- PROCESS FOR MONO N-ALKYLATION OF AMINOPHENOL
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The invention relates to a process for the preparation of a compound represented by formula (I) wherein X is selected from the group consisting of -H, -halogen, linear or branched C1-C7 alkyl group, linear or branched C1-C5 alkoxy group, - NO2
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Page/Page column 5; 6
(2019/01/07)
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- Method for sorting of pluripotent cells
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A method for sorting pluripotent cells using a compound which is eliminated from the pluripotent cells through the MDR1 transporter.
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Page/Page column 32; 33
(2016/06/01)
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- Diethylenetriamine-Mediated Direct Cleavage of Unactivated Carbamates and Ureas
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Diethylenetriamine is effective for the direct cleavage of unactivated carbamates and ureas without additional reagents and catalysts. Various carbamates and ureas were cleaved to afford products in good yield, and the reactions were not affected by air or moisture. Unique chemoselective cleavage of carbamate and urea in the presence of amides was also achieved.
- Noshita, Megumi,Shimizu, Yuhei,Morimoto, Hiroyuki,Ohshima, Takashi
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supporting information
p. 6062 - 6065
(2016/12/09)
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- Palladium-catalyzed ortho-acyloxylation of N-nitrosoanilines via direct sp2 C-H bond activation
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The palladium-catalyzed N-nitroso-directed ortho-acyloxylation of N-nitrosoanilines has been demonstrated via sp2 C-H activation with a stoichiometric amount of PhI(OAc)2 as the oxidant and Ac2O/AcOH (1 : 1) or C2H5CO2H as the reaction medium. This protocol can be applied to various N-nitrosoanilines with both electron-donating and electron-withdrawing groups. In addition, the products can be further transformed to 2-(methylamino)phenols expediently by a simple reduction method.
- Li, Dan-Dan,Cao, Yi-Xuan,Wang, Guan-Wu
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p. 6958 - 6964
(2015/06/25)
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- PRODUCTION METHOD FOR COMPOUND COMPRISING AMINO GROUP AND/OR HYDROXYL GROUP
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Disclosed is a method for producing a compound having an amino group and/or a hydroxyl group from a substrate compound having an atomic group containing CO or CS by eliminating said atomic group. The substrate compound having an atomic group containing CO or CS (for example, an amide, a carbamate, or the like) is allowed to react with a compound expressed by formula (I) below, at a temperature of 120°C or lower, preferably in the presence of an ammonium salt, to eliminate said atomic group containing CO or CS. In formula (I) A may not be present, and in a case where A is present, A represents an alkyl group having 1 to 6 carbon atoms. ????????H2N-A-NH2?????(I)
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Paragraph 0095
(2015/01/18)
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- Novel benzoxazine and benzothiazine derivatives as multifunctional antihyperlipidemic agents
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Atherosclerosis is a multifactorial disease with several mechanisms participating in its manifestation. To address this disorder, we applied a strategy involving the design of a single chemical compound able to simultaneously modulate more than one target
- Matralis, Alexios N.,Katselou, Maria G.,Nikitakis, Anastasios,Kourounakis, Angeliki P.
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experimental part
p. 5583 - 5591
(2011/10/02)
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- A highly efficient and widely functional-group-tolerant catalyst system for copper(I)-catalyzed S-arylation of thiols with aryl halides
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A mild, general, and efficient copper-catalyzed system for C-S bond formation with high chemoselectivity and wide functional group tolerance is developed. With CuBr as catalyst and 1,2,3,4-tetrahydro-8-hydroxy-quinoline as ligand, the S-arylation of thiols with aryl halides performed well, the activated aryl iodides could take place even at room temperature, and the activated aryl bromides and chlorides give the corresponding products with good to excellent yields as well.
- Feng, Yang,Wang, Huifeng,Sun, Fangfang,Li, Yaming,Fu, Xinmei,Jin, Kun
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supporting information; experimental part
p. 9737 - 9741
(2010/02/27)
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- Mono-N-methylation of functionalized anilines with alkyl methyl carbonates over NaY faujasites. 4. Kinetics and selectivity
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(Chemical Equation Presented) In the presence of NaY faujasite as the catalyst, the reaction of bifunctional anilines (1-4: XC6H 4-NH2; X = OH, CO2H, CH2OH, and CONH2) with methyl alkyl carbonates [MeOCO2R′: R′ = Me or MeO(CH2)2O(CH2)2] proceeds with a very high mono-N-methyl selectivity (XC6H 4NHMe up to 99%), and chemoselectivity as well, with other nucleophilic functions (OH, CO2H, CH2OH, CONH2) fully preserved from alkylation and/or transesterification reactions. Aromatic substituents, however, modify the relative reactivity of amines 1-4: good evidence suggests that, not only steric and electronic effects, but, importantly, direct acid-base interactions between substituents and the catalyst are involved. Weakly acidic groups (OH, CH2OH, CONH2, pKa ≥ 10) may help the reaction, while aminobenzoic acids (pK a of 4-5) are the least reactive substrates. The solvent polarity also affects the reaction, which is faster in xylene than in the more polar diglyme. The mono-N-methyl selectivity is explained by the adsorption pattern of reagents within the zeolite pores: a BAl2 displacement of the amine on methyl alkyl carbonate should occur aided by the geometric features of the NaY supercavities. Different factors account for the reaction chemoselectivity. Evidence proves that the polarizability of the two nucleophilic terms (NH 2 and X groups) of anilines is relevant, although adsorption and confinement phenomena of reagents promoted by the zeolite should also be considered.
- Selva, Maurizio,Tundo, Pietro,Foccardi, Tommaso
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p. 2476 - 2485
(2007/10/03)
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- AZOLIDINONE-VINYL FUSED-BENZENE DERIVATIVES
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The present invention is related to azolidinedione-vinyl fused-benzene derivatives of formula (I) for the treatment and/or prophylaxis of autoimmune disorders and/or inflammatory diseases, cardiovascular diseases, neurodegenerative diseases, bacterial or viral infections, kidney diseases, platelet aggregation, cancer, graft rejection or lung injuries. Formula (I), wherein A, X, Y, Z, R1 , R2 and n are as described in the description.
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- Synthesis of mono-N-substituted functionalized anilines
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The present invention relates to a process for direct and selective synthesis of mono-N-substituted functionalized anilines by using alkylating agents selected from the class of organic carbonates, preferably of the dialkyl, dibenzyl and diallyl types, in the presence of suitable catalysts that are chemically related to the class of aluminosilicates.
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- Synthesis of mono-N-substituted functionalized anilines
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The present invention relates to a process for direct and selective synthesis of mono-N-substituted functionalized anilines by using alkylating agents selected from the class of organic carbonates, preferably of the dialkyl, dibenzyl and diallyl types, in the presence of suitable catalysts that are chemically related to the class of aluminosilicates.
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- Reaction of functionalized anilines with dimethyl carbonate over NaY faujasite. 3. Chemoselectivity toward mono-N-methylation
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In the presence of NaY faujasite, dimethyl carbonate (MeOCO2Me, DMC) is a highly chemoselective methylating agent of functionalized anilines such as aminophenols (1), aminobenzyl alcohols (2), aminobenzoic acids (3), and aminobenzamides (4). The reaction proceeds with the exclusive formation of N-methylanilines without any concurrent O-methylation or N-/O-methoxy carbonylation side processes. Particularly, only mono-N-methyl derivatives [XC6H4NHMe, X = o-, m-, and p-OH; o- and p-CH 2OH; o- and P-CO2H; o- and p-CONH2] are obtained with selectivity up to 99% and isolated yields of 74-99%. DMC, which usually promotes methylations only at T > 120 °C, is activated by the zeolite catalyst and it reacts with compounds 1, 2, and 4, at 90 °C. Aminobenzoic acids (3) require a higher reaction temperature (≥130 °C).
- Selva, Maurizio,Tundo, Pietro,Perosa, Alvise
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p. 7374 - 7378
(2007/10/03)
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- Covalent modification of cyclooxygenase-2 (COX-2) by 2-acetoxyphenyl alkyl sulfides, a new class of selective COX-2 inactivators
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All of the selective COX-2 inhibitors described to date inhibit the isoform by binding tightly but noncovalently at the substrate binding site. Recently, we reported the first account of selective covalent modification of COX-2 by a novel inactivator, 2-acetoxyphenyl hept-2-ynyl sulfide (70) (Science 1998, 280, 1268-1270). Compound 70 selectively inactivates COX-2 by acetylating the same serine residue that aspirin acetylates. This paper describes the extensive structure-activity relationship (SAR) studies on the initial lead compound 2-acetoxyphenyl methyl sulfide (36) that led to the discovery of 70. Extension of the S-alkyl chain in 36 with higher alkyl homologues led to significant increases in inhibitory potency. The heptyl chain in 2-acetoxyphenyl heptyl sulfide (46) was optimum for COX-2 inhibitory potency, and introduction of a triple bond in the heptyl chain (compound 70) led to further increments in potency and selectivity. The alkynyl analogues were more potent and selective COX-2 inhibitors than the corresponding alkyl homologues. Sulfides were more potent and selective COX-2 inhibitors than the corresponding sulfoxides or sulfones or other heteroatom-containing compounds. In addition to inhibiting purified COX-2, 36, 46, and 70 also inhibited COX-2 activity in murine macrophages. Analogue 36 which displayed moderate potency and selectivity against purified human COX-2 was a potent inhibitor of COX-2 activity in the mouse macrophages. Tryptic digestion and peptide mapping of COX-2 reacted with [1-14C-acetyl]-36 indicated that selective COX-2 inhibition by 36 also resulted in the acetylation of Ser516. That COX-2 inhibition by aspirin resulted from the acetylation of Ser516 was confirmed by tryptic digestion and peptide mapping of COX-2 labeled with [1- 14C-acetyl]salicyclic acid. The efficacy of the sulfides in inhibiting COX- 2 activity in inflammatory cells, our recent results on the selectivity of 70 in attenuating growth of COX-2-expressing colon cancer cells, and its selectivity for inhibition of COX-2 over COX-1 in vivo indicate that this novel class of covalent modifiers may serve as potential therapeutic agents in inflammatory and proliferative disorders.
- Kalgutkar, Amit S.,Kozak, Kevin R.,Crews, Brenda C.,Hochgesang Jr., G. Phillip,Marnett, Lawrence J.
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p. 4800 - 4818
(2007/10/03)
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- Synthesis and protein tyrosine phosphatase inhibitory activity of dephostatin analogs
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We have synthesized derivatives of dephostatin, a protein tyrosine phosphatase (PTPase) inhibitor, to study the structure-activity relationships of this inhibitor. Inactive analogs revealed some insight into structural requirements for PTPase inhibitory activity of dephostatin. Both a nitroso group and phenolic hydroxyl groups were found to be essential for the inhibitory activity. Among the dephostatin derivatives synthesized, one of the regioisomers of dephostatin showed PTPase inhibitory activity equivalent to that of dephostatin, and also had increased stability.
- Watanabe,Takeuchi,Otsuka,Tanaka,Umezawa
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p. 1460 - 1466
(2007/10/03)
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- SYNTHESIS AND REACTIONS OF 3,4-DIHYDRO-2H-1,4-BENZOXAZINE DERIVATIVES
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Several 3,4-dihydro-2H-1,4-benzoxazine derivatives were prepared from commercially available benzoxazoles by use of an efficient two step sequence.Aryl functionalization reactions allowing access to further benzoxazine derivatives are also described.
- Kotha, Sambasivarao,Bindra, Vandana,Kuki, Atsuo
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- Intramolecular ureido and amide group participation in reactions of carbonate diesters
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The cyclization of ethyl and phenyl 2-ureidophenylcarbonates in H2O at 30 °C involves two discrete steps with benzoxazolinone as the final product. The formation of benzoxazolinone is quantitative. Phenol is released in the initial step from both esters in an apparent OH--catalyzed reaction, which shows that intramolecular nucleophilic attack by the ureido group is via an anionic species. The pH-rate constant profile for the second step in the reaction of the ethyl ester is sigmoidal with pKapp = 8.9. The initial reaction involves a rearrangement, and the neighboring phenoxide ion of the intermediate participates in the second step. In view of the D2O solvent isotope effect (kH2O/kD2O = 1.2), this participation must be via a nucleophilic mechanism. The second step of the reaction of the phenyl ester, in which benzoxazolinone is formed, involves an apparent OH--catalyzed reaction of a cyclic intermediate. This intermediate was identified as N-carbamoylbenzoxazolinone, which thereby indicates that the initial nucleophilic attack is by nitrogen through a 5-membered-ring transition state. p-Nitrophenol release from p-nitrophenyl 2-ureidophenylcarbonate is only 18-fold faster than phenol release from the corresponding phenyl ester. Ratios of kOH(ortho) for phenol release from the 2-ureido-substituted esters to kOH(para) for OH--catalyzed hydrolysis of the corresponding 4-ureido-substituted esters are approximately 104 in all cases. In the intramolecular nucleophilic reactions of the ureido-substituted carbonate esters, a neutral species reaction is not observed, even at pH values as low as 3, in contrast with substituted benzoate esters having phenolic leaving groups. Also, in the apparent OH--catalyzed reactions of the carbonate diesters, only one cyclic product is obtained, whereas both oxygen and nitrogen attack occur in the nucleophilic reactions of carboxylate esters. The neighboring amide group of p-nitrophenyl o-(carboxamido)phenylcarbonate participates with nitrogen attack and apparent OH- catalysis. Intramolecular attack of nitrogen provides a rate enhancement of 103 in the release of p-nitrophenol over the OH--catalyzed hydrolysis of the para-substituted compound. Thus, in the intramolecular nucleophilic reactions of the carbonate diesters, nitrogen anion attack takes place preferentially when such attack is sterically favored (five-membered-ring transition state) and when there is an equal opportunity for oxygen or nitrogen attack.
- King, Stephen W.,Natarajan,Bembi, Ramesh,Fife, Thomas H.
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p. 10715 - 10721
(2007/10/02)
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- A New Synthetic Approach to Unusually Electron Rich α-Amino Acids
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An electron rich dihydrobenzoxazine based α-amino acid has been synthesized using the Schollkopf chiral auxiliary giving a new adaptation of the standard Cα-Cβ bond formation strategy, as required by the electron rich nature of the s
- Kotha, Sambasivarao,Kuki, Atsuo
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p. 404 - 406
(2007/10/02)
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- Selective Cleavage of Benzoxazoles to o-Hydroxy-N-substituted Anilines with Sodium Borohydride-acetic Acid
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The utility of sodium borohydride in the presence of acetic acid in efficiently and selectively cleaving substituted benzoxazoles to o-hydroxy-N-substituted anilines in the presence of other functional groups is described.These conditions offer practical advantages over existing ring opening procedures with normally resistant benzoxazoles.
- Yadagiri, Bathini,Lown, J. William
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p. 175 - 181
(2007/10/02)
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- 1H-Azepin-3(2H)-ones
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The reactivity of the title compounds (1) with acids, bases, and electrophiles, and in pericyclic processes is compared to the chemistry of the structurally related pyrrol-3-ones (2), pyridin-2-ones (3), and azepin-2-ones (4).
- McNab, Hamish,Monahan, Lilian C.
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p. 141 - 142
(2007/10/02)
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- Tertiary Amine-Catalyzed Acyl Group-Exchange Reactions of N,O-Diacyl-o-aminophenols
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A kinetic study on the base-catalyzed acyl group-exchange reactions of N,O-diacyl-o-aminophenols was undertaken to show that the formation of the amidate ion should be the rate-determining step in these intramolecular acyl exchange reactions, and that the
- Sakurai, Tadamitsu,Yamada, Shuichi,Inoue, Hiroyasu
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p. 2666 - 2668
(2007/10/02)
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- 4-NITROPYROCATECHOL ETHERS AS POSSIBLE PHOTOAFFINITY LABELS. PHOTOCHEMICAL REACTIONS OF 4-NITROPYROCATECHOL ETHERS OF BIOLOGICALLY ACTIVE COMPOUNDS
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The photochemical reactions of O- and N-(2-methoxy-4-nitro)phenoxyalkyl derivatives of estrone and of the antibiotic cycloheximide with methylamine afford clean substitutions of the methoxy group.From these experiments it is inferred that 2-methoxy-4-nitrophenyl ethers can be good photoaffinity labels.
- Castello, A.,Cervello, J.,Marquet, J.,Moreno-Manas, M.,Sirera, X.
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p. 4073 - 4082
(2007/10/02)
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- Photochemically Induced Reactions of 3-Amino-2H-azirines
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Irradiation of 3-(N-methylanilino)-2H-azirines with a mercury low pressure lamp induces the cleavage of the C(2), C(3)-ring bond thus affording nitriliomethanide dipols, substituted by an amino group at C(1).Depending on the substitution pattern at C(3),
- Dietliker, Kurt,Heimgartner, Heinz
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p. 262 - 295
(2007/10/02)
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- A HIGHLY EFFICIENT AND GENERAL N-MONOMETHYLATION OF FUNCTIONALIZED PRIMARY AMINES VIA FORMYLATION -- BORANE:METHYL SULFIDE REDUCTION
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Formylation of functionalized primary aromatic and aliphatic amines with acetic formic anhydride (AFA) followed by borane:methyl sulfide reduction in the same pot affords the corresponding N-methylamines in excellent isolated yields, uncontaminated by bis alkylation; the reaction sequence is applicable to even very weakly basic and sterically hindered amines.
- Krishnamurthy, S.
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p. 3315 - 3318
(2007/10/02)
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- Studies on the Preparation of N-Alkyl-O-phenylhydroxylamines
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Several possible routes to the title compounds have been investigated.The reaction of N-hydroxycarbamates (1) with diphenyliodonium bromide gave, unexpectedly, N-hydroxy-N-phenylcarbamates (2), while N-methyl-N-hydroxycarbamates (6) gave 2-(N-methyl-N-alkoxycarbonylamino)phenols (7).Mechanistic aspects of the N-arylations and subsequent rearrangements are discussed.The desired N-alkyl-O-phenylhydroxylamines were obtained by the reduction of O-phenyloximes (15) with sodium cyanoborohydride.
- Sheradsky, Tuvia,Nov, Eliahu
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p. 2781 - 2786
(2007/10/02)
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