WO2023228114A1 - Dérivés d'amines aromatiques coordonnés à des métaux utilisés en tant que matières bactéricides et leur procédé de production - Google Patents

Dérivés d'amines aromatiques coordonnés à des métaux utilisés en tant que matières bactéricides et leur procédé de production Download PDF

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Publication number
WO2023228114A1
WO2023228114A1 PCT/IB2023/055353 IB2023055353W WO2023228114A1 WO 2023228114 A1 WO2023228114 A1 WO 2023228114A1 IB 2023055353 W IB2023055353 W IB 2023055353W WO 2023228114 A1 WO2023228114 A1 WO 2023228114A1
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formula
aromatic amine
coordinated
added
amine derivatives
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PCT/IB2023/055353
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English (en)
Inventor
Yenny Patricia Avila Torres
Edwin Florez Lopez
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Universidad Santiago De Cali
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Publication of WO2023228114A1 publication Critical patent/WO2023228114A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C333/14—Dithiocarbamic acids; Derivatives thereof
    • C07C333/16—Salts of dithiocarbamic acids

Definitions

  • the present invention is directed to the field of chemical synthesis, mainly tp the technical field of coordination compounds obtained from dithiocarbamates derived from para-phenyldiamine and metal ions and the obtaining process thereof useful to combat Escherichia coli and Staphylococcus aureus and a wide application as antifungals, removers of heavy metals in contaminated water sources, antimicrobial and anticancer agents.
  • dialkylamino dithiocarbamate alkyl ester plays a very important role because they have broad biological characteristics and pharmacological activity and can be used as a myocardial imaging agent. It is known that dialkylamino dithiocarbamate alkyl ester and derivatives thereof can be taken as HIV-1 NCp7 inhibitors, antiviral agents and non-flavonoid TRPV1 antagonists.
  • the invention further provides a method for efficiently synthesizing amino dialkyl dithiocarbamate alkyl ester, under Cui catalysis, via a chiral quaternary ammonium salt and an aminodialkyl dithioformylate for C-S cross-coupling, and the dialkylamino dithiocarbamate alkyl ester is prepared.
  • CN112661685 reports a process method for the one-step synthesis of dithiocarbamate using a microflow field technology.
  • the method consists of the steps of pumping alkylamine, carbon disulfide, zinc chloride and alkaline liquor into a reactor according to a given flow rate by using a microflow field reactor, maintaining a given temperature and retention time, discharging, resting and separating the liquid, washing with water and distillation at reduced pressure to obtain the product.
  • the operation steps are optimized, the reaction time is significantly shortened and a continuous production of the product is realized.
  • CN103804258 discloses a dithiocarbamate synthesis process, which comprises the steps: (a) adding an amount of carbon disulfide, alkali liquid and carbamide in a reaction vessel; (b) stirring continuously, after uniform mixing, controlling the temperature and adding carbon disulfide dropwise; (c) controlling the temperature and stirring; (d) heating the solution; (e) once the reaction is finished, stirring, cooling to crystallization and filtering; (f) performing vacuum drying to obtain dithiocarbamate.
  • Dithiocarbamate is synthesized using carbon disulfide and carbamide according to the process parameters; the synthesis method is simple in synthesis step, high synthesis efficiency and low synthesis cost. In addition, the synthesized dithiocarbamate is effective and has a wide range of applications.
  • Infrared spectra indicated the coordination of dithiocarbamate through the two sulfur atoms in a symmetrical bidentate fashion.
  • the thermal behavior of these complexes showed that the hydrated complexes lost water molecules in the first step, followed by the decomposition of the ligand molecules in the final steps.
  • the antimicrobial potentials of the complexes were evaluated against selected bacterial strains (Escherichia coli, Pseudomonas aureginosa, Salmonella typhi and Staphylococcus aureus) and fungal organisms (Aspergillus flavus and Fasiparium oxysporium).
  • the present invention is directed to coordination compounds obtained from thiocarbamates derived from para-phenyldiamine and metal ions and their obtaining process to combat Escherichia coli and Staphylococcus aureus and a wide application as antifungals, heavy metal removers in contaminated water sources, antimicrobial and anticancer agents.
  • Figure 1 shows a 1 H Nuclear Magnetic Resonance ( 1 H NMR) spectrum of amine 4, wherein the hydrogens present in the molecule are observed.
  • Figure 2 shows the 13 Carbon Nuclear Magnetic Resonance (- 13 C NMR) spectrum of amine 4, wherein the carbons present in the molecule are observed.
  • Figure 3 shows the infrared spectrum of amine 4 wherein the different functional groups present in the molecule are observed.
  • Figure 4 shows the infrared spectrum of the copper coordination compound (5), wherein the vibrations of the bonds that are present in the molecule can be observed.
  • Figure 5 shows the electronic spectrum of the copper coordination compound
  • Figure 6 shows the infrared spectrum of the nickel coordination compound (6), wherein the vibrations of the bonds that are present in the molecule can be observed.
  • Figure 8 shows the infrared spectrum of the manganese coordination compound (7), wherein the vibrations of the bonds present in the molecule can be observed.
  • Figure 9 shows the electronic spectrum of the manganese coordination compound (7), wherein the most important electronic transitions exhibited by the molecule can be observed.
  • the present invention refers to metal-coordinated aromatic amine derivatives with applications as bactericidal materials, wherein the general formula (I) of said compounds has the following structure: wherein M is a metal selected from the group consisting of copper, nickel and manganese.
  • the present invention relates to a procedure for the preparation of the compounds of formula (I) by a series of steps: Step 1
  • the process of obtaining metal-coordinated aromatic amine derivatives comprises the following steps: a) Contacting a diamine of formula (1) with benzaldehyde of formula (2) in an anhydrous solvent in a microwave oven at a power of 300 W, for a time between 10 and 30 minutes at a temperature between 50°C and 70°C; b) Adding sodium borohydride (NaBH 4 ) at room temperature and continue the reaction in a microwave oven for between 30 minutes and 60 minutes at the same power as in the first step; and c) Obtaining the coordination compound of formula (I) in situ by dissolving N',N'- dibenzylbenzene-1 ,4-diamine of formula (4) in methanol (MeOH), addition of ammonium hydroxide (NH4OH), dropwise addition of carbon disulfide while stirring at room temperature and addition of the respective salts: CuCI 2 .2H 2 O, NiCl2.6H 2 O, and MnCI
  • the first step (a) is the reaction of the p-diamine of formula (1 ) with benzaldehyde of formula (2) in an anhydrous solvent, such as dry methanol, wherein the reaction is carried out in a microwave for a time between 10 and 30 minutes, more preferably 20 minutes, a temperature between 50°C and 70°C more preferably at 60°C and a power of 300 W until the corresponding imine of formula (3) is obtained.
  • anhydrous solvent such as dry methanol
  • step (b) to the imine of formula (3) is added sodium borohydride (NaBH 4 ) at room temperature (18°C to 25°C) continuing the reaction in a microwave for a given time, for example, between 30 minutes and 60 minutes, more preferably 40 minutes and at the same power as in the first step.
  • NaBH 4 sodium borohydride
  • the reaction mixture is subjected to evaporation at a rotavap until dryness and subsequently, a saturated aqueous solution of sodium chloride is added and extraction with dichloromethane (DCM) is performed in triplicate, wherein the organic phases are collected and again subjected to evaporation at a rotary evaporator until the volume is reduced to between 5% and 10% of the initial volume of the collected organic phases. Then distilled water is added and with constant agitation a hydrochloric acid solution is added until a pH between 1 and 3 is obtained.
  • DCM dichloromethane
  • dichloromethane DCM
  • DMC dichloromethane
  • the reaction of the coordination compound is carried out In situ starting from the amine of formula (4), without isolation of dithiocarbamate (DTC) in a ligand:metal ratio of 1.00:1.20. Initially N',N'-dibenzylbenzene-1 ,4-diamine (4) is dissolved in methanol (MeOH) and ammonium hydroxide (NH4OH) is added with constant stirring for 12 hours. Subsequently, carbon disulfide is added dropwise with stirring at room temperature for a period of 2 hours, the reaction is monitored by plate chromatography until the disappearance of the amine. After this time the respective salts are added:
  • the reaction is left stirring at room temperature for 2 hours and for the nickel and manganese compounds the reaction is left stirring at reflux for a period of 12 hours. After these times crystals are obtained which are filtered and washed with methanol to obtain the copper coordination compound of formula (5) as a dark brown solid; the nickel coordination compound of formula (6) as a black solid and finally the manganese compound of formula (7) was obtained as a dark green solid.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne des dérivés d'amine aromatique coordonnés à des métaux avec des applications en tant que matières bactéricides, la formule générale (I) desdits composés ayant la structure : (I) dans laquelle M est un métal choisi dans le groupe constitué par le cuivre, le nickel et le manganèse et leur procédé de production.
PCT/IB2023/055353 2022-05-25 2023-05-24 Dérivés d'amines aromatiques coordonnés à des métaux utilisés en tant que matières bactéricides et leur procédé de production WO2023228114A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CONC2022/0007001 2022-05-25
CONC2022/0007001A CO2022007001A1 (es) 2022-05-25 2022-05-25 Derivados de aminas aromáticas coordinados a metales como materiales bactericidas y su proceso de producción

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WO2023228114A1 true WO2023228114A1 (fr) 2023-11-30

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103804258A (zh) 2012-11-13 2014-05-21 张红梅 二硫代氨基甲酸盐的合成工艺
CN110483355A (zh) 2019-07-30 2019-11-22 上海裕诚化工有限公司 二烃基二硫代氨基甲酸锌盐的合成方法
CN110683975A (zh) 2019-10-23 2020-01-14 成都理工大学 一种二烷基氨基二硫代甲酸烷酯的合成方法
CN112661685A (zh) 2019-10-15 2021-04-16 中石化南京化工研究院有限公司 一步合成二硫代氨基甲酸盐的方法
CN113444114A (zh) 2021-04-16 2021-09-28 吴超君 二苄基二硫代氨基甲酸铜药物治疗三阴性乳腺癌的应用

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103804258A (zh) 2012-11-13 2014-05-21 张红梅 二硫代氨基甲酸盐的合成工艺
CN110483355A (zh) 2019-07-30 2019-11-22 上海裕诚化工有限公司 二烃基二硫代氨基甲酸锌盐的合成方法
CN112661685A (zh) 2019-10-15 2021-04-16 中石化南京化工研究院有限公司 一步合成二硫代氨基甲酸盐的方法
CN110683975A (zh) 2019-10-23 2020-01-14 成都理工大学 一种二烷基氨基二硫代甲酸烷酯的合成方法
CN113444114A (zh) 2021-04-16 2021-09-28 吴超君 二苄基二硫代氨基甲酸铜药物治疗三阴性乳腺癌的应用

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
H.S. RATHORE ET AL.: "Fungicidal and bactericidal activity of metal diethyldithiocarbamate fungicides", JOURNAL OF THERMAL ANALYSIS AND CALORIMETRY, 2008
ITOHOWO G. ASUQUO ET AL.: "Synthesis, characterization and antibacterial studies of nickel (II) mixed ligand complexes of dithiocarbamate ligands with Schiff base", ELIXIR APPLI. CHEM, 2014
ONWUDIWE DAMIAN C ET AL: "Synthesis, characterization, thermal, antimicrobial and antioxidant studies of some transition metal dithiocarbamates", RESEARCH ON CHEMICAL INTERMEDIATES, AMSTERDAM, NL, vol. 43, no. 3, 12 September 2016 (2016-09-12), pages 1465 - 1485, XP036154237, ISSN: 0922-6168, [retrieved on 20160912], DOI: 10.1007/S11164-016-2709-2 *
THAMMAKAN NIRAWAN ET AL: "Synthesis and thermal decomposition of cadmium dithiocarbamate complexes", MATERIALS LETTERS, vol. 60, no. 9, 2005, pages 1161 - 1165, XP029168361, ISSN: 0167-577X, DOI: 10.1016/J.MATLET.2005.10.107 *

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