Ethylacetate reactions

Recently, Suzuki and Taniguchi93 hydrolyzed n-butylacetate, ethylacetate, and methylacetate with HPSt and 41 (PVA B) (partially-o-benzalsulfonated polyvinylalcohol). The volume of activation, A P+, was obtained from the pressure dependence of reaction rates [ F + = -kT(d Ink/dP)]. The A + increased with increasing hydro-phobidty of the substrate. 

Urine ( -aminolevuli nic acid) Dilution of sample reaction with ethylacetoacetate and ethylacetate to form -amino-levulinic acid-pyrrole reaction with Erhlich s reagent Spectrophotometry No data No data Tomokuni and Ichiba 1988... 

Syntheses are limited to mercuric salts of weak acids (2,110). Generally, increasing the length of the straight alkyl chain decreases the extent of decarboxylation (e.g., Ref. 133). Electron-withdrawing substituents suppress decarboxylation. For example, mercurials are not formed with Me02C, Cl, and Me(CH2)nO substituents on the a carbon (137,148,149), but some decarboxylation occurs with these on the j8 carbon (135-137). Chain decarboxylation predominated in reactions in benzene, butyric acid [R = Me(CH2)2] (150), or acetic acid (R = Me) (124). The chain reaction was also observed for R = Me(CH2)2 in the absence of solvent and in ethylacetate or heptane solution, but in these media the radical displacement reaction was dominant (2,150). When benzene was used as solvent... 

The sulfur-specific pathway for desulfurization of benzothiophene (BT) has been reported in Gordonia sp. Strain 213E. The metabolites of BT conversion were determined by ethylacetate extraction of the culture medium followed by GC-MS analysis [33,34], The reaction mechanism was proposed to be very similar to that of DBT for the first two steps (Fig. 4) however, the third step was quite different. 

Additions to quinoline derivatives also continued to be reported last year. Chiral dihydroquinoline-2-nitriles 55 were prepared in up to 91% ee via a catalytic, asymmetric Reissert-type reaction promoted by a Lewis acid-Lewis base bifunctional catalyst. The dihydroquinoline-2-nitrile derivatives can be converted to tetrahydroquinoline-2-carboxylates without any loss of enantiomeric purity <00JA6327>. In addition the cyanomethyl group was introduced selectively at the C2-position of quinoline derivatives by reaction of trimethylsilylacetonitrile with quinolinium methiodides in the presence of CsF <00JOC907>. The reaction of quinolylmethyl and l-(quinolyl)ethylacetates with dimethylmalonate anion in the presence of Pd(0) was reported. Products of nucleophilic substitution and elimination and reduction products were obtained . Pyridoquinolines were prepared in one step from quinolines and 6-substituted quinolines under Friedel-Crafts conditions <00JCS(P1)2898>. 

Both acid- and base-promoted reactions may be affected by acidic surfaces and, hence, by the factors which influence the surface acidity. Kinetic evidence for increased Br nsted acidity at clay surfaces has been presented by McAuliffe and Coleman (80) who studied the hydrolysis of ethylacetate and the inversion of sucrose. They noted that potentionmetrie pH measurements did not explain the catalytically effective H+-concentration at the clay surface. 

The reactions of lanthanide thiocyanates, nitrates, and chlorides with TPPO have been studied by Cousins and Hart (202, 203, 205). The reactions of lanthanide nitrates with TPPO in ethanol, acetone, ethylacetate and tetrahydrofuran are given in Fig. 1. The nature of the complexes isolated depends on the concentrations of the ligand and the metal ion, temperature of mixing, presence or absence of the seed of the desired complex, size of the cation, and the nature of the solvent. Tetrakis-TPPO complexes of Ce(III) and Nd(III) perchlorates have been reported (206, 207). Two of the perchlorates are coordinated to the metal ion in these complexes. 

Interestingly, Qi, Smith, and co-workers reported that addition of an organic solvent such as acetone, DMSO, methanol, ethanol, ethylacetate, or supercritical carbon dioxide to BMIM Cl allowed the reaction to proceed at room temperature. For instance, in the presence of Amberlyst 15 as solid acid catalyst, authors showed that addition of 5 wt% of acetone to BMIM CF yielded, at room temperature, HMF with 86% selectivity at 90% conversion. Further investigations revealed that addition of an organic solvent to BMIM CF allowed one to overcome important mass transfer at room temperature due to the high viscosity of BMIM CD [96]. 

The catalytic activities of hydrolysis of ethylacetate at 341 K were measured in aqueous phase (0.68 M). 250 mg of catalyst was suspended in aqueous solution of ethylacetate, and the reaction rates were measured by GC (PORAPAK Q, 2-m). 

The acidic function of single zirconium phosphonate showed rather poor catalytic activities for hydrolysis of ethylacetate in aqueous solutions. In addition, over Zr(03PCH2S03H)2 catalyst, the reaction proceeds as a homogeneous reaction, even though the catalytic activity is higher than other acidic zirconium phosphonates. The objective of this study is to explore the role of a second phosphonate function in single crystal phase on the catalytic performance of acidic function and hydrophobic function of zirconium phosphonates and to learn how to exploit this second function to achieve a catalytic advantage in certain applications. 

Reaction condition mcaiaiyst=0.1g Solvent V=8ml Substrate O.lg T=100°C P=10MPa t=5h. Abbreviations CH=cyclohexane, EtOAc=ethylacetate. 

Expression of the catalytic capacity of the immobilized laccase was also observed in more than a dozen different solvents, provided that they were either saturated with water or, in the case of solvents miscible with water, small amounts of water had been added (Table III). No enzymatic reaction was observed when the solvents tested were free of water. No correlation was found between the activity of the immobilized laccase and the hydrophobicity of the solvent in which the reaction took place. The rate of laccase reaction in ethylacetate was only twice that in toluene, despite the fact that water-saturated ethylacetate contains 50 times more water than... 

Hanson et a/.149 hydrogenated the prochiral olefin methyl a-acetamidocinna-mate using rhodium catalysts modified with the tenside chiral sulfonated diphosphine 34 (Table 2) in an ethylacetate/H20 micellar system at 25° C and 1 bar H2. The yield (100%) and enantiomeric excess (69%) were considerably higher than with the tetrasulfonated diphosphine 31 (Table 2 m=0, n=0) which gave 32% yield and 20% e.e. and the reaction time was shorter (1.5 versus 20h). Rh/34 and Rh/31 (m=0, n=0) gave nearly the same results (100% yield and 72-75% e.e. within < lh) in homogeneous methanol solutions.149... 

Figure 1 shows deterioration of catalyst performance with repeated uses. After a batch reaction at 60 °C for 4 h, the catalyst was separated, rinsed with ethylacetate solvent, and reused with fresh charge of the reactants. The conversion of IICHO continuously decreased. Most significant change in selectivity was emergence of the N-benzyl compound starting from the second batch reaction. When the used catalyst was rinsed with water, and dried at 100 °C in a vacuum oven overnight, the catalyst recovered the performance of the fresh catalyst both in IICIIO conversion and selectivity (the fifth batch). 

A mixture of ketone or aldehyde (1 mmol), fine powder of CaO (0.5 g, 8.9 mmol) were heated in an oil bath for a few minutes. Then hydroxylamine hydrochloride (0.208 g, 3 mmol) was added and the mixture was stirred with a magnetic stirrer in the presence of air for appropriate time. Afterwards, the reaction mixture was mixed with ethylacetate, filtered to remove CaO then mixed with water and extracted. The ethylacetate solution was dried over Na2S04. The solvent was removed in vacuo to give the product. 

A mixture of amide (1 mmol), aldehyde (1 mmol and in the case of 2a, 1.5 mmol as 40% solution in water) and amine (1.5 mmol) were mixed and ground with the solid support in a mortar. The mixture was transferred to a screw-cap Teflon container and irradiated in microwave oven for the required time. The progress of reaction was monitored with TLC. After cooling, the mixture was extracted with ethylacetate and filtered off. Evaporation of the solvent and remaining amine under reduced pressure gives the crude product that if necessary can be purified by recrystallization or chromatography. 

Aldehyde (5 mmol), ethane 1,2-diol (5 mmol) and metal sulfate (5 mmol) supported on silica gel (1.65 g) were mixed in a Pyrex test tube and subjected to microwave irradiation for 36 min. After complete conversion, as indicated by TLC, the reaction mass was charged directly on small silica gel column (100-200 mesh) and eluted with ethylacetate-hexane (2 8) to afford pure acetal in 80-98% yield. 

It is extremely useful to have available a technique for rapidly monitoring reaction progress or assessing sample purity. An ideal technique for these purposes is thin layer chromatography (TLC). The method is fast, very sensitive, readily set up, and inexpensive. Uncharged complexes can generally be developed on silica gel plates with a variety of solvents recently we have had good success with ethylacetate. 

Primary alcohols of n-carbon atoms are readily converted to symmetrical ketones of 2n — 1 carbon atoms by vapor-phase contact with various catalysts. A synthesis involving a Tischenko condensation (1) is a variation of an ester synthesis used commercially in Russia (2). In the conversion of ethyl alcohol to acetone by reaction with steam, ethylacetate is considered an important intermediate in the chain of reactions involved. 

A mixture of 59.5 g (0.2 mol) 2-(4-methoxybenzyl)-l,3,3-trimethyl-4-piperidone hydrochloride and 53.8 g (0.4 mol) of aluminum trichloride and 54.0 g of nitrobenzene in 1500 ml of dry benzene are boiled under reflux for 1 h. After cooling the reaction mixture is extracted with 750 ml 4 N sodium hydroxide solution, the temperature being maintained below 35°C. The organic phase is separated and extracted with 750 ml 1 N hydrochloric acid. The acid aequeous phase is rendered alkali by the addition of 100 ml 25% ammonia and extracted three times with 250 ml chloroform. The collected chloroformic phases are dried with sodium sulfate and evaporated under reduced pressure. The residue, 46.7 g, is converted into the hydrochloride by reaction with iso-propanol/HCI and crystallized from a mixture of methanol and ethylacetate. 44.6 g of the 5-hydroxy-2 -methoxy-2,9,9-trimethyl-6,7-benzomorphan hydrochloride are obtained, melting point 233-236° C (dec.). 

To a suspension of 7-amino-3-vinyl-3-cephem-4-carboxylic acid (11.25 g), 2-(aminothiazol-4-yl)-2-(tert-butoxycarbonylmethoxyimino)acetic acid S-mercaptobenzothiazole ester (23.88 g) in ethylacetate (266 ml) and water (9 ml) at 2°C is added triethylamine. After completion of the reaction, water is added and pH is adjusted to 2.1 with diluted sulfuric acid. The phases are separated and the aqueous phase is extracted with ethylacetate. The organic extracts are combined and concentrated to a volume of 120 ml, then acetonitrile (100 ml) and formic acid (22 ml) are added. The mixture is stirred at 30-35°C for 1 hour. The mixture is cooled to 2°C, the precipitate is filtered, washed with acetonitrile and dried to obtain 20.86 g of 5-thia-l-azabicyclo(4.2.0)oct-2-ene-2-carboxylic acid, 7-(((2Z)-(2-amino-4-thiazolyl)(carboxymethoxy)imino)acetylamino)-3-ethenyl-8-oxo-, (6R,7R)-(Cefixime). 

A mixture of 6.63 g of 2-hydroxymethyl-3-methyl-4-(2,2,2-trifluoroethoxy) pyridine (30 mmol), 4.5 g of 2-mercaptobenzimidazol (30 mmol) and 8.67 g of triphenylphosphine (33 mmol) was dissolved in 100 ml of tetrahydrofuran, 5.75 g of diethyl azodicarboxylate (33 mmol) dissolved in 30 ml of tetrahydrofuran was added dropwise thereto at room temperature, and stirred for 1 hour. The reaction mixture was concentrated under a reduced pressure, the resulting residue was combined with 100 ml of ethylacetate, and extracted twice with 50 ml portions of 1 N HCI. The aqueous layer was then washed with 50 ml of diethylether neutralized with 1 N NaOH to adjust the pH to 7. The resulting precipitates were filtrated, washed with water, and dried, to obtain 10.06 g of 2-[3-methyl-4-(2,2,2-trifluoroethoxy)-2-pyridyl]methylthio-lH-benzimidazole as a white solid (yield 95%), m.p.l42-144°C. 

HCPT (0.364 g 0.01 mmol) and 40% aqueous dimethylamine (12 ml) was added in dichloromethane (50 ml) in which anhydrous potassium carbonate (2.17 g, 15 mmol) has been suspended. The reaction mixture was stirred at room temperature for 5 h, then filtered and solid extracted with ethylacetate (20 ml). The solvent is evaporated in vacuo giving a residue. The residue was triturated with 0.5% aq HCI (50 ml) to dissolve the water-soluble adduct. Water-soluble were partitioned with petroleum ether (3 times 50 ml) and followed by ethylacetate (3 times 50 ml). The aqueous layer was lyophilized as an off white hydrochloride salt of 9-[(dimethylamino)methyl]10-hydroxy(20S)-camptothecin (topotecan hydrochloride) yield 0.236 g (65%). 

J. R. Pliego, Jr., and J. M. Riveros, Free energy profile of the reaction between the hydroxide ion and ethylacetate in aqueous and dimethylsulfoxide solutions A theoretical analysis of the changes induced by the solvent on the different reaction pathways, J. Phys. Chem. A, 108 (2004) 2520-2526. 

Therefore, without isotopic labeling, it is impossible to distinguish between azide-products and nitrene-products. That is the reason why only one NCN-olefin reaction (the thermolysis of NCN3 in cyclooctatetraene) was studied in detail. Cyclooctatetraene 49) reacts with NCN3 very slowly at room temperature and leads exclusively to the alkylidenecyanamide. Thermolysis of NCN3 in diluted (ethylacetate) cyclooctatetraene at 78 °C afforded 50, 51, 52 02.93). 

DCA is not consumed in the reaction medium and, for example, no conversion of tetraphenylethylene (Eox = 1.33 V vs SCE) 8 into benzophenone 12 (57%) and tetraphenyloxirane 16 (15%) occurs in the absence of oxygen or in less polar solvents, such as diethyl ether, ethylacetate, carbon tetrachloride, p-dioxane, or cyclohexane [84,95]. 

A powerful oxidizer. Explosive reaction with acetaldehyde, acetic acid + heat, acetic anhydride + heat, benzaldehyde, benzene, benzylthylaniUne, butyraldehyde, 1,3-dimethylhexahydropyrimidone, diethyl ether, ethylacetate, isopropylacetate, methyl dioxane, pelargonic acid, pentyl acetate, phosphoms + heat, propionaldehyde, and other organic materials or solvents. Forms a friction- and heat-sensitive explosive mixture with potassium hexacyanoferrate. Ignites on contact with alcohols, acetic anhydride + tetrahydronaphthalene, acetone, butanol, chromium(II) sulfide, cyclohexanol, dimethyl formamide, ethanol, ethylene glycol, methanol, 2-propanol, pyridine. Violent reaction with acetic anhydride + 3-methylphenol (above 75°C), acetylene, bromine pentafluoride, glycerol, hexamethylphosphoramide, peroxyformic acid, selenium, sodium amide. Incandescent reaction with alkali metals (e.g., sodium, potassium), ammonia, arsenic, butyric acid (above 100°C), chlorine trifluoride, hydrogen sulfide + heat, sodium + heat, and sulfur. Incompatible with N,N-dimethylformamide. 

---