Efficient C-N Formation for Preparing α-Branched Primary Amines by Recycled Intramolecular Reactions of 1,8-Naphthosultone Using Ammonia as Nitrogen Source

Amination of tertiary and secondary alcohols using aqueous ammonia as nitrogen source was carried out by a process with recyclable intramolecular reaction of 1,8-naphthosultone, which lead to α-branched primary amines. Sulfonic resin serves as the heterogeneous catalyst for C N bond formation and protects the neighboring hydroxyl group until the required hydrolysis starts in the alkaline solution. The process can be conducted under mild conditions, no additional solvent is needed and no overreaction to secondary or tertiary amines occurs.

Asymmetric Transfer Hydrogenation of Stable NH Imines for the Synthesis of Enantiopure α-Chiral Primary Amines

Although it offers a direct route to access synthetically valuableα-chiral primary amines,asymmetric transfer hydrogenation of NH imines has been rarely studied,due in large part to the inaccessibility and instability of NH imines.Herein,we report a Rh-catalyzed asymmetric transfer hydrogenation of a kind of novel and stable NH imines which are prepared via condensation of easily available sulfonylated 2'-aminoacetophenones with NH3 in methanol.With this method,enantioenriched chiral 2-(1-aminoalkyl)anilines,which are privileged pharmacore groups,have been synthesized with good functional group compatibility,and with up to 99%ee.A gram-scale reaction using 0.2 mol%of catalyst has been successfully performed to highlight the practicality.Furthermore,the products can be derivatized into enantiopure bioactive molecules as well as chiral tridentate ligands for metal catalysis.

A versatile AIE fluorogen with selective reactivity to primary amines for monitoring amination,protein labeling,and mitochondrial staining

Specific bioconjugation for native primary amines is highly valuable for both chemistry and biomedical research.Despite all the efforts,scientists lack a proper strategy to achieve high selectivity for primary amines,not to mention the requirement of fast response in real applications.Herein,we report a chromone-based aggregation-induced emission(AIE)fluorogen called CMVMN as a self-reporting bioconjugation reagent for selective primary amine identification,and its applications for monitoring bioprocesses of amination and protein labeling.CMVMN is AIE-active and capable of solid-state sensing.Thus,its electrospun films are manufactured for visualization of amine diffusion and leakage process.CMVMN also shows good biocompatibility and potential mitochondria-staining ability,which provides new insight for organelle-staining probe design.Combined with its facile synthesis and good reversibility,CMVMN would not only show wide potential applications in biology,but also offer new possibilities for molecular engineering.

Reductive Amination of Aldehydes and Ketones with Primary Amines by Using Lithium Amidoborane as Reducing Reagent

A variety of secondary amines were obtained in high isolated yields in the reductive amination of aldehydes and ketones by using lithium amidoborane as reducing agent. Compared to ammonia borane, lithium amidoborane has higher reducibility, and thus, exhibits faster reaction rate.

Ce(SO_4)_2-mediated Oxidative Coupling of Primary Aromatic Amines in Water

The oxidative coupling of primary aromatic amines was investigated. Ce（SO4）2 can mediate the oxidative coupling of primary aromatic amines in water to dimers, trimers and/or tetramers, which depended on the substituents of primary aromatic amines. When 2,6-dimethylaniline or 2,6-diethylaniline was used as substrate, dimer, and tetramer were formed as major products. When 2,6-diisopropylaniline or 2,6-dihaloanilines was used as substrate, dimer, and trimer were formed. The mechanistic aspect was also investigated.

Microwave-enhanced Mannich Condensation of Terminal Alkynes, Primary Amines with Paraformaldehyde on Cuprous Iodide Doped Alumina under Solvent Free Conditions

A microwave enhanced, solventless Mannich condensation of terminal alkynes, primary amines with paraformaldehyde on cuprous iodide doped alumina has been investigated. The structures of products depend on the ratio of alkyne to amine and paraformaldehyde.

Asymmetric catalyzed intramolecular aza-Michael reaction mediated by quinine-derived primary amines

An intramolecular organocatalytic enantioselective aza-Michael reaction of carbamates, sulfonamides and acetamides to a,b-unsaturated ketones was developed. This process is promoted by 9-amino-9-deoxy-epi-quinine and diphenyl hydrogen phosphate to afford a straightforward and expeditious synthesis of several synthetically useful five-and six-membered heterocycles with excellent enantioselectivity（92%–97.5% ee） and very good yields（up to 99%）.

Synthesis and Antimicrobial Properties of the Novel Fluonnated Bis-ammonium Salts with Two Primary Amine Groups

In order to resolve the increasing resistance phenomena of the Gram-negative bacteria against single chain quaternary ammonium salts （QAS）, lysine with a pedant fluorinated bis-ammonium salts was synthesized and its antimicrobial properties were evaluated in this work. The novel fluorinated bis-ammonium salts shows similar activity with conventional single chain quaternary ammonium salts against Gram-positive bacteria but stronger activity against Gram-negative bacteria and yeast compared with the single chained counterpart.

SYNERGISTIC EXTRACTION OF Cd(Ⅱ)WITH PRIMARY AMINE N-1923 AND NEUTRAL ORGANOPHOSPHORUS REAGENTS

The synergistic extraction of Cd(Ⅱ)with primary amine N-1923 and neutral organophosphorus reagents(TBP,DBBP,B)from hydrochloric acid has been investigated at μ=0.5,t=25℃.The compositions of the synergistic extraction complexes and the mechanism of the synergistic extraction have been determined by the methods of slope and constant mole. The synergistic extraction complexes with composition(RNH_3Cl)_2·CdCl_2·B have been demonstrated.The synergistic extraction reactions and additional reaction of Cd(Ⅱ)have been proposed as follows: CdCl_2+2RNH_3Cl_(o)+B_(o)(RNH_3Cl)_2·CdCl_2·B_(o) (RNH_3Cl)_3·CdCl_(2(o)+B_(o)(RNH_3Cl)_2·CdCl_2·B_(o)+RNH_3Cl_(o) In addition,the equilibrium constants and the thermodynamic functions of the synergistic ex- traction reactions have been calculated.The IR and NMR spectra of the synergistic ext-ac- tion complexes of Cd(Ⅱ)have been studied as well.

MECHANISM OF EXTRACTION AND STRIPPING OF Fe(Ⅲ) WITH PRIMARY AMINE N1923 AS EXTRACTANT AND n-OCTANE AS DILUENT

Mechanism of extraction of Fe (III) from sulphate solution by primary amine N1923 and stripping of Fe loaded organic phase with dilute H_2SO_4 was investigated. The organic phase was characterized by FT-IR and photon correlation spectroscopy. The composition of extracted species as well as the content of H_2O in organic phase were determined. The dependence of both the rate of extraction and stripping on the formation of reverse micelle in primary amine (N1923)system has been confirmed. It is shown that the extraction of Fe(III) by primary amine sulphate may be related to the adduct formation or cation exchange reaction under different concentrations of H_2SO_4 in aqueous solution.

Synthesis of Unprotectedα-Tertiary Amines and 1,2-Amino Alcohols from Vinyl Azides by Light Induced Denitrogenative Alkylarylation/Dialkylation

Sterically congestedα-tertiary primary amines are ubiquitous substructures in pharmaceutical and agrochemical agents yet are challenging to access.Herein,straightforward photoredox-catalyzed access to structurally diverseα,α,α-trisubstituted primary amines from denitrogenative alkylarylation or dialkylation of vinyl azides with N-hydroxyphthalimide(NHPI)esters and cyanoarenes or aryl aldehydes has been developed.The use of vinyl azide as a precursor to a primary aminewas enabled by the dual role of the Hantzsch ester to form an electron donor-acceptor complex and serve as a sacrificial reductant.This strategy provides a modular synthesis ofα-tertiary primary amines,including unprotected 1,2-amino alcohols,from simple materials with excellent functional group tolerance.The synthetic applicability of this method was demonstrated by streamlined access to 2,2-disubstituted tetrahydroquinolines.Preliminary investigations support two parallel reductive photocatalytic cycles allowing for the denitrogenative alkylarylation or dialkylation of vinyl azides via decarboxylative radical addition followed by heteroradical cross-coupling betweenα-amino radicals and aryl anion radicals or ketyl anion radicals.

SAPO-34 synthesized with n-butylamine as a template and its catalytic application in the methanol amination reaction

SAPO-34 was synthesized with n-butylamine（BA） as a template for the first time.Crystallization temperature and initial Si amount were important factors leading to successful syntheses.Lamellar AlPO-kanemite tends to form as the major phase or as an impurity of SAPO-34 at lower crystallization temperatures,though a higher initial Si amount may offer a positive effect on the crystallization of SAPO-34 that mitigates the low temperature.Higher temperature（240℃） can effectively suppress the generation of lamellar materials and allow the synthesis of pure SAPO-34 with a wider range of Si incorporation.The crystallization processes at 200 and 240℃ were investigated and compared.We used the aminothermal method to synthesize SAPO-34-BA at 240℃ and also found n-propylamine is a suitable template for the synthesis of SAPO-34.The SAPO-34-BA products were characterized by many techniques.SAPO-34-BA has good thermal stability,crystallinity and porosity.BA remained intact in the crystals with ~1.8 BA molecule per chabazite cage.The catalytic performance of SAPO-34 was tested in the methanol amination reaction,which showed high methanol conversion and selectivity for methylamine plus dimethylamine under the conditions investigated,suggesting that this material is a good candidate for the synthesis of methylamines.

Facile synthesis of microporous carbon through a soft-template pathway and its performance in desulfurization and denitrogenation

Wormlike/lamellar microporous carbons were prepared by using long alkyl chain primary amine hydrochloride as the template and resorci- nol/formaldehyde as the carbon source under highly acidic conditions. The template can be eliminated by high temperature treatment under an inert atmosphere. The obtained carbon materials were characterized by N2 adsorption-desorption, transmission electron microscopy, ther- mogravimetry and scanning electron microscopy. The results show that dodecylamine hydrochloride surfactant can be used as the template of wormlike micropores structure while octadecylamine hydrochloride results in both lamellar and wormlike micropores. The obtained carbon materials have the similar pore size in the range of 0.5-0.59 nm, but with various morphologies such as monolith, spheres, and coralline. The microporous carbon obtained from dodecylamine hydrochloride surfactant shows good adsorption performance to remove the refractory sulfur compounds and nitrogen-containing compounds in fuel.

农产品中阿维菌素QuEChERS测定方法研究

实验研究了农产品中阿维菌素Qu ECh ERS测定方法,样品通过乙腈震荡提取,丙基乙二胺(primary secondary amine sorbent,PSA)、十八(烷)基硅烷C18(octadecyl silane,ODS C18)简称C18、多壁碳纳米管(multi walled carbon nanotubes,MWCNTs)净化,过滤膜上机检测。结果表明,当PSA、C18、CNT用量分别为0.5 g,1 g,0.03 g时,净化效果最好,回收率高。回收率在80%~120%之间,可以达到检测要求,阿维菌素检出限为0.02 mg/kg,RSD小于10%,满足实验要求。

A new method for the synthesis of N-substituted pyrroles

An unexpected reaction of 10-bromomethyl-12-oxocalanolide A（2） with primary amine was demonstrated and studied. Consequentially,a new method for the preparation of N-substituted pyrroles starting fromγ-halo-α,β-unsaturated ketone was presented.

Native amine-directed site-selective C(sp^3)-H arylation of primary aliphatic amines with aryl iodides

Direct C(sp3)-H functionalization of N-unprotected aliphatic amines represents one of the most efficient and straightforward strategies for amine synthesis.Despite some recent progress in this field,the NH2-directed y-C(sp3)-H arylation of primary aliphatic amines exceptα-amino esters remained an unmet challenge.In this report,we established a simple and efficient method for site-selective C(sp3)-H arylation of primary aliphatic amines by aryl iodides.In the presence of only 5 mol%Pd(OAc)2,a wide range of aliphatic amines including O-benzyl and O-silyl amino alcohols were arylated at y-orδ-positions by aryl iodides containing a broad scope of functional groups.The synthetic application of this method had also been demonstrated by large-scale synthesis,the synthesis of a fingolimod analogue,and the conjugation with natural D-menthol and fluorescent 1,8-naphthalimide.

Asymmetric α-Pentadienylation of β-Ketocarbonyls and Aldehydes by Synergistic Pd/Chiral Primary Amine Catalysis

Direct alkylation with skipped enynes or cyclopropropylacetylenes represents an ideal process for the installation of pentadienyl group in terms of atom- and step-economy.The development of catalytic asymmetric versions has been frequently pursued and most of the successes have been achieved with enolizable aldehydes.We herein describe a synergistic chiral primary amine/Pd catalysis for asymmetric α-pentadienylation of β-ketocarbonyls and aldehydes with skipped enynes or cyclopropropylacetylenes.The reaction features the construction of acyclic all-carbon quaternary centers with high enantioselectivity,and good functional group tolerance and scalability.

Solvent-free synthesis of substituted five membered heterocycles: One-pot reaction of primary amine and alkyl propiolate or isothiocyanate in the presence of oxalyl chloride

A novel, convenient and efficient approach to the synthesis of pyrrole and imidazole derivatives via the reaction between primary amines, alkyl propiolates or isothiocyanate and oxalyl chloride is described. The method offers several advantages including high yields of products and performing reaction under solvent-free conditions.

Primary amine-functionalized mesoporous phenolic resin as an effective and stable solid base catalyst for Knoevenagel reactions in water

A primary amine functionalized ordered mesoporous phenolic resin(NH2-MPR)was obtained by an evaporationinduced self-assembly method.The as-prepared NH2-MPR material possessed large surface area and ordered twodimensional hexagonal mesoporous structure.Also,the amine groups were well-dispersed in the mesoporous channels.It can act as an efficient solid base to promote Knoevenagel condensation of various aldehydes with ethyl cyanoacetate in water with high conversion and selectivity.This excellent performance was attributed ordered mesopores and hydrophobic pore surface,which resulted in the decreased the interference of water solvent and the increased active sites accessibility.Noted that it was comparable with homogenous base catalysts in the water-medium Knoevenagel condensation reaction,and it can be reused for at least five times without significant reduction in the catalytic efficiency.

Microcalorimetric Study on the Oscillating System of Two-phase Reaction of Aqueous Acid with Primary Amine in Chloroform

It has been found that the two-phase reactions of aqueous HCl, HOAc or H_3PO_4 with primary amine N_ 1923 in chloroform are oscillating reactions. Their power-time curves were measured by the titration microcalorimetric method, and the induction period (t_ in). The first oscillating period (t_ p.1) and the second oscillating period (t_ p.2) were determined. The apparent activating parameters and the orders of the oscillating systems were calculated and the following relationships were established: for the oscillating system of hydrochloric acid t_ in∝c 0.147_ HClexp(1.35×10 3T), t_ p.1∝c 0.241_ HCl· exp(4.33×10 3T), t_ p.2∝c 0.290_ HClexp(5.59×10 3T); for the oscillating system of acetic acid, t_ in∝c 0.883_ HOAcexp(2.32×10 3T), t_ p.1∝c 0.399_ HOAc· exp(4.50×10 3T), t_ p.2∝c 0.301_ HOAcexp(5.88×10 3T); for the oscillating system of phosphoric acid, t_ in∝c 1.14_ H_3PO_4exp(7.70×10 4T), t_ p.1∝c 1.42_ H_3PO_4exp(1.14×10 4T), t_ p.2∝c 1.47_ H_3PO_4exp(1.27×10 4T).