- Reaction of 3,4-Di-t-butylthiophene 1-oxide with 2-methylene-1,3-dimethylimidazolidine: Methylene transfer and [4+4] dimerization
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The reaction of 3,4-di-t-butylthiophene 1-oxide (1) with 2-methylene-1,3-dimethylimidazolidine (2) gave 4,4a-di(t-butyl)-1a,4a-dihydro-1H-cyclopropa[b]thiophene and 1,3-dimethyl-2-imidazolidinone through a methylene transfer from 2 to 1, in addition to a [4+4] cyclodimerization product of 1.
- Nakayama, Juzo,Takayama, Jun,Sugihara, Yoshiaki,Ishii, Akihiko
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Read Online
- A DIPOLE MOMENT STUDY OF N-METHYL AND N,N'-DIMETHYL-IMIDAZOLIDIN-2-ONES, IMIDAZOLIDINE-2-THIONES AND -2-SELENONES
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The electric dipole moments in benzene and dioxan of potentially tautomerizable N-methylimidazolidin-2-one, N-methylimidazolidine-2-thione and -2-selenone clearly support the lactam structure for these compounds.The fact that their dipole moments in dioxan are markedly greater than those in benzene is explained by a higher (HN-C=Y) mesomeric moment in the hydrogen-bonded solute...dioxan complexes.Analysis of the dipole moments in benzene of N,N'-dimethylimidazolidin-2-one, N,N'dimethylimidazolidine-2-thione and -2-selenone shows that the mesomeric moment (due to contribution of +N=C-Y- zwitterionic valence structures) gradually increases on going from Y=O to Y=S, and Y=Se.Finally, preferred conformations, from their dipole moments in benzene, are suggested for tetramethylurea and tetramethylthiourea.
- Lumbroso, H.,Liegeois, Ch.,Devillanova, F. A.,Verani, G.
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Read Online
- Mesoporous silica-catalysed continuous chemical fixation of CO2 with N,N′-dimethylethylenediamine in supercritical CO2: The efficient synthesis of 1,3-dimethyl-2-imidazolidinone
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MCM-41- and HMS-type mesoporous silicas were found to be efficient catalysts for the continuous chemical fixation of CO2 into 1,3-dimethyl-2-imidazolidinone with N,N′-dimethylethylenediamine in supercritical CO2. The Royal Society of Chemistry.
- Seki, Tsunetake,Kokubo, Yoshiaki,Ichikawa, Shinichiro,Suzuki, Tomoyuki,Kayaki, Yoshihito,Ikariya, Takao
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Read Online
- Optochemical Control of Bacterial Gene Expression: Novel Photocaged Compounds for Different Promoter Systems
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Photocaged compounds are applied for implementing precise, optochemical control of gene expression in bacteria. To broaden the scope of UV-light-responsive inducer molecules, six photocaged carbohydrates were synthesized and photochemically characterized, with the absorption exhibiting a red-shift. Their differing linkage through ether, carbonate, and carbamate bonds revealed that carbonate and carbamate bonds are convenient. Subsequently, those compounds were successfully applied in vivo for controlling gene expression in E. coli via blue light illumination. Furthermore, benzoate-based expression systems were subjected to light control by establishing a novel photocaged salicylic acid derivative. Besides its synthesis and in vitro characterization, we demonstrate the challenging choice of a suitable promoter system for light-controlled gene expression in E. coli. We illustrate various bottlenecks during both photocaged inducer synthesis and in vivo application and possibilities to overcome them. These findings pave the way towards novel caged inducer-dependent systems for wavelength-selective gene expression.
- Bier, Claus,Binder, Dennis,Bitzenhofer, Nora Lisa,Drepper, Thomas,Haase, Mona,Hilgers, Fabienne,Hogenkamp, Fabian,Jaeger, Karl-Erich,Ophoven, Vera,Pietruszka, J?rg
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- SBA-15 Supported Dendritic ILs as a Green Catalysts for Synthesis of 2-Imidazolidinone from Ethylenediamine and Carbon Dioxide
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In this work, a simple and facile approach is conducted for preparing many new SBA-15 supported dendritic imidazolium ILs heterogeneous catalysts SBA-15/IL(1–3) having high ionic density from SBA-15. SBA-15/IL(3) as a green heterogeneous catalyst can be used for synthesis of 2-imidazolidinone from ethylenediamine and carbon dioxide and considering solvent-free condition. SBA-15/IL(3) showed to have the highest catalytic activity besides a positive dendritic influence on the yields of the synthesis of 2-imidazolidinone in the presence of CO2 is seen because of existing the high-density peripheral zwitterionic ionic liquid functional groups on the biobased SBA-15/IL(3) catalyst surfaces. Graphical Abstract: [Figure not available: see fulltext.]
- Liu, Jinghan,Ma, Jianjun,Miao, Penghua,Min, Qingwang,Qi, Meijuan,Shamsa, Farzaneh
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- Reaction of Nitroxyl (HNO) with Hydrogen Sulfide and Hydropersulfides
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Nitroxyl (HNO) has gained a considerable amount of attention because of its promising pharmacological effects. The biochemical mechanisms of HNO activity are associated with the modification of regulatory thiol proteins. Recently, several studies have suggested that hydropersulfides (RSSH), presumed signaling products of hydrogen sulfide (H2S)-mediated thiol (RSH) modification, are additional potential targets of HNO. However, the interaction of HNO with reactive sulfur species beyond thiols remains relatively unexplored. Herein, we present characterization of HNO reactivity with H2S and RSSH. The reaction of H2S with HNO leads to the formation of hydrogen polysulfides and sulfur (S8), suggesting a potential role in sulfane sulfur homeostasis. Furthermore, we show that hydropersulfides are more efficient traps for HNO than their thiol counterparts. The reaction of HNO with RSSH at varied stoichiometries has been examined with the observed production of various dialkylpolysulfides (RSSnSR) and other nitrogen-containing dialkylpolysulfide species (RSS-NH-SnR). We do not observe evidence of sulfenylsulfinamide (RS-S(O)-NH2) formation, a pathway expected by analogy with the known reactivity of HNO with thiol.
- Zarenkiewicz, Jessica,Khodade, Vinayak S.,Toscano, John P.
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p. 868 - 877
(2021/01/14)
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- Fast Cyclization of a Proline-Derived Self-Immolative Spacer Improves the Efficacy of Carbamate Prodrugs
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Self-immolative (SI) spacers are sophisticated chemical constructs designed for molecular delivery or material degradation. We describe herein a (S)-2-(aminomethyl)pyrrolidine SI spacer that is able to release different types of anticancer drugs (possessing either a phenolic or secondary and tertiary hydroxyl groups) through a fast cyclization mechanism involving carbamate cleavage. The high efficiency of drug release obtained with this spacer was found to be beneficial for the in vitro cytotoxic activity of protease-sensitive prodrugs, compared with a commonly used spacer of the same class. These findings expand the repertoire of degradation machineries and are instrumental for the future development of highly efficient delivery platforms.
- Belvisi, Laura,Borlandelli, Valentina,Corno, Cristina,Dal Corso, Alberto,Gennari, Cesare,Perego, Paola,Pignataro, Luca
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p. 4176 - 4181
(2020/02/05)
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- Alkylamine-Substituted Perthiocarbamates: Dual Precursors to Hydropersulfide and Carbonyl Sulfide with Cardioprotective Actions
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The recent discovery of hydropersulfides (RSSH) in mammalian systems suggests their potential roles in cell signaling. However, the exploration of RSSH biological significance is challenging due to their instability under physiological conditions. Herein, we report the preparation, RSSH-releasing properties, and cytoprotective nature of alkylamine-substituted perthiocarbamates. Triggered by a base-sensitive, self-immolative moiety, these precursors show efficient RSSH release and also demonstrate the ability to generate carbonyl sulfide (COS) in the presence of thiols. Using this dually reactive alkylamine-substituted perthiocarbamate platform, the generation of both RSSH and COS is tunable with respect to half-life, pH, and availability of thiols. Importantly, these precursors exhibit cytoprotective effects against hydrogen peroxide-mediated toxicity in H9c2 cells and cardioprotective effects against myocardial ischemic/reperfusion injury, indicating their potential application as new RSSH- and/or COS-releasing therapeutics.
- Khodade, Vinayak S.,Pharoah, Blaze M.,Paolocci, Nazareno,Toscano, John P.
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supporting information
p. 4309 - 4316
(2020/03/05)
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- A near-infrared fluorescence probe for imaging of pantetheinase in cells and mice: In vivo
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Pantetheinase is an amidohydrolase that cleaves pantetheine into pantothenic acid and cysteamine. Functional studies have found that ubiquitous expression of this enzyme is associated with many inflammatory diseases. However, the lack of near-infrared fluorescence probes limits the better understanding of the functions of the enzyme. In this work, we have developed a new near-infrared fluorescence probe, CYLP, for bioimaging of pantetheinase by using pantothenic acid with a self-immolative linker as a recognition group. The probe produces a sensitive fluorescence off-on response at 710 nm to pantetheinase with a detection limit of 0.02 ng mL-1 and can be used to image the intraperitoneal pantetheinase activity in mice in vivo. Moreover, with the probe we have observed that pantetheinase is significantly increased in the tissues of mouse inflammatory models as well as in the intestines of mice with inflammatory bowel disease. Therefore, CYLP may provide a convenient and intuitive tool for studying the role of pantetheinase in diseases.
- Hu, Yiming,Ma, Huimin,Shi, Wen,Yang, Yuantao
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p. 12802 - 12806
(2020/12/29)
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- THIOL COMPOUND PRODUCTION METHOD AND NOVEL THIATING AGENT
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PROBLEM TO BE SOLVED: To provide: a thiol compound production method which allows selective production of a thiol compound of interest, inhibits production of by-products ending up wastes, is excellent in production efficiency, and can reduce production costs; and a novel thiating agent used for the method. SOLUTION: The thiol compound production method comprises: a step 1 of preparing a thiuronium salt by reacting at least one compound represented by the general formula (1) defined by R-(X)m with a thiating agent comprising at least one compound selected from compounds represented by the general formula (2) in the figure; and a step 2 of hydrolyzing the thiuronium salt to prepare a compound represented by the general formula (3) defined by R-(SH)m. SELECTED DRAWING: None COPYRIGHT: (C)2020,JPOandINPIT
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Paragraph 0067
(2019/12/25)
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- Synthesis method of 1,3-dimethyl-2-imidazolone
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The invention discloses a synthesis method of 1,3-dimethyl-2-imidazolone. The method comprises steps as follows: (1) montmorillonite, palladium on carbon, 2-imidazolidone and a formaldehyde water solution are sequentially added to a heatable and inflatable autoclave, and hydrogen is introduced into the autoclave for a reaction at the temperature of 110-160 DEG C for 1-5 h; (2) a material obtainedin the step (1) is filtered to recover montmorillonite and palladium on carbon, remaining formaldehyde and by-product water in filtrate are removed through distillation after the filtrate is collected, and a crude product is obtained; (3) the crude product is purified by rectification, and 1,3-dimethyl-2-imidazolone is obtained. The used catalyst is montmorillonite which is low in cost, can be directly used without further treatment or modification and is easy to recycle.
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Paragraph 0021-0022; 0025-0026; 0027-0028
(2018/05/16)
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- A new fluorogenic probe for the selective detection of carbon monoxide in aqueous medium based on Pd(0) mediated reaction
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A coumarin-based fluorogenic probe, PCO-1, senses carbon monoxide (CO) selectively in HEPES buffer at pH 8.0 through the intramolecular cyclization-elimination pathway based on Pd(0) mediated reaction. The probe exhibits a 'turn-on' response of CO over a variety of relevant reactive oxygen, nitrogen and sulfur species. This journal is
- Pal, Siddhartha,Mukherjee, Manjira,Sen, Buddhadeb,Mandal, Sushil Kumar,Lohar, Somenath,Chattopadhyay, Pabitra,Dhara, Koushik
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p. 4410 - 4413
(2015/03/18)
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- A reagent for safe and efficient diazo-transfer to primary amines: 2-azido-1,3-dimethylimidazolinium hexafluorophosphate
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Organic azides were prepared from primary amines in high yields by a metal free diazo-transfer reaction using 2-azido-1,3-dimethylimidazolinium hexafluorophosphate (ADMP), which is safe and stable crystalline. The choice of base was important in the diazo-transfer reaction. In general, 4-(N,N-dimethyl)aminopyridine (DMAP) was efficient, but a stronger base such as alkylamine or DBU was more appropriate for the reaction of nucleophilic primary amines. X-ray single crystal structural analysis and geometry optimization using density functional theory (B3LYP/6-31G**) were conducted to study the ADMP structure, and the diazo-transfer reaction mechanism was explained with the help of the results of these analyses. the Partner Organisations 2014.
- Kitamura, Mitsuru,Kato, So,Yano, Masakazu,Tashiro, Norifumi,Shiratake, Yuichiro,Sando, Mitsuyoshi,Okauchi, Tatsuo
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p. 4397 - 4406
(2014/06/23)
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- Highly efficient synthesis of cyclic ureas from CO2 and diamines by a pure CeO2 catalyst using a 2-propanol solvent
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Pure cerium oxide (CeO2) acts as an effective and reusable heterogeneous catalyst for direct synthesis of cyclic ureas from CO2 and diamines even at a low CO2 pressure of 0.3 MPa. 2-Propanol is the most preferable solvent to provide good selectivity. The system composed of a CeO2 catalyst and a 2-propanol solvent is applied to various diamines to provide the corresponding cyclic ureas in high yields (78-98%), including six-membered-ring ureas that are difficult to be synthesized from CO 2. Based on the kinetic studies on the effect of CO2 pressure and amine concentration and FTIR studies on adsorption of ethylenediamine and CO2 onto CeO2, the following mechanism for the synthesis of cyclic urea is proposed: (1) formation of carbamic acid and carbamate species on CeO2, (2) decomposition of carbamic acid to a free amino group and CO2, (3) nucleophilic attack of the amino group on the carbamate on CeO2 to produce the cyclic urea and (4) desorption of the product and regeneration of CeO2.
- Tamura, Masazumi,Noro, Kensuke,Honda, Masayoshi,Nakagawa, Yoshinao,Tomishige, Keiichi
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supporting information
p. 1567 - 1577
(2013/09/24)
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- Kinetics of self-immolative degradation in a linear polymeric system: Demonstrating the effect of chain length
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We describe here a study demonstrating that the degradation time of self-immolative linear polymers is dependent on chain length. These materials are unique relative to most degradable polymers, in that they undergo end-to-end depolymerization in response to the cleavage of an end-cap. Although one of their cited attributes is a dependence of their degradation time on chain length, no conclusive study has been conducted to demonstrate and study this effect. In this work, using a linear self-immolative polymer backbone derived from alternating 4-hydroxybenzyl alcohol and N,N′-dimethylethylenediamine based spacers, we show that there is a proportional relationship between chain length and depolymerization time. This is first accomplished using a series of oligomers synthesized using a convergent, iterative route and then applied to the polydisperse case on a set of polymers displaying varying molecular weights. We also report the first development and validation of a self-immolative degradation model relating monomer kinetics to polymer degradation and show its application in explaining oligomeric and polymeric degradation profiles.
- McBride, Ryan A.,Gillies, Elizabeth R.
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p. 5157 - 5166
(2013/07/26)
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- Self-immolative polymers containing rapidly cyclizing spacers: Toward rapid depolymerization rates
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Self-immolative polymers containing 4-hydroxybenzyl alcohol alternating with either N-methylaminoethanol or 2-mercaptoethanol spacers were synthesized and demonstrated to controllably depolymerize in response to the cleavage of a stabilizing end-cap from
- Chen, Eric K. Y.,McBride, Ryan A.,Gillies, Elizabeth R.
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p. 7364 - 7374
(2013/01/14)
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- A Simple synthesis of sugar nucleoside diphosphates by chemical coupling in water
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Sugar nucleotides made easy: The new reagent ImIm , which is formed in-situ in water, is shown to activate nucleoside 5'-phosphates to their imidazolides, these can subsequently couple with sugar-1-phosphates; the whole procedure takes place in water. This truly simple method yields a crude product mixture that can be used directly as a source of donors for glycosyltransferase- mediated oligsaccharide synthesis. In the scheme, B stands for the nucleobases U, A, or G. Copyright
- Tanaka, Hidenori,Yoshimura, Yayoi,Jürgensen, Malene R.,Cuesta-Seijo, Jose A.,Hindsgaul, Ole
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p. 11531 - 11534
(2013/01/15)
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- Reduction of dipyrido ureas via 6-alkyloxydipyrido[1,2-c;2′,1′- e]imidazolium salts
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Dipyrido uronium salts can readily be synthesized by alkylation of dipyrido ureas with Meerwein's reagent. Compared to the corresponding ureas, the uronium salts are more reactive towards basic or reducing agents like metal hydrides. Reactivity studies show that the uronium salts can react as alkylating agents towards DMSO, DBU and NaOEt along with release of the respective dipyrido ureas. In contrast, reduction of the dipyrido uronium salts with sodium borohydride or sodium trimethoxyborohydride in dry and degassed acetonitrile leads to the imidazolium salts 7a and 7b in moderate yields. Analysis of the by-products reveals an in situ carbene formation which can be reversed by using degassed but wet acetonitrile as solvent. The yield of 7b was increased significantly by these means.
- Kunz, Doris,Deissler, Christine,Gierz, Verena,Rominger, Frank,Oeser, Thomas
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scheme or table
p. 861 - 872
(2011/01/08)
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- Efficient solvent-free synthesis of urea derivatives using selenium-catalyzed carbonylation of amines with carbon monoxide and oxygen
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In the presence of a catalytic amount of selenium under ambient pressure of carbon monoxide with oxygen, solvent-free facile synthesis of urea derivatives was developed; the aim is for green and sustainable chemistry. For example, N,N-dimethylethylenediamine (20 mmol) successfully afforded 1,3- dimethylimidazolidin-2-one (DMI) in 74% yield (1487% based on Se) using selenium catalyst (5 mol%) under mixed gas (CO/O2, 2:1) at 0.1 MPa, 20 C without any additive or solvent
- Mizuno, Takumi,Nakai, Takeo,Mihara, Masatoshi
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experimental part
p. 4251 - 4255
(2011/03/17)
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- PROCESS FOR STRAIGHTENING KERATIN FIBRES WITH A HEATING MEANS AND DENATURING AGENTS
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The invention relates to a process for straightening keratin fibres, comprising: (i) a step in which a straightening composition containing at least two denaturing agents is applied to the keratin fibres, (ii) a step in which the temperature of the keratin fibres is raised, using a heating means, to a temperature of between 110 and 250° C.
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- Novel synthesis of N, n′-dialkyl cyclic ureas using sulfur-assisted carbonylation and oxidation
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The first example of cyclic urea synthesis from secondary amines by the use of sulfur-assisted carbonylation and oxidation was established. By combined sulfur-assisted carbonylation of secondary a, ay diamines under an ambient pressure of carbon monoxide
- Mizuno, Takumi,Nakai, Takeo,Mihara, Masatoshi
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experimental part
p. 64 - 68
(2009/05/31)
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- 2-azido-1,3-dimethylimidazolinium chloride: An efficient diazo transfer reagent for 1,3-dicarbonyl compounds
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Diazo transfer from 2-azido-1,3-dimethylimidazolinium chloride to 1,3-dicarbonyl compounds has been developed. The -reaction proceeds under mild conditions to give 2-diazo-1,3-dicarbonyl compounds in high yields, which are easily isolated because the by-products are highly soluble in water. Georg Thieme Verlag Stuttgart.
- Kitamura, Mitsuru,Tashiro, Norifumi,Okauchi, Tatsuo
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scheme or table
p. 2943 - 2944
(2010/01/21)
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- Development of a new nonpeptidic self-immolative spacer. application to the design of protease sensing fluorogenic probes
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The design and synthesis of novel self-immolative spacer systems aiming at the release of phenol-containing compounds are described. The newly designed traceless linkers proved to be conveniently stable under physiological conditions and operate through spontaneous decomposition of an hemithioaminal intermediate under neutral aqueous conditions. Their utility was then illustrated by the preparation of original fluorogenic substrates of penicillin amidase whose strong fluorescence is unveiled through enzyme-initiated domino reactions.
- Meyer, Yves,Richard, Jean-Alexandre,Massonneau, Marc,Renard, Pierre-Yves,Romieu, Anthony
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supporting information; experimental part
p. 1517 - 1520
(2009/04/18)
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- Synthesis and purification of aggregation-prone hydrophobic peptides by the incorporation of an Fmoc dipeptide with the peptide bond protected with a modified 2-hydroxy-4-methoxybenzyl (Hmb) group
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The dipeptide Fmoc-Val-(2-hydroxy-4-methoxybenzyl)Gly-OBzl was synthesized and the 2-hydroxyl group carbamoylated to give a Boc-N(CH3)CH2CH2N(CH3)CO-, (Boc-Nmec-) modification of the 2-hydroxy-4-methoxybenzyl (Hmb) group. After catalytic hydrogenation and purification, the resulting dipeptide Fmoc-Val-(Boc-Nmec-Hmb)Gly-OH was used in solid phase peptide synthesis. During treatment with TFA, the peptide was released from the resin and the Boc group cleaved. The peptide could then be purified with an alkylated peptide bond carrying a cationic charge that both increased the solubility of the peptide during the purification steps and facilitated analysis by MALDI-TOF mass spectrometry. The Nmec group was cleaved by intramolecular cyclization under slightly alkaline conditions, followed by cleavage of the Hmb group by TFA to give the fully deprotected peptide.
- Wahlstr?m, Karolina,Planstedt, Ove,Undén, Anders
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p. 3921 - 3924
(2008/09/21)
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- Substituent-dependent disassembly of self-immolative dendrimers
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Self-immolative dendrimers are tree-like platforms, which can spontaneously release all their end-group molecules through a single activation event at the dendrimer's focal point. This triggering event induces domino-like fragmentations, which leads to co
- Perry, Rotem,Amir, Roey J.,Shabat, Doron
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p. 1307 - 1312
(2008/03/12)
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- Method for producing cyclic carbamate ester
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A method for producing a cyclic carbamate ester produces the cyclic carbamate ester by reacting an organic compound having at least two halogen atoms per molecule, an amine having at least two hydrogen atoms on a nitrogen atom, and carbon dioxide.
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Page/Page column 4
(2008/06/13)
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- Ring enlargement and sulfur-transfer processes in SiO2-catalyzed reactions of thiocarbonyl compounds with optically active oxiranes
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The reactions of 1,3-dioxolane-2-thione (3) with (S)-2-methyloxirane ((S)-1) and with (R)-2-phenyloxirane ((R)-2) in the presence of SiO2 in anhydrous dichloroalkanes led to the optically active spirocyclic 1,3-oxathiolanes 8 with Me at C(7) and 9 with Ph at C(8), respectively (Schemes 2 and 3). The analogous reaction of 1,3-dimethylimidazolidine-2-thione (4a) with (R)-2 yielded stereoselectively (S)-2-phenylthiirane ((S)-10) in 83% yield and 97% ee together with 1,3-dimethylimidazolidin-2-one (11a). In the cases of 3-phenyloxazolidine-2-thione (4b) and 3-phenylthiazolidine-2-thione (4c), the reaction with (RS)-2 yielded the racemic thiirane (RS)-10, and the corresponding carbonyl compounds 11b and 11c (Scheme 4 and Table 1). The analogous reaction of 4a with 1,2-epoxycyclohexane (=7-oxabicyclo[4.1.0]heptane; 7) afforded thiirane 12 and the corresponding carbonyl compound 11a (Scheme 5). On the other hand, the BF3-catalyzed reaction of imidazolidine-2-thione (5) with (RS)-2 yielded the imidazolidine-2-thione derivative 13 almost quantitatively (Scheme 6). In a refluxing xylene solution, 1,3-diacetylimidazolidine-2-thione (6) and (RS)-2 reacted to give two imidazolidine-2-thione derivatives, 13 and 14 (Scheme 7). The structures of 13 and 14 were established by X-ray crystallography (Fig.).
- Malaschichin, Sergej,Fu, Changchun,Linden, Anthony,Heimgartner, Heinz
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p. 3253 - 3262
(2007/10/03)
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- A process for recovering 1,3-dimethyl-2-imidazolidinone
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The present invention provides a process for recovering 1,3-dimethyl-2-imidazolidinone comprising extracting 1,3-dimethyl-2-imidazolidinone from an aqueous solution containing it with n-butanol in the presence of an inorganic salt to obtain an n-butanol layer and subjecting the n-butanol layer to distillation.As 1,3-dimethyl-2-imidazolidinone can be recovered at high purity from an aqueous solution containing 1,3-dimethyl-2-imidazolidinone easily and efficiently without using alkali, the present process is industrially advantageous.
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Page/Page column 3
(2008/06/13)
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- Guanidines as a nitrogen source for direct conversion of epoxides to aziridines
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Direct conversion of epoxides to aziridines was achieved with guanidines as a nitrogen source. Stereochemical inversion at the chiral centers of epoxides was observed without loss of optical purity.
- Tsuchiya, Yukiko,Kumamoto, Takuya,Ishikawa, Tsutomu
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p. 8504 - 8505
(2007/10/03)
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- Flow cytometric screening of aldolase catalytic antibodies
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High-throughput screening of cells expressing active catalytic antibody clones by flow cytometry is described. A fluorogenic retro-aldol retro-Michael substrate was designed and synthesized with incorporation of a chloromethyl moiety for intracellular retention. Hybridoma or transfected mammalian cells expressing catalytic antibody molecules could be rapidly isolated.
- Shim, Hyunbo,Karlstroem, Amelie,Touami, Sofia M.,Fuller, Roberta P.,Barbas III, Carlos F.
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p. 4065 - 4068
(2007/10/03)
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- A chemical adaptor system designed to link a tumor-targeting device with a prodrug and an enzymatic trigger
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Targeting tumors can be achieved by using a novel chemical adaptor system (see picture) comprising, for example, the anticancer drug epotoside, an N-(2-hydroxypropyl) methacrylamide (HPMA) copolymer as the tumor-targeting device, and catalytic antibody 38C2 as the triggering enzyme in a single entity. When the enzyme cleaves the substrate, it triggers a spontaneous reaction that releases the active drug from the targeting moiety.
- Gopin, Anna,Pessah, Neta,Shamis, Marina,Rader, Christoph,Shabat, Doron
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p. 327 - 332
(2007/10/03)
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- Process for producing 1,3-dialkyl-2-imidazolidinone compound
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There is provided a process for preparing a 1,3-dialkyl-2-imidazolidinone by using an alkylene oxide as a first component, using at least one of (A) carbon dioxide and a monoalkylamine; (B) a carbon dioxide compound of the monoalkylamine; and (C) an 1,3-dialkylurea, reacting the first and second components by heating at 50 ° C. or higher to give 1,3-dialkyl-2-imidazolidinone, characterized in that the total molar amount of a molar feed amount of the monoalkylamine included in the component (A), a molar feed amount of the monoalkylamine part of the carbon dioxide compound of monoalkylamine, component (B), and the double of a molar feed amount of the 1,3-dialkylurea, component (C), is at least three folds of a molar feed amount of the alkylene oxide. The preparation process of this invention uses an industrially readily available alkylene oxide as a starting material and can be suitably conducted with a higher yield in an industrial scale.
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- 1,3-dialkyl-2-imidazolidinones and a manufacturing process therefor
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This invention provides a convenient process for manufacturing 1,3-dialkyl-2-imidazolidinones in a direct one-step reaction from industrially available alkylene carbonate, N-alkylethanolamine or 1,2-diol, which can minimize forming solid materials and be readily conducted in an industrial large-scale production with a higher yield and less byproducts. The process is characterized in that alkylene carbonate, N-alkylethanolamine or 1,2-diol is reacted with monoalkylamine and carbon dioxide, alkylcarbamate alkylamine salt, and/or 1,3-dialkylurea, by heating them at 50° C. or higher in a reactor whose area in contact with at least part of the reactants and/or products is made of a metal comprising titanium or zirconium and/or an oxide thereof or inorganic glass.
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- Fluorination agent and preparation and use of same
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The invention disclose a hydrogen fluoride containing composition comprising hydrogen fluoride and a compound which is liquid in the standard state (25° C., 1 atmosphere) and has a boiling point of 120° C. or more and pka of 12 or more at 25° C., and use of the composition for a fluorination agent. The compound which can be preferably used is represented by the formula (1): wherein R1 to R4 are a substituted or unsubstituted alkyl or aryl group and can be the same or different, and R1 or R2 or R3 and R4 can bond to form a ring having a nitrogen atom or a nitrogen atom and other hetero atom, or R1 and R3 can bond to form a ring having a nitrogen atom or a nitrogen atom and other hetero atom. The fluorination agent of the invention exerts effect with a similar reaction mechanism to hydrogen fluoride, can be applied to the halogen exchange reaction of a halogen containing organic compound, and can produce a fluorine containing compound with safety and ease without specific equipment or technique.
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- Catalytic oxidative carbonylation of primary and secondary α,ω-diamines to cyclic ureas
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(matrix presented) Primary and secondary diamines can be catalytically carbonylated to cyclic ureas using W(CO)6 as the catalyst, I2 as the oxidant, and CO as the carbonyl source. Preparation of five-, six-, and seven-membered cyclic ureas from the diamines RNHCH2(CH2)nCH2NHR (n = 0-2; R = H, Me) and RNHCH2CH2NHR (R = Et, i-Pr, Bz) was achieved in moderate to good yields.
- McCusker, Jennifer E.,Grasso, Cara A.,Main, Andrea D.,McEiwee-White, Lisa
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p. 961 - 964
(2008/02/09)
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- Process for the preparation of 1,3-disubstituted imidazolidinones
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2-Imidazolidinones are prepared by reacting 1,3-dioxalan-2-one (ethylene carbonate) with at least one compound of the formula RNH2 where R can be, inter alia, H, alkyl, aryl, heteroalkyl or heteroaryl.
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- Preparation process of acyl halide or sulfonyl halide
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A preparation process of acyl halide or sulfonyl halide which comprises reacting corresponding carboxylic acid or sulfonic acid with a haloiminium salt represented by the general formula (1): STR1 wherein R1 and R2 are same or different lower alkyl groups, X is a halogen atom, and n is an integer of 2 or 3.
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- Synthesis and antimicrobial activity of electron rich olefin derived cyclic ureas
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Seventeen cyclic ureas containing imidazolidine and benzimidazoline nuclei were synthesised by the reaction of electron-rich olefins with appropriate group 16 elements (O, S, Se, Te). The compounds synthesised were identified by 1H, 13C-NMR, FT-IR and mass spectroscopic techniques and micro analysis. All compounds studied in this work were screened for their in vitro antimicrobial activity against standard strains: Enterococcus faecalis (ATCC 29212), Staphylococcus aureus (ATCC 29213), Escherichia coli (ATCC 25922) and Pseudomonas aeruginosa (ATCC 27853). Eight of the compounds were found effective to inhibit the growth of Gram-positive bacteria (Enterococcus faecalis and Staphylococcus aureus) at MIC values between 25-400 μg/ml. None of the compounds exhibit antimicrobial activity against gram-negative bacteria (Escherichia coli and Pseudmonas aeruginosa) at the concentrations studied (6.25-800 μg/ml).
- Cetinkaya, Bekir,Cetinkaya, Engin,Kuecuekbay, Hasan,Durmaz, Riza
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p. 1154 - 1158
(2007/10/03)
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- Process for producing 1,3-dialkyl-2-imidazolidinone
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A novel bis-urea compound, preparation process of the compound, and preparation process of 1,3-dialkyl-2-imidazolidinone are disclosed and the disclosure provides a novel preparation process of 1,3-dialkyl-2-imidazolidinone and simultaneously enables effective utilization of N,N',N"-trialkyldiethylentriamine which lacks a large amount use and is desired to develop new application.
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- Carbonylation of Amines by Carbon Dioxide in the Presence of an Organoantimony Catalyst
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1,3-Dialkylureas (RNHCONHR; where R = Bu, i-Bu, s-Bu, t-Bu, allyl, Ph) and tetramethylurea were successfully prepared at 80 deg C under an initial CO2 pressure of 4.9 MPa, from the corresponding amines and carbon dioxide with catalysis by triphenylstibine oxide and assistance from tetraphosphorus decasulfide (Ph3SbO/P4S10).Monitoring of the reaction by 13C NMR revealed that the successive thiolation of carbamic acid to an intermediate antimony carbamate species and aminolysis of the carbamothioic acid thus formed constitute the reaction course.Cyclic ureas can also be synthesized by similar carbonylations of diamines (RNHCH2CH2NHR'; where R, R' = H, H; Me, H; Ph, H; HOCH2CH2, H; HOCHMeCH2, H; Me, Me).Furthermore, the Ph3SbO/P4S10 catalyst system enabled the preparation of trisubstituted ureas such as 1-butyl-3,3-diethylurea by a selective cocarbonylation of butylamine and diethylamine.
- Nomura, Ryoki,Hasegawa, Yasuhiro,Ishimoto, Mikio,Toyosaki, Takayuki,Matsuda, Haruo
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p. 7339 - 7342
(2007/10/02)
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- Aminosilylation of heterocumulenes and the intramolecular decomposition of their silyl-functionalized adducts
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Heteroorganic amidosilanes are readily obtained by interaction of CO2, CS2 and other heterocumulenes with pentacoordinated diaminosilanes.A comparison is made with the corresponding reactions of tetracoordinated species.Decompositon of these bifunctional organosilanes gives 2-substituted ureido derivatives and base-stabilized low coordinated silicon species, seemingly by a unimolecular thermal β-elimination.
- Corriu, R. J. P.,Lanneau, Gerard F.,Mehta, V. D.
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- Cyclization-Activated Prodrugs. Basic Carbamates of 4-Hydroxyanisole
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A series of basic carbamates of 4-hydroxyanisole was prepared and evaluated as progenitors of this melanocytotoxic phenol.All of the carbamates were relatively stable at low pH but released 4-hydroxyanisole cleanly at pH 7.4 at rates that were structure dependent.A detailed study of the N-methyl-N-carbamate showed that generation of the parent phenol followed first-order kinetics with t1/2 = 36.3 min at pH 7.4, 37 deg C, and was accompanied by formation of N,N'-dimethylimidazolidinone.These basic carbamates are examples of cyclization-activated prodrugs in which generation of the active drug is not linked to enzymatic cleavage but rather depends solely upon a predictable, intramolecular cyclization-elimination reaction.
- Saari, Walfred S.,Schwering, John E.,Lyle, Paulette A.,Smith, Steven J.,Engelhardt, Edward L.
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- Synthesis of acylguanidine analogues: inhibitors of ADP-induced platelet aggregation
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Routine screening of compounds for inhibition of ADP-induced platelet aggregation in vitro revealed that 1'-hexamethylenebis[3-cyclohexyl-3-[(cyclohexylimino)(4-morpholinyl)methyl] urea] was active and represented the first example of a bis(acylguanidine) with possible antithrombotic activity. In order to develop a structure-activity relationship for this class of compounds, we synthesized a number of new bis(acylguanidines). These were tested in vitro, and several analogues were also active. Ex vivo testing revealed that compounds 22, 41, 58, and 70-73 were orally active in rats or guinea pigs.
- Thomas,Nishizawa,Zimmermann,Williams
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p. 228 - 236
(2007/10/02)
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- Method of manufacturing N-alkyl-N'-methyl-alkyleneureas, particularly N,N'-d
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A method of manufacturing N-alkyl-N'-methyl-alkyleneureas, by reacting an alkyleneurea with formaldehyde to produce a hydroxymethyl-alkyleneurea, and further reacting said hydroxymethyl-alkyleneurea with formic acid to yield a N-alkyl-N'-methyl-alkyleneurea product, wherein the molar ratio of the N-alkyl-N'-hydroxymethyl-alkyleneureas or N,N'-(bis)hydroxymethyl-alkyleneureas is from 1-2 to 1-10, preferably 1-4 to 1-7.
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- PHASE TRANSFER CATALYTIC PREPARATION OF THE DIPOLAR APROTIC SOLVENTS DMI AND DMPU
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The title compounds are prepared by methylation of the respective cyclic ureas Me2SO4/catalyst/powdered NaOH (for DMI) or K2CO3 (for DMPU).Improved procedures are communicated for the preparation of 2-imidazolidine and trimethylene urea.
- Dehmlow, Eckehard V.,Rao, Y. Ramachandra
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p. 487 - 494
(2007/10/02)
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- Process for preparing cyclic urea derivatives
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A process for preparing a cyclic N,N'-dimethyl urea derivative by reacting a cyclic urea compound with formaldehyde, in a medium, in the presence of hydrogen and a hydrogenation catalyst. The reaction is carried out in the presence of a solid acid obtained by calcining sulfuric acid and aluminum oxide or sulfuric acid, phosphoric acid and aluminum oxide.
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- Process for preparing cyclic urea derivatives
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A process for preparing a cyclic N,N'-dimethyl urea derivative by reacting a cyclic urea compound with formaldehyde, in a medium, in the presence of hydrogen and a hydrogenation catalyst. The reaction is carried out in the presence of a solid acid obtained by calcining sulfuric acid and aluminum oxide or sulfuric acid, phosphoric acid and aluminum oxide.
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- PUSH-PULL OLEFINS FROM BIS(FORMAMIDINIUM) ETHERS
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Bis(N,N,N',N'-tetraalkyl)formamidinium ethers, readily prepared from a N,N,N',N'-tetraalkyl urea and triflic anhydride, yield push-pull olefins with activated methylene compounds H2CXY, where X, Y are CN, COOR, C6H4-4-NO2.
- Maas, Gerhard,Feith, Bernhard
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p. 1073 - 1080
(2007/10/02)
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- MACROHETEROCYCLES. XV. SYNTHESIS AND ION-SELECTIVE CHARACTERISTICS OF CYCLIC N,N'-DIALKYLUREAS
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A convenient method is proposed for the production of cyclic N,N'-dialkylureas by the reaction of cyclic thioureas with alkyl halides in the presence of aqueous alkali and phase-transfer catalysts.It was established that the reaction takes place through the formation of isothioureas with subsequent alkylation of the nitrogen atoms and hydrolytic cleavage of the obtained N,N'-dialkylthiouronium salt.This method was used for the synthesis of macrocyclic N,N'-dimethylpolyoxyethyleneureas.The ion-selective characteristics of the obtained crown compounds were studied.
- Bogat-skii, A. V.,Luk'yanenko, N. G.,Kirichenko, T. I.,Limich, V. V.,Karpenko, L. P.
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- 1H and 13C NMR study on some substituted azolidine derivatives
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The 1H and 13C NMR spectra carried out on (where for R = H, X = NH, NMe, NEt, CH2, S, O; for R = Me, X = NMe, CH2; for R = Et, X = NEt) are reported.The comparison of these results with those obtained for the thionic and selonic isologues shows that sulphur and selenium have a greater deshielding effect on the ring than oxygen.The resonance of the carbons not involved in the ? system have been correlated with the ? charges calculated by the DEL RE method.
- Cerioni, Giovanni,Cristiani, Franco,Devillanova, Francesco A.,Diaz, Angelo,Verani, Gaetano
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p. 929 - 932
(2007/10/02)
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