- An efficient method to prepare aryl acetates by the carbonylation of aryl methyl ethers or phenols
-
Synthesis of valuable chemicals from lignin based compounds is critical for the application of biomass. Here, we develop a method of preparing aryl acetates by the carbonylation of aryl methyl ethers or phenols under low CO pressure. Good to excellent yields of aryl acetates were obtained using different substrates, and a possible reaction mechanism was proposed by conducting a series of control experiments. This method may provide a potential way for the utilization of lignin.
- Zhang, Dejin,Yang, Guoqiang,Xiong, Junping,Liu, Jia,Hu, Xingbang,Zhang, Zhibing
-
p. 2683 - 2687
(2021/02/16)
-
- Polyhydroxybenzoic acid derivatives as potential new antimalarial agents
-
With more than 200 million cases and 400,000 related deaths, malaria remains one of the deadliest infectious diseases of 2021. Unfortunately, despite the availability of efficient treatments, we have observed an increase in people infected with malaria since 2015 (from 211 million in 2015 to 229 million in 2019). This trend could partially be due to the development of resistance to all the current drugs. Therefore, there is an urgent need for new alternatives. We have, thus, selected common natural scaffolds, polyhydroxybenzoic acids, and synthesized a library of derivatives to better understand the structure–activity relationships explaining their antiplasmodial effect. Only gallic acid derivatives showed a noticeable potential for further developments. Indeed, they showed a selective inhibitory effect on Plasmodium (IC50 ~20 μM, SI > 5) often associated with interesting water solubility. Moreover, this has confirmed the critical importance of free phenolic functions (pyrogallol moiety) for the antimalarial effect. Methyl 4-benzoxy-3,5-dihydroxybenzoate (39) has, for the first time, been recognized as a potential lead for future research because of its marked inhibitory activity against Plasmodium falciparum and its significant hydrosolubility (3.72 mM).
- Degotte, Gilles,Francotte, Pierre,Pirotte, Bernard,Frédérich, Michel
-
-
- 4-Imidazol-1-yl-butane-1-sulfonic acid ionic liquid: Synthesis, structural analysis, physical properties and catalytic application as dual solvent-catalyst
-
4-Imidazol-1-yl-butane-1-sulfonic acid (ImBu-SO3H) has been successfully synthetized and fully characterized by FT-IR and high-resolution NMR spectroscopy (1H, 13C). The “plausible” alternative structures of ImBu-SO3H were discussed on the basis of its NMR data. The ionic liquid showed interesting dual solvent-catalyst property, which was studied experimentally for the acetylation of a variety of functionalized alcohols, phenols, thiols, amines and α-tocopherol (α-CTP) as the most active form of vitamin E with acetic anhydride and which provided good yields within a short reaction time. ImBu-SO3H was successfully recycled by product extraction with an average recovered yield of 82% for 5 subsequent runs. The catalytic activity of the recycled ImBu-SO3H showed almost no loss even after five consecutive runs.
- Khaligh, Nader Ghaffari,Mihankhah, Taraneh,Johan, Mohd Rafie,Juan, Joon Ching
-
p. 866 - 878
(2019/07/12)
-
- Highly efficient and recyclable acetylation of phenols and alcohols by nickel zirconium phosphate under solvent-free conditions
-
Nickel zirconium phosphate nanoparticles have been used as an efficient catalyst for the acetylation of a wide range of alcohols and phenols with acetic anhydride in good to excellent yields under solvent-free conditions. The steric and electronic properties of the different substrates had a significant influence on the reaction conditions required to achieve the acetylation. The catalyst used in the current study was characterized by inductively coupled plasma optical emission spectroscopy, X-ray diffraction, N2 adsorption-desorption, scanning electron microscopy, and transmission electron microscopy. This nanocatalyst could also be recovered and reused at least six times without any discernible decrease in its catalytic activity.
- Hajipour, Abdol Reza,Karimi, Hirbod,Kohi, Afshin
-
-
- Preparation, characterization and application of RHA/TiO2 nanocomposites in the acetylation of alcohols, phenols and amines
-
In this work, anatase-phase nano-titania was prepared by embedding in rice husk ash, and identified using a variety of techniques. The obtained nanocomposite (RHA/TiO2) was used as a green and inexpensive catalyst for the promotion of the acetylation of alcohols, phenols and amines with Ac2O at room temperature under solvent free conditions. The procedure gave the products in excellent yields during all reaction times. Also this catalyst can be reused for several times without loss of its catalytic activity.
- Seddighi, Mohadeseh,Shirini, Farhad,Goli-Jolodar, Omid
-
p. 1003 - 1010
(2016/08/08)
-
- Acetylation of alcohols and phenols under solvent-free conditions using iron zirconium phosphate
-
Iron zirconium phosphate (ZPFe) nanoparticles were found to function as an efficient catalyst for the acetylation of a wide range of alcohols and phenols using acetic anhydride, generating good to excellent yields under solvent-free conditions. The steric and electronic properties of various substrates had a significant influence on the reaction conditions required to achieve the acetylation. The catalyst used in the current study was characterized by inductively coupled plasma-optical emission spectrometry, X-ray diffraction, N2 adsorption-desorption, scanning electron microscopy, and transmission electron microscopy. These analyses revealed that the interlayer distance in the catalyst increased from 7.5 to 9.3 ? when Fe3+ was intercalated between the layers, whereas the crystallinity of the material was reduced. This nanocatalyst could also be recovered and reused at least six times without any discernible decrease in its catalytic activity. This new method for the acetylation of alcohols and phenols has several important advantages, including mild and environmentally friendly reaction conditions, as well as good to excellent yields and a facile work-up.
- Hajipour, Abdol R.,Karimi, Hirbod,Masti, Amir
-
p. 595 - 602
(2015/09/28)
-
- Acetylation of alcohols and phenols under solvent-free conditions using copper zirconium phosphate
-
Copper zirconium phosphate nanoparticles have been used as an efficient catalyst for the acetylation of a wide range of alcohols and phenols with acetic anhydride in good to excellent yields under solvent-free conditions. The steric and electronic properties of the different substrates had a significant influence on the reaction conditions required to achieve the acetylation. The catalyst used in the current study was characterized by inductively-coupled plasma optical emission spectroscopy, energy dispersive spectroscopy, X-ray diffraction, N2 adsorption-desorption, scanning electron microscopy, and transmission electron microscopy. These analyses revealed that the interlayer distance in the catalyst increased from 7.5 to 8.0 ? when Cu2+ was intercalated between the layers, whereas the crystallinity of the material was reduced. This nanocatalyst could also be recovered and reused at least six times without any discernible decrease in its catalytic activity. This new method for the acetylation of alcohols and phenols has several key advantages, including mild and environmentally friendly reaction conditions, as well as good to excellent yields and a facile work-up.
- Hajipour, Abdol R.,Karimi, Hirbod
-
p. 1982 - 1989
(2015/09/28)
-
- Poly(N-vinylimidazole) as an efficient catalyst for acetylation of alcohols, phenols, thiols and amines under solvent-free conditions
-
Poly(N-vinylimidazole) is able to promote instantaneous quantitative acetylation of a variety of functionalized alcohols, phenols, thiols and amines with acetic anhydride at room temperature under solvent-free conditions. This new method consistently has excellent yields and the catalyst can be reused and recovered several times. Furthermore, the reaction can even be carried out on a larger scale. The Royal Society of Chemistry.
- Khaligh, Nader Ghaffari
-
-
- A succinimide-N-sulfonic acid catalyst for acetylation reactions in absence of a solvent
-
A small amount of succinimide-N-sulfonic acid efficiently catalyzed the acetylation of a variety alcohols, phenols, thiols, amines and aldehydes with acetic anhydride at room temperature under solvent free conditions. This catalyst has the advantages of excellent yields and short reaction times and the reaction can be carried out on a large scale, which makes it potentially useful for industrial applications.
- Shirini, Farhad,Khaligh, Nader Ghaffari
-
p. 695 - 703
(2013/08/25)
-
- New porphyrin-polyoxometalate hybrid materials: Synthesis, characterization and investigation of catalytic activity in acetylation reactions
-
New hybrid complexes based on covalent interaction between 5,10,15,20-tetrakis(4-aminophenyl)porphyrinatozinc(ii) and 5,10,15,20- tetrakis(4-aminophenyl)porphyrinatotin(iv) chloride, and a Lindqvist-type polyoxometalate, Mo6O192-, were prepared. These new porphyrin-polyoxometalate hybrid materials were characterized by 1H NMR, FT IR and UV-Vis spectroscopic methods and cyclic voltammetry. These spectro- and electrochemical studies provided several spectral data for synthesis of these compounds. Cyclic voltammetry showed the influence of the polyoxometalate on the redox process of the porphyrin ring. The catalytic activity of tin(iv)porphyrin-hexamolybdate hybrid material was investigated in the acetylation of alcohols and phenols with acetic anhydride. The reusability of this catalyst was also investigated.
- Araghi, Mehdi,Mirkhani, Valiollah,Moghadam, Majid,Tangestaninejad, Shahram,Mohammdpoor-Baltork, Iraj
-
p. 11745 - 11752
(2013/02/23)
-
- Preparation, characterization and use of poly(4-vinylpyridinium) perchlorate as a new, efficient, and versatile solid phase catalyst for acetylation of alcohols, phenols and amines
-
Poly(4-vinylpyridine) perchlorate, is a supported, recyclable, eco-benign catalyst for the reaction acetylation of structurally diverse alcohols, phenols and amines at room temperature under solvent-free conditions. The catalyst was studied by FT-IR, X-ray diffraction, Scanning Electron Microscope and Thermo-gravimetric Analyses. All the products were extensively characterized by 1H NMR, FT-IR, GC-MS and melting point analyses. The catalyst can be recovered and reused without loss of activity. The work-up of the reaction consists of a simple filtration, followed by concentration of the crude product and purification. It is important to point out that a large-scale reaction is possible using a same amount of catalyst.
- Khaligh, Nader Ghaffari
-
-
- O-acetylation: Synthesis of acetylated phenols from aryl-methyl ethers over boron alkoxides
-
A new acetylation procedure has been applied to 13 aryl-methyl ethers using boron chemistry. In this procedure, demethylation of aryl-methyl ethers and acetylation of the resulting phenols were combined into one procedure in order to shorten the number of stages and to achieve easy purification. Eleven known with/without bromine and two new [bis(3,4-diacetoxyphenyl)methanone and 5,5'-methylenebis(1,2-diacetoxy-3,4-dibromobenzene) (a natural bromophenol's acetylated derivative)] acetylated arene compounds were synthesised from their methoxy derivatives by this method. The effectiveness of the method was illustrated by producing an acetylated natural bromophenol from its methyl ether. The phenol form was obtained by hydrolysing the acetylated natural bromophenol. Thus, the advantage of this method in the natural product chemistry of phenolic compounds was confirmed.
- Balaydin, Halis T.
-
scheme or table
p. 238 - 240
(2012/09/08)
-
- Synthesis, characterization and application of poly(4-vinylpyridine)- supported Bronsted acid as reusable catalyst for acetylation reaction
-
Poly(4-vinylpyridine)-supported Bronsted acids (P4VP-HX) were prepared by wet impregnation technique. These supported acids were found as efficient heterogeneous green catalysts for acetylation of alcohol, amine and phenol with different catalytic activities. The wide application of P4VP-HX as reusable solid acid catalyst in organic reactions is possible because of its simple preparation and handling, stability, simple work up procedure.
- Borah, Kalyan Jyoti,Dutta, Papia,Borah, Ruli
-
experimental part
p. 225 - 228
(2011/11/06)
-
- Highly efficient and versatile acetylation of alcohols, phenols and amines catalyzed by methylenediphosphonic acid (MDP) under solvent-free conditions
-
Methylenediphosphonic Acid (MDP) was found to be a simple, cheap and reusable heterogeneous catalyst for the acetylation of structurally diverse alcohols, phenols and amines with acetic anhydride under solvent-free conditions at room temperature. This method showed preferential selectivity for the acetylation of the amino group in the presence of hydroxyl group. The method is very mild and the yields were in excellent.
- Xie, Minhao,Wang, Hongyong,Wu, Jun,He, Yongjun,Liu, Yaling,Zou, Pei
-
experimental part
p. 884 - 886
(2012/04/23)
-
- Electron-deficient [TiIV(salophen)(OTf)2]: A new and highly efficient catalyst for the acetylation of alcohols and phenols with acetic anhydride
-
In the present work, a highly efficient method for acetylation of alcohols and phenols with acetic anhydride catalyzed by high-valent [Ti IV(salophen)(OTf)2] is reported. Under these conditions, primary, secondary and tertiary alcohols as well as phenols were acetylated with short reaction times and high yields. The catalyst was reused several times without loss of its catalytic activity.
- Yadegari, Maryam,Moghadam, Majid,Tangestaninejad, Shahram,Mirkhani, Valiollah,Mohammadpoor-Baltork, Iraj
-
experimental part
p. 2237 - 2243
(2011/10/03)
-
- Investigation of catalytic activity of high-valent vanadium(IV) tetraphenylporphyrin: A new, highly efficient and reusable catalyst for acetylation of alcohols and phenols with acetic anhydride
-
In the present work, the catalytic activity of high-valent tetraphenylporphyrinatovanadium(IV) trifluoromethanesulfonate, [V IV(TPP)(OTf)2], in the acetylation of alcohols and phenols with Ac2O is reported. This new V(IV) catalyst was used as an efficient catalyst for not only primary alcohols (benzylic and aliphatic) but also sterically-hindered secondary and tertiary alcohols with acetic anhydride and the corresponding acetates were obtained in 85-99% yield and 0.5-15 min. Acetylation of phenols with acetic anhydride was also performed to afford the desired acetates in 88-99% and 1.5-20 min. This catalyst can be reused several times without loss of its catalytic activity.
- Taghavi, S. Abdolmanaf,Moghadam, Majid,Mohammadpoor-Baltork, Iraj,Tangestaninejad, Shahram,Mirkhani, Valiollah,Khosropour, Ahmad Reza
-
experimental part
p. 159 - 164
(2011/12/16)
-
- Polystyrene-bound electron-deficient tin(IV) porphyrin: A new, highly efficient, robust and reusable catalyst for acetylation of alcohols and phenols with acetic anhydride
-
In the present work, tetrakis(p-aminophenyl)porphyrinatotin(IV) trifluoromethanesulfonate, [SnIV(TNH2PP)(OTf) 2], supported on chloromethylated polystyrene was prepared and characterized by elemental analysis, FT IR and diffuse reflectance UV-Vis spectroscopic methods. This new heterogenized catalyst was used for acetylation of alcohols and phenols with acetic anhydride in short reaction times and high yields. The catalyst is of high reusability and stability in the acetylation reactions and was recovered several times without loss of its initial activity and catalyst leaching.
- Moghadam, Majid,Tangestaninejad, Shahram,Mirkhani, Valiollah,Mohammadpoor-Baltork, Iraj,Gharaati, Shadab
-
scheme or table
p. 1080 - 1087
(2012/03/11)
-
- Air-stable titanocene bis(perfluorooctanesulfonate) as a new catalyst for acylation of alcohols, phenols, thiols, and amines under solvent-free condition
-
Air-stable titanocene bis(perfluorooctanesulfonate) [Cp2Ti(OSO2C8F17)2] that shows high Lewis acidity was prepared from Cp2TiCl2 and AgOSO2C8F17. The compound was characterized by different techniques, and examined as a catalyst for acylation reactions. It was found that using equimolar acetic anhydride as acetylating agent and under solvent-free condition, Cp2Ti(OSO2C8F17)2 exhibits high activity and selectivity in the acetylation of various alcohols, phenols, thiols, and amines. Also, good catalytic efficiency is observed in the acylation of 2-phenylethanol across various acylating reagents. The catalyst can be reused without loss of activity in a test of ten cycles. The Cp2Ti(OSO2C8F17)2 catalyst affords a simple, efficient and general method for the acylation of alcohols, phenols, thiols, and amines.
- Qiu, Renhua,Zhang, Guoping,Ren, Xiaofang,Xu, Xinhua,Yang, Ronghua,Luo, Shenglian,Yin, Shuangfeng
-
experimental part
p. 1182 - 1188
(2010/06/13)
-
- Magnesium bistrifluoromethanesulfonimide as a new and efficient acylation catalyst
-
Magnesium bistrifluoromethanesulfonimide catalyzed the acetylation of phenols, alcohols, and thiols under solvent-free conditions at room temperature and in short times. Electron-deficient and sterically hindered phenols provided excellent yields. The catalyst was found to be general for acylation with other anhydrides, such as propionic, isobutyric, pivalic, chloroacetic, and benzoic anhydrides. The rate of acylation was influenced by the electronic and steric factors associated with the anhydride. The reaction with less electrophilic anhydrides (e.g., chloroacetic and benzoic anhydrides) required higher temperature (～80 °C). Chemoselective acetylation, pivalation, and benzoylation took place with acid-sensitive alcohols without any competitive dehydration/rearrangement.
- Chakraborti, Asit K.,Shivani
-
p. 5785 - 5788
(2007/10/03)
-
- Rapid formation of acetates under microwave irradiation using montmorillonite acid clay catalyst
-
The combination of microwave irradiation and montmorillonite [H +] clay catalyst dramatically enhances the rate of formation of acetates of alcohols, phenols and amines when treated with acetic anhydride. A series of acetates have been prepared with significantly low reaction times in very good to excellent yields.
- Mallavadhani, Uppuluri V.,Sahoo, Laxmidhar,Roy, Subhra
-
p. 2175 - 2177
(2007/10/03)
-
- Zirconiuni(IV) chloride as a new, highly efficient, and reusable catalyst for acetylation of phenols, thiols, amines, and alcohols under solvent-free conditions
-
Zirconium(IV) chloride has been found to be a new, highly efficient, and reusable catalyst for acetylation of structurally diverse phenols, thiols, amines, and alcohols under solvent-free condtions. Acetylation of sterically hindered and electron deficient phenols is achieved in excellent yields with stoichiometric amounts of Ac2O at room temperature. Acid-sensitive alcohols undergo acetylation with excellent chemoselectivity without competitive side reactions such as dehydration or rearrangement. The mild Lewis acid property of the catalyst enables the acetylation to be carried out with optically active substrates without any detrimental effect on the optical purity.
- Chakraborti, Asit K.,Gulhane, Rajesh
-
p. 627 - 630
(2007/10/03)
-
- Electrostatic catalysis by ionic aggregates: Scope and limitations of Mg(ClO4)2 as acylation catalyst
-
Alkali and alkaline earth metal perchlorates exhibit electrostatic catalysis in the activation of anhydrides for the acylation reaction. Perchlorates with higher values of the charge-size function of the metal ion exhibit better catalytic activity following the order Mg(ClO4) 2>Ba(ClO4)2>LiClO4. Acylation of structurally diverse phenols, thiols, alcohols, and amines have been carried out with stoichiometric amounts of anhydride at room temperature under solvent free conditions in the presence of catalytic amount of Mg(ClO4) 2. Sterically hindered and electron deficient phenols are efficiently acylated. Acylation with sterically hindered anhydrides such as iso-butyric, pivalic, and benzoic anhydrides are carried out with phenols and alcohols in excellent yields. Acid-sensitive alcohols are acylated in excellent yields without any competitive side reactions.
- Chakraborti, Asit K.,Sharma, Lalima,Gulhane, Rajesh,Shivani
-
p. 7661 - 7668
(2007/10/03)
-
- Fluoroboric acid adsorbed on silica gel as a new and efficient catalyst for acylation of phenols, thiols, alcohols, and amines
-
Fluoroboric acid supported on silica gel efficiently catalyzes acylation of structurally diverse phenols, alcohols, thiols, and amines under solvent free conditions. Acid-sensitive alcohols are smoothly acylated without competitive side reactions.
- Chakraborti, Asit K.,Gulhane, Rajesh
-
p. 3521 - 3525
(2007/10/03)
-
- Perchloric acid adsorbed on silica gel as a new, highly efficient, and versatile catalyst for acetylation of phenols, thiols, alcohols, and amines
-
Perchloric acid adsorbed on silica gel efficiently catalyses acetylation of structurally diverse phenols, alcohols, thiols, and amines under solvent free conditions.
- Chakraborti, Asit K.,Gulhane, Rajesh
-
p. 1896 - 1897
(2007/10/03)
-
- Indium(III) chloride as a new, highly efficient, and versatile catalyst for acylation of phenols, thiols, alcohols, and amines
-
Indium(III) chloride efficiently catalyses the acylation of structurally diverse phenols, alcohols, thiols, and amines under solvent free conditions. Acid sensitive alcohols are smoothly acylated without competitive side reactions. Acylation of 2-hydroxynaphthalene is carried out with carboxylic acids adopting the mixed anhydride protocol using trifluoroacetic anhydride.
- Chakraborti, Asit K.,Gulhane, Rajesh
-
p. 6749 - 6753
(2007/10/03)
-
- Rapid and efficient acetylation of alcohols and phenols with acetic anhydride using tin(IV) porphyrin as catalyst
-
The efficient and rapid esterification of alcohols and phenols in acetic anhydride was achieved by tin(IV) tetraphenylporphyrin perchlorate [SnIV (tpp) (ClO4)2] as catalyst in high yields. SnIV (tpp) (ClO4)2 showed highly catalytic activity on the acetylation reaction.
- Tangestaninejad, Shahram,Habibi, Mohammad Hossein,Mirkhani, Valiollah,Moghadam, Majid
-
p. 1337 - 1343
(2007/10/03)
-
- Cobalt polyoxometalate, CoW12O405- as a new reusable catalyst for the direct, fast, and efficient acetylation of alcohols and phenols under solventless conditions
-
Alcohols and phenols were efficiently acetylated with acetic anhydride without solvent in the presence of 0.01 molar equiv. of cobalt polyoxometalate (CoW12O405-).
- Habibi,Tangestaninejad,Mirkhani,Yadollahi
-
p. 863 - 867
(2007/10/03)
-
- Preparation of chlorosyringols and chloropyrogallols - Components of pulp bleaching effluents
-
The preparation and properties of chlorosyringols and chloropyrogallols, components of pulp bleaching effluents, and their acetates are given. The compounds are obtained mainly by direct chlorination of both phenols or of syringol acetate with various chlorinating reagents. 5-Chloropyrogallol and 4,5-dichloropyrogallol were the products of demethylation of 5-chloro-3-methoxycatechol acetate and 4,5-dichloro-3-methoxycatechol acetate, respectively. The acetates of all ten chloro compounds were separated by gas chromatography. Electron impact mass spectra and 1H and 13C NMR data for the acetates are given.
- Smith,Wearne,Wallis
-
p. 921 - 930
(2007/10/03)
-
- Process for preparing an organic compound
-
Pyrogallol or a salt thereof is prepared by a process comprising deoximating cyclohexane-1,2,3-trione oxime or an oxime derivative thereof or a salt of either. Preferably the oxime itself is exployed, especially the 1,3-dioxime. The deoximation is preferably effected by hydrolysis.
- -
-
-
