- Efficient isonitrile hydration through encapsulation within a hexameric self-assembled capsule and selective inhibition by a photo-controllable competitive guest
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Catalytic hydration of neutral isonitriles to yield the corresponding N-formylamides was achieved by reversible encapsulation in a self-assembled hexameric resorcin[4]arene capsule. Encapsulation of a photochromic dithienylethene bis-cation provides different levels of competitive inhibition depending on the geometry assumed by the cationic inhibitor. The Royal Society of Chemistry 2013.
- Bianchini, Giulio,Sorella, Giorgio La,Canever, Nicolo,Scarso, Alessandro,Strukul, Giorgio
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Read Online
- SOME APPROACHES TO THE SYNTHESIS OF FLUORINATED ALCOHOLS AND ESTERS. III. SYNTHESIS OF 2-(F-ALKYL)ETHANOLS FROM 2-(F-ALKYL)-1-IODOETHANES AND AMIDES
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1-iodo-2-(F-alkyl)ethanes, RFCH2CH2I, when heated with a large excess of N-methylformamide (NMF) give in high yield, mixtures of predominately RFCH2CH2OH, some formate ester and a little RFCH=CH2.In a study of this process, significant variables were examined, including solvent, reactant ratio, effect of water, and alternative amide reactants.The coproduct from NMF is the amidine salt, (1+)*I(1-).By contrast, RFCH2CH2I with N,N-dimethylformamide (DMF) and water (one or two mols) gives chiefly the formate ester; the coproduct is Me2NH2(1+)*I(1-).A mechanistic scheme is proposed: in the first step, an alkyl imidate salt, e.g., F>(1+)*I(1-) is formed by O-alkylation of NMF; reaction of the imidate with more NMF gives a tetrahedral intermediate that breaks down rapidly to RFCH2CH2OH, and HC(=NHMe)NMeCHO(1+)*I(1-).The formate ester is derived from the alcohol and this N-formyl acylating agent, in a subsequent step.Analogously, the alkyl imidate salt from DMF and RFCH2CH2I reacts with water as nucleophile (but not with DMF) to give a tetrahedral intermediate that cleaves under stereoelectronic control to formate ester and amine salt, but not to alcohol.Quantitative isolation of amine salt and amidine salt, and observed rates of reaction give solid support to this proposed mechanism.
- Brace, Neal O.
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Read Online
- Facile N-Formylation of Amines on Magnetic Fe3O4?CuO Nanocomposites
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A facile, eco-friendly, efficient, and recyclable heterogeneous catalyst is synthesized by immobilizing copper impregnated on mesoporous magnetic nanoparticles. The surface chemistry analysis of Fe3O4?CuO nanocomposites (NCs) by XRD and XPS demonstrates the synergistic effect between Fe3O4 and CuO nanoparticles, providing mass-transfer channels for the catalytic reaction. TEM images clearly indicate the impregnation of CuO onto mesoporous Fe3O4. This hydrothermally synthesized eco-friendly and highly efficient Fe3O4?CuO NCs are applied as a magnetically retrievable heterogeneous catalyst for the N-formylation of wide range of aliphatic, aromatic, polyaromatic and heteroaromatic amines using formic acid as a formylating agent at room temperature. The catalytic activity of the NCs for N-formylation is attributable to the synergistic effect between Fe3O4 and CuO nanoparticles. The N-formylated product is further employed for the synthesis of biologically active quinolone moieties.
- Datta Khanal, Hari,Mishra, Kanchan,Rok Lee, Yong
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p. 4477 - 4484
(2021/08/30)
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- A substituent- And temperature-controllable NHC-derived zwitterionic catalyst enables CO2upgrading for high-efficiency construction of formamides and benzimidazoles
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Chemocatalytic upgrading of the greenhouse gas CO2 to valuable chemicals and biofuels has attracted broad attention in recent years. Among the reported approaches, N-formylation of CO2 with an amine is of great significance due to its versatility in the construction of N-containing linear and cyclic skeletons. Herein, a stable N-heterocyclic carbene-carboxyl adduct (NHC-CO2) was facilely prepared and could be used as a recyclable zwitterionic catalyst for efficient CO2 reductive upgrading via either N-formylation or further coupling with cyclization under mild conditions (25 °C, 1 atm CO2) using hydrosilane as a hydrogen source. More than 30 different alkyl and aromatic amines could be transformed into the corresponding formamides or benzimidazoles with remarkable yields (74%-98%). The electronic effect of the introduced substituent on NHC-CO2 was found to evidently affect the thermostability and nucleophilicity of the zwitterionic catalyst, which is directly correlated with its catalytic activity. Moreover, NHC-CO2 could supply CO2 by in situ decarboxylation at a specific temperature that is dependent on the introduced substituent type. Experimental and computational studies showed that the carboxyl species on NHC-CO2 was not only a nucleophilic center, but also a C1 source which rapidly captures or substitutes ambient CO2 during hydrosilylation. In addition, a simple and green conceptual process was designed for the product purification and catalyst recycling, with a good feasibility for small-scale production.
- Li, Hu,Li, Zhengyi,Wu, Hongguo,Yang, Song,Yu, Zhaozhuo,Zhang, Lilong,Zhu, Kaixun
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supporting information
p. 5759 - 5765
(2021/08/23)
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- ORGANIC SILVER COMPLEX COMPOUND, METHOD FOR PREPARING THE SAME, AND SILVER INK, SILVER ELECTRODE, ELECTRONIC DEVICE AND DISPLAY COMPOSITION COMPRISING THE SAME
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The present invention relates to an organic silver complex compound, a manufacturing method thereof, a silver ink composition, a silver electrode, an electric device and display comprising the same. The organic silver complex compound is indicated as a chemical formula 1. [The chemical formula 1] (In the chemical formula 1, R1-R9 respectively are at least one substituent selected from the group consisting of hydrogen, an alkyl group of C2-C16, a cycloalkyl group of C1-C30, an aryl group of C3-C30 and a heteroaryl group of C2-C30) The organic silver complex compound exhibits excellent stability and solubility and is able to for silver thin films by being disassembled at low temperatures.
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Paragraph 0073-0075
(2020/05/01)
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- Sustainable Co-Synthesis of Glycolic Acid, Formamides and Formates from 1,3-Dihydroxyacetone by a Cu/Al2O3 Catalyst with a Single Active Sites
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Glycolic acid (GA), as important building block of biodegradable polymers, has been synthesized for the first time in excellent yields at room temperature by selective oxidation of 1,3-dihyroxyacetone (DHA) using a cheap supported Cu/Al2O3 catalyst with single active CuII species. By combining EPR spin-trapping and operando ATR-IR experiments, different mechanisms for the co-synthesis of GA, formates, and formamides have been derived, in which .OH radicals formed from H2O2 by a Fenton-like reaction play a key role.
- Dai, Xingchao,Adomeit, Sven,Rabeah, Jabor,Kreyenschulte, Carsten,Brückner, Angelika,Wang, Hongli,Shi, Feng
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supporting information
p. 5251 - 5255
(2019/03/07)
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- Carisoprodol method for synthesizing intermediate
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The invention belongs to the field of medicine, and particularly relates to a synthesis method of a carisoprodol intermediate compound, which comprises the following steps: reacting formic acid and isopropylamine to generate N-isopropyl formamide; and adding oxydol into the N-isopropyl formamide, then adding 2-methyl-2-propyl-1,3-propanediol, and reacting to obtain the carisoprodol intermediate compound 2-methyl-2-propyl-3-hydroxypropyl-N-isopropyl carbamate. According to the method, the raw materials are accessible, the reaction process is easy to control, and no serious pollutant is generated in the intermediate process; the stereoselectivity of the reaction is high, and no obvious competing reaction exists; and the method is simple to operate, has specificity and reduces generation of foreign matters, and the product purity is up to 99.5% or above.
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Paragraph 0041; 0042
(2016/10/07)
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- Palladium-catalyzed direct coupling of 2-vinylanilines and isocyanides: An efficient synthesis of 2-aminoquinolines
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Palladium-catalyzed oxidative coupling of 2-vinylanilines and isocyanides constitutes a direct, facile, and efficient approach to 2-aminoquinolines. The procedure, employing palladium acetate and silver carbonate, is attractive in terms of assembly efficiency, functional group tolerance, and operational simplicity. A variety of 2-aminoquinolines were prepared in good to excellent yields.
- Wang, Lijie,Ferguson, Jamie,Zeng, Fanlong
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supporting information
p. 11486 - 11491
(2015/12/04)
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- Multicomponent cascade cycloaddition involving tropone, allenoate, and isocyanide: A rapid access to a 7,6,5-fused tricyclic skeleton
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Multicomponent cascade cycloaddition of tropone, allenoate, and isocyanide has been disclosed. This method allows for the rapid construction of a highly unusual tricyclic skeleton in an efficient manner. The proposed transformation proceeds through [8 + 2 + 1] cycloaddition, [1,5]-H shift, and cyclization followed by an alkoxy group migration process.
- Jia, Shuanglong,Su, Shikuan,Li, Chunju,Jia, Xueshun,Li, Jian
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supporting information
p. 5604 - 5607
(2015/02/19)
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- Melamine trisulfonic acid-catalyzed N-formylation of amines under solvent-free conditions
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A highly convenient method for N-formylation of amines via treatment by formic acid in the presence of melamine trisulfonic acid as a catalyst has been developed. This method showed improvements over previous reports in terms of yield, reaction time and chemoselectivity.
- Yang, Xiao Juan,Zhang, Yong Sen
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p. 2843 - 2848
(2013/07/26)
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- Formylation of amines and alcohols using aminopropylated mesoporous SBA-15 silica (APMS) as an efficient and recyclable catalyst
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Aminopropylated mesoporous SBA-15 silica (APMS) is introduced as a new, recyclable and efficient catalyst for the formylation of a variety of amines and alcohols by using readily available formic acid under solvent-free conditions.
- Malakooti, Reihaneh,Sobhani, Sara,Razavi, Nasrin,Shafiei, Soheila,Mokhtari, Rezvan
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experimental part
p. 1979 - 1990
(2012/04/17)
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- A convenient one-pot synthesis of formamide derivatives using thiamine hydrochloride as a novel catalyst
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Formamide derivatives have been synthesized in excellent yields from amine and formic acid in the presence of a catalytic amount of thiamine hydrochloride (VB1) at 80 °C. The advantages of this method are the use of a cheap, stable, non-toxic, and readily available catalyst, easy work-up, improved yields, and solvent-free conditions.
- Lei, Min,Ma, Lei,Hu, Lihong
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experimental part
p. 4186 - 4188
(2010/09/12)
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- 5-Methyl-1,2,3-thiadiazoles synthesized via ugi reaction and their fungicidal and antiviral activities
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1,2,3-Thiadiazoles, an important synthetic active substructure, are nowadays becoming one of the important branches in novel pesticide development. To develop pesticide candidates with diverse biological activities and probe their structure-activity relat
- Zheng, Qingxiang,Mi, Na,Fan, Zhijin,Zuo, Xiang,Zhang, Haike,Wang, Huan,Yang, Zhikun
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experimental part
p. 7846 - 7855
(2011/09/20)
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- Reaction of carboxylic acids and isonitriles in small spaces
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Reversible encapsulation complexes are applied to the reaction of isonitriles with carboxylic acids. Encapsulation facilitates these reactions by amplifying the concentration of reactants, arranging the acid and isonitrile in the appropriate orientations,
- Hou, Jun-Li,Ajami, Dariush,Rebek Jr., Julius
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supporting information; experimental part
p. 7810 - 7811
(2009/02/01)
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- 4-Oxa and 4-thia steroids
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The compounds of the present invention are those of structural formula (I) STR1 wherein X is oxygen or sulfur. Pharmaceutical compositions and methods of use of the compounds in the treatment of hyperandrogenic conditions are disclosed. In addition, the combination of the compounds with other active agents such as finasteride, minoxidil and retinoic acid or a derivative thereof is disclosed.
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- Inhibition of human alcohol dehydrogenases by formamides
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Human alcohol dehydrogenase (HsADH) comprises class I (α, β, and γ), class II (π), and class IV (σ) enzymes. Selective inhibitors of the enzymes could be used to prevent the metabolism of alcohols that form toxic products. Formamides are unreactive analog
- Schindler, John F.,Berst, Kristine B.,Plapp, Bryce V.
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p. 1696 - 1701
(2007/10/03)
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- Some reactions of ammonia and primary amines with propanal, 2-chloroethanal, 2,2-dichloroethanal and 2,2,2-trichloroethanal in acetonitrile
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The reaction of ammonia with propanal in acetonitrile produces the hexahydrotriazine, 1, in good yield. The corresponding reaction of chloroethanal yields the cyclic trimer 16 but only in poor yield. Increasing chloro-substitution in the aldehyde stabilises the initially formed carbinolamines and disfavours trimerisation. Imines formed by reaction of primary amines with the aldehydes are relatively stable. Those formed from aliphatic amines may undergo slow dimerisation by C-C bond formation and this may be accompanied by loss of amine to yield products containing a conjugated double-bond system. Kinetic and equilibrium data are reported for both the forward and reverse reactions involving interconversion of propanal and ammonia with 1 in acetonitrile-water mixtures. The results indicate that dehydration of the carbinolamine is rate determining.
- Crampton, Michael R.,Lord, Simon D.,Millar, Ross
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p. 909 - 914
(2007/10/03)
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- The Schmidt reaction of dialkyl acylphosphonates
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The scope of the Schmidt rearrangement of ketones has been extended to dialkyl acylphosphonates (11a-11l). Surprisingly, it was found that 11a-11d and 11g, in which the acyl moiety was benzoyl alone or benzoyl bearing an electron-attracting or mildly electron-releasing substituent, yielded an overwhelming portion of products resulting from C-to-N migration of the aryl group (N-arylcarbamoylphosphonates, 12, and N-arylformamides, 15). Contrariwise, the arenecarbonylphosphonates, which carry a powerful electron-releasing p-alkoxy group, yielded products resulting from phosphonate group migration from C to N or elimination (dialkyl N-arenecarbonylphosphoramidates, 13, and arenecarbonitriles, 17, respectively). These counterintuitive results are rationalized by application of the concept of "degree of electron demand" to this area of intramolecular rearrangements. The possible existence of an additional pathway for the Schmidt rearrangement, involving protonation of the iminodiazonium ion, is proposed.
- Sprecher, Milon,Kost, Daniel
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p. 1016 - 1026
(2007/10/02)
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- Therapeutic agents
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Compounds of formula I STR1 in which R1 is C1-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, C3-7 cycloalkyl, cycloalkylalkyl or optionally substituted phenyl; R2 is H or C1-3 alkyl; R3 and/or R4 are H, formyl, C1-3 alkyl, C3-6 alkenyl, C3-6 alkynyl, C3-7 cycloalkyl or R3 and R4 together with the nitrogen atom form a heterocyclic ring system; R5 and/or R6 are H, halo, CF3, C1-3 alkyl, C1-3 alkoxy, C1-3 alkylthio or R5 and R6 together with the carbon atoms to which they are attached form a second benzene ring show therapeutic activity in the treatment of depression. Pharmaceutical compositions and processes for preparing compounds of formula I are disclosed.
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- N-Alkyl-N-iminomethyl derivatives of thienamycin
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Disclosed are N-alkyl-N-iminomethyl derivatives of thienamycin which may be represented by the following structural formula: STR1 wherein R5 is, inter alia, alkyl, alkenyl, aryl, or aralkyl, R6 is selected from R, OR, SR and NR1
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- Nitrogen-15 Nuclear Magnetic Rasonance Spectroscopy. Natural Abundance Nitrogen-15 Spectra of the cis and trans Isomers of Secondary Alkylformamides
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The 15N NMR chemical shifts were measured of a number of N-substituted formamides and acetamides at the natural abundance level.The ratios of the cis and trans isomers for several N-alkylformamides were also determined.Substituent effects on the 15N chemical shifts of formamides are compared with those of some other nitrogen-containing compounds.There is a consistent pattern of behavior of the one bond spin-spin coupling constants 1J(15NH)> wherein the trans isomers of N-alkylformamides are larger than those of the cis isomers.
- Nakanishi, Hiroshi,Roberts, John D.
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- Substituted N-methylene derivatives of thienamycin sulfoxide and sulfone
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Disclosed are substituted N-methylene derivatives of thienamycin sulfoxide (I, n=1) and sulfone (I, n=2) which may be represented by the following structural formula: STR1 wherein X and Y are selected from the group consisting of hydrogen, R, OR, SR, and NR1 R2 wherein, inter alia, R is substituted or unsubstituted: alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heteroaryl, heteroaralkyl, heterocyclyl, and heterocyclylalkyl; R1 and R2 are hydrogen or R. Such compounds and their pharmaceutically acceptable salt, ether, ester and amide derivatives are useful as antibiotics. Also disclosed are processes for the preparation of such compounds; pharmaceutical compositions comprising such compounds; and methods of treatment comprising administering such compounds and compositions when an antibiotic effect is indicated.
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- Substituted N-methylene derivatives of thienamycin
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Disclosed are substituted N-methylene derivatives of thienamycin which may be represented by the following structural formula: STR1 wherein X and Y are selected from the group consisting of hydrogen, R, OR, SR, and NR1 R2 wherein, in
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- Process for producing N-monosubstituted formamides
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An N-monosubstituted formamide having the formula: EQU1 in which R represents an optionally substituted aliphatic, cycloaliphatic or aromatic radical; is prepared by reacting a formaldimine having the formula: in which R is as defined above; or a hexahydrotriazine having the formula: EQU2 in which R is as defined above, with hydrogen peroxide. The reaction is generally carried out at temperatures in the range of from about 0° to about 100° C.
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- The carbonyl insertion reaction of iron pentacarbonyl with nonarotnatic nitro compounds
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Aliphatic, cycloalkyl, and α,β-unsaturated nitro compounds were allowed to react with iron pentacarbonyl in dry diglyme. Carbonyl insertion products were obtained from nitroalkanes and nitrocycloalkanes, the product distribution being dependent on the size of the group attached to the nitro function. Treatment of 1-nitropropane and 2-methyl-2-nitropropane with diiron enneacarbonyl in benzene gave organoiron carbonyl complexes of the types (RN)2Fe3(CO)9, (RN)2Fe2(CO)6, (RNH)2Fe2(CO)6, and (RN)2Fe2(CO)7, identified by elemental and infrared and mass spectral analyses. The complexes were converted to formamide and/or ureas by heating in diglyme. A multistep reaction sequence involving these iron carbonyl complexes is proposed for the reductive carbonylation reaction. α,β-Unsaturated nitro compounds failed to react with iron pentacarbonyl in diglyme.
- Alper, Howard
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p. 976 - 980
(2007/10/05)
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