4044-60-4Relevant academic research and scientific papers
Friedel-crafts acylation of p-Xylene over sulfonated zirconium terephthalates
Chung, Young-Min,Kim, Hee-Young,Ahn, Wha-Seung
, p. 817 - 824 (2014)
In this study, a sulfonated Zr-terephthalate metal-organic framework (MOF) (UiO-66-SO3H) was prepared using two different methods: post-synthetic grafting onto the Zr open metal sites and direct solvothermal method using monosodium 2-sulfoterephthalate. Their catalytic activities for the acid-catalyzed Friedel- Crafts acylation of p-xylene with benzoyl chloride were compared. The physicochemical properties and catalytic performance of the functionalized MOF structure was found to be strongly dependent on the synthesis scheme. UiO-66-SO3H prepared by a direct solvothermal route exhibited excellent catalytic activity and stability compared to that prepared by post-synthetic grafting. Springer Science+Business Media New York 2014.
Acidic Alkali Metal Salts and Ammonium Salts of Keggin-type Heteropolyacids as Efficient Solid Acid Catalysts for Liquid-phase Friedel-Crafts Reactions
Izumi, Yusuke,Ogawa, Mayumi,Nohara, Wataru,Urabe, Kazuo
, p. 1987 - 1990 (1992)
Acidic salts of the Keggin-type heteropolytungstic acids prepared through partial neutralization with alkali metal carbonates or ammonium hydroxide had relatively large surface areas, and showed high catalytic efficiency as insoluble solid acid catalysts in Friedel-Crafts alkylation and acylation using benzyl chloride, benzoyl chloride, benzoic anhydride, benzoic acid, acetic anhydride, and acetic acid as electrophiles.
High activity of Ga-containing nanosponge MTW zeolites in acylation of p-xylene
Zhang, Jin,Vesely, Ond?ej,Shamzhy, Mariya V.,Opanasenko, Maksym,?ejka, Ji?i
, p. 110 - 115 (2020)
Aluminosilicate and gallosilicate MTW zeolites were prepared in the bulk and nanosponge form by direct hydrothermal synthesis. Designed materials were tested in acylation of p-xylene with benzoyl chloride and compared with large pore zeolite *BEA and medium pore zeolite MFI. Nanosponge MTW exhibited generally better performance than bulk MTW zeolites due to higher accessibility of the catalyst′s active sites in nanosponge zeolite. Selective transformation of benzoyl chloride towards target 2,5-dimethylbenzophenone was achievable over nanosponge MTW zeolites. The gallosilicate nanosponge MTW exhibited significantly higher conversion (61%) of benzoyl chloride than its aluminosilicate counterpart (27%) with the same concentration of Br?nsted acid sites (0.04 mmol/g). This result is clearly caused by the suitable strength of acid centres in Ga-MTW, which enables the sufficient activation of BzCl molecules as well as efficient desorption of formed polar products. Additionally, the gallosilicate MTW outperformed both conventional zeolites *BEA and MFI used as reference materials.
Selective Oxidation of Alkylarenes to the Aromatic Ketones or Benzaldehydes with Water
Du, Jihong,Duan, Baogen,Liu, Kun,Liu, Renhua,Yu, Feifei,Yuan, Yongkun,Zhang, Chenyang,Zhang, Jin
supporting information, (2022/02/09)
Here a palladium-catalyzed oxidation method for converting alkylarenes into the aromatic ketones or benzaldehydes with water as the only oxygen donor is reported. This C-H bond oxidation functionalization does not require other oxidants and hydrogen accep
A palladium-catalyzed C-H functionalization route to ketones: Via the oxidative coupling of arenes with carbon monoxide
Arndtsen, Bruce A.,Kinney, R. Garrison,Levesque, Taleah M.
, p. 3104 - 3109 (2020/03/27)
We describe the development of a new palladium-catalyzed method to generate ketones via the oxidative coupling of two arenes and CO. This transformation is catalyzed by simple palladium salts, and is postulated to proceed via the conversion of arenes into high energy aroyl triflate electrophiles. Exploiting the latter can also allow the synthesis of unsymmetrical ketones from two different arenes.
Stereochemical outcomes of C–F activation reactions of benzyl fluoride
Champagne, Pier Alexandre,Desroches, Justine,Keddie, Neil S.,O'Hagan, David,Paquin, Jean-Fran?ois
supporting information, p. 106 - 113 (2020/05/06)
In recent years, the highly polar C–F bond has been utilised in activation chemistry despite its low reactivity to traditional nucleophiles, when compared to other C–X halogen bonds. Paquin's group has reported extensive studies on the C–F activation of benzylic fluorides for nucleophilic substitutions and Friedel–Crafts reactions, using a range of hydrogen bond donors such as water, triols or hexafluoroisopropanol (HFIP) as the activators. This study examines the stereointegrity of the C–F activation reaction through the use of an enantiopure isotopomer of benzyl fluoride to identify whether the reaction conditions favour a dissociative (SN1) or associative (SN2) pathway. [2H]-Isotopomer ratios in the reactions were assayed using the Courtieu 2H NMR method in a chiral liquid crystal (poly-γ-benzyl-L-glutamate) matrix and demonstrated that both associative and dissociative pathways operate to varying degrees, according to the nature of the nucleophile and the hydrogen bond donor.
Controlled photo-flow oxidative reaction (UV-FOR) platform for ultra-fast phthalide and API synthesis
Aand, Dnyaneshwar,Karekar, Sanjeev,Mahajan, Bhushan,Pawar, Amit B.,Singh, Ajay K.
supporting information, p. 4584 - 4590 (2018/10/23)
An integrated photo-flow oxidative reaction (UV-FOR) platform approach is presented for the synthesis of phthalides. The current protocol is catalyst-free, and uses economical and abundant hydro-carbons and hydrocarbon derivatives such as benzoic acid, benzene, and xylene, as starting materials. The reaction is performed using oxygen as a green oxidant in a time- and labour-efficient manner. This integrated approach has been shown to be successful in making a UV-FOR platform suitable for the on-demand synthesis of phthalides and their further syntheses to 2-arylmethylbenzoic acids and arylogous Michael addition products under relatively mild conditions. The current protocol was further extended to the gram scale synthesis of an ischemic stroke-relevant active pharmaceutical ingredient (API), 3-N-butylphthalide (NBP), in a continuous flow process.
Stereochemical outcomes of C-F activation reactions of benzyl fluoride
Keddie, Neil S.,Champagne, Pier Alexandre,Desroches, Justine,Paquin, Jean-Fran?ois,O'Hagan, David
supporting information, p. 106 - 113 (2018/02/06)
In recent years, the highly polar C-F bond has been utilised in activation chemistry despite its low reactivity to traditional nucleophiles, when compared to other C-X halogen bonds. Paquin's group has reported extensive studies on the C-F activation of benzylic fluorides for nucleophilic substitutions and Friedel-Crafts reactions, using a range of hydrogen bond donors such as water, triols or hexafluoroisopropanol (HFIP) as the activators. This study examines the stereointegrity of the C-F activation reaction through the use of an enantiopure isotopomer of benzyl fluoride to identify whether the reaction conditions favour a dissociative (SN1) or associative (SN2) pathway. [2H]-Isotopomer ratios in the reactions were assayed using the Courtieu 2H NMR method in a chiral liquid crystal (poly-γ-benzyl-L-glutamate) matrix and demonstrated that both associative and dissociative pathways operate to varying degrees, according to the nature of the nucleophile and the hydrogen bond donor.
P -Selective (sp2)-C-H functionalization for an acylation/alkylation reaction using organic photoredox catalysis
Pandey, Ganesh,Tiwari, Sandip Kumar,Singh, Bhawana,Vanka, Kumar,Jain, Shailja
, p. 12337 - 12340 (2017/11/20)
p-Selective (sp2)-C-H functionalization of electron rich arenes has been achieved for acylation and alkylation reactions, respectively, with acyl/alkylselenides by organic photoredox catalysis involving an interesting mechanistic pathway.
An efficient and green method for regio- and chemo-selective Friedel-Crafts acylations using a deep eutectic solvent ([CholineCl][ZnCl2]3)
Tran, Phuong Hoang,Nguyen, Hai Truong,Hansen, Poul Erik,Le, Thach Ngoc
, p. 37031 - 37038 (2016/05/24)
[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.
