- Copper(I) halide complexes with N,N′-diallyl-N,N,N′,N′- tetramethylethylenediaminium (L2+). Synthesis and crystal structures of the complexes [L0.5CuCl2], [L0.5CuCl 0.72Br1.28], and [L0.5CuBr2]
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The Eschweiler-Clarke reaction of ethylenediamine with formaldehyde and formic acid yielded N,N,N′,N′-tetramethylethylenediamine, which was alkylated with allyl chloride or allyl bromide to give the corresponding N,N′-diallyl-N,N,N′,N′-tetramethylethylenediaminium (L 2+) dihalides. In methanolic solutions of copper(II) halide and an appropriate ligand, ac electrochemical synthesis with copper wire electrodes afforded single crystals of Cu(I) complexes with L2+: [L 0.5CuCl2] (I), [L0.5CuCl0.72Br 1.28] (II), and [L0.5CuBr2] (III). The crystal structures of complexes I-III were determined by X-ray diffraction study. The isostructural crystals of I and II are monoclinic, space group P21/n, Z = 4. For I: a = 7.632(4) A, b = 11.318(5) A, c = 10.635(5) A, β = 98.551(7)°, V = 908.4(7) A3. For II: a = 7.7415(7) A, b = 11.4652(9) A, c = 10.7267(10) A, β = 98.351(4)°, V = 942.0(2) A3. The organic cation L 2+ acts as a bridge linking a pair of separate cuprous halide fragments Cu2X4. Although being isostoichiometric with I and II, complex III has a different structure. The crystals of III are monoclinic, space group P21/c, a = 6.519(2) A, b = 9.060(3) A, c = 16.284(6) A, β = 97.219(4)°, V = 954.2(6) A3, Z = 4. In structure III, the inorganic fragment forms infinite polymer chains (CuBr 2 - ) n . The organic and inorganic parts are held together only by electrostatic interactions. Structures I-III are stabilized by hydrogen bonds (C)H...X (2.6-2.9 A).
- Monchak,Goreshnik,Mys'Kiv
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- REACTIONS OF ZINC HYDRIDE AND MAGNESIUM HYDRIDE WITH PYRIDINE; SYNTHESIS AND CHARACTERIZATION OF 1,4-DIHYDRO-1-PYRIDYLZINC AND -MAGNESIUM COMPLEXES
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The synthesis and characterization of 1,4-dihydro-1-pyridylzinc and -magnesium complexes are described.Zinc hydride and magnesium hydride dissolve in and react with pyridine, and the reaction has been studied in detail in the case of zinc hydride.Evaporation of the solvent after 1-2 hours at 0 deg C yielded a product containing pyridine, a 1,4-dihydropyridyl moiety and zinc hydrogen bonds, and two alternative structures are proposed for this complex.When the reaction was carried on for a long period, a yellow precipitate began to separate after about 40 hours, andreaction was complete after 7 days.The yellow product was identified as the pyridine complex of bis(1,4-dihydro-1-pyridyl)zinc.The corresponding magnesium complex was obtained from the reaction between magnesium hydride and pyridine for 50 hours at room temperature.
- Koning, A. J. De,Boersma, J.,Kerk, G. J. M. van der
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- Dimethyl(N,N,N′,N′-tetramethylethanediamine)palladium(II) and dimethyl[1,2-bis(dimethylphosphino)ethane]palladium(II): Syntheses, X-ray crystal structures, and thermolysis, oxidative-addition, and ligand-exchange reactions
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PdMe2(tmeda) (2a) (tmeda = N,N,N′,N′-tetramethylethanediamine) has been prepared and characterized by means of NMR spectroscopy and X-ray crystallography. Crystals of PdMe2(tmeda) are monoclinic, space group P21/n, with un
- De Graaf, Wim,Boersma, Jaap,Smeets, Wilberth J. J.,Spek, Anthony L.,Van Koten, Gerard
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- Cleavable cationic antibacterial amphiphiles: Synthesis, mechanism of action, and cytotoxicities
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The development of novel antimicrobial agents having high selectivity toward bacterial cells over mammalian cells is urgently required to curb the widespread emergence of infectious diseases caused by pathogenic bacteria. Toward this end, we have developed a set of cationic dimeric amphiphiles (bearing cleavable amide linkages between the headgroup and the hydrocarbon tail with different methylene spacers) that showed high antibacterial activity against human pathogenic bacteria (Escherichia coli and Staphylococcus aureus) and low cytotoxicity. The Minimum Inhibitory Concentrations (MIC) were found to be very low for the dimeric amphiphiles and were lower or comparable to the monomeric counterpart. In the case of dimeric amphiphiles, MIC was found to decrease with the increase in the spacer chain length (n = 2 to 6) and again to increase at higher spacer length (n > 6). It was found that the compound with six methylene spacers was the most active among all of the amphiphiles (MICs = 10-13 μM). By fluorescence spectroscopy, fluorescence microscopy, and field-emission scanning electron microscopy (FESEM), it was revealed that these cationic amphiphiles interact with the negatively charged bacterial cell membrane and disrupt the membrane integrity, thus killing the bacteria. All of the cationic amphiphiles showed low hemolytic activity (HC50) and high selectivity against both gram-positive and gram-negative bacteria. The most active amphiphile (n = 6) had a 10-13-fold higher HC50 than did the MIC. Also, this amphiphile did not show any cytotoxicity against mammalian cells (HeLa cells) even at a concentration above the MIC (20 μM). The critical micellar concentration (CMC) values of gemini surfactants were found to be very low (CMC = 0.30-0.11 mM) and were 10-27 times smaller than the corresponding monomeric analogue (CMC = 2.9 mM). Chemical hydrolysis and thermogravimetric analysis (TGA) proved that these amphiphiles are quite stable under both acidic and thermal conditions. Collectively, these properties make the newly synthesized amphiphiles potentially superior disinfectants and antiseptics for various biomedical and biotechnological applications.
- Hoque, Jiaul,Akkapeddi, Padma,Yarlagadda, Venkateswarlu,Uppu, Divakara S. S. M.,Kumar, Pratik,Haldar, Jayanta
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- Antibacterial and Antibiofilm Activity of Cationic Small Molecules with Spatial Positioning of Hydrophobicity: An in Vitro and in Vivo Evaluation
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More than 80% of the bacterial infections are associated with biofilm formation. To combat infections, amphiphilic small molecules have been developed as promising antibiofilm agents. However, cytotoxicity of such molecules still remains a major problem. Herein we demonstrate a concept in which antibacterial versus cytotoxic activities of cationic small molecules are tuned by spatial positioning of hydrophobic moieties while keeping positive charges constant. Compared to the molecules with more pendent hydrophobicity from positive centers (MIC = 1-4 μg/mL and HC50 = 60-65 μg/mL), molecules with more confined hydrophobicity between two centers show similar antibacterial activity but significantly less toxicity toward human erythrocytes (MIC = 1-4 μg/mL and HC50 = 805-1242 μg/mL). Notably, the optimized molecule is shown to be nontoxic toward human cells (HEK 293) at a concentration at which it eradicates established bacterial biofilms. The molecule is also shown to eradicate preformed bacterial biofilm in vivo in a murine model of superficial skin infection.
- Hoque, Jiaul,Konai, Mohini M.,Sequeira, Shanola S.,Samaddar, Sandip,Haldar, Jayanta
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- Modulation spectroscopy. Kinetics for the self-reactions of some α-aminoalkyl radicals in solution
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The optical spectra and reaction kinetics of some α-aminoalkyl radicals, RCHN(CH2R)2; R = H, Me, Ph, were measured in solution using the technique of modulation spectroscopy.These radicals undergo diffusion controlled self-reaction with rate constants ca. 109 M-1 s-1.When R=Ph, the absorption spectrum has a well defined maximum at 346 nm; ε = 3390 M-1 cm-1, while the spectra when R = H or Me were less intense (ε346nm ca. 500 M-1 cm-1) and tailed into the visible.These spectra are substantially red-shifted when compared with those of simple alkyl radicals, an effect which is thought to be due to the interaction between the unpaired electron and the lone pair of electrons on nitrogen.
- Marriott, Paul R.,Castelhano, Arlindo L.,Griller, David
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- Unusual reactivity patterns of 1,3,6,8-tetraazatricyclo-[4.4.1.1 3,8]-dodecane (TATD) towards some reducing agents: Synthesis of TMEDA
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N,N,N′,N′-Tetramethylethylenediamine (TMEDA) can be synthesized by simple reduction of 1,3,6,8-tetraazatricyclo-[4.4.1.1.3,8] dodecane (TATD), an aminal cage type amine, with formic acid. The aminal can be converted to TMEDA in high yield very easily and in a very short time. We comment on the scope and limitations of the reduction of this aminal and propose a possible reaction mechanism.
- Rivera, Augusto,Rios-Motta, Jaime
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- Boron-nitrogen compounds. CXX. Complexes of B-triethylboroxin with ethylenediamine and derivatives thereof
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B-Triethylboroxin forms colorless 1/1 molar complexes of the type (C2H5BO)3.L with L=ethylenediamine (1) and various derivatives of the latter, i.e., N,N-dimethylethylenediamine (2), N,N,N',N'-tetramethylethylenediamine (3), piperazine (4), 1,4-diazabicyclooctane (5), diethylenetriamine (6), and tris(2-aminoethyl)amine (7).The cited boroxin also forms 2/1 molar complexes, 2(C2H5BO)3.L, with L=ethylenediamine (8) and those derivatives of the latter which may be considered as symmetrical species, i.e., N,N,N',N'-tetramethylethylenediamine (9), piperazine (10), 1,4-diazabicyclooctane (11), and diethylenetriamine (12).NMR spectroscopic data suggest that the complexes are fluxional in solution at room temperature with a single nitrogen coordinating to the three boron atoms of a given boroxin ring and where, in solution, the 1/1 molar complexes of symmetrical amines appear to exchange their donor sites.There seem to be no principal differences in the complexing of (RBO)3 with R=C2H5 or C6H5.Two species of the unusual composition 3(RBO)3.2H2NCH2NH2 were also identified.
- Mariategui, J. Francisco,Niedenzu, Kurt
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- COMPLEXES OF 9-PROPYLFLUORENYL ION PAIRS WITH TERTIARY POLYAMINES IN APOLAR SOLVENTS
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The complexation of tetramethylethylenediamine (TMEDA), hexamethyltriethylenetetramine (HMTT) and tetramethyltetraazacyclotetradecane (TMTCT) with ion pairs of 9-(n-propyl)fluorenyllithium (PFl-, Li+) and n-butyl-9-(n-propyl)fluorenylmagnesium (BuPFlMg) in cyclohexane was studied by optical spectroscopy.The results can be explained in terms of externally complexed tight ion pairs and ligand-separated ion pairs, the latter complexes being much less soluble.With HMTT and PFl-, Li+, the only complexes formed are (PFl-, Li+)2 HMTT (λm 357 nm) and PFl-, HMTT, Li+ (λm 383 nm).The reaction of PFl-, Li+, TMEDA with TMTCT to form the loose ion pair complex PFl-, TMTCT, Li+ has a rate constant in toluene of 250 M-1 sec-1.With the magnesium compound, the amines form only a loose ion pair complex, e.g., BuMg+, TMEDA, PFl- (λm 382 nm).
- Helary, G.,Lefevre-Jenot, L.,Fontanille, M.,Smid, J.
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- A METHOD FOR THE ALKYLATION OF AMINES
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The present invention pertains to a method for the alkylation of amines. In particular, the present invention relates to a method for preparing N, N, N', N , N -pentamethyldiethylenetriamine by reacting diethylenetriamine with methanol in the presence of hydrogen and a metal catalyst.
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(2021/09/11)
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- A METHOD FOR PREPARING ALKYLATED AMINES
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The present invention pertains to a method for preparing an alkylated amine by reacting a primary or secondary amine with an alcohol in the presence of hydrogen, a metal catalyst supported by photosensitive titanium oxide, and UV irradiation. Advantageously, the reaction can be carried out under mild reaction conditions.
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(2021/09/11)
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- PROCESS FOR PREPARING N-SUBSTITUTED ALKANOLAMINES AND/OR N-SUBSTITUTED DIAMINES FROM GLYCOLALDEHYDE
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A process for preparing a N-substituted alkanolamine of formula (I) and/or a N-substituted diamine of formula (II) from glycolaldehyde is provided, which comprises reacting glycolaldehyde with an aminating agent of formula (III) in a solvent comprising at least one C1-C3 alkanol and/or tetrahydrofuran in the presence of hydrogen and a supported noble metal catalyst, wherein in formulas (I) - (III) : R and R', independently from each other, represent hydrogen, linear or branched C1-C20 alkyl, C3-C12 cycloalkyl, C2-C30 alkoxyalkyl, or C3-30 dialkylaminoalkyl, provided that at least one of R and R' is not hydrogen.
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(2021/06/22)
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- Preparation method of tetramethylethylenediamine
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The invention discloses a preparation method of tetramethylethylenediamine, and the method comprises the following steps: adding a pyrrolidone series solvent and composite catalyst TZOH into an autoclave, covering the autoclave with an autoclave cover, carrying out nitrogen displacement, introducing acetylene, introducing dimethylamine after the temperature is stable, heating the autoclave to 70-120 DEG C, and keeping the temperature for 3-8 hours; after the heat preservation is finished, cooling, discharging the residual pressure into the pyrrolidone series solvent, applying to the next batch, filtering materials in the autoclave, and recovering a catalyst; and rectifying mother liquor to obtain the product tetramethylethylenediamine; according to the method, the tetramethylethylenediamine can be prepared, basically no waste water or waste residue is generated, excessive raw materials, solvents and catalysts can be recycled, the element utilization rate is high, and compared with theprior art that a large amount of formaldehyde-containing waste water or industrial waste salt is generated, the environment-friendly advantage is obvious.
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Paragraph 0051-0067
(2020/08/02)
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- Low-Temperature Reductive Aminolysis of Carbohydrates to Diamines and Aminoalcohols by Heterogeneous Catalysis
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Short amines, such as ethanolamines and ethylenediamines, are important compounds in today's bulk and fine chemicals industry. Unfortunately, current industrial manufacture of these chemicals relies on fossil resources and requires rigorous safety measures when handling explosive or toxic intermediates. Inspired by the elegant working mechanism of aldolase enzymes, a novel heterogeneously catalyzed process—reductive aminolysis—was developed for the efficient production of short amines from carbohydrates at low temperature. High-value bio-based amines containing a bio-derived C2 carbon backbone were synthesized in one step with yields up to 87 C%, in the absence of a solvent and at a temperature below 405 K. A wide variety of available primary and secondary alkyl- and alkanolamines can be reacted with the carbohydrate to form the corresponding C2-diamine. The presented reductive aminolysis is therefore a promising strategy for sustainable synthesis of short, acyclic, bio-based amines.
- Pelckmans, Michiel,Vermandel, Walter,Van Waes, Frederik,Moonen, Kristof,Sels, Bert F.
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p. 14540 - 14544
(2017/10/23)
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- RANEY nickel-catalyzed reductive N-methylation of amines with paraformaldehyde: Theoretical and experimental study
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RANEY Ni-catalyzed reductive N-methylation of amines with paraformaldehyde has been investigated. This reaction proceeds in high yield with water as a byproduct. RANEY Ni can be easily recovered and reused with a slight decrease of the yield. Using density functional theory (DFT), the mechanism of RANEY Ni-catalyzed reductive N-methylation is discussed in detail. The reaction pathway involves the addition of amine with formaldehyde, dehydration to form the imine and hydrogenation. In the transition state of hemiaminal dehydration, the C-O bond cleavage of the aromatic amine is more difficult than that of the aliphatic amine. For the aromatic amine, a higher energy barrier must be overcome, which results in a relatively low yield. After addition of amine with formaldehyde and dehydration, imine is obtained and preferred to adsorb on the bridge site of the Ni(111) surface. The preferential pathways of imine hydrogenation involve the pre-adsorbed hydrogen atom attacking the nitrogen atom of the imine. The energy barrier of hydrogenation is much lower than that of addition and dehydration. Thus, the hydrogenation of imine is a relatively rapid reaction step. In the reductive N-methylation of secondary amine, the possible dehydration pathway is different from the one of the primary amine. In the dehydration of the secondary amine, the intermediate hemiaminal is initially adsorbed on the bridge site of the Ni(111) surface, then undergoes C-O bond cleavage, and eventually the hydroxyl is located in the bridge site. With the final hydrogenation, the product is obtained by adsorption on the top site of the Ni(111) surface.
- Ge, Xin,Luo, Chenxi,Qian, Chao,Yu, Zhiping,Chen, Xinzhi
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p. 43195 - 43203
(2015/02/19)
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- The dinitrosyliron complex [Fe4(μ3-S) 2(μ2-NO)2(NO)6]2- containing bridging nitroxyls: 15N (NO) NMR analysis of the bridging and terminal NO-coordinate ligands
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The fluxional terminal and semibridging NO-coordinate ligands of DNIC [Fe4(μ3-S)2(μ2-NO) 2(NO)6]2-, a precursor of Roussin's black salt (RBS), are characterized by IR ν(NO), 15N (NO) NMR and single-crystal X-ray diffraction. the Partner Organisations 2014.
- Yeh, Shih-Wey,Tsou, Chih-Chin,Liaw, Wen-Feng
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supporting information
p. 9022 - 9025
(2014/06/10)
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- Polymerization of propylene promoted by zirconium benzamidinates
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New bis(N,N-trimethylsilylarylamidinate) zirconium dichloride complexes with various carbon substituents were prepared, and their solid as well as solution state structures were studied. In the polymerization of propylene, after activation by MAO, these catalysts provided two fractions. Ether soluble polymers were obtained at a low activity as sticky polymers with lower molecular weights, except with the o-OMe substituted complex. The solid fractions were composed of a highly isotactic polymer and a moderately syndiotactic polymer. An interesting linear correlation was found between the rates of the 2,1 and 3,1 insertions for the ether soluble fractions.
- Aharonovich, Sinai,Kulkarni, Naveen V.,Zhang, Jia-Sheng,Botoshansky, Mark,Kapon, Moshe,Eisen, Moris S.
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p. 16762 - 16772
(2013/12/04)
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- Reactivity of ortho-palladated benzamides toward CO, isocyanides, and alkynes. synthesis of functionalized isoindolin-1-ones and 4,5-disubstituted benzo[ c ]azepine-1,3-diones
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Aryl palladium complexes [Pd{C6H4C(O)NRR′-2} I(tmeda)] [NRR′ = NH2 (1a), NHMe (1b), NMe2 (1c); tmeda = N,N,N′,N′-tetramethylethylenediamine] are prepared by oxidative addition of the corresponding 2-iodophenylbenzamides to "Pd(dba)2" ([Pd2(dba)3]·dba; dba = dibenzylideneacetone) in the presence of tmeda. Cationic cyclometalated derivatives [Pd{κ2C,O-C6H4C(O)NRR′- 2}(tmeda)]TfO (2a-c) are obtained by iodide abstraction from the appropriate complex 1 with AgTfO, while the deprotonation of the amide function of 1a or 1b with KOtBu gives the neutral amidate complexes [Pd{κ 2C,N-C6H4C(O)NR-2}(tmeda)] [R = H (3a), Me (3b)]. Complexes 2a,b and 3a,b react with CO under mild conditions to yield phthalimide (4a) or N-methylphthalimide (4b), whereas the reactions of derivatives 1c and 2c with CO are very slow and give N1,N 1,N2,N2-tetramethylphthalamide and phthalic anhydride. The reaction of 1b with 1 equiv of XyNC (Xy = 2,6-dimethylphenyl) or tBuNC affords Pd(0), (tmedaH)I, and 3-(2,6-dimethylphenylimino)-2- methylisoindolin-1-one (5b) or 3-(tert-butylimino)-2-methylisoindolin-1-one (5b′), respectively, while complex 1c reacts with 3 equiv of XyNC to give trans-[Pd{C(i=NXy)C6H4C(O)NMe2-2}I(CNXy) 2] (6). The seven-membered palladacycles [Pd{κ2C,O- C(X)i=C(X′)C6H4C(O)NRR′-2}(tmeda)]TfO [NRR′ = NH2 and X = Ph, X′ = Me (7a); NRR′ = NHMe and X = Ph, X′ = Me (7b), X = X′ = Ph (8b), Et (9b), CO 2Me (10b), X = CO2Me, X′ = Ph (11b), X = CO 2Et, X′ = Ph (12b); NRR′ = NMe2 and X = X′ = Ph (8c), Et (9c)] are obtained from the reactions of 2a-c with alkynes. Treatment of complexes 7a, 7b, 8b, and 9b with CO at room temperature gives the corresponding 2H-benzo[c]azepine-1,3-diones (14), resulting from the insertion of a molecule of CO into the Pd-C bond followed by a C-N reductive coupling. In contrast, the reactions of 11b or 12b with CO in the presence of residual water or 2 equiv of ROH (R = Me, Et) lead to 2-methyl-3- phenylisoindolin-1-one derivatives (15), resulting from a CO insertion followed by an intramolecular aza-Michael addition of the NHMe moiety to the activated vinyl group and subsequent hydrolysis or alcoholysis of the acyl-Pd bond. The neutral complex [Pd(κ2C,O-C14H13O 5)(tmeda)] (18) was synthesized by reacting the cationic derivative 10b with NaOMe in MeOH. Depalladation of 18 gives (E)-4- [methoxy(methoxycarbonyl)methylene]-2-methylisoquinoline-1,3(2H,4H)-dione (19).
- Frutos-Pedreno, Roberto,Gonzalez-Herrero, Pablo,Vicente, Jose,Jones, Peter G.
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p. 4664 - 4676
(2013/09/23)
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- N-alkylation of ethylenediamine with alcohols catalyzed by CuO-NiO/γ-Al2O3
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A simple method for N-alkylation of 1, 2-diaminoethane with different alcohols in a fixed-bed reactor using cheap CuO-NiO/γ-Al2O 3 as the catalyst has been developed. The present catalytic system was applicable in the N-alkylation of 1, 2-diaminoethane with both primary and secondary alcohols. Mono-N-alkylation of 1, 2-diaminoethane with low-carbon alcohols resulted in high yields; the yields of tetra-N-alkylation of 1, 2-diaminoethane with low-carbon alcohols declined markedly with the increase of the molecular volume of alcohols.
- Huang, Jia-Min,Xu, Lu-Feng,Qian, Chao,Chen, Xin-Zhi
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experimental part
p. 304 - 307
(2012/08/28)
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- N-alkylation of ethylenediamine with alcohols catalyzed by CuO-NiO/?3-Al2O3
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A simple method for N-alkylation of 1,2-diaminoethane with different alcohols in a fixed-bed reactor using cheap CuO-NiO/?3-Al2O3 as the catalyst has been developed. The present catalytic system was applicable in the N-alkylation of
- Huang, Jia-Min,Xu, Lu-Feng,Qian, Chao,Chen, Xin-Zhi
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p. 304 - 307
(2015/03/03)
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- PROCESS FOR THE PRODUCTION OF ETHYLENE GLYCOL AND RELATED COMPOUNDS
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The present invention provide a process for the production of compounds of general formula (I), Y-CH2CH2-Z (I) wherein Y and Z are functional groups independently selected from the group consisting of a hydroxyl group and R1R2N and wherein R1 and R2 may be the same or different and are functional groups selected from the group consisting of hydrogen and substituted or non- substituited alkyl groups comprising 1 to 8 carbon atoms, or R1R2N is a cyclic compound selected from the group of aromatic and non-aromatic cyclic compounds optionally comprising one or more heteroatoms in addition to the nitrogen atom, said process comprising the steps of: (i) reacting carbon monoxide and an amine in the presence of oxygen to provide a compound of general formula (II) wherein R1 and R2 or R1R2N are as defined above and X is selected from the group consisting of R1R2N and R3O, wherein R3 is selected from alkyl groups comprising 1 to 8 carbon atoms; and (ii) converting the compound of general formula (II) into a compound of general formula (I) by a process that comprises a hydrogenation reaction.
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(2010/12/17)
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- METHOD FOR PRODUCING N-MONOALKYL-SUBSTITUTED ALKYLENE AMINE
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PROBLEM TO BE SOLVED: To provide a method for producing an N-monoalkyl-substituted alkylene amine especially useful for uses such as medicine intermediates, agrochemical intermediates, urethane resin-foaming catalysts, surfactants and the like among alkyl-substituted alkylene amine compounds from an alcohol and an alkylene amine as raw materials. SOLUTION: This method for producing the N-monoalkyl-substituted alkylene amine is characterized by reacting the alkylene amine with a ≥2C alkyl alcohol in the presence of a copper-containing oxide catalyst system. The N-monoalkyl-substituted alkylenamine is produced in high conversion and in N-monoalkylation selectivity.
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- A solvent-free and formalin-free Eschweiler-Clarke methylation for amines
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Primary and secondary amines are N-methylated by a mixture of paraformaldehyde and oxalic acid dihydrate in good to excellent yields. The reaction proceeds without involvement of organic solvents and toxic formalin. Reaction temperatures of 100°C are required for the decomposition of oxalic acid into the intermediate formic acid which acts as the actual reductant. The reaction conditions have been optimized, and the mechanism has been elucidated by means of deuteration experiments.
- Rosenau, Thomas,Potthast, Antje,Roehrling, Juergen,Hofinger, Andreas,Sixta, Herbert,Kosma, Paul
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p. 457 - 466
(2007/10/03)
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- HIV protease inhibitors
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HIV protease inhibitors, obtainable by chemical synthesis, inhibit or block the biological activity of the HIV protease enzyme, causing the replication of the HIV virus to terminate. These compounds, as well as pharmaceutical compositions that contain these compounds and optionally other anti-viral agents as active ingredients, are suitable for treating patients or hosts infected with the HIV virus, which is known to cause AIDS.
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- Preparation of tetramethylethylenediamine
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Process for the production of TMEDA in high yield by reducing 2,3-dimethyl-2,3-dinitrobutane with hydrogen in the presence of a chromium promoted Raney cobalt catalyst. A solution of 2,3-dimethyl-2,3-dinitrobutane in a suitable solvent is fed to a reactor while avoiding the accumulation of 2,3-dimethyl-2,3-dinitrobutane in the reaction medium, such as by feeding it at a rate no greater than its rate of reaction with hydrogen. In a preferred embodiment, the resulting TMEDA is recovered by converting it to an amine salt by sparging carbon dioxide through the solution.
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- HIV protease inhibitors
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HIV protease inhibitors, obtainable by chemical synthesis, inhibit or block the biological activity of the HIV protease enzyme, causing the replication of the HIV virus to terminate. These compounds, as well as pharmaceutical compositions that contain these compounds and optionally other anti-viral agents as active ingredients, are suitable for treating patients or hosts infected with the HIV virus, which is known to cause AIDS.
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- Intermediate and process for making
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The present invention provides novel HIV protease inhibitors, pharmaceutical formulations containing those compounds and methods of treating and/or preventing HIV infection and/or AIDS.
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- Process for converting heat stable amine salts to heat regenerable amine salts
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Processes are disclosed for converting heat stable amine salts to heat regenerable amine salts using a modified electrodialysis zone (140). The processes of the present invention can be used to reduce the level of heat stable salts in a lean solvent stream in an acid gas removal process and can be integrated with the acid gas removal process to utilize process streams as a source of ions.
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- Nucleophilicity towards a Vinylic Carbon Atom: Rate Constants for the Addition of Amines to the 1-Methyl-4-vinylpyridinium Cation in Aqueous Solution
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Second-order rate constants (kNu) have been measured for the addition of 44 primary amines (including five α-effect amines), 28 secondary amines, 19 tertiary amines, ammonia and hydroxide ion to the vinyl group of the 1-methyl-4-vinylpyridinium cation (1) in aqueous solution at 25 deg C (ionic strength 0.1 mol dm-3).Nucleophilic attack is shown to be rate-determining for primary and secondary amines being generally more reactive than primary amines, with secondary amines of the same basicity.After classification of these species in terms of structure, they describe a number of Broensted-type correlations having βnuc in the range 0.35-0.54 for six structural classes of primary amine, βnuc = 0.48 for α-effect amines, and βnuc in the range 0.23-0.34 for four structural classes of secondary amine.Substitution upon the α-carbon atom reduces amine nucleophilicity of both primary and secondary amines.The presence of an unsaturated carbon atom (either sp2- or sp-hybridized) as the β-carbon atom leads to an enhanced reactivity relative to the corresponding β-sp3 species in all cases.Tertiary amines are in general less reactive than other amines of the same basicity.Broensted-type plots for tertiary amines present the appearance of random scatter which is not readily decipherable in terms of structure. β-Hydroxy and β-amino tertiary amines are unusually reactive relative to their basicity.All of these phenomena suggest that protonation of the carbanionic intermediate by a molecule of water is the rate-determining step for the addition of tertiary amines to 1.Rate constants for the attack of primary and secondary amines on 1 are shown to correlate with literature data for a variety of other reactions involving rate-determining nucleophilic attack of amines upon electrophilic carbon.These kNu for primary and secondary amines reacting with 1 are also shown to correlate with Ritchie's N+ parameters for nucleophilic attack at electrophilic sp2-carbon.N+ parameters for amine nucleophiles have not been widely available previously; the parameters that have been available for selected amines are known to be sensitive to the nature of the defining electrophile.The minimal steric hindrance at the electrophilic centre in nucleophilic attack upon 1 suggests that this species is an appropriate electrophile for the definition of N+ parameters for amine nucleophiles; these parameters are evaluated for 70 primary and secondary amines and ammonia and are suggested to provide an appropriate data base for future investigations of the reactivity and selectivity of amine attack upon sp2-carbon electrophiles in aqueous solution.
- Heo, Christina K. M.,Bunting, John W.
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p. 2279 - 2290
(2007/10/02)
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- Catalysts for addition of siicon hydrides to α,β-unsaturated olefinic nitriles
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The present invention is a process for the preparation of hydrolyzable β-cyanoalkylsilanes. More particularly, this invention relates to the catalytic addition of hydrolyzable silicon hydrides to α,β-unsaturated olefinic nitriles to form β-cyanoalkylsilanes. The instant process employs novel catalysts comprising a diamine and non-activated copper, selected inorganic copper compounds, or di-coordinate organic copper compounds.
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- Models for organometallic polymers. Zigzag chains of Mo2(O2CCH3)4 units linked by DMPE and TMED ligands
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Infinite zigzag chains of Mo2(O2CCH3)4 units linked by the bidentate ligands 1,2-bis(dimethylphosphino)ethane (dmpe) and tetramethylethylenediamine (tmed) crystallize from solutions of Mo2(O2CCH3)4 (1) dissolved in the respective neat ligand. Single-crystal X-ray structures of the light yellow polymers ∞1[Mo2(O2CCH3) 4(dmpe)] (2) and ∞1[Mo2(O2CCH3) 4(tmed)] (3) showed that the compounds were isostructural. Compound 2 crystallizes in space group P1 (-135°C) with a = 8.473 (2) A?, b = 9.562 (3) A?, c = 7.654(3) A?, α = 110.59 (2)°, β = 100.06 (2)°, ? = 69.26 (2)°, Z = 1, V = 541.9(3) A?3, R = 0.058, and Rw = 0.058. Compound 3 crystallizes in space group P1 (20°C) with a = 8.388 (1) A?, b = 8.445 (2) A?, c = 8.840 (2) A?, α = 105.95 (2)°, β = 115.62(1)°, γ = 91.63(2)°, Z = 1, V = 535.1 (2) A?3, R = 0.025, and Rw = 0.033. The ligands dmpe and tmed are coordinated axially through weak Mo-L bonds to relatively unperturbed Mo2(O2CCH3)4 centers. The solid-state Raman spectrum of 3 reveals a small decrease in the Mo-Mo stretching frequency 1 (νMo-Mo = 391 cm-1) relative to 1 (νMo-Mo = 405 cm-1). TGA and powder X-ray diffraction studies involving 3 showed that solid-state thermolysis results in the expulsion of tmed at 92 °C and the formation of crystalline 1.
- Kerby, Michael C.,Eichhorn, Bryan W.,Creighton, J. Alan,Vollhardt, K. Peter C.
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p. 1319 - 1323
(2008/10/08)
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- Oxo(tri-tert-butylphenyl)borane ArBO as an Intermediate
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The borane ArB(OMe)2 (1) (Ar = 2, 4, 6-tri-tert-butylphenyl) was transformed into ArBH3*Li(tmeda) (2) by the action of LiAlH4 in Et2O.The product 2 can be hydrolysed to ArB(OH)H (3), but in strongly acidic media the hydrolysis involves the attack of a neighbouring methyl group to give the 1-hydroxy-1-boraindane derivative 4.Borane 3 can be dehydrogenated to 4 in the gas-phase at 600 deg C.The formation of ArBO (5) as an intermediate in this dehydrogenation has been proved by starting from ArB(OD)H (3') which gives the product 4 with an OH-group in the 1-position.
- Groteklaes, Michael,Paetzold, Peter
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p. 809 - 810
(2007/10/02)
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- Catalyst system for amine transalkylation
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In the transalkylation of tertiary amines, unexpected higher yields are achieved requiring substantially less catalyst and much shorter reaction times at lower reaction temperatures using a homogeneous catalyst in the presence of an alcohol solvent and carbon monoxide. The process may be exemplified by reacting triethylamine and tripropylamine in the presence of a homogeneous triosmiumdodecacarbonyl catalyst, ethanol, and carbon monoxide to prepare diethylpropylamine and ethyldipropylamine.
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- Metal salts of polyacetylenic compounds and uses thereof
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Water-soluble polyacetylenic alkali metal salts from monomers and polymers of carboxymethyl urethanes of di-, tetra-, and hexayne diols, or from the corresponding diacids; useful in thermal and irradiation exposure indicators and/or in detection and/or removal of nonalkali metal ions dissolved in aqueous media.
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- Homogeneously Catalyzed Synthesis of β-Amino Alcohols ans Vicinal Diamines from Ethylene Glycol and 1,2-Propanediol
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Disubstituted β-amino alcohols and tetrasubstituted vicinal alkanediamines have been synthesized in high yield and at mild temperatures by the selective amination of ethylene glycol and 1,2-propanediol catalyzed by ruthenium or iridium complexes.
- Marsella, John A.
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p. 467 - 468
(2007/10/02)
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- Polymeric quaternary ammonium compounds and their uses
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Novel polyquaternary ammonium compounds prepared from N,N'-bis(dialkylaminoalkyl)ureas, hydrochloric acid, epichlorohydrin and tertiary amines are useful as microbicides, corrosion inhibitors, debonding agents, flocculants, softeners, anti-static agents, and demulsifiers.
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- AFFINITIES OF CROWN ETHERS, GLYMES, AND POLYAMINES FOR ALKALI PICRATES IN TOLUENE. APPLICATION OF POLYMER-SUPPORTED LINEAR POLYETHERS.
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This work reports the measurements of K values for polyamines, glymes, a few glycols (including that of a long-chain polyethylene glycol, carbowax 6000), and some frequently used cation-binding ligands as complexers of lithium or sodium picrate in toluene as solvent. K values for different resins obtained with the same soluble ligand provide a comparison of the effectiveness of these resins in binding ionic solutes.
- Xu,Smid
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p. 3790 - 3796
(2007/10/02)
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- Organometallic compounds of the lanthanides. 17. Tris[(tetramethylethylenediamine)lithium] hexamethyl derivatives of the rare earths
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The trichlorides of yttrium, lanthanum, and the lanthanides react with methyllithium in diethyl ether in the presence of tetramethylethylenediamine (tmed) to give the complexes [Li(tmed)]3[Ln(CH3)6] with Ln = Y, La, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. From the reaction of lutetium tri-tert-butoxide, tmed, and tert-butyllithium in pentane, [Li(tmed)2][Lu(t-C4H9)4] has been obtained. The new compounds have been characterized by elemental analyses and IR and NMR spectra. The structure of [Li(tmed)]3[Ho(CH3)6] has been elucidated through complete X-ray analysis. The crystals are rhombohedral with a = 1280.7 (20) pm, α = 79.84 (13)°, space group R3c, Z = 2, D(calcd) = 0.96 g cm-3, R = 0.050, and 1535 observed reflections. The potential of methylating α,β-unsaturated aldehydes and ketones has been explored for [Li(tmed)]3[Pr(CH3)6] and [Li(tmed)]3[Sm(CH3)6], and it was found that 1,2 methylation is favored over 1,4 addition.
- Schumann, Herbert,Müller, Jochen,Bruncks, Norbert,Lauke, Harald,Pickardt, Joachim,Schwarz,Eckart, Klaus
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- Hair dyeing compositions containing quaternized polymer
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A quaternized polymer for use as a cosmetic agent, has recurring units of the formula STR1 wherein R is lower alkyl or -CH2 -CH2 OH; R' is an aliphatic, alicyclic or arylaliphatic radical containing a maximum of 20 carbon atoms, or R and R' together with the nitrogen atom to which they are attached form a heterocycle capable of containing a heteroatom other than nitrogen; A is a divalent group selected from (1) o-, m- or p-xylylidene of the formula STR2 wherein x, y and t are whole numbers ranging from 0 to 11 such that the sum (x+y+t) is greater than or equal to 0 and lower than 18, and E and K represent hydrogen or an aliphatic radical having less than 18 carbon atoms, (3) --(CH2)n --S--(CH2)n --, (4) --(CH2)n --O--(CH2)n --, (5) --(CH2)n --S--S--(CH2 (n --, (6) --(CH2)n --SO--(CH2)n --, (7) --(CH2)n --SO2 --(CH2)n --and STR3 wherein n is equal to 2 or 3; B represents a divalent group selected from (1) o-, m- or p-xylylidene of the formula STR4 wherein D and G represent hydrogen or an aliphatic radical having less than 18 carbon atoms and v, z and u are whole numbers ranging from 0 to 11, with two of v, z and u simultaneously being capable of being 0, such that the sum (v+z+u) is greater than or equal to 1 and lower than 18 and such that the sum (v+z+u) is greater than 1 when the sum (x+y+t) is equal to 0, STR5 (4) --(CH2)n --O--(CH2)n -- wherein n is 2 or 3; and X? is an anion derived from an organic or mineral acid. The quaternized polymer is employed in cosmetic compositions for the hair and skin.
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- Olefine, Arene, and Allyl Complexes of Vanadium from Vanadocene
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Vanadocene (Cp2V) was reduced with potassium metal in tetrahydrofuran (THF) to give a 1:1 adduct K which has been isolated as .The reactions of this compound with various molecules (L) capable of functioning as ligands were investigated.They cause the liberation of KCp and the formation of several new organovanadium compounds.The products of these reactions were: for L = butadiene (C4H6), for L = P(C6H5)3, CpV(C4H6)P(CH3)3 for L = mixture of C4H6 and P(CH3)3.Vanadocene was reacted with allyllithium to yield LiCp and (TMEDA = (CH3)2NCH2CH2N(CH3)2), which was transformed via allylbromide to CpV(C3H5)2.Structures and reactivities of these new organovanadium complexes are discussed. - Key words: Vanadium, Potassium, Vanadocene, Allyllithium, Olefines
- Jonas, Klaus,Wiskamp, Volker
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p. 1113 - 1121
(2007/10/02)
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- Activation of CO2 at Transition Metal Centers: Structure and Reactivity of a C-C-Coupling Product of CO2 and 2,3-Dimethylbutadiene at Electron-Rich Nickel(0)
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Carbon dioxide reacts with 2,3-dimethylbutadiene and bis-cyclooctadiene(1,5)-nickel(0) in the presence of N,N'-tetramethyl-ethylendiamine (tmeda) to form 3)-3,4-dimethyl-3-pentenylato>(N,N'-tetramethylethylendiamine)-nickel(II) as the product of the oxidative coupling of CO2 and the diene.The deep red complex crystallizes in the rhombic space group Pbca.The structure was determined by an X-ray analysis.The monodendate carboxylate group, the ?-allyl system and a N-atom of tmeda form a planar coordination sphere around the central atom.The distances between Ni and the second N-atom of tmeda is very long (2.314 Angstroem).Reaction of the complex with R-X (R: H, CH3) yield 3-unsaturated carboxylic acids; tmeda can be substituted by 2,2'-bipyridine. - Keywords: Carbon Dioxide, 2,3-Dimethylbutadiene, Nickel(II) Complex, Crystal Structure
- Walther, Dirk,Dinjus, Eckhard,Sieler, Joachim,Thanh, Nguyen Ngoc,Schade, Wolfgang,Leban, Ivan
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p. 835 - 840
(2007/10/02)
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- Proton Affinities and the Site of Protonation of Enamines in the Gas Phase
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The gas-phase proton affinities of a number of methyl-substituted enamines and imines have been measured using ion cyclotron resonance spectroscopy.Comparison of the effect of substituents on the proton affinities of the enamines with those of corresponding amines is used to show that protonation in the gas phase occurs at carbon leading to the formation of an iminium ion.The observation of a large substituent effect for substitution of an α-methyl group also suggests that there is a significant amount of delocalization of positive charge in the iminium ion.A comparison with solution-phase basicities of enamines is also presented.
- Ellenberger, Mark R.,Dixon, David A.,Farneth, William E.
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p. 5377 - 5382
(2007/10/02)
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- Preparation of 3,3,3-trifluoropropene-1
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Process for preparing 3,3,3-trifluoropropene-1 by contacting and reacting at least one of 1,1,1,3-tetrachloropropane, 1,1,3-trichloropropene-1 and 3,3,3-trichloropropene-1 and HF, under autogenous pressure, at 140°-250° C., in the presence of at least a catalytic amount of an organic monoamine, a salt of the monoamine or an alkylene diamine, said monoamine and salt being of the formula R3 N.(R'X)n wherein n is 0 or 1, X is an appropriate anion, each R and R' is selected independently from H, alkyl of 1-16 carbon atoms, cycloalkyl of 6-10 carbon atoms, aryl of 6-10 carbon atoms and alkylaryl of 6-10 carbon atoms, provided, however, when n is 0, no more than two of the R groups are H and when n is 1, no more than three of the R and R' groups are H, and provided, however, R3 N taken jointly is piperidine, pyrrolidine, indoline, isoindoline, pyridine, quinoline or isoquinoline, each optionally substituted with 1-3 methyl groups, said alkylene diamine being of the formula R"2 N--CH2 --NR"2 wherein m is 2-10 and each R" is selected independently from H, alkyl of 1-4 carbon atoms and phenyl, provided, however, when m is 2, each R" is selected independently from alkyl of 1-4 carbon atoms and phenyl.
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- Antibacterial 1,2,4-oxadiazolylacetamido cephalosporins
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1,2,4-Oxadiazolylacetic acid derivatives. The derivatives include penicillin and cephalosporin amides which have antibiotic properties.
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- Preparation of hydroxy-terminated conjugated diene polymers
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Preparation of hydroxy-terminated conjugated diene polymers, particularly polybutadienes, by capping of organodilithium- and organopolylithium- terminated conjugated diene polymers or polybutadienes with lower alkylene oxide or epoxide capping agents in the presence of certain potentiating agents or catalysts exemplified particularly by small proportions of N,N,N1, N1 -tetramethylenediamine (TMEDA).
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