摘要:
The method relates to the field of asymmetric allylic amination and comprises preparing a chiral N-substituted allylic amine compound from the corresponding allylic substrates and substituted hydroxylamines, in the presence of a catalyst, said catalyst comprising copper compounds and a chiral ligand. Examples of chiral amine compounds which can be made using the method include Vigabatrin, Ezetimibe Terbinafine, Naftifine 3-methylmorphine, Sertraline, Cinacalcet, Mefloquine hydrochloride, and Rivastigmine. There are over 20,000 known bioactive molecules with chiral N-substituted allylic amine substructure. The method may also be used to produce non-natural chiral β-aminoacid esters, a sub-class of chiral N-substituted allylic amine compounds. Examples of β-aminoacid ester which can be produced by the disclosed method, include, but are not limited to, N-(2-methylpent-1-en-3-yl)benzenamine and Ethyl 2-methylene-3-(phenylamino)butanoate. Further, the products of the method described herein can be used to produce chiral heterocycles and bioactive molecules or materials. A novel chiral copper-ligand nitrosoarene complex is also set forth.
摘要:
A process for preparing high molecular weight, branched, acyclic polyalkyleneamines comprising transaminating a reaction mixture that includes at least a first polyalkyleneamine component that contains at least two non-tertiary amine groups separated from one another by a ternary or higher carbon atom and a second polyalkyleneamine component having the formula wherein x, y, and z are the same or different and are integers of from 1 to 10; a, b, c, d, e, and f are the same or different and are H or hydrocarbyl of from 1 to 10 carbon atoms; A, B, C, D, E, are the same or different and are H or hydrocarbyl of from 1 to 10 carbon atoms; provided that at least two of the amine groups are primary or secondary.
摘要:
An organometallic complex of a tridentate bis(phosphine)-carbodicarbene ligand and a transition metal, is described. In some embodiments the ligand has the structure of Formula (I): The complexes are useful in methods of making an allylic amine carried out by reacting a 1,3-diene with a substituted amine in the presence of such an organometallic complex to produce by intermolecular hydroamination the allylic amine.
摘要:
The present invention provides novel synthetic methods for making acyclic secondary amines by reacting an azide with a compound bearing one or more C—H groups, catalyzed by a FeII-dipyrromethene complex. The acyclic secondary amines are thought to be formed through an intermolecular nitrene transfer. Also provided herein are methods of synthesizing protected (e.g., Boc- or Fmoc-protected) cyclic secondary amines (e.g., 5-, 6-, and 7-membered cyclic secondary amines) by reacting an azide that bears one or more C—H groups, catalyzed by a FeII-dipyrromethene complex. The protected cyclic secondary amines are thought to be formed through an intramolecular nitrene transfer and may be subsequently deprotected to yield cyclic secondary amines.
摘要:
Process for the direct amination of hydrocarbons to aminohydrocarbons, which comprises the steps: a) reaction of a feed stream E comprising at least one hydrocarbon and at least one aminating reagent to form a reaction mixture R comprising aminohydrocarbons and hydrogen and b) electrochemical separation of at least part of the hydrogen formed in the reaction from the reaction mixture R by means of a gastight membrane-electrode assembly having at least one selectively proton-conducting membrane and at least one electrode catalyst on each side of the membrane, where at least part of the hydrogen is oxidized to protons over the anode catalyst on the retentate side of the membrane and the protons are, after passing through the membrane, b1) reduced to hydrogen and/or b2) reacted with oxygen from an oxygen-comprising stream O which is brought into contact with the permeate side of the membrane to form water over the cathode catalyst on the permeate side.
摘要:
Process for the direct amination of hydrocarbons to aminohydrocarbons by reaction of a feed stream E comprising at least one hydrocarbon and at least one aminating reagent to form a reaction mixture R comprising aminohydrocarbon and hydrogen in a reaction zone RZ and electrochemical separation of at least part of the hydrogen formed in the reaction from the reaction mixture R by means of a gastight membrane-electrode assembly having at least one selectively proton-conducting membrane and at least one electrode catalyst on each side of the membrane, where at least part of the hydrogen is oxidized to protons at the anode catalyst on the retentate side of the membrane and the protons pass through the membrane and on the permeate side are reacted with oxygen to form water, where the oxygen originates from an oxygen-comprising stream O which is brought into contact with the permeate side of the membrane, over the cathode catalyst.
摘要:
The invention teaches novel process steps for the rapid high yield manufacture of diphenylamines of the formula wherein R1 is selected from hydrogen, alkyl, and aryl; wherein each R2 and R3 is the same or different and each is independently selected from hydrogen, alkyl, alkoxy, aralkyl, dialkylamino, alkylarylamino and substituted or unsubstituted aryl, the substituents on aryl being each independently selected from alkyl (C1-C8), alkoxy (C1-C8), aroxy, aralkoxy and halogen; wherein n and m are each independently an integer from 1 to 5. Diphenylamines are key intermediates for the production of leuco dyes used in pressure-sensitive and heat-sensitive imaging systems. The process in at least one embodiment comprises reacting at elevated temperature an aryl halide with an aromatic amine in an organic solvent and aqueous alkaline solution and optionally in some embodiments, phase-transfer agent, followed by addition of catalytic amounts of bis[tri(t-butylphosphine)]palladium at a suitable temperature to rapidly form diphenylamine.
摘要:
A process is disclosed for preparing ortho substituted phenylamines comprising contacting phenylhydroxylamine, optionally substituted with at least one inert substituent, with a nucleophilic reagent in the presence of a manganese oxide at a temperature between about 10° C. and about 170° C. and a pressure from subatmospheric to superatmospheric such that an ortho substituted phenylamine, optionally correspondingly substituted with at least one inert substituent, is predominantly formed.
摘要:
Process for the production of an aromatic amine by reacting an aromatic hydrocarbon with ammonia at a temperature of less than 500null C. and a pressure of less than 10 bara in the presence of a catalyst comprising at least one metal selected from the group consisting of the transition elements, lanthanides and actinides, preferably in the presence of an oxidant.
摘要:
Process for the production of an aromatic amine by reacting an aromatic hydrocarbon with ammonia at a temperature of less than 500° C. and a pressure of less than 10 bara in the presence of a catalyst comprising at least one metal selected from the group consisting of the transition elements, lanthanides and actinides, preferably in the presence of an oxidant.