F:Flammable;
124-02-7Relevant articles and documents
Preparation method of diallylamine and hydrochloride thereof
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Paragraph 0047; 0048; 0051; 0052; 0053, (2019/03/08)
The invention belongs to the technical field of organic synthesis, and in particular relates to a preparation method of diallylamine and hydrochloride thereof. The preparation method comprises the following steps: inputting ammonia water into a reaction kettle, adding a catalyst, dropwise adding 3-chloropropene at a constant temperature and a constant pressure, heating the mixture to 50-55 DEG C after dropwise addition, keeping the temperature for 1 hour, and reducing the temperature to 35-40 DEG C to obtain slurry; extracting the slurry to a distilling kettle, adding sodium hydroxide and a byproduct ammonium chloride into the distilling kettle to react, absorbing generated ammonia water with water and reusing the same, neutralizing the same, starting distillation till a water phase is obtained, adding caustic soda flakes to dehydrate, cyclically using the dehydrated alkaline liquor t o obtain a diallylamine coarse product; and inputting the coarse product into a rectifying kettle, taking a small amount of precomponent first, then receiving diallylamine, and returning the precomponent to a reaction kettle to be used. The diallylamine and hydrochloride thereof are prepared by adopting an amination process, so that the method is safe and is guaranteed, and meanwhile, excessive ammonia water and alkaline water are fully recycled, so that the preparation method is low in energy consumption and little in pollution, and the three wastes can be recycled.
Preparation method of allyl amine mixture
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Paragraph 0013; 0014; 0015; 0016; 0017, (2017/04/27)
The invention discloses a preparation method of an allyl amine mixture. The preparation method includes following steps: S1, pouring a catalyst into a reation kettle, adding a certain amount of ammonium hydroxide, rising temperature, and adding chloropropene for ammonolysis reaction; S2, holding the temperature of the step 1, and adding liquid caustic soda; S3, rectifying a reaction product to evaporate water and excessive ammonia; S4, at corresponding temperature, collecting fraction-monoallyl amine; S, at corresponding temperature, collecting fraction-diallyl amine; S6, at corresponding temperature, collecting fraction-trially amine; S7, adding caustic soda flakes into a collected fraction mixture, and performing liquid separation to obtain. The preparation method is mild in reaction condition, ammonium hydroxide is used to replace ammonia in existing methods, and complex ventilation equipment is not needed, so that production cost is saved; by adding the caustic soda flakes, water absorbing effect can be realized, purity of the allyl amine mixture prepared by the method can be effectively improved, and the preparation method is simple to operate, high in yield and worthy of popularization.
O -Phthalaldehyde catalyzed hydrolysis of organophosphinic amides and other P(O)-NH containing compounds
Li, Bin-Jie,Simard, Ryan D.,Beauchemin, André M.
supporting information, p. 8667 - 8670 (2017/08/10)
Over 50 years ago, Jencks and Gilchrist showed that formaldehyde catalyses the hydrolysis of phosphoramidate through electrophilic activation, induced by covalent attachment to its nitrogen atom. Given our interest in the use of aldehydes as catalysts, this work was revisited to identify a superior catalyst, o-phthalaldehyde, which facilitates hydrolyses of various organophosphorus compounds bearing P(O)-NH subunits under mild conditions. Interestingly, chemoselective hydrolysis of the P(O)-N bonds could be accomplished in the presence of P(O)-OR bonds.
Aerobic oxidative N-dealkylation of tertiary amines in aqueous solution catalyzed by rhodium porphyrins
Ling, Zhen,Yun, Lin,Liu, Lianghui,Wu, Bing,Fu, Xuefeng
supporting information, p. 4214 - 4216 (2013/05/22)
Aerobic oxidative N-dealkylation of a variety of aliphatic tertiary amines and anilines catalyzed by rhodium(iii) tetra (p-sulfonatophenyl) porphyrin ((TSPP)RhIII) is achieved in aqueous solution using dioxygen as the sole oxidant.
GOLD CATALYZED HYDROAMINATION OF ALKYNES AND ALLENES
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Page/Page column 21; 23; 2/13, (2010/01/29)
Methods are provided for the catalytic hydroamination of compounds having an alkyne or allene functional group, in which the compound is contacted with ammonia or an amine in the presence of a catalytic amount of a gold complex under conditions sufficient for hydroamination to occur.
METHOD FOR PRODUCING PRIMARY AMINE COMPOUND
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Page/Page column 6, (2008/12/08)
Disclosed is a method for producing a primary amine compound represented by the formula (2) below, which is characterized in that a halogen compound represented by the formula (1) below, ammonia and formaldehyde are reacted with each other, and then the thus-obtained reaction product is [1] brought into contact with an aqueous solution of an acid or [2] reacted with a hydroxylamine under acidic conditions. By this method, a primary amine compound can be commercially advantageously produced by using a low-cost ammonia while suppressing production of a secondary amine as a by-product. (1) (In the formula, R1 and R2 independently represent a hydrogen atom, a C1-C5 alkyl group which may be substituted by a halogen atom or the like, a C1-C5 alkoxy group which may be substituted by a halogen atom, a cyano group, a C2-C11 alkenyl group or a phenyl group or the like; R3 represents a hydrogen atom, a linear or branched C1-C5 alkyl group or a cyano group; and X represents a halogen atom.) (2) (In the formula, R1, R2 and R3 are as defined above.)
Discovery and mechanistic study of AlIII-catalyzed transamidation of tertiary amides
Hoerter, Justin M.,Otte, Karin M.,Gellman, Samuel H.,Cui, Qiang,Stahl, Shannon S.
, p. 647 - 654 (2008/10/09)
Cleavage of the C-N bond of carboxamides generally requires harsh conditions. This study reveals that tris(amido)AlIII catalysts, such as Al2(NMe2)6, promote facile equilibrium-controlled transamidation of tertiary carboxamides with secondary amines. The mechanism of these reactions was investigated by kinetic, spectroscopic, and density functional theory (DFT) computational methods. The catalyst resting state consists of an equilibrium mixture of a tris(amido)AlIII dimer and a monomeric tris(amido)Al III-carboxamide adduct, and the turnover-limiting step involves intramolecular nucleophilic attack of an amido ligand on the coordinated carboxamide or subsequent rearrangement (intramolecular ligand substitution) of the tetrahedral intermediate. Fundamental mechanistic differences between these tertiary transamidation reactions and previously characterized transamidations involving secondary amides and primary amines suggest that tertiary amide/secondary amine systems are particularly promising for future development of metal-catalyzed amide metathesis reactions that proceed via transamidation.
Homogeneous catalytic hydroamination of alkynes and allenes with ammonia
Lavallo, Vincent,Frey, Guido D.,Donnadieu, Bruno,Soleilhavoup, Michele,Bertrand, Guy
experimental part, p. 5224 - 5228 (2009/04/11)
(Chemical Equation Presented) A golden ticket to the synthesis of reactive nitrogen-containing compounds, such as imines, enamines, and allyl amines, through the addition of NH3 to unsaturated bonds is the cationic cyclic (alkyl)-(amino)carbene-gold(I) catalyst shown in blue (Dipp=diisopropylphenyl). An ideal initial step for the preparation of simple bulk chemicals, this reaction is also useful for the synthesis of more complex molecules (see examples).
Why platinum catalysts involving ligands with large bite angle are so efficient in the allylation of amines: Design of a highly active catalyst and comprehensive experimental and DFT study
Mora, Guilhem,Piechaczyk, Olivier,Houdard, Romaric,Mezailles, Nicolas,Le Goff, Xavier-Frederic,Le Floch, Pascal
experimental part, p. 10047 - 10057 (2009/11/30)
The platinum-catalyzed allylation of amines with allyl alcohols was studied experimentally and theoretically. The complexes [Pt(η3-allyl)- (dppe)]OTf (2) and [Pt(η3-allyl)(DPP-Xantphos)]PF6 (5) were synthesized and structurally characterized, and their reactivity toward amines was explored. The bicyclic aminopropyl complex [Pt(CH2CH 2CH2NHBn-κ-C,N)-(dppe)]OTf (3) was obtained from the reaction of complex 2 with an excess of benzylamine, and this complex was shown to be a deactivated form of catalyst 2. On the other hand, reaction of complex 5 with benzylamine and allyl alcohol led to formation of the 16-VE platinum(0) complex [P(η2-C3H3OH)-(DPP-Xantphos)] (7), which was structurally characterized and appears to be a catalytic intermediate. A DFT study showed that the mechanism of the platinum-catalyzed allylation of amines with allyl alcohols differs from the palladium-catalyzed process, since it involves an associative ligand-exchange step involving formation of a tetracoordinate 18-VE complex. This DFT study also revealed that ligands with large bite angles disfavor the formation of platinum hydride complexes and therefore the formation of a bicyclic aminopropyl complex, which is a thermodynamic sink. Finally, a combination of 5 and a proton source was shown to efficiently catalyze the allylation of a broad variety of amines with allyl alcohols under mild conditions.
Deallyloxy- and debenzyloxycarbonylation of protected alcohols, amines and thiols via a naphthalene-catalysed lithiation reaction
Behloul, Cherif,Guijarro, David,Yus, Miguel
, p. 9319 - 9324 (2007/10/03)
The naphthalene-catalysed lithiation of Alloc- and Cbz-protected alcohols, amines and thiols in THF at 0°C led, after quenching with methanol, to the recovery of the free alcohols, amines and thiols in short reaction times and with very good yields. The selectivity for the removal of the Alloc- or the Cbz- group in a polyfunctionalised substrate has been studied. The selective reductive cleavage of a benzylic carbon-oxygen bond was achieved in the presence of an allylic carbon-oxygen or carbon-nitrogen bond. This method represents a great improvement in comparison with the previously reported deprotection procedures by dissolving metals, since it avoids the use of the toxic liquid ammonia and, therefore, the need to perform the reaction at low temperatures.
