cas 830-81-9, 1-Naphthyl acetate | Articles data

Articles about 830-81-9Total 140 be found

Article title
Article abstract
Author
Journal number and time
Download

Aromatic Carbon-Hydrogen Bond Activation. Novel Synthesis of 1-Naphthol Derivatives by Palladium Catalysed Cyclocarbonylation of Cinnamyl Compounds
Palladium catalysed cyclocarbonylation of cynnamyl compounds gives 1-naphthol derivatives in good yields whereas the similar carbonylation of trans-β-bromostyrene yields a polymer containing benzindanone units.
Koyasu, Yukio,Matsuzaka, Hiroyuki,Hiroe, Yoshitaka,Uchida, Yasuzo,Hidai, Masanobu
p. 575 - 576
(1987)
Read Online

Isotopic Fractionation Factor of the Hydrogen-Bonded Complex AcO(1-)...(HOAc)n and Kinetic and Equilibrium Solvent Isotope Effects on Reactions of Acetate Ion in Acetic Acid
A value of φ 0.58+/-0.05 has been obtained for the deuterium fractionation factor of the hydrogen-bonded complex AcO(1-)...(HOAc)n from (1)H n.m.r. studies of solutions of potassium acetate in AcOH and 97percent AcOD-3percent AcOH.The result is used to account for the kinetic solvent isotope effect 0.66+/-0.10 measured for formation of acetic anhydride from 2,4,6-trinitrophenyl acetate in AcOH and AcOD in the presence of potassium acetate.The equilibrium solvent isotope effect on complex formation between 2,4,6-trinitrophenol and acetate ion in AcOH and 97percent AcOD-3percent AcOH KAcOH/KAcOD 0.83+/-0.1, leads to a value φ ca. 0.7 for the complex (1-).
Clark, David R.,Emsley, John,Hibbert, Frank
p. 919 - 922
(1988)
Read Online

Method for promoting acylation of amine or alcohol by carbon dioxide
The invention relates to a method for promoting acylation of amine or alcohol by carbon dioxide, which comprises the following steps of: mixing an amine compound, carboxylate or thiocarboxylate compound and a reaction solvent under the action of carbon dioxide, and reacting to obtain an amide compound, or under the action of carbon dioxide, mixing the alcohol compound, the thiocarboxylate compound and the reaction solvent [gamma]-valerolactone, and reacting to obtain the ester compound. According to the invention, under the promotion action of carbon dioxide, carboxylate or thiocarboxylate is used as an acylation reagent, and amine and alcohol are converted into amide and ester compounds in the absence of a transition metal catalyst, so that acylation reagents such as acyl chloride or anhydride with irritation and corrosivity are avoided; and the method has the advantages of simple operation, mild reaction conditions, high tolerance of substrate functional groups, strong applicability and high yield, and provides an efficient, reliable and economical preparation method for synthesis of amide and ester compounds.
-
Paragraph 0034-0035

(2021/05/29)

Direct Acetoxylation of Arenes
Acetoxylation of arenes is an important reaction and an unmet need in chemistry. We report a metal-free, direct acetoxylation reaction using sodium nitrate under an anhydrous environment of trifluoroacetic acid, acetic acid, and acetic anhydride. Arenes (31 examples), with oxidation potentials (Eox, in V vs SCE) lower than benzene (2.48 V), were acetoxylated with good yields and regioselectivity. A stepwise, single electron-transfer mechanism is proposed.
Hong Nguyen, Thi Anh,Hou, Duen-Ren
supporting information
p. 8127 - 8131
(2021/08/23)

Novel naphthyl based 1,2,4-trioxanes: Synthesis and in vivo efficacy in the Plasmodium yoelii nigeriensis in Swiss mice
A new series of 1,2,4-trioxanes 9a1-a4, 9b1-b4, 10–13 and 9c1-c4 were synthesized and evaluated against multidrug-resistant Plasmodium yoelii nigeriensis in Swiss mice via oral and intramuscular (i.m.) routes. Adamantane-based trioxane 9b4, the most active compound of the series, provided 100% protection to the infected mice at the dose 48 mg/kg × 4 days and 100% clearance of parasitemia at the dose 24 mg/kg × 4 days via oral route. Adamantane-based trioxane 9b4, is twice active than artemisinin. We have also studied the photooxygenation behaviour of allylic alcohols 6a-b (3-(4-alkoxynaphthyl)-but-2-ene-1-ols) and 6c (3-[4-(tert-butyl-dimethyl-silanyloxy)-naphthalen-1-yl]-but-2-en-1-ol). Being behaving as dienes, they furnished corresponding endoperoxides, while behaving as allylic alcohols, they yielded β-hydroxyhydroperoxides. All the endoperoxides (7a-c) and β-hydroxyhydroperoxides (8a-c) have been separately elaborated to the corresponding 1,2,4-trioxanes, except from endoperoxide 7c. It is worthy to note that TBDMS protected naphthoyl endoperoxide 7c unable to deliver 1,2,4-trioxane, which demonstrated the strength of the O-Si bond is not easy to cleave under acidic condition.
Hassam, Mohammad,Karnatak, Manvika,Kumar Yadav, Dinesh,Prakash Verma, Ved,Puri, Sunil K.,Rawat, Varun,Sharma, Siddharth,Singh, Chandan,Vanangamudi, Murugesan
(2021/09/28)

Steric effect of NHC ligands in Pd(II)–NHC-catalyzed non-directed C–H acetoxylation of simple arenes
Although there has been a lot of progress in oxidative arene C–H functionalization reactions catalyzed by Pd(II/IV) system, the non-directed, site-selective functionalization of arene molecules is still challenging. It has been established that ligands play a pivotal role in controlling rate- as well as selectivity-determining step in a catalytic cycle involving well-defined metal-ligand bonding. N-heterocyclic carbene (NHC) ligands have had a tremendous contribution in the recent extraordinary success of achieving high reactivity and excellent selectivity in many catalytic processes including cross-coupling and olefin-metathesis reactions. However, the immense potential of these NHC ligands in improving site-selectivity of non-directed catalytic C–H functionalization reactions of simple arenes is yet to be realized, where overriding the electronic bias on deciding selectivity is a burdensome task. The presented work demonstrated an initiative step in this regard. Herein, a series of well-defined discrete [Pd(NHCR′R)(py)I2] complexes with systematically varied degree of spatial congestion at the Pd centre, exerted through the R and R’ substituents on the NHC ligand, were explored in controlling the activity as well as the site-selectivity of non-directed acetoxylation of representative monosubstituted and disubstituted simple arenes (such as toluene, iodobenzene and bromobenzene, naphthalene and 1,2-dichlorobenzene). The resulting best yields were found to be 75% for toluene and 65% for bromobenzene with [Pd(NHCMePh)(py)I2], 75% for iodobenzene and 79% for naphthalene with [Pd(NHCMeMe)(py)I2], and 41% for 1,2-dichlorobenzene with [Pd(NHCCyCy)(py)I2]. Most importantly, with increasing the bulkiness of the NHC ligand in the complexes, the selectivity of the distal C-acetoxylated products in comparison to the proximal ones, was enhanced to a great extent in all cases. Considering the vast library of NHC ligands, this study underscores the future opportunity to develop more strategies to improve the activity and the crucial site-selectivity of C–H functionalization reactions in simple as well as complex organic molecules.
Mandal, Tanmoy,Yadav, Sudha,Choudhury, Joyanta
(2021/09/06)

Photo/Thermal Dual Responses in Aqueous-Soluble Copolymers Containing 1-Naphthyl Methacrylate
Photoresponsive polymers capable of luminescence switching are attracting significant interest due to their potential application in fluorescence patterning, bioimaging, optical data storage, and anti-counterfeiting. In this work, we have developed aqueous-soluble copolymers of 1-naphthyl methacrylate and oligo(ethylene glycol) methyl ether methacrylate [P(1-NMA-co-OEGMA)] that undergo a significant shift in fluorescence emission wavelength after UV irradiation. Irradiation of the 1-naphthyl methacrylate moieties results in the photo-Fries rearrangement to form hydroxy aryl ketones, which exhibit strong emission at 475 nm through excited-state intramolecular proton transfer (ESIPT) and excited-state proton transfer (ESPT). The resultant shift in fluorescence emission maximum from 338 to 475 nm after rearrangement can potentially be exploited for fluorescence patterning. Furthermore, the copolymers are thermally sensitive in aqueous solutions. The lower critical solution temperature (LCST) of the copolymers depends on the content of hydrophobic 1-naphthyl methacrylate units; the photo-Fries rearrangement results in a more polar structure, shifting the LCST to a higher temperature. Of note, the temperature-triggered volume phase transition of copolymer hydrogels selectively ″switches off″ fluorescence arising from the ESPT mechanism, while the ESIPT emission is unaffected. We also demonstrate that films formed by coating the copolymers onto various substrates can be selectively patterned to form gradients in fluorescence intensity. These versatile P(1-NMA-co-OEGMA) copolymers are simple to prepare at low cost, demonstrate effective photoswitching, and have excellent water solubility, thus ensuring potential applications in a number of important areas.
Zhao, Jiacheng,Er, Gerald Tze Kwang,McCallum, Francis J.,Wang, Sisi,Fu, Changkui,Kaitz, Joshua A.,Cameron, James F.,Trefonas, Peter,Blakey, Idriss,Peng, Hui,Whittaker, Andrew K.
p. 4860 - 4870
(2021/05/29)

Copper-Catalyzed Acetylation of Electron-Rich Phenols and Anilines
An approach has been developed for the copper-catalyzed acetylation of phenols and anilines with potassium thioacetate as an acetylating reagent. Although only electron-rich phenols and anilines are compatible with this protocol, the reaction can provide moderate to high yields under mild conditions. Compared with other acetylating reagents, the current reagent has certain advantages, such as its low cost, easy availability, stability, insensitivity to water or air, and ease of storage.
Zhang, Jieyu,Ke, Qiumin,Tian, Feitao,Jiang, Bei,Ji, Chang-An,Zhang, Lingling,Yu, Jian,Huang, Dayun,Yan, Guobing
supporting information
p. 726 - 730
(2019/03/26)

Method for synthesizing phenyl acetate derivatives
The invention discloses a method for synthesizing phenyl acetate derivatives. The method of the invention comprises the following steps: 1, adding a phenol derivative, potassium thioacetate, copper acetate and acetonitrile to a reaction tube, and tightening the bottle stopper of the reaction tube, and magnetically stirring at 80 DEG C and reacting for 4 h; and 2, extracting with ethyl acetate, mixing organic phases, removing most of the solvent by reduced pressure distillation, and carrying out column chromatography separation and purification on residual mixed liquor by using petroleum etherand ethyl acetate at the volume ratio of 10:1 as a leacheate so as to obtain a target product. By using a phenol derivative as the raw material and using stable potassium thioacetate, which is cheap and easily available and is easy to operate, as an acetylation reagent, a series of phenyl acetate derivatives are efficiently synthesized, and the yield is considerable.
-
Paragraph 0021-0026

(2019/05/08)

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)

Preparation method for synthesis of phenolic ester through thiocarboxylic acid mediated visible light catalyzed phenol acylation reaction
The invention discloses a preparation method for synthesis of phenolic ester through a thiocarboxylic acid mediated visible light catalyzed phenol acylation reaction. Thiocarboxylic acid compounds andphenol compounds are subjected to a site specific reaction under certain conditions to produce phenolic ester compounds, wherein the certain conditions are as follows: under the conditions of normaltemperature, normal pressure and visible light, K2CO3 is used as an alkaline catalyst, terpyridyl ruthenium dichloride hexahydrate is used as a photosensitizer and acetonitrile is used as a reaction solvent. Synthesis of phenolic ester under catalysis of visible light is realized, thiocarboxylic acid is used as an acylation reagent, and the site specific phenol esterification reaction is realizedefficiently under mild conditions of normal temperature, normal pressure and visible light. The method has mild reaction conditions, large substrate functional group tolerance, high applicability andhigh yield, and an efficient, reliable and economical preparation method is provided for synthesis of phenolic ester.
-
Paragraph 0079; 0080; 0094; 0095; 0096

(2018/07/30)

Na 2 CO 3-Catalyzed O-Acylation of Phenols for the Synthesis of Aryl Carboxylates with Use of Alkenyl Carboxylates
Inorganic base-catalyzed O-acylation of phenol and its derivatives has been developed. The procedure provides an efficient catalysis system for the preparation of aryl carboxylates with alkenyl carboxylates as acyl reagents. The reaction proceeded smoothly by using ?-Na 2 CO 3 as the catalyst in MeCN to produce the corresponding aryl carboxylates in good to excellent yields.
Zhou, Xiao-Yu,Chen, Xia
supporting information
p. 2321 - 2325
(2018/10/20)

ATF3 INDUCTION COMPOUNDS
Provided are compounds for treating and/or preventing obesity and obesity-related disorders. Particularly, provided are chromanone derivatives used as ATF3 inducer and for treating and/or preventing obesity and obesity-related disorders such as heart disease, hypertension, hyperlipidemia and diabetes.
-
Paragraph 0075-0077

(2018/10/19)

Unprecedented acetylation of phenols using a catalytic amount of magnesium powder
The acetylation of phenols with acetic anhydride was achieved using a catalytic amount of magnesium metal powder under air and solvent-free conditions to afford corresponding phenyl acetates in excellent yield (up to 98%).
Bajracharya, Gan B.,Shrestha, Suryaman Sama
supporting information
p. 1688 - 1693
(2018/06/15)

Werner transition-metal complex (WTMC)-mediated mild and efficient chemo-selective acylation of phenols and anilines under solvent-free condition
Werner-type transition-metal complexes (WTMC) such as [Co(NH3)5Cl]Cl2, Cu[(NH3)4]SO4, Mn(acac)3, Ni[(NH3)6]Cl2, Ni[(en)3]S2O3, and Hg[Co(SCN)4] efficiently promote the chemoselective acetylation of phenols and anilines under solvent-free condition. The results of this study clearly shows that the optimal condition for the acetylation of anilines/phenols (1 mmol) (2a–r) with acetic anhydride (1.2 mmol) in the presence of WTMC (1 mmol) and two drops of H3PO4 on heating for 10 min under solvent-free condition gives the corresponding acetanilides/phenyl acetate (3a–r) in good to excellent yield. Furthermore, the method is simple, efficient, chemoselective, and eco-friendly under solvent-free condition for the acetylation of anilines and phenols promoted by WTMC by using acetic anhydrate as the acetylating agent. The simple preparation of the catalyst, easy procedure of the acetylation reaction, and simple work-up indicate the importance of WTMC for such reactions.
Sarief, Abdulla,Haque, SK Manirul,Feroze, Syed Mudabbir,Arifuddin, Mohammed
p. 1104 - 1109
(2018/09/27)

Reusable and efficient polyvinylpolypyrrolidone-supported triflic acid catalyst for acylation of alcohols, phenols, amines, and thiols under solvent-free conditions
Abstract: A triflic acid-functionalized polyvinylpolypyrrolidone was prepared and fully characterized by FT-IR, TGA, and SEM. This super acidic solid catalyst shows high catalytic activity for selective acylation of alcohols, phenols, amines, and thiols with anhydrides under solvent-free conditions at room temperature. In addition, this method features an easy to handle solid super acid catalyst and an operationally simple procedure, affording the desired acylated products in excellent yields. Graphical abstract: [Figure not available: see fulltext.].
Tajbakhsh, Mahgol,Tajbakhsh, Mahmoud,Khaksar, Samad,Gazvini, Helia Janatian,Heidary, Marzieh
p. 1117 - 1122
(2017/05/10)

Copper-Catalyzed C-S Bond Formation via the Cleavage of C-O Bonds in the Presence of S8 as the Sulfur Source
Useful and applicable methods for one-pot and odorless synthesis of unsymmetrical and symmetrical diaryl sulfides via C-O bond activation are presented. First, a new efficient procedure for the synthesis of unsymmetrical sulfides using the cross-coupling reaction of phenolic esters such as acetates, tosylates, and triflates and with arylboronic acid or triphenyltin chloride as the coupling partners is reported. Depending on the reaction, S 8 /KF or S 8 /NaO t -Bu system is found to be an effective source of sulfur in the presence of copper salts and in poly(ethylene glycol) as a green solvent. Then, the synthesis of symmetrical diaryl sulfides from phenolic compounds by using S 8 as the sulfur source and NaO t -Bu in anhydrous DMF at 120 °C under N 2 is described. By these protocols, the synthesis of a variety of unsymmetrical and symmetrical sulfides become easier than the available protocols in which thiols and aryl halides are directly used for the preparation of the sulfides.
Rostami, Abed,Rostami, Amin,Ghaderi, Arash,Gholinejad, Mohammad,Gheisarzadeh, Sajedeh
p. 5025 - 5038
(2017/10/06)

Polymer-Supported Palladium(II) Carbene Complexes: Catalytic Activity, Recyclability, and Selectivity in C?H Acetoxylation of Arenes
Heterogeneous catalysts for selective oxidation of C?H bonds were synthesized by co-polymerization of new N-heterocyclic carbene-palladium(II) (NHC-PdII) monomers with divinylbenzene. The polymer-supported NHC-PdII-catalysed undirect
Majeed, Maitham H.,Shayesteh, Payam,Wallenberg, L. Reine,Persson, Axel R.,Johansson, Niclas,Ye, Lei,Schnadt, Joachim,Wendt, Ola F.
supporting information
p. 8457 - 8465
(2017/06/28)

Asymmetric Oxidative Cycloetherification of Naphtholic Alcohols
The catalytic, enantioselective oxidative cyclization of naphthol-derived carboxylic acids mediated by chiral hypervalent iodine reagents has been studied extensively in the recent past, but analogous reactions of non-carboxylic substrates are yet unknown. This paper describes a catalytic, enantioselective, hypervalent iodine-promoted oxidative cycloetherification reaction of naphtholic alcohols. The new process relies on a variant of the Uyanik–Ishihara catalyst, in which the stereogenic centers have been relocated closer to the iodine atom. The new catalyst design affords optical yields comparable to those available with Uyanik–Ishihara iodides, but chemical yields are sensibly higher, at least with the tests substrates. An even more problematic reaction is the catalytic, enantioselective oxidative cyclization of naphtholic sulfonamides. In this case, the new catalyst affords significantly higher optical inductions than Uyanik–Ishihara iodides. The kinetic resolution of particular naphtholic alcohols is demonstrated. The absolute configuration of a numver of enantioenriched compounds obtained in this study was ascertained by X-ray diffractometry.
Jain, Nikita,Xu, Sanjia,Ciufolini, Marco A.
supporting information
p. 4542 - 4546
(2017/04/13)

Ligand-Promoted Palladium-Catalyzed C?H Acetoxylation of Simple Arenes
The palladium-catalyzed C?H oxidation of simple arenes is an attractive strategy to obtain phenols, which have many applications in the fine chemicals industry. Although some advances have been made in this research area, low reactivity and selectivity are, in general, observed. This report describes a new catalytic system for the efficient C?H acetoxylation of simple arenes based on Pd(OAc)2 and a pyridinecarboxylic acid ligand.
Valderas, Carolina,Naksomboon, Kananat,Fernández-Ibá?ez, M. ángeles
p. 3213 - 3217
(2016/10/24)

Doping of copper (I) oxide onto a solid support as a recyclable catalyst for acetylation of amines/alcohols/phenols and synthesis of trisubstituted imidazole
A study of copper-mediated C-heteroatom especially C-N and C-O bond formations using simpler methodologies has been carried out. In the present work, acetylation of various substrates such as amines, phenols and alcohols; synthesis of 2,4,5-trisubstituted imidazole is done using simple and easily available starting materials. Copper (I) oxide was synthesized in situ by the reduction of Fehling's solution with glucose followed by its anchoring onto different supports like silica, HAP, basic alumina and cellulose. Comparison and contrasts between the reactivity of copper (I) oxide supported onto different supports for these reactions are made. The reactivity of copper (I) oxide seems to be largely dependent on the nature of support and the most active catalyst for a particular reaction was further characterized by different spectroscopic techniques such as FTIR, XRD, TGA, XPS, SEM, TEM and AAS. The catalysts were found to be stable, easily recyclable without any significant loss in activity. Graphical abstract: Applications of solid supported copper (I) oxides (where solid support is silica, HAP, cellulose and basic alumina) are studied for various organic transformations with special emphasis on C-N and C-O bond formation reactions.[Figure not available: see fulltext.]
Gupta, Manjulla,Gupta, Monika
p. 231 - 241
(2016/01/09)

The first vinyl acetate mediated organocatalytic transesterification of phenols: A step towards sustainability
The present report outlines our efforts toward a simple yet elegant protocol for O-acylation of a wide variety of phenols. This highly enabling and solventless method relies on vinyl acetate as an innocuous acyl donor and DABCO as an organocatalyst. Operational simplicity, excellent yields, higher and faster conversion rates without excess reagents, a simple workup and essentially no need of columns are some of the salient features of the reported protocol.
Kumar, Manoj,Bagchi, Sourav,Sharma, Anuj
supporting information
p. 8329 - 8336
(2015/11/10)

Tribromoisocyanuric acid (TBCA) as a mild and metal free catalyst for the acetylation and formylation of hydroxyl groups under solvent free conditions
A convenient approach for acetylation and formylation of various types of alcohols and phenols with acetic anhydride and formic acid in the presence of Tribromoisocyanuric acid (TBCA) as catalyst is reported. The reactions were carried out under solvent-free condition and in good to high yields at room temperature. This present method is featured with relatively mild reaction conditions, simple operation, broad substrate scope, clean work-up, short reaction times, good to high yields, excellent selectivity and also avoids tedious purifications and the use of toxic reagents.
Hekmatian, Zahra,Khazaei, Ardeshir
p. 1565 - 1570
(2016/01/26)

Iron-Catalyzed Cross-Coupling of Alkenyl Acetates
Stable C-O linkages are generally unreactive in cross-coupling reactions which mostly employ more electrophilic halides or activated esters (triflates, tosylates). Acetates are cheap and easily accessible electrophiles but have not been used in cross-couplings because the strong C-O bond and high propensity to engage in unwanted acetylation and deprotonation. Reported herein is a selective iron-catalyzed cross-coupling of diverse alkenyl acetates, and it operates under mild reaction conditions (0 C, 2 h) with a ligand-free catalyst (1-2 mol%). Iron clad: Acetates are underutilized electrophiles in metal-catalyzed cross-coupling reactions because of the strong alkenyl C-O bond and their propensity to engage in unwanted reactions. Combination of a ligand-free low-valent Fe catalyst with nucleophilic organomagnesium reagents, low temperature, and short reaction times results in highly selective cross-couplings with alkenyl acetates.
G?rtner, Dominik,Stein, André Luiz,Grupe, Sabine,Arp, Johannes,Von Wangelin, Axel Jacobi
supporting information
p. 10545 - 10549
(2015/09/02)

Rice husk ash: A new, cheap, efficient, and reusable reagent for the protection of alcohols, phenols, amines, and thiols
Amild, efficient, and eco-friendly protocol for the protection of alcohols and phenols as trimethylsilyl ethers has been developed using rice husk ash as a reagent. This reagent is also able to catalyze the acetylation of alcohols, phenols, thiols, and amines with acetic anhydride. All reactions were performed under mild conditions in good to high yields. Copyright
Shirini,Akbari-Dadamahaleh, Somayeh,Mohammad-Khah, Ali
p. 577 - 586
(2014/06/09)

Rice husk: Introduction of a green, cheap and reusable catalyst for the protection of alcohols, phenols, amines and thiols
A mild, efficient and eco-friendly protocol for the chemoselective protection of benzylic and primary and less hindered secondary aliphatic alcohols and phenols as trimethylsilyl ethers and different types of amines as N-tert-butylcarbamates is developed using rice husk (RiH) as the catalyst. This reagent is also able to catalyze the acetylation of alcohols, phenols, thiols and amines with acetic anhydride. Easy work-up, relatively short reaction times, excellent yields and low cost, availability and reusability of the catalyst are the striking features of this methodology, which can be considered to be one of the best and general methods for the protection of alcohols, phenols, thiols and amines. In addition, the use of a green reagent in the above-mentioned reactions results in a reduction of environmental pollution and of the cost of the applied methods.
Shirini, Farhad,Akbari-Dadamahaleh, Somayeh,Mohammad-Khah, Ali,Aliakbar, Ali-Reza
p. 164 - 170
(2014/03/21)

ZnAl2O4@SiO2 nanocomposite catalyst for the acetylation of alcohols, phenols and amines with acetic anhydride under solvent-free conditions
A ZnAl2O4@SiO2 nanocomposite was prepared from metal nitrates and tetraethyl orthosilicate by the sol-gel process, and characterized by X-ray diffraction, Fourier transform infrared, transmission electron microscopy, and N2 adsorption-desorption measurements. The nanocomposite was tested as a heterogeneous catalyst for the acetylation of alcohols, phenols, and amines under solvent-free conditions. Under optimized conditions, efficient acetylation of these substrates with acetic anhydride over the ZnAl2O4@SiO2 nanocomposite was obtained. Acetylation of anilines and primary aliphatic amines proceeded rapidly at room temperature, while the reaction time was longer for the acetylation of alcohols and phenols, showing that an amine NH2 group can be selectively acetylated in the presence of alcoholic or phenolic OH groups. The catalyst can be reused without obvious loss of catalytic activity. The catalytic activity of the ZnAl2O4@SiO2 nanocomposite was higher than that of pure ZnAl2O4. The method gives high yields, and is clean, cost effective, compatible with substrates having other functional groups and it is suitable for practical organic synthesis.
Farhadi, Saeed,Jahanara, Kosar
p. 368 - 375
(2014/04/03)

Solventless acetylation of alcohols and phenols catalyzed by supported iron oxide nanoparticles
Supported iron oxide nanoparticles on silicate catalysts were found to be efficient and easily recoverable materials in the acetylation of alcohols and phenols to their corresponding acetyl compounds using acetic anhydride under mild and solvent-less conditions. The supported iron oxide nanoparticles could be easily recovered from the reaction mixture and reused ten times without any loss in activity.
Rajabi, Fatemeh,Luque, Rafael
p. 129 - 132
(2014/01/06)

Acetylation of alcohols and phenols by zinc zirconium phosphate as an efficient heterogeneous catalyst under solvent-free conditions
An efficient method for the acetylation of a wide range of alcohols as well as phenols with acetic anhydride in good to excellent yields under solvent-free conditions, using zinc zirconium phosphate as the catalyst was investigated. The catalyst was characterized by XRD, inductivity coupled plasma-optical emission spectroscopy, and scanning electron microscope. Products are easily isolated and the protocol is mild and green, compared to the existing methods. Graphical abstract: [Figure not available: see fulltext.]
Hajipour, Abdol Reza,Karimi, Hirbod,Karimzadeh, Morteza
p. 1461 - 1472
(2014/09/30)

Vitamin B1 supported on silica-encapsulated γ-Fe 2O3 nanoparticles: Design, characterization and application as a greener biocatalyst for highly efficient acylation
A new magnetic catalyst was synthesized by the immobilization of vitamin B1 (thiamine hydrochloride) on the surface of silica-encapsulated γ-Fe2O3 nanoparticles. Its capability was evaluated in the acylation of alcohols and phenols with acetic anhydride under solvent-free conditions and afforded the desired products in high yield. This novel magnetic organocatalyst could be separated from the reaction vessel by use of an external magnet and recovered 5 times without a significant loss of its activity. The amount of loaded vitamin B1 on the silica-encapsulated γ-Fe2O3 was assigned by TGA and confirmed by back titration. Availability, cheapness and low toxicity are reasons associated with the utilization of vitamin B1 as a catalyst. The catalyst has been characterized by FT-IR, XRD, SEM, VSM and TG/DTA. The Royal Society of Chemistry.
Azizi, Kobra,Heydari, Akbar
p. 8812 - 8816
(2014/03/21)

Synthesis, characterization and application of poly(N,N'-dibromo- Nethylnaphthyl-2,7-disulfonamide) as an efficient catalyst for the acetylation and deacetylation reactions
In this work, a novel polymer namely poly(N,N'-dibromo-N-ethylnaphthyl-2,7- disulfonamide) (PBNS) is synthesized and characterized by studying its IR, 1H NMR, 13C NMR and thermal gravimetric analysis (TGA). This polymer is utilized as a highly efficient, heterogeneous and recyclable N-bromo reagent to catalyze acetylation of various compounds such as alcohols, phenols, thiol and amine with acetic anhydride under solvent-free conditions, and also it worthily catalyzes deacetylation of acetate esters in aqueous media.
Khazaei, Ardeshir,Saednia, Shahnaz,Roshani, Liela,Kazem-Rostami, Masoud,Zare, Abdolkarim
p. 159 - 167
(2014/05/20)

Microwave-assisted acetylation of phenols without catalyst under solvent free condition
Etherification between phenols with acetic anhydride was tested under different conditions. Phenols were efficiently acylated with acetic anhydride to give phenol acetate derivatives in good high yields without catalyst and solventless conditions under microwave irradiation.
Zhang, Yu-Quan,Li, Yan-Chun,Zhu, Ji-Hua,Li, Zhi-Feng,Guo, Guo-Zhe,Chen, Dong-Ping
p. 7746 - 7748
(2015/02/02)

Sol-gel derived LaFeO3/SiO2 nanocomposite: Synthesis, characterization and its application as a new, green and recoverable heterogeneous catalyst for the efficient acetylation of amines, alcohols and phenols
LaFeO3/SiO2 nanocomposite was synthesized by the sol-gel process from metal nitrates and tetraethyl orthosilicate (TEOS) as the SiO2 source. The nanocomposite product was characterized by XRD, FT-IR, SEM, and surface area measurements and was used as a heterogeneous catalyst for the efficient acetylation of amines, alcohols and phenols to the corresponding acetates using acetic anhydride under solvent-free conditions. Among the various substrates, acetylation of amines was preceded rapidly, so that an amine group could be selectively acetylated in the presence of alcoholic or phenolic hydroxyl groups by the appropriate choice of reaction time. The catalyst can also be reused several times without the loss of activity. In addition, the catalytic activity of the LaFeO3/SiO2 nanocomposite was higher than that of the pure LaFeO3 nanoparticles. The method is high yielding, clean, cost effective, compatible with the substrates having other functional groups and very suitable for the practical organic synthesis.
Farhadi, Saeed,Jahanara, Kosar,Sepahdar, Asma
p. 1103 - 1112
(2014/08/05)

Preparation and characterization of multi-walled carbon nanotubes (MWCNTs), functionalized with phosphonic acid (MWCNTs-C-PO3H2) and its application as a novel, efficient, heterogeneous, highly selective and reusable catalyst for acetylation of alcohols, phenols, aromatic amines, and thiols
A novel, efficient, heterogeneous, and reusable multi-walled carbon nanotubes (MWCNTs), functionalized with phosphonic acid (MWCNTs-C-PO 3H2) has been synthesized. The synthesized CNTs were characterized using some electron microscopic techniques such as scanning electron microscopy (SEM), atomic force microscopy (AFM), Energy dispersive X-ray spectroscopy (EDAX), and also some thermal and spectroscopic methods such as thermogravimetry (TG). The nitrogen adsorption behavior of the MWCNTs-C-PO3H2 catalyst was evaluated using the TG instrumentation system at 25°C. The catalyst was applied successfully for highly efficient and selective acetylation of alcohols, phenols, thiols and aromatic amines with acetic anhydride at room temperature under solvent-free conditions. The reusability of the catalyst was checked and the recovered catalyst was reused for five runs without significant loss in activity.
Dehghani, Farzaneh,Sardarian, Ali Reza,Doroodmand, Mohammad Mehdi
p. 673 - 684
(2014/05/20)

Efficient acetylation of alcohols and phenols catalyzed by recyclable lithium bis(perfluoroalkylsulfonyl)imide
An efficient acetylation of alcohols and phenols catalyzed by lithium bis(perfluoroalkylsulfonyl)-imide was developed. This acetylation features good yields, mild reaction condtions, and simple workup procedures. Furthermore, the catalyst bearing a long perfluoroalkyl chain is recoverable and readily reusable without losing any activity. Copyright
Li, Guilong,Zhao, Gang
p. 34 - 43,10
(2020/08/24)

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
p. 99 - 110
(2013/04/10)

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)

A new ferrocene-based bulky pyridine as an efficient reusable homogeneous catalyst
An effective approach to reusing a homogeneous catalyst has been demonstrated. A ferrocene-based bulky pyridine has been synthesized and utilized as a homogeneous catalyst for the synthesis of benzoylfumarates as well as for acetylation. After the reaction, the catalyst was separated by simple precipitation and reused without appreciable loss of activity. The Royal Society of Chemistry 2013.
Kashyap, Bishwapran,Phukan, Prodeep
p. 15327 - 15336
(2013/09/02)

Solvent-free acetylation and tetrahydropyranylation of alcohols catalyzed by recyclable sulfonated ordered nanostructured carbon
Rapid and practical green acetylation and tetrahydropyranylation routes of structurally diverse alcohols and phenols were applied under solvent-free reaction conditions providing excellent yields, using catalytic amounts of environmentally friendly sulfonated ordered nanoporous carbon (CMK-5-SO 3H). Non-toxic nature of the catalyst, its easy handling, recovery and reusability, and the absence of any solvent characterize the presented procedures as efficient methods. These procedures provide methods for the separation of the product by simple filtration.
Zareyee, Daryoush,Alizadeh, Parastoo,Ghandali, Mohammad S.,Khalilzadeh, Mohammad A.
p. 713 - 721
(2013/07/26)

Palladium-catalyzed acetoxylation of arenes by novel sulfinyl n-heterocyclic carbene ligand complexes
A series of novel ligands based on N-heterocyclic carbene and sulfoxide functionalities have been prepared and characterized. Pd(II) complexes have been synthesized by transmetalation from the corresponding NHC-Ag derivatives, and their behavior as catalysts has been studied in arene C-H bond oxidative activation. Studies conducted toward the elucidation of the reaction mechanism of the acetoxylation suggest a C-H activation step at Pd(IV) rather than Pd(II) intermediates.
Tato, Francisco,Garcia-Dominguez, Andres,Cardenas, Diego J.
supporting information
p. 7487 - 7494
(2014/04/03)

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
p. 90 - 100
(2012/11/06)

Highly efficient solvent-free acetylation of alcohols with acetic anhydride catalyzed by recyclable sulfonic acid catalyst (SBA-15-Ph-Pr-SO3H)- An environmentally benign method
The catalytic activity of highly thermal stable, hydrophobic, and complete heterogeneous propylsulfonic acid functionalized nanostructured SBA-15 for excellent acetylation of alcohols and phenols with acetic anhydride at ambient temperature in solvent-free conditions was examined under environmentally benign reaction conditions. The salient features of this protocol are the absence of solvent, a green experimental procedure, and simple reusability of the catalyst (at least five reaction cycles).
Zareyee, Daryoush,Ghadikolaee, Abdollah Razaghi,Khalilzadeh, Mohammad A.
experimental part
p. 464 - 468
(2012/06/16)

Iron(III) tosylate catalyzed acylation of alcohols, phenols, and aldehydes
Iron(III) p-toluenesulfonate (tosylate) is an efficient catalyst for acetylation of alcohols, phenols, and aldehydes. The acetylation of 1° and 2° alcohols, diols, and phenols proceeded smoothly with 2.0 mol % of catalyst. However, the reaction worked well with only a few 3° alcohols. The methodology was also applicable to the synthesis of a few benzoate esters but required the use of 5.0 mol % catalyst. Aldehydes could also be converted into the corresponding 1,1-diesters (acylals) under the reaction conditions. Iron(III) tosylate is an inexpensive, and easy to handle, commercially available catalyst.
Baldwin, Neil J.,Nord, Anna N.,O'Donnell, Brendan D.,Mohan, Ram S.
p. 6946 - 6949
(2013/01/15)

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)

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)

Amorphous carbon-silica composites bearing sulfonic acid as solid acid catalysts for the chemoselective protection of aldehydes as 1,1-diacetates and for N-, O- and S-acylations
Amorphous carbon-silica composites bearing sulfonic acid derived from inexpensive natural organic compounds (glucose, maltose, cellulose, chitosan and starch) were prepared by partial carbonization followed by sulfonation and their catalytic activity was evaluated for the protection of aldehydes as 1,1-diacetates and for N-, O- and S-acylations under solvent-free conditions. Different biomaterials have been chosen, with a view to select the most active solid acid catalyst. Carbon-silica composites were characterized by FTIR, XRD and elemental analysis. Sulfonated carbon-silica composite derived from starch was found to be the most active and could be recycled for several runs without loss of significant activity. It was also characterized by TGA, SEM and TEM.
Gupta, Princy,Paul, Satya
experimental part
p. 2365 - 2372
(2011/10/31)

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)

H6GeMo10V2O40·16H 2O nanoparticles prepared by hydrothermal method: A new and reusable heteropoly acid catalyst for highly efficient acetylation of alcohols and phenols under solvent-free conditions
A new Keggin-type heteropoly acid, namely decamolybdodivanadogermanic acid (H6GeMo10V2O40·16H 2O), with nanosized particles (5-8 nm), has been synthesized by a hydrothermal method and characterized by elemental analysis, thermogravimetric analysis (TGA), powder X-ray diffractometry (XRD), Fourier-transform infrared spectroscopy (FTIR), UV-Visible spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and potentiometric titration. H6GeMo10V2O40·16H 2O revealed high catalytic activity for acetylation of various alcohols and phenols with acetic anhydride at room temperature (298 ± 2 K) and under solvent-free conditions. The catalyst can be easily recovered and used repeatedly for five cycles with a slight loss of activity. The catalytic activity of H6GeMo10V2O40· 16H2O was higher than that of other Keggin-type heteropoly acids, such as H3PW12O40, H3PMo 12O40 and H4SiW12O40.
Farhadi, Saeid,Zareisahamieh, Reza,Zaidi, Masoumeh
experimental part
p. 1323 - 1332
(2012/04/04)

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)

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)

Comparisons of O-acylation and Friedel-Crafts acylation of phenols and acyl chlorides and Fries rearrangement of phenyl esters in trifluoromethanesulfonic acid: Effective synthesis of optically active homotyrosines
Reactions involving phenol derivatives and acyl chlorides have to be controlled for competitive O-acylations and C-acylations (Friedel-Crafts acylations and Fries rearrangements) in acidic condition. The extent for these reactions in trifluoromethanesulfonic acid (TfOH), which is used as catalyst and solvent, is examined. Although diluted TfOH was needed for effective O-acylation, concentrated TfOH was required for effective C-acylations in mild condition. These results have been applied to the novel synthesis of homotyrosine derivatives. Both Fries rearrangement of N-TFA-Asp(OBn)-OMe and Friedel-Crafts acylation of phenol with N-TFA-Asp(Cl)-OMe in TfOH afforded the homotyrosine skeleton, followed by reduction and deprotection afforded homotyrosines maintaining stereochemistry of Asp as an optically pure form.
Murashige, Ryo,Hayashi, Yuka,Ohmori, Syo,Torii, Ayuko,Aizu, Yoko,Muto, Yasuyuki,Murai, Yuta,Oda, Yuji,Hashimoto, Makoto
experimental part
p. 641 - 649
(2011/03/19)