Methylation of phenol by methyl formate

Conclusions In the presence of ZnCl₂ and ZrO₂, methyl formate methylates phenol to anisole with a high degree of selectivity.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 787–790, April, 1989.     

从4-戊烯醛经增碳反应合成5-己烯酸甲酯类化合物

通过4,8,12-三甲基-4,8,12-三烯醛(1)类四戊烯醛衍生物的增一碳反应合成了5,9,13-三甲基-5,9,13-十四三烯醛甲酯(3)及5-己烯酸甲酯衍生物(7-9)。用甲氧基甲基三苯基膦处理4-戊烯醛类化合物生成烯基醚,PCC氧化所生成的烯醚则得到标题化合物,5-己烯酸甲酯类化合物。     

Barriers to rotation in methyl formate by dynamic NMR spectroscopy and barriers to 1,3 oxygen-to-oxygen migration in methyl formate and trifluoromethyl formate by ab initio calculations

Free-energy barriers of 9.85 and 11.91 +/- 0.15 kcal/mol at -70.8 degrees C were found by dynamic NMR spectroscopy for the E-to-Z and Z-to-E conversions, respectively, of methyl formate (1) enriched in 13C to 99% for the carbonyl carbon [methyl formate 13C (2)]. These barriers are higher than the literature values reported for -53 degrees C. The free-energy barrier to 1,3 oxygen-to-oxygen migration of the methyl group in methyl formate was determined by ab initio calculations at several levels. The value of 58.7 kcal/mol obtained at the MP2/6-311+G (df,pd) level was compared to a literature barrier for this process (MINDO/3) and to barriers for related compounds. A free-energy barrier of 63.0 kcal/mol for the oxygen - to - oxygen migration of the CF3 group in trifluoromethyl formate (3) was calculated at the MP2/6-31+G level.     

A novel preparation of methyl ketones through one-carbon homologation of aldehydes

A novel two-step aldehyde homologation procedure for the preparation of methyl ketones has been developed, which involves the use of 1,1-dibromo-1-alkenes as precursors and zinc metal as mediator in near-critical water.     

A comparative ab initio study of methyl formate, methyl thiolformate and methyl thionoformate

Ab initio SCF-MO calculations have been carried out for HCOOCH₃, HC(=O)SCH₃ and HC(=S)OCH₃. Relative stabilities of s-trans/s-cis conformers are reported and discussed in terms of specific intramolecular interactions. The energy difference between the s-trans and the s-cis form increases in the order methyl thiolformate < methyl thionoformate < methyl formate. The major stabilizing factors of the s-cis forms are the bond dipolar interaction and the mesomeric delocalization through the five member ring involving both the X=C---Y---C (X, Y = O, S) skeleton and the out-of-plane hydrogen atoms. These effects are used to explain the trends mentioned. The non-planarity previously proposed for the thionoester is reinvestigated. Our calculations show that this molecule is planar. Molecular atomic charges, dipole moments and ionisation potentials are determined and compared with available experimental values.     

Synthesis of biaryl compounds using tandem ruthenium-catalyzed ring-closing metathesis

Tandem ring-closing enyne metathesis (RCEM)/ring-closing olefin metathesis (RCM) of tetraenynes with Grubbs second-generation catalyst, followed by elimination, was found to be a new and efficient synthetic approach to biaryl compounds. A preliminary asymmetric version of this approach, which used homochiral Ru-alkylidene catalysts, is also presented.     

The gas-phase molecular structure of methyl formate,determined by electron diffraction

The structure of methyl formate in the gas phase has been reinvestigated by electron diffraction. The results confirm that the molecular skeleton is cis-planar, with bond lengths and angles in close agreement with those found by microwave techniques. Principal parameters (r_a) are: r(CO) 120.2(2) pm, r(C-O) 134.0(2), and 143.5(3) pm; ∠ (OC-O) 125.4(5)°, and ∠ (C-O-C) 115.9(5)°.     

Semiempirical quantum-chemical calculations on the conformations of methyl formate and methyl thiolformate

The cis, trans, and gauche conformations of the methyl esters of formic and thiolformic acids have been investigated by different semiempirical methods. Total geometry optimization (CNDO/2, MINDO/3) and bond angle optimization (PCILO, NDDO) have been performed for the O-alkyl ester. The S-alkyl ester has been studied by the MINDO/3 method at the total geometry optimization level and by CNDO/2 and PCILO methods at the bond angle optimization level. The influence of sulphur d orbitals on the optimized molecular geometry as well as on the magnitude and direction of the dipole moment vector has been investigated in the CNDO/2 framework. The total energy differences of the conformers are compared to the experimental and ab initio results. CNDO/2 and NDDO energy partitioning have been performed to obtain information on the origin of the cis—trans energy difference and of the rotation barrier. The extent of the lone-pair delocalization has been studied in the different conformations using localized molecular orbitals. Calculations have been performed on the staggered and eclipsed positions of the methyl group in the planar conformations of both esters.     

Partial chain transfer constants in the telomerization of ethylene by methyl formate

Conclusions The authors determine the partial chain transfer constants of telomeric radicals forming methyl formate by radiation-chemical telomerization of ethylene, and the relative constant of isomerization of radicals with 1,6 migration of hydrogen.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 909–912, April, 1976.     

Methoxyphenylthiotrimethylsilylmethyllithium a convenient reagent for the homologation of carbonyl compounds

A facile homologation procedure for the conversion of carbonyl compounds into ketene-O,S-acetals is described. These intermediates are readily converted into ketene-O-silyl,S-acetals, thioesters, and carboxamides.     

Mechanistic study of the gas-phase decomposition of methyl formate

The major products of the thermal decomposition of methyl formate in the gas phase are CH(3)OH, CH(2)O, and CO. Experimental studies have proposed that the mechanism to describe these observations involves two key steps: (1) unimolecular decomposition of methyl formate to yield CH(3)OH + CO, followed by (2) thermal decomposition of methanol to yield CH(2)O + H(2). The present study shows that there exists an alternative mechanism that is energetically more favorable. The new mechanism involves two competing parallel unimolecular decomposition pathways to yield the observed major products.     

Oxidation of phosphorus compounds by Fenton's reagent

In the present work a Fenton's treatment for the oxidation of a phosphorous compounds mixture, simulating a match manufacturing industry wastewater, were studied. Experimental tests were performed on three sample solutions at a phosphorus concentration of 250, 500 and 750 mg/l. In each solution an equal amount of sodium phosphite and sodium hypophosphite was dissolved. The investigation of pH, temperature and reagents ratio on the oxidation rate led to the individuation of the optimal process operating conditions. The results show that Fenton's reagent provides a powerful conversion to phosphate of the phosphorous solution. In particular at pH=3.5 and 20 degrees C a residual concentration of non oxidized phosphorus in compliance with the Italian regulation limits for industrial wastewater disposal. Tests performed on sample solution of 500 mg/l P and 750 mg/l P by adding hydrogen peroxide and bivalent iron in three sequential steps led to similar reaction efficiencies to tests carried out adding both Fenton's reagents in one step, but with a remarkably lower reagents consumption.     

Catalytic reaction of methyl formate with amines to formamides

A feasible procedure of using methyl formate as cheap reagent for the conversion of aliphatic and aromatic amines into formamides with high yields is reported. The improved amine formylation method proceeds mainly at room temperature and in presence of bicyclic guanidines as catalysts. A verifiable key intermediate of outstanding formylating activity is generated from methyl formate and the catalyst in the reaction mixture.     

Condensation reaction of formaldehyde and methyl formate catalyzed by a composite catalyst system

The condensation reaction of formaldehyde and methyl formate to form methyl glycolate and methyl methoxy acetate catalyzed by p-toluenesulfonic acid and different Lewis acid compounds has been investigated. The composite catalytic system consisting of p-toluenesulfonic acid and NiX2 （X = Cl, Br, I）, especially NiI2, exhibited a high catalytic performance for the condensation reaction, the total yield of MG and MMAc was up to 72.37%.     

Photopromoted methoxycarbonylation of olefin with methyl formate by Co（OAc）2

The photopromoted methoxycarbonylation of olefin with methyl formate catalyzed by Co(OAc)2 at ambient conditions has been carried out.The results indicated that the reaction activity increased with the increasing temperature.Methyl formate decomposed into CO and CH_3OH firstly under irradiation,and then the methoxycarbonylation of olefin proceeded under catalysis of Co(OAc)_2. The mechanism of methyl formate participating in the methoxycarbonylation is verified by the IR analysis and the labeling experiments of CD_3OD and CH_3~(18)OH.