- Phosphine-catalyzed sequential (2+3)/(2+4) annulation of γ-vinyl allenoates: Access to the synthesis of chromeno[4,3-: B] pyrroles
-
A phosphine-catalyzed cascade (2+3)/(2+4) cyclization reaction of γ-vinyl allenoates with aldimine esters has been developed to provide a series of chromeno[4,3-b]pyrrole derivatives that contain three contiguous stereogenic centers. The method gives a good yield, excellent chemoselectivity and diastereoselectivity under mild conditions.
- Huang, You,Li, Xiaohu
-
supporting information
p. 9934 - 9937
(2021/10/12)
-
- METHODS OF PRODUCING PYRAZOLE COMPOUNDS
-
The present invention is directed to methods of producing substituted pyrazole based compounds through novel intermediates and unique processes for preparing such intermediates which enables synthesis of final product through commercially viable route of synthesis. The present invention is also directed to novel methods of producing substituted pyrazole based thyroid like compounds, and solid forms of 3-{4-[(7-hydroxy-6-methyl-indan-4-yl)methyl]-3,5-dimethyl-1H-pyrazol-1-yl}-propanoic acid, its pharmaceutical compositions, and methods of preparation thereof.
- -
-
Page/Page column 67; 68
(2020/04/25)
-
- BICYCLIC COMPOUNDS AS INHIBITORS OF PD1/PD-L1 INTERACTION/ACTIVATION
-
The compounds of Formula I is described herein along with their polymorphs, stereoisomers, tautomers, prodrugs, solvates, and pharmaceutically acceptable salts thereof. The compounds described herein, their polymorphs, stereoisomers, tautomers, prodrugs, solvates, and pharmaceutically acceptable salts thereof are bicyclic compounds that are inhibitors of PD-1/PD-L1 interaction/activation.
- -
-
Paragraph 00098
(2019/10/04)
-
- Phosphine-Catalyzed [3+2] Annulation of β-Sulfonamido-Substituted Enones with Sulfamate-Derived Cyclic Imines
-
Phosphine-catalyzed [3+2] annulation of β-sulfonamido-substituted enones and sulfamate-derived cyclic imines has been developed, giving a series of imidazoline derivatives in moderate to excellent yields with good to excellent diastereoselectivities. A scale-up reaction worked well under mild reaction conditions. A possible mechanism was proposed on the basis of the results obtained.
- Shi, Wangyu,Zhou, Leijie,Mao, Biming,Wang, Qijun,Wang, Chang,Zhang, Cheng,Li, Xuefeng,Xiao, Yumei,Guo, Hongchao
-
supporting information
p. 679 - 685
(2019/01/24)
-
- Efficient microwave-assisted regioselective one pot direct: Ortho -formylation of phenol derivatives in the presence of nanocrystalline MgO as a solid base catalyst under solvent-free conditions
-
In this research, at first nanocrystalline MgO was prepared and then the solvent-free reactions of phenol derivatives with paraformaldehyde in the presence of the obtained nanocrystalline MgO as a new catalyst under microwave irradiation were investigated. In this reaction, ortho-hydroxyaromatic aldehydes were yielded as products. This method seems to be comparable with other reported methods due to its high yield and regioselectivity. The significant features of this method are short reaction times, high yields, and easy and quick isolation of the products.
- Naeimi, Hossein,Zakerzadeh, Elham
-
p. 4590 - 4595
(2018/03/21)
-
- Synthesis of chiral salalen ligands and their in-situ generated Cu-complexes for asymmetric Henry reaction
-
Chiral salalen ligands derived from (S)-proline and derivatives of salicyaldehydes were synthesized, and their in-situ generated Cu (II) complexes were evaluated in the asymmetric Henry reaction. Salalen ligand of different substituents on the phenyl moiety showed remarkable effect on the enantioselectivity of nitro-aldol product of 4-nitrobenzaldehyde and nitromethane. Cu (II) complex generated in situ with (S)-2-(tert-butyl)-6-((2-(((2-hydroxy-3-methylbenzylidene)amino)methyl)pyrrolidin-1-yl)methyl) phenol (10?mol%) and Cu (OAc)2.H2O (10?mol%), found to be better catalyst for nitro-aldol reaction between 4-nitrobenzaldehyde and nitromethane, gave corresponding product in 85% yield and 88% enantiomeric excess (ee) in isopropanol at 35°C after 40?hours. The catalyst also used for the Henry reaction with different substituted benzaldehydes and corresponding products were obtained in 22% to 99% yields with 66% to 92% ee. Henry reaction of 4-nitrobenzaldehyde and prochiral nitroethane gave anti-selective product (dr?=?79/21; anti/syn) in a 91% yield with 80% ee.
- Dixit, Ashish,Kumar, Pramod,Singh, Surendra
-
p. 1257 - 1268
(2018/09/25)
-
- Efficient synthesis of chiral benzofuryl β-amino alcohols via a catalytic asymmetric Henry reaction
-
Chiral β-amino alcohol ligands were found effective for the copper(ii)-catalyzed asymmetric Henry reaction of benzofuran-2-carbaldehydes with nitromethane, which led to the formation of (S)-enriched benzofuryl β-nitro alcohols with satisfactory enantioselectivities (up to 98% ee). Using this catalytic protocol, bioactive (S)-benzofuryl β-amino alcohols could be conveniently prepared in short steps.
- Chen, Wei,Zhou, Zhao-Hui,Chen, Hong-Bin
-
supporting information
p. 1530 - 1536
(2017/02/15)
-
- Dual roles of sulfonyl hydrazides in the catalyst-free sulfonylation of unsaturated benzylic alcohols in water
-
An atom-economical sulfonylation of unsaturated benzylic alcohols in water is described. In this transformation, dual roles of sulfonyl hydrazides serving as both a sulfonyl source and a reductant have been demonstrated, which enabled a facile and green method to synthesize alkyl sulfones from unsaturated benzylic alcohols. Moreover, this approach provides a practical access to deuterated alkanes from the corresponding alkenes by employing the combination of sulfonyl hydrazides and the solvent D2O.
- Xu, Kun,Li, Lijun,Yan, Wen,Wu, Yuanyuan,Wang, Zhiqiang,Zhang, Sheng
-
supporting information
p. 4494 - 4497
(2017/10/13)
-
- Phosphine-Catalyzed [4 + 2] Annulation of Allenoate with Sulfamate-Derived Cyclic Imines: A Reaction Mode Involving γ′-Carbon of α-Substituted Allenoate
-
A phosphine-catalyzed [4 + 2] cycloaddition of cyclic α-substituted allenoates with sulfamate-derived cyclic imines has been reported. Using dibenzylphenylphosphine as the nucleophilic catalyst, the reaction worked efficiently to yield various fused multicyclic heterocyclic compounds in high yields with excellent diastereoselectivities. It undergoes a new reaction mode involving γ′-carbon of α-substituted allenoate.
- Mao, Biming,Shi, Wangyu,Liao, Jianning,Liu, Honglei,Zhang, Cheng,Guo, Hongchao
-
supporting information
p. 6340 - 6343
(2017/12/08)
-
- Transition Metal Ions as Efficient Catalysts for Vilsmeier-Haack Formylation of Hydrocarbons with Reagents: Kinetics and Mechanism
-
The Vilsmeier-Haack formylation reactions with hydrocarbons are sluggish in acetonitrile medium. The VH reactions follows second-order kinetics and affords formyl derivatives under kinetic conditions that are also irrespective of the nature of the oxychloride (POCl3 or SOCl2) used for the preparation of VH reagent along with DMF. However, the reactions undergo significant rate accelerations in the presence of transition metal ions such as Cu(II), Ni(II), Co(II) and Cd(II). Transition metal ion catalyzed VH formylation is explained through the formation of a mixed ligand complex of the [M(II)S(VHR)] type prior to the rate determining rearrangement step, before yielding formyl derivatives of hydrocarbons.
- Rajanna,Ferdose, Aneesa,Rajendar Reddy,Arifuddin,Moazzam Ali
-
p. 371 - 394
(2016/03/12)
-
- Structure-activity relationship study of E6 as a novel necroptosis inducer
-
Necroptosis inducers represent a promising potential treatment for drug-resistant cancer. We herein describe the structure modification of E6, which was identified recently as a potent and selective necroptosis inducer. The studies described herein demonstrate for the first time that functionalized biphenyl derivatives possess necroptosis inducer activity. Furthermore, these studies have led to the identification of two promising compounds (5h and 5j) that can be used for further optimization studies as well as mechanism of action investigations.
- Mou, Jianfeng,Park, Ann,Cai, Yu,Yuan, Junying,Yuan, Chengye
-
supporting information
p. 3057 - 3061
(2015/06/22)
-
- Selective Aromatic Hydroxylation with Dioxygen and Simple Copper Imine Complexes
-
The formation of a bis(μ-oxido)dicopper complex with the ligand 2-(diethylaminoethyl)-6-phenylpyridine (PPN) and its subsequent hydroxylation of the pendant phenyl group (studied earlier by Holland et al., Angew. Chem. Int. Ed. 1999, 38, 1139-1142) has been reinvestigated to gain a better understanding of such systems in view of the development of new synthetic applications. To this end, we prepared a simple copper imine complex system that also affords selective o-hydroxylation of aromatic aldehydes by using dioxygen as the oxidant: Applying the ligand N′-benzylidene-N,N-diethylethylenediamine (BDED), salicylaldehyde was prepared in good yields and we show that this reaction also occurs through an intermediate bis-μ-oxido copper complex. The underlying reaction mechanism for the PPN-supported complex was studied at the BLYP-D/TZVP level of density functional theory and the results for representative stationary points along reaction paths of the BDED-supported complex reveal a closely related mechanistic scenario. The results demonstrate a new facile synthetic way to introduce OH groups into aromatic aldehydes.
- Becker, Jonathan,Gupta, Puneet,Angersbach, Friedrich,Tuczek, Felix,N?ther, Christian,Holthausen, Max C.,Schindler, Siegfried
-
p. 11735 - 11744
(2015/08/11)
-
- METHOD OF PREPARING POLY(ALKYLENE CARBONATE) VIA COPOLYMERIZATION OF CARBON DIOXIDE/EPOXIDE IN THE PRESENCE OF NOVEL COMPLEX
-
Provided is a method of preparing poly(alkylene carbonate) using a molecular weight regulator in a process of preparing a copolymer of carbon dioxide/epoxide using a novel complex synthesized from salen-type ligand including a quaternary ammonium salt as a catalyst. According to the present invention, even though the molecular weight regulator is used, an activity of the catalyst may be stably maintained, whereby the low molecular weight of poly(alkylene carbonate) having a desirable level may be effectively provided. In addition, it is expected that since the novel complex as the catalyst of the present invention has a simple structure as compared to the existing copolymerization catalyst, due to the economical preparation cost thereof, the novel complex may be effectively applied to a large-scale commercial process.
- -
-
Paragraph 316 - 319
(2014/10/04)
-
- The one pot synthesis salicylaldehyde prepared by reactive grinding with derivative phenol and paraformaldehyde in absence magnesium methoxide
-
The formylation phenols are mono-formylated using a mixture of paraformaldehyde, Mg(OMe)2, by reactive grinding. In all cases but one, only one regioisomer of the salicylaldehyde is obtained in good to high yield.
- Balali, Ebrahim,Shameli, Abolghasem,Naeimi, Hoseein,MehdiGhanbari, Mohammad
-
p. 1611 - 1614
(2014/05/06)
-
- Photocycloaddition of arenes and allenes
-
In this work, we report on a new intramolecular para cycloaddition of arenes with allenes, yielding attractive rigid scaffolds bearing several reactive functionalities to build in further diversity. Bicyclo[2.2.2]octadiene- type products and benzoxepine acetals are formed in this reaction, in ratios and yields depending on the substitution pattern on the aromatic ring, the nature of the chromophore, and the tether. This unprecedented reaction has remarkable features that distinguish it from many other photochemical transformations: it is particularly robust with respect to substituents, it can be scaled up without a notable loss of efficiency, and it can lead to structures with a high degree of complexity in low to good yields. All photochemical precursors could be synthesized readily in three steps. We confirmed the compatibility of the nitrogen atom in the photocycloaddition step, which gives access to a bicyclo[2.2.2]octadiene scaffold with two points that allow further diversification. This reaction was scaled up to multigram quantities without erosion of the typically high yields in photocycloadducts. Sequential deprotection of the N- or C-terminus of bicyclic amino acids gave access to two conformationally constrained unnatural amino acids with different dispositions of the two anchor points.
- Streit, Ursula,Birbaum, Frederic,Quattropani, Anna,Bochet, Christian G.
-
p. 6890 - 6910
(2013/08/23)
-
- Asymmetric induction via short-lived chiral enolates with a chiral C-O axis
-
A novel method has been developed for the asymmetric cyclization of alkyl aryl ethers. The reactions were assumed to proceed via short-lived chiral enolate intermediates with a chiral C-O axis to give cyclic ethers with tetrasubstituted carbon in up to 99% ee. The half-life of racemization of the chiral enolate intermediate was roughly estimated to be ~1 s at -78 C.
- Yoshimura, Tomoyuki,Tomohara, Keisuke,Kawabata, Takeo
-
supporting information
p. 7102 - 7105
(2013/06/27)
-
- Enantioselective synthesis of multisubstituted biaryl skeleton by chiral phosphoric acid catalyzed desymmetrization/kinetic resolution sequence
-
Described herein is the enantioselective synthesis of multisubstituted biaryl derivatives by chiral phosphoric acid catalyzed asymmetric bromination. Two asymmetric reactions (desymmetrization and kinetic resolution) proceeded successively to afford chiral biaryls in excellent enantioselectivities (up to 99% ee). Both experimental and computational studies suggested that this excellent selectivity could be achieved via a highly organized hydrogen bond network among a substrate, a catalyst (chiral phosphoric acid), and a brominating reagent (N-bromophthalimide).
- Mori, Keiji,Ichikawa, Yuki,Kobayashi, Manato,Shibata, Yukihiro,Yamanaka, Masahiro,Akiyama, Takahiko
-
p. 3964 - 3970
(2013/04/24)
-
- Cu(OAc)2·H2O-promoted tandem β-alkynyl elimination of α-or β-hydroxy propargylic alcohols and homocoupling of the resulting alkynyl species
-
α or β-hydroxy propargylic alcohols undergo tandem C(sp)-C(sp3) bond cleavage via β-alkynyl elimination and homocoupling of the resulted alkynyl species in the presence of Cu(OAc)2·H2O to produce the corresponding hydroxycarbonyl com
- Xu, Xiangsheng,Huang, Zhenyong,Lu, Yanfeng
-
p. 546 - 549
(2013/10/22)
-
- Pd(II)-catalyzed asymmetric Wacker-type cyclization for the preparation of 2-vinylchroman derivatives with biphenyl tetraoxazoline ligands
-
This article describes an efficient method for the preparation of chiral chroman derivatives by the Pd(II)-catalyzed asymmetric Wacker-type cyclization using a chelation-induced axially chiral tetraoxazoline ligand. Under the optimized conditions, up to 80% yield and up to 92% ee were obtained. This is the first example to utilize o-trisubstituted 3-butenylphenols as substrates in such transformation.
- Liu, Qingchuan,Wen, Ke,Zhang, Zhenfeng,Wu, Zhengxing,Zhang, Yong Jian,Zhang, Wanbin
-
experimental part
p. 5209 - 5215
(2012/08/08)
-
- Insertion of arynes into the carbon-oxygen double bond of amides and its application into the sequential reactions
-
The reaction of arynes, generated from ortho-(trimethylsilyl)aryl triflates, with the CO bond of formamides gave salicylaldehyde derivatives via the formation of formal [2+2] adducts. The sequential transformation of arynes into ortho-disubstituted arenes, o-aminoalkylphenols or o-hydroxyalkylphenols, was achieved by one-pot procedure using dialkylzincs.
- Yoshioka, Eito,Miyabe, Hideto
-
experimental part
p. 179 - 189
(2012/02/15)
-
- Effective synthesis of ortho-substituted trithiophenol amines by Miyazaki-Newman-Kwart rearrangement
-
An efficient synthesis of ortho-substituted trithiophenol amines from commercially available salicaldehydes by Miyazaki-Newman-Kwart rearrangement/threefold reductive amination is reported. The rearrangement has been carried out on salicaldehyde-O-thiocarbamates using microwave induced heating, which furnishes a series of thiosalicaldehyde-S-carbamates in high yield. The thiocarbamate has three roles: it enables effective S-O rearrangement, acts as a protecting group during the threefold reductive amination and can be easily removed under reductive conditions. The three-step synthesis has an overall yield ranging from 30-35 %, and it enables access to a series of increasingly important C3v symmetric ligands in a structurally systematic way.
- Gjoka, Blerina,Romano, Francesco,Zonta, Cristiano,Licini, Giulia
-
scheme or table
p. 5636 - 5640
(2011/11/29)
-
- A general and convenient route to oxazolyl ligands
-
A diverse range of chiral and achiral oxazolyl ligands, which have many applications including catalysis and luminescent devices, are synthesized simply in three steps from readily available and inexpensive phenol and amino alcohol starting materials. The method can be applied to ligands with electron-donating/-withdrawing and sterically demanding/undemanding substituents, and can conveniently be scaled up to >25 g of product.
- Aspinall, Helen C.,Beckingham, Oliver,Farrar, Michael D.,Greeves, Nicholas,Thomas, Christopher D.
-
supporting information; experimental part
p. 5120 - 5123
(2011/10/19)
-
- PAI-1 INHIBITOR
-
The compound represented by the following formula (I) and the like have PAI-1 inhibition activity; wherein: R1 represents a C6-10 aryl group which may be substituted or the like; T represents a single bond or the like; m represents 0
- -
-
Page/Page column 272
(2011/02/17)
-
- Production of Substituted Phenylene Aromatic Diesters
-
The present disclosure is directed to the production of 5-tert-butyl-3-methyl-1,2-phenylene dibenzoate and the purification thereof. Synthesis pathways for a precursor to 5-tert-butyl-3-methyl-1,2-phenylene dibenzoate are provided. The precursor is 5-tert-butyl-3-methylcatechol.
- -
-
Page/Page column 7-8
(2010/07/10)
-
- Expeditious synthesis of benzopyrans via lewis acid-catalyzed C-H functionalization: Remarkable enhancement of reactivity by an ortho substituent
-
An expeditious construction of a benzopyran skeleton via Lewis acid-catalyzed C-H functionalization was achieved. In this process, a [1,5] hydride shift and 6-endo cyclization successively occurred to give benzopyrans. The presence of substituents ortho to the alkoxy group significantly enhanced the reactivity, affording the desired compounds in excellent chemical yields with short reaction times.
- Mori, Keiji,Kawasaki, Taro,Sueoka, Shosaku,Akiyama, Takahiko
-
supporting information; experimental part
p. 1732 - 1735
(2010/09/05)
-
- Syntheses, characterization, and ethylene polymerization of titanium and zirconium complexes with [N, O] ligands
-
Bidentate monoanionic ligands 2-(benzo[d]thiazol-2-yl) phenol (La), 2-(benzo[d]thiazol-2-yl)-6-methylphenol (Lb), 2-(benzo[d]thiazol-2-yl)-6-tert- butyl-4-methylphenol (Lc), 2-(benzo[d]thiazol-2-yl)-6-chlorophenol (Ld), and 2-(benzo[d]thiazol-2-yl)-4-chlorophenol (Le) have been synthesized. Reactions of TiCl4(THF)2 or ZrCl4 with La-Le afford the corresponding titanium complexes Ti[ON]2RCl2 [R = 6-Me (2b); R = 4-Me-6-But (2c)], and zirconium complexes Zr[ON]2RCl2 [R = H (3a); R = 6-Me (3b); R = 4-Me-6-But (3c); R = 6-Cl (3d); R = 4-Cl (3e)], and Zr[ON R]HCl4·THF [R = 6-Me (4b)], respectively. Complexes 2a-4b were characterized by IR, 1H NMR spectra and elemental analysis. The molecular structures of La, 2b, 2c, 3b, 3c and 4b have been characterized by single-crystal X-ray diffraction analyses. The effect of steric hindrance and the coordination metal on the structure of the products has been investigated. When activated by excess methylaluminoxane (MAO), 2b and 2c, 3a-3e and 4b can be used as catalysts for ethylene polymerization and exhibit moderate to good activities.
- Jia, Ai-Quan,Jin, Guo-Xin
-
scheme or table
p. 8838 - 8845
(2010/02/16)
-
- NbCl5 mediated deprotection of methoxy methyl ether
-
An efficient cleavage of methoxy methyl ether using NbCl5 is described. This protocol works efficiently with MOM ethers of alkyl, allyl, propargyl, benzyl alcohol and phenol derivatives. MOM esters are also found to be effectively cleaved under the present conditions.
- Yadav,Ganganna,Bhunia, Dinesh C.,Srihari
-
experimental part
p. 4318 - 4320
(2009/10/26)
-
- Asymmetric Henry reaction catalyzed by a copper tridentate chiral schiff-base complex
-
A series of copper-tridentate chiral Schiff-base complexes were prepared and employed in an asymmetric Henry reaction, affording the corresponding adducts in good yields and with high enantioselectivities (up to 96% ee).
- Lai, Guoyin,Wang, Sujing,Wang, Zhiyong
-
p. 1813 - 1819
(2008/12/22)
-
- Synthesis of chromanones: A novel palladium-catalyzed Wacker-type oxidative cyclization involving 1,5-hydride alkyl to palladium migration
-
A series of 2-methylchromanone derivatives have been prepared by using a novel palladium-catalyzed Wacker-type oxidative cyclization, in which a 1,5-hydride alkyl to palladium migration and a direct chirality transfer were involved. The Royal Society of Chemistry.
- Zhang, Zuhui,Pan, Chongfeng,Wang, Zhiyong
-
p. 4686 - 4688
(2008/10/09)
-
- Synthesis of substituted salicylamines and dihydro-2H-1,3-benzoxazines
-
Phenols were converted to their magnesium salts with the MgCl2-Et3N base system and subsequently reacted with Eschenmoser's salt, affording N,N-dimethyl substituted benzylamines in high to excellent yields. A series of mono N-substituted benzylamines were prepared in one-pot syntheses by ortho-formylation of phenols to corresponding salicylaldehydes, which in turn reacted with amines to imines. The imines were subsequently reduced to mono N-substituted benzylamines. Some of these benzylamines were further converted, without work-up, to mono N-substituted dihydro-2H-1,3-benzoxazines.
- Anwar, Hany F.,Skatteb?l, Lars,Hansen, Trond Vidar
-
p. 9997 - 10002
(2008/02/13)
-
- The synthesis of 2-hydroxymethyl derivatives of phenols
-
2-Hydroxymethylphenols have been prepared in good yield by reduction with sodium borohydride of the precursor aldehydes, obtained regiospecifically from reaction of phenols with paraformaldehyde in toluene containing stannic chloride and tri-n-butylamine. By contrast, reaction of phenols with either paraformaldehyde under anhydrous conditions or with aqueous formaldehyde results in formation of both the hydroxymethyl and the bishydroxymethyl derivatives. Cyclic acetals of the precursor aldehydes are readily accessible.
- Payne, Peter,Tyman, John H. P.,Mehet, Satinder K.,Ninagawa, Akira
-
p. 402 - 405
(2007/10/03)
-
- One-pot synthesis of substituted catechols from the corresponding phenols
-
Phenols are converted to salicylaldehydes with paraformaldehyde, MgCl 2-Et3N in THF, and when subsequently treated with aqueous NaOH and H2O2 afford the corresponding catechols. The sequence is conveniently carried out as a one-pot procedure.
- Hansen, Trond Vidar,Skatteb?l, Lars
-
p. 3357 - 3358
(2007/10/03)
-
- One-pot synthesis of ortho-hydroxycinnamate esters
-
Phenols are converted to salicylaldehydes with paraformaldehyde, MgCl 2-Et3N in THF, and subsequent treatment with methyl (triphenylphosphoranylidene)acetate gave the corresponding methyl ortho-hydroxycinnamate derivatives. The sequence is conveniently carried out as a one-pot procedure.
- Anwar, Hany F.,Skatteb?l, Lars,Skramstad, Jan,Hansen, Trond Vidar
-
p. 5285 - 5287
(2007/10/03)
-
- AROYLFURANES AND AROYLTHIOPHENES
-
The invention relates to compounds of formula (I) and of formula (II) wherein ring A is a phenyl, pyridine, pyrimidine or pyrazine ring, W and X are carbon or nitrogen, Y is oxygen or sulfur, R0 is different from hydrogen, Rx is -(C=O)R1 or cyano; R1 is hydrogen, optionally substituted hydroxy or optionally substituted amino, and the other substituents are as described in the specification. The invention further relates to methods of synthesis of such compounds, to pharmaceutical compositions containing compounds of formula (I) and of formula (II), to the use of compounds of formula (I) and of formula (II) for the preparation of a pharmaceutical composition for the treatment of neoplastic and autoimmune diseases, and to methods of treatment of neoplastic and autoimmune diseases using compounds of formula (I), of formula (II) or of pharmaceutical compositions containing same.
- -
-
Page/Page column 83
(2010/02/12)
-
- Salicylaldimine-aluminum complexes for the facile and efficient ring-opening polymerization of ε-caprolactone
-
A facile and efficient catalytic system of salicylaldimine-aluminum complexes for the ring-opening polymerization (ROP) of ε-caprolactone (CL) was investigated. The polymerization of Cl was examined at 25 °C in the presence of 1 mol % of benzyl alcohol (B
- Nomura, Nobuyoshi,Aoyama, Takuji,Ishii, Ryohei,Kondo, Tadao
-
p. 5363 - 5366
(2008/02/01)
-
- Non-metallocene compounds, method for the production thereof and use of the same for the polymerisation of olefins
-
The invention relates to a method for producing special transition metal compounds, to novel transition metal compounds and to the use of the same for the polymerisation of olefins.
- -
-
-
- Syndiospecific living propylene polymerization catalyzed by titanium complexes having fluorine-containing phenoxy-imine chelate ligands
-
The propylene polymerization behavior of a series of Ti complexes featuring fluorine-containing phenoxy-imine chelate ligands is reported. The Ti complexes combined with methylalumoxane (MAO) can be catalysts for living and, at the same time, stereospecific polymerization of propylene at room temperature or above. DFT calculations suggest that the attractive interaction between a fluorine ortho to the imine nitrogen and a β-hydrogen of a growing polymer chain is responsible for the achievement of room-temperature living propylene polymerization. Although the Ti complexes possess C2 symmetry, they are capable of producing highly syndiotactic polypropylenes. 13C NMR is used to demonstrate that the syndiotacticity is governed by a chain-end control mechanism and that the polymerization is initiated exclusively via 1,2-insertion followed by 2,1-insertion as the principal mode of polymerization. 13C NMR spectroscopy also elucidated that the polypropylenes produced with the Ti complexes possess regio-block structures. Substitutions on the phenoxy-imine ligands have profound effects on catalytic behavior of the Ti complexes. The steric bulk of the substituent ortho to the phenoxy oxygen plays a decisive role in achieving high syndioselectivity for the chain-end controlled polymerization. Over a temperature range of 0-50 °C, Ti complex having a trimethylsilyl group ortho to the phenoxy oxygen forms highly syndiotactic, nearly monodisperse polypropylenes (94-90% rr) with extremely high peak melting temperatures (Tm = 156- 149 °C). The polymerization behavior of the Ti complexes can be explained well by the recently proposed site-inversion mechanism for the formation of syndiotactic polypropylene by a Ti complex having a pair of fluorine-containing phenoxy-imine ligands.
- Mitani, Makoto,Furuyama, Rieko,Mohri, Jun-ichi,Saito, Junji,Ishii, Seiichi,Terao, Hiroshi,Nakano, Takashi,Tanaka, Hidetsugu,Fujita, Terunori
-
p. 4293 - 4305
(2007/10/03)
-
- Benzoxazepinones and their use as squalene synthase inhibitors
-
There is disclosed a compound represented by the formula [I]: wherein R1 is optionally substituted 1-carboxyethyl group, optionally substituted alkyl-sulfonyl group, optionally substituted (carboxy-cycloalkyl)-alkyl group, -X1-X2-Ar-X3-X4-COOH (wherein X1 and X4 are a bond or alkylene group, X2 and X3 are a bond, -O-, -S-, Ar is divalent aromatic group etc.), R2 is alkyl group optionally substituted with alkanoyloxy group and/or hydroxy group, R3 is alkyl group, and W is halogen atom, etc., or a salt thereof. The compound has the cholesterol lowering activity and the triglyceride lowering activity and is useful for preventing and/or treating hyperlipidemia.
- -
-
-
- Method for producing optically active salicylaldimine copper complex
-
There is provided a method for producing an optically active salicylaldimine copper complex, which method is characterized in that an optically active amino alcohol compound represented by the following formula (1) is reacted with copper hydroxide (II) in an organic solvent. wherein R1 and R2 which are the same or different, each represent lower alkyl groups and the like which may be substituted, X1 and X2 which are the same or different, each represent a hydrogen atom, lower alkyl groups and the like, and the symbol * designates an asymmetric carbon atom.
- -
-
-
- A family of zirconium complexes having two phenoxy - imine chelate ligands for olefin polymerization
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A zirconium complex having two phenoxy - imine chelate ligands, bis[N-(3-tert-butylsalicylidene)-anilinato]zirconium(IV)dichloride (1), was found to display a very high ethylene polymerization activity of 550 kg of polymer/mmol of cat·h with a viscosity average molecular weight, (Mv) value of 0.9 × 104 at 25 °C at atmospheric pressure using methylalumoxane (MAO) as a cocatalyst. This activity is 1 order of magnitude larger than that exhibited by Cp2ZrCl2 under the same polymerization conditions. The use of Ph3CB(C6F5)4/i-Bu3Al in place of MAO as a cocatalyst resulted in extremely high molecular weight polyethylene, Mv 505 × 104, with an activity of 11 kg of polymer/mmol of cat·h at 50 °C. This Mv value is one of the highest values displayed by homogeneous olefin polymerization catalysts. Complex 1, using Ph3CB(C6F5)4/i-BU3Al as a cocatalyst, provided a high molecular weight ethylene-propylene copolymer, Mv 109 × 104, with 8 kg of polymer/mmol of cat·h activity at a propylene content of 20.7 mol %. X-ray analysis revealed that complex 1 adopts a distorted octahedral coordination structure around the zirconium metal and that two oxygen atoms are situated in trans position while two nitrogen atoms and two chlorine atoms are situated in cis position. DFT calculations suggest that the active species derived from complex 1 possesses two available cis-located sites for efficient ethylene polymerization. Changing the tert-butyl group in the phenoxy benzene ring enhanced the polymerization activity. Bis[N-(3-cumyl-5-methylsalicylidene)cyclohexylaminato]zirconium(IV)dichloride (7) with MAO displayed an ethylene polymerization activity of 4315 kg of polymer/mmol of cat·h at 25 °C at atmospheric pressure. This activity corresponds to a catalyst turnover frequency (TOF) value of 42 900/s· atm. This TOF value is one of the largest not only for olefin polymerization but also for any known catalytic reaction. Ligands with additional steric congestion near the polymerization reaction center gave increased Mv values. The maximum Mv value, 220 × 104 using MAO, was obtained with bis[N-(3,5-dicumylsalicylidene)-2′-isopropylanilinato]zirconium (IV)dichloride (15). Thus, polyethylenes ranging from low to exceptionally high molecular weights can be obtained from these zirconium complexes by changing the ligand structure and the choice of cocatalyst.
- Matsui,Mitani,Saito,Tohi,Makio,Matsukawa,Takagi,Tsuru,Nitabaru,Nakano,Tanaka,Kashiwa,Fujita
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p. 6847 - 6856
(2007/10/03)
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- Flash vacuum pyrolysis of methoxy-substituted lignin model compounds
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The flash vacuum pyrolysis (FVP) of methoxy-substituted fi-O-4 lignin model compounds has been studied at 500 °C to provide mechanistic insight into the primary reaction pathways that occur under conditions of fast pyrolysis. FVP of PhCH2CH2OPh (PPE), a model of the dominant β-O-4 linkage in lignin, proceeds by C-O and C-C cleavage, in a 37:1 ratio, to produce styrene plus phenol as the dominant products and minor amounts of toluene, bibenzyl, and benzaldehyde. From the deuterium isotope effect in the FVP of PhCD2CH2OPh, it was shown that C-O cleavage occurs by homolysis and by 1,2- elimination in a ratio of 1.4:1, respectively. Methoxy substituents enhance the homolysis of the β-O-4 linkage, relative to PPE, in o-CH3O- C6H4OCH2CH2Ph (o-CH3O-PPE) and (o-CH3O)2-C6H3OCH2CH2Ph ((o- CH3O)2-PPE) by a factor of 7.4 and 21, respectively. The methoxy- substituted phenoxy radicals undergo a complex series of reactions, which are dominated by 1,5-, 1,6-, and 1,4-intramolecular hydrogen abstraction, rearrangement, and α-scission reactions. In the FVP of o-CH3O-PPE, the dominant product, salicylaldehyde, forms from the methoxyphenoxy radical by a 1,5-hydrogen shift to form 2-hydroxyphenoxymethyl radical, 1,2-phenyl shift, and β-scission of a hydrogen atom. The 2-hydroxyphenoxymethyl radical can also cleave to form formaldehyde and phenol in which the ratio of 1,2-phenyl shift to β-scission is ca. 4:1. In the FVP of o-CH3O-PPE and (o-CH3O)2- PPE, products (ca. 20 mol %) are also formed by C-O homolysis of the methoxy group. The resulting phenoxy radicals undergo 1,5- and 1,6-hydrogen shifts in a ratio of ca. 2:1 to the aliphatic or benzylic carbon, respectively, of the phenethyl chain. In the FVP of (o-CH3O)2-PPE, o-cresol was the dominant product. It was formed by decomposition of 2-hydroxy-3- hydroxymethylbenzaldehyde and 2-hydroxybenzyl alcohol, which are formed from a complex series of reactions from the 2,6-dimethoxyphenoxy radical. The key step in this reaction sequence was the rapid 1,5-hydrogen shift from 2- hydroxy-3-methoxybenzyloxy radical to 2-hydroxymethyl-6-methoxyphenoxy radical before β-scission of a hydrogen atom to give the substituted benzaldehyde. The 2-hydroxybenzyl alcohols rapidly decompose under the reaction conditions to o-benzoquinone methide and pick up hydrogen from the reactor walls to form o-cresol.
- Britt, Phillip F.,Buchanan III,Cooney, Mark J.,Martineau, Dan R.
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p. 1376 - 1389
(2007/10/03)
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- Trialkylamine controlled phenol-for maldehyde reaction over clay catalysts: Selective and environmentally benign synthesis of salicylic aldehydes
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Substituted salicylic aldehydes 6 are synthesised in good yields and excellent selectivities by reaction of phenols 1 with formaldehyde 2 over montmorillonite KSF-Et3N as a heterogeneous and reusable catalyst. (C) 2000 Elsevier Science Ltd.
- Bigi, Franca,Conforti, Maria Lina,Maggi, Raimondo,Sartori, Giovanni
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p. 2709 - 2712
(2007/10/03)
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- Process of producing catechol derivatives
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PCT No. PCT/JP96/03650 Sec. 371 Date Jun. 19, 1998 Sec. 102(e) Date Jun. 19, 1998 PCT Filed Dec. 13, 1996 PCT Pub. No. WO97/22574 PCT Pub. Date Jun. 26, 1997An improved process for producing a catechol derivative (1) useful as a intermediate of pharmaceuticals and agricultural chemicals, being shown by the following reaction scheme. The process is characterized in that formulation in the first step is carried out in the two stages, that is, the reaction is carried out in the presence of a tin catalyst at 60-85 DEG C. to a conversion of 30 to 80% and then is completed at 95-105 DEG C. to produce a salicylaldehyde derivative (3) in a high yield and a high selectivity. Thereby, the objective catechol derivative (1) can be obtained in a high yield and with a high purity. In the above formula, R is alkyl, cycloalkyl, aralkyl, alkoxy, halogen atom, allyl, or aryl, and R1 is a hydroxy protective group.
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- Convenient Method for the ortho-Formylation of Phenols
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Phenolic derivatives are formylated selectively ortho to the hydroxy group by paraformaldehyde with magnesium dichloride-triethylamine as base. With alkyl-substituted phenols excellent yields of the corresponding salicylaldehyde derivatives were obtained. Similar results were obtained with chloro-substituted phenols and with 3- and 4-methoxyphenol, while 2-methoxyphenol was unreactive. A good yield of methyl 3-formyl-4-hydroxybenzoate was obtained by this method as well, but generally phenols with electron-attracting groups reacted sluggishly; the long reaction times required caused the formation of by-products, particularly MOM-derivatives of the phenols.
- Hofslokken, Nini U.,Skattebol, Lars
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p. 258 - 262
(2007/10/03)
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- Coumarin 1,4-dihydropyridine derivatives
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A series of 1,4-dihydropyridines bearing a coumarin moiety in 4-position was synthesized. The compounds were evaluated for inotropic, chronotropic and calcium antagonist activities. The replacement of the o-nitrophenyl moiety of nifedipine with a coumarin
- Valenti,Rampa,Budriesi,Bisi,Chiarini
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p. 803 - 810
(2007/10/03)
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- Pancreatic imaging agents
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A novel group of radiolabelled diamines are provided, effective for pancreatic imaging and represented by the formula STR1 wherein n is 1 to 10; R1 and R2 are the same or different and are hydrogen, hydroxyl or lower alkyl having 1 to 6 carbon atoms; R3 is lower alkyl having 1 to 6 carbon atoms; and N' is a nitrogen atom forming part of a 4- to 8-membered heterocyclic ring containing one or two hetero atoms, one of which is said nitrogen, said heterocyclic ring being unsubstituted or substituted with one or more lower alkyl groups and pharmaceutically acceptable acid addition salts thereof.
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- A modified synthesis of O-hydroxyaryl aldehydes
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A modified method for the synthesis of o-hydroxyaryl aldehydes in moderate yields has been developed by treating aryloxymagnesium bromides with formaldehyde using triethylamine in place of hexamethylphosphoric triamide (HMPA).
- Wang,You,Meng,Mintz,Bu
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p. 1757 - 1760
(2007/10/02)
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- Steric acceleration of intramolecular cycloaddition reactions
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Use of conformational constraints, induced by different ortho-substituents in 1-allyloxy-2-(substituted)methylbenzenes, where the substituent is a 1,3-dipole such as the azide or 3-oxidopyridinium group, can be employed to accelerate the 1,3-dipolar cycloaddition reaction. In this manner cycloadditions that otherwise do not proceed can be forced to react.
- Orlek, Barry S.,Sammes, Peter G.,Weller, David J.
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p. 8179 - 8194
(2007/10/02)
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- Photoformylation of Phenols
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Photoformylation of phenol, o-, p- and m-cresols, p-chlorophenol, p-bromophenol, p-nitrophenol and p-hydroxydiphenyl with chloroform in the presence of aq.KOH or pyridine affords the corresponding aldehydes; formyl group entering the position ortho to OH function.A plausible mechanism, different from that of well known Reimer-Tiemann, has been suggested.
- Fahmy, A. M.,Mahgoub, S. A.,Aly, M. M.,Badr, M. Z. A.
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p. 474 - 475
(2007/10/02)
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