RU2477271C2 - Mono and diketimines based on 4,4'-diacetyldiphenyl oxide and guanidine and method for production thereof - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: disclosed are novel organic compounds

which are based on 4,4'-diacetyldiphenyl oxide and guanidine, having ketimine bonds in their structure and a method for production thereof, which involves reaction of an alcohol solution of guanidine carbonate or bicarbonate with 4,4'-diacetyldiphenyl oxide in ethanol at temperature of 70°C for 4 hours at pH=3 in molar ratio of guanidine to 4,4'-diacetyldiphenyl oxide of 1:1 or 2:1. The disclosed compounds are of interest when producing hetero-chain polymers and copolymers which are characterised by a combination of high heat resistance, high strength, good dielectric properties and high chemical and radiation resistance.

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

2 cl, 3 ex, 1 tbl

Description

The invention relates to organic compounds based on mono- and dipro derivatives of 4,4'-diacetyldiphenyl oxide and guanidine containing ketimine bonds in their structure.

These compounds can be used in polycondensation reactions for the synthesis of aromatic heterochain polymers, the distinguishing feature of which is the combination of high heat and heat resistance. In addition, they are characterized by high strength indicators, 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 fragment of guanidine or its derivative have bactericidal properties and are used as therapeutic agents and fungicides [Chemical Encyclopedia. T.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 new organic compounds synthesized based on guanidine are of undoubted interest.

It is known that the interaction of guanidine and its derivatives with ketones produces ketimine bonds [Brief chemical encyclopedia. T.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 diacetyldiphenyl ether with aminoguanidine [Fusco R. The method of purification of wastewater containing organic compounds of anionic nature. US patent, No. 4120789., Publ. 10/17/1978].

The present invention is the creation of new organic compounds based on guanidine and 4,4'-diacetyldiphenyl oxide, which can be used as monomers and biocidal substances.

The task is realized by obtaining ketimines of the following structure:

The compounds obtained by us represent a promising series of monomers for the production of (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 capable of prolonged deimmobilization.

In the document [Fusco R. A method for treating wastewater containing organic compounds of anionic nature. US patent, No. 4120789., Publ. 10.17.1978] describes the closest method for producing ketimine based on 4,4'-diacetyldiphenyl oxide and aminoguanidine (prototype). According to this method, 13.6 g of aminoguanidine bicarbonate is treated with 17 ml of an 18% hydrochloric acid solution. Then add 12.7 g of 4,4'-diacetyldiphenyl ether in 100 ml of absolute methanol. The mixture is heated at 90 ° C for 2 hours. The solution was concentrated and, upon cooling, the bisguanyl hydrazone salt was obtained.

When using this method, the temperature of the process remains unclear. The boiling point of methanol is 64.5 ° C, which means the reaction is carried out either in the vapor phase or at elevated pressure.

The objective of the proposed method is the optimization of the process of obtaining ketimines. We propose to carry out a reaction of the interaction of guanidine carbonate or bicarbonate with 4,4'-diacetyldiphenyl oxide in ethanol at a temperature of 70 ° C for 4 hours at pH 3. The concentration of 4,4'-diacetyl diphenyl oxide is 0.5 mol / l, molar ratio 4, 4'-diacetyldiphenyl oxide: guanidine = 1: 1 upon receipt of monoketimine; molar ratio of 4,4'-diacetyldiphenyl oxide: guanidine = 1: 2 upon receipt of diketimine.

The proposed method is illustrated by the following examples.

Example 1. 3.6 g (0.02 mol) of guanidine carbonate and 5.08 g (0.02 mol) of 4,4'-diacetyldiphenyl oxide were dissolved in 40 ml of ethyl alcohol, the mixture was acidified with concentrated hydrochloric acid to pH 3 and kept at temperature of 70 ° C for 4 hours. Diketimine was precipitated into distilled water, made basic with sodium carbonate to a neutral medium, and filtered. After recrystallization from alcohol, the melting point of diketimine based on guanidine and 4,4'-diacetyl diphenyl oxide is 201 ° C.

Example 2. As in example 1, only 1.8 g (0.01 mol) of guanidine carbonate and 5.08 g (0.02 mol) of 4,4'-diacetyldiphenyl oxide were taken. After recrystallization from alcohol, the melting point of guanidine-based monoketimine and 4.4'-diacetyl diphenyl oxide is -194 ° C.

Example 3. As in example 1, only 2.42 g (0.02 mol) of guanidine bicarbonate and 5.08 g (0.02 mol) of 4,4'-diacetyldiphenyl oxide were taken. After recrystallization from alcohol, the melting point of guanidine-based monoketimine and 4.4'-diacetyl diphenyl oxide is -194 ° C.

The purity and structure of the obtained ketimines was determined using elemental analysis, IR spectroscopy. Elemental analysis was performed by pyrolysis chromatography on a Carlo Erba CHN-1108 instrument (Italy). The results are presented in the table.

Elemental analysis of synthesized ketimines Ketimine gross formula Elemental analysis * FROM,% N% N% C ₁₇ H ₁₇ O ₂ N ₃ 65.95 / 65.80 5.67 / 5.80 18.20 / 18.06 C ₁₈ H ₂ oON ₆ 64.16 / 64.28 5.86 / 5.95 24.96 / 25.04 * In the numerator - found, and in the denominator - calculated.

The IR spectra of the synthesized ketimines contain signals corresponding to the proposed structures. 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 -ν _as and ν _s (respectively) for C = C bonds in aromatic rings, 1266 cm ^-1 Ph- O-Ph, 844 cm ^-1 - δ _CCH for para-substituted phenyl rings. A signal of 1676 cm ^-1 ν _{C = O} , characteristic of methylphenylketone, is present in diacetyldiphenyl oxide, monoketimine and absent in diketimine. The remaining bands are in good agreement with the guanidine fragment.

Thus, the formation of mono- and diketimines based on 4,4'-diacetyldiphenyl oxide and guanidine has been proved.

Diketimine based on 4,4'-diacetyldiphenyl oxide and guanidine contains two amino groups and can be used to obtain different classes of polyheteroarylenes, in particular aromatic polyamides (when reacted with dicarboxylic acids or their acid chlorides), polyamines (reaction with hexamethylene diamine or aliphatic polydenides) reaction with tetracarboxylic acids), etc. These classes of polymers combine high heat and heat resistance, they are characterized by high strength characteristics, good dielectric properties, as well as high chemical and radiation resistance [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 mono- and diketimines are well combined with polymers produced on an industrial scale, while the introduction of even 0.2% by weight of the above ketimines into the polymer composite increases the MFI to 1 ,5 times.

It is known that ketimines containing guanidine fragments as a biocidal component retain their biological activity [A.D. Virnik. / Antimicrobial cellulosic fibrous materials. - Results of science and technology - Series "chemistry and technology of macromolecular compounds." - t.21. - M.: VINITI, 1986]. At the same time, in the case of the formation of polymers, a fairly easy hydrolysis by the ketimine bond is possible, while the active antimicrobial component is released [Report of the branch No. 5 of the Institute of Biophysics of the USSR Ministry of Health Angarsk, 1991]. Our preliminary bacteriological studies showed that the obtained ketimines are effective against Proteus vulgaris, Pseudomonas aeruginosa (Ps. Aureginosa) and Staphylococcus aureus (Staph. Aureus).

Claims (2)

1. Mono- and diketimines based on 4,4'-diacetyldiphenyl oxide and guanidine of the following structure:

2. The method of producing ketimines according to claim 1, characterized in that the reaction of the reaction of 4,4'-diacetyldiphenyl oxide with guanidine carbonate or bicarbonate is carried out in ethanol at a temperature of 70 ° C for 4 hours at a pH of 3 at a molar ratio of 4.4'- diacetyldiphenyl oxide: guanidine = 1: 1 (monoketimin) or 1: 2 (diketimin).