Ethyl acetate chloride

Add in turn benzyl chloride (8 3 g., 8 o ml.) and powdered thiourea (5 gm.) to 10 ml. of 95% ethanol in a 100 ml. flask fitted with a reflux condenser. Warm the mixture on the water-bath with gentle shaking until the reaction occurs and the effervescence subsides then boil the mixture under reflux for 30 minutes. Cool the clear solution in ice-water, filter off the crystalline deposit of the benzylthiouronium chloride at the pump, wash it with ice-cold ethyl acetate, and dry in a desiccator. Yield, 11-12 g., m.p. 170-174°. The white product is sufficiently pure for use as a reagent. It is very soluble in cold water and ethanol, but can be recrystallised by adding ethanol dropwise to a boiling suspension in ethyl acetate or acetone until a clear solution is just obtained, and then rapidly cooling. 

Fit a 750 ml, bolt-head flask (also by a rubber stopper) to a reflux water-condenser closed at the top by a calcium chloride tube ensure that flask and condenser are quite dr). Place 150 ml. of the dried ethyl acetate in the flask and add 15 g. of sodium. The sodium for this purpose should preferably be added in the form of wire directly from a sodium press (Fig. 55, p. 82) alternatively the sodium may be added as thin slices, but in this case each slice should be quickly pressed between drying-paper before being added to the acetate to remove the wet film which may have formed during the weighing and cutting of the metal. 

Selection of solvents. The choice of solvent will naturally depend in the first place upon the solubility relations of the substance. If this is already in solution, for example, as an extract, it is usually evaporated to dryness under reduced pressure and then dissolved in a suitable medium the solution must be dilute since crystallisation in the column must be avoided. The solvents generally employed possess boiling points between 40° and 85°. The most widely used medium is light petroleum (b.p. not above 80°) others are cycZohexane, carbon disulphide, benzene, chloroform, carbon tetrachloride, methylene chloride, ethyl acetate, ethyl alcohol, acetone, ether and acetic acid. 

Pure commercial ethyl acetate is allowed to stand for 2 days over anhydrous calcium chloride, the desiccant removed by filtration, and the ester is then finally dried over anliydrous calcium sulphate for several hours. 

Ben2onitri1e [100-47-0] C H CN, is a colorless Hquid with a characteristic almondlike odor. Its physical properties are Hsted in Table 10. It is miscible with acetone, ben2ene, chloroform, ethyl acetate, ethylene chloride, and other common organic solvents but is immiscible with water at ambient temperatures and soluble to ca 1 wt% at 100°C. It distills at atmospheric pressure without decomposition, but slowly discolors in the presence of light. 

Other acetyl chloride preparations include the reaction of acetic acid and chlorinated ethylenes in the presence of ferric chloride [7705-08-0] (29) a combination of ben2yl chloride [100-44-7] and acetic acid at 85% yield (30) conversion of ethyUdene dichloride, in 91% yield (31) and decomposition of ethyl acetate [141-78-6] by the action of phosgene [75-44-5] producing also ethyl chloride [75-00-3] (32). The expense of raw material and capital cost of plant probably make this last route prohibitive. Chlorination of acetic acid to monochloroacetic acid [79-11-8] also generates acetyl chloride as a by-product (33). Because acetyl chloride is cosdy to recover, it is usually recycled to be converted into monochloroacetic acid. A salvage method in which the mixture of HCl and acetyl chloride is scmbbed with H2SO4 to form acetyl sulfate has been patented (33). 

Norethindrone may be recrystakhed from ethyl acetate (111). It is soluble in acetone, chloroform, dioxane, ethanol, and pyridine slightly soluble in ether, and insoluble in water (112,113). Its crystal stmcture has been reported (114), and extensive analytical and spectral data have been compiled (115). Norethindrone acetate can be recrystakhed from methylene chloride/hexane (111). It is soluble in acetone, chloroform, dioxane, ethanol, and ether, and insoluble in water (112). Data for identification have been reported (113). The preparation of norethindrone (28) has been described (see Fig. 5). Norethindrone acetate (80) is prepared by the acylation of norethindrone. Norethindrone esters have been described ie, norethindrone, an appropriate acid, and trifiuoroacetic anhydride have been shown to provide a wide variety of norethindrone esters including the acetate (80) and enanthate (81) (116). 

The alcohols, proprietary denatured ethyl alcohol and isopropyl alcohol, are commonly used for E-type inks. Many E-type inks benefit from the addition of small amounts of ethyl acetate, MEK, or normal propyl acetate to the solvent blends. Aromatic hydrocarbon solvents are used for M-type inks. Polystyrene resins are used to reduce the cost of top lacquers. T-type inks are also reduced with aromatic hydrocarbons. Acryflc resins are used to achieve specific properties for V-type inks. Vehicles containing vinyl chloride and vinyl acetate copolymer resins make up the vinyl ink category. Ketones are commonly used solvents for these inks. 

PMMA is not affected by most inorganic solutions, mineral oils, animal oils, low concentrations of alcohols paraffins, olefins, amines, alkyl monohahdes and ahphatic hydrocarbons and higher esters, ie, >10 carbon atoms. However, PMMA is attacked by lower esters, eg, ethyl acetate, isopropyl acetate aromatic hydrocarbons, eg, benzene, toluene, xylene phenols, eg, cresol, carboHc acid aryl hahdes, eg, chlorobenzene, bromobenzene ahphatic acids, eg, butyric acid, acetic acid alkyl polyhaHdes, eg, ethylene dichloride, methylene chloride high concentrations of alcohols, eg, methanol, ethanol 2-propanol and high concentrations of alkahes and oxidizing agents. 

Solvent Evaporation. This encapsulation technology involves removing a volatile solvent from either an oil-in-water, oil-in-oil, or water-in-oH-in-water emulsion (19,20). In most cases, the shell material is dissolved in a volatile solvent such as methylene chloride or ethyl acetate. The active agent to be encapsulated is either dissolved, dispersed, or emulsified into this solution. Water-soluble core materials like hormonal polypeptides are dissolved in water that contains a thickening agent before dispersion in the volatile solvent phase that contains the shell material. This dispersed aqueous phase is gelled thermally to entrap the polypeptide in the dispersed aqueous phase before solvent evaporation occurs (21). 

Stannous Chloride Dihydrate. A white crystalline soHd, stannous chloride dihydrate is prepared either by treatment of granulated tin with hydrochloric acid followed by evaporation and crystallisation or by reduction of a stannic chloride solution with a cathode or tin metal followed by crystallisation. It is soluble in methanol, ethyl acetate, glacial acetic acid, sodium hydroxide solution, and dilute or concentrated hydrochloric acid. It is soluble in less than its own weight of water, but with much water it forms an insoluble basic salt. 

Stannous Oxalate. Stannous oxalate, Sn(C20 (mol wt 206.71, dec 280°C, sp gr 3.56 at 18°C), is a white crystalline powder, is soluble in hot concentrated hydrochloric acid and mixtures of oxaHc acid and ammonium oxalate, and is insoluble in water, toluene, ethyl acetate, dioctyl phthalate, THF, isomeric heptanes, and acetone (171). It is prepared by precipitation from a solution of stannous chloride and oxaHc acid and is stable indefinitely. 

Addition compounds form with those organics that contain a donor atom, eg, ketonic oxygen, nitrogen, and sulfur. Thus, adducts form with amides, amines, and A/-heterocycles, as well as acid chlorides and ethers. Addition compounds also form with a number of inorganic compounds, eg, POCl (6,120). In many cases, the addition compounds are dimeric, eg, with ethyl acetate, in titanium tetrachloride-rich systems. By using ammonia, a series of amidodichlorides, Ti(NH2) Cl4, is formed (133). 

Acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, ethyl acetate, and tetrahydrofuran are solvents for vinyhdene chloride polymers used in lacquer coatings methyl ethyl ketone and tetrahydrofuran are most extensively employed. Toluene is used as a diluent for either. Lacquers prepared at 10—20 wt % polymer sohds in a solvent blend of two parts ketone and one part toluene have a viscosity of 20—1000 mPa-s (=cP). Lacquers can be prepared from polymers of very high vinyhdene chloride content in tetrahydrofuran—toluene mixtures and stored at room temperature. Methyl ethyl ketone lacquers must be prepared and maintained at 60—70°C or the lacquer forms a sohd gel. It is critical in the manufacture of polymers for a lacquer apphcation to maintain a fairly narrow compositional distribution in the polymer to achieve good dissolution properties. 

The physical piopeities of ethyl chloiide aie hsted in Table 1. At 0°C, 100 g ethyl chloride dissolve 0.07 g water and 100 g water dissolve 0.447 g ethyl chloride. The solubihty of water in ethyl chloride increases sharply with temperature to 0.36 g/100 g at 50°C. Ethyl chloride dissolves many organic substances, such as fats, oils, resins, and waxes, and it is also a solvent for sulfur and phosphoms. It is miscible with methyl and ethyl alcohols, diethyl ether, ethyl acetate, methylene chloride, chloroform, carbon tetrachloride, and benzene. Butane, ethyl nitrite, and 2-methylbutane each have been reported to form a binary azeotrope with ethyl chloride, but the accuracy of this data is uncertain (1). 

Ghlorohydrination with Nonaqueous Hypochlorous Acid. Because the presence of chloride ions has been shown to promote the formation of the dichloro by-product, it is desirable to perform the chlorohydrination in the absence of chloride ion. For this reason, methods have been reported to produce hypochlorous acid solutions free of chloride ions. A patented method (48) involves the extraction of hypochlorous acid with solvents such as methyl ethyl ketone [78-93-3J, acetonitrile, and ethyl acetate [141-78-6J. In one example hypochlorous acid was extracted from an aqueous brine with methyl ethyl ketone in a 98.9% yield based on the chlorine used. However, when propylene reacted with a 1 Af solution of hypochlorous acid in either methyl ethyl ketone or ethyl acetate, chlorohydrin yields of only 60—70% were obtained (10). 

After the flask has been cooled by immersion in ice water, 44 g- (o-5 mole) of dry ethyl acetate (Note i) in an equal volume of ether is added over a period of twelve minutes. The cooling bath is removed and stirring is continued for ten minutes. When the reaction flask has again been cooled by the ice-water bath, a previously prepared ammonium chloride solution (Note 2) is added, very slowly at first, over a period of ten minutes, during which a pasty solid separates. 

Rhodamine B chloride [3,5-his-(diethylamino)-9-(2-carboxyphenyl)xanthylium chloride] [81-88-9] M 479.0, m 210-211"(dec), Cl 45170, A,max 543nm, Free base [509-34-2] Cl 749, pK 5.53. Major impurities are partially dealkylated compounds not removed by crystn. Purified by chromatography, using ethyl acetate/isopropanol/ammonia (conc)(9 7 4, Rp 0.75 on Kieselgel G). Also crystd from cone soln in MeOH by slow addition of dry diethyl ether or from EtOH containing a drop of cone HCl by slow addition of ten volumes of dry diethyl ether. The solid was washed with ether and air dried. The dried material has also been extracted with benzene to remove oil-soluble material prior to recrystn. Store in the dark. 

Examples of mono-layer adsorption isotherms obtained for chloroform and butyl chloride are shown in Figure 5. The adsorption isotherms of the more polar solvents, ethyl acetate, isopropanol and tetrahydro-furan from -heptane solutions on silica gel were examined by Scott and Kucera [4]. Somewhat surprisingly, it was found that the experimental results for the more polar solvents did not fit the simple mono-layer... 

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