The invention pertains to a process for the manufacture of a perfluorovinylether by hydrodehalogenation of a halofluoroether (HFE) having general formula (I-A) or (I-B):
RfOCRfXCRfRfX(I-A)
wherein Rf represents a C1-C6 perfluoro(oxy)alkyl group; Rf, Rf and Rf, equal or different from each other, independently represent fluorine atoms or C1-C5 perfluoro(oxy)alkyl groups; X and X, equal or different from each other, are independently chosen among Cl, Br or I; ##STR00001##
wherein Rf* and Rf*, equal or different from each other, independently represent fluorine atoms or C1-C3 perfluoro(oxy)alkyl groups; Y1 and Y2, equal or different from each other, independently represent fluorine atoms or C1-C3 perfluoroalkyl groups; X and X are as above defined;
said process comprising contacting said halofluoroether (HFE) with hydrogen in the presence of a catalyst comprising palladium and at least one transition metal (M) selected from the group consisting of the metals of group VIIIB, other than palladium, and of group IB.

The invention pertains to a process for the manufacture of a perfluorovinylether by hydrodehalogenation of a halofluoroether (HFE) having general formula (I-A) or (I-B):
RfOCRfXCRfRfX(I-A)
wherein Rf represents a C1-C6 perfluoro(oxy)alkyl group; Rf, Rf and Rf, equal or different from each other, independently represent fluorine atoms or C1-C5 perfluoro(oxy)alkyl groups; X and X, equal or different from each other, are independently chosen among Cl, Br or I; ##STR00001##
wherein Rf* and Rf*, equal or different from each other, independently represent fluorine atoms or C1-C3 perfluoro(oxy)alkyl groups; Y1 and Y2, equal or different from each other, independently represent fluorine atoms or C1-C3 perfluoroalkyl groups; X and X are as above defined;
said process comprising contacting said halofluoroether (HFE) with hydrogen in the presence of a catalyst comprising palladium and at least one transition metal (M) selected from the group consisting of the metals of group VIIIB, other than palladium, and of group IB.

The invention pertains to a process for the manufacture of a perfluorovinylether by hydrodehalogenation of a halofluoroether (HFE) having general formula (I-A) or (I-B):
RfOCRfXCRfRfX(I-A)
wherein Rf represents a C1-C6 perfluoro(oxy)alkyl group; Rf, Rf and Rf, equal or different from each other, independently represent fluorine atoms or C1-C5 perfluoro(oxy)alkyl groups; X and X, equal or different from each other, are independently chosen among Cl, Br or I; ##STR00001##
wherein Rf* and Rf*, equal or different from each other, independently represent fluorine atoms or C1-C3 perfluoro(oxy)alkyl groups; Y1 and Y2, equal or different from each other, independently represent fluorine atoms or C1-C3 perfluoroalkyl groups; X and X are as above defined;
said process comprising contacting said halofluoroether (HFE) with hydrogen in the presence of a catalyst comprising palladium and at least one transition metal (M) selected from the group consisting of the metals of group VIIIB, other than palladium, and of group IB.

Device and methods for use in a biosensor comprising a multisite array of test sites, the device and methods being useful for modulating the binding interactions between a (biomolecular) probe or detection agent and an analyte of interest by modulating the pH or ionic gradient near the electrodes in such biosensor. An electrochemically active agent that is suitable for use in biological buffers for changing the pH of the biological buffers. Method for changing the pH of biological buffers using the electrochemically active agents. The methods of modulating the binding interactions provided in a biosensor, analytic methods for more accurately controlling and measuring the pH or ionic gradient near the electrodes in such biosensor, and analytic methods for more accurately measuring an analyte of interest in a biological sample.

Device and methods for use in a biosensor comprising a multisite array of test sites, the device and methods being useful for modulating the binding interactions between a (biomolecular) probe or detection agent and an analyte of interest by modulating the pH or ionic gradient near the electrodes in such biosensor. An electrochemically active agent that is suitable for use in biological buffers for changing the pH of the biological buffers. Method for changing the pH of biological buffers using the electrochemically active agents. The methods of modulating the binding interactions provided in a biosensor, analytic methods for more accurately controlling and measuring the pH or ionic gradient near the electrodes in such biosensor, and analytic methods for more accurately measuring an analyte of interest in a biological sample.

An object is to provide a process for providing hydrogen or heavy hydrogens conveniently without the necessity of large-scale equipment and a process capable of performing hydrogenation (protiation, deuteration or tritiation) reaction conveniently without the use of an expensive reagent and a special catalyst. The production process includes a process for producing hydrogen or heavy hydrogens, containing subjecting water or heavy water to mechanochemical reaction in the presence of a catalyst metal, and a process for producing a hydrogenated (protiated, deuterated or tritiated) organic compound, containing subjecting an organic compound and water or heavy water to mechanochemical reaction in the presence of a catalyst metal.

An object is to provide a process for providing hydrogen or heavy hydrogens conveniently without the necessity of large-scale equipment and a process capable of performing hydrogenation (protiation, deuteration or tritiation) reaction conveniently without the use of an expensive reagent and a special catalyst. The production process includes a process for producing hydrogen or heavy hydrogens, containing subjecting water or heavy water to mechanochemical reaction in the presence of a catalyst metal, and a process for producing a hydrogenated (protiated, deuterated or tritiated) organic compound, containing subjecting an organic compound and water or heavy water to mechanochemical reaction in the presence of a catalyst metal.

An object is to provide a process for providing hydrogen or heavy hydrogens conveniently without the necessity of large-scale equipment and a process capable of performing hydrogenation (protiation, deuteration or tritiation) reaction conveniently without the use of an expensive reagent and a special catalyst. The production process includes a process for producing hydrogen or heavy hydrogens, containing subjecting water or heavy water to mechanochemical reaction in the presence of a catalyst metal, and a process for producing a hydrogenated (protiated, deuterated or tritiated) organic compound, containing subjecting an organic compound and water or heavy water to mechanochemical reaction in the presence of a catalyst metal.

In accordance with the purpose(s) of the present disclosure, as embodied and broadly described herein is versatile polyene cyclization strategy that exploits conjugated -ionyl derivatives. Photomediated disruption of the extended -system within these chromophores unveils a contra-thermodynamic polyene that engages in a Heck-type cyclization to afford [4.4.1]-propellanes. The connectivity of overbred polycycles generated from this process is controlled by the position of the requisite C-Halide bond. Thus, compared to conventional biomimetic polyene cyclization, this approach allows for complete control of regiochemistry and facilitates incorporation of both electron-rich and electron-deficient (hetero)aryl groups. This strategy was successfully applied to the total synthesis of abietanes such as, for example, taxodione and salviasperanol, two isomeric abietane-type diterpenes that previously could not be prepared along the same synthetic pathway.

In accordance with the purpose(s) of the present disclosure, as embodied and broadly described herein is versatile polyene cyclization strategy that exploits conjugated -ionyl derivatives. Photomediated disruption of the extended -system within these chromophores unveils a contra-thermodynamic polyene that engages in a Heck-type cyclization to afford [4.4.1]-propellanes. The connectivity of overbred polycycles generated from this process is controlled by the position of the requisite C-Halide bond. Thus, compared to conventional biomimetic polyene cyclization, this approach allows for complete control of regiochemistry and facilitates incorporation of both electron-rich and electron-deficient (hetero)aryl groups. This strategy was successfully applied to the total synthesis of abietanes such as, for example, taxodione and salviasperanol, two isomeric abietane-type diterpenes that previously could not be prepared along the same synthetic pathway.