Synthesis of primary amines from alcohols is an economical and green route to access high-value N-compounds.However,challenges remain to develop both cost-effective and efficient catalysts.In this study,we developed a...Synthesis of primary amines from alcohols is an economical and green route to access high-value N-compounds.However,challenges remain to develop both cost-effective and efficient catalysts.In this study,we developed a Ru-Co/ZrO_(2)single-atom alloy catalyst which afforded diverse primary amines from alcohols in the presence of ammonia and hydrogen with exceptional conversion(up to 90%)and selectivity(80%)under mild conditions(0.7 MPa NH_(3),0.3 MPa H_(2),160℃)and exhibited satisfactory stability upon regeneration.The turnover rate was approximately 8.4 times higher than that observed over the Co/ZrO_(2)catalyst.Characterizations indicated that the alloyed Ru facilitated the reduction of Co,strengthened the interaction with H_(2)and mitigated the over-strong adsorption of aldehyde intermediates.These combined effects contributed significantly to the enhanced catalytic performances.This work presents a promising strategy for the development of advanced catalysts in the amination of alcohols.展开更多
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...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.展开更多
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...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.展开更多
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 substitu...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.展开更多
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 metho...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.展开更多
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 extracti...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.展开更多
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 ...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.展开更多
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 amine...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.展开更多
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...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.展开更多
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 ...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%）.展开更多
We report herein the first example of asymmetric hydroazidation of α-substituted vinyl ketones by using chiral primary amines as the catalysts.A simple chiral primary-tertiary diamine catalyst derived from lphenylala...We report herein the first example of asymmetric hydroazidation of α-substituted vinyl ketones by using chiral primary amines as the catalysts.A simple chiral primary-tertiary diamine catalyst derived from lphenylalanine was found to readily promote this aza-Michael addition reaction with enamine protonation as the key stereogenic step,thus enabling the effective synthesis of α-chiral β-azido ketones with good yields and moderate enantioselectivities.展开更多
Isothiocyanates(ITCs)are an important class of organic compounds characterized by the functional group R-N=C=S.These functional groups are widely found in multiple natural products and pharmaceutical important drugs.M...Isothiocyanates(ITCs)are an important class of organic compounds characterized by the functional group R-N=C=S.These functional groups are widely found in multiple natural products and pharmaceutical important drugs.Moreover,due to their high and versatile reactivity,they are widely used as an intermediate in organic synthesis.Keeping in view ITCs importance,this review summarizes their synthesis from nitrogen rich raw materials like amines,isocyanides,azides and some other compounds like oximes.Besides their synthesis,their application in organic compound synthesis as an intermediate will also be covered.Future research will likely focus on optimizing the synthesis of multifunctional isothiocyanates,understanding their complex biological mechanisms,exploring new applications,and highlighting the continued importance of isothiocyanates in modern chemistry and biotechnology.展开更多
A transition-metal-free strategy for the synthesis of carboline derivatives via sequential dual C—N bond formation in a one-pot reaction is reported.Using 2,2'-dihalogenated pyridyl biaryls and primary amines as ...A transition-metal-free strategy for the synthesis of carboline derivatives via sequential dual C—N bond formation in a one-pot reaction is reported.Using 2,2'-dihalogenated pyridyl biaryls and primary amines as starting materials,this method efficiently constructs a series ofα-,β-,γ-andδ-carbolines under alkaline conditions.The reaction proceeds smoothly in the presence of lithium tert-butoxide(t-BuOLi)or cesium carbonate(Cs_(2)CO_(3))without requiring transition metal catalysts,demonstrating good functional group tolerance.This approach enables gram-scale synthesis and has been successfully applied to the preparation of the organic material 2,6-CbPy,achieving high conversion efficiency.展开更多
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...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.展开更多
The formation of toxic nitrogenous disinfection byproducts （N-DBPs）, such as nitrosamines, halonitromethanes and haloacetonitriles, from reactions between chlorine/chloramine and dissolved organic nitrogen in drinki...The formation of toxic nitrogenous disinfection byproducts （N-DBPs）, such as nitrosamines, halonitromethanes and haloacetonitriles, from reactions between chlorine/chloramine and dissolved organic nitrogen in drinking water has caused great concern with regarding public health. This study revealed the occurrence of 17 aliphatic amines, some of which have been confirmed to be the precursors of N-DBPs, in source water across China. A sensitive method based on benzenesulfonyl chloride derivatization and liquid-liquid extraction followed by GC-MS analysis was established for the simultaneous analysis of the selected amines in aqueous samples. In total, 37 source water samples from the capital cities of 20 provinces were collected for the survey. Among the 17 amines, 14 were detected with an average frequency of detection of 36%. The most relevant amines in terms of frequency and maximum concentrations detected were dimethylamine （100%, 24.82 μg/L）, methylamine （78%, 0.92 μg/L）, N-methylethylamine （70%, 8.84 μg/L）, propylamine （59%, 10.69 μg/L）, diethylamine （54%, 3.76μg/L）, N-methylbutylamine （35%, 3.07 μg/L）, N-ethylpropylamine （35%, 0.52μg/L）, and piperidine （32%, 2.35 μg/L）. This is the first large scale survey of the aliphatic amines occurrence in source water in the world. The wide presence of nitrosamine precursors like dimethylamine, N-methylethylamine and diethylamine, and the precursors of haloacetonitriles and halonitromethanes like methylamine and propylamine suggests that better source water management is required to ensure the safety of drinking water.展开更多
Ion-absorbed rare earth ores radioactive residues(IREORR)are a class of waste residue from the production of rare earth elements(REEs).Because of its radioactive dose,IREORR are usually stored in waste warehouses.IREO...Ion-absorbed rare earth ores radioactive residues(IREORR)are a class of waste residue from the production of rare earth elements(REEs).Because of its radioactive dose,IREORR are usually stored in waste warehouses.IREORR are difficult to be disposed of.However,it contains relatively high concentrations of REEs,which can be considered as a valuable secondary resource.In this paper,a novel process is developed for the separation of thorium(Th)and recovery of REEs from IREORR hydrochloric acid leachate with primary amine N1923 and Cyanex?572,respectively.The effects of sulfate concentration,extractant concentration and pH on N1923 extraction in hydrochloric acid solution were investigated in detail.The results show that the extraction capacity of N1923 can be improved by adding sulfate to the solution and increasing the concentration of N1923.Acidity has little effect on the extraction of Th when pH is higher than 1.As for the stripping,REEs are more easily stripped from loaded organic phase than Th,and nitric acid is a better stripping agent than hydrochloric acid.Combined with the extraction of Cyanex■572 for REEs,a fractional extraction experiment for separating Th and enriching of REEs was performed.The yield of Th is higher than 99.9%and the concentration of REEs is enriched to 183.84 g/L.展开更多
Under the guidance of the finding that the tyrosine residues in proteins could undergo three-component Mannich-type reactions with formaldehyde and electron-rich aniline-containing compounds,which forms covalent bondi...Under the guidance of the finding that the tyrosine residues in proteins could undergo three-component Mannich-type reactions with formaldehyde and electron-rich aniline-containing compounds,which forms covalent bonding connections between the protein of interest and the aniline with high levels of selectivity under relatively mild conditions,an orange aromatic primary amine-containing acid dye AMODB was designed and readily synthesized.The molecular structure was characterized by FTIR,^1H NMR,mass spectrometry and elemental analysis.The synthesized dye and a similar control dye（C.I.Acid Yellow 11） without primary amine groups were applied to dye silk fabric by three dyeing processes：Mannich-type dyeing（with and without the addition of formaldehyde） and acidic dyeing.Their washing and rubbing fastness properties with different dyeing methods were examined and compared.It was found that the dyed silk fabric with AMODB by the Mannich-type dyeing showed higher color depth,better anti-stripping ability to DMF and better washing fastness than those of the dyed silk fabric with C.I.Acid Yellow 11 by acidic dyeing due to the covalent bond formation between the dye chromophore of AMODB and silk fiber.In addition,mild Mannich dyeing conditions suitable for silk（AMODB at 3%owf,75：1 liquor-to-goods ratio,dyebath pH 5.5,30℃,10 h） were provided.展开更多
Ethyl α-（dimethylaminomethylene）-2-cyanomethyl-4-phenylquinoline-3-carboxylate（2） as new synthons directed to 1-oxo-1,2-dihydrobenzo[b][1,6]naphthyridine-4-carbonitriles was obtained by the condensation of ethyl ...Ethyl α-（dimethylaminomethylene）-2-cyanomethyl-4-phenylquinoline-3-carboxylate（2） as new synthons directed to 1-oxo-1,2-dihydrobenzo[b][1,6]naphthyridine-4-carbonitriles was obtained by the condensation of ethyl 2-cyanomethyl-4-phenylquinoline-3-carboxylate（1） and N,N-dimethylformamide dimethyl acetal（DMFDMA）.Reaction of this enamine with primary amines（3） in HOAc-DMF at120 ℃then affords 2-substituted 1-oxo-1,2-dihydrobenzo[b][1,6]naphthyridine-4-carbonitrile derivatives（4） in good yields by a tandem addition-elimination-cyclization reaction.展开更多
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 h...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.展开更多
A series of 1 3-thiazolane derivatives have been synthesized via multicomponent reactions of activated acetylenes,primary amines and isothiocyanates in the presence of a catalytic amount of Nmethylimidazole under solv...A series of 1 3-thiazolane derivatives have been synthesized via multicomponent reactions of activated acetylenes,primary amines and isothiocyanates in the presence of a catalytic amount of Nmethylimidazole under solvent-free conditions.展开更多
文摘Synthesis of primary amines from alcohols is an economical and green route to access high-value N-compounds.However,challenges remain to develop both cost-effective and efficient catalysts.In this study,we developed a Ru-Co/ZrO_(2)single-atom alloy catalyst which afforded diverse primary amines from alcohols in the presence of ammonia and hydrogen with exceptional conversion(up to 90%)and selectivity(80%)under mild conditions(0.7 MPa NH_(3),0.3 MPa H_(2),160℃)and exhibited satisfactory stability upon regeneration.The turnover rate was approximately 8.4 times higher than that observed over the Co/ZrO_(2)catalyst.Characterizations indicated that the alloyed Ru facilitated the reduction of Co,strengthened the interaction with H_(2)and mitigated the over-strong adsorption of aldehyde intermediates.These combined effects contributed significantly to the enhanced catalytic performances.This work presents a promising strategy for the development of advanced catalysts in the amination of alcohols.
基金supported by the National Natural Science Foundation of China(21676262,21476228,21506207)the Key Research Program of Frontier Sciences of CAS(QYZDB-SSW-JSC040)~~
文摘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.
文摘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.
基金Supported by the National Natural Science Foundation of China(No.20572058)
文摘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.
文摘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.
文摘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.
文摘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.
基金Supported by the National Natural Science Foundation of China(21076036)
文摘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.
基金the National Natural Science Foundation of China(No.21502006)Beijing National Laboratory for Molecular Sciences and Beijing Institute of Technology(BIT)for financial support。
文摘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.
基金financial support from the National Natural Science Foundation of China (No. 21262022)
文摘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%）.
基金National Natural Science Foundation of China(NSFC Nos.21390400,21521002 and 21502198)the Ministry of Science and Technology,Chinese Academy of Sciences(No.QYZDJSSW-SLH023)for generous financial supportsupported by National Program for Support of Top-notch Young Professionals,CAS Youth Innovation Promotion Association and CAS onehundred talented program(D)
文摘We report herein the first example of asymmetric hydroazidation of α-substituted vinyl ketones by using chiral primary amines as the catalysts.A simple chiral primary-tertiary diamine catalyst derived from lphenylalanine was found to readily promote this aza-Michael addition reaction with enamine protonation as the key stereogenic step,thus enabling the effective synthesis of α-chiral β-azido ketones with good yields and moderate enantioselectivities.
文摘Isothiocyanates(ITCs)are an important class of organic compounds characterized by the functional group R-N=C=S.These functional groups are widely found in multiple natural products and pharmaceutical important drugs.Moreover,due to their high and versatile reactivity,they are widely used as an intermediate in organic synthesis.Keeping in view ITCs importance,this review summarizes their synthesis from nitrogen rich raw materials like amines,isocyanides,azides and some other compounds like oximes.Besides their synthesis,their application in organic compound synthesis as an intermediate will also be covered.Future research will likely focus on optimizing the synthesis of multifunctional isothiocyanates,understanding their complex biological mechanisms,exploring new applications,and highlighting the continued importance of isothiocyanates in modern chemistry and biotechnology.
基金Project supported by the National Natural Science Foundation of China(No.22371303)the Zhongshan Municipal Bureau of Science and Technology(Nos.2021B2014,CXTD2022013)the Shanghai Rising-Star Program(21QA1411000)。
文摘A transition-metal-free strategy for the synthesis of carboline derivatives via sequential dual C—N bond formation in a one-pot reaction is reported.Using 2,2'-dihalogenated pyridyl biaryls and primary amines as starting materials,this method efficiently constructs a series ofα-,β-,γ-andδ-carbolines under alkaline conditions.The reaction proceeds smoothly in the presence of lithium tert-butoxide(t-BuOLi)or cesium carbonate(Cs_(2)CO_(3))without requiring transition metal catalysts,demonstrating good functional group tolerance.This approach enables gram-scale synthesis and has been successfully applied to the preparation of the organic material 2,6-CbPy,achieving high conversion efficiency.
基金sponsored by the Foundation for the Author of National Excellent Doctoral Dissertation of PR China (NO.200346)Program for New Century Excellent Talents in University (NCET-04-0270)National Natural Science Foundation of China (NO.20406005)
文摘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.
基金supported by the National Natural Science Foundation of China (No.21077118)the National Special Funding Project for Water Pollution Control and Management of China (No.2009ZX07419-001)
文摘The formation of toxic nitrogenous disinfection byproducts （N-DBPs）, such as nitrosamines, halonitromethanes and haloacetonitriles, from reactions between chlorine/chloramine and dissolved organic nitrogen in drinking water has caused great concern with regarding public health. This study revealed the occurrence of 17 aliphatic amines, some of which have been confirmed to be the precursors of N-DBPs, in source water across China. A sensitive method based on benzenesulfonyl chloride derivatization and liquid-liquid extraction followed by GC-MS analysis was established for the simultaneous analysis of the selected amines in aqueous samples. In total, 37 source water samples from the capital cities of 20 provinces were collected for the survey. Among the 17 amines, 14 were detected with an average frequency of detection of 36%. The most relevant amines in terms of frequency and maximum concentrations detected were dimethylamine （100%, 24.82 μg/L）, methylamine （78%, 0.92 μg/L）, N-methylethylamine （70%, 8.84 μg/L）, propylamine （59%, 10.69 μg/L）, diethylamine （54%, 3.76μg/L）, N-methylbutylamine （35%, 3.07 μg/L）, N-ethylpropylamine （35%, 0.52μg/L）, and piperidine （32%, 2.35 μg/L）. This is the first large scale survey of the aliphatic amines occurrence in source water in the world. The wide presence of nitrosamine precursors like dimethylamine, N-methylethylamine and diethylamine, and the precursors of haloacetonitriles and halonitromethanes like methylamine and propylamine suggests that better source water management is required to ensure the safety of drinking water.
基金supported by the National Key R&D Program of China(2017YFE0106900)Science and Technology Major Project of Ganzhou(2018)Fujian Program for High-Level Entrepreneurial and Innovative Talents Introduction and Science and Technology Service Network Initiative from Chinese Academy of Sciences。
文摘Ion-absorbed rare earth ores radioactive residues(IREORR)are a class of waste residue from the production of rare earth elements(REEs).Because of its radioactive dose,IREORR are usually stored in waste warehouses.IREORR are difficult to be disposed of.However,it contains relatively high concentrations of REEs,which can be considered as a valuable secondary resource.In this paper,a novel process is developed for the separation of thorium(Th)and recovery of REEs from IREORR hydrochloric acid leachate with primary amine N1923 and Cyanex?572,respectively.The effects of sulfate concentration,extractant concentration and pH on N1923 extraction in hydrochloric acid solution were investigated in detail.The results show that the extraction capacity of N1923 can be improved by adding sulfate to the solution and increasing the concentration of N1923.Acidity has little effect on the extraction of Th when pH is higher than 1.As for the stripping,REEs are more easily stripped from loaded organic phase than Th,and nitric acid is a better stripping agent than hydrochloric acid.Combined with the extraction of Cyanex■572 for REEs,a fractional extraction experiment for separating Th and enriching of REEs was performed.The yield of Th is higher than 99.9%and the concentration of REEs is enriched to 183.84 g/L.
基金supported by the National Natural Science Foundation of China(Nos.21106135 and 51173168)Zhejiang Provincial Key Innovation Team(No.2010R50038)+1 种基金Zhejiang Provincial Top Key Academic Discipline of Chemical Engineering and Technology"521" Talent Project of Zhejiang Sci-Tech University
文摘Under the guidance of the finding that the tyrosine residues in proteins could undergo three-component Mannich-type reactions with formaldehyde and electron-rich aniline-containing compounds,which forms covalent bonding connections between the protein of interest and the aniline with high levels of selectivity under relatively mild conditions,an orange aromatic primary amine-containing acid dye AMODB was designed and readily synthesized.The molecular structure was characterized by FTIR,^1H NMR,mass spectrometry and elemental analysis.The synthesized dye and a similar control dye（C.I.Acid Yellow 11） without primary amine groups were applied to dye silk fabric by three dyeing processes：Mannich-type dyeing（with and without the addition of formaldehyde） and acidic dyeing.Their washing and rubbing fastness properties with different dyeing methods were examined and compared.It was found that the dyed silk fabric with AMODB by the Mannich-type dyeing showed higher color depth,better anti-stripping ability to DMF and better washing fastness than those of the dyed silk fabric with C.I.Acid Yellow 11 by acidic dyeing due to the covalent bond formation between the dye chromophore of AMODB and silk fiber.In addition,mild Mannich dyeing conditions suitable for silk（AMODB at 3%owf,75：1 liquor-to-goods ratio,dyebath pH 5.5,30℃,10 h） were provided.
基金financial support from the Science and Technology Department of Liaoning Province(No.2011220022)
文摘Ethyl α-（dimethylaminomethylene）-2-cyanomethyl-4-phenylquinoline-3-carboxylate（2） as new synthons directed to 1-oxo-1,2-dihydrobenzo[b][1,6]naphthyridine-4-carbonitriles was obtained by the condensation of ethyl 2-cyanomethyl-4-phenylquinoline-3-carboxylate（1） and N,N-dimethylformamide dimethyl acetal（DMFDMA）.Reaction of this enamine with primary amines（3） in HOAc-DMF at120 ℃then affords 2-substituted 1-oxo-1,2-dihydrobenzo[b][1,6]naphthyridine-4-carbonitrile derivatives（4） in good yields by a tandem addition-elimination-cyclization reaction.
文摘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.
文摘A series of 1 3-thiazolane derivatives have been synthesized via multicomponent reactions of activated acetylenes,primary amines and isothiocyanates in the presence of a catalytic amount of Nmethylimidazole under solvent-free conditions.
