- An efficient Fe2O3/HY catalyst for Friedel-Crafts acylation of m-xylene with benzoyl chloride
-
Iron oxide supported on HY zeolite was prepared and exhibited excellent catalytic performance in the acylation of m-xylene with benzoyl chloride. It was characterized by XRD, BET, XPS, NH3-TPD and Py-IR. The obtained results indicated that the catalytic activity of Fe2O3/HY is enhanced with the increase of Lewis acidic sites. Furthermore, the reaction parameters, including load of Fe2O3, temperature, molar ratio and the dose of catalyst, were optimized. Thus the acylation proceeds effectively to afford 2,4-dimethylphenylacetophenone in 94.1% yield under optimum conditions. Finally, the catalyst was examined for the acylations of a series of arenes, all of the alkyl substituted benzenes were transformed to the corresponding products in satisfactory yields while the acylation of chlorobenzene was sluggish. The catalyst was easily separated from the reaction mixture and reused for five runs without appreciable loss of catalytic activity. the Partner Organisations 2014.
- Mu, Manman,Chen, Ligong,Liu, Yunlong,Fang, Wangwang,Li, Yang
-
-
Read Online
- Experimental and DFT study on the indium-mediated synthesis of benzophenones via arylstannanes
-
Experimental results of the solvent-free, indium-promoted reaction of aroyl chlorides with arylstannanes showed a narrow scope; its efficiency depends both on the extent of methylation in the latter and on the nature, number and position of the substituents in the former. With the purpose of explaining experimental results, a theoretical analysis with DFT methods was performed for a set of selected cases. This journal is
- Lo Fiego, Marcos J.,Dorn, Viviana B.,Badajoz, Mercedes A.,Lockhart, Mara T.,Chopa, Alicia B.
-
-
Read Online
- Friedel-crafts benzoylation of alkylbenzenes with brazoic anhydride catalyzed by solid superacids
-
The liquid-solid phase benzoylation of mono-alkylbenzenes with methyl, ethyl, propyl, and butyl groups and xylenes was carried out with benzoic anhydride at 100-110°C over solid superacids: SO4/ZrO 2, WO3/ZrO2, and SO4/ HfO 2. The reactivity ratio obtained by the competitive method of reaction over WO3/ZrO2 was 1 to 4.6 for toluene to p-xylene and 1.1:10:1 among o-, m-, and p-xylenes, respectively. Although the SO4/ZrO2 catalyst gave high yields of 92 and 97% for toluene and ethylbenzene in a 3:7 distribution of o- and p-isomers, respectively, low yields were observed with propyl and butylbenzenes over the catalyst: that is, 5 and 2% for propylbenzene and isopropylbenzene, 14% for isobutylbenzene, and trace yields for butylbenzene, s-butylbenzene, and t-butylbenzene, respectively. The usual Friedel-Crafts benzoylation using AlCl3 was examined in the present alkylbenzenes in order to confirm the low reactivity of both propyl and butylbenzenes. The results were similar to those with the SO4/ZrO2 catalyst; that is, the yields at 0°C for 1 h were 37, 21, 6, 1, 0, 3, and 2% for toluene, ethylbenzene, propylbenzene, isopropylbenzene, butylbenzene, s-butylbenzene, and t-butylbenzene, respectively, showing an unexpected result where there was no distinction between homogeneous and heterogeneous conditions.
- Nakamura, Hideo,Arata, Kazushi
-
-
Read Online
- Sterically Hindered Ketones via Palladium-Catalyzed Suzuki-Miyaura Cross-Coupling of Amides by N-C(O) Activation
-
Herein, we report a new protocol for the synthesis of sterically hindered ketones that proceeds via palladium-catalyzed Suzuki-Miyaura cross-coupling of unconventional amide electrophiles by selective N-C(O) activation. Mechanistic studies demonstrate that steric bulk on the amide has a major impact, which is opposite to the traditional Suzuki-Miyaura cross-coupling of sterically hindered aryl halides. Structural and computational studies provide insight into ground-state distortion of sterically hindered amides and show that ortho-substitution alleviates the N-C(O) bond twist.
- Liu, Chengwei,Lalancette, Roger,Szostak, Roman,Szostak, Michal
-
p. 7976 - 7981
(2019/10/10)
-
- Ketone Synthesis by a Nickel-Catalyzed Dehydrogenative Cross-Coupling of Primary Alcohols
-
An intermolecular coupling of primary alcohols and organotriflates has been developed to provide ketones by the action of a Ni(0) catalyst. This oxidative transformation is proposed to occur by the union of three distinct catalytic cycles. Two competitive oxidation processes generate aldehyde in situ via hydrogen transfer oxidation or (pseudo)dehalogenation pathways. As aldehyde forms, a Ni-catalyzed carbonyl-Heck process enables formation of the key carbon-carbon bond. The utility of this rare alcohol to ketone transformation is demonstrated through the synthesis of diverse complex and bioactive molecules.
- Verheyen, Thomas,Van Turnhout, Lars,Vandavasi, Jaya Kishore,Isbrandt, Eric S.,De Borggraeve, Wim M.,Newman, Stephen G.
-
supporting information
(2019/05/08)
-
- Ketone Synthesis by a Nickel-Catalyzed Dehydrogenative Cross-Coupling of Primary Alcohols
-
An intermolecular coupling of primary alcohols and organotriflates has been developed to provide ketones by the action of a Ni(0) catalyst. This oxidative transformation is proposed to occur by the union of three distinct catalytic cycles. Two competitive oxidation processes generate aldehyde in situ via hydrogen transfer oxidation or (pseudo)dehalogenation pathways. As aldehyde forms, a Ni-catalyzed carbonyl-Heck process enables formation of the key carbon-carbon bond. The utility of this rare alcohol to ketone transformation is demonstrated through the synthesis of diverse complex and bioactive molecules.
- Verheyen, Thomas,Van Turnhout, Lars,Vandavasi, Jaya Kishore,Isbrandt, Eric S.,De Borggraeve, Wim M.,Newman, Stephen G.
-
supporting information
p. 6869 - 6874
(2019/05/10)
-
- Ligand-free Palladium-Catalyzed Carbonylative Suzuki Coupling of Aryl Iodides in Aqueous CH3CN with Sub-stoichiometric Amount of Mo(CO)6 as CO Source
-
A new method for the synthesis of diaryl and heterodiaryl ketones has been established based on the palladium-catalyzed carbonylative Suzuki coupling approach with sub-stoichiometric Mo(CO)6 as CO source. Using 0.5 mol% of Pd(TFA)2 as catalyst, 0.5 equivalent of Mo(CO)6 as solid carbonyl reagent and 3 equivalent of K3PO4 as base, a wide range of functionalized (hetero)aryl iodides and (hetero)aryl boronic acids could smoothly proceed the carbonylative cross-coupling reaction in aqueous CH3CN at 50 °C, affording the corresponding ketones in good to excellent yields. The newly developed method was easy to operate under mild conditions with high efficiency. (Figure presented.).
- Sun, Nan,Sun, Qingxia,Zhao, Wei,Jin, Liqun,Hu, Baoxiang,Shen, Zhenlu,Hu, Xinquan
-
p. 2117 - 2123
(2019/03/28)
-
- Palladium-Catalyzed Ligand-Free Decarboxylative Coupling of α- Oxocarboxylic Acid with Aryl Diazonium Tetrafluoroborate: An Access to Unsymmetrical Diaryl Ketones
-
Diaryl ketones are of much importance in organic synthesis as versatile intermediates and in industry for their useful properties. A mild and efficient palladium-catalyzed traditional ligand-free decarboxylative coupling of aryl α-keto carboxylic acid with aryl diazonium fluoroborate has been developed. A series of unsymmetrical diaryl ketones has been synthesized in moderate to good yields using this procedure. A radical pathway involving the acyl radical has been suggested.
- Panja, Subir,Maity, Pintu,Ranu, Brindaban C.
-
p. 12609 - 12618
(2018/10/20)
-
- Carbonylative Suzuki cross-coupling reaction catalyzed by bimetallic Pd-Pt nanodendrites under ambient CO pressure
-
Pd-catalyzed reactions between aryl boronic acids and aryl halides have undergone rapid development since the pioneering work of Suzuki and co-workers in 1979. In this paper, we described a high-efficient and cost-effective bimetallic Pd-Pt nanodendrites catalyst based on a ligand-free strategy to synthesize diaryl ketones via CO direct insertion to boronic acids and aryl halides. A variety of aryl boronic acids and aryl halides were investigated, which showed great functional group tolerance and versatile aryl ketone products in high yield.
- Wang, Zheng-Jun,Wang, Xue-Yan,Wang, Xia,Liang, Zhi-Wu,Xu, Xinhua
-
-
- Palladium-Catalyzed Denitrogenative Synthesis of Aryl Ketones from Arylhydrazines and Nitriles Using O2 as Sole Oxidant
-
An efficient and simple palladium-catalyzed approach for the synthesis of aryl ketones from low-cost nitriles and arylhydrazines using molecular oxygen (O2) as sole oxidant via C-N bond cleavage is reported. Various aryl ketones were synthesized in moderate to good yields under mild conditions. A possible mechanism involving the PdII/Pd0 catalytic cycle process is depicted, and a cationic palladium intermediate was detected by ESI-MS.
- Wang, Xu,Huang, Yubing,Xu, Yanli,Tang, Xiaodong,Wu, Wanqing,Jiang, Huanfeng
-
p. 2211 - 2218
(2017/02/26)
-
- An efficient and green method for regio- and chemo-selective Friedel-Crafts acylations using a deep eutectic solvent ([CholineCl][ZnCl2]3)
-
[CholineCl][ZnCl2]3, a deep eutectic solvent between choline chloride and ZnCl2, has been used as a dual function catalyst and green solvent for the Friedel-Crafts acylation of aromatic compounds instead of using the moisture-sensitive Lewis acids and volatile organic solvents. The reactions are performed with high yields under microwave irradiation with short reaction times for the synthesis of ketones. Interestingly, indole derivatives are regioselectively acylated in the 3-position under mild conditions with high yields without NH protection. Three new ketone products are synthesized. [CholineCl][ZnCl2]3 is easily synthesized from choline chloride and zinc chloride at a low cost, with easy purification and environmentally benign compounds. [CholineCl][ZnCl2]3 can be reused up to five times without loss of catalytic activity, making it ideal in industrial processes.
- Tran, Phuong Hoang,Nguyen, Hai Truong,Hansen, Poul Erik,Le, Thach Ngoc
-
p. 37031 - 37038
(2016/05/24)
-
- Discovery of an 8-methoxytetrahydroisoquinoline derivative as an orally active N-type calcium channel blocker for neuropathic pain without CYP inhibition liability
-
In lead optimization efforts starting from the tetrahydroisoquinoline (S)-1, we identified 2-{[(2R)-2-hydroxypropyl]amino}-1-[(1S)-8-methoxy-1-phenyl-3,4-dihydroisoquinolin-2(1H)-yl]ethanone ((1S)-8t) as a novel orally active small-molecule N-type calcium channel blocker without CYP inhibition liability. CYP3A4 inhibition profile was improved by reducing the lipophilicity of compound (S)-1. Moreover, introduction of a methoxy group to the C-8 position of tetrahydroisoquinoline led to identification of (1S)-8t, which eliminated CYP2D6 inhibition liability. Oral administration of (1S)-8t exerted efficacy in a rat spinal nerve ligation (SNL) model of neuropathic pain with an ED50 value of 2.8 mg/kg.
- Ogiyama, Takashi,Yonezawa, Koichi,Inoue, Makoto,Katayama, Naoko,Watanabe, Toshihiro,Yoshimura, Seiji,Gotoh, Takayasu,Kiso, Tetsuo,Koakutsu, Akiko,Kakimoto, Shuichiro,Shishikura, Jun-Ichi
-
supporting information
p. 4638 - 4648
(2015/08/03)
-
- Facile access to sterically hindered aryl ketones via carbonylative cross-coupling: Application to the total synthesis of luteolin
-
A general and mild protocol for achieving the carbonylative cross-coupling of sterically hindered, ortho-disubstituted aryl ketones is reported. The commercially available PEPPSI-IPr catalyst is shown to efficiently promote the carbonylative cross-coupling of hindered ortho-disubstituted aryl iodides to give diaryl ketones; traditional phosphine catalysts are less effective. Carbonylative Suzuki-Miyaura cross-couplings provide a diverse array of biaryl ketones in good to excellent yields. The same catalyst is also shown to catalyze a carbonylative Negishi cross-coupling reaction, utilizing a variety of alkynyl-zinc reagents to give the corresponding alkynyl aryl ketones. Application of this new methodology to the synthesis of the natural product luteolin is reported.
- O'Keefe, B. Michael,Simmons, Nicholas,Martin, Stephen F.
-
experimental part
p. 4344 - 4351
(2011/07/29)
-
- 1-SUBSTITUTED TETRAHYDROISOQUINOLINE COMPOUND
-
Provided is a compound useful as an N-type Ca2+ channel blocker. As a result of intensive studies of compounds having an action of blocking N-type Ca2+ channels, the present inventors found that a tetrahydroisoquinoline compound of the present invention having a substituent at the 1-position has an action of blocking the N-type Ca2+ channels, an antinociceptive pain action, an antineuropathic pain action, an abdominal pain-inhibitory action and an opioid-induced constipation-improving action, and the present invention has been completed based on these findings. The compound of the present invention can be used as a pharmaceutical composition for preventing and/or treating various pains such as neuropathic pain and nociceptive pain, headaches such as migraine and cluster headache, central nervous system diseases such as anxiety, depression, epilepsy, cerebral stroke and restless legs syndrome, abdominal symptoms such as abdominal pain and abdominal distension, stool abnormalities such as diarrhea and constipation, digestive system diseases such as irritable bowel syndrome, urinary system diseases such as overactive bladder and interstitial cystitis, etc.
- -
-
Page/Page column 39
(2010/03/02)
-
- PROCESS FOR PREPARING KETONES FROM ALPHA-OXO CARBOXYLATES AND ARYL BROMIDES
-
A process for preparing ketones of the general formula (III) where R is an optionally substituted carbocyclic aromatic radical having 6 to 24 carbon atoms or an optionally substituted alkyl radical or an optionally substituted heteroaromatic radical having 5 to 24 carbon atoms, andR1 is an optionally substituted carbocyclic aromatic radical having 6 to 24 carbon atoms or an optionally substituted heteroaromatic radical having 5 to 24 carbon atoms, by reacting alpha-oxo carboxylates of the general formula (I) wherein n and m is a number in the range from 1 to 6, M(m+) is a cation, and R has the meaning indicated for formula (III), with aryl bromides of the general formula (II) [in-line-formulae]R1—Br ??(II)[/in-line-formulae] where R1 has the meaning indicated for formula (III), in the presence of two transition metals or compounds thereof as catalyst, is described.
- -
-
Page/Page column 3-4
(2009/09/08)
-
- Carbonylative cross-coupling of ortho-disubstituted aryl iodides. Convenient synthesis of sterically hindered aryl ketones
-
(Chemical Equation Presented) A mild and general protocol for the carbonylative cross-coupling of sterically hindered ortho-disubstituted aryl iodides is reported. Carbonylative Suzuki-Miyaura couplings of a variety of aryl boronic acids provide an array of substituted biaryl ketones in modest to excellent yield. A carbonylative Negishi coupling that utilizes alkynyl nucleophiles is also described.
- Michael O'Keefe,Simmons, Nicholas,Martin, Stephen F.
-
supporting information; experimental part
p. 5301 - 5304
(2009/06/18)
-
- Synthesis of ketones from α-oxocarboxylates and aryl bromides by Cu/Pd-catalyzed decarboxylative cross-coupling
-
(Chemical Equation Presented) The power of two metals: A Pd/Cu catalyst system mediates the in situ formation of acyl nucleophiles by decarboxylation of readily accessible and stable salts of α-oxocarboxylic acids and their cross-coupling with aryl or heteroaryl bromides to give ketones. The reaction may be usedin the presence of many functional groups and provides good yields.
- Goossen, Lukas J.,Rudolphi, Felix,Oppel, Christoph,Rodriguez, Nuria
-
p. 3043 - 3045
(2008/12/23)
-
- A catalyst-free synthesis of asymmetric diaryl ketones from aryltins
-
A series of diaryl ketones have been synthesized in good yields (40-78%) through the catalyst-free reaction of trimethylarylstannanes with aroyl chlorides in chlorobenzene as solvent. In addition, an attractive feature is that these reactions are completely regioselective making possible the synthesis of diarylketones which are not usually available under the influence of the directing forces of the substituents present in the aromatic ring. Also, the reaction conditions are mild enough to be applied to acid sensitive molecules.
- Silbestri, Gustavo F.,Masson, Romina Bogel,Lockhart, María T.,Chopa, Alicia B.
-
p. 1520 - 1524
(2007/10/03)
-
- Aluminum dodecatungstophosphate (AlPW12O40) as a non-hygroscopic Lewis acid catalyst for the efficient Friedel-Crafts acylation of aromatic compounds under solvent-less conditions
-
Stable and non-hygroscopic aluminum dodecatungstophosphate (AlPW 12O40), which is prepared easily from cheap and commercially available compounds was found to be an effective catalyst for Friedel-Crafts acylation reactions using carboxylic acids, acetic anhydride and benzoyl chloride in the absence of solvent under mild reaction conditions.
- Firouzabadi, Habib,Iranpoor, Nasser,Nowrouzi, Farhad
-
p. 10843 - 10850
(2007/10/03)
-
- Synthesis of Diaryl Ketones Catalyzed by Al2O 3-ZrO2/S2O82- Solid Superacid
-
The acylation of a variety of aromatic compounds with benzoyl chloride or its derivatives and catalytic amounts of Al2O3-ZrO 2/S2O82- solid superacid affords the corresponding diaryl ketones in good to excellent yields 75-93% at appropriate temperature.
- Jin, Tong-Shou,Yang, Mi-Na,Feng, Guo-Liang,Li, Tong-Shuang
-
p. 479 - 485
(2007/10/03)
-
- Friedel-Crafts Acylation of Arenes Catalysed by Bromopentacarbonylrhenium(I)
-
The intermolecular Friedel-Crafts acylation of aromatic compounds (such as toluene, m-xylene, and anisole) with various acid chlorides proceeds by using a catalytic amount of bromopentacarbonylrhenium(I) to afford aryl ketones.Intramolecular acylation is also catalyzed by the above-mentioned catalyst to give indanone and tetralone derivatives.
- Kusama, Hiroyuki,Narasaka, Koichi
-
p. 2379 - 2384
(2007/10/03)
-
- Carboxylic Trifluoromethanesulfonic Anhydrides as Highly Effective Acylation Agents. - Perfluoroalkanesulfonic Acid Catalyzed Acylation of Arenes
-
Arene- and alkanecarboxylic trifluoromethanesulfonic anhydrides 2 and 5 are highly effective acylation agents, which react without Friedel-Crafts catalysts even with deactivated aromatics to yield aryl ketones 3 and 6, respectively.Acylation of arenes with carbonyl chlorides 4 and catalytic amounts of perfluoroalkanesulfonic acid gives ketones 3 and 6, resp., in good yields.Under similar conditions other strong Broensted acids show a considerably smaller degree of catalytic effect.
- Effenberger, Franz,Sohn, Erich,Epple, Gerhard
-
p. 1195 - 1208
(2007/10/02)
-
- Production of dimethylbenzophenone
-
The production of anthraquinone-1-carboxylic acid by reacting a benzoyl halide with a tert.-butylxylene in the presence of ferric chloride, adding aluminum chloride, oxidizing the dimethylbenzophenone formed and cyclizing the resulting benzophenonedicarboxylic acid. The product is a starting material for the production of dyes and pesticides.
- -
-
-