Scientific novelty of the monography consists in the following:

- It is established, that aminoimine equilibrium 5-amino-1H-tetrazol and an encore (aminoazol-N-il) alkanes in solution N, N '-dimetilacetamide (DMAA) it is shifted aside imino-form;

- On the basis of this concept dependence of antifungal activity on quantity aminoazoles fragments in a molecule is established;

- The method of chemical kinetics investigates process of passing of reaction of alkylation 4-amino-1,2,4-triazol 1-brombutan and by 1,2-dibromoethane and the mathematical schema for calculation of constants of series-parallel reactions is offered in view of hydrolysis;

- New ways of reception of dibromides an encore - 1,1'-(4-amino-1,2,4-triazole-1-ил) alkanes, an encore - 3,3'-(5-amino-1,2,4-triazole-1-ил) alkanes (BATH), an encore (1,2,4-triazoleил-1-ил) alkanes are offered;

- The explanation of a reactionary duality of С-amines of 1,2,4-azimide in reactions of acylation in conditions of low-temperature polyfunctional condensation is offered and the new class of connections - linear oligoamides, containing fragments aminoazoles in a stem nucleus of a macromolecule is synthesized;

- The method of quantum chemistry designs molecular characteristics of new azoles, and method РСА establishes structure an encore - 1,1-(Н-amino-1,2,4-triazoleио) ethane;

It is practically established fundamental dependence in number BAL between a structure (quantity aminoazoles fragments in a molecule) and the antifungal activity increasing with reduction of their quantity.

Thus, in the monography the new scientific direction consisting in research of chemistry BAL and forecasting of their efficiency as fungicides is submitted.

INTRODUCTION.

The big interest developed now to chemistry of heterogeneous ring compound, in particular, amino-1,2,4-triazoles (АТР) and 5-amino-1Н-1,2,3,4-tetrazol (5-АТ) is connected to an originality of a structure and these properties aminoazoles The practical importance of work consists that on the basis of complex research of physical and chemical and operational properties of the synthesized connections some from them are offered as the active working beginnings in antifungal compositions.

The purpose of the present work is creation of scientific bases and new paths of synthesis aminoazoles for their use in an agriculture.

Material and methods:

- Researches Aminoimine dynamic isomerism aminoazoles and an encore (aminoazol-N-ил) alkanes in organic solvents;

- Calculations of molecular characteristics of possible structures aminoazoles with the help of methods of quantum chemistry, molecular mechanics, dynamics and thermodynamics;

- Studying kinetics of alkylation 4-amino-1,2,4-triazol dihaloalkans;

- Optimization of a way and conditions of carrying out of process of polyamidation aminoazoles and an encore (aminoazol) alkanes dihloranhydrides dicarboxylic acids in conditions of a cold process in dimetilacetamide;

- Studying a structure and properties of the synthesized connections;

- Definitions of efficiency of use of new azoles in antifungal compositions.

The decision of tasks in view becomes step to an establishment of mechanisms of alkylation and acylation aminoazoles in the environment of dipolar aprotic solvents, will expand an opportunity of forecasting at research of new fungicides.

Results and discussion:

1.THE CONCEPT OF SHIFT AMINOIMINE OF EQUILIBRIUM IN SOLUTION AMINOAZOLES AND THEIR DERIVANTS.

Aminoimine equilibrium aminoazoles and their derivants in a solution is investigated with a different set of solvents, without dependence from a structure of connections and with various substituents in a cycle. Еquilibrium should be displaced aside imino-form aminoazolа and increasing fragrance quasi-aromatic systems to rise{elevate;improve;raise} antifungal activity. Results of researches Aminoimine are submitted to dynamic isomerism æ-amino-1,2,4-triazoles (АТР), 5-АТ and BAL in a crystal kind and in solutions, and new results in of this area received.

2. NUCLEOPHILIC SUBSTITUTION aminoazoles DIBROMALKANAMI (2:1)

IN N ENVIRONMENT; N' - DIMETHYL FORMAMIDE.

Dependence of antifungal activity on a structure in a number: aminoazolы - an encore (aminoazol-N-il) alkanes -oligoamides with aminoazolами in a stem nucleus of a macromolecule, that is with increase in quantity aminoazoles fragments, it is not investigated.

With the purpose of reception of new connections with two cycles in a molecule it is possible with the greater, than the monoreplaced azoles activity, utilised as initial amino-1,2,4-triazoles and 5-amino-1Н-1,2,3,4- tetrazol. Alkylation aminoazoles dihaloalkans in the environment of dimethylformamide (2:1) is investigated insufficiently. Therefore for specification of the schema of interaction, the factors influencing reaction rate and drawing up of model of alkylation on an example 4-АТР research of its kinetics is lead.

3. INFLUENCE OF SHIFT amino- IMINNOGO

EQUILIBRIUMS IN CONDITIONS OF LOW-TEMPERATURE POLYFUNCTIONAL CONDENSATION.

Thus, the spent calculation of frequencies and forms of normal fluctuations of modelling connections and also Would show an opportunity of identification амидной and азолидной groups in composition oligoamides 1,2,4-azimide on frequency of valence vibrations of a carbonyl group (ΝCO). It is necessary to note, that results the references made earlier by empirical way in experimental spectrums acylated aminotriazoles [1], [2]. Speed of the basic reaction of polyamidation drops and simultaneously the role of the side reactions, resulting in to stopping of chain of a macromolecule, such as hydrolysis of terephthaloyl chloride, his interaction with solvent and on three possible reactionary centers, разнозвенность grows.

4. RANGES OF APPLICATION OF SALTS aminoazoles AND aminoazol-N-ИЛ DERIVANTS.

The use of derivants of 1,2,4-azimide is known as insecticides, regulators of propagation, antiseptic agents - противогрибковых means [3].

In the review in chemistry of tetrazoles [4] the basic ranges of application of tetrazoles are described: medicine, biochemistry, an agriculture, analytical chemistry, systems of record of the information, rust inhibitors, power-intensive processes and materials.

The [5] tetrazoles - inhibitors used at display of films, and salts тетразолия - catalysts of interphase conduction [6] are known.

We for the first time describe in work [7] use of phosphate 5-amino-1,2,4-triazol at floatation апатитовых ores with the high maintenance{contents} of carbonates. With the purpose to raise (maintenance P2О5 in a concentrate and extraction) floatations of apatite - carbonaceous ores excretion of a useful component manufacture technological indexs the collector at whom follow-up there is a salt 5-АТР. At the charge of salt of 25-50 grammes on ton of a concentrate maintenance{contents} P2О5 increases on 20,4 %.

Salts aminoazoles are offered as components of the compositions used as fluxes for the soldering and tinning of radio-electronic instrumentation [8], [9]. Salts of azoles as fungicides are described in works [10], [11].

On соновании the researches submitted above dependence of antifungal activity on quantity{amount} aminoazoles fragments in a molecule is established.

Thus, in work new groups of a known class of connections which can be applied as fungicides with the raised{increased} antifungal activity in comparison with bajletonom and solubility in an aqueous medium that rises ecological compatibility of these connections are described.

5. TECHNIQUES OF RECEPTION AND CLEARING THE ENCORE (aminoazol-N-ИЛ) ALKANES AND THEIR DERIVANTS.

Methods of physical and chemical and express researches. Clearing and desiccation of reagents. Techniques of synthesis an encore (aminoazol-N-ил) derivants. Dibromides an encore (4-amino-1,2,4-triazoleил) alkanes [3,12]. An encore (4-amino-5-тиоксо-1,2,4-triazole-1-ил) alkanes [13].) 1,2-бис-(1,2,4-triazole-1-ил) ethane [14]. An encore (1,2,4-triazole-1-ил) alkanes. An encore (5-aminoтетразол-N-ил) alkanes. Techniques of reception oligoamides amino-1,2,4-triazol and 5-amino-1Н-1,2,3,4-tetrazol. Interphase polyfunctional condensation in system "Gas - liquid". Interphase polyfunctional condensation in system "Liquid - liquid". Polyfunctional condensation in a solution. Salts aminoazoles[15].

CONCLUSIONS:

In the monography the recent trend consisting in chemistry an encore (amino-1,2,4-triazoleил and тетразолил) alkanes, and also derivants with more than to two aminoazolьными cycles in a molecule is described.

Alkylation and acylation aminoazoles is considered in conditions undocumented in the literature. From positions of the concept of shift offered by us Aminoimine dynamic isomerism in a solution are established features of passing of these reactions, resulting in to the new connections having raised antifungal activity.

With the help complex physical and chemical and квантовохимического studying of an electronic structure of new connections and their antifungal activity the fundamental interrelation of a structure and properties of the described series of compounds is established: at increase in quantity aminoazoles cycles in a molecule antifungal activity decreases. Connections in the salt form have higher antifungal activity.

Novelty of work consists in new ways of reception an encore (aminoazol-N-ил) alkanes, their salts, oligoamides with aminoazolами in a stem nucleus of a macromolecule.

Thus, within the framework of the specified direction in a class aminoazoles new connections with the raised antifungal activity can be received.

Recenzenty:

Barmin Mihail Ivanovich, professor Rossijskoj Akademii Estestvoznanija (RAE) g.Moskva, kandidat himicheskih nauk, repetitor po himii, pisatel', dejstvitel'nyj chlen N'ju-Jorkskoj Akademii nauk (1995-1998), Sorosovskij docent (2001, 2002), laureat premii "Grant Sankt-Peterburga" (2002).

Tyutrina Mariya Valer'evna, studentka GOU VPO «Rossijskij gosudarstvennyj pedagogicheskij universitet im. A. I. Gercena» , Sankt-Peterburg, Rossija. (191186, g. Sankt-Peterburg, naberezhnaja reki Mojki, d. 48.)

2. Shejnker V.N., Minjaev R.N., Minkin V.I., etc. Research of a structure and properties of heterogeneous ring compounds and their complexes. XI. Theoretical studying a cis – trance of an isomerism and barriers of internal rotation in carbonyl derivativ azoles // Журн. орг. Chemistry. – 1977. – Т. 13. – № 11. – With. 2416 – 2421.

3. Koldobskij G.I., Ostrovsky V.A.Tetrazoly // Усп. химии.-1994.-Т. 63.-№ 10.-With. 847 – 865.

4. Butler R.N. In Book: Comprehensive Heterocycle Chemistry/Tetrazoles // Ed. Potts K.T.-1984.-Vol. 5.-P. 791 – 838.

5. Pat3295976 (USA.) Novel Inhibitors for Use in the Black and White Development of Color Reversol Film // Abbott J.R., SainhevenI.F. – Заявл. 12.12.63. – Опубл. 3.12.84.

6. Zhivich A.V., Myznikov J.E., Koldobskij G.I., etc. Salts тетразолия – new catalysts of interphase conduction // Журн. орг. Chemistry. – 1988. – № 8. – With. 1906 – 1914.

7. Ampere-second. 1757747 (USSR). A way of selective floatation of apatite – carbonaceous ores // V.I.Bragina, N.V.Vvedensky L.M.Bondar Kulikova L.V., Barmin M.I., Karaulova I.B.-1992.-Б.И.-№ 32.-With. 41,42.

8. Ampere-second. 1291339 (USSR) МКИ В23К 35/363. Flux for the soldering and tinning of radio-electronic instrumentation / N.V.Vvedensky G.V.Sokolova, M.I.Barmin, S.N.Andreev. // Зарегестрир. In Гос the register of the USSR 22.10.87.

9. Ampere-second. 1336391 (USSR) МКИ В23К 35/363. Flux for the low-temperature soldering / N.V.Vvedensky, M.I.Barmin V.I.Beljavskij. // Зарегестрир. In Гос. The register of the USSR 08.05.87.

10. Shemjakin A.I., Barmin M.I., Kasatikova E.L., etc. Salts of azoles // Деп. In ОНИИТЭХИМ, Cherkassy, 19.03.91. – № l23-xn-91.

11. Lebedintseva O.V., Barmin M.I., Millers В.В., etc. // In кн.: Scientific bases of chemical protection of agricultural crops from illnesses. Л.: ВИЗР.-1991. – With. 87.

12. Barmin M.I., Shemjakin A.I., Petrov В.В.. Millers V.V.synthes, research of a structure исвойств an encore – 5-aminotetrazol // Деп. In ОНИИТЭХИМ., Cherkassy, 17.09.84, № 1009хп-84.

13. Gromova S.A., Barmin M.I., Karaulova I.B., etc. Research of products of alkylation 4-amino-!, 2,4-azimide дибромалканами // Журн. орг. Chemistry. – 1996. – Т. 32. – Вып. 8. – With. 1234 – 1237. chemistry // potassium salt

14. Barmin M.I., Gromova S.A., Andrianova I.N., V.V.alkylation's Millers 5-amino-1,2,4-triazol 1,2-dibromoethane // Журн. The general{common} chemistry. – 2001. – Т. 71. – Вып.4. – With. 696 – 697.

15. Tverdohlebov V.P., Tselinskij I.V., Vasiljeva N.J., etc. Alkylation of anions of the replaced tetrazoles and 1,2,4-azimides derivants of ferrocene // Журн. орг. химии.-Æ. 16.-Вып. 1.-With. 218-222.