Methyl acetate purification

Methyl acetate. An anhydrous product of 99 per cent, purity (b.p. 56-5-57°) i.s available coniniercially this is comparatively cheap so that purification of inferior products is not worth while. It is appreciably soluble in water (ca. 24 per cent, at 20°). The pure compound has b.p. 57°/760 mm. 

Purification of luciferin (Rudie etal., 1976). The luciferin fractions from the DEAE-cellulose chromatography of luciferase were combined and concentrated in a freeze-dryer. The concentrated solution was saturated with ammonium sulfate, and extracted with methyl acetate. The methyl acetate layer was dried with anhydrous sodium sulfate, concentrated to a small volume, then applied on a column of silica gel (2 x 18 cm). The luciferin adsorbed on the column was eluted with methyl acetate. Peak fractions of luciferin were combined, flash evaporated, and the residue was extracted with methanol. The methanol extract was concentrated (1 ml), then chromatographed on a column of SephadexLH-20 (2 x 80 cm) usingmethanol asthe solvent. The luciferin fractions eluted were combined and flash evaporated. The residue was... 

The novel approach finally taken was to conduct the reaction and purification steps in a reactor-distillation column in which methyl acetate could be made with no additional purification steps and with no unconverted reactant streams. Since the reaction is reversible and equilibrium-limited, high conversion of one reactant can be achieved only with a large excess of the other. However, if the reacting mixture is allowed to flash, the conversion is increased by removal of the methyl acetate from the liquid phase. With the reactants flowing countercurrently in a sequence of... 

A major challenge will be to develop new processes or step-up technologies that increase the yield and/or selectivity, use cheaper raw materials, decrease energy consumption, minimize the product separation and purification needs and lower capital investment. Iimoyative step-out technologies can still have a major impact on existing processes. An excellent example of such an accomplishment is the reactive distillation process developed by Eastman Chemicals for production of methyl acetate by via the reaction [2]... 

The conventional process consists of a reactor followed by eight distillation columns, one liquid-liquid extractor and a decantor. The reactive distillation process consists of one column that produces high-purity methyl acetate that does not require additional purification and there is no need to recover unconverted reactant. The reactive distillation process costs one fifth of the conventional process and consumes only one fifth of the energy. 

All solvents used for general applications were of reagent grade. For special purposes, purification of solvents was effected using standard procedures. All other reagents were used as supplied commercially except as noted. A solution of chloromethyl methyl ether (6 mmole/mL) in methyl acetate was prepared by adding acetyl chloride (141.2 g, 1.96 mol) to a mixture of dimethoxy methane (180 mL, 2.02 mol) and anhydrous methanol (5.0 mL, 0.12 mol).20 The solution was diluted with 300 mL of 1,1,2,2-tetrachloroethane and used as a stock solution for the chloromethylation experiments. 

The ease with which dissolution of the acetylated products can be achieved is affected by the method of isolation. In the author s experience, drying of the acetate with alcohol and ether results in apparent insolubility (even though the product was soluble at one stage of the purification process), and should be avoided. Drying, under diminished pressure, of the product precipitated by petroleum ether is sufficient. Chloroform is probably the best solvent. Nitroethane, tetrachlorethane, 2,4-pentanedione, pyridine, methyl acetate, ethyl acetate, and benzene, which have also been suggested, have disadvantages in that either they are unstable or they may cause aggregation in solution.44,116 116... 

Anhydrous methyl acetate was purchased from Aldrich Chemical Company, Inc., and used without further purification. 

The total synthesis of the immunosuppressant (-)-pironetin (PA48153C) was accomplished by G.E. Keck and co-workers. The six-membered a,(3-unsaturated lactone moiety was installed using a lactone annulation reaction by reacting the advanced aldehyde intermediate with the lithium enolate of methyl acetate. The aldehyde was prepared by the Ley oxidation of the corresponding primary alcohol and was used without purification in the subsequent annulation step. 

The liquid effluent leaving the reactor is flashed. The containing acetic acid, moisture, methyl iodide, and formic and propionic acids, etc. are sent to the purification section. The liquid fraction, chiefly formed of the catalyst complex, methyl acetate and acetic acid, is cooled and sent to the reaction zone. 

Product separation and purification the first distillation column is designed to produce a cut enriched with acetic acid by the removal of the lighter and heavier components (methyl iodide, methyl acetate, etc.. This-cut is then dehydrated by heteroazeotropic distillation. The aqueous fraction recovered at the top is refractionated to remove excess water. The heavy stream is treated in a finishing column which produces glads acetic add in the distillate, while the residual acetic add at the bottom is also recovered in a complementary fractionation that separates the heavy products such as propionic add. These high-alloy steel columns each have between 35 and 45 actual trays. 

The purification of the exhaust gas of PTA plants is one application where halohydrocarbon destruction catalysts have found use at a global scale (12, 13, 17, 18). Typically the untreated exhaust contains a mixture of volatile organic components including methyl bromide, carbon monoxide, hydrocarbons, methyl acetate, and organic acids. The presence of the methyl bromide sets forth the requirement that a catalyst such as the HDC be used. Additionally, the catalyst must be able to effectively destroy all the other organic components (with their widely different intrinsic reactivities toward air oxidation) of the mixture at reasonably low temperatures. Currently most PTA offgas remediation catalysts are used at an inlet temperature higher than 350°C. An improvement of catalyst activity is desired to... 

The equilibrium constant for this reaction is 5.2, so only moderate conversion could be obtained in a plug-flow or batch reactor. Purification of the product mixture would be very difficult, because there are two azeotropes, with boiling points close to that of methyl acetate. With reactive distillation, the higher boiling reactant, acetic acid, is fed near the top of the column, as shown in Figure 10.11, and methanol is fed near the bottom. This counter-... 

A methyl acetate-water mixture is produced in large quantities by the purification of terephthalic acid (PTA). The manufacture of poly vinyl alcohol (PVA) also produces large quantities of methyl acetate (1.68 kg/kg PVA). Methyl acetate is a comparatively low-value solvent, hence it has to be sold at a lower price. Alternatively, it can be hydrolyzed efficiently to recover methanol and acetic acid for reuse in the process [26-28]. 

The purification unit consists of three valve-tray columns. The production medium for AA in the purification stage at 130-200 °C contains up to 16% water, 26% methyl iodide, and other components, such as methyl acetate (MA), methanol (MeOH), hydrogen iodide (HI), formic acid (FA), and propionic acid (PA) (PEP Report, 1994). The fractionation column removes the light components and portions of water in the mixture, and the dehydration column treats both water and FA. The last column, which is an SSC, produces the final AA product from the side draw by cutting off the remaining light and heavy components from... 

Finally, a chiral 2-phenylpyrrolidine-derived thiourea was demonstrated to be an efficient organocatalyst to promote the clean substitution of 1-chloro-isochromans by silyl ketene acetals to provide the corresponding chiral substituted isochromans with high yields and enantioselectivities of up to 90% ee. Actually, the 1-chloroisochromans were prepared from the corresponding more stable methyl acetals, which were directly used without purification in the protocol evolving through a cationic oxocarbenium ion (Scheme 5.13). 

Air emissions from PTA production mostly come from the reactor vent gas of the TA production stage. There are no VOC emissions associated with the purification of TA. After passing through aqueous adsorbers, the reactor vent gas still contains the VOCs of p-xylene, acetic acid, methyl acetate, toluene, benzene, methyl bromide and CO. With increasingly stringent environmental regulations combined with the expansion of PTA capacity, more and more PTA plants are required to further reduce air emissions from the adsorber vent gas. 

The N-oxide function has proved useful for the activation of the pyridine ring, directed toward both nucleophilic and electrophilic attack (see Amine oxides). However, pyridine N-oxides have not been used widely ia iadustrial practice, because reactions involving them almost iavariably produce at least some isomeric by-products, a dding to the cost of purification of the desired isomer. Frequently, attack takes place first at the O-substituent, with subsequent rearrangement iato the ring. For example, 3-picoline N-oxide [1003-73-2] (40) reacts with acetic anhydride to give a mixture of pyridone products ia equal amounts, 5-methyl-2-pyridone [1003-68-5] and 3-methyl-2-pyridone [1003-56-1] (11). 

In the case of low temperature tar, the aqueous Hquor that accompanies the cmde tar contains between 1 and 1.5% by weight of soluble tar acids, eg, phenol, cresols, and dihydroxybenzenes. Both for the sake of economics and effluent purification, it is necessary to recover these, usually by the Lurgi Phenosolvan process based on the selective extraction of the tar acids with butyl or isobutyl acetate. The recovered phenols are separated by fractional distillation into monohydroxybenzenes, mainly phenol and cresols, and dihydroxybenzenes, mainly (9-dihydroxybenzene (catechol), methyl (9-dihydtoxybenzene, (methyl catechol), and y -dihydroxybenzene (resorcinol). The monohydric phenol fraction is added to the cmde tar acids extracted from the tar for further refining, whereas the dihydric phenol fraction is incorporated in wood-preservation creosote or sold to adhesive manufacturers. Naphthalene Oils. Naphthalene is the principal component of coke-oven tats and the only component that can be concentrated to a reasonably high content on primary distillation. Naphthalene oils from coke-oven tars distilled in a modem pipe stiU generally contain 60—65% of naphthalene. They are further upgraded by a number of methods. 

Fractionally distd under vacuum, then fractionally crystd twice from its melt. Impurities include acetic acid, methyl amine and H2O. For detailed purification procedure, see Knecht and Kolthoff, Inorg Chem 1 195 1962. Although /9-methylacetamide is commercially available it is often extensively contaminated with acetic acid, methylamine, water and an unidentified impurity. The recommended procedure is to synthesise it in the laboratory by direct reaction. The gaseous amine is passed into hot glacial acetic acid, to give a partially aq soln of methylammonium acetate which is heated to ca 130° to expel water. Chemical methods of purificatn such as extractn by pet ether, treatment with H2SO4, K2CO3 or CaO can be used but are more laborious. 

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