- SYNTHESIS OF N-(1-URACILYLALKYL)POLYMETHYLENEDIAMINES
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The alkylation of polymethylenediamines with 2-(1-uracilyl)ethyl bromide and 3-(1-uracilyl)propyl bromide yields the corresponding N-(1-uracilylalkyl)polymethylendiamines.
- Lulle, I. Zh.,Kagan, T. I.,Paegle, R. A.,Lidak, M. Yu.
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Read Online
- Phase change ink compositions comprising crystalline diurethanes and derivatives thereof
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A phase change ink composition comprising an amorphous component, a crystalline material, and optionally, a colorant, which are suitable for ink jet printing, including printing on coated paper substrates and are suitable for fast printing processes. In p
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Page/Page column 7; 17
(2017/01/19)
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- Method for Preparing Dicarbamate Compounds
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The present invention provides a preparing method of dicarbamate, comprising: a first step of obtaining an alcohol solution including diureido obtained by reacting diamine having 2 to 13 carbon atoms with urea in the presence of alcohol having 3 to 12 carbon atoms at low temperature of 150anddeg;C or less; and a second step of obtaining dicarbamate by reacting the alcohol solution including the diureido at high temperature of 200anddeg;C or more under carbon dioxide pressure. According to the preparing method of the present invention, yield and selectivity of dicarbamate are significantly increased, and formation of an alkylated amine by-product can be minimized.COPYRIGHT KIPO 2016
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Paragraph 0032-0033; 0056-0057; 0071-0073
(2017/01/02)
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- Amorphous Amides
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An amorphous amide compound of the formula wherein R is selected from the group consisting of an alkyl group, an aryl group, an alkylaryl group, an arylalkyl group, and combinations thereof. An amorphous diamide compound of the formula wherein R1 /s
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Paragraph 0139
(2015/04/22)
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- Malic acid derivatives as amorphous materials for phase change ink
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Disclosed herein is a component that is substantially amorphous, the component comprising at least one non-ester material and at least one ester of malic acid having a formula of wherein R1 and R2 each, independently of the other, is
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Page/Page column 15
(2015/11/03)
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- Ligand-directed selective protein modification based on local single-electron-transfer catalysis
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A photocatalyst ([Ru(bpy)3]2+) bound to a protein ligand was essential for the title method. Local single-electron transfer from the catalyst resulted in the formation of tyrosyl radicals. N′-Acetyl-N,N- dimethyl-1,4-phenylenediamine was used as the tyrosyl radical trapping agent and used in a radical addition to afford selective modification of the target protein. Copyright
- Sato, Shinichi,Nakamura, Hiroyuki
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supporting information
p. 8681 - 8684
(2013/09/12)
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- Replacing conventional carbon nucleophiles with electrophiles: Nickel-catalyzed reductive alkylation of aryl bromides and chlorides
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A general method is presented for the synthesis of alkylated arenes by the chemoselective combination of two electrophilic carbons. Under the optimized conditions, a variety of aryl and vinyl bromides are reductively coupled with alkyl bromides in high yields. Under similar conditions, activated aryl chlorides can also be coupled with bromoalkanes. The protocols are highly functional-group tolerant (-OH, -NHTs, -OAc, -OTs, -OTf, -COMe, -NHBoc, -NHCbz, -CN, -SO2Me), and the reactions are assembled on the benchtop with no special precautions to exclude air or moisture. The reaction displays different chemoselectivity than conventional cross-coupling reactions, such as the Suzuki-Miyaura, Stille, and Hiyama-Denmark reactions. Substrates bearing both an electrophilic and nucleophilic carbon result in selective coupling at the electrophilic carbon (R-X) and no reaction at the nucleophilic carbon (R-[M]) for organoboron (-Bpin), organotin (-SnMe3), and organosilicon (-SiMe2OH) containing organic halides (X-R-[M]). A Hammett study showed a linear correlation of σ and σ(-) parameters with the relative rate of reaction of substituted aryl bromides with bromoalkanes. The small ρ values for these correlations (1.2-1.7) indicate that oxidative addition of the bromoarene is not the turnover-frequency determining step. The rate of reaction has a positive dependence on the concentration of alkyl bromide and catalyst, no dependence upon the amount of zinc (reducing agent), and an inverse dependence upon aryl halide concentration. These results and studies with an organic reductant (TDAE) argue against the intermediacy of organozinc reagents.
- Everson, Daniel A.,Jones, Brittany A.,Weix, Daniel J.
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supporting information; experimental part
p. 6146 - 6159
(2012/05/07)
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- METHOD FOR PRODUCING CARBAMATE COMPOUND
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A task of the present invention is to provide a process for preparation a carbamate compound using a carbonic acid ester and an amide compound in the presence of a basic compound(s), wherein the process is a novel industrial method which is advantageous in that the reaction rate is faster than conventional and the by-produced ester compound can be recovered, and the present invention is directed to a method comprising reacting an amide compound represented by the formula (1) with a carbonic acid ester represented by the formula (2) in the presence of a basic compound(s) to obtain a carbamate compound represented by the formula (3).
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Page/Page column 16
(2011/06/24)
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- Nickel-catalyzed, sodium iodide-promoted reductive dimerization of alkyl halides, alkyl pseudohalides, and allylic acetates
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The first general method for the reductive dimerization of alkyl halides, alkyl mesylates, alkyl trifluoroacetates, and allylic acetates is reported which proceeds with low catalyst loading (0.5 to 5 mol%), generally high yields (80% ave yield), and good functional-group tolerance.
- Prinsell, Michael R.,Everson, Daniel A.,Weix, Daniel J.
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supporting information; experimental part
p. 5743 - 5745
(2010/09/18)
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- Nickel-catalyzed reductive cross-coupling of aryl halides with alkyl halides
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(Chemical Equation Presented) The direct reductive cross-coupling of alkyl halides with aryl halides is described. The transformation is efficient (equimolar amounts of the starting materials are used), generally high-yielding (all but one between 55 and 88% yield), highly functional-group-tolerant [OH, NHBoc, NHCbz, Bpin, C(O)Me, CO2Et, and CN are all tolerated], and easy to perform (uses only benchtop-stable reagents, tolerates small amounts of water and oxygen, changes color when complete, and uses filtration workup). The reaction appears to avoid the formation of intermediate organomanganese species, and a synergistic effect was found when a mixture of two ligands was employed.
- Everson, Daniel A.,Shrestha, Ruja,Weix, Daniel J.
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supporting information; experimental part
p. 920 - 921
(2010/03/31)
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- Synthetic studies on 4,5-dihydro-3H-1,2,4-triazole-3,5-diones bearing fluorogenic residues at N-4
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A number of fluorescent 4,5-dihydro-3H-1,2,4-triazole-3,5-diones have been made. Intra-inter-electrophilic substitution by the triazoledione moiety on the activated naphthalene ring of 4-[6-(5-dimethylamino-1-naphthylsulfonamido)hexyl]-4,5-dihydro-3H-1,2,4- triazole-3,5-dione 4a3 leads to rapid decomposition. The dienophilicity of the triazoledione moiety in 4-pyren-1-yl-4,5-dihydro-3H-1,2,4-triazole-3,5-dione 4d is dramatically lowered by steric shielding. Insertion of a three-carbon spacer unit into the latter compound, to give the 3-pyren-1-ylpropyl analogue 4e, affords a valuable fluorogenic reagent for the analysis of trace levels of 1,3-dienes. Powdered barium manganate is shown to be an excellent solid-phase oxidant for conversion of urazoles into 1,2,4-triazole-3,5-diones.
- Read, Gordon,Richardson, Nigel R.
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p. 167 - 174
(2007/10/03)
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- Carbon Dioxide as a Phosgene Replacement: Synthesis and Mechanistic Studies of Urethanes from Amines, CO2, and Alkyl Chlorides
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Several carbamate esters were synthesized from amines, carbon dioxide, and alkyl chlorides.The effect of added base on the yield and selectivity of carbamate ester formation was found to be highly important with the use of sterically hindered guanidine bases giving the best results.Relative rate studies were carried out giving the following order of reactivity between carbamate anions in acetonitrile with benzyl chloride giving carbamate esters: Et2NCO2(-) = Bu2NCO2(-) > t-BuNHCO2(-) = CyNHCO2(-) = s-BuNHCO2(-) > PhNHCO2(-) > CyCH2NHCO2(-) = n-octylNHCO2(-) = n-BuNHCO2(-).Rate studies were carried out with the diethyl, s-butyl, phenyl, and n-butyl carbamates and activation parameters were determined to be Et2NCO2(-), ΔH(excit.) = 11.8 kcal/mol, ΔS(excit.) = -33 eu; s-BuNHCO2(-), ΔH(excit.) = 12.8 kcal/mol, ΔS(excit.) = -33 eu; PhNHCO2(-), ΔH(excit.) = 14.3 kcal/mol, ΔS(excit.) = -28 eu; n-BuNHCO2(-), ΔH(excit.) = 23.4 kcal/mol, ΔS(excit.) = -3 eu.The unusual results obtained from the use of n-BuNHCO2(-) prompted further studies which showed that the rate of the reaction was inversely dependent on carbon dioxide pressure (20 psig CO2, k = 4.84E-4 M-1 s-1; 120 psig CO2, k = 1.83E-4 M-1 s-1).Nitrogen NMR spectroscopy indicated, via a labeling study with 15N amines and 13C enriched carbon dioxide, the formation of doubly inserted product from the addition of two carbon dioxides to ethylamine in acetonitrile.
- McGhee, William,Riley, Dennis,Christ, Kevin,Pan, Yi,Parnas, Barry
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p. 2820 - 2830
(2007/10/02)
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- Spermexatin and Spermexatol: New Synthetic Spermidine-Based Siderophore Analogues
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Syntheses of hexanediamine-based dihydroxamate (Hexamate), spermidine-based trihydroxamate (Spermexatins), and spermidine-based mixed siderophore analogues (Spermexatols) are described.Key intermediates include the N-hydroxysuccinimide esters of various hydroxamic acids, e.g., malonohydroxamate, succinohydroxamate, and glutarohydroxamate.These intermediates were synthesized, characterized, and incorporated as the ligating chains on spermidine.Also, mixed iron chelating compounds (Spermexatols) with both catechol and hydroxamic acid side chains were synthesized.Thereagent carbobenzoxyimidazole was employed to distinguish between the primary and secondary amino groups of spermidine.The ability of these iron chelators to stimulate microbial growth is also described.
- Sharma, Sushil K.,Miller, Marvin J.,Payne, Shelley M.
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p. 357 - 367
(2007/10/02)
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- NOVEL UNSYMMETRICAL N,N-BIS(METHYLENE)BIPHOSPHONIC ACIDS OF α,ω-DIAMINES. PREPARATION AND CHARACTERIZATION OF BIS(METHYLENE)>-BIPHOSPHONIC ACID AND BIS(METHYLENE)>-BIPHOSPHONIC ACID
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Reaction of ethylenediamine with phosphorous acid and formaldehyde in molar ratio 1:2:2 gives bis(methylene)>biphosphonic acid (2a) as the major product.Similarly, reaction of hexamethylenediamine with phosphorous acid and formaldehyde in molar ratio 1:2:2 yields bis(methylene)>biphosphonic acid (2b) which is isolated either as bis(methylene>biphosphonic acid (3b) or as bis(methylene)>biphosphonic acid (4b).Removal of the carbobenzoxy group with HBr 3b or the benzoyl group with HCl from 4b gives pure bis(methylene)>biphosphonic acid (2b).All compounds were characterized by 13C NMR, 31P NMR and elemental analysis.
- Redmore, Derek,Dhawan, Balram
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p. 233 - 238
(2007/10/02)
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