METHOD FOR THE INDUSTRIAL PRODUCTION OF 2-HALO-4,6-DIALKOXY-1,3,5-TRIAZINES AND THEIR USE IN THE PRESENCE OF AMINES

[0001] The present invention relates to the sector of activating agents for condensation, crosslinking, grafting, and curing reactions that intervene in the processes of stabilization of collagen matrices, and for the condensation of natural and synthetic polymers. [0002] In particular, the invention regards the process of synthesis, which can be implemented also on an industrial scale, of 2-halo-4,6-dialkoxy-1,3,5-triazines, which act as activating agents for condensation, crosslinking, grafting, and curing reactions, and for stabilization of collagen matrices, as well as for the condensation of polymers, and the multiple applications of said reagents in various industrial sectors, amongst which the tanning industry and the leather-processing industr

REAGENTS COMPRISING 2-HALO-4,6-DIALKOXY-1,3,5-TRIAZINES IN THE PRESENCE OF AMINES AND THEIR USE IN A STABILIZATION METHOD

[0001] The present invention relates to the sector of activating agents for condensation, crosslinking, grafting, and curing reactions that intervene in the processes of stabilization of collagen matrices, and for the condensation of natural and synthetic polymers. [0002] In particular, the invention regards 2-halo-4,6-dialkoxy-1,3,5-triazines, which act as activating agents for condensation, crosslinking, grafting, and curing reactions, and for stabilization of collagen matrices, as well as for the condensation of polymers, and the multiple applications of said reagents in various industrial sectors, amongst which the tanning industry and the leather-processing industry

Tris-isocyanide copper(I) complex enabling copper azide-alkyne cycloaddition in neat conditions

The three-coordinated homoleptic Cu(I) complex with 2,6-dimethylphenyl isocyanide in the coordination sphere was easily synthesized and isolated as tetrafluoroborate salt. The structure of the compound was determined by single-crystal X-ray diffraction. The complex is highly stable, active and selective toward the copper-catalyzed azide-alkyne cycloaddition, working in neat conditions and in the absence of bases at room temperature. Substrate scope was assessed by testing several different alkynes and azides. In most cases the corresponding 1,4-disubstituted-1,2,3-triazoles were isolated in high yields

Efficient Triazine Derivatives for Collagenous Materials Stabilization

Nowadays, the need to reduce plastic waste and scantly biodegradable fossil-based products is of great importance. The use of leather as an alternative to synthetic materials is gaining renewed interest, but it is fundamental that any alternative to plastic-based materials should not generate an additional environmental burden. In the present work, a simple protocol for collagen stabilization mediated by 2-chloro-4,6-diethoxy-1,3,5-triazine (CDET) and a tert-amine has been described. Different tert-amines were tested in combination with CDET in a standard amidation reaction between 2-phenylethylamine and benzoic acid. Best performing condensation systems have been further tested for the cross-linking of both collagen powder and calf hides. The best results were achieved with CDET/NMM giving high-quality leather with improved environmental performances.Nowadays, the need to reduce plastic waste and scantly biodegradable fossil-based products is of great importance. The use of leather as an alternative to synthetic materials is gaining renewed interest, but it is fundamental that any alternative to plastic-based materials should not generate an additional environmental burden. In the present work, a simple protocol for collagen stabilization mediated by 2-chloro-4,6-diethoxy-1,3,5-triazine (CDET) and a tert-amine has been described. Different tert-amines were tested in combination with CDET in a standard amidation reaction between 2-phenylethylamine and benzoic acid. Best performing condensation systems have been further tested for the cross-linking of both collagen powder and calf hides. The best results were achieved with CDET/NMM giving high-quality leather with improved environmental performances

Tris‐isocyanide copper(I) complex enabling copper azide‐alkyne cycloaddition in neat conditions

The three‐coordinated homoleptic Cu(I) complex with 2,6‐dimethylphenyl isocyanide in the coordination sphere was easily synthesized and isolated as tetrafluoroborate salt. The structure of the compound was determined by single‐crystal X‐ray diffraction. The complex is highly stable, active and selective toward the copper‐catalyzed azide‐alkyne cycloaddition, working in neat conditions and in the absence of bases at room temperature. Substrate scope was assessed by testing several different alkynes and azides. In most cases the corresponding 1,4‐disubstituted‐1,2,3‐triazoles were isolated in high yields.Università Ca' Foscari di Venezia | Ref. Bando Spin 2018, D. R. 1065/2018 prot. 6741

The intriguing methoxycarbonylation of trimethylsilylacetylene in the presence of Drent's catalytic system

The alkoxycarbonylation of trimethylsilylacetylene has been studied in order to develop an atom economic sustainable synthesis of 2-(trimethylsilyl)acrylates, a family of valuable intermediates. Pd(OAc)2 in combination with CH3SO3H and diphenyl-(pyridin-2-yl)phosphine or diphenyl-(6-methyl-pyridin-2-yl)phosphine is an active catalyst for the reaction affording mixtures of the sought 2-(trimethylsilyl)acrylate and the isomeric 3-(trimethylsilyl)acrylate. The phosphine ligand has a dramatic effect on the reaction. When employing diphenyl-(pyridin-2-yl)phosphine, it is necessary to carry out the reaction at 80°C in order to observe a modest catalytic activity, and the product is an almost equimolecular mixture of the two isomeric esters. On the contrary, when employing diphenyl-(6-methyl-pyridin-2-yl)phosphine, the reaction proceeds under much milder conditions affording with high rate (turnover frequency [TOF] up to 1200 h−1) and selectivity (>95%) of the sought 2-(trimethylsilyl)acrylate. The reaction conditions have been optimized, and the effects of phosphine/palladium, acid/palladium, reaction time, temperature, and CO pressure have been investigated. © 2021 The Authors. Applied Organometallic Chemistry published by John Wiley & Sons Ltd

Synthesis of 2-Alkylaryl and Furanyl Acetates by Palladium Catalysed Carbonylation of Alcohols

The one-pot alkoxycarbonylation of halo-free alkylaryl and furanyl alcohols represents a sustainable alternative for the synthesis of alkylaryl and furanyl acetates. In this paper, the reaction between benzyl alcohol, chosen as a model substrate, CH3OH and CO was tested in the presence of a homogeneous palladium catalyst, an activator (isopropenyl acetate (IPAc) or dimethyl carbonate (DMC)) and a base (Cs2CO3). The influence of various reaction parameters such as the CO pressure, ligand and palladium precursor employed, mmol% catalyst load, temperature and time were investigated. The results demonstrate that decreasing the CO pressure from 50 bar to 5 bar at 130 °C for 18 h increases yields in benzyl acetate from 36% to over 98%. Further experiments were performed in the presence of piperonyl and furfuryl alcohol, interesting substrates employed for the synthesis of various fine chemicals. Moreover, furfuryl alcohol is a lignocellulosic-derived building block employed for the synthesis of functionalized furans such as 2-alkylfurfuryl acetates. Both the alcohols were successfully transformed in the corresponding acetate (yields above 96%) in rather mild reaction conditions (5–0.01 mol% catalyst, 5–2 bar CO pressure, 130 °C, 4–18h), demonstrating that the alkoxycarbonylation of alcohols represents a promising sustainable alternative to more impactful industrial practices adopted to date for the synthesis of alkylaryl and furfuryl acetates