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  Method for the functionalization of conjugated or conjugatable derivatives assisted by a tempo-type electrophoric mediatorUSPTO Application #: 20070197790Title: Method for the functionalization of conjugated or conjugatable derivatives assisted by a tempo-type electrophoric mediator Abstract: The invention relates to a method for the functionalization of a chemical molecule having at least two double bonds or containing a double bond which is conjugated with a structure that is rich in electrons in the presence of a TEMPO-type electrophoric mediator and a nucleophilic agent. The functionalization method can also include a system for electrochemical regeneration of the electrophoric mediator. (end of abstract)
Agent: David R Preston & Associates Apc - San Diego, CA, US Inventors: El Mustapha Belgsir, Tony Breton, Denis Liaigre USPTO Applicaton #: 20070197790 - Class: 546184000 (USPTO) Related Patent Categories: Organic Compounds -- Part Of The Class 532-570 Series, Azo Compounds Containing Formaldehyde Reaction Product As The Coupling Component, Carbohydrates Or Derivatives, Hetero Ring Is Six-membered Consisting Of One Nitrogen And Five Carbons, Piperidines The Patent Description & Claims data below is from USPTO Patent Application 20070197790. Brief Patent Description - Full Patent Description - Patent Application Claims
[0001] The present invention relates to a method of functionalising a chemical molecule having at least two conjugated or conjugatable double bonds or containing at least one double bond conjugated with an electron-rich structure. Said functionalisation is obtained by the addition of nucleophile compounds (Nu) comprising at least one atom chosen from among oxygen (O), nitrogen (N), sulphur (S), fluorine (F) or iodine (I). [0002] Among the advantages of the method according to the invention, the following are notable: [0003] the rate of unsaturation of the functionalised molecule is not reduced after functionalisation; [0004] the functionalisation is assisted by an oxidation mediator, [0005] the transformations are carried out under normal conditions of temperature and pressure. [0006] In very general terms, the invention relates to a method of functionalising a chemical molecule having at least two double bonds or containing at least one double bond conjugated with an electron-rich structure, in the presence of an electrophorus mediator and a nucleophile compound. [0007] According to a specific embodiment of the invention, the functionalisation method can also include a system of electrochemical regeneration of the electrophorus mediator. [0008] Functionalisation is used in the context of the present invention to refer to the introduction of functional grouping in an unsaturated molecule, linear or cyclic, conjugated or conjugatable, having at least two double bonds or containing at least one double bond conjugated with an electron-rich structure. By way of example, the functionalisation of a non-conjugated diolefin produces a functionalised conjugated diolefin (Formula I): [0009] Nucleophile compound is used in the context of the invention to refer to any chemical molecule with excess electrons and which is therefore capable of affecting species that are lacking electrons and which comprise at least one atom chosen from among oxygen (O), nitrogen (N), sulphur (S), fluorine (F) or iodine (I). The nucleophile compound preferably comprises an atom chosen from between oxygen (O) and sulphur (S). [0010] Electrophorus mediatoris used in the context of the invention to refer to the so-called oxidised form (called oxoammonium or nitrosonium) of a molecule comprising at least one aminoxyl radical (Formula II): p in which R.sub.1 and R.sub.2 are groups, identical or different, cyclic or linear. [0011] According to the invention, the electrophorus mediator is preferably the oxoammonium form of a chemical molecule of the bi-permethylated aminoxyl radical family containing at least one aminoxyl radical. [0012] An example of the above is 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO) or 4-acetamido-TEMPO (Formula III): [0013] The preparation of the mediator based on the aminoxyl radical can be carried out: [0014] either by electrochemical oxidation of said aminoxyl radical with the anode of an electrochemical system according to, for example, Semmelhack et al. (J. Am. Chem. Soc., 1983, 105, 4492-4494); [0015] or by the action of a strong acid on said aminoxyl radical. The oxoammonium form is then obtained in the form of salts according to Golubev et al. (Ser. Khim. 1965, 1927). [0016] According to the invention, the mediator can be used in stoichiometric quantity or in catalytic quantity, assisted by an electrochemical system. [0017] When the mediator is used in stoichiometric quantity, the functionalisation can be carried out at temperatures ranging from 0.degree. C. to 80.degree. C., preferably from 5.degree. C. to 40.degree. C., with a pH ranging from 0 to 13, preferably from 4 to 7, according to two methods: The Chemical Method: [0018] In a first step, the molecule to be functionalised, at least one equivalent of mediator and at least one equivalent of a nucleophile compound are successively added to a reaction chamber containing an organic or hydro-organic reaction medium. In a second step, the mixture is subjected to mechanical or magnetic stirring for 1 to 10 hours, preferably for 2 to 5 hours. In a third step, the reaction mixture is purified according to protocols known to those skilled in the trade. The Electrochemical Method: [0019] In a first step, an aminoxyl radical is inserted in at least stoichiometric quantity in an electrolytic solution containing a support electrolyte. The aminoxyl is oxidised in oxoammonium (the mediator). The oxidation reaction takes place by subjecting the working electrode to a potential that can be comprised between 0 and 1.2 volts, preferably between 0 and 0.6 volts in relation to an Ag/AgNO.sub.3 reference electrode. The potential is applied with the help of a generator and controlled by means of a potentiostat, until the aminoxyl radical is completely transformed into oxoammonium ions. [0020] In a second step, with zero potential, the molecule to be functionalised and at least one equivalent of nucleophile are successively inserted. [0021] In this case, the amount of mediator can be 0.5 to 5 equivalents in relation to the molecule to be functionalised, preferably from 1 to 4 equivalents, according to the desired speed of reaction and the type of nucleophile. [0022] The solution can be stirred for a time comprised between 1 and 10 hours, preferably comprised between 2 and 5 hours. Continue reading... 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