RU2477272C2 - Ketimine based on 4,4'-dichlorobenzophenone and guanidine and method for production thereof - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: disclosed is a novel ketimine based on 4,4'-dichlorobenzophenone and guanidine, which is characterised by the formula

, as well as a method for production thereof, which involves reaction of guanidine carbonate (bicarbonate) with 4,4'-dichlorobenzophenone in ethanol at temperature of 70°C for 4 hours at pH=3 in molar ratio of guanidine to 4,4'-dichlorobenzophenone of 1:1. The synthesised ketimine can be used in polycondensation reactions during synthesis of polyheteroarylenes which are characterised by a combination of high heat resistance, high strength, good dielectric properties and chemical and radiation resistance.

EFFECT: use of the disclosed ketimine increases melt flow index.

2 cl, 2 ex

Description

The invention relates to an organic compound based on 4,4'-dichlorobenzophenone and guanidine containing a ketimine bond in its structure.

This compound can be used in polycondensation reactions for the synthesis of polyheteroarylenes, the distinguishing feature of which is the combination of high heat and heat resistance. In addition, such polymers are characterized by high strength characteristics, good dielectric properties, high chemical and radiation resistance. Due to this, they are used in aviation, space technology, electronics, mechanical engineering and other industries. [Korshak V.V. Heat resistant polymers. M., 1969]. It is also well known that organic compounds containing a guanidine fragment have bactericidal properties and are used as therapeutic agents and fungicides [Chemical Encyclopedia vol. 1 / Ed. I.L. Knunyantsa. - M .: Soviet Encyclopedia, 1988, p. 1209]. They are not inactivated by proteins and at the same time biodegradable, therefore they are widely used as physiologically active substances: drugs, antiseptics, pesticides [Report of the branch No. 5 of the Institute of Biophysics of the USSR Ministry of Health, Angarsk, 1991]. The guanidine group serves as the beginning of many medicinal substances (sulgin, ismeline, pharyngosept) and antibiotics (streptomycin, blasticidin, mildomycin).

All of the above indicates that the synthesis of new organic compounds based on guanidine is of undoubted interest.

It is known that the interaction of guanidine and its derivatives with ketones produces ketimines. [Brief chemical encyclopedia vol. 1. / Ed. I.L. Knunyantsa et al. - M.: Soviet Encyclopedia, 1961, p.139].

Closest to the claimed compounds is the previously obtained product of the interaction of 4,4'-dichlorobenzophenone with aminoguanidine, [Bairwa, Ranjeet et al. - Novel molecular hybrids of cinnamic acids and guanilhydrazones as potential antitubercular agents / Bioorganic & Medicinal Chemistry Letters 2010, 20 (5), 1623-1625], used in the synthesis of an anti-tuberculosis drug.

The objective of the present invention is the creation of a new organic compound based on guanidine and 4,4'-dichlorobenzophenone of the following structure:

The compound obtained by us is a monomer for producing (co) polymers using polycondensation reactions, while the resulting polymers can preserve the complex of valuable properties of the initial monomer, being convenient carriers of biologically active substances.

The literature describes a method of obtaining the closest to the claimed ketimine based on benzophenone and aminoguanidine (prototype) [[Nordmann J., Mattioda G., Loiseau G. - New drugs with analgesic, antispasmodic and anti-inflammatory effects. - French patent, cl. A61k, from 07 s, No. 7858. M., declared 12.30.68, publ. 04/20/70; RZH 5N 330P, 1973]. According to this method, to a suspension of 136 parts of aminoguanidine bicarbonate in 200 vol. including water, 85 parts of concentrated hydrochloric acid are gradually added. At the end of dissolution, a solution of 40 parts of sodium hydroxide in 100 parts of water is added quickly and with stirring, it is poured into a mixture of 91 parts of benzophenone and 500 parts by volume of alcohol, the solution is cooled to 0 ° C, boiled for 40 hours under nitrogen atmosphere, water was evaporated in vacuo, the residue was filtered. T _pl. = 192 ° C. The disadvantages of this method include the long-term stage of boiling (40 hours) and evaporation of water under vacuum.

To reduce energy consumption, to optimize the process of producing ketimine based on guanidine and 4,4'-diacetyl diphenyl oxide, to eliminate long-term stages, we propose to carry out the reaction of interaction of guanidine with 4,4'-dichlorobenzophenone in ethanol at a temperature of 70 ° C for 4 hours at pH = 3. The proposed method is illustrated by the following examples.

Example 1. 6.05 g (0.05 mol) of guanidine bicarbonate and 12.55 g (0.05 mol) of 4,4'-dichlorobenzophenone were mixed in 50 ml of ethyl alcohol, the mixture was acidified with concentrated hydrochloric acid to pH = 3 and kept at a temperature of 70 ° C for 4 hours. The resulting ketimine was precipitated in distilled water, made basic with sodium carbonate and filtered. Recrystallized from aqueous alcohol. The melting point of ketimine after recrystallization was = 107 ° C. The yield is 94%.

Example 2. As in example 1, only 4.5 g (0.025 mol) of guanidine carbonate and 12.55 g (0.05 mol) of 4,4'-dichlorobenzophenone were taken. The melting point of ketimine after recrystallization was = 107 ° C. The yield is 97%.

The structure and purity of the obtained monomer was determined using elemental analysis (laboratory microanalysis INEOS RAS); by PC spectroscopy (laboratory of spectral analysis of the Department of Inorganic and Physical Chemistry of KBSU).

Elemental analysis of ketimine based on 4,4'-dichlorobenzophenone and guanidine. Found,%: C = 57.25; Cl = 23.92; N = 14.51; H = 3.69. Calculated for C ₁₄ H ₁₁ Cl ₁₂ N ₃ ,%: C = 57.53; Cl = 24.32; N = 14.38; H = 3.77. The IR spectra of synthesized ketimine contain signals corresponding to the intended structure. Two wide split bands in the region of 3450-3070 cm ^-1 correspond to stretching vibrations of NH in the associated and unassociated groups NH ₂ and -NH-. There are absorption bands in the region of 1658 and 1570 cm ^-1 (stretching vibration of the bonds N = C), 1597 and 1500 cm ^-1 -v _as and v _s (respectively) for C = C bonds in aromatic rings. The remaining bands are in good agreement with the guanidine fragment.

Thus, the formation of ketimine based on 4,4'-dichloro-benzophenone and guanidine is proved.

Ketimine based on 4,4'-dichlorobenzophenone and guanidine contains two chlorine atoms and can be used to obtain different classes of polyheteroarylenes, in particular aromatic polyethers (when reacting with diphenolates), polyamines (reaction with hexamethylene diamine or aromatic diamines), polysulfides ( reaction with Na ₂ S), etc. These classes of polymers combine high heat and heat resistance, they are characterized by high strength characteristics, good dielectric properties, high chemical and radiation resistance of the bond [S.V. Vinogradova. V.A. Vasnev / Polycondensation processes and polymers. - M.: Science, MAIK "Science / Interperiodica", 2000. - 373 p.].

Using the example of polyvinyl chloride (PVC) and PVC compound, we found that the synthesized ketimine is well compatible with polymers produced on an industrial scale, while the introduction of even 0.2 wt.% Of the above ketimine into polymers increases the MFI of the melt up to 1.7 times.

It is known that the introduction of halogen atoms into an organic molecule containing a fragment of an antimicrobial compound usually enhances the biological activity of the latter [A.D. Virnik / Antimicrobial cellulosic fibrous materials - Results of science and technology - series “Chemistry and Technology of High Molecular Compounds”, v.21 . - M.: VINITI, 1986].

Preliminary bacteriological studies have established that the obtained ketimine is effective against Proteus vulgaris, Pseudomonas aeruginosa (Ps.aureginosa) and Staphylococcus aureus (Staph.Aureus).

Claims (2)

1. Ketimin based on 4,4'-dichlorobenzophenone and guanidine of the following structure

2. The method of producing ketimine according to claim 1, which consists in the interaction of guanidine derivatives and ketones, characterized in that the reaction of the interaction of guanidine with 4,4'-dichlorobenzophenone is carried out in ethanol at a concentration of 4,4'-dichlorobenzophenone 1 mol / l, temperature 70 ° C for 4 hours at pH 3 with a molar ratio of guanidine: 4,4'-dichlorobenzophenone = 1: 1.