- 1,2,3-Trimethoxypropane and glycerol ethers as bio-sourced solvents from glycerol: Synthesis by solvent-free phase-transfer catalysis and utilization as an alternative solvent in chemical transformations
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1,2,3-Trimethoxypropane (2), 1-alkoxy-2,3-dimethoxy-propanes, and 1-aryloxy-2,3-dimethoxypropanes were prepared in good yields and selectivity by solid-liquid phase-transfer catalysis in the presence of an inorganic base and an ammonium salt as the phase-transfer catalyst with no additional solvent. No heating was required, and the synthesis was easily performed under atmospheric pressure on a 150g scale. For the preparation of 2, the conversion of glycerol was complete and the selectivity for the expected glycerol trimethylether was above 95%. This product was utilized as a solvent in organic reactions such as transesterifications between glycerol and vegetable oil, organometallic reactions (Grignard- and Barbier-type reactions), carbon-carbon coupling reactions (Suzuki, Sonogashira, Heck), and in etherification reactions by dehydrogenative alkylation. The solvent showed interesting properties for the solubilization of polymers.
- Sutter, Marc,Dayoub, Wissam,Metay, Estelle,Raoul, Yann,Lemaire, Marc
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p. 2893 - 2904
(2013/10/21)
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- Cyclopentadienyl and pentamethylcyclopentadienyl ruthenium complexes as catalysts for the total deoxygenation of 1,2-hexanediol and glycerol
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The ruthenium aqua complexes [cp*Ru(OH2)(N-N)](OTf) (cp* = η5-pentamethylcyclopentadienyl, N-N = 2,2′-bipyridine, phen = 1,10-phenanthroline, OTf- = trifluoromethanesulfonate) and the acetonitrile complex [cpRu(CH 3CN)(bipy)](OTf) (cp = η5-cyclopentadienyl) are water-, acid-, and thermally stable (>200°C) catalysts for the hydrogenation of aldehydes and ketones in sulfolane solution. In the presence of HOTf as a co-catalyst, they effect the deoxygenation of 1,2-hexanediol to 1-hexanol and hexane. Glycerol is deoxygenated to 1-propanol in up to 18% yield and under more forcing conditions completely deoxygenated to propene. The structure of the acetonitrile pro-catalyst [cpRu(CH3CN)(bipy)](OTf) has been determined by X-ray crystallography (space group P1 (a = 9.3778(10) A; b = 10.7852(10) A; c = 11.1818(13) A; α = 101.718(5)°; β = 114.717(4)°; γ = 102.712(5)°; R = 3.95%).
- Thibault, Michelle E.,Dimondo, Domenico V.,Jennings, Michael,Abdelnur, Patricia Verardi,Eberlin, Marcos N.,Schlaf, Marcel
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experimental part
p. 357 - 366
(2011/04/18)
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- BORON-CONTAINING SMALL MOLECULES
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Compounds, pharmaceutical formulations, and methods of treating anti-inflammatory conditions and/or helminth-associated diseases are disclosed.
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Page/Page column 162
(2011/08/21)
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- 2-PHENYL-6-AMINOCARBONYL-PYRIMIDINE DERIVATIVES AND THEIR USE AS P2Y12 RECEPTOR ANTAGONISTS
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The invention relates to 2-phenyl-6-aminocarbonyl-pyrimidine derivatives and their use as P2Y12 receptor antagonists in the treatment and/or prevention and/or treatment of peripheral vascular, of visceral-, hepatic- and renal-vascular, of cardiovascular and of cerebrovascular diseases or conditions associated with platelet aggregation, including thrombosis in humans and other mammals. Formula (I).
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Page/Page column 21
(2010/01/29)
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- 2-PHENYL-6-AMINOCARBONYL-PYRIMIDINE DERIVATIVES AND THEIR USE AS P2Y12 RECEPTOR
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The invention relates to 2-phenyl-6-aminbcarbonyl-pyrimidinc derivatives and their use as P2Y12 receptor antagonists in the treatment and/or prevention and/or treatment of peripheral vascular, of visceral-, hepatic- and renal-vascular, of cardiovascular and of cerebrovascular diseases or conditions associated with platelet aggregation, including thrombosis in humans and other mammals. Formula (1).
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Page/Page column 13
(2009/12/05)
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- α-(Acyloxy)dialkylnitrosamines: Effects of structure on the formation of N-nitrosiminium ions and a predicted change in mechanism
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The decay of α-(acyloxy)dialkylnitrosamines in aqueous solutions has been studied with a view toward elucidating mechanistic details and effects of structure on mechanism and reactivity. Rate constants (k1) for the pH-independent decay of 43 α-(acyloxy)dialkylnitrosamines have been determined. Observations from these and other experiments rule out decomposition via an anchimeric assistance mechanism involving the Z isomer that had previously been suggested. All of the reported data for most of the compounds is consistent with a mechanism involving the formation of N-nitrosiminium ions in or before the rate-limiting step. Structure -reactivity correlations indicate that the stability of α-(acyloxy)dialkylnitrosamines is determined by electronic properties of substituents at RN and RC as well as by the ability of substituents RC to engage in hyperconjugative interactions of C-H bonds with the developing cationic center in the transition state for nitrosiminium ion formation. Attachment of substituents of sufficient electron-withdrawing power at RN and RC results in a predicted change in mechanism to what appears to be an acyl group attack mechanism.
- Hongliang, Cai,Fishbein, James C.
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p. 1826 - 1833
(2007/10/03)
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- 2-SACCHARINYLMETHYL ARYL CARBOXYLATES USEFUL AS PROTEOLYTIC ENZYME INHIBITORS AND COMPOSITIONS AND METHOD OF USE THEREOF
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A compound having the formula: STR1 wherein Ar, R 4 and R 5 are defined herein have pharmaceutical utility as proteolytic enzyme inhibitors.
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- 2-SACCHARINYLMETHYL ARYL AND ARYLOXY ACETATES USEFUL AS PROTEOLYTIC ENZYME INHIBITORS
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4-R 4--R 5-2-Saccharinylmethyl aryl and aryloxy acetates, useful in the treatment of degenerative diseases, are prepared by reacting a 4-R. sup.4--R 5-2-halomethylsaccharin with an aryl or aryloxyacetic acid in the presence of an acid-acceptor.
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- Asymmetric synthesis using reactions with modest group selectivity
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The isomeric purity of products from certain group-selective reactions can be significantly amplified when reactions can occur sequentially.The theoretical basis for a strategy that exploits reactions with modest enantiotopic group selectivity for asymmet
- Ward, Dale E.,Liu, YaDong,Rhee, Chung K.
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p. 1429 - 1446
(2007/10/02)
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- 2-SACCHARINYLMETHYL PHOSPHATES, PHOSPHONATES AND PHOSPHINATES USEFUL AS PROTEOLYTIC ENZYME INHIBITORS AND COMPOSITIONS AND METHOD OF USE THEREOF
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4-R 1-R 2-R 3-2-Saccharinylmethyl and 4,7-C-4,5, 6,7-tetrahydro-2-saccharinylmethyl phosphates, phosphonates and phosphinates of formulas I and IIA respectively herein, useful in the treatment of degenerative diseases, and compositions containing them, methods for using them to treat degenerative diseases, and processes for their preparation by reaction of the corresponding 2-halomethylsaccharins with a phosphate, phosphonate or phosphinic acid of formula III herein in the presence of an acid-acceptor.
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- 2-SACCHARINYLMETHYL HETEROCYCLIC CARBOXYLATES USEFUL AS PROTEOLYTIC ENZYME INHIBITORS
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4-R 4-R 5-2-Saccharinylmethyl heterocyclic carboxylates, useful in the treatment of degenerative diseases, are prepared by reacting a 4-R. sup.4-R 5-2-halomethylsaccharin with either a heterocyclic carboxylic acid in the presence of an acid-acceptor or th
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- TETRAHYDRO 2-SACCHARINYLMERTHYL ARYL CARBOXYLATES
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4-R 4-R 5-Saccharinylmethyl aryl carboxylates, useful in the treatment of degenerative diseases, are prepared by reacting a 4-R 4-R 5-2-halomethylsaccharin with an arylcarboxylic acid in the presence of an acid-acceptor.
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- 2-SACCHARINYLMETHYL AND 4,5,6,7-TETRAHYDRO-2-SACCHARINYLMETHYL PHOSPHATES, PHOSPHONATES AND PHOSPHINATES USEFUL AS PROTEOLYTIC ENZYME INHIBITORS AND COMPOSITIONS AND METHOD OF USE THEREOF
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4-R 1-R 2-R 3-2-Saccharinylmethyl, 4-R 4-4-R 5-6-R 6-4,5,6,7-tetrahydro-2-saccharinylmethyl and 4,7-C-4,5, 6,7-tetrahydro-2-saccharinylmethyl phosphates, phosphonates and phosphinates of formulas I, II and IIA respectively herein, useful in the treatment of degenerative diseases, and compositions containing them, methods for using them to treat degenerative diseases, and processes for their preparation by reaction of the corresponding 2-halomethylsaccharins with a phosphate, phosphonate or phosphinic acid of formula III herein in the presence of an acid-acceptor.
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- PROTEOLYTIC ENZYME INHIBITION METHOD
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4-R 4-R 5-2-Saccharinylmethyl aryl carboxylates, useful in the treatment of degenerative diseases, are prepared by reacting a 4-R. sup.4-R 5-2-halomethylsaccharin with an arylcarboxylic acid in the presence of an acid-acceptor.
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