- Palladium-Catalyzed 5-exo-dig Cyclization Cascade, Sequential Amination/Etherification for Stereoselective Construction of 3-Methyleneindolinones
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An cascade intramolecular 5-exo-dig cyclization of N-(2-iodophenyl)propiolamides and sequential amination/etherification (with N-hydroxybenzamides, phenyl hydroxycarbamate) protocol for the synthesis of amino- and phenoxy-substituted 3-methyleneindolinones using unexpensive Pd(PPh3)4 as catalyst has been developed. The protocol enables the assembly of structurally important oxindole cores featuring moderate functional group tolerance (particularly the halo group), affording a broad spectrum of products with diverse substituents in good to excellent yields. (Figure presented.).
- Zuo, Youpeng,He, Xinwei,Tang, Qiang,Hu, Wangcheng,Zhou, Tongtong,Hu, Wenbo,Shang, Yongjia
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supporting information
p. 2117 - 2123
(2020/12/22)
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- Palladium-catalyzed C–P bond activation of aroyl phosphine oxides without the adjacent “anchoring atom”
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A novel palladium-catalyzed decarbonylation of aroyl phosphine oxides to prepare phosphine oxides from carboxylic acids is developed. Without the adjacent “anchoring atom”, the challenging C–P bond activation is achieved in high selectivity. The disclosure of this reaction provides a new example of C–P bond activation and helps to extend the understanding of the property of C–P bond.
- Chen, Xingyu,Liu, Xiaoyan,Zhu, Hong,Wang, Zhiqian
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- Palladium-Catalyzed Nondirected Late-Stage C-H Deuteration of Arenes
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We describe a palladium-catalyzed nondirected late-stage deuteration of arenes. Key aspects include the use of D2O as a convenient and easily available deuterium source and the discovery of highly active N,N-bidentate ligands containing an N-acylsulfonamide group. The reported protocol enables high degrees of deuterium incorporation via a reversible C-H activation step and features extraordinary functional group tolerance, allowing for the deuteration of complex substrates. This is exemplified by the late-stage isotopic labeling of various pharmaceutically relevant motifs and related scaffolds. We expect that this method, among other applications, will prove useful as a tool in drug development processes and for mechanistic studies.
- Farizyan, Mirxan,Mondal, Arup,Mal, Sourjya,Deufel, Fritz,Van Gemmeren, Manuel
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supporting information
p. 16370 - 16376
(2021/10/21)
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- One-step Conversion of Amides and Esters to Acid Chlorides with PCl3
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A general and efficient iodine-promoted chlorination of amides and esters with phosphorus trichloride is described. For the first time. Various inactivated amides including secondary and tertiary amides were directly converted to the corresponding acid chlorides in one-step. The substrate scope of methyl esters including aromatic and aliphatic esters was also explored under this system. This method is simple, scalable and wide in scope, which provides an approach to preparation of these acid chlorides.
- Li, Fangshao,Wu, Xiaofang,Guo, Fengzhe,Tang, Zi-Long,Xiao, Jing
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supporting information
p. 4314 - 4317
(2021/07/16)
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- PCl3-mediated transesterification and aminolysis of tert-butyl esters via acid chloride formation
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A PCl3-mediated conversion of tert-butyl esters into esters and amides in one-pot under air is developed. This novel protocol is highlighted by the synthesis of skeletons of bioactive molecules and gram-scale reactions. Mechanistic studies revealed that this transformation involves the formation of an acid chloride in situ, which is followed by reactions with alcohols or amines to afford the desired products.
- Wu, Xiaofang,Zhou, Lei,Li, Fangshao,Xiao, Jing
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p. 491 - 497
(2021/01/20)
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- Preparation method of 2,4,6-trimethylbenzoyl chloride and acyl chloride co-production technology
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The invention relates to the field of new materials of fine chemicals, in particular to 2,4,6-trimethylbenzoyl chloride (also known as trimesoyl chloride) and an environment-friendly and economical novel preparation process technology for co-producing series acyl chloride products.
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Paragraph 0018-0020
(2020/11/25)
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- Wavelength-Orthogonal Photocleavable Monochromophoric Linker for Sequential Release of Two Different Substrates
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A wavelength-orthogonal photocleavable monochromophoric linker was developed that is based on a 3-acetyl-9-ethyl-6-methylcarbazole (AEMC) moiety substituted at both the phenacyl and benzylic positions with different carboxylic acids. The different carboxylic acids were released sequentially upon irradiation with light of λ ≥ 365 nm and λ ≥ 290 nm, respectively.
- Venkatesh, Yarra,Chaudhuri, Amrita,Mondal, Saugat,Shah, Sk. Sheriff,Singh, N. D. Pradeep
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p. 295 - 299
(2020/01/02)
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- Palladium-catalyzed cascade decarboxylative amination/6- endo-dig benzannulation of o-alkynylarylketones with n-hydroxyamides to access diverse 1-naphthylamine derivatives
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An efficient and practical one-pot strategy to produce highly substituted 1-naphthylamines via sequential palladium-catalyzed decarboxylative amination/intramolecular 6-endo-dig benzannulation reactions has been described. In this reaction, a broad range of electron-rich, electron-neutral, and electron-deficient o-alkynylarylketones react well with N-hydroxyl aryl/alkylamides to give a diversity of 1-naphthylamines in good to excellent yields under mild reaction conditions. The gram-scale synthesis, with benefits such as undiminished product yield and easy transformation, illustrated the practicality of this method.
- Zuo, Youpeng,He, Xinwei,Tang, Qiang,Hu, Wangcheng,Zhou, Tongtong,Shang, Yongjia
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supporting information
p. 3890 - 3894
(2020/05/18)
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- Base-promoted Lewis acid catalyzed synthesis of quinazoline derivatives
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A one-pot protocol has been developed for the synthesis of quinazolinones from amide-oxazolines with TsCl via a cyclic 1,3-azaoxonium intermediate and 6π electron cyclization in the presence of a Lewis acid and base. The process is operationally simple and has a broad substrate scope. This method provides a unique strategy for the construction of quinazolinones.
- Cui, Xin-Feng,Hu, Fang-Peng,Huang, Guo-Sheng,Lu, Guo-Qiang
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supporting information
p. 4376 - 4380
(2020/10/20)
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- A practical chlorination of tert-butyl esters with PCl3 generating acid chlorides
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For the first time, using PCl3, a range of tert-butyl esters is chlorinated successfully, allowing access of both aromatic acid chlorides and aliphatic acid chlorides in good yields. The method features simple reaction conditions and wide substrate scope. Various tert-butyl esters including aryl esters, alkenyl esters, and alkyl esters were tolerated well in the reaction. A plausible mechanism is proposed.
- Wu, Xiaofang,Zhou, Lei,Yang, Ruoqi,Guo, Fengzhe,Tang, Zi-Long,Xiao, Jing
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p. 301 - 304
(2020/01/29)
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- Substituted arene formyl chloride synthesis method
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The invention relates to the technical field of synthesis of fine chemical intermediates, particularly to a substituted arene formyl chloride synthesis method, which comprises: carrying out a reactionon substituted arene formic acid and substituted trichloromethyl arene under the action of a catalyst 3 to obtain the substituted arene formyl chloride. According to the present invention, the synthesis method has characteristics of inexpensive and easily-available raw materials, short process route, good production safety, easy separation of catalyst, high atomic utilization rate, less waste acid discharge, simple post-treatment, high yield and good quality, and is suitable for industrial continuous production.
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Paragraph 0093; 0096; 0097; 0100
(2019/04/18)
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- Preparation method of aromatic acyl chloride
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The invention discloses a preparation method of aromatic acyl chloride. An aromatic acyl chloride compound is prepared through a reaction of aryl carboxylic acid and phosphorus trichloride. The preparation method of the aromatic acyl chloride has the advantages that the phosphorus trichloride is taken as a chloride reagent, the corresponding acyl chloride is synthesized from the aryl carboxylic acid, so that the production cost is low, the operation is simple, a by-product is low in toxicity, the environmental friendliness is achieved, the yield is high, and the method is conductive to industrial production.
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Paragraph 0087-0090
(2019/07/11)
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- Preparation method of 2, 4, 6-trimethylbenzoyldiphenylphosphine oxide
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The invention relates to a preparation method of 2, 4, 6-trimethylbenzoyldiphenylphosphine oxide and particularly relates to a method, which comprises that phosphorus trichloride, benzene and aluminumtrichloride as raw materials undergo a reaction, the reaction product undergoes a hydrolysis reaction to produce diphenylphosphine oxide, diphenylphosphine oxide and 2, 4, 6-trimethylbenzoyl chloridedirectly undergo a reaction to produce 2, 4, 6-trimethylbenzoyldiphenylphosphine oxide. The preparation method of TPO solves the problems that the raw materials are difficult to prepare, the cost ishigh, the reaction steps are many, and the yield is low. The preparation method is an eco-friendly preparation process.
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Page/Page column 4-6
(2019/02/13)
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- Preparation method of phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide
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The invention provides a preparation method of phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide. The preparation method comprises the following steps: using phenyl phosphorus dichloride as an initial raw material, under the protection of nitrogen, adopting a catalyst (the catalyst is a mixture of potassium tert-butoxide and serine) to replace chlorine with powdery metal sodium, carrying out reduction under a weak alkaline condition, and carrying out condensation and oxidation reaction with 2,4,6-trimethylbenzoyl chloride to prepare a phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide product. The preparation method of phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide has better catalytic effect and higher yield; and the metal sodium is prepared into powder in a toluene solvent, and all reaction processes are carried out under the protection of nitrogen, so that the safety is high.
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Paragraph 0032; 0035; 0039; 0041; 0045; 0047
(2019/10/01)
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- Preparation methods of acyl chloride and thioxanthone
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The present invention relates to the field of fine chemicals and pharmaceutical chemicals, particularly to new economical preparation process technologies of ortho-chlorosulfenyl aroyl chloride and thioxanthone compounds, and applications of the thioxanthone compounds in synthesis of photoinitiators or other new material chemicals.
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Paragraph 0012
(2018/04/01)
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- Gold-Catalyzed Hydrohydrazidation of Terminal Alkynes
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Facile gold-catalyzed hydrohydrazidation of alkynes with various hydrazides R2CONHNH2 (R = Alk or Ar; including those with an additional nucleophilic moiety) in the presence of Ph3PAuNTf2 (6 mol %) leading to a wide range of substituted keto-N-acylhydrazones (18 examples) in excellent to good yields (99-66%) is reported. This novel metal-catalyzed coupling proceeds under mild conditions (chlorobenzene, 60 °C), exhibits high functional group tolerance, and is insensitive to the electronic and steric effects of the substituents in the reactants.
- Zimin, Dmitry P.,Dar'In, Dmitry V.,Rassadin, Valentin A.,Kukushkin, Vadim Yu.
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supporting information
p. 4880 - 4884
(2018/08/24)
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- Cu(II)-catalyzed coupling of aromatic C-H bonds with malonates
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A new Cu(II)-catalyzed oxidative coupling of arenes with malonates has been developed using an amide-oxazoline directing group. The reaction proceeds via C(sp2)-H activation and malonate coupling, followed by intramolecular oxidative N-C bond formation. A variety of arenes bearing different substituents are shown to be compatible with this reaction.
- Wang, Hong-Li,Shang, Ming,Sun, Shang-Zheng,Zhou, Zeng-Le,Laforteza, Brian N.,Dai, Hui-Xiong,Yu, Jin-Quan
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supporting information
p. 1228 - 1231
(2015/03/14)
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- Direct conversion of N -alkoxyamides to carboxylic esters through tandem nbs-mediated oxidative homocoupling and thermal denitrogenation
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Treatment of N-alkoxyamides with NBS in toluene was found to conveniently afford the corresponding carboxylic esters, including those bearing a bulky or long-chain substituent, in satisfactory to excellent yields. This approach not only represents a convenient and economic approach to a direct transformation of an alkoxyamide moiety into the carboxylic ester functional group, via oxidative homocoupling and the subsequent thermal denitrogenation, but also facilitates the synthesis of sterically hindered carboxylic esters.
- Zhang, Ningning,Yang, Rui,Zhang-Negrerie, Daisy,Du, Yunfei,Zhao, Kang
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p. 8705 - 8711
(2013/09/24)
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- Observation of 1,3-diketones formation in the reaction of bulky acyl chlorides with methyllithium
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The formation of 1,3-diketones was observed in the reactions of bulky acyl chlorides with methyllithium. The reaction products depend on the steric hindrance around the carbonyl group of the acyl chloride and the electronic effect of the group(s) linked to the carbonyl. When the steric hindrance around the carbonyl group of the acyl chloride is big enough, the 1,3-diketone is the only product. In the case of the moderate hindrance around the carbonyl group of the acyl chloride, a moderate yield of 1,3-diketone is obtained and some tertiary alcohol is generated. When there is no steric hindrance around the carbonyl group of the acyl chloride, the tertiary alcohol is the only product. When the steric hindrance around the carbonyl group is moderate and an electron-donating group is connected to the carbonyl of the acyl chloride, all three products-ketone, 1,3-diketone and tertiary alcohol-can be isolated from the reaction mixture after long reaction times.
- Zhang, Jian,Yang, Nianfa,Yang, Liwen
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body text
p. 6415 - 6423
(2012/09/08)
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- METHOD FOR PRODUCING SUBSTITUTED ARYLCARBOXYLIC ACID CHLORIDES
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The invention relates to a method for producing arylcarboxylic acid chlorides (I) substituted at least once by aryl (C1-C20) and/or halogen consisting, at a first stage thereof, in reacting an aromatic compound (II) substituted at least once by alkyl (C1-C20) and/or halogen with CCl4 in the presence of a Friedel-craft catalyst in such a way that corresponding trichlormethylated aromatic compounds (III) at least once substituted by aryl (C1-C20) and/or halogen are obtainable. At a second stage, the trichlormethylated aromatic compound (III) is treated with water or a proton acid in the presence of a catalyst, whereby making it possible to obtain an arylcarboxylic acid chloride (I). In the preferred embodiment, said trichlormethylated aromatic compound (III) is not isolated in the form of an intermediate product and, at the second stage used dissolved in the solvent of the first stage.
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Page/Page column 10; 11
(2008/06/13)
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- Structural effects of carbon monoxide coordination to carbon centers, π and σ bindings in aliphatic acyl versus aromatic aroyl cations
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The binding of carbon monoxide to carbon centers has been examined with two series of aromatic and aliphatic oxocarbonium ions that are successfully isolated as crystalline and highly reactive (hygroscopic) aroylium and acylium salts with poorly coordinating counteranions. X-Ray crystallographic analyses at -150°C afford precise structural parameters for the characteristic linear carbonyl bond (rCO) and the bond to the carbon centers (r Cα). The correlations of these structural parameters evaluated for alkyl (Me, Et and i-Pr) and aryl (p-Me, 2,4,6-trimethyl, p-MeO and p-fluorophenyl) oxocarbonium ions with the corresponding carbonyl stretching frequencies in the solid-state (reflectance) IR spectra yield valuable insight into the binding mode of carbon monoxide. Most noteworthy is the synergic (π-σ) bonding in aroylium structures in contrast to the mainly σ bonding in acylium structures that are organic mimics for carbon monoxide bonding in classical and nonclassical metal carbonyls, respectively.
- Davlieva, Milya G.,Lindeman, Sergey V.,Neretin, Ivan S.,Kochi, Jay K.
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p. 1568 - 1574
(2007/10/03)
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- Indenyl esters as potential electronically modified cyclopentadienyl ligands for transition metal complexes
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The preparation of two new indenyl esters 2-(2,4,6-trimethylbenzoyloxy)indene (1) and 2-(adamantanoyloxy)indene (2) is reported. Both compounds can be deprotonated with alkyllithiums such as n-BuLi and the resulting anions trapped by addition of TMSCl or iodomethane, rendering them as potential electronically modified cyclopentadienyl ligand analogues for complexation with transition metals.
- Leino, Reko,Luttikhedde, Hendrik J.G.,L?ngstedt, Lena,Penninkangas, Antti
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p. 4149 - 4151
(2007/10/03)
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- O-pyrazolylpropynyl-hydroxylamines as versatile intermediates in the synthesis of compounds of pharmacological interest
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Through an optimised Pd/Cu-catalysed cross-coupling reaction of 4-iodopyrazoles with 2-propyn-1-ol, followed by Mitsunobu transformation with N-hydroxyphthalimide and subsequent hydrazinolysis, O-[(pyrazol-4-yl)-prop-2-ynyl]-hydroxylamines were obtained in good yields. Their usefulness as intermediates in the synthesis of pharmaceuticals is exemplified by the first reported intramolecular cyclization of O-(2-propynyl)-hydroxylamines to yield 4,5-dihydro-isoxazoles.
- Rodriguez-Franco,Dorronsoro,Martinez
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p. 1711 - 1715
(2007/10/03)
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- Prodrugs activated by targeted catalytic proteins
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Prodrugs that are activated by and conjugated to a catalytic antibody conjugated to a moiety that binds to a tumor cell population are provided.
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- Enantioselective enolate protonation: Matching chiral aniline and substrate acidity
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A comparison of chiral anilines 1a-f in the asymmetric protonation of enolate 15 shows that the optimum ΔpK(a) value (chiral acid vs protonated enolate) for the highest enantioselectivity is ca. 3 (Table 2). An extension of this concept to amino acid enolates was possible, and 1e was found to give the best enantioselectivity (85% ee) with the alanine-derived N-lithioenolate 5a (Table 3). Changes in aniline pK(a) due to variation of substituents at the aniline nitrogen were evaluated briefly, but these changes did not show consistent trends in the enantioselectivity vs pK(a).
- Vedejs,Kruger,Suna
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p. 7863 - 7870
(2007/10/03)
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- Process for the preparation of alkylated aromatic carboxylic acids and acyl halides
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The invention relates to a process for the preparation of polyalkylated aromatic carboxylic acids of formula I STR1 wherein R1, R2, R3, R4 and R5 are each independently of one another hydrogen, C1 -C20 alkyl, halogen or C5 -C8 cycloalkyl, with the proviso that at least two of the substituents R1, R2, R3, R4 or R5 are alkyl and/or cycloalkyl, by reacting corresponding aromatic hydrocarbons with carbon dioxide, which reaction is carried out observing special ratios of temperature and pressure. The invention furthermore relates to a one-pot process for the preparation of the corresponding acyl halides.
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- Coupling N-Methylated Amino Acids Using PyBroP and PyCloP Halogenophosphonium Salts: Mechanism and Fields of Application
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PyBroP (1) and PyCloP (2), two halotripyrrolidinophosphonium hexafluorophosphates, are peptidecoupling reagents highly efficient for coupling N-methylated amino esters, in contrast with PyBOP (3), the hydroxybenzotriazolyl analogue.These halogenophosphonium salts 1 and 2 are convenient (one-pot reactions) stable solids soluble in conventional solvents.Use of them gave an excellent peptide yield with essentially no epimerization.Activation with these reagents probably involves the formation of an (acyloxy)phosphonium, as shown in the case of 2,4,6-trimethylbenzoic acid activation.In the case of reagents 1 and 2, oxazolone and/or a symmetrical anhydride were intermediates which were rapidly aminolyzed.In contrast, the benzotriazolyl ester intermediate which was formed with PyBOP (3) was poorly reactive with N-methylated amino esters.PyBroP (1) and PyCloP (2) were less efficient in the coupling of some Boc-amino acids because of N-carboxyanhydride formation; this was particularly the case when Boc-Val-OH or Boc-MeVal-OH was coupled with MeVal-OMe.
- Coste, Jacques,Frerot, Eric,Jouin, Patrick
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p. 2437 - 2446
(2007/10/02)
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- Pesticidal cyclic malonylphosphonic diamides
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Novel pesticidally active cyclic malonylphosphonic diamides of the formula STR1 in which X represents O or S, R1 represents alkyl, alkenyl, alkinyl, cycloalkyl, aryl or heteroaryl, each of which can be optionally substituted, R2 represents hydrogen, alkyl, aryl or aralkyl, R3 represents hydrogen, alkyl, aryl or aralkyl, and R4 represents an acyl radical, or salts thereof, Many intermediates are new,
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- A DIPOLE MOMENT STUDY OF HINDERED BENZOPHENONES
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Dipole moment analysis of 4-X-2,6-dimethylbenzophenones, 4'-X-2,6-dimethyl- and 4'-X-2,4,6-trimethylbenzophenones, with X=OMe and X=NMe2, showed that the (X...C=O) interaction moments are much lower in the first family of compounds. 2,6-Dimethyl-, and 2,4,6-trimethylbenzophenone exhibit an asymmetric gauche model with φ=55 deg and φ'=0 deg. 2,6-Dimethyl-3'-chloro- and 2,4,6-trimethyl-3'-chlorobenzophenones occur as equimolecular mixtures of cis-(Cl,O) and trans-(Cl,O) conformers.Preferred conformations are proposed for p-chloro, p-methoxy- and p-dimethylaminobenzophenone, and the delicate problem posed by the actual conformation of benzophenone in solution is discussed.In the present work, 25 benzophenones were examined, and their dipole moments were analysed according to a coherent pattern.
- Lumbroso, H.,Liegeois, Ch.,Goethals, G.,Uzan, R.
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p. 133 - 146
(2007/10/02)
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- Circular Dichroism of Some N-Monosubstituted and N,N-Disubstituted Benzamides
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The circular dichroism (CD) spectra of some N-benzoyl-1-alkyl-2-propynylamines and N-benzoyl-1-alkyl-2-propenylamines show three Cotton effects (CE's) in the near ultraviolet region.These are assigned to 1Lb, n->?* and 1La transitions of the N-monosubstituted benzamide chromophore.The 1Lb and n->?* CE's are negative and positive, respectively, for the R configuration.In the N-benzoyl-1-alkyl-2-propenylamines, the 1La CE's appear to be developed primarily through dipole - dipole coupling between allowed (?-?*) transitions of the benzamide chromophore and the ethenyl group.The benzoyl derivatives of some 2- and 3-substituted pyrrolidines also exhibit three CE's which are assigned to 1Lb n->?* and 1La transitions of the N,N-substituted benzamide chromophore.In benzoyl derivatives of 2-substituted pyrrolidines, these CE's are negative, positive and negative, respectively, for the D-proline configuration.The effect of increasing nonplanarity of the phenyl and amide groups, brought about by ortho-methyl substitution, on the CD behaviour of both N-monosubstituted and N,N-disubstituted benzamides is discussed.
- Ringdahl, Bjoern
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p. 141 - 152
(2007/10/02)
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- The synthesis of aldehydes by means of a modified Rosenmund reduction of acid chlorides
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Aliphatic as well as aromatic acid chlorides are reduced smoothly into aldehydes at room temperature and atmospheric pressure by hydrogenation, using palladium on carbon as the catalyst, acetone or ethyl acetate as solvent and ethyldiisopropylamine as hydrogen chloride acceptor.The reaction has a high selectivity and under the conditions used, no over-reduction nor reduction of aromatic rings, of nitro and chloro substituents in benzoyl chlorides, or double bonds in cinnamoyl chlorides, was observed.The selectivity is probably the result of a combination of factors, such as selective adsorption of the acid chloride on the catalyst (with respect to the aldehyde) and partial poisoning of the catalyst surface by co-adsorption of ethyldiisopropylamine and its hydrochloride.
- Peters, J. A.,Bekkum, H. van
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- N-[Diaminophosphinyl]arylcarboxamides
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A series of N-[diaminophosphinyl]arylcarboxamides are useful as inhibitors of the enzyme urease.
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