- INJECTIBLE CYANOACRYLATE-FUNCTIONALIZED POLYISOBUTYLENES
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The present invention generally relates to injectible polyisobutylene polymer compounds. More specifically, the present invention relates to injectible polyisobutylene polymer compounds that are designed for various biological and medical applications. In one embodiment, the present invention relates to injectible functionalized polyisobutylene polymer compounds that are designed for various biological and medical applications. In another embodiment, the present invention relates to injectible cyanoacrylate-functionalized polyisobutylene polymer compounds.
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Paragraph 0100
(2016/08/03)
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- Generation of iminyl copper species from α-azido carbonyl compounds and their catalytic C-C bond cleavage under an oxygen atmosphere
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Figure presented A copper-catalyzed reaction of α-azidocarbonyl compounds under an oxygen atmosphere is reported where nitriles are formed via C-C bond cleavage of a transient iminyl copper intermediate. The transformation is carried out by a sequence of denitrogenative formation of iminyl copper species from α-azidocarbonyl compounds and their C-C bond cleavage, where molecular oxygen (1 atm) is a prerequisite to achieve the catalytic process and one of the oxygen atoms of O2 was found to be incorporated into the β-carbon fragment as a carboxylic acid.
- Chiba, Shunsuke,Zhang, Line,Ang, Gim Yean,Hui, Benjamin Wei-Qiang
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supporting information; experimental part
p. 2052 - 2055
(2010/07/04)
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- Alkane oxygenation with H2O2 catalysed by FeCl 3 and 2,2′-bipyridine
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The H2O2-FeCl3-bipy system in acetonitrile efficiently oxidises alkanes predominantly to alkyl hydroperoxides. Turnover numbers attain 400 after 1 h at 60°C. It has been assumed that bipy facilitates proton abstraction from a H2O2 molecule coordinated to the iron ion (these reactions are stages in the catalytic cycle generating hydroxyl radicals from the hydrogen peroxide). Hydroxyl radicals then attack alkane molecules finally yielding the alkyl hydroperoxide.
- Shul'pin, Georgiy B.,Golfeto, Camilla C.,Süss-Fink, Georg,Shul'pina, Lidia S.,Mandelli, Dalmo
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p. 4563 - 4567
(2007/10/03)
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- Hydrocarbon Oxidations with Hydrogen Peroxide Catalyzed by a Soluble Polymer-Bound Manganese(IV) Complex with 1,4,7-Triazacyclononane
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Soluble manganese(IV) complexes with polymer-bound 1,4,7-triazacyclononanes as ligands (compound 2) catalyze the oxidation of alkanes by hydrogen peroxide in acetonitrile at room and lower temperatures. The corresponding alkyl hydroperoxides are the main products. The presence of a relatively small amount of acetic acid is obligatory for this reaction. The oxidation of alkanes and olefins exhibits some features (kinetic isotope effect, bond selectivities) that distinguish this system from an analogous one based on the dinuclear Mn(IV) complex 1.
- Nizova, Galina V.,Bolm, Carsten,Ceccarelli, Simona,Pavan, Chiara,Shul'pin, Georgiy B.
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p. 899 - 905
(2007/10/03)
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- The kinetics and selectivity of the decomposition of diacyl peroxides under high pressure in hydrocarbon solution
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The decomposition kinetics of bis(3,5,5-trimethylhexanoyl) peroxide (BTMHP), dioctanoyl peroxide and dibenzoyl peroxide have been monitored under high pressure using time-resolved FTIR spectroscopy. Two experimental methods, one discontinuous the other continuous, were used for BTMHP, and their complementary nature allows measurement of the kinetics in an extended range of decomposition half-lives. Using n-heptane as solvent, investigations were carried out at temperatures from 60 up to 160°C, and in the pressure range 1 to 2500 bar. For BTMHP an activation energy of (131.2±6.5) kJ mor-1 was determined at 1500 bar. The value found at the same pressure for dioctanoyl peroxide is identical within experimental error, whilst that of dibenzoyl peroxide is slightly lower. An activation volume of ΔV≠ = (2.9±0.1) cm3 mol-1 was evaluated for the decomposition of BTMHP, and those of the remaining two peroxides found to be similar. The selectivity of the decomposition of BTMHP was considered by means of GC analysis. Using n-heptane and n-pentadecane as solvents, the effect of pressure on product distributions has been gauged from 1 to 2000 bar at 80°C. For the two main decomposition products, 2,4,4-trimethyl pentane (TMP) and 2,2,4,7,9,9-hexamethyl decane (HMD), pressure was found to enhance the formation of in-cage alkane dimer (HMD) relative to out-of-cage alkane (TMD). ? by R. Oldenbourg Verlag, 1996.
- Buback, Michael,Hinton, Cassandra
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- ORGANOBORANES FOR SYNTHESIS. 5. STOICHIOMETRICALLY CONTROLLED REACTION OF ORGANOBORANES WITH OXYGEN UNDER MILD CONDITIONS TO ACHIEVE QUANTITATIVE CONVERSION TO ALCOHOLS
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The reaction of organoboranes with oxygen under mild conditions can be controlled to give an essentially quantitative conversion of all three alkyl groups on boron to the corresponding alcohol.The controlled oxidation is a very clean reaction, with only minor amounts of carbonyl and hydrocarbon products formed.All organoboranes react quite rapidly in the initial stages, but vary considerably in the time required to achieve the desired uptake of oxygen.In contrast to oxidation by alkaline hydrogen peroxide, a portion of this reaction proceeds through alkyl radicals, thus resulting in some loss of stereospecificity.Oxidation of mixed organoboranes reveals that the relative rates of oxidation of alkyl groups on boron are consistent with a radical mechanism, with tertiary > secondary > primary in the rate of oxidation.The selective oxidation of one alkyl group in the presence of the other is not possible, due to small differences in relative rates of oxidation.However, thexyl and cyclohexyl groups can be selectively removed from boron in the presence of alkenyl groups.Thus, controlled oxidation of thexyldialkenylborane affords pure dialkenylborinic acid.
- Brown, Herbert C.,Midland, M. Mark,Kabalka, George W.
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p. 5523 - 5530
(2007/10/02)
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- ORGANOBORANES FOR SYNTHESIS. 2. OXIDATION OF ORGANOBORANES WITH ALKALINE HYDROGEN PEROXIDE AS A CONVENIENT ROUTE FOR THE cis-HYDRATION OF ALKENES via HYDROBORATION
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Aqueous hydrogen peroxide in the presence of dilute alkali effects the oxidation of organoboranes.The conditions necessary for a clean and quantitative transformation of organoboranes into the corresponding alcohols have been established.Thus, one mole of trialkylborane reacts with three moles of hydrogen peroxide in the presence of one mole of sodium hydroxide to provide three moles of the corresponding alcohol.The concentrations of these reagents or the reaction temperature can be varied widely without affecting the yield significantly.Oxidation proceeds well in water-miscible solvents, such as diglyme and THF.However, the reaction is slow and incomplete in diethyl ether.The addition of ethanol as a cosolvent circumvents this difficulty.Wide variations in the structure of organoboranes do not affect the reaction greatly.A variety of common organic functional groups, such as alkenes, alkynes, esters, ketones, nitriles, etc., are unaffected under the normal oxidation conditions.However, aldehydes are somewhat unstable under these conditions, although they do not interfere with the oxidation of organoboranes
- Brown, Herbert C.,Snyder, Carl,Rao, B. C. Subba,Zweifel, George
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p. 5505 - 5510
(2007/10/02)
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