- Mechanism of solvolysis of substituted benzyl chlorides in aqueous ethanol
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The mechanism of solvolyses of activated ortho-, meta- and para-substituted benzyl chlorides in aqueous ethanol has been studied by using the Hammett-Brown and Yukawa-Tsuno treatments as well as by correlating logarithms of solvolysis rate constants with relative stabilities of corresponding benzyl carbocations in water calculated at the IEFPCM-M06–2X/6-311+G(3df,3pd) level of theory. Benzyl chlorides containing strong conjugative electron-donors in the para-position solvolyze by the SN1 mechanism, whereas other activated benzyl chlorides solvolyze by the SN2 mechanism via loose transition states.
- Denegri, Bernard,Mati?, Mirela,Va?ko, Monika
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supporting information
(2021/11/22)
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- Pyrrolopyrazole derivative, preparation method and medical application thereof
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The invention relates to pyrrolopyrazole derivative, a preparation method and application thereof in medicines. Specifically, the invention relates to a new pyrrolopyrazole derivative as shown in a general formula (I), a preparation method and application of the pyrrolopyrazole derivative or a pharmaceutical composition containing the pyrrolopyrazole derivative as a therapeutic agent, particularlyas a gastric acid secretion inhibitor and potassium-competitive acid blockers (P-CABs) in biological medicines. Specifically, the substituents (R1, R2, R3 and R4) in the general formula (I) are the same as the definitions in the specification.
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Paragraph 0154-0155
(2021/02/24)
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- Structure-activity relationship and molecular modelling studies of quinazolinedione derivatives MMV665916 as potential antimalarial agent
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A series of new quinazolinedione derivatives have been readily synthesized and evaluated for their in vitro antiplasmodial growth inhibition activity. Most of the compounds inhibited P. falciparum FcB1 strain in the low to medium micromolar concentration. The 2-ethoxy 8ag’, 2-trifluoromethoxy 8ai’ and 4-fluoro-2-methoxy 8ak’ showed the best inhibitory activity with EC50 values around 5 μM and were non-toxic to the primary human fibroblast cell line AB943. However, these compounds were less potent than the original hit MMV665916, which showed remarkable growth inhibition with EC50 value of 0.4 μM and presented the highest selectivity index (SI > 250). In addition, a novel approach for determining the docking poses of these quinazolinedione derivatives with their potential protein target, the P. falciparum farnesyltransferase PfFT, was investigated.
- Albrecht, Sébastien,Florent, Isabelle,Mouray, Elisabeth,Mourot, Laura,Schmitt, Marjorie,Spichty, Martin
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supporting information
(2021/11/22)
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- Synthesis and Evaluation of Novel Quinazolinone Derivatives as Potential Anti-HCC Agents
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Hepatocellular carcinoma (HCC), a common malignancy worldwide, has a high mortality rate and limited effective therapeutic options. In this work, a series of quinazolinone compounds (6a–t and 7a–i) were synthesized as potential anti-HCC agents. Among them, compound 7b more potently inhibited HepG2, HUH7 and SK-Hep-1 cells proliferation than classical anti-HCC drug sorafenib, indicating its potential anti-HCC effect. Interestingly, 7b could dose-dependently decrease Cyclin D1 and CDK2 levels, and increase p21 protein expression, thus inducing HepG2 cells cycle arrest at G0/G1 phase. In addition, 7b also displayed potent apoptosis-induced effect on HepG2 cells by interfering Bad, Bax, Bcl-2 and Bcl-xl proteins expression. Notably, 7b could efficiently block the activity of PI3K pathway by dose-dependently reducing the phosphorylation of PI3K (Y607) and AKT (S473). Moreover, predicted ADME properties indicated that 7b possessed a good pharmacokinetic profile. Collectively, compound 7b might be a promising lead to the development of novel therapeutic agents towards HCC.
- Chen, Wang,Gu, Xiaoke,Jiang, Chunyu,Li, Shuqiong,Li, Zheng,Liu, Qingchuan,Qiu, Jingying,Zhou, Qingqing,Zou, Yueting
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- In vitro study and structure-activity relationship analysis of stilbenoid derivatives as powerful vasorelaxants: Discovery of new lead compound
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The development of vasorelaxant as the antihypertensive drug is important as it produces a rapid and direct relaxation effect on the blood vessel muscles. Resveratrol (RV), as the most widely studied stilbenoid and the lead compound, inducing the excellent vasorelaxation effect through the multiple signalling pathways. In this study, the in vitro vascular response of the synthesized trans-stilbenoid derivatives, SB 1-8e were primarily evaluated by employing the phenylephrine (PE)-precontracted endothelium-intact isolated aortic rings. Herein we report trans-3,4,4′-trihydroxystilbene (SB 8b) exhibited surprisingly more than 2-fold improvement to the maximal relaxation (Rmax) of RV. This article also highlights the characterization of the aromatic protons in terms of their unique splitting patterns in 1H NMR.
- Chan, Sock Ying,Loh, Yean Chun,Oo, Chuan Wei,Yam, Mun Fei
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- AN EFFICIENT AND ENVIRONMENT FRIENDLY PROCESS FOR CHLOROMETHYLATION OF SUBSTITUTED BENZENES
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Disclosed herein is an efficient, environment friendly and commercially viable process for preparation of chloromethylated compound of formula I in substantially pure form and high yield, from the compound of formula II. The process includes contacting the compound of formula II with a chloromethylating agent generated in-situ by reaction of a formaldehyde precursor and hydrogen chloride, in a suitable solvent/contacting medium and in the presence of a catalytic amount of a short chain/low molecular weight carboxylic acid of formula III. I II III wherein, R1, R2, R3 and R4 are as defined in the description.
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Paragraph 0076; 0077; 0078; 0080
(2020/12/30)
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- Discovery of novel quinazolinone derivatives as potential anti-HBV and anti-HCC agents
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As a continuation of earlier works, a series of novel quinazolinone derivatives (5a-s) were synthesized and evaluated for their in vitro anti-HBV and anti-hepatocellular carcinoma cell (HCC) activities. Among them, compounds 5j and 5k exhibited most potent inhibitory effect on HBV DNA replication in both drug sensitive and resistant (lamivudine and entecavir) HBV strains. Interestingly, besides the anti-HBV effect, compound 5k could significantly inhibit the proliferation of HepG2, HUH7 and SK- cells, with IC50 values of 5.44, 6.42 and 6.75 μM, respectively, indicating its potential anti-HCC activity. Notably, the in vitro anti-HCC activity of 5k were more potent than that of positive control 5-fluorouracil and sorafenib. Further studies revealed that compound 5k could induce HepG2 cells apoptosis by dose-dependently upregulating Bad and Bax expression and decreasing Bcl-2 and Bcl-xl protein level. Considering the potent anti-HBV and anti-HCC effect, compound 5k might be a promising lead to develop novel therapeutic agents towards HBV infection and HBV-induced HCC.
- Qiu, Jingying,Zhou, Qingqing,Zhang, Yinpeng,Guan, Mingyu,Li, Xin,Zou, Yueting,Huang, Xuan,Zhao, Yali,Chen, Wang,Gu, Xiaoke
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- Ionic-Liquid-Supported 1,3-Dimethylimidazolidin-2-one: Application as a Reusable Halogenation Reagent
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We describe the synthesis of ionic-liquid-supported 1,3-dimethylimidazolidin-2-one, together with the halogenation of alcohols in a reaction system in which this reagent is combined with oxalyl chloride. A new method was established that does not require additives such as bases, and which permits the ready isolation and purification of the product. Good conversions were obtained, and good reusability of the reagent was observed.
- Koguchi, Shinichi,Shibuya, Yuga,Igarashi, Yusuke,Takemura, Haruka
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supporting information
p. 943 - 946
(2019/05/10)
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- On the Necessity of Nucleobase Protection for 2-Thiouracil for Fmoc-Based Pseudo-Complementary Peptide Nucleic Acid Oligomer Synthesis
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A selection of benzyl-based protecting groups for thiouracil (SU) for the synthesis of pseudo-complementary peptide nucleic acid (PNA) has been evaluated. The 4-methoxybenzyl-protecting group that has found use for SU during Boc-based oligomerization is also suitable for Fmoc-based oligomerization. Furthermore, it is demonstrated that SU protection is unnecessary for the successful synthesis of thiouracil-containing PNA. The new 2-thiothymine (ST) PNA monomer has also been prepared and incorporated into an oligomer and its binding to complementary PNA evaluated.
- Hudson, Robert H.E.,Heidari, Ali,Martin-Chan, Timothy,Park, Gyeongsu,Wisner, James A.
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p. 13252 - 13261
(2019/11/16)
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- COMPOUNDS AND USES THEREOF
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The present invention features compounds useful in the treatment of neurological disorders. The compounds of the invention, alone or in combination with other pharmaceutically active agents, can be used for treating or preventing neurological disorders.
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Paragraph 0876
(2019/11/11)
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- α-Diimine-Niobium Complex-Catalyzed Deoxychlorination of Benzyl Ethers with Silicon Tetrachloride
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α-Diimine niobium complexes serve as catalysts for deoxygenation of benzyl ethers by silicon tetrachloride (SiCl4) to cleanly give two equivalents of the corresponding benzyl chlorides, where SiCl4 has the dual function of oxygen scavenger and chloride source with the formation of a silyl ether or silica as the only byproduct. The reaction mechanism has two successive trans-etherification steps that are mediated by the niobium catalyst, first forming one equivalent of benzyl chloride along with the corresponding silyl ether intermediate that undergoes the same reaction pathway to give the second equivalent of benzyl chloride and silyl ether.
- Parker, Bernard F.,Hosoya, Hiromu,Arnold, John,Tsurugi, Hayato,Mashima, Kazushi
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supporting information
p. 12825 - 12831
(2019/10/19)
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- Assessment of quinazolinone derivatives as novel non-nucleoside hepatitis B virus inhibitors
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Hepatitis B virus (HBV)infection is a worldwide public health issue. Search for novel non-nucleoside anti-HBV agents is of great importance. In the present study, a series of quinazolinones derivatives (4a-t and 5a-f)were synthesized and evaluated as novel anti-HBV agents. Among them, compounds 5e and 5f could significantly inhibit HBV DNA replication with IC50 values of 1.54 μM and 0.71 μM, respectively. Interestingly, the selective index values of 5f was higher than that of lead compound K284–1405, suggesting 5f possessed relatively safety profile than K284–1405. Notably, 5e and 5f exhibited remarkably anti-HBV activities against lamivudine and entecavir resistant HBV strain with IC50 values of 1.90 and 0.84 μM, confirming their effectiveness against resistant HBV strain. In addition, molecular docking studies indicated that compounds 5e and 5f could well fit into the dimer-dimer interface of HBV core protein dominated by hydrophobic interactions. Notably, their binding modes were different from the lead compound K284–1405, which may be attributed to the additional substituent groups in the quinazolinone scaffold. Taken together, 5e and 5f possessed novel chemical structure and potent anti-HBV activity against both drug sensitive and resistant HBV strains, thus warranting further research as potential non-nucleoside anti-HBV candidates.
- Qiu, Jingying,Chen, Wang,Zhang, Yinpeng,Zhou, Qingqing,Chen, Jing,Yang, Lihua,Gao, Jian,Gu, Xiaoke,Tang, Daoquan
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- NMP-mediated chlorination of aliphatic alcohols with aryl sulfonyl chloride for the synthesis of alkyl chlorides
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NMP-mediated chlorination of aliphatic alcohols has been developed for the synthesis of alkyl chlorides. This facile, efficient and practical approach used simple and readily available aryl sulfonyl chlorides as the chlorination reagent for the construction of C–Cl bond in good to excellent yields with mild conditions and broad substrate scope.
- Zheng, Dagui,Mao, Liu-Liang,Zhu, Xian-Hong,Zhou, An-Xi
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supporting information
p. 2793 - 2800
(2018/11/06)
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- 2-OXO-3,4-DIHYDROPYRIDINE-5-CARBOXYLATES AND THEIR USE
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The present invention is directed to novel compounds of Formula (I), pharmaceutically acceptable salts or solvates thereof, and their use.
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Page/Page column 105-106
(2016/04/20)
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- Formamides as Lewis Base Catalysts in SNReactions—Efficient Transformation of Alcohols into Chlorides, Amines, and Ethers
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A simple formamide catalyst facilitates the efficient transformation of alcohols into alkyl chlorides with benzoyl chloride as the sole reagent. These nucleophilic substitutions proceed through iminium-activated alcohols as intermediates. The novel method, which can be even performed under solvent-free conditions, is distinguished by an excellent functional group tolerance, scalability (>100 g) and waste-balance (E-factor down to 2). Chiral substrates are converted with excellent levels of stereochemical inversion (99 %→≥95 % ee). In a practical one-pot procedure, the primary formed chlorides can be further transformed into amines, azides, ethers, sulfides, and nitriles. The value of the method was demonstrated in straightforward syntheses of the drugs rac-Clopidogrel and S-Fendiline.
- Huy, Peter H.,Motsch, Sebastian,Kappler, Sarah M.
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supporting information
p. 10145 - 10149
(2016/08/16)
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- FeCl3-catalyzed self-cleaving deprotection of methoxyphenylmethyl-protected alcohols
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4-Methoxyphenylmethyl ethers are widely utilized as alcohol protecting groups. FeCl3 effectively catalyzes the deprotection of methoxyphenylmethyl-type ethers in a self-cleaving manner to produce oligomeric derivatives and alcohols. Remarkably, the highly pure mother alcohols can be obtained without silica gel column chromatography by using the 2,4-dimethoxyphenylmethyl group as a protective group.
- Sawama, Yoshinari,Masuda, Masahiro,Asai, Shota,Goto, Ryota,Nagata, Saori,Nishimura, Shumma,Monguchi, Yasunari,Sajiki, Hironao
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supporting information
p. 434 - 437
(2015/03/03)
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- Simplifying nickel(0) catalysis: An air-stable nickel precatalyst for the internally selective benzylation of terminal alkenes
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The synthesis and characterization of the air-stable nickel(II) complex trans-(PCy2Ph)2Ni(o-tolyl)Cl is described in conjunction with an investigation of its use for the Mizoroki-Heck-type, room temperature, internally selective coupling of substituted benzyl chlorides with terminal alkenes. This reaction, which employs a terminal alkene as an alkenylmetal equivalent, provides rapid, convergent access to substituted allylbenzene derivatives in high yield and with regioselectivity greater than 95:5 in nearly all cases. The reaction is operationally simple, can be carried out on the benchtop with no purification or degassing of solvents or reagents, and requires no exclusion of air or water during setup. Synthesis of the precatalyst is accomplished through a straightforward procedure that employs inexpensive, commercially available reagents, requires no purification steps, and proceeds in high yield.
- Standley, Eric A.,Jamison, Timothy F.
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supporting information
p. 1585 - 1592
(2013/03/14)
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- Palladium-catalyzed carboxylative coupling of benzyl chlorides with allyltributylstannane: Remarkable effect of palladium nanoparticles
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Palladium-catalyzed carboxylative coupling of benzyl chlorides with allyltributylstannane was successfully conducted to produce benzyl but-3-enoates in satisfactory to good yields. The carboxylative coupling reaction occurred smoothly under mild conditions in the presence of palladium nanoparticles in tetrahydrofuran.
- Feng, Xiujuan,Sun, Anle,Zhang, Sheng,Yu, Xiaoqiang,Bao, Ming
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supporting information
p. 108 - 111
(2013/04/10)
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- Regio- and chemoselective palladium-catalyzed benzylallylation of activated olefins: The remarkable effect of palladium nanoparticles
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The palladium-catalyzed three-component reactions of benzyl halides, activated olefins, and allyltributylstannane were successfully conducted to produce the corresponding benzylallylation products in satisfactory to high yields. The benzylallylation reaction proceeded smoothly under mild conditions in the presence of palladium nanoparticles in tetrahydrofuran. The Royal Society of Chemistry 2013.
- Zhang, Xuan,Feng, Xiujuan,Yu, Xiaoqiang,He, Ren,Bao, Ming
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p. 4016 - 4024
(2013/07/05)
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- Pyridine derivatives
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Pyridine compounds of general formula: wherein —R1represents in which R11is hydrogen, C1-6alkyl, halogen, hydroxy, C1-12alkoxy, nitro, amino, C1-6alkylsulfonylamino, C1-6alkoxycarbonyl, C1-6alkylamino, di(C1-6alkyl)amino, C1-6alkanoylamino, phenyl C1-6alkylamino, phenylsulfonylamino, or —O—(CH2)n—R111; R2represents hydrogen or halogen; R3represents hydrogen, —CR31R32R33, or —NR34R35; R4is hydrogen, carbamoyl, CN, carboxyl, etc.; R5is amino, C1-6alkylamino, di C1-6alkylamino, etc. or salt thereof. The compound has an excellent anti-inflammatory activity, and other biological activity.
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- Novel cyclic amide derivatives
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Novel compounds represented by the following formula (I) that act as a ligand to sigma receptor/binding cite and a medicament comprising the same as an active ingredient: wherein X represents an alkyl group, an aryl group, a heterocyclic group or the like; Q represents a group represented by —CH2—, —CO—, —O—, —CH(OR7)— or the like wherein R7 represents a hydrogen atom, an alkyl group or the like; n represents an integer of from 0 to 5; R1 and R2 each represent a hydrogen atom, an alkyl group or the like; B represents either of the following groups: wherein R3, R4, R5, and R6 each represent a hydrogen atom, a halogen atom, an alkoxyl group or the like; m represents 1 or 2; and the ring of: represents an aromatic heterocyclic ring.
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- Design, synthesis and antiproliferative activity of tripentones: A new series of antitubulin agents
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Structure-activity relationship studies of a new series of tripentones (thieno[2,3-b]pyrrolizin-8-ones), led us to prepare several derivatives with antiproliferative activities. The most promising 3-(3-hydroxy-4-methoxyphenyl)thieno[2,3-b]pyrrolizin-8-one 20 (leukemia L1210, IC50 = 15 nM) was shown to be a potent inhibitor of tubulin polymerization.
- Lisowski, Vincent,Enguehard, Cecile,Lancelot, Jean-Charles,Caignard, Daniel-Henri,Lambel, Stephanie,Leonce, Stephane,Pierre, Alain,Atassi, Ghanem,Renard, Pierre,Rault, Sylvain
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p. 2205 - 2208
(2007/10/03)
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- Binding activity of substituted benzyl derivatives of chloronicotinyl insecticides to housefly-head membranes, and its relationship to insecticidal activity against the housefly Musca domestica
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Variously substituted benzyl derivatives of chloronlcotinyl insecticides were synthesized with a wide range of substituents including halogens, NO2, CN, CF3 and small alkyl and alkoxy groups at the ortho, meta and para positions, as well as multiple-substituted benzyl analogues. Their binding activity to the α-bungarotoxin binding site in housefly (Musca domestica) head membrane preparations was measured. Among the compounds tested, the activity of the meta-CN derivative was the highest, being 20-100 times higher than those of imidacloprid, acetamiprid and nitenpyram. The synergized insecticidal activity against houseflies was also measured for selected compounds with the metabolic inhibitor, NIA16388 (propargyl propyl phenylphosphonate). For the nitromethylene analogues, including both benzyl and pyridylmethyl analogues, higher binding activity usually resulted in higher insecticidal activity. (C) 2000 Society of Chemical Industry.
- Nishiwaki, Hisashi,Nakagawa, Yoshiaki,Takeda, David Y.,Okazawa, Atsushi,Akamatsu, Miki,Miyagawa, Hisashi,Ueno, Tamio,Nishimura, Keiichiro
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p. 875 - 881
(2007/10/03)
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- ANTIVIRAL ETHERS OF ASPARTATE PROTEASE SUBSTRATE ISOSTERES
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Antiretroviral compounds (which are effective, for example, against HIV) of the formula I STR1 in which R 1 is an acyl radical lower-alkoxyl-lower-alkanoyl whose lower alkoxy radical is unsubstituted or is substituted by halogen, phenyl, lower alkoxy or a heterocyclic radical selected from piperidinyl, pyrrolidinyl, tetrahydropyranyl, tetrahydrofuranyl, thiazolidinyl, thiazolyl, indolyl or 4H-1-benzopyranyl which is unsubstituted or substituted by oxo, hydroxyl, amine, lower alkyl, lower-alkoxycarbonyl and/or phenyl-lower-alkoxycarbonyl; lower alkanoyl which is unsubstituted or is substituted by one of the said unsubstituted or substituted heterocyclic radicals; arylcarbonyl or heterocyclylcarbonyl which are substituted by heterocyclyl or heterocyclyl-lower-alkyl; phenyl-lower-alkanoyl which is substituted by hydroxyl and lower alkyl; or arylsulfonyl;or the residue of an amino acid which is defined in accordance with the description (and which may be acylated on the amino nitrogen by one of the abovementioned acyl radicals);R 2 and R 3 are in each case cyclohexyl, cyclohexenyl, phenyl, naphthyl or tetrahydronaphthyl which are unsubstituted or substituted by lower alkyl, phenyl, cyanophenyl, phenyl-lower-alkyl, halogen, halo-lower-alkyl, cyano, hydroxyl, lower alkoxy, phenyl-lower-alkoxyl, pyridyl-lower-alkoxy, lower-alkoxy-lower-alkoxy, lower-alkoxycarbonyl-lower-alkoxy, carboxyl-lower-alkoxy, hydroxyl-lower-alkoxy, carbamoyl-lower-alkoxy, cyano-lower-alkoxy, and phenyl-lower-alkanesulfonyl which is unsubstituted or substituted by halogen;R 4 is lower alkyl, cyclohexyl or phenyl; and R 5 is lower alkyl; and n is 1 or 2, or salts thereof, are novel.
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- 5-amino-4-hydroxyhexanoic acid derivatives
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Compounds of formula I STR1 or their hydroxy-protected derivatives, and compounds of formula I' STR2 wherein T is an acyl radical of formula Z STR3 wherein Rz is unsubstituted or substituted hydrocarbyl wherein at least one carbon atom has been replaced by a hetero atom with the proviso that a hetero atom is not bonded directly to the carbonyl to which the radical Rz is bonded, alkyl having two or more carbon atoms, lower alkenyl, lower alkynyl, aryl or unsubstituted or substituted amino, and wherein the radicals R1, B1, R2, R3, A1, A2 and NR4 R5 are as defined in the description, and precursors thereof, are described. The compounds have pharmaceutical activity, for example in the treatment of retroviral diseases, such as AIDS.
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- Selective Cross Coupling via Oxovanadium(V)-Induced Oxidative Desilylation of Benzylic Silanes
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Benzylic silanes bearing an electron-donating group at the ortho- or para-position underwent the oxovanadium(V)-induced one-electron oxidative desilylation due to low ionization potential, which was applied to the intermolecular regioselective coupling with allylic silanes or silyl enol ether.
- Hirao, Toshikazu,Fujii, Takashi,Ohshiro, Yoshiki
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p. 8005 - 8008
(2007/10/02)
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- Prostanoids and related compounds. VI. Synthesis of isoindolinone derivatives possessing inhibitory activity for thromboxane A2 analog (U- 46619)-induced vasoconstriction
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We have synthesized 3-(o, m or p-substituted benzylidene)isoindolinone and 3-(2-o, m or p-substituted phenylethylidene)isoindolinone, which possess inhibitory activity for thromboxane A2 analog (U-46619)-induced vasoconstriction.
- Kato,Takemoto,Achiwa
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p. 2003 - 2006
(2007/10/02)
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- A new synthesis of 8-hydroxy-2-di-n-propylamino-tetralin (8-OH-DPAT)
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A new synthesis method for 8-OH-DPAT, a specific agonist at the 5-HT(1A) serotonin receptor, is described. It employs the Curtius degradation of a tetralin carboxylic acid easily prepared from (2-methoxy benzyl) succinic acid by Friedel-Craft cyclisation.
- Langlois,Gaudy
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p. 1723 - 1734
(2007/10/02)
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- Enantioselective Catalysis, VIII. - New 1,2-Bisphosphane Ligands with Four Stereogenic Centers and Additional Methoxy Groups for Asymmetric Catalytic Hydrogenation
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The synthesis of N-acyl derivatives of all possible diastereomers of -3,4-bispyrrolidine and -3,4-bispyrrolidine in optical pure form is described.Palladium and rhodium complexes with these ligands were prepared.The enantioselective hydrogenation of acetamidocinnamic acid with these rhodium complexes was studied at H2 pressures between 1 and 75 bar.There is only a small influence of the 2-methoxy group in the ligand on the catalytic hydrogenation when compared with the respective unsubstituted diastereomer.Te structure of pyrrolidine-P,P'>diiodopalladium was determined by X-ray diffraction.Key Words: 3,4-Bis(phosphanyl)pyrrolidines / Palladium complexes / Rhodium complexes / Asymmetric hydrogenation
- Nagel, Ulrich,Bublewitz, Alexander
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p. 1061 - 1072
(2007/10/02)
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- Relative Reactivity and Stereoselectivity in the Wittig Reactions of Substituted Benzaldehydes with Benzylidenetriphenylphosphorane
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Carbonyl carbon-14 kinetic isotope effects and substituent effects on the relative reactivity and on the cis-trans product ratio were determined in the Wittig reaction of XC6H4CHO with Ph3P=CHC6H4Y in THF at 0 deg C.The isotope effect and the Hammett ρ value were positive under both Li salt-free (12k/14k = 1.060 +/- 0.003 and ρx = 2.77 +/- 0.15) and Li salt-present (12k/14k = 1.015 +/- 0.004 and ρx = 1.38 +/- 0.12) conditions, although they were much larger in the former case.These, together with the absence of enone isomerization for the benzylidene ylide reported previously, suggested that the reactions proceed via a polar cycloaddition transition state of considerable nucleophilic character.The cis-trans ratio of the product stilbene was essentially unchanged (40:60 in the salt-free and 60:40 in the Li salt-present reaction) by the change in concentration, the mode of addition, and the molar ratio of aldehyde and ylide, and it was varied only slightly for most substituents X and Y.However, the ratio was significantly varied when o-MeO or o-Cl was introduced as X.The results could be rationalized by assuming a chelating interaction between the lone pair of the ortho substituents and the phosphorous of the ylide.
- Yamataka, Hiroshi,Nagareda, Katsushi,Ando, Katsuhiro,Hanafusa, Terukiyo
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p. 2865 - 2869
(2007/10/02)
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- Therapeutic agent for liver disease and piperazine derivatives
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A therapeutic agent for liver disease containing as an active ingredient a piperazine derivative having the formula: STR1 wherein, A represents a phenyl, p-benzoquinonyl or cumarinyl group which may have at least one substituent selected from the group consisting of halogen, alkyl, fluoroalkyl, formyl, alkoxycarbonyl, acyl, hydroxy, alkoxy, acyloxy, glycosyloxy, amino, alkylamino, mercapto, alkylthio and nitro; B represents a single bond or a straight chain alkylene group containing 1-4 carbon atoms which may have at least one substituent selected from the group consisting of alkyl, aryl, aralkyl, hydroxy and oxo; R represents an atom or a group selected from the group consisting of hydrogen, alkali metal, alkaline earth metal, alkyl, cycloalkyl, aralkyl and aryl; and n is 2 or 3, or its pharmaceutically acceptable salt is disclosed.
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- Tandem Wessely oxidation and intramolecular Diels-Alder reactions. III. Synthesis of isotwistanes
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Wessely oxidation of o-(3-alkenyl) phenols (5) with lead tetraacetate gives 6-acetoxy-6-(3-alkenyl)-2,4-cyclohexadien-1-ones (6), which undergo intramolecular Diels-Alder reactions to give isotwistene (hexahydro-1,5-methanoindene) derivatives (7).These, on hydrolysis followed by oxidation with periodic acid, give hexahydro-1-oxo-1H-indene-5-carboxylic acids (41, 46).Compounds 5 were prepared either by Grignard coupling of o-methoxybenzyl chloride with allyl halides followed by de-O-methylation with sodium thioethoxide or via reduction of dihydrocoumarins (18-20) to 2-chromanols (21-23) with diisobutylaluminum hydride, followed by Wittig reaction of these with ethyl (triphenylphosphoranylidene)acetate.
- Yates, Peter,Macas, Tadas S.
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- Amino substituted benzenepropanols
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Hypotensive activity is exhibited by compounds having the formula STR1 and pharmaceutically acceptable salts thereof wherein R1 is hydrogen or alkyl; R2 and R3 are each independently phenyl, substituted phenyl, cycloalkyl, or R2 is hydrogen and R3 is heteroaryl; R4 and R5 are the same or different and each is hydrogen, hydroxy, alkoxy, alkanoyl or alkyl; R6 is hydrogen or alkyl; and n is 1, 2, 3 or 4; with the proviso that if R2 and R3 are each phenyl, at least one of R1, R4, R5 and R6 is other than hydrogen.
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- REACTION OF 4-CHLORO-1-NITROBENZENE WITH o-SUBSTITUTED PHENYLACETONITRILES; SYNTHESIS OF 8-CHLORO-1-METHYL(AND METHYLTHIOMETHYL)-6-(2-SUBSTITUTED PHENYL)-4H-s-TRIAZOLO-1,4-BENZODIAZEPINES
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Reactions of 4-chloro-1-nitrobenzene with 2-methyl-, 2-methoxy- and 2-(methylthio)phenylacetonitrile in methanolic potassium hydroxide gave mixture from which the excepted 3-aryl-5-chloro-2,1-benzisoxazoles Ia-c were isolated in addition to the 2H-indoles IIIa and IIIc and acridines VIII and IX.The 2,1-benzisoxazoles were reduced to the 2-aminobenzophenones XIIa-c which were transformed via the phthalimidoacetamido compounds XIIIa-c to 5-aryl-7-chloro-1,3-dihydro-1,4-benzodiazepine-2-ones XVa-c.Treatment with phosphorus pentasulfide led to the thiones XVIa-c which reacted in boiling butanol either with acetohydrazide or with (methylthio)acetohydrazide to give the title compounds XVIIa-c and XVIIIa-c.They showed only weak anticonvulsant, incoordinating and central depressant effects.
- Vejdelek, Zdenek,Holubek, Jiri,Ryska, Miroslav,Koruna, Ivan,Svatek, Emil,et.al.
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p. 2545 - 2563
(2007/10/02)
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- Compounds and process for preparing the same
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Cis and trans isomers of 1,2-diphenyl-1,2,3,4-tetrahydronaphthalenes, novel processes for the preparation thereof, and novel intermediates are disclosed herein. The novel 1,2-diphenyl-1,2,3,4-tetrahydronaphthalenes have utility as antifertility estrogenic, anti-estrogenic, anti-spermatogenic, cholesterol lowering and lipid normalizing agents.
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