Methyl acetate acetylene

Methyl(/i-amyl)ketone (2-heptanone) 5-Methyl-3-heptanone Methyl acetate Methyl acetylene... 

ETHYLENE GLYCOL ETHYL MERCAPTAN DIMETHYL SULPHIDE ETHYL AMINE DIMETHYL AMIDE MONOETHANOLAMINE ETHYLENEDIAMINE ACRYLONITRILE PROPADIENE METHYL ACETYLENE ACROLEIN ACRYLIC ACID VINYL FORMATE ALLYL CHLORIDE 1 2 3-TRICHLOROPROPANE PROPIONITRILE CYCLOPROPANE PROPYLENE 1 2-DICHLOROPROPANE ACETONE ALLYL ALCOHOL PROPIONALDEHYDE PROPYLENE OXIDE VINYL METHYL ETHER PROPIONIC ACID ETHYL FORMATE METHYL ACETATE PROPYL CHLORIDE ISOPROPYL CHLORIDE PROPANE... 

In this chapter we discuss the mechanistic and other details of a few industrial carbonylation processes. These are carbonylation of methanol to acetic acid, methyl acetate to acetic anhydride, propyne to methyl methacrylate, and benzyl chloride to phenyl acetic acid. Both Monsanto and BASF manufacture acetic acid by methanol carbonylation, Reaction 4.1. The BASF process is older than the Monsanto process. The catalysts and the reaction conditions for the two processes are also different and are compared in the next section. Carbonylation of methyl acetate to acetic anhydride, according to reaction 4.2, is a successful industrial process that has been developed by Eastman Kodak. The carbonylation of propyne (methyl acetylene) in methanol to give methyl methacrylate has recently been commercialized by Shell. The Montedison carbonylation process for the manufacture of phenyl acetic acid from benzyl chloride is noteworthy for the clever combination of phase-transfer and organometallic catalyses. Hoechst has recently reported a novel carbonylation process for the drug ibuprofen. 

Methyl-3-heptanone Methyl acetate Methyl acetylene... 

N-Methyl acetamide Methyl acetate Methyl acetylene Methyl acrylate Methyl amine Methyl benzoate 3-Methyl- 1,2-butadiene 2-Methylbutane... 

Parkesine). Nitrocellulose is mixed with wood naphtha (a mixture of methanol, acetone, acetic acid, and methyl acetate formed during the distillation of wood) to produce a malleable solid. It is marketed, with little success, as a sculpting material. German chemist Eriedrich Wohler first makes calcium carbide, from which he later obtains acetylene. 

Monochloroacetic Acid Glycolic Acid Hydroxyacetic Acid Methyl Acetate Peracetic Acid Acetylene Tetrabromide 1,1/2,2-Tetrabromoethane Isobutyric Acid 2-Methylpropanoic Acid... 

Explain the following observations (a) Ru(CO) Ij and Pt(CO)jIj act as promoters in Ir-catalyzed carbonylation but not in Rh-catalyzed carbonylation of methanol (b) in the concentration of LP ([LP]) versus initial rate plots of methyl acetate carbonylation, at low [Li ] the initial rate increases and then at higher [LP] it levels off (c) acetaldehyde and propionic acid are side products of Rh- and Ir-catalyzed carbonylations (d) instead of methyl acetate, dimethylether can also be carbonylated to give acetic anhydride (e) in the Pd-catalyzed carbonylation of methyl acetylene, the amount of CHjCH=CH(C02Me) formed is very httle (f) Co-catalyzed carbonylation of benzyl chloride to phenyl acetic acid requires a phase-transfer catalyst (g) a neutral catalytic intermediate may be involved in Rh-catalyzed WGS reaction (h) complexes of the general formula A X where A is a Lewis acid are effective catalysts for polymerizing epoxides with CO (i) reaction... 

The direct combination of selenium and acetylene provides the most convenient source of selenophene (76JHC1319). Lesser amounts of many other compounds are formed concurrently and include 2- and 3-alkylselenophenes, benzo[6]selenophene and isomeric selenoloselenophenes (76CS(10)159). The commercial availability of thiophene makes comparable reactions of little interest for the obtention of the parent heterocycle in the laboratory. However, the reaction of substituted acetylenes with morpholinyl disulfide is of some synthetic value. The process, which appears to entail the initial formation of thionitroxyl radicals, converts phenylacetylene into a 3 1 mixture of 2,4- and 2,5-diphenylthiophene, methyl propiolate into dimethyl thiophene-2,5-dicarboxylate, and ethyl phenylpropiolate into diethyl 3,4-diphenylthiophene-2,5-dicarboxylate (Scheme 83a) (77TL3413). Dimethyl thiophene-2,4-dicarboxylate is obtained from methyl propiolate by treatment with dimethyl sulfoxide and thionyl chloride (Scheme 83b) (66CB1558). The rhodium carbonyl catalyzed carbonylation of alkynes in alcohols provides 5-alkoxy-2(5//)-furanones (Scheme 83c) (81CL993). The inclusion of ethylene provides 5-ethyl-2(5//)-furanones instead (82NKK242). The nickel acetate catalyzed addition of r-butyl isocyanide to alkynes provides access to 2-aminopyrroles (Scheme 83d) (70S593). 

The principal components of the cut are butene-1, butene-2, isobutylene and butadiene-1,3. Methyl, ethyl, and vinyl acetylenes, butane and butadiene-1,2 are present in small quantities. Butadiene is recovered from the C4 fraction by extraction with cuprous ammonium acetate (CAA) solution, or by extractive distillation with aqueous acetonitrile (ACN). The former process is a liquid-liquid separation, and the latter a vapor-liquid separation. Both take advantage of differences in structure and reactivity of the various C4 components to bring about the desired separation. 

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)-1 -cyclohexenyl t-butyl sulfone 328. The resulting a-sulfonyl carbanions 329 can be trapped stereospecifically by electrophiles such as water and methyl iodide417. When the nucleophile was an sp3-hybridized primary anion (Nu = CH2Y), the resulting product was mainly 330, while in the reaction with (trimethylsilyl)acetylide anion the main product was 331. 

The hydration of triple bonds is generally carried out with mercuric ion salts (often the sulfate or acetate) as catalysts. Mercuric oxide in the presence of an acid is also a common reagent. Since the addition follows Markovnikov s rule, only acetylene gives an aldehyde. All other triple-bond compounds give ketones (for a method of reversing the orientation for terminal alkynes, see 15-16). With allqmes of the form RC=CH methyl ketones are formed almost exclusively, but with RC=CR both possible products are usually obtained. The reaction can be conveniently carried out with a catalyst prepared by impregnating mercuric oxide onto Nafion-H (a superacidic perfluorinated resinsulfonic acid). ... 

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