Methanol and derivatives

Ammonia is the basis for industrial fertilizer production and, therefore, the most important bulk chemical in the world. About one-quarter comes from coal gasification [1]. It is produced by the Haber-Bosch synthesis, which takes place at 90-180 bar and 400-530°C using the following reaction [28]  

Consequently, the feed gas should feature a molar H2/N2 ratio of 3, while the sum of oxygen species (O2, CO, CO2, and H2O) should be below 30 ppmv, total sulfur below 0.1 ppmv and inerts including CH4 below 2 vol% [3,29]. 

Such conditions indicate that all the CO contained in the raw gas must be converted to H2 in a water-gas shift reactor (CO + H2O H2 -F CO2, see also 

Hydrogen and carbon monoxide as well as minor quantities of carbon dioxide may react in the presence of a catalyst to form methanol  

The typical size of methanol plants is between 2000 and 3000 t/d. More than one-third of the total world methanol production was based on coal gasification in 2013. Only 14.3% of total world production of methanol is used directly for blending into gasoline or combustion. The remaining part is converted to derivatives, such as formaldehyde (29.9%), methyl tert-butyl ether (MTBE, 13.2%), olefins (9.1%), acetic add (8.8%), dimethyl ether (DME, 7.3%), and various other chemical products and gasoline totaling to 17.4% [1,30]. 

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Suspend 0 25 g. of 2 4-dinitrophenylhydrazine in 5 ml. of methanol and add 0-4 0-5 ml. of concentrated sulphuric acid cautiously. FUter the warm solution and add a solution of 0 1-0-2 g. of the carbonyl compound in a small volume of methanol or of ether. If no sohd separate within 10 minutes, dUute the solution carefuUy with 2N sulphuric acid. CoUect the solid by suction filtration and wash it with a little methanol. RecrystaUise the derivative from alcohol, dUute alcohol, alcohol with ethyl acetate or chloroform or acetone, acetic acid, dioxan, nitromethane, nitrobenzene or xylene. 

Physical properties of A-4-thiazoline-2-one and derivatives have received less attention than those of A-4-thiazoline-2-thiones. For the protomeric equilibrium, data obtained by infrared spectroscopy favors fbrm 51a in chloroform (55, 96, 887) and in the solid state (36. 97. 98) (Scheme 23). The same structural preference is suggested by the ultraviolet spectroscopy studies of Sheinker (98), despite the fact that previous studie.s in methanol (36) suggested the presence of both 51a and... 

The thiazolium ring, as most heterocycloammoniums, is a Lewis acid conferring to the carbon atom in the 2-position the carbocationic property of adding the free pair of a base either organic or mineral that may be the molecule of solvent as ROH (Scheme 11). For many nuclei of suitable acidity, these equilibria can be observed in dilute solution by means of absorption spectra when species A and C possess different characteristics (24). For example, benzothiazolium and benzoxazolium in methanol and ethanol give at 10 mole liter 8 and 54% of the alkoxy derivatives for the former and 29 and 90% for the latter respectively. 

The Eastman acetic anhydride [108-24-7] process provides an extension of carbonylation chemistry to carboxyUc acid esters. The process is based on technology developed independendy in the 1970s by Eastman and Halcon SD. The Eastman acetic anhydride process involves carbonylation of methyl acetate [79-20-9] produced from coal-derived methanol and acetic acid [64-19-7]. 

Capacity Limitations and Biofuels Markets. Large biofuels markets exist (130—133), eg, production of fermentation ethanol for use as a gasoline extender (see Alcohol fuels). Even with existing (1987) and planned additions to ethanol plant capacities, less than 10% of gasoline sales could be satisfied with ethanol—gasoline blends of 10 vol % ethanol the maximum volumetric displacement of gasoline possible is about 1%. The same condition apphes to methanol and alcohol derivatives, ie, methyl-/-butyl ether [1634-04-4] and ethyl-/-butyl ether. 

There are some chemicals that can be made economically from coal or coal-derived substances. Methanol and CO are used to make acetic anhydride and acetic acid. Methanol itself can be made from synthesis gas over a copper-2inc catalyst (see Feedstocks, coal chemicals). 

Selected physical properties of various methacrylate esters, amides, and derivatives are given in Tables 1—4. Tables 3 and 4 describe more commercially available methacrylic acid derivatives. A2eotrope data for MMA are shown in Table 5 (8). The solubiUty of MMA in water at 25°C is 1.5%. Water solubiUty of longer alkyl methacrylates ranges from slight to insoluble. Some functionalized esters such as 2-dimethylaniinoethyl methacrylate are miscible and/or hydrolyze. The solubiUty of 2-hydroxypropyl methacrylate in water at 25°C is 13%. Vapor—Hquid equiUbrium (VLE) data have been pubHshed on methanol, methyl methacrylate, and methacrylic acid pairs (9), as have solubiUty data for this ternary system (10). VLE data are also available for methyl methacrylate, methacrylic acid, methyl a-hydroxyisobutyrate, methanol, and water, which are the critical components obtained in the commercially important acetone cyanohydrin route to methyl methacrylate (11). 

Acetic Acid. Methanol carbonylation has become the process of choice for production of this staple of the organic chemical industry, which is used in the manufacture of acetate fibers, acetic anhydride [108-24-7] and terephthaUc acid, and for fermentation (see Acetic acid and derivatives). 

Acrylic Acid. In Europe some acryHc acid [79-10-7] and ester is manufactured by the Reppe reaction from acetjdene, methanol, and carbon monoxide (eq. 10) (see Aacrylic acid and derivatives). 

This process, to which the raw materials are suppHed at low pressures, is continuous and gives good yields of acrylates (see Acrylic acid and derivatives). In the presence of catalytic amounts of Co2(CO)g, acetylene has been carboxylated in methanol yielding dimethyl succinate as the principal product (135). 

Acetic acid (qv) can be produced synthetically (methanol carbonylation, acetaldehyde oxidation, butane/naphtha oxidation) or from natural sources (5). Oxygen is added to propylene to make acrolein, which is further oxidized to acryHc acid (see Acrylic acid and derivatives). An alternative method adds carbon monoxide and/or water to acetylene (6). Benzoic acid (qv) is made by oxidizing toluene in the presence of a cobalt catalyst (7). 

Whereas this reaction was used to oxidize ethylene (qv) to acetaldehyde (qv), which in turn was oxidized to acetic acid, the direct carbonylation of methanol (qv) to acetic acid has largely replaced the Wacker process industrially (see Acetic acid and derivatives). A large number of other oxidation reactions of hydrocarbons by oxygen involve coordination compounds as detailed elsewhere (25). 

Esterification. The formation of an ester from an acid (or its derivative) and an alcohol is of limited appHcation siace carboxyUc esters are comparatively rare substitueats ia dyes. Esters of A/-(3-hydroxyethylaniLiaes are important iatermediates for azo disperse dyes for polyester. Another example is methyl anthranilate, formed by the classical esterification of anthranilic acid usiag methanol and sulfuric acid. 

COMPARISON FOR SEPARATION OF AMINO DERIVATIVES OF 3-CHLORO-l,4-NAPHTOQUINONE BY RP-HPLC WITH METHANOL AND ACETONITRILE ELUENT... 

Early [1, 2] it was reported about RP-HPLC the separation of amino derivatives of 3-chloro-l,4-naphtoquinone with methanol mobile phase. In some cases changing organic modificator in eluent leads to the progress in effectiveness of sepai ation. In present work the compaiison was performed for separation of some amino derivatives of 3-chloro-I,4-naphtoquinone by RP-HPLC with methanol and acetonitrile eluent. It has been shown that certain differences exist for vaiious derivatives mentioned above. 

Generally it was found that resolution R is practically the same for isoeluotropic mixtures methanol and acetonitrile with water. The dependencies were obtained between capacity factors for derivatives of 3-chloro-l,4-naphtoquinone at their retention with methanol and acetonitrile. Previous prediction of RP-HPLC behaviour of the compounds was made by ChromDream softwai e. Some complications ai e observed at weak acetonitrile eluent with 40 % w content when for some substances the existence of peak bifurcation. 

The separated aqueous layer is extracted with chloroform and the eombined chloroform solution washed with water and evaporated to a volume of 10 ml in vacuo. 5 % Aqueous potassium carbonate (10 ml) is added and the mixture stirred 1 hr at room temperature. The chloroform is distilled under reduced pressure and the resulting crystalline product filtered, washed with water and methanol, and dried to give 82 mg (79 %) of the 3-ethylenedioxy derivative of cortisone acetate mp 248-260° (dec). 

Perfluorotetramethylthiadiphosphanorbornadiene and bis(trifluoromethyl) thiadiphosphole can be prepared by thermolysis of an adduct of methanol and hexakis(trifluoromethyl)-l,4-diphosphabarrelene with sulfur [113] (equation 23) Pyrolysis of the adduct of hexafluorinated Dewar benzene and phenyl azide results in ring expansion giving azepine, which photochemically yields an intramolecular 2-1-2 adduct, a good dienophile for the Diels-Alder reaction [114, //5] (equation 24) Thermolysis of fluonnated derivatives of 1,5-diazabicyclo-... 

The stable adducts form salts with perchloric acid in methanol and the ultraviolet absorption spectra of these salts fall into two classesd The spectra of the cations from both tetramethyl 4f/-quino-lizine-l,2,3,4-tetracarboxylate and its 7-methyl derivative are very similar and closely resemble that of 3,4-dihydroquinolizinium iodide. This strongly suggests that the proton has added at position 3 yielding cations such as (97). 

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