Methyl acetate amine

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... 

The reaction of alcohols with CO was catalyzed by Pd compounds, iodides and/or bromides, and amides (or thioamides). Thus, MeOH was carbonylated in the presence of Pd acetate, NiCl2, tV-methylpyrrolidone, Mel, and Lil to give HOAc. AcOH is prepared by the reaction of MeOH with CO in the presence of a catalyst system comprising a Pd compound, an ionic Br or I compound other than HBr or HI, a sulfone or sulfoxide, and, in some cases, a Ni compound and a phosphine oxide or a phosphinic acid.60 Palladium(II) salts catalyze the carbonylation of methyl iodide in methanol to methyl acetate in the presence of an excess of iodide, even without amine or phosphine co-ligands platinum(II) salts are less effective.61 A novel Pd11 complex (13) is a highly efficient catalyst for the carbonylation of organic alcohols and alkenes to carboxylic acids/esters.62... 

Initial theoretical studies focused on steps (1) and (2). Several model systems were examined with ab initio calculations.1191 For the reaction of methyl amine with methyl acetate, it was shown that the addition/elimi-nation (through a neutral tetrahedral intermediate) and the direct displacement (through a transition state similar to that shown in Figure 5a) mechanisms for aminolysis had comparable activation barriers. However, in the case of methyl amine addition to phenyl acetate, it was shown that the direct displacement pathway is favored by approximately 5 kcal/mol.1201 Noncovalent stabilization of the direct displacement transition state was therefore the focus of the subsequent catalyst design process. 

Amine promoters tend to give higher acetaldehyde rates relative to phosphines. Increasing the temperature to 200 increases the rate to 7.1 M/hr whereas decreasing the pressure to 2000 psig markedly lowers the rate. Lil is a critical component of the catalyst. Substituting Lil with Nal, KI, or CH I results in a substantial loss in catalytic activity. A key step in the postulated reaction mechanism, as outlined in Equations 16-18, is cleavage of methyl acetate by Lil to yield CH I and LiOAc (27). ... 

The catalyst is generally a palladium compound promoted with a trivalent amine or phosphine in the presence of methyl iodide as described earlier. Systems proven to bias acetaldehyde are utilized, of course (e.g. see Table I, run 12). A yield of 85% acetaldehyde from methyl acetate is typical by this method. It can be utilized in stoichiometric addition to easily prepared acetic anhydride resulting in EDA formation. When considering that the "boiling pot" reaction by-products are recyclable acetic acid, acetic anhydride and small amounts of EDA, the yield to vinyl acetate related products is 95%. 

Rhodium(II) acetate catalyzes C—H insertion, olefin addition, heteroatom-H insertion, and ylide formation of a-diazocarbonyls via a rhodium carbenoid species (144—147). Intramolecular cyclopentane formation via C—H insertion occurs with retention of stereochemistry (143). Chiral rhodium (TT) carboxamides catalyze enantioselective cyclopropanation and intramolecular C—N insertions of CC-diazoketones (148). Other reactions catalyzed by rhodium complexes include double-bond migration (140), hydrogenation of aromatic aldehydes and ketones to hydrocarbons (150), homologation of esters (151), carbonylation of formaldehyde (152) and amines (140), reductive carbonylation of dimethyl ether or methyl acetate to 1,1-diacetoxy ethane (153), decarbonylation of aldehydes (140), water gas shift reaction (69,154), C—C skeletal rearrangements (132,140), oxidation of olefins to ketones (155) and aldehydes (156), and oxidation of substituted anthracenes to anthraquinones (157). Rhodium-catalyzed hydrosilation of olefins, alkynes, carbonyls, alcohols, and imines is facile and may also be accomplished enantioselectively (140). Rhodium complexes are moderately active alkene and alkyne polymerization catalysts (140). In some cases polymer-supported versions of homogeneous rhodium catalysts have improved activity, compared to their homogenous counterparts. This is the case for the conversion of alkenes direcdy to alcohols under oxo conditions by rhodium—amine polymer catalysts... 

In spite of a long-time paradigm that enzymes can be active only in their natural aqueous media and other solvents cause deactivation and denaturation of proteins, at present a growing number of investigations are devoted to enzymatic reactions in organic solvents (Klibanov, 2001 Ke et al., 1996 Koskinen and Klibanov, 1996 and references therein). Such enzymes as a-chymotrypsin, subtilisin ribonuclease, pancreatuc lipase, and horse radish peroxidase have been found to be markedly active in organic solvents (alcohols, amines, tiols,anhydrous alkanes, acetonitril, dichloromethane, methyl acetate, etc.). 

Write condensed formulas for (a) acetone, (b) acetic acid, (c) methyl acetate, (d) ethyl alcohol, (e) methyl amine, and (f) formaldehyde. 

Dimethyl amine also reacts with the azeotrope of methyl acetate and methanol to give DAIAC in 45% yield (5). 

Methyl-2-morpholino- E15/1, 608 (Keton-0,0-acetal Amin), 616 (Keton Amin)... 

Table 1 demonstrates that NaBH4 may be used in the presence of heterocyclic rings (entries 8-10, 13-17), esters (entries 8-10, 17), amides (entries 1, 9), conjugated double bonds (entry 7), alkynes (entry 5) and acetals (entry 4). The process can also be used to methylate an amine with formaldehyde as the carbonyl (entry 13). With certain structures, further reactions may occur subsequent to reduction (e.g. entry 6). Entry 15 illustrates a synthetically useful amine alkylation reaction which may occur in acetic acid. This remarkable reaction is attributed to self-reduction of an acyloxyborohydride to an aldehyde... 

The equilibrium point lies far to the left and little methyl acetate (CH3COOCH3) is formed if water in not removed. By reactive distillation it is possible to continuously remove water and considerably intensify the reaction. Eastman Chemical pioneered one of the first major applications of reactive distillation, to significantly simplify the production of methyl acetate (Figure 3.7). This unit first went into operation in 1983. Among typical reactions where a by-product prevents the reaction from going to the right are esterification, trans-esterification, hydrolysis, acetalization and amination. Other types of reactions that could benefit from reactive distillation include alkylation/transalkylation/dealkylation, isomerization and chlorination. 

A simple and straightforward application was outlined in the synthesis of hydrohydrastinine as depicted in Scheme 10. Michael addition of 3,4-methyle-nedioxyphenylmethyl amine to vinyl sulfoxide 36 took place smoothly in refluxing methanol. Pummerer rearrangement in acetic anhydride afforded acetoxysulfide 37 in 90% yield and this was then cyclized to 38 with BF3 etherate in 93 % yield. Sulfide 38, which was rather unstable, was desulfurized with Raney nickel in 80 % yield. Hydrolysis of the acetyl group followed by reductive methy-lation afforded hydrohydrastinine (39) in good yield [24]. 

Methoxy-methoxyethanol Methyl acetate acrylic acid (a-) alcohol -amine... 

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

Diethyl- amine Acetone Methyl acetate Diethyl- amine Aceto- nitrile /-PrOH MeOH ... 

Amine Acetate KK. See Cocamine acetate Amine C4. See n-Butylamine Amine Cs- SeePentylamine Amine C(8). See 1-Octanamine Amine y-glutamyltransferase. See Transglutaminase Amines, N-(3-aminopropyl)-N-cocoalkyltrimethylenedi-. See N-Coco dipropylene triamine Amines, N-(3-aminopropyl)-N-tallow alkyltrimethylenedi-. See N-3-Aminopropyl-N-tallow alkyl trimethylene diamines Amines, bis (hydrogenated tallow alkyl)-. See Hydrogenated ditallowamine Amines, bis (hydrogenated tallow alkyl) methyl. 

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