- Kinetics of C-C and C-H bond cleavage in phenyl alkane radical cations generated by photoinduced electron transfer
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Employing nanosecond laser flash photolysis, we determined the relative importance of two fragmentation modes, namely, C-C bond cleavage and deprotonation, for the radical cation of 1,1,2,2-tetraphenylethane photogenerated by electron transfer to cyanoaromatic singlet excited states in acetonitrile at room temperature. Analysis of the kinetic data for this phenyl alkane suggests that the C-C bond cleavage dominates over the deprotonation by a ratio of about 2:1. In addition, the deprotonation kinetics of diphenylmethane, 1,1-diphenylethane, triphenylmethane, and several phenyl-substituted alcohols have been investigated. To aid identification and characterization, experiments based on two laser pulses in tandem (308 and 337.1 nm) were performed to probe fluorescence and photochemistry of the transient radicals formed as products of radical ion fragmentation. The first-order rate constants for growth of transient absorptions due to fragmentation-derived radicals were measured to be ≥1 × 106 s-1. Activation parameters, with activation enthalpies in the range 10-18 kJ/mol and activation entropies between -60 and -91 J/(mol.K), are also reported for fragmentation kinetics of radical cations of several systems under study. (Graph Presented).
- Cyr, Douglas,Das, Paritosh
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- Triphenylbismuth Dichloride-Mediated Conversion of Thioamides to Nitriles
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Thioamides were efficiently converted to nitriles using the pentavalent triphenylbismuth dichloride in combination with triethylamine. The reaction involved the dehydrosulfurization of primary thioamides to afford substituted aromatic or aliphatic nitriles in good to excellent yields. The process was also successfully extended to the synthesis of cyanamides starting from the corresponding thioureas and of thiocyanates from dithiocarbamates.
- Gopi, Elumalai,Gravel, Edmond,Doris, Eric
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supporting information
p. 4043 - 4045
(2019/06/24)
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- Catalytic Dehydrosulfurization of Thioamides to Nitriles by Gold Nanoparticles Supported on Carbon Nanotubes
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A gold-carbon nanotube nanohybrid was shown to act as an efficient heterogeneous catalyst in the smooth and selective conversion of thioamides to the corresponding nitriles. The reaction was performed under mild conditions (room temperature, atmospheric pressure of oxygen) using only a gold loading of 0.35 mol %. Substituted aromatic or aliphatic nitriles were produced in very good to excellent yields and the catalyst could be easily recycled and reused over several consecutive cycles with no loss in dehydrosulfurization performances.
- Gopi, Elumalai,Geertsen, Valérie,Gravel, Edmond,Doris, Eric
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p. 5758 - 5761
(2019/05/21)
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- Corresponding amine nitrile and method of manufacturing thereof
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The present invention relates to a nitrile manufacturing method, which has characteristics of significantly-reduced ammonia source consumption, low environmental pressure, low energy consumption, low production cost, high nitrile purity, high nitrile yield and the like compared with the method in the prior art, wherein nitrile having a complicated structure can be obtained through the method. The present invention further relates to a method for producing a corresponding amine from the nitrile.
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Paragraph 0135; 0136; 0137; 0140; 0141
(2018/05/24)
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- Corresponding amine nitrile and method of manufacturing thereof
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The invention relates to a preparation method of nitrile. Compared with the prior art, the preparation method has the characteristics of obvious reduction of the usage amount of ammonia sources, low environmental pressure, low energy consumption, low production cost, high purity and yields of nitrile products, and the like, and can be used for obtaining nitrile with a more complex structure. The invention also relates to a method for preparing corresponding amine with nitrile.
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Paragraph 0132; 0133; 0134; 0136; 0138
(2018/05/24)
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- Corresponding amine nitrile and method of manufacturing thereof (by machine translation)
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The invention relates to a method of manufacturing one kind of nitrile, compared with the prior art, has significantly reduced the amount of ammonia, the environmental pressure of the small, low energy consumption, low production cost, nitrile product purity and yield and the like, and can obtain more complex structure of the nitriles. The invention also relates to the corresponding amine by the nitrile manufacture method. (by machine translation)
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Paragraph 0134; 0138-0139
(2017/10/22)
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- Environmentally benign and economic synthesis of covalent triazine-based frameworks
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Covalent triazine-based frameworks (CTFs) are important microporous materials with a wide range of applications. Here, we demonstrate an environmentally benign and economic synthetic pathway to CTFs. The monomers used for CTFs, aromatic nitriles, were obtained by cyanation using nontoxic potassium hexacyanoferrate(II) in place of commonly used toxic cyanides. Then, the CTFs were synthesized by trimerization of the corresponding cyano monomers in molten zinc chloride. A series of CTFs was synthesized, and the highest Brunauer-Emmett-Teller surface area measured in this series was 2404 m2/g. Among the synthesized CTFs, CTFDCP exhibited excellent CO2 adsorption properties, with a CO2 uptake of 225 mg/g at 0 °C.
- Zhang, Ling,Liu, Xue,Yang, Rui-Xia,Huang, Nian-Yu,Deng, Wei-Qiao
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p. 583 - 588
(2017/04/04)
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- An environmentally benign procedure for the synthesis of aryl and arylvinyl nitriles assisted by microwave in ionic liquid
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Aryl and arylvinyl nitriles have been prepared in good yields from the corresponding bromides with potassium hexacyanoferrate (II) using palladium-catalyzed reactions in ionic liquid under microwave irradiation. Georg Thieme Verlag Stuttgart.
- Li, Lian-Hua,Pan, Zhen-Liang,Duan, Xin-Hua,Liang, Yong-Min
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p. 2094 - 2098
(2008/02/05)
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- Bromination of tetralin. Short and efficient synthesis of 1,4-dibromonaphthalene
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High-temperature bromination of tetralin (1,2,3,4-tetrahydronaphthalene) with bromine resulted in benzylic biomination to give 1,4-dibromo-1,2,3,4-tetrahydronaphthalene (4) as a major product and several secondary products. Photolytic bromination of tetralin and subsequent double dehydrobromination of 1,1,4,4-tetrabromo-1,2,3,4-tetrahydronaphthalene (10) gave 1,4-dibromonaphthalene (11) as the sole product in a high yield. 1,4-Dibromonaphthalene is efficiently converted to the corresponding methoxy (12 and 13) and cyano (14 and 15) derivatives of naphthalene.
- Cakmak, Osman,Kahveci, Ismail,Demirtas, Ibrahim,Hoekelek, Tuncer,Smith, Keith
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p. 1791 - 1804
(2007/10/03)
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- Set Photochemical Reactions between 1,4-Naphthalenedicarbonitrile and Benzylic Donors. Medium Effects
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The electron transfer induced photochemical reactions 1,4-naphthalenedicarbonitrile (NDN) with toluene (1a), diphenylmethane (1b), p-methoxytoluene (1c), and benzyltrimethylsilane (1d) in MeOH-MeCN and 0.1 M KOH-MeOH-MeCN were examined.The results were compared with those of reactions occurring in neat MeCN.Under the former conditions, the cation radical derived from 1a undergoes deprotonation after diffusion from (rather than within) the geminate ion pair (as in MeCN).The formed benzyl radical abstracts a hydrogen from MeOH leading to hydroxymethylation of NDN competitively with its benzylation.Under basis conditions MeO(-) adds to 1a(+.) yielding 1c.The reaction of 1b in MeOH-MeCN and 0.1 M KOH-MeOH-MeCN is similar to that of 1a.However, in the reaction of 1c under these conditions, the arene cation radical undergoes deprotonation out of cage.Finally, desilylation of the cation radical from 1d is a fast process occurring from the geminate pair in all the media explored.
- Fasani, E.,d'Alessandro, N.,Albini, A.,Mariano, P. S.
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p. 829 - 835
(2007/10/02)
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- SRN1 SYNTHESES OF BIS(PHENYLTHIO)- AND DICYANO-NAPHTHALENES VIA DIAZOSULFIDES
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The reactions of bromonaphthalenediazonium tetrafluoroborates (6a,b and 11a,b) with sodium benzenethiolate in DMSO give, through the preliminary formation of the corresponding diazosulfides (7a,b and 12a,b) bis(phenylthio)naphthalenes (8a,b and 13a,b) deriving from substitution of both the diazo group and the bromine.Isolated diazosulfides (7a,b and 12a,b) likewise furnish satisfactory yields of dinitriles (9a,b and 14a,b) by reaction with excess tetrabutylammonium cyanide in DMSO under photostimulation by a sunlamp.The intervention of an SRN1 process accounting for the formation of the disubstitution products is postulated.
- Novi, M.,Garbarino, G.,Petrillo, G.,Dell'Erba, C.
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p. 2205 - 2212
(2007/10/02)
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- New Dyes from Naphthostyril-5-carboxylic Acid: Synthesis of 6,12-Anthanthrenedione-3,4,9,10-tetracarboxylic Diimides, Naphthostyril-5,6-dicarboximides and 1-Amino-4-arylaminonaphthalene-5,8-dicarboxylic Bislactams
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The novel vat dyes 6,12-anthanthrenedione-3,4,9,10-tetracarboxylic diimides (XIa-c) and the disperse dyes, naphthostyril-5,6-dicarboximides (XVIIIa-f) and bislactams (XIXa-d) have been synthesised from a common intermediate, naphthostyril-5-carboxylic acid (V).An improved method has also been developed for the synthesis of V.
- Dalvi, S.S.,Seshadri, S.
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p. 377 - 382
(2007/10/02)
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- Chemistry of anti- and syn-1,2:3,4-Naphthalene Dioxides and Their Potential Relevance as Metabolic Intermediates
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The reactivity, site of attack, and stereochemistry of reactions of a variety of nucleophiles with the anti- and syn-1,2:3,4-naphthalene dioxides have been explored.In most cases, substituted tetrahydronaphthalene products arising through attack at the C-1 and C-4 positions in the anti mode were obtained.These isomeric dioxides provide excellent precursors for a number of difficultly accessible 1,4-disubstituted naphthalene derivatives such as 1,4-diphenoxynaphthalene and 1,4-dicyanonaphthalene.Evidence is also presented that anti-naphthalene dioxide constitutes an intermediate metabolite in the rat.
- Tsang, Wing-Sum,Griffin, Gary W.,Horning, M. G.,Stillwell, W. G.
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p. 5339 - 5353
(2007/10/02)
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- Naphtholactam dyestuffs
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A naphtholactam dyestuff of the general formula (I) STR1 in which R represents alkyl, alkenyl, cycloalkyl, aralkyl, aryl or, preferably, hydrogen, M represents hydrogen or a cation, X represents =O, =NH or =NR', Y represents a free or modified carboxyl group, Z represents a non-ionic substituent, n represents 0, 1 or 2, B represents a group which completes ring A to give a heterocyclic structure, R' represents alkyl, alkenyl, cycloalkyl, aralkyl, aryl, or, preferably, hydrogen and E and F can carry further non-ionic substituents. The new dyestuffs give brilliant yellow and red shades on polyester fibres.
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- New Synthesis of 1,4-Naphthalenedicarbonitrile
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o-Phenylenediacetonitrile (1) reacts with Schiff bases 2 of glyoxal via elimination of corresponding imines to 1,4-naphthalenedicarbonitrile (3).The adduct 4 is isolated as an intermediate of this reaction.By addition of a further molecule of 2 to 4 the tricycle 5 can be obtained; its structure is characterized by X-ray structure analysis.
- Heiss, Lorenz,Paulus, Erich F.,Rehling, Herbert
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p. 1583 - 1596
(2007/10/02)
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- Process for the preparation of 1,4-naphthodinitrile
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Process for the preparation of 1,4-naphthodinitrile, by reacting o-phenylene-diacetonitrile with a glyoxalbisaldimine. By this process the 1,4-naphthodinitrile is easily obtained in a one-step process. This compound is an important intermediate for the production of 1,4-naphthalene-dicarboxylic acid.
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- Process for the manufacture of 1,4-disubstituted bicyclic or tricyclic compounds and new 1,4-disubstituted bicyclic compounds
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The present invention provides a new process for the manufacture of 1,4-disubstituted bicyclic or tricyclic compounds by reacting a 1,2-bis-cyanomethyl-benzene or 2,3-bis-cyanomethyl-naphthalene with glyoxal in the presence of a base and a solvent as well as new 1,4-disubstituted bicyclic compounds.
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