- Amine compound as well as preparation method and application thereof
-
The invention discloses an amine compound containing allyl or benzyl as well as a preparation method and application of the amine compound. The preparation method comprises the steps of sequentially adding a raw material 1, amine, a catalyst and an additive into a reaction solvent, and stirring and reacting for 12-24 hours in an air atmosphere at the temperature of 50-120 DEG C to obtain a reaction solution, wherein the raw material 1 is allyl alcohol or benzyl alcohol, and the molar volume ratio of the raw material 1 to the amine to the catalyst to the additive to the reaction solvent is (0.2 to 8) mmol: (0.4 to 12) mmol: (0.01 to 0.4) mmol: (0.01 to 0.4) mmol: (2 to 40) mL; and removing the reaction solvent of the reaction solution, and then carrying out purification through thin layer chromatography/column chromatography, wherein a developing solvent system is petroleum ether/ethyl acetate, and the amine compound containing allyl or benzyl is obtained. The amine compound can be applied to preparation of framework of biological and pharmaceutical active molecules. The preparation method disclosed by the invention is wide in applicable substrate range, convenient to operate, green and environment-friendly.
- -
-
-
- Synthesis method of terbinafine
-
The invention provides a synthetic method of terbinafine. Monomethylamine, 1-chloromethyl naphthalene and 1-chloro-6,6-dimethyl-2-heptene-4-alkyne are subjected to a one-step reaction to generate theterbinafine. Particularly, the monomethylamine is slowly added into a solvent, and then an acid-binding agent is added; the 1-chloromethyl naphthalene and the 1-chloro-6,6-dimethyl-2-heptene-4-alkyneare simultaneously slowly dropwise added, and a dropwise adding speed is controlled so as to enable both the 1-chloromethyl naphthalene and the 1-chloro-6,6-dimethyl-2-heptene-4-alkyne to be simultaneously dropwise added up; a temperature control reaction is performed for 2 to 3 hours at a temperature of 10 to 20 DEG C; chloroform is added to extract reaction liquid, vacuum concentration is carried out on an organic layer to a dry state, and ethyl acetate is added into residues to carry out crystallization to obtain the terbinafine. The synthetic method is high in yield, simple in step and convenient to operate, generates few byproducts, and is beneficial to industrial production.
- -
-
Paragraph 0027-0029
(2020/05/19)
-
- Removal of heavy metals from organic reaction mixtures: Preparation and application of functionalized resins
-
Using a toolbox, sulfur and amine ligands are attached to a variety of hydrophobic and hydrophilic resins, and the combinations were tested for the removal of heavy metals from a number of products, prepared by metal-catalyzed reactions. As a result, cheap combinations of silica resins and simple polyamines proved to be among the most effective metal scavengers particularly in apolar solvents such as cyclohexane. Expensive cyclic polyamines are not suitable, owing to kinetic retardation of complexation. Functionalized PEGbased polymers, originally designed for solid phase synthesis, show promising performance as metal scavengers. The results are discussed and compared to alternative approaches for purification such as salt-formation and chemical downstream transformation.
- Barbaras, Damien,Brozio, Joerg,Johannsen, Ib,Allmendinger, Thomas
-
scheme or table
p. 1068 - 1079
(2010/04/22)
-
- Expeditious enyne construction from alkynes via oxidative Pd(II)-catalyzed Heck-type coupling
-
The enyne, ubiquitous in natural products, can be a challenge to generate since these moieties require many synthetic transformations to assemble them. We developed a simpler protocol to construct enynes while we found that this oxidative reaction was tolerant in substrate scope. In addition, the utility of this reaction was demonstrated through the attempt in synthesizing antifungal agent Lamisil.
- Hadi, Victor,Yoo, Kyung Soo,Jeong, Min,Jung, Kyung Woon
-
scheme or table
p. 2370 - 2373
(2009/07/19)
-
- IMPROVED PROCESS FOR THE PREPARATION OF TERBINAFINE HYDROCHLORIDE AND NOVEL CRYSTALLINE FORM OF TERBINAFINE
-
Improved process for the preparation of Terbinafme Hydrochloride compound of formula (I): substantially free of Genotoxic impurity compound of formula (II) and Novel crystalline form of Terbinafine.
- -
-
Page/Page column 22-23
(2010/11/28)
-
- Process for the preparation of naphthylmethylamine derivatives
-
Disclosed is a process for the preparation of a naphthylmethylamine derivative or a pharmaceutically acceptable salt thereof of Formula I wherein R1 is a lower straight or branched alkyl group and R2 is a lower straight or branched alkyl group, aryl group or araylalkyl group, the process comprising reacting a N-alkyl-1-naphthylmethylamine HCl compound of Formula II: wherein R1 has the aforestated meaning, with a compound of Formula III wherein X is a halogen and R2 has the aforestated meaning in the presence of at least one base and in at least one solvent.
- -
-
Page/Page column 3
(2008/06/13)
-
- Process for the preparation of terbinafine and salts thereof
-
A process for the preparation of Terbinafine and salts thereof by reacting 1-chloro-6,6-dimethylhept-2-en-4-yne and N-methyl-N-(1-naphthylmethyl)amine in a basic aqueous medium is disclosed. Also disclosed is a process for the preparation of 1-chloro-6,6-dimethylhept-2-en-4-yne.
- -
-
Page/Page column 10-11
(2008/06/13)
-
- A PROCESS FOR THE SYNTHESIS OF TERBINAFINE AND DERIVATIVES THEREOF
-
The present invention relates to a synthetic method for terbinafine and analogues thereof using metal catalysts, preferably Ni (II) salts and/or complexes.
- -
-
Page/Page column 27-28
(2010/02/15)
-
- PURIFICATION PROCESS
-
Purification process for the preparation of the allylamine pharmaceutical terbinafine of formula (I), in free base form or acid addition salt form, by distilling crude terbinafine base, preferably by short path distillation, e.g. at a temperature above 100°C and reduced pressure, e.g. 0.2 mbar, and recovering the purified product in free base or acid addition salt form.
- -
-
Page/Page column 7
(2008/06/13)
-
- PROCESS FOR PREPARING TERBINAFINE BY USING PLATINUM AS CATALYST
-
A process for the preparation of terbinafine, comprising the reaction of a compound of formula (II), or a salt thereof, wherein X is a leaving group, with tert-butylacetylene, in the presence of a platinum catalyst.
- -
-
-
- Process for preparing terbinafine and HCI salt thereof
-
Provided are a process for preparing terbinafine or its HCl salt, which comprises: (a) reacting a furan derivative with a base; (b) performing a reductive alkylation of the resulting compound obtained in the step (a) with N-methyl-1-naphthalenemethylamine or its HCl salt; and (c) purifying the resulting compound obtained in the step (b).
- -
-
-
- Process for the preparation of terbinafine
-
A process for the preparation of terbinafine which comprises the reaction of tert-butylacetylene with a compound of formula (II) characterized in that the reaction is carried out in the presence of copper (I) salts and of a base, in the absence of palladium.
- -
-
-
- A process for the preparation of terbinafine
-
A process for the preparation of terbinafine which comprises the reaction of tert-butylacetylene with a compound of formula (II)???characterized in that the reaction is carried out in the presence of copper (I) salts and of a base, in the absence of palladium.
- -
-
-
- Weakly ligated palladium complexes PdCl2(RCN)2 in piperidine: Versatile catalysts for Sonogashira reaction of vinyl chlorides at room temperature
-
Copper iodide and weakly ligated palladium complexes PdCl2(RCN)2 (R = Ph, Me) catalyzed efficiently the coupling reaction of vinyl chlorides with 1-alkynes in the presence of piperidine to give the corresponding conjugated enynes in good to excellent yields. The reaction takes place rapidly and cleanly at room temperature. Application to the synthesis of terbinafine which exhibits strong antimycotic activity has been realized.
- Alami, Mouad,Crousse, Benoit,Ferri, Fabiola
-
p. 114 - 123
(2007/10/03)
-
- Efficient coupling reactions of lithium alkynyl(triisopropoxy)borates with aryl halides: Application to the antifungal terbinafine synthesis
-
Thermally stable lithium alkynyl(triisopropoxy)borates were reacted with several aryl halides in the presence of palladium catalysts to give the corresponding cross-coupling products in excellent yields. The present methodology has been successfully appli
- Chang Ho Oh,Seung Hyun Jung
-
p. 8513 - 8516
(2007/10/03)
-
- Methods for the manufacture of terbinafine
-
Process for the manufacture of naphthylmethylamine derivatives and among them terbinafine as potential antimycotic agents.
- -
-
-
- A two-step synthesis of terbinafine
-
An efficient and high yielding synthesis of terbinafine 1a and amino enyne derivatives 1b-f is described from amino vinyl chlorides 2a-b and 1-alkynes in the presence of a weak ligated palladium complex: PdCl2(PhCN)2 in piperidine.
- Alami, Mouad,Ferri, Fabiola,Gaslain, Yann
-
-
- -
-
In exploring versatile synthetic routes to (E)-allylamine derivatives with antimycotic properties, a new method has been found in the trans-reduction of tertiary 2-alkinylanunes by diisobutylaluminum hydride (DIBAH). The stereoselectivity of this reaction, which is in contrast to the well-known cis-hydroalumination of disubstituted alkynes, and the regioselectivity have been studied in detail. Tertiary 2-alkinylamines 1 were generally reduced to (E)-2-alkenylamines 2 in toluene at 40°, and tertiary 2,4-alkadiynylamines 3 yielded a mixture of(E)-2-alken-4-ynylamines 4 and 2(E),4(Z)-alkadienylamines 5 in high stereochemical purity. This reduction was clearly different with respect to reactivity and selectivity in comparison with other reactions also proceeding via trans-hydroalumination, namely the lithium aluminum hydride reduction of α-hydroxyacetylenes and the reaction of alkynes with LiAlH(iso-Bu)2(n-Bu). Tertiary 6-hydroxy-2, 4-alkadiynylamines 10 were reduced to 6-hydroxy-2(E)-alken-4-ynylamines 11 with diisobutylaluminum hydride, whereas on treatment with lithium aluminum hydride 6-hydroxy-4(E)-alken-2-ynylamines 12 were obtained. LiAlH (iso-Bu)2(n-Bu) did not react with 2-alkinylamine 1a and the 2,4-alkadiynylamine 3a was only monohydroaluminated without discrimination of the two acetylene groups. A possible mechanism for the diisobutylaluminum hydride reduction of 2-alkinylamines is presented.
- Stuetz, Anton,Granitzer, Waltraud,Roth, Sabine
-
p. 5685 - 5696
(2007/10/02)
-
- Synthesis and Antifungal Activity of (E)-N-(6,6-Dimethyl-2-hepten-4-ynyl)-N-methyl-1-naphthalenemethanamine (SF 86-327) and Related Allylamine Derivatives with Enhanced Oral Activity
-
The allylamine derivatives are a new class of synthetic antifungal agents inhibiting fungal squalene epoxidase.A new subclass, which features an acetylene group conjugated with the allylamine double bond, is characterized by enhanced antifungal activity, especially on oral treatment of guinea pig dermatophytoses.Increased branching of the alkyl group next to the triple bond led to the tert-butylacetylene derivative SF 86-327, a compound with strikingly increased activity in vitro and in vivo, which is now under clinical evaluation.Versatile synthetic routes, comparative biological data, and structure-activity relationship are presented.
- Stuetz, Anton,Petranyi, Gabor
-
p. 1539 - 1543
(2007/10/02)
-