- Photo-induced oxidative cleavage of C-C double bonds of olefins in water
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The carbonyl compounds, synthesized by the oxidative cleavage of their corresponding olefins, are of great significance in organic synthesis, especially aryl ketones. We have developed a gentle and effective protocol, using acid red 94 as the organic metal-free photocatalyst, O2 as the oxidant, and water as the solvent. Under visible light irradiation, aryl ketone derivatives were obtained in moderate to excellent yields, showing good economic and environmental advantages.
- Zhang, Yilan,Yue, Xiaoguang,Liang, Chenfeng,Zhao, Jianming,Yu, Wenbo,Zhang, Pengfei
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supporting information
(2021/08/27)
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- Selective oxidation of alkenes to carbonyls under mild conditions
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Herein, a practical and sustainable method for the synthesis of aldehydes, ketones, and carboxylic acids from an inexpensive olefinic feedstock is described. This transformation features very sustainable and mild conditions and utilizes commercially available and inexpensive tetrahydrofuran as the additive, molecular oxygen as the sole oxidant and water as the solvent. A wide range of substituted alkenes were found to be compatible, providing the corresponding carbonyl compounds in moderate-to-good yields. The control experiments demonstrated that a radical mechanism is responsible for the oxidation reaction.
- Huo, Jie,Xiong, Daokai,Xu, Jun,Yue, Xiaoguang,Zhang, Pengfei,Zhang, Yilan
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supporting information
p. 5549 - 5555
(2021/08/16)
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- Aryl aldiketone and synthesis method thereof
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The invention discloses an aryl aldehyde ketone and a synthesis method thereof, wherein an aryl aldehyde is synthesized from cheap olefin as a raw material. A commercially available inexpensive olefin is used as a raw material, ether is used as an additive, molecular oxygen serves as a sole oxidizing agent, water is used as a solvent, and the aldehyde and ketone are synthesized by column chromatography under a photocatalytic condition. The invention has the advantages of mild reaction conditions, green and environmental protection, simple experimental operation, good reaction selectivity, high product yield and the like.
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Paragraph 0031
(2021/09/26)
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- Kinetically Controlled, Highly Chemoselective Acylation of Functionalized Grignard Reagents with Amides by N?C Cleavage
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The direct transition-metal-free acylation of amides with functionalized Grignard reagents by highly chemoselective N?C cleavage under kinetic control has been accomplished. The method offers rapid and convergent access to functionalized biaryl ketones through transient tetrahedral intermediates. The direct access to functionalized Grignard reagents by in situ halogen–magnesium exchange promoted by the versatile turbo-Grignard reagent (iPrMgCl?LiCl) permits excellent substrate scope with respect to both the amide and Grignard coupling partners. These reactions enable facile, operationally simple and chemoselective access to tetrahedral intermediates from amides under significantly milder conditions than chelation-controlled intermediates. This novel direct two-component coupling sets the stage for using amides as acylating reagents in an alternative paradigm to the metal-chelated approach, acyl metals and Weinreb amides.
- Li, Guangchen,Szostak, Michal
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supporting information
p. 611 - 615
(2020/01/02)
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- Synthesis of biaryl ketones by arylation of Weinreb amides with functionalized Grignard reagents under thermodynamic controlvs.kinetic control ofN,N-Boc2-amides
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A highly efficient method for chemoselective synthesis of biaryl ketones by arylation of Weinreb amides (N-methoxy-N-methylamides) with functionalized Grignard reagents is reported. This protocol offers rapid entry to functionalized biaryl ketones after Mg/halide exchange with i-PrMgCl·LiCl under operationally-simple and practical reaction conditions. The scope of the method is highlighted in >40 examples, including bioactive compounds and pharmaceutical derivatives. Collectively, this transition-metal-free approach offers a major advantage over the recently established cross-coupling of amides by oxidative addition of N-C(O) bonds. Considering the utility of amide acylation reactions in modern synthesis, we expect that this method will be of broad interest.
- Li, Guangchen,Szostak, Michal
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supporting information
p. 3827 - 3831
(2020/06/03)
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- Transition-metal-free carbonylation of aryl halides with arylboronic acids by utilizing stoichiometric CHCl3 as the carbon monoxide-precursor
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Under transition-metal-free conditions, carbonylative Suzuki couplings of aryl halides with arylboronic acid using stoichiometric CHCl3 as the carbonyl source has been developed. The simple, efficient, and environmentally benign method was successfully applied to the synthesis of Fenofibric acid, naphthyl phenstatin, and carbon-13 labeled biaryl ketone.
- Xu, Fangning,Li, Dan,Han, Wei
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supporting information
p. 2911 - 2915
(2019/06/18)
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- Pd-Catalyzed Suzuki–Miyaura Cross-Coupling of Arylboronic Acids and α-Iminonitriles through C–CN Bond Activation
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A Pd-catalyzed Suzuki–Miyaura cross-coupling reaction between arylboronic acids and α-iminonitriles has been developed. The reaction proceeds through selective activation of the C–CN bond, tolerates a wide range of substituents, and delivers the versatile ketone products in moderate to excellent yields.
- Liu, Kui,Tao, Shou-Wei,Qian, Chun,Zhu, Yong-Ming
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supporting information
p. 4769 - 4775
(2018/09/06)
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- Pd(II)-Catalyzed Denitrogenative and Desulfinative Addition of Arylsulfonyl Hydrazides with Nitriles
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A Pd(II)-catalyzed denitrogenative and desulfinative addition of arylsulfonyl hydrazides with nitriles has been successfully achieved under mild conditions. This transformation is a new method for the addition reaction to nitriles with arylsulfonyl hydrazides as arylating agent, thus providing an alternative synthesis of aryl ketones. The reported addition reaction is tolerant to many common functional groups, and works well in the presence of electron-donating and electron-withdrawing substituents. Notably, the reported denitrogenative and desulfinative addition was also appropriate for alkyl nitriles, making this newly developed transformation attractive.
- Meng, Mengting,Yang, Liangfeng,Cheng, Kai,Qi, Chenze
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p. 3275 - 3284
(2018/03/25)
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- Method for preparing aromatic ketone in aqueous phase
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The invention discloses a method for preparing aromatic ketone in an aqueous phase, comprising the following steps: enabling aryl formyl potassium formate and aryl potassium fluoborate to generate decarboxylation acylation reaction in water under the actions of a silver catalyst and an oxidizing agent, and performing treatment after reaction is ended to obtain the disclosed aromatic ketone. According to the preparation method, the silver catalyst replaces a noble metal catalyst, water is taken as a solvent, an aromatic ketone product is obtained with relatively high yield, the adopted catalystis low in cost and easy to obtain, reaction conditions are mild, and meanwhile, the product is good in university, and therefore, the method has good application potential.
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Paragraph 0042-0045
(2018/04/26)
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- Preparation method of aromatic ketone
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The invention discloses a preparation method of aromatic ketone. Under the effects of a palladium catalyst and a nitrogen-containing ligand, nitrile compounds and arylsulfonylhydrazide take desulfurization addition reaction in an organic solvent; after the reaction is completed, post treatment is performed to obtain aromatic ketone. The reaction is applicable to aromatic nitrile compounds, and isalso applicable to aliphatic nitrile compounds; the reaction realizes the wide substrate applicability and functional group tolerance; the potential application value is realized in the aspect of aryl-carbonyl building.
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Paragraph 0046; 0047; 0048; 0050
(2018/09/11)
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- Ag(i)/persulfate-catalyzed decarboxylative coupling of α-oxocarboxylates with organotrifluoroborates in water under room temperature
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The decarboxylative coupling reaction of α-oxocarboxylates and organotrifluoroborates was carried out smoothly in the presence of catalytic AgNO3 using K2S2O8 as oxidant to generate diarylketone products in high
- Chang, Sheng,Wang, Jian Feng,Dong, Lin Lin,Wang, Dan,Feng, Bo,Shi, Yuan Tai
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p. 51928 - 51934
(2017/11/22)
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- Oxidative decarboxylation of arylacetic acids in water: One-pot transition-metal-free synthesis of aldehydes and ketones
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One-pot transition-metal-free synthesis of aromatic aldehydes and ketones via oxidative decarboxylation of arylacetic acids in water is developed. Protocol relies on the direct decarboxylation of sp3-hybridized carbon in water without any over oxidation into carboxylic acids with minimal waste. Reaction mechanism is investigated and application of this protocol is demonstrated on a gram scale.
- Mete, Trimbak B.,Khopade, Tushar M.,Bhat, Ramakrishna G.
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supporting information
p. 2822 - 2825
(2017/06/27)
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- T-BuONa-Mediated Transition-Metal-Free Autoxidation of Diarylmethanes to Ketones
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Autoxidative sp3 C-H transformation of diarylmethanes has been demonstrated using O2-mediation by t-BuONa. This protocol enables an alternative route for the access to diaryl ketones from benzyl derivatives in good to excellent yields under mild reaction conditions, without transition metal catalysts or additional chemical oxidants.
- Li, Jiang-Sheng,Yang, Fan,Yang, Qian,Li, Zhi-Wei,Chen, Guo-Qin,Da, Yu-Dong,Huang, Peng-Mian,Chen, Chao,Zhang, Yuefei,Huang, Ling-Zhi
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supporting information
p. 994 - 998
(2017/05/10)
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- A kind of alkali to promote self-oxidation of diaryl alkane preparation diarylketones method (by machine translation)
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The invention discloses a kind of alkali to promote self-oxidation of diaryl alkane preparation diarylketones method. The method is that the diaryl paraffins compound is dissolved in an organic solvent in the drying of, the addition of a base, in the 25 - 80o C reaction under air or oxygen atmosphere for 0.5 - 5 hours, to obtain diarylketones; said two aryl paraffins compound and alkali molar ratio of 1:1 - 1:3. The method overcomes the need in the prior art strong acid or expensive metal reagent or a strong oxidizing agent and the like, has the following advantages: 1) to oxygen as the oxidizing agent, avoids the use of strong or expensive chemical oxidizing agent; 2) transition metal-free catalyst, avoids the heavy metal ion in the product; 3) the process is simple, low cost, wide range of the substrate, friendly to the environment. The synthesis method disclosed in this invention in the preparation of diarylketones industrialization of the play an important role in the production. (by machine translation)
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Paragraph 0019
(2017/08/28)
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- Carbonylative coupling of aryl tosylates/triflates with arylboronic acids under CO atmosphere
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The carbonylative Suzuki-Miyaura reaction between aryl tosylates/triflates with arylboronic acid is herein reported, using base-free conditions and a balloon pressure of carbon monoxide. Under these conditions, unsymmetrical biaryl ketones were obtained in modest to excellent yields. This method was adapted to the synthesis of oxybenzone and ketoprofen in good yields under mild conditions.
- Hao, Cheng Yi,Wang, Dan,Li, Ya Wei,Dong, Lin Lin,Jin, Ying,Zhang, Xiu Rong,Zhu, He Yun,Chang, Sheng
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p. 86502 - 86509
(2016/09/23)
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- Silver-catalyzed decarboxylative acylation of arylglyoxylic acids with arylboronic acids
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The silver-catalyzed coupling of arylboronic acids with arylglyoxylic acids was found to be an extremely efficient route for the synthesis of unsymmetrical diaryl ketones. It can be conducted on a gram scale under mild and open-flask conditions with good functional group compatibility, avoiding the addition of expensive and/or toxic metals. This journal is
- Cheng, Kai,Zhao, Baoli,Qi, Chenze
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p. 48698 - 48702
(2014/12/10)
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- Synthesis of structurally diverse diarylketones through the diarylmethyl sp3 C-H oxidation
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Under open-flask conditions, an efficient method to assemble a series of diversely functionalized diarylketones in the presence of commercially available NBS has been developed. Yields of up to 99% have been achieved employing diarylmethanes as starting material. Based on 18O-labeled experiment, the addition of stoichiometric water eventually leads to excellent yields in all carbonylation cases.
- He, Chao,Zhang, Xiaohui,Huang, Ruofeng,Pan, Jing,Li, Jiaqiang,Ling, Xuege,Xiong, Yan,Zhu, Xiangming
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p. 4458 - 4462
(2014/08/05)
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- Rhodium-catalyzed aerobic coupling between aldehydes and arenesulfinic acid salts: A novel synthesis of aryl ketones
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A novel rhodium-catalyzed desulfinative coupling between aldehydes and arenesulfinic acid sodium salts was developed, generating a new protocol for the synthesis of aryl ketones. Most importantly, the coupling reaction uses molecular oxygen (O2) as the oxidant and finally releases sodium hydrogen sulfate (NaHSO4) from the reaction system; furthermore, this reaction occurs without the need for any additives. Copyright
- Rao, Honghua,Yang, Luo,Shuai, Qi,Li, Chao-Jun
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supporting information; experimental part
p. 1701 - 1706
(2011/09/14)
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- Direct benzylic oxidation with sodium hypochlorite using a new efficient catalytic system: TEMPO/Co(OAc)2
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Direct benzylic oxidation of arenes was achieved using NaClO/TEMPO/Co(OAc) 2. Various aromatic aldehydes and ketones were obtained from alkylarenes directly by benzylic oxidation in good to excellent yields. The reaction reactivity, selectivity, and scope of the reaction were investigated. Georg Thieme Verlag Stuttgart - New York.
- Jin, Can,Zhang, Li,Su, Weike
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supporting information; experimental part
p. 1435 - 1438
(2011/08/03)
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- Intermolecular N-heterocyclic carbene catalyzed hydroacylation of arynes
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A formal introduction: The conceptually new N-heterocyclic carbene catalyzed formal insertion of arynes into the Cformyl-H bond of aldehydes demonstrates the compatibility of nucleophilic NHCs with electrophilic arynes. This NHC-catalyzed hydroacylation of arynes allows the conversion of aliphatic, α,β-unsaturated, and aromatic aldehydes into aryl ketones; 27 examples and a preliminary mechanistic investigation are provided. Copyright
- Biju, Akkattu T.,Glorius, Frank
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supporting information; experimental part
p. 9761 - 9764
(2011/03/16)
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- Domino N-H/C-H bond activation: Palladium-catalyzed synthesis of annulated heterocycles using dichloro(hetero)arenes
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(Chemical Equation Presented) One after the other: A novel palladium-catalyzed domino reaction consisting of an amination and a direct C-H bond arylation allows for a general synthesis of annulated heterocycles starting from readily available 1,2-dichloroarenes and primary as well as secondary anilines (see scheme; Cy = cyclohexyl). This is high-lighted by an efficient synthesis of the natural product murrayafoline A.
- Ackermann, Lutz,Althammer, Andreas
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p. 1627 - 1629
(2008/02/13)
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- IMPROVED MANUFACTURING PROCEDURE FOR THE PREPARATION OF POLYMORPHIC FORM II OF CIS-(1S)-N-METHYL-4-(3,4-DICHLOROPHENYL)-1,2,3,4-TETRAHYDRO-1-NAPTHLENEAMINE HYDROCHLORIDE (SERTRALINE HYDROCHLORIDE)
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The present invention relates to the improved, scalable and efficient manufacturing procedure for the preparation of the antidepressant Cis-(1S)-N-Methyl-4-(3,4-Dichlorophenyl)-1,2,3,4-tetrahydro-1-napthaleneamine hydro chloride, Sertraline Hydrochloride polymorphic form II. The present invention further relates to the improved and modified procedures for preparing, separating and isolating the key intermediates involved in the preparationof Sertraline Hydrochloride polymorphic form II. The present invention also further relates to the use of novel reagents or a combination thereof and new methodologies to prepare some o'f the key intermediates involved in the preparation of Polymorphic Form II of Sertraline Hydrochloride.
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Page/Page column 20
(2008/06/13)
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- Cu-Mg (24: 76) alloy: An efficient catalyst for Friedel-Crafts acylation of arenes
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Friedel-Crafts acylation of different arenes was carried out in the presence of Cu-Mg (24:76) alloy under microwave irradiation and solvent-free conditions. Different substrates undergo acylation predominantly at the para-position. An efficient, simple, selective Friedel-Crafts acylation reaction affords good yields of the products and the catalyst could be easily recovered and recycled.
- Manjula, Krishnappa,Jayashankara, Vaderapura P.,Pasha, Mohamed A.
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p. 333 - 334
(2008/02/01)
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- Synthesis and photochromic properties of substituted 3H-naphtho[2,1-b] pyrans
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The synthesis and spectroscopic properties of novel 3H-naphtho[2,1-b]pyrans are described. Subtle variation of the colour of the photo-generated merocyanine dyes derived from these naphthopyrans can be accomplished by controlling the steric interactions between a terminal pyrrolidine donor group and a proximal substituent.
- Gabbutt, Christopher D.,Heron, B. Mark,Instone, Alicia C.,Horton, Peter N.,Hursthouse, Michael B.
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p. 463 - 471
(2007/10/03)
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- Synthesis of Diaryl Ketones Catalyzed by Al2O 3-ZrO2/S2O82- Solid Superacid
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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
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p. 479 - 485
(2007/10/03)
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- Zinc Mediated Friedel-Crafts Acylation in Solvent-Free Conditions under Microwave Irradiation
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Zn powder is found to catalyze the Friedel-Crafts acylation of aromatic compounds with acyl halides efficiently under microwave irradiation in solvent-free conditions. Activated substrates undergo acylation predominantly at the para-position. The Zn powder can be re-used up to six times after simple washing with diethyl ether and dilute HCl.
- Paul, Satya,Nanda, Puja,Gupta, Rajive,Loupy, Andre
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p. 2877 - 2881
(2007/10/03)
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- Aromatic sulfonium compounds, photoacid generators comprising the same, photopolymerizable compositions containing the same, stereolithographic resin compositions, and stereolithographic process
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Novel aromatic sulfonium compounds of general formula (I), photoacid generators comprising the same, and photopolymerizable compositions containing the same, capable of providing stereolithographic resin compositions which do not suffer from the hindrance to curing by oxygen, can easily give shaped articles having desired sizes by virtue of the high accuracy thereof in curing, and can attain a satisfactory curing depth owing to the high sensitivity thereof for radiant energy; and a stereolithographic process.
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- Gallium nonafluorobutanesulfonate as an efficient catalyst in Friedel- Crafts acylation
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Catalytic Friedel-Crafts acylation of even inactivated benzenes has been successfully carded out using a gallium compound. In the presence of a catalytic amount of gallium nonafluorobutanesulfonate (1-5 mol%), aromatics including inactivated benzenes such as fluorobenzene, chlorobenzene, and dichlorobenzene reacted with carboxylic acid chlorides or anhydrides to afford the corresponding aromatic ketones in good to excellent yields. Contrary to traditional understandings, catalytic Friedel-Crafts acylation was successfully carried out using the group 13 compound.
- Matsuo, Jun-Ichi,Odashima, Kazunori,Kobayashi, Shu
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p. 403 - 405
(2007/10/03)
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- (Trichloromethyl)benzene: A versatile reagent for the preparation of substituted benzophenones
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Aromatic and heteroaromatic compounds were benzoylated efficiently with (trichloromethyl)benzene in 1,2-dichloroethane in the presence of aluminium chloride in good yield.
- Ayyanger,Lahoti,Srinivasan,Daniel
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p. 322 - 324
(2007/10/02)
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- Extent of Charge Transfer in the Photoreduction of Phenyl Ketones by Alkylbenzenes
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Rate constants for triplet-state reaction of various ring-substituted benzophenones (BPs), acetophenones (APs), and α,α,α-trifluoroacetophenones (TFAs) with toluene and p-xylene have been determined by a combination of flash kinetics, steady-state quenching, and quantum yield measurements.The relative amounts of primary and tertiary radicals formed by reaction of the same ketons with p-cymene have also been measured.For all three types of ketones, rate constants correlate well with triplet ketone reduction potentials.The magnitude of the kinetic isotope effects observed with toluene-d8 and p-xylene-d10 diminishes as the ketones become easier to reduce.All of the ketone triplets react with alkylbenzenes primarily by a charge-transfer mechanism, with the rate-determining step changing from complexation to hydrogen transfer as the ketones become harder to reduce.The least reactive AP triplets probably react significantly via simple hydrogen atom abstraction as well.Those ketones with n,?* lowest triplets (all BPs and some APs) react with p-cymene to give primary/tertiary radical ratios that vary no more than a factor of 2 from the 0.40 value displayed by tert-butoxy radicals; those with ?,?* lowest triplets (TFAs and some APs) give ratios that favor primary radicals and that vary by an order of magnitude with the triplet ketone reduction potential.The variation in cymene product ratios reflect different orientations for attack on cymene by n,?* and ?,?* triplets and differing degrees of partial electron transfer within the exciplexes, which are not tight radical ion pairs.The variation seen for ?,?* triplets represents a stereoelectronic effect within face-to-face exciples, as evidenced by the excerptional behavior of p-diacylbenzenes, which give the highest ratio of tertiary radicals from cymene.There is no set intrinsic ratio of reactivity for ?,?* triplets vs. n,?* triplets in these CT reactions.The two types of triplets show similar reactivity for the more easily reduced triplets, with the harder to reduce ?,?* triplets being only one-tenth as reactive as n,?* triplets of comparable triplet reduction potential.When the extent of electron transfer in the exciplex is small, hydogen transfer is rate determining and ?,?* reactivity drops.A study of two radical reactions which generate benzyl and α-hydroxy-α-methylbenzyl radicals indicates that radical disproportionation cannot explain the low quantum yields (0.10) of most ketone-toluene photoreductions, which apparently involve substantial radiation less decay by the exciplex intermediates.
- Wagner, Peter J.,Truman, Royal J.,Puchalski, Alan E.,Wake, Ronald
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p. 7727 - 7738
(2007/10/02)
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- Process for the preparation of phenyl ketones
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A process for the preparation of phenyl ketones, characterized in that, in a first stage, a halo- or trihalomethylbenzene is reacted with a trihalomethylated aliphatic or aromatic compound in the presence of boron trifluoride in an amount such that the absolute pressure of boron trifluoride within the reaction vessel exceeds 1 bar, and in the presence of hydrofluoric acid as a solvent, and in that, in a second stage, the resultant product is hydrolyzed. The products are used as intermediates in the synthesis of compounds having a pharmaceutical or phytosanitary (e.g., herbicidal) activity.
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