Ethyl acetate iodide

Allow a mixture of 0-5 g. of the tertiary amine and 0-5 ml. of colourless methyl iodide to stand for 5 minutes. If reaction has not occurred, warm under reflux for 5 minutes on a water bath and then cool in ice water. The mixture will generally set solid if it does not, scratch the sides of the tube with a glass rod. RecrystaUise the solid product from absolute alcohol, ethyl acetate, acetone, glacial acetic acid or alcohol-ether. 

Ethyl phenylethylmalonate. In a dry 500 ml. round-bottomed flask, fitted with a reflux condenser and guard tube, prepare a solution of sodium ethoxide from 7 0 g. of clean sodium and 150 ml. of super dry ethyl alcohol in the usual manner add 1 5 ml. of pure ethyl acetate (dried over anhydrous calcium sulphate) to the solution at 60° and maintain this temperature for 30 minutes. Meanwhile equip a 1 litre threenecked flask with a dropping funnel, a mercury-sealed mechanical stirrer and a double surface reflux condenser the apparatus must be perfectly dry and guard tubes should be inserted in the funnel and condenser respectively. Place a mixture of 74 g. of ethyl phenylmalonate and 60 g. of ethyl iodide in the flask. Heat the apparatus in a bath at 80° and add the sodium ethoxide solution, with stirring, at such a rate that a drop of the reaction mixture when mixed with a drop of phenolphthalein indieator is never more than faintly pink. The addition occupies 2-2 -5 hoius continue the stirring for a fiuther 1 hour at 80°. Allow the flask to cool, equip it for distillation under reduced pressure (water pump) and distil off the alcohol. Add 100 ml. of water to the residue in the flask and extract the ester with three 100 ml. portions of benzene. Dry the combined extracts with anhydrous magnesium sulphate, distil off the benzene at atmospheric pressure and the residue under diminished pressure. C ollect the ethyl phenylethylmalonate at 159-160°/8 mm. The yield is 72 g. 

Tetra-n-butylammonium iodide [311-28-4] M 369.4, m 146". Crystd from toluene/pet ether (see entry for the corresponding bromide), acetone, ethyl acetate, EtOH/diethyl ether, nitromethane, aq EtOH or water. Dried at room temperature under vac. It has also been dissolved in MeOH/acetone (1 3, lOmL/g), filtered and allowed to stand at room temperature to evaporate to ca half its original volume. Distilled water (ImL/g) was then added, and the ppte was filtered off and dried. It was also dissolved in acetone, ppted by adding ether and dried in vac at 90" for 2 days. It has also been recrystallised from CH2Cl2/pet ether or hexane, or anhydrous methanol and stored in a vacuum desiccator over H2SO4. [Chau and Espenson J Am Chem Soc 108 1962... 

Tetraethylammonium iodide [68-05-3] M 257.2, m 302 , >300 (dec). Crystd from acetone/MeOH, EtOH/water, dimethylacetamide or ethyl acetate/EtOH (19 1). Dried under vacuum at 50° and stored over P2OS. 

Tetramethylammonium iodide [75-58-1] M 201.1, m >230°(dec). Crystd from water or 50% EtOH, EtOH/diethyl ether, ethyl acetate, or from acetone/MeOH (4 1) by adding an equal volume of acetone. Dried in a vacuum desiccator. 

The tetrahydropyranyi ether is prepared and reduced exactly as in Procedures 8a and 8c up to the point at which ethylene dibromide would be added. At this point 27 ml (61.5 g, 0.43 mole) of methyl iodide is added instead the addition requires 1-2 min and should be cautious at first. The mixture is stirred for 1 hr and the ammonia is allowed to boil off overnight. The product is isolated as described in Procedures 8a and 8c except that a larger volume of ethyl acetate is required to dissolve the product than in 8c. After removal of the ethyl acetate, the residual material is crystallized from methanol (400 ml). 

The mixture is cooled to room temperature, then filtered. The solvent is removed under reduced pressure, leaving the tribromide (47) as a foam. The foam is mixed with sodium iodide (9.55 g, 0.064 mole) and acetone (74 ml) and heated under reflux in a nitrogen atmosphere for 3.5 hr. The acetone is removed under reduced pressure and the residue is treated with chloroform and aqueous sodium thiosulfate solution. The chloroform layer is separated and washed with sodium thiosulfate solution until it is free from iodine, then dried over magnesium sulfate, filtered and evaporated to dryness under reduced pressure. The crude product (48) is obtained as a brown sohd (4.85 g) which is chromatographed over alumina (122 g, Merck acid-washed). The column is developed with hexane, benzene and ethyl acetate mixtures. The product (3.43 g) is eluted by benzene and benzene-ethyl acetate (10 1). Recrystallization from acetone yields purified 3jS-acetoxy-pregna-5,14,16-trien-20-one (48), 3.25 g, mp 158-159° 309 m/ (e 10,700). 

Acetylindole (213) was obtained by the action of ethyl acetate on indole magnesium iodide at low temperatures slightly higher yields were obtained when the reaction was carried out in anisole rather than in ether. Putochin subsequently observed that when the reaction was carried out in benzene at 85° both 213 and 3-acetylindole (109)... 

Replacement of silver nitrite by inexpensive sodiiunor potassium nitrite enhances the imlity of this process Treatment of alkenes v/ith sodiiun nitrite and iodine in ethyl acetate and water in the presence of ethylene glycol gives conjngatednitroalkenesin49-82% yield The method for generation of nitryl iodide is improved by the treatment of iodme v/ith potassium nitrite complexed v/ith 18-crovm-6 in THF under sonicadon, as shovmin Eq 2 32 ... 

Xthyl at, n. ethylate, -atber, m. ethyl ether, >azetat, n, ethyl acetate, -blau, n, ethyl blue. AthyleQi n, ethylene, -bindung, /, ethylene linkage, double bond, -jodid, n. ethylene iodide, -oryd, n. ethylene oxide, -reihe, /. ethylene series, -verbindung, /. ethylene compound,... 

A mixture of 10 parts of 7-chloro-4-fluorobutyrophenone, 5.5 parts of 1-(1,2,3,6-tetrahydro-4-pyridyl)-2-benzimidazolinone, 4 parts of sodium carbonate, and 0.1 part of potassium iodide in 176 parts of 4-methyl-2-pentanone is stirred and refluxed for 64 hours. The cooled reaction mixture is filtered and the solvent is evaporated from the filtrate to leave an oily residue which is dissolved in toluene. The toluene solution is filtered and the solvent is evaporated. The resultant residue is recrystallized from a mixture of 32 parts of ethyl acetate and 32 parts of diisopropyl ether to give 1-[1-[(4-fluorobenzoyl)propyll-1,2,3,6-tetrahydro-4-pyridyl]-2-benzimidazolinone hydrate melting at about 145°-146.5°C. 

A sample of distilled base in cold isopropanol is treated with excess methyl iodide, left at room temperature overnight, diluted with 5 volumes of ethyl acetate and filtered from the methiodide salt. This is purified by crystallization from mixtures of isopropanol and ethyl acetate, filtering hot to remove an impurity of low solubility. The pure methiodide is obtained as a white solid, MP 124° to 124.5°C, containing 99 mol percent thiol isomer. 

Diisopropylamino-a,a-diphenylbutyramide in propanol was refluxed 4 hours in the presence of excess methyl iodide. Upon dilution of the solution with ethyl acetate (100 ml per 50 ml isopropyl alcohol) and cooling 7-diisopropylamino-a,a-diphenylbutyramide methiodide precipitated, was collected by filtration and recrystallized (9.0 g) by dissolving in a hot mixture of 100 ml isopropyl alcohol and 10 ml methanol and then diluting with 90 ml Skellysolve B, to give B.3 g recrystallized product, MP 1B2° to 1B4°C. 

A) PivaloyloxymethylD(—j-Oi-azidobenzylpenicillinate Toa suspension ofpotassiumD(—)-a-azidobenzylpenicillinate (4.14g) and potassium dicarbonate (1.5 g) in acetone (100 ml) and 10% aqueous sodium iodide (2 ml), chloromethyl pivalate (2.7 ml) was added and the mixture refluxed for 2 hours. After cooling, the suspension was filtered and the filtrate evaporated to dryness in vacuo. The remaining residue was washed repeatedly by decantation with petroleum ether to remove unreacted chloromethyl pivalate. The oily residue was taken up in ethyl acetate (100 ml), and the resulting solution washed with aqueous sodium bicarbonate and water, dried and evaporated in vacuo to yield the desired compound as a yellowish gum, which crystallized from ether, melting point 114°C to 115°C. 

Methylene Iodide, 1, 57 7, 90 0-Methyl Esculetin, 4, 45 df-METHYL Ethyl Acetic Acid, 5,75 Methyl formate, 3, 67 a-M ETHYL d-GLUCOSIDE, 6, 64... 

The reaction is a sensitive one, but is subject to a number of interferences. The solution must be free from large amounts of lead, thallium (I), copper, tin, arsenic, antimony, gold, silver, platinum, and palladium, and from elements in sufficient quantity to colour the solution, e.g. nickel. Metals giving insoluble iodides must be absent, or present in amounts not yielding a precipitate. Substances which liberate iodine from potassium iodide interfere, for example iron(III) the latter should be reduced with sulphurous acid and the excess of gas boiled off, or by a 30 per cent solution of hypophosphorous acid. Chloride ion reduces the intensity of the bismuth colour. Separation of bismuth from copper can be effected by extraction of the bismuth as dithizonate by treatment in ammoniacal potassium cyanide solution with a 0.1 per cent solution of dithizone in chloroform if lead is present, shaking of the chloroform solution of lead and bismuth dithizonates with a buffer solution of pH 3.4 results in the lead alone passing into the aqueous phase. The bismuth complex is soluble in a pentan-l-ol-ethyl acetate mixture, and this fact can be utilised for the determination in the presence of coloured ions, such as nickel, cobalt, chromium, and uranium. 

A solution of 4.5 g (19.9 mmol) 4-(fm-butyldimethylsilyloxy)-2-cyclohexenone and 452 mg (1 mmol) of mercury(II) iodide is stirred at r.t. for 15 min and then cooled to — 78 °C. 5.03 g (24.8 mmol) of 1-ethoxy-1-(tm-bulyl(iimethylsilyloxy)ethene are added dropwise during 15 min. The mixture is stirred at — 78 °C for 2 h, quenched with 302 mg (3 mmol) of triethylamine and allowed to warm to r.t. The mixture is filtered through a short (3 cm) column of silica gel (deactivated with a 5% triethylamine solution in hexane/ethyl acetate, 10 1) eluting with hexane/ethyl acetate (10 1) and concentrated in vacuo. Purification of the crude material by flash chromatography (silica gel, hcxanc/cthyl acetate 30 1) gave the adduct as a colorless oil yield 7.98 g (18.7 mmol, 94%) d.r. (cisjtrans) 95.2 4.8. 

Diiodosilane l2SiH2 1872, prepared by treatment of phenylsilane PhSiHs with iodine, via PhSiH2l, in the presence of catalytic amounts of ethyl acetate at -20 °C, is much more electrophilic than Me3SiI 17 and therefore converts secondary alcohols such as 2-octanol 1871, at room temperature with Walden inversion, into iodides such as 1873 in 93% yield whereas the diol 1874 is nearly quantitatively converted into the monoiodobutane 1875 and only traces of the diiodobutane 1876 [88, 89] (Scheme 12.26). 

Potassium or lithium derivatives of ethyl acetate, dimethyl acetamide, acetonitrile, acetophenone, pinacolone and (trimethylsilyl)acetylene are known to undergo conjugate addition to 3-(t-butyldimethylsiloxy)-l-cyclohexenyl f-butyl sulfone 328. The resulting a-sulfonyl carbanions 329 can be trapped stereospecifically by electrophiles such as water and methyl iodide . When the nucleophile was an sp -hybridized primary anion (Nu = CH2Y), the resulting product was mainly 330, while in the reaction with (trimethylsilyl)acetylide anion the main product was 331. 

As in the earlier examinations, the amount of methyl iodide detected in the purged product was still averaged ca. 0.3 wt.%. However, unlike the earher ran with [MePy]I, we took a close look at the effluent from the operation with l,2-dimethyl-5-ethyl-pyridinium iodide ([DMEpy] ). All the product was distilled overhead leaving a residue that upon examination by NMR contained a ca. 3 1 acetate [DMEpyratio. Closer examination by NMR revealed that only about 3% of [DMEpy]l in the overhead distillate had been dealkylated to 2-methyl-5-ethyl pyridium hydroiodide. 

Titanium(IV) iodide is extremely hygroscopic. It dissolves in water with decomposition, and it fumes in air owing to hydrolysis. It forms 2 1 adducts with ammonia,7 pyridine,33 and ethyl acetate.34 With excess ammonia it undergoes ammo-nolysis to give ammonobasic titanium(IV) iodides.7 Analogous aminolysis reactions occur when titanium(IV) iodide is treated with an excess of primary or secondary amine.36 Titanium(IV) iodide is sparingly soluble in petroleum ether, moderately soluble in benzene, and even more soluble in chlorinated hydrocarbons and carbon disulfide. At elevated temperatures it... 

The principal competing reactions to ruthenium-catalyzed acetic acid homologation appear to be water-gas shift to C02, hydrocarbon formation (primarily ethane and propane in this case) plus smaller amounts of esterification and the formation of ethyl acetate (see Experimental Section). Unreacted methyl iodide is rarely detected in these crude liquid products. The propionic acid plus higher acid product fractions may be isolated from the used ruthenium catalyst and unreacted acetic acid by distillation in vacuo. 

The yields of propionic and higher acids are also definitely improved with increasing initial methyl iodide concentration (Figure 1) but here the relationship is complicated by the fact that at low methyl iodide concentrations (and thereby [MeI]/[Ru] <5) the corresponding esters, particularly ethyl acetate and ethyl propionate, become the principal products, rather than the corresponding free acids, while at much higher iodide concentrations, where [MeI]/[Ru] ratios are 30 or more, there is a phase separation of the product liquids into aqueous-rich and water-poor fractions. 

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