Abstract:
PURPOSE: To efficiently obtain an indene derivative expressed by a specific formula and useful as a synthetic intermediate for CD ring part in simple synthesis of 1α,25-dihydroxyvitamine D3 in a short process. CONSTITUTION: This derivative is expressed by formula I [R is H, a 2-8C acyl or a tri(1-6C hydrocarbon)-substituted silyl, e.g. (6R)-6-[(4S, 7aS)-4-benzoyloxy-7a- methylinden-1-yl]-2-nitro-3-heptanol. Furthermore, the compound is preferably obtained by reacting a compound of formula II in the presence of a basic catalyst such as triethylamine in an organic solvent such as nitroethane or tetrahydrofuran or a mixed solvent of an organic solvent with water at 0 deg.C to ambient temperature. The compound of formula I is used as a raw material and successively reacted and converted into a compound of formula III, which is then reacted with a methylating agent (e.g. methyllithium) and as necessary, an OH-protecting group is removed. Thereby, a compound of formula IV is preferably obtained.
Abstract:
PURPOSE:To provide a method for synthesizing hydrazinium nitroformate, capa ble of securing the safety, simply synthesizing the objective compound and raising the yield, by maintaining optimum reaction conditions and establishing safe handling of an intermediate. CONSTITUTION:In synthesizing hydrazinium nitroformate (HNF) by using acetic anhydride and nitric acid, (1) acetic anhydride 18 reacted with fuming nitric acid (1.52 specific gravity) at 25 to 30 deg.C while successively continuing stirring to synthesize tetranitromethane. (2) The tetranitromethane is reacted with potassium.hydroxide in an aqueous solution of glycerol to provide a potassium salt of trinitromethane (nitroform as another name) and then (3) the potassium salt is reacted with sulfuric acid prepared by diluting concentrated sulfuric acid with water (about 1:1). Nitroform dissolved in water together with nitroform made into an oily state and floating on the upper layer is extracted with an ether while cooling with water and the ether recovered to provide the nitroform. (4) The prepared nitroform is dissolved in methanol and reacted with hydrazine hydrate to provide HNF.
Abstract:
The present invention relates to a new chemical synthesis, intermediates and catalysts useful for the preparation of the neprilysin (NEP) inhibitor sacubitril, inter alia via nitro 5 compounds. It further relates to new intermediate compounds and their use for said new chemical synthesis route, as well as a new catalyst ligand.
Abstract:
This application discloses provides a process for the introduction of nitro-group functionality into a compound which contains also a site of unsaturation and/or oxygen functionality by direct (one step) oxidation of an oxime functional group mediated by a molybdenum VI/VII peroxo complex, the process comprising: (a) providing a substrate of Formula I containing an oxime functional group; Chemical formula should be inserted here as it appears on the abstract in paper form. wherein R 1 and R 2 are selected independently from linear, branched or cyclic alkyl and linear, branched or cyclic alkenyl groups, optionally substituted, with the proviso that at least one of R 1 or R 2 contains a carbon/carbon double bond; and (b) contacting said substrate of Formula I with a molybdenum oxidation complex, thereby oxidizing said oxime functional group to a nitro functional group to yield the structure of Formula III. Chemical formula should be inserted here as it appears on the abstract in paper form. Where R 1 and R 2 are as defined above.
Abstract:
A process for the preparation of nitro compounds by reacting an organic substrate with nitrogen dioxide either in the presence of oxygen or under such conditions that the nitrogen dioxide/organic substrate ratio is less than 1 by mole. The reaction may be conducted in the presence of an imide compound such as N-hydroxyphthalimide and the organic substrate includes (a) aliphatic hydrocarbons, (b) alicyclic hydrocarbons, (c) nonaromatic heterocyclic compounds having ring-constituent carbon atoms bonded to hydrogen atoms, (d) compounds bearing aromatic rings and carbon-hydrogen bonds adjacent to the rings, (e) carbonyl compounds bearing carbon-hydrogen bonds adjacent to the carbonyl groups, and so on. This process enables efficient nitration of organic substrates even under relatively mild conditions.