104810-18-6Relevant academic research and scientific papers
Iron(II) and copper(II) phthalocyanine-catalyzed synthesis of 2-nitro-4-methylsulfonylbenzoic acid under mild conditions
Huang, Cheng,Liu, Rui,Zhang, Caiting,Cheng, Qipeng,Zhu, Hongjun
, p. 1587 - 1594 (2017)
Abstract : A novel method was?developed?to produce 2-nitro-4-methylsulfonylbenzoic acid (NMSBA) from the oxidation of 2-nitro-4-methylsulfonyltoluene (NMST) by oxygen catalyzed by iron(II) phthalocyanine (FePc) and copper(II) phthalocyanine (CuPc). The order of activity for oxidation of NMST was found to be: FePc > CuPc. Meanwhile, major reaction parameters such as concentrations of catalyst and NaOH, reaction temperature and oxygen pressure have been investigated. Through optimization of the reaction parameters, the highest yield of NMSBA and conversion of NMST (up to 53%, 89.3%, respectively) were achieved with oxygen (2.0 MPa), FePc (1.0×10-4molL-1), NaOH (0.6molL-1), in methanol at 55°C for 8 h. A plausible mechanism for this catalytic process is proposed which involved deprotonation and radical pathways. Graphical Abstract: A novel method to produce 2-nitro-4-methylsulfonylbenzoic acid (NMSBA) from the oxidation of 2-nitro-4-methylsulfonyltoluene (NMST) by oxygen catalyzed by iron(II) phthalocyanine (FePc) and copper(II) phthalocyanine (CuPc) has been developed. The reaction parameters and mechanism were studied. The catalytic system will be readily applicable to large-scale production of NMSBA. [Figure not available: see fulltext.].
Kinetics and mechanism of the oxidation of substituted benzaldehydes by bis(2,2′-bipyridylyl)copper(II) permanganate
Mohnot, Kavita,Sharma, Pradeep K.,Banerji, Kalyan K.
, p. 1310 - 1314 (1996)
The oxidation of 35 monosubstituted benzaldehydes by bis(2,2′-bipyridylyl)copper(II) permanganate (BBCP) in aqueous acetic acid leads to the formation of the corresponding benzoic acids. The reaction is first order with respect to BBCP. Michaelis - Menten-type kinetics were observed with respect to the aldehyde concentrations. The oxidation of [2H]benzaldehyde (PhCDO) indicated the presence of a substantial kinetic isotope effect. The rates of oxidation of meta- and para-substituted benzaldehydes were correlated in terms of Charton's triparametric LDR equation, whereas the oxidation of ortho-substituted benzaldehydes was correlated with the four parametric LDRS equation. The oxidation of para-substituted benzaldehydes is more susceptible to the delocalization effect than is the oxidation of ortho- and meta-substituted compounds which displays a greater dependence on the field effect. The positive value of η suggests the presence of an electron-deficient reaction center in the rate-determining activated complex. The reaction is subjected to steric acceleration when ortho-substituents are present.
A novel CuCl2/BIL catalyst for direct oxidation of alcohol to acid at ambient temperature
Karthikeyan, Parasuraman,Aswar, Sachin Arunrao,Muskawar, Prashant Narayan,Bhagat, Pundlik Rambhau,Kumar, S. Senthil
, p. 189 - 193 (2012)
A clean and highly efficient alcohol oxidizing system, using hydrogen peroxide in the presence of CuCl2/Bifunctional ionic liquid (CuCl2/BIL), under solvent free condition has been developed. The oxidation proceeds smoothly with 0.01 mmol of CuCl2/BIL and 30% of H2O2 to give the carboxylic acids with excellent yield. Especially, this green reaction also exemplifies advances toward the synthesis of aliphatic and aromatic acid from the corresponding alcohol. The advantages of the present protocol include solvent free condition, wide functional group tolerance and convenient product isolation. The BIL can be recycled and reused for five runs without any significant loss of its activity.
Kinetics and mechanism of the oxidation of substituted benzaldehydes by benzyltrimethylammonium chlorobromate
Raju, V. Sitarama,Sharma, Pradeep K.,Banerji, Kalyan K.
, p. 3322 - 3325 (2000)
The oxidation of 35 monosubstituted benzaldehydes by benzyltrimethylammonium chlorobromate (BTMACB) in aqueous acetic acid leads to the formation of the corresponding benzoic acids. The reaction is first order with respect to both benzaldehyde and BTMACB. The reaction failed to induce the polymerization of acrylonitrile. There is no effect of benzyltrimethylammonium chloride or potassium bromide on the reaction rate. The oxidation of [2H]benzaldehyde (PhCDO) indicated the presence of a substantial kinetic isotope effect. The effect of solvent composition indicated that the reaction rate increases with an increase in the polarity of the solvent. The rates of oxidation of meta- and para-substituted benzaldehydes were correlated in terms of Charton's triparametric LDR equation, whereas the oxidation of ortho-substituted benzaldehydes was correlated with the tetraparametric LDRS equation. The oxidation of para- substituted benzaldehydes is more susceptible to the delocalization effect, whereas the oxidation of ortho-and meta-substituted compounds displayed a greater dependence on the field effect. The positive value of η suggests the presence of an electron-deficient reaction center in the rate-determining step. The reaction is subjected to steric hindrance by the ortho substituents.
Trichloroisocyanuric/TEMPO oxidation of alcohols under mild conditions: A close investigation
De Luca, Lidia,Giacomelli, Giampaolo,Masala, Simonetta,Porcheddu, Andrea
, p. 4999 - 5001 (2003)
Efficient oxidation of primary alcohols to the corresponding carboxylic acids can be carried out at room temperature and in acetone/water, using trichloroisocyanuric acid (TCCA) in the presence of catalytic TEMPO. The mild conditions of this procedure and the total absence of any transition metal make this reaction suitable for safe laboratory use. A possible mechanism is presented and discussed.
An efficient and mild procedure for the preparation of benzoic acids via oxidation of aromatic carbonyl compounds by employing N-bromoimides and mercuric acetate system
Anjum, Amena,Srinivas
, p. 900 - 901 (2001)
Aromatic carbonyl compounds are efficiently converted into the corresponding benzoic acids under mild reaction conditions by employing N-bromoimide and mercuric acetate in good to excellent yields. This procedure works efficiently at room temperature for aromatic aldehydes as well as aromatic ketones to give the corresponding benzoic acids.
Indium-mediated chemoselective deprotection and demonochlorination of 2,2,2-trichloroethyl esters
Mineno, Tomoko,Kansui, Hisao,Kunieda, Takehisa
, p. 5027 - 5030 (2007)
On treatment with indium metal, the 2,2,2-trichloroethyl carboxylates smoothly undergo deprotection to carboxylic acids and reductive demonochlorination to 2,2-dichloroethyl esters, sharply depending on their structures.
Manganese dioxide and N-hydroxyphthalimide. An effective catalytic system for oxidation of nitrotoluenes with molecular oxygen
Yang, Guanyu,Zheng, Liwen,Wu, Guanghui,Lin, Xuesong,Song, Maoping
, p. 2445 - 2448 (2007)
The inexpensive manganese dioxide has been proven to be an efficient auxiliary for oxidizing N-hydroxyphthalimide (NHPI) to form the phthalimide N-oxyl radical via reduction and reoxidation. The combination of manganese dioxide and NHPI could catalyze effectively the oxidation of nitrotulenes by molecular oxygen. Thus, the oxidation of p-nitrotoluene with molecular oxygen (0.4 MPa) in the presence of manganese dioxide (10 mol%) and NHPI (10 mol%) in acetic acid at 110° for 4 h proceeded with 97 % conversion, and gave p-ni-trotoluene in 89 % isolated yield.
Equilibria and kinetics of reactions between carboxylic acids and the carbinol base of crystal violet in apolar aprotic solvents: Relative strengths of m- and o-substituted benzoic acids in toluene
Sen Gupta, Susanta K.,Arvind, Udai
, p. 466 - 471 (1997)
Equilibria and kinetics of proton-transfer reactions in toluene between a set of m- and o-substituted (methyl, methoxy, chloro, nitro and hydroxy) benzoic acids and the carbinol base (colourless) of Crystal Violet were studied spectrophotometrically. The data on equilibrium and kinetic parameters were critically analysed. The rate constant for the forward step of the acid-carbinol equilibrium was found to be an appropriate criterion for determining acidities in toluene. Toluene-phase acidities were found to be significantly more susceptible than aqueous-phase acidities to the structure of the substituents, particularly for the m-substituted acids. Quantitative analysis of the substituent effect on toluene-phase acidities using the Fujita-Nishioka model for the extended Hammett equation showed that the predominant factor contributing to the 'ortho effect' for benzoic acid-dye carbinol reactions in toluene is the proximity polar effect rather than the steric effect for most of the o-substituents
Pd(II) porphyrins: Synthesis, singlet oxygen generation and photoassisted oxidation of aldehydes to carboxilic acids
Pandey, Vijayalakshmi,Jain, Drishti,Pareek, Nitesh,Gupta, Iti
, (2020)
The synthesis and spectral studies of A3B and A2B2 type porphyrins and their Pd(II) complexes are reported. The meso-positions on porphyrin macrocycle are substituted with pentafluorophenyl and N-butylcarbazole or triphenylamine groups. Pd(II) porphyrins displayed decent phosphorescence ～670 nm and are able to produce singlet oxygen by type II pathway, after photoirradiation. The calculated singlet oxygen quantum yields for Pd(II) porphyrins are (ΦΔ = 30%–63%). The catalytic application of Pd(II) porphyrins towards photoassisted aerobic oxidation of aromatic aldehydes to carboxylic acids is demonstrated.
