- Semiconductor Photocatalysis.ZnS-Catalyzed Photoreduction of Aldehydes and Related Derivatives: Two-Electron-Transfer Reduction and Relationship with Spectroscopic Properties
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Photocatalytic activity and spectroscopic properties of ZnS suspensions for the two-electron reduction of aldehydes or related compounds in aqueous medium are described.The ZnS suspension (ZnS-0) prepared by cooling from aqueous ZnSO4 and Na2S solutions catalyzes photoredox reactions of acetaldehyde, giving ethanol without much H2 evolution as a two-electron-reduction product, and acetic acid, biacetyl, and acetoin as oxidation products.When the ZnS-0 suspension is refluxed (giving ZnS-100) or dried to powder, the resulting ZnS shows an increased activity for H2 evolution but a decreased activity for the two-electron reduction.The two-electron photoreduction is ascribed to the sequential transfer of active electrons in the conduction band of defect-free aggregates of ZnS microcrystallites (quantized ZnS).This mechanism is supported by product analysis, energetics at ZnS interfaces, the sharp and blue-shifted onset of absorption and excitation spectra, and the long-life band gap emission of the active ZnS-0 suspension.UV, emission, and ESR spectra, as well as the enhancement of the particle size and crystallinity, suggest that the activity change observed after heating or drying to powder is due to the formation of surface states which may trap active electrons.This interpretation is also supported by the generated activity of ZnS-100 for the H2 photoevolution under >350-nm irradiation.ZnS photocatalysis under >350-nm irradiation and relationship with spectroscopic properties are also discussed.
- Yanagida, Shozo,Ishimaru, Yoshiteru,Miyake, Yoshio,Shiragami, Tsutomu,Pac, Chyongjin,et al.
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Read Online
- Regioselectivity and stereoelectronic effects in the reactions of the dinitroaniline herbicides trifluralin and benefin with nucleophiles
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The reactions of two members of the dinitroaniline class of herbicides, N,N-di-n-propyl-2,6-dinitro-4-(trifluoromethyl)aniline (trifluralin; 1) and N-ethyl-N-n-butyl-2,6-dinitro-4-(trifluoromethyl)aniline (benefin; 2), along with their analogue, N-phenyl-2,6-dinitro-4-(trifluoromethyl)aniline (3), with the nucleophiles, OD- and SO32-, have been investigated using 400 MHz 1H NMR spectroscopy. The reactions of both 1 and 2 with OD- result in formation of Meisenheimer anionic σ-complexes according to a K3T1 (kinetic preference for formation of the C-3 adduct with thermodynamic preference for formation of the C-1 adduct) reaction sequence while the reaction of 3 with OD- and that of 1 with SO32- follow a K3T3 (kinetic and thermodynamic preference for formation of the C-3 adduct) sequence. There was no observation of the C-1 adducts of 1 and 2 with OD-, but the products of S(N)Ar displacement at C-1 were observed as the final thermodynamic products. Geometry optimization calculations support our hypothesis of n → σ* stabilization of the C-1 adduct leading to S(N)Ar displacement. In the reaction of 3 with OD-, initial N-deprotonation to form the anion, 3a, is followed by σ-complex formation. The final thermodynamic product observed in this system is 3,5-dinitro-4-(N-phenylamino)benzoic acid formed through hydrolysis of the trifluoromethyl group on the anion, 3a. Aryl H-D exchange has been found for the systems of 1 and 2 with OD-, but not for the SO32- system and neither for the reaction of 3 with OD-. Since dimethylpicramide showed significantly slower H-D exchange under identical conditions, it is argued that this discrepancy has as origin the ability of the amino N lone electron pair to interact with the π-system of the ring. With both 1 and 2 the larger size of the amino alkyl chains prevent the amino N lone pair from aligning with the π-system of the ring, thus hindering electron density donation to the electron-deficient ring carbons.
- Annandale, Michael T.,VanLoon, Gary W.,Buncel, Erwin
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- A New and Convenient Process for Separation of Carbon Monoxide
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A new method for the efficient separation of carbon monoxide from a binary mixture of carbon monoxide and hydrogen has been established by use of a selenium/secondary amine reaction system.This system consists of the selective uptake of carbon monoxide by the reaction with selenium and secondary amines to form the corresponding ammonium carbamoselenoates (1) in solution and the release of carbon monoxide by thermolysis of 1 into starting components.The amount of separated carbon monoxide was stoichiometric and the purity was higher than 99.9percent.
- Sonoda, Noboru,Miyoshi, Noritaka,Tsunoi, Shinji,Ogawa, Akiya,Kambe, Nobuaki
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- Highly selective synthesis of primary amines from amide over Ru-Nb2O5 catalysts
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Amines are an important class of compounds in natural products and medicines. The universal availability of amides provides a potential way for the synthesis of amines. Herein, Ru/Nb2O5 catalyst is demonstrated to be highly efficient and stable for the selective hydrogenation of propionamide to propylamine (as a model reaction), with up to 91.4% yield of propylamine under relatively mild conditions. Results from XPS analyses, CO chemisorption, TEM images and DRIFTS spectra revealed that the unique properties of Nb2O5 can effectively activate the C=O group of amides, and the smaller Ru particles on Nb2O5 could further promote the activation, leading to superior catalytic performance of Ru/Nb2O5 for amide hydrogenation. Meanwhile, reducing the surface acidity of Nb2O5 can greatly inhibit the side reactions to by-products, and further enhance the selectivity to amine. Moreover, this catalytic system is also applicable for the hydrogenation of a variety of amides and provides high potential for the industrial production of primary amines from amides.
- Guo, Wanjun,Guo, Yong,Jia, Hongyan,Liu, Xiaohui,Pan, Hu,Wang, Yangang,Wang, Yanqin,Xia, Qineng
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supporting information
(2021/12/22)
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- A Lewis Base Nucleofugality Parameter, NFB, and Its Application in an Analysis of MIDA-Boronate Hydrolysis Kinetics
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The kinetics of quinuclidine displacement of BH3 from a wide range of Lewis base borane adducts have been measured. Parameterization of these rates has enabled the development of a nucleofugality scale (NFB), shown to quantify and predict the leaving group ability of a range of other Lewis bases. Additivity observed across a number of series R′3-nRnX (X = P, N; R′ = aryl, alkyl) has allowed the formulation of related substituent parameters (nfPB, nfAB), providing a means of calculating NFB values for a range of Lewis bases that extends far beyond those experimentally derived. The utility of the nucleofugality parameter is explored by the correlation of the substituent parameter nfPB with the hydrolyses rates of a series of alkyl and aryl MIDA boronates under neutral conditions. This has allowed the identification of MIDA boronates with heteroatoms proximal to the reacting center, showing unusual kinetic lability or stability to hydrolysis.
- García-Domínguez, Andrés,Gonzalez, Jorge A.,Leach, Andrew G.,Lloyd-Jones, Guy C.,Nichol, Gary S.,Taylor, Nicholas P.
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supporting information
(2022/01/04)
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- Titanium-Catalyzed Hydroaminoalkylation of Ethylene
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The first examples of titanium-catalyzed hydroaminoalkylation reactions of ethylene with secondary amines are presented. The reactions can be achieved with various titanium catalysts and they do not require the use of high pressure equipment. In addition, the first solid-state structure of a titanapyrrolidine that is formed by insertion of an alkene into the Ti?C bond of a titanaaziridine is reported.
- Rosien, Michael,T?ben, Iris,Schmidtmann, Marc,Beckhaus, Rüdiger,Doye, Sven
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supporting information
p. 2138 - 2142
(2020/02/05)
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- Sustainable hydrogenation of aliphatic acyclic primary amides to primary amines with recyclable heterogeneous ruthenium-tungsten catalysts
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The hydrogenation of amides is a straightforward method to produce (possibly bio-based) amines. However current amide hydrogenation catalysts have only been validated in a rather limited range of toxic solvents and the hydrogenation of aliphatic (acyclic) primary amides has rarely been investigated. Here, we report the use of a new and relatively cheap ruthenium-tungsten bimetallic catalyst in the green and benign solvent cyclopentyl methyl ether (CPME). Besides the effect of the Lewis acid promotor, NH3 partial pressure is identified as the key parameter leading to high primary amine yields. In our model reaction with hexanamide, yields of up to 83% hexylamine could be achieved. Beside the NH3 partial pressure, we investigated the effect of the catalyst support, PGM-Lewis acid ratio, H2 pressure, temperature, solvent tolerance and product stability. Finally, the catalyst was characterized and proven to be very stable and highly suitable for the hydrogenation of a broad range of amides.
- Coeck, Robin,Berden, Sarah,De Vos, Dirk E.
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supporting information
p. 5326 - 5335
(2019/10/11)
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- Reduction of Amides to Amines under Mild Conditions via Catalytic Hydrogenation of Amide Acetals and Imidates
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A simple and general protocol was developed for selective conversion of amides into amines. Amides were converted into amide acetals and imido esters by O-alkylation and then hydrogenated without isolation into amines under very mild reaction conditions over standard hydrogenation catalysts. Triethyloxonium tertafluoroborate, methyl trifluoromethanesulfonate, dimethyl sulfate and ethyl chloroformate were validated as alkylating agent. The synthetic utility of this approach was demonstrated by the selective carbonyl reduction of peptide groups. Carbonyl reduction of peptide group proceeds chemoselective without racemization of the neighboring chiral center. (Figure presented.).
- Kadyrov, Renat
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p. 185 - 191
(2018/11/23)
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- Continuous Production of Dialkylamines by Selective Hydrogenation of Nitriles on a Nickel-Zeolite Catalyst
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Hydrogenation of aliphatic nitriles in the presence of nickel supported by NaX zeolite was studied. The data obtained were used to develop a continuous method for obtaining dialkylamines with the yield of the target product of up to 98%.
- Popov, Yu. V.,Mokhov,Latyshova,Panov,Pletneva, M. Yu.
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p. 1778 - 1782
(2018/03/21)
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- Colloid and nanosized catalysts in organic synthesis: XVI.1 Continuous hydrogenation of carbonitriles catalyzed by nickel nanoparticles applied on a support
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Conversion of the starting nitriles and selectivity of the products formation during continuous hydrogenation of various nitriles catalyzed by Ni0/Ceokar-2 have been studied as functions of temperature. Performing the process at temperature 120–260°С has led to the formation of a mixture of products containing di- and trialkylamines as well as the corresponding imines and enamines.
- Popov, Yu. V.,Mokhov,Latyshova,Nebykov,Panov,Pletneva, M. Yu.
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p. 2276 - 2281
(2017/11/24)
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- Amphipathic monolith-supported palladium catalysts for chemoselective hydrogenation and cross-coupling reactions
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A palladium catalyst immobilized on an amphipathic and monolithic polystyrene-divinylbenzene polymer bearing strongly acidic cation exchange functions (sulfonic acid moieties) (Pd/CM) was developed. It was used as a catalyst for hydrogenation and ligand-free cross-coupling reactions, such as the Suzuki-Miyaura, Mizoroki-Heck, and copper- and amine-free Sonogashira-type reactions, together with a palladium catalyst supported on monolithic polymer (Pd/AM) bearing basic anion exchange functions (ammonium salt moieties), which has been in practical use for the decomposition of hydrogen peroxide produced as a byproduct during the manufacture of ultrapure water. While the Pd/CM was highly active as a catalyst for the hydrogenation and a variety of reducible functional groups could be reduced, the use of Pd/AM led to a unique chemoselective hydrogenation. Aromatic carbonyl groups were tolerant under the Pd/AM-catalyzed hydrogenation conditions, although benzyl esters, benzyl ethers, and N-Cbz groups could be smoothly hydrocracked. The cross-coupling reactions readily proceeded using either catalyst. The palladium leaching from the Pd/CM into the reaction media was never observed during the Sonogashira-type reaction, which was hardly achieved by other palladium-supported heterogeneous catalysts due to the good affinity of the palladium species with alkynes.
- Monguchi, Yasunari,Wakayama, Fumika,Ueda, Shun,Ito, Ryo,Takada, Hitoshi,Inoue, Hiroshi,Nakamura, Akira,Sawama, Yoshinari,Sajiki, Hironao
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p. 1833 - 1840
(2017/01/21)
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- Low-valent titanium-catalyzed deprotection of allyl- and propargyl-carbamates to amines
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In the presence of Me3SiCl, Ti(O-i-Pr)4/Mg and CpTiCl3/Mg reagents effectively catalyzed the deprotection of allyloxycarbonyl (alloc)- and propargyloxycarbonyl (poc)-protected amines in THF at around room temperature to produce parent amines in good yields. Alloc- and poc-protected secondary amines were smoothly deprotected to parent amines by a reaction catalyzed by a Ti(O-i-Pr)4/Me3SiCl/Mg reagent. The deprotection of alloc- and poc-protected primary amines was successfully catalyzed by a CpTiCl3/Me3SiCl/Mg reagent.
- Madhavan, Suchithra,Takagi, Hiromasa,Fukuda, Shunpei,Okamoto, Sentaro
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p. 2074 - 2077
(2016/04/26)
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- Development of chelate resin-supported palladium catalysts for chemoselective hydrogenation
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Abstract Two kinds of palladium catalysts immobilized on a chelate resin bearing diiminoacetate or polyamine moieties on the polystyrene-divinylbenzene polymer were newly prepared by the adsorption of palladium (II) ions on these resins followed by the reduction to palladium (0) with hydrazine monohydrate. Both catalysts showed a similar activity for hydrogenation. A variety of reducible functionalities, except for benzylic alcohol, alkyl benzyl ether, silyl ether, and epoxide, could be reduced under the hydrogenation conditions using either catalyst. Since the palladium metal elution from the immobilized catalysts was never observed, the catalysts could be reused without any decrease in the catalyst activity for at least 5 runs.
- Monguchi, Yasunari,Ichikawa, Tomohiro,Nozaki, Kei,Kihara, Kensuke,Yamada, Yuuko,Miyake, Yutaka,Sawama, Yoshinari,Sajiki, Hironao
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supporting information
p. 6499 - 6505
(2015/08/18)
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- A study of the selective catalytic hydroconversion of biomass-derived pyrolysis or fermentation liquids using propylamine and acetic acid as model reactants
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Silica-supported P or In modified Ni catalysts were active in the hydrodenitrogenation (HDN) and hydrodeoxygenation (HDO) of reactant propylamine (PA) and acetic acid (AA), respectively, in which reactants were selected to model platform molecules of biomass origin. The undesired CC hydrogenolysis activity of supported Ni catalyst, resulting in low value gaseous products, could be reined by the modification, generating silica-supported Ni2P and Ni2In active phases.
- Badari,Harnos, Sz.,Lónyi,Onyestyák, Gy.,?tolcová,Kaszonyi,Valyon
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- Unique Chemoselective Hydrogenation using a Palladium Catalyst Immobilized on Ceramic
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A heterogeneous palladium catalyst supported on a ceramic (5 % Pd/ceramic) was developed. The catalyst exhibited a specific chemoselectivity for hydrogenation that has never been achieved by other palladium-catalyzed methods. Either aliphatic or aromatic N-Cbz groups could be deprotected to the corresponding free-amines, while the hydrogenolysis of benzyl esters and ethers did not proceed. Furthermore, aryl chlorides and epoxides were tolerant under the Pd/ceramic-catalyzed hydrogenation conditions. 5 % Pd/ceramic could be reused without any loss of catalyst activity, as no palladium leaching was detected in the reaction media.
- Monguchi, Yasunari,Marumoto, Takahisa,Ichikawa, Tomohiro,Miyake, Yutaka,Nagae, Yoshiyuki,Yoshida, Michiyuki,Oumi, Yasunori,Sawama, Yoshinari,Sajiki, Hironao
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p. 2155 - 2160
(2015/11/24)
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- Iron-catalyzed Cα-H oxidation of tertiary, aliphatic amines to amides under mild conditions
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De novo syntheses of amides often generate stoichiometric amounts of waste. Thus, recent progress in the field has focused on precious metal catalyzed, oxidative protocols to generate such functionalities. However, simple tertiary alkyl amines cannot be used as starting materials in these protocols. The research described herein enables the oxidative synthesis of amides from simple, noncyclic tertiary alkyl amines under synthetically useful, mild conditions through a biologically inspired approach: Fe-catalyzed Cα-H functionalization. Mechanistic investigations provide insight into reaction intermediates and allow the development of a mild Cα-H cyanation method using the same catalyst system. The protocol was further applied to oxidize the drug Lidocaine, demonstrating the potential utility of the developed chemistry for metabolite synthesis. Let′s iron it out! The title reaction enables the oxidative synthesis of amides directly from tertiary, noncyclic alkyl amines under synthetically useful, mild conditions through a biologically inspired approach employing oxidative iron catalysis. Mechanistic studies suggest that hemiaminals are likely intermediates in this reaction and that the catalytic system can be employed for other Cα-H oxidations of amines.
- Legacy, Christopher J.,Wang, Anqi,O'Day, Brian J.,Emmert, Marion H.
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supporting information
p. 14907 - 14910
(2016/02/05)
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- Amination of alcohols with ammonia in water over Rhin catalyst
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Amination of various C3 alcohols such as 1,2-propanediol with ammonia was catalyzed by RhIn/C in water while Rh/C was totally inactive. Activated carbon FAC-10 was the best support in terms of activity and resistance to metal leaching. In the amination of 1,2-propanediol, RhIn/C produced amino alcohols in 68% total selectivity and 38% conversion. XRD and TEM measurements showed that RhIn alloy particle with size of 34 nm was formed on the carbon support.
- Takanashi, Tsukasa,Nakagawa, Yoshinao,Tomishige, Keiichi
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p. 822 - 824
(2014/06/23)
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- Catalytic hydrogenation of amides to amines under mild conditions
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Under (not so much) pressure: A general method for the hydrogenation of tertiary and secondary amides to amines with excellent selectivity using a bimetallic Pd-Re catalyst has been developed. The reaction proceeds under low pressure and comparatively low temperature. This method provides organic chemists with a simple and reliable tool for the synthesis of amines. Copyright
- Stein, Mario,Breit, Bernhard
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supporting information
p. 2231 - 2234
(2013/03/28)
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- An efficient synthesis of tertiary amines from nitriles in aprotic solvents
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Tertiary amines are utilized extensively as non-nucleophilic proton scavengers for a number of organic transformations. Herein we report the efficient syntheses of tertiary alkyl amines from their corresponding alkyl nitriles in the presence of a heterogeneous palladium catalyst and a source of dihydrogen in aprotic solvents. The reaction is atom economic, the conditions are mild, and the isolated yields are virtually quantitative. The degree of amine alkylation shows some solvent dependency; in polar protic solvents such as ethanol or methanol, the reaction affords a mixture of products with the secondary alkyl amine as the major product.
- Shares, Jonathan,Yehl, Jenna,Kowalsick, Amanda,Byers, Philip,Haaf, Michael P.
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experimental part
p. 4426 - 4428
(2012/09/25)
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- Novel antimalarial 3-azabicyclo[3.2.2]nonane derivatives
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The present invention relates to novel 3-azabicyclo[3.2.2]nonane derivatives of the general formula (I) or a pharmaceutically acceptable salt thereof wherein R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 are as defined in the specification. The novel 3-azabicyclo[3.2.2]nonane derivatives are particularly useful for treatment and prevention of malaria and trypanosomiasis.
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- Transformations of dialkyl(4-hydroxy-2-butynyl)-(3-phenylallyl)ammonium bromides in an KOH aqueous solution or in the presence of powdered KOH
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Under the action of a twofold excess of KOH and heating in aqueous solution, and also under the conditions of the Stevens rearrangement (with KOH powder and a small amount of methanol) dialkyl-(4-hydroxy-2-butynyl)(3- phenylallyl)ammonium bromides form dialkyl[4-(1-phenylallyl)-2,5-dihydro-2- furyl]amines. Rearrangement-cleavage reaction also occurs under the same conditions.
- Chukhadjian,Gabrielyan,Chukhadjian,Shahkhatuni,Panosyan
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p. 418 - 424
(2012/01/13)
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- Rapid and convenient approach to amines: Reduction of imines using metallic calcium in ethylalcohol
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The reduction of imines using metallic calcium in alcohol rapidly gave the corresponding secondary amines, in good yields.
- Mitoma, Yoshiharu,Egashira, Naoyoshi,Simion, Cristian,Tashiro, Masashi
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p. 839 - 842
(2007/10/03)
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- Highly chemoselective hydrogenation method using novel finely dispersed palladium catalyst on silk-fibroin: Its preparation and activity
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A palladium-fibroin complex (Pd/Fib) was prepared by soaking silk-fibroin in MeOH solution of Pd(OAc)2 for 2 days (under Ar atmosphere) - 4 days (under air). Pd(OAc)2 was gradually absorbed by fibroin and the rapid reduction of fibroin conjugated Pd(OAc)2 proceeded with MeOH as a reductant at room temperature to be the Pd(0) complex. Pd/Fib catalyzed chemoselective hydrogenation of acetylenes, olefins and azides in the presence of aromatic ketones and aldehydes, halides, N-Cbz protective groups and benzyl esters which are readily hydrogenated using Pd/C or Pd/C(en) as a catalyst.
- Ikawa, Takashi,Sajiki, Hironao,Hirota, Kosaku
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p. 2217 - 2231
(2007/10/03)
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- HOMOGENOUS PROCESS FOR THE HYDROGENATION OF CARBOXYLIC ACIDS AND DERIVATIVES THEREOF
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A homogenous process for the hydrogenation of the carboxylic acids and/or derivatives thereof in the presence of a catalyst comprising ruthenium, rhodium, iron, osmium or palladium, and an organic phosphine is described in which the hydrogenation is carried out in the presence of at least about 1% by weight water. A process for regenerating a catalyst comprising ruthenium, rhodium, iron, osmium or palladium and an organic phosphine is also described in which the regeneration is carried out in the presence of hydrogen and water.
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Page/Page column 13
(2008/06/13)
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- Therapeutically useful 2-aminotetralin derivatives
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This invention is therapeutically useful 2-aminotetralins and pharmaceutically acceptable acid addition salts thereof of the formula These compounds are useful to treat central nervous system disorders, hypertension, diabetes, sexual impotency and to control appetite.
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- Phenylureas. Part 2. Mechanism of the acid hydrolysis of phenylureas
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The mechanism of the hydrolytic decomposition of phenylureas in acid media is investigated. It includes, in part, knowledge already present in the literature. Over the investigated pH range the occurrence of a rate maximum in the pH curves due to the strongly reduced water activity at higher acid strengths is observed. An addition-elimination mechanism with rate-determining attack of water at the N-protonated substrate is proposed. The reversion of the substituent influence on the reaction rate with increasing acidity of the reaction medium points to a change of the hydrolytic decomposition mechanism in strongly acidic media.
- Laudien, Robert,Mitzner, Rolf
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p. 2230 - 2232
(2007/10/03)
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- The conversion of 1-propanamine on copper-containing MFI and BEA zeolites prepared by aqueous and vapor ion-exchange
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A process has been developed for exchanging one Cu atom per ion exchange site in an MFI zeolite. The material is synthesized by reaction of the acidic zeolite with CuCl vapor, followed by oxidation with oxygen, and conversion of the Cu2+ species to copper hydroxyl ions and copper hydroxyl dimers by reaction of the oxidized material with water upon exposure to humid air. This material, a similarly prepared BEA material, and copper-containing MFI and BEA zeolites prepared by conventional aqueous ion-exchange have been comparatively investigated for the conversion of 1-propanamine. Reaction products include C6 products such as dipropanamine and 1-propanamine, N-(1-propylidene). A bifunctional acid/metal reaction pathway is proposed to account for the observed products.
- Guidry, Trent F.,Price, Geoffrey L.
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- Preparation of amines
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A process for preparing an amine by catalytic reaction of an olefin with ammonia or a primary or secondary amine by contacting a mixture of the reactants in a reactor at 200° to 400° C. and an elevated pressure up to 700 bar in the presence of a catalyst consisting essentially of an X-ray amorphous (non-crystalline) mesoporous catalyst, some of which may have a microporous non-crystalline content. The catalyst has the composition where Q is at least one of the trivalent elements aluminum, boron, chromium, iron or gallium, and M is at least one of the tetravalent elements silicon, titanium or germanium. The molar ratio of a:b is from 0.5:1 to 1000:1 and the molar ratio of c:b is from 0 to 2:1. As prepared and used in the process, this non-crystalline catalyst has a specific BET surface area of from 200 to 1000 m2 /g.
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- THERAPEUTICALLY USEFUL 2-AMINOTETRALIN DERIVATIVES
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This invention is therapeutically useful 2-aminotetralins and pharmaceutically acceptable acid addition salts thereof of the formula STR1 R, R 1 to R 5 and p are as defined in the specification, these compounds are useful to treat central nervous system disorders, hypertension, diabetes, sexual impotency and to control appetite.
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- N-SUBSTITUTED DERIVATIVES OF (ALPHA)-MERCAPTO ALKYLAMINES, THEIR PREPARATION PROCESS AND THE INTERMEDIATES OBTAINED, THEIR USE AS MEDICAMENTS AND THE COMPOSITIONS CONTAINING THEM
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Novel α-mercapto-alkylamines in all possible racemic, enantiomeric and diastereoisomeric forms of the formula STR1 wherein n, R 1, R 2, X, A, R 3A and R 4A are set forth in the claims and their non-toxic, pharmaceutically acceptable acid addition salts having excellent analgesic, psychotropic and enkephalinase inhibiting properties.
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- Temperature and Pressure Effects on the Reversible Reaction of a Parent Phenol (GH) Corresponding to Galvinoxyl with Aliphatic Amines
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The effects of temperature and pressure on the reversible reaction between GH and aliphatic amines in acetonitrile have been studied spectrophotometrically.The formation of the free ions rather than that of ion pairs has been confirmed by the modified Benesi-Hildebrand (B-H) plot.From the plot the equilibrium constants were estimated.From the temperature dependence of the equilibrium constant (K), the heat and entropy of reactions were estimated to be: (ΔH0)av=-44.5 kJ mol-1, and (ΔS0)av=-193 J K-1 mol-1.From the pressure dependence of K the reaction volume (ΔV0)av was estimated to be -40 dm3 mol-1.When unbranched primary amines were used, a side reaction took place for which an explanation has been given.
- Nishimura, Norio,Iga, Siroh,Satoh, Masahiro,Yamamoto, Shunzo
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p. 2437 - 2441
(2007/10/02)
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- PHOSPHONIUM DIAZA-DIYLIDS AND AZA-YLDIID AS NEW AND EFFICIENT REAGENTS FOR PRIMARY AND SECONDARY AMINES SYNTHESIS
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Metallated aminophosphonium ylids, diaza-diylids and aza-yldiid, are investigated as reagents for primary and secondary amines synthesis.
- Cristau, Henri-Jean,Garcia, Chantal,Kadoura, Jumah,Torreilles, Eliane
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p. 151 - 154
(2007/10/02)
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- NEW ACYCLIC AND FUSED TRICYCLIC PHOSPHORUS COMPOUNDS AFFORDED BY NOVEL CONDENSATION
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The condensation of 1-(2-benzothiazolyl)-4-phenylsemicarbazide with (R2N)2PX (X = R2N, RO, Ph) proceeds with cleavage of the N-C(O) bond and formation of the title compounds which were also synthesized via similar treatment of 2-hydrazinobenzothiazole in good yields.Reactivities of (R2N)2PX, spectroscopic properties of the products and preliminary mechanism of these reactions were discussed.
- Zhang, Jing-Lin,Ma, Xiao-Bo
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p. 291 - 298
(2007/10/02)
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- The selective preparation of n-propylamines by the rhodium catalysed reaction of ethylene and syngas with alkylamines
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The aminoethylation of ethylene with a primary amine has been shown to provide a highly selective route to n-propylamines; the rhodium catalysed reaction of n-propylamine with ethylene and syngas (2/1, H2/CO) affords di-n-propylamine with 98percent selectivity (with respect to ethylene).The reaction of amines of the type RR1NH with the ethylene/syngas mixture and a rhodium catalyst provides a highly selective and general route to the n-propylamines RR1NPr (R=Pr, R1=H; R=t-Bu, R1=H; R=n-Bu, R1=H; R=C8H17, R1=H, R=R1=Pr; R=HOCH2Ch2, R1=H, and R=PhCH(OH)CH2, R1=H).
- Jones, M. D.
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p. 403 - 408
(2007/10/02)
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- ZINC SULFIDE-CATALYZED PHOTOCHEMICAL CONVERSION OF PRIMARY AMINES TO SECONDARY AMINES
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Nonmetallized ZnS catalizes efficiently the photochemical conversion of primary amines to secondary amines with liberation of ammonia under irradiation of the UV light of λ>290 nm.The conversion is interpreted as due to the two-hole-oxidation of primary amines to Schiff bases and their two-electron-reduction to secondary amines by the photogenerated electrons in ZnS.
- Yanagida, Shozo,Kizumoto, Hirotoshi,Ishimaru, Yoshiteru,Pac, Chyongjin,Sakurai, Hiroshi
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p. 141 - 144
(2007/10/02)
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- FACILE GENERATION OF DIALKYLAMINYL RADICALS FROM N-HYDROXYPYRIDINE-2-THIONE CARBAMATES. APPLICATION IN KINETIC STUDIES OF SMALL RING CYCLOALKYLAMINYL RADICAL RING OPENINGS
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The preparation of N-hydroxypyridine-2-thione carbamates and the formation of dialkylaminyl radicals from these species are described, and the application of this methodology in kinetic studies of aminyl radical rearrangements is demonstrated.
- Newcomb, Martin,Park, Seung-Un,Kaplan, Jere,Marquardt, Donald J.
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p. 5651 - 5654
(2007/10/02)
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- COMPETITIVE HYDROGENATION OF A NITRILE FUNCTION AND OF AN OLEFINIC UNSATURATION ON RANEY NICKEL
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The selectivity in the competitive hydrogenation of the carbon-carbon double bond and the carbon-nitrogen triple bond has been studied on Raney nickel.This selectivity is different in the case of intramolecular competition (bifunctional molecules) and intermolecular competition (two monofunctional molecules).For intermolecular competition, the adsorption factor is decisive: nitriles are hydrogenated and olefins are unreactive.In the case of bifunctional molecules, the olefinic unsaturation reacts first.Therefore, a more intricate mechanism must be assumed.
- Dallons, Jean Luc,Jannes, Georges,Delmon, Bernard
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p. 223 - 232
(2007/10/02)
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- Reduction of Nitrosamines with Aqueous Titanium Trichloride: Convenient Preparation of Aliphatic Hydrazines
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The reduction of selected nitrosamines by aqueous TiCl3 has been investigated.In general, aliphatic nitrosamines were converted in good yield to the corresponding hydrazines, with little overreduction to the amines.Reaction proceeded rapidly at room temperature in both alkaline and acidic media.A variety of N,N-dialkylhydrazines have been isolated by using the TiCl3 method, which compares favorably with previously reported procedures for preparatively converting nitrosamines to hydrazines.In the reduction of N-nitroso-N-methylaniline, the proportion of amine in the product increased significantly as the pH of the reaction mixture was lowered, presumably reflecting the known instability of arylalkylnitrosamines in strong acid, coupled with a ready reducibility of the corresponding Fischer-Hepp intermediates; some tendency toward reductive cleavage of the N-aryl-N-alkylhydrazine's N-N-bond was also noted.Reduction of an α-nitrosamino ether gave the monoalkylhydrazine as the major product, while all other reducing agents studied converted this starting material chiefly to a mixture of primary and secondary amines.
- Lunn, George,Sansone, Eric B.,Keefer, Larry K.
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p. 3470 - 3473
(2007/10/02)
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- INVESTIGATION OF THE SALTS FORMED AS A RESULT OF THE REACTION OF HETEROCUMULENES CO2, COS, AND CS2 WITH SECONDARY AMINES BY 13C AND 1H NMR
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The properties of the salts formed as a result of the reactions of carbon dioxide, carbon sulfoxide and carbon disulfide with dimethyl-, diethyl-, dipropyl-, ethylcyclohexyl-, and dicyclohexylamines, morpholine, piperidine, and hexamethyleneimine were investigated by 13C and 1H NMR methods.The free energies of activation were obtained for restricted rotation about the N-COS bond in the thiocarbamate ions of the alkylammonium thiocarbamates and also for the formation and decomposition of the carbamate ions of the alkylammonium carbamates.
- Savin, V. P.,Talzi, V. P.,Bek, N. O.
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p. 1680 - 1688
(2007/10/02)
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- CYCLIZATION OF YNAMINES OF THE VINYLACETYLENIC SERIES WITH BINUCLEOPHILIC REAGENTS
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The reactions of 1-dialkylamino-3-penten-1-ynes with ethylenediamine and ethanolamine lead to 2-substituted imidazolines and oxazolines.The reaction with 2-mercaptoethanol and 1,2-ethanethiol gives 2-substituted 1,3-oxathiolanes and 1,3-dithiolanes without elimination of dialkylamino group.
- Sokolova, E. A.,Maretina, I. A.,Petrov, A. A.
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p. 820 - 825
(2007/10/02)
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- Denitrosation of Nitrosamines to Secondary Aliphatic Amines with Chlorosulphonyl Isocyanate
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A novel method for the denitrosation of nitrosamines with chlorosulphonyl isocyanates is described.
- Dhar, Durga N.,Bag, Amal K.
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- Photochemical and Photophysical Studies of Amines with Excited Flavins. Relevance to the Mechanism of Action of the Flavin-Dependent Monoamine Oxidase
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The photochemical reactions between 3-methyllumiflavin (3-MLF) and β,γ-acetylenic, β,γ,δ-allenic, and saturated amines, in aqueous and nonhydroxylic solvents, have been investigated.The fluorescence of 3-MLF in nonhydroxylic solvents is efficiently quenched by all amine studied, with values of ks (the rate constant for quenching of singlet of 3-MLF) near the calculated rate of diffusion.Quenching rates in aqueous solution are pH and concentration dependent and indicate that the free amine is required for the observation of fluorescence quenching.Whereas amine quenching of singlet 3-MLF is nonproductive, quenching of triplet 3-MLF leads to adducts that can be isolated from the reaction of the allenic and β,γ-acetylenic amines but that are unstable in the case of saturated amines.The isolated products from β,γ,δ-allenic amines 2a and 2b are flavocyanines.The reactions of β,γ-acetylenic amines with triplet 3-MLF give more complicated product mixtures that include flavocyanines and C4a,N5 adducts in similar amounts.These studies are consistent with a pathway involving one-electron transfer from amine to triplet 3-MLF, followed by succesive proton and one-electron transfers leading to reduced flavin and iminium ion intermediates.
- Simpson, J. T.,Krantz, A.,Lewis, F. D.,Kokel, B.
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p. 7155 - 7161
(2007/10/02)
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- Comparison of the Activity and Lifetime of Raney Nickel and Nickel Boride in the Hydrogenation of Various Functional Groups
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Nickel borides (Ni2B) are prepared by the reduction of a nickel salt with sodium borohydride.These materials have been shown to be active hydrogenation catalysts.The activity and lifetime of a P-1.50 nickel boride catalyst, which is prepared in a 50percent water/ethanol solvent, are reported for the hydrogenation of unsaturated carbon and nitrogen bonds and for aldehydes.The data are compared to those obtained for similar reductions which employ Raney nickel as the catalyst.The nickel boride is more active and productive than Raney nickel in the hydrogenation of hexene,cyclohexene, and acrylonitrile.The properties of the two catalysts are similar for the reduction of cinnamaldehyde, 2-ethylhexanal, and benzaldehyde.The data for the reduction of nitrobenzene, adiponitrile, and propionitrile indicate that the nickel boride is more susceptible to nitrogen poisoning than Raney nickel.
- Schreifels, John A.,Maybury, P. Calvin,Swartz, William E.
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p. 1263 - 1269
(2007/10/02)
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- Synthesis of β-aminostyrenes
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A simple process for the preparation of β-aminostyrenes proceeds from anilines by successively diazotizing, reacting with a vinyl ester, and reacting with a secondary amine without purification of the intermediate products. The compounds are reactive enamines useful in organic synthesis.
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- Mecansime de cyclisation des dialkylamino-3 hydroxy-7 heptanenitriles en milieu basique; mise en evidence par spectroscopie Raman Laser rapide d'un intermediaire ethylenique
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-3-dialkylamino 7-hydroxy heptanonitrile and 2-methyl 3-dialkylamino 7-hydroxy heptanonitrile undergo cyclization at 180 deg C to α-tetrahydropyrannyl acetonitrile and 2 (α-tetrahydropyrannyl) propionitrile in presence of a catalytic amount of base.Two possible mechanisms may be proposed for this reaction 1) An intramolecular nucleophilic substitution (SN2 type). 2) An elimination-addition process.We study the reaction mechanism by deuterium substitution and by Raman Laser rapid spectrometry.The latter technique allows to identify the conjugated double bond of the intermediate.This evidence strongly supports the two-step elimination-addition mechanism for this cyclization reaction.
- Maciejewski, Lucien,Brocard, Jacques,Glacet, Charles
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p. 255 - 260
(2007/10/02)
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- 5 (6)-Benzene ring substituted benzimidazole-2-carbamate derivatives having anthelmintic activity
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Benzene ring substituted benzimidazole-2-carbamate derivatives represented by the formula: STR1 where R is a lower alkyl group having 1 to 4 carbon atoms; R' is lower alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 7 carbon atoms, lower alkenyl or lower alkynyl having 3 to 6 carbon atoms, or phenyl; R2 is hydrogen or R'; the R'R2 NC(O)- substitution being at the 5(6)-position; and the pharmaceutically acceptable salts thereof. The compounds are useful as pesticides, particularly as anthelmintic and antifungal agents.
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- Antimicrobial composition and method containing N-(3,5-dihalophenyl)-imide compounds
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Novel N-(3,5-dihalophenyl)imide compounds, which exhibit a strong antimicrobial activity against microorganisms including phytopathogenic fungi, parasites of industrial products and pathogenic microorganisms, represented by the formula, STR1 wherein X and X' each represent halogens and A represents a substituted ethylene such as chloroethylene, C1 - C4 alkylthioethylene, C1 - C2 alkyl-ethylene or 1,2-di-C1 - C2 -alkyl-ethylene, a cyclopropylene such as 1,3-dimethylcyclopropylene, trimethylene, a cyclohexylene-1,2-, cyclohexenylene-1,2-, cyclohexadienylene-1,2- or o-phenylene. The N-(3,5-dihalophenyl)imide compounds can be obtained by any of methods which produce imide compounds or reaction of an N-(3,5-dihalophenyl)maleimide compound with a mercaptan, a hydrogen halide, phosphorus chloride or thionylchloride.
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