratogenic, embryotoxic and carcinogenic properties. The drug selectively dehydrates the tissue has intravitally locking action on the fabric. After removal of pathological tissue healing and regeneration is completed within two weeks without significant side effects.

The concentration of zinc in the product depends on the type of source chemical ingredients and can be between 2.5-25%. Chemical product invariant for many years when stored at room temperature in a closed dark glass jar.

The stated substance may be used only for local use. As a medicine it could be in the form of a solution in a concentration of from 5 to 45%. The recommended dose for one defeat from 0.1 to 2.0 cm2in liquid form, from 0.03 to 0.2 ml For numerous defeats, the dose may be from 0.2 to 2.00 ml

Achieved technical result consists in the creation of original drug for the treatment of benign tumors of the skin and visible mucous membranes of the skin, low-toxic, fast-acting with a pronounced therapeutic effect, with good tolerability, lack of treatment complications, healing without education the Oia scar tissue. The creation of the drug allows to expand the range of products for the treatment of such diseases.

The product is easy to use, safe for patients and health professionals, and requires no particular restrictions on its behavior.

From patent and scientific and technical information is not known chemical formula zinc salts and haloalkaliphilic acids of the aliphatic series, which could be used for local treatment of benign tumors of the skin and visible mucous membranes of the skin.

The synthesis of the claimed substances based on the use of available and inexpensive raw materials and ease.

The claimed substance obtained by reaction of the oxide or hydroxide, or carbonate of zinc with haloalkaline acids in the aquatic environment and stabilization of the obtained solutions of the additive 0,72-1,36% of salts of succinic or citric acid.

The structure of the new substance is confirmed by elemental analysis data.

Example 1. Di-(bromoacetate) zinc.

To a suspension of 2.44 g (0.03 mol) of zinc oxide in 30 ml of distilled water is added at once to 8.34 g (0.06 mol) bromoxynil acid. The reaction mixture is stirred until almost complete dissolution of the precipitate (about 15 min) at room temperature, filtered slight mixture through filter paper on a Buchner funnel. Get 32 ml of 23.8% is astora salt bromoxynil acid and zinc. After freeze-drying an aliquot of the solution was obtained dry salt, and defined its elementary composition. C4H4Br2O4Zn. To stabilize the solution to it was added succinic acid in the amount of 0.3 was Calculated, %: C 14,06; N 1,17; Br 46,87; Zn 19,16. Found, %: C 13,95; N 1,12; Br 46,55; Zn 19,24.

Example 2. Di-(trichloracetic) zinc.

Obtained according to example 1 of the 2,44 g (0.03 mol) of zinc oxide, 9.81 g (0.06 mole) of trichloroacetic acid and 20 ml of distilled water. The concentration of the salts - 36,3%. C4Cl6O4Zn. To stabilize the solution was added 0.3 g of citric acid.

Calculated, %: 12,30; Cl 54,56; Zn X 16.75.

Found, %: C KZT 12.39; Cl 54,47; Zn 16,62.

Example 3. Di-(CHLOROACETATE) zinc.

To a suspension of zinc hydroxide was obtained from 4.1 g (0.03 mol) of zinc chloride and 2.4 g (0.06 mol) of sodium hydroxide, add a solution 5,67 g (0.06 mol) of Chloroacetic acid in 25 ml of distilled water. Stirred at room temperature until almost complete dissolution of the precipitate, is filtered through filter paper on a Buchner funnel and get 22,5% solution of salt of Chloroacetic acid and zinc. After drying the aliquot was obtained dry salt, and defined its elementary composition. C4H4Cl2O4Zn. The solution is stabilized by the addition of 0.3 g of succinic acid.

Calculated, %: C 19,02; N 1,59; Cl 28,13; Zn 25,91.

Found, %: C 19,89; N 1,63; Cl 28,01; Zn 26,03.

p> Example 4. Di-(2-chloropropionate) zinc.

Obtained according to example 3 of 4.1 g (0.03 mol) of zinc chloride, 2.4 g (0.06 mol) of the hydroxide nartia with the subsequent processing of zinc hydroxide with a solution of 6.5 (0.06 mol) of 2-chloropropionic acid in 20 ml of distilled water. The concentration of the salts is 28.5%. C6H8Cl2O4Zn. The solution is stabilized by the addition of 0.3 g of citric acid.

Calculated, %: C 25,68; N 2,85; Cl 25,32; Zn 23,32.

Found, %: C 25,75; N 2,71; Cl 25,42; Zn 23,27.

Example 5. Di-(2-methyl-3-bromopropionate) zinc.

Obtained according to example 1 of the 2,44 g (0.03 mol) of zinc oxide, 10 g (0.06 mol) of 2-methyl-3-bromopropionic acid and 25 ml of distilled water. The concentration of the salts is to 30.3%. C8H12Br2O4Zn. The stable solution of 0.3 g of succinic acid.

Calculated, %: C 24,16; N 3,02; Br 40,26; Zn 16,46.

Found, %: C 24,03; N 3,15; Br 40,37; Zn 16,38.

Example 6. Di-(3-bromopropionate) zinc.

To a suspension 3,76 g (0.03 mol) of zinc carbonate in 30 ml of distilled water is added at once with stirring 9,18 g (0.06 mol) of 3-bromopropionic acid. The reaction mixture is stirred until complete cessation of carbon dioxide emissions is filtered turbidity through filter paper on a Buchner funnel. Get 25,9% solution of salt 3 bromopropionic acid and zinc. After freeze-drying an aliquot of the solution was obtained dry salt and studied its elementary composition. C H8Br2O4Zn. The stable solution of 0.3 g of citric acid.

Calculated, %: C 19,49; N 2,17; Br 43,31; Zn 17,71.

Found, %: C 19,58; N To 2.29; Br 43,22; Zn 17,62.

Example 7. Di-(2,3-dibromopropionate)zinc.

Obtained according to example 6 of the 3,76 g (0.03 mol) of zinc carbonate, 13,92 g (0.06 mol) of 2,3-dibromopropionate acid and 25 ml of distilled water. The concentration of the salts - 36,9%. With6H6Br4Zn. The stable solution of 0.3 g of succinic acid.

Calculated, %: C 13,65; N 1,14; Br 60,68; Zn 12,40.

Found, %: C 13,53; N 1,19; They Accounted For 60,54 Br; Zn 12,51.

Example 8. Di-(...-iodated) zinc.

Obtained according to example 1 of the 2,44 g (0.03 mol) of zinc oxide, 12 g (0.06 mol)...-todokanai acid and 30 ml of distilled water. The concentration of the salts to 30.1%. C4H4J2O4Zn. The stable solution of 0.3 g of citric acid.

Calculated, %: C 11,02; H 0,92; J 58,34; Zn 15,02.

Found, %: C 10,91; N 1,01; J 58,01; Zn 15,14.

Example 9. Di-(triptorelin) zinc.

Obtained according to example 1 of the 2,44 g (0.03 mol), at 6.84 g (0.06 mol) triperoxonane acid and 15 ml of distilled water. The concentration of the salts of 33.8%. C4F6O4Zn...

Calculated, %: 16,47; F 39,12; Zn Of 22.44.

Found, %: C 16,56; F 39,24; Zn 22,32.

Example 10. Di-(fluoroacetate) zinc.

Obtained according to example 6 of the 3,76 (0.03 mol) of zinc carbonate, 4.68 g (0.06 mol) forexpros acid and 15 ml of distilled water. The concentration of the salts is 27.3%. C4 H4F2O4Zn...

Calculated, %: C 21,88; N 1,82; F 17,32; Zn 29,81.

Found, %: C 21,82; N 1,73; F 17,44; Zn 29,69.

Example 11. Di-(dichloroacetate) zinc.

Obtained according to example 1 of the 2,44 g (0.03 mol) of zinc oxide, 7,74 g (0.06 mol) dichloracetic acid and 20 ml of distilled water. The concentration of the salts-30,2%. C4H2Cl4O4Zn.

Calculated, %: C 14,94; N 0,62; Cl 44,18; Zn 20,35.

Found, %: C 14.83; N 0.57; Cl 44,27; Zn 20,00.

Example 12. Treatment of 11 patients with a diagnosis of ectopia of the cervix (uterine), which saw a recurrent pseudo (age from 26 to 32 years). For processing ectopy used a 30% solution of zinc salt malodorous acid. Depending on the volume of the nidus number of applications of the drug was different. When ectopia not exceeding a diameter of 0.5-0.8 mm, processing was performed 1 time per 2 days. For large volumes of defeat applique was used 1 time double overlay, then daily or every other day, for a total of 3-4 applications. The drug was applied with a swab in the form of an application on the affected area. The immediate effect was manifested in the appearance of whitish-yellow fabric with a clear, white color ischemic roller around the affected area, 2-3 day fabric was gray-white, with 3 days was a decrease in the size of the scab and it is rejection. On the place of rejection, the mucous of the cervix acquired a reddish tint. Duration epithelialization ranged from 10 to 14 days, during which came the young regeneration epithelium cervical mucous. With extensive lesions of the cervix, requiring deep destruction of tissue, the duration of epithelialization was increased to 3-5 weeks. As a side effects at the time of processing was observed a slight burning sensation.

At the control examination after 3-4 day after the last treatment in almost all cases, it was noted the rejection of the scab and the presence of reddish-purple color of the mucous of the cervix.

At the control examination after 2 weeks, the mucous of the cervix becoming pink-red hue, i.e. close to the normal color of the mucous of the cervix. When colposcopically study indicated the emergence of metaplastic (young) epithelium over the entire surface, i.e. the process of epithelialization. Cytology revealed stratified squamous epithelium.

The follow-up period for patients with ectopia ranged from 12 days to 2 months. During this period only one (9,1%) patient in the presence of a previously extensive eroded surface of the cervix and probably because of the depth of the lesion is not marked complete epithelialization of the mucous.

Thus, the overall efficiency is ü use of a solution of zinc salts malodorous acid allows 90% of cases to achieve a positive result in the treatment of ectopy (background diseases of the cervix.

Example 13. Treatment of 7 patients diagnosed with genital warts, papillomaviruses infection (HPV) (age from 20 to 68 years). For the treatment of patients with papillomas were used 30% solution of zinc salt malodorous acid, was carried out 3-4 applications daily, if a large papillomas to 6. Directly in the process, there was a decrease in the volume of education "seivane", i.e. dehydration, mummification with the formation of whitish-yellow plaque. Before each subsequent treatment was removal of dead tissue. After the gradual exclusion on the skin remained within 7-14 days dark-bluish-brown spots.

Cytological examination after treatment revealed the presence of squamous epithelium with no evidence of pathology.

Of the 7 patients with papillomas after 2 months was observed recurrence of the disease in 1 patient, who initially had a papilloma in diameter not less than 4, see

Thus, the primary effect in the treatment of warts is 100%.

As follows from the examples, the use of the drug zinc salts and haloalkaliphilic acid shows its high efficiency in the treatment of ectopic cervix and papillomatosis skin of the genitals.

The advantages of the drug is its good tolerability, no complications, healing without scar formation and the changes, the ease of implementation, safety for patients and medical staff, as well as no particular restrictions on its behavior.

Thus, the claimed chemical substance zinc salts and haloalkaliphilic acids of the aliphatic series may be used effectively as a treatment for benign tumors of the skin and visible mucous membranes of the skin.

Zinc salts and haloalkaliphilic acids of the aliphatic series

where in the formula the halogen atom may be fluorine (F), chlorine (Cl), bromine (Br), or iodine (J).



 

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