Exchange with methanol

All of the reactions so far mentioned involved as nucleophiles either organometallic reagents or one, PhNH-, that is much more basic than any of those in Table 6. That complete inversion is also the stereochemical course of a substitution involving a rather weak nucleophile has also been neatly demonstrated by Mikolajczyk et al. (1979). In the presence of a small amount of an acid catalyst optically active,, 4C-labeled methyl p-toluenesulfinate undergoes exchange with methanol as shown in (151), a process that also... 

Further oxidation of the carbon at position 21 is interestingly consistent with antiinflammatory activity. Thus oxidation of flucinolone with copper (II) acetate affords initially the hydrated ketoaldehyde exchange with methanol gives the 21 dimethyl acetal (69), flumoxonide. ... 

Tosylation of the primary alcohol is followed by ester exchange with methanol to release the anior. of a secondary alcohol, which promptly closes to the epoxide. There is no change at the chira. centre. 

The thermodynamics of this process are described in detail in references (67 —72, 80,81). Let us examine a typical methanol injection system. In a typical methanol injection and recovery system for a cold-oil absorption or turboexpander plant, feed gas passes through a free-water knockout drum and into a gas-gas exchanger with methanol being sprayed on exchanger tube-sheets. Methanol inhibits hydrate formation and aqueous methanol condenses in the exchanger (and the chiller following it) and is pumped to a primary separator. The methanol-water solution is then flashed in a flash drum and filtered into a methanol still to recover methanol. Normally, methanol dissolves in the hydrocarbon liquids and is distilled as a mixture of propane and methanol. Some of the methanol is recovered as the overhead product to recover the methanol dissolved in the heavier solution, the bottoms of the methanol still (propane product or hydrocarbon liquids from the demethanizer)... 

Figure 3. Top nigeran single crystals grown from ether. Bottom nigeran single crystals after solvent exchange with methanol.

The slightly different physical properties of deuterium allow its concentration in ordinary hydrogen (or the concentration of a deuterium-containing compound in a hydrogen compound) to be determined. Exchange of deuterium and hydrogen occurs and can be used to elucidate the mechanism of reactions (i.e. the deuterium is a non-radioactive tracer). Methanol exchanges with deuterium oxide thus ... 

Methyl formate and propylene oxide have close boiling poiats, making separation by distillation difficult. Methyl formate is removed from propylene oxide by hydrolysis with an aqueous base and glycerol, followed by phase separation and distillation (152,153). Methyl formate may be hydrolyzed to methanol and formic acid by contacting the propylene oxide stream with a basic ion-exchange resia. Methanol and formic acid are removed by extractive distillation (154). 

Methyl tert-Butyl Ether (MTBE). Methyl tert-hutyi ether [1634-04-4] is made by the etherification of isobutylane with methanol, and there are six commercially proven technologies available. These technologies have been developed by Arco, IFF, CDTECH, Phillips, Snamprogetti, and Hbls (hcensed jointly with UOP). The catalyst in all cases is an acidic ion-exchange resin. The United States has been showing considerable interest in this product. Western Europe has been manufacturing it since 1973 (ANIC in Italy and Huls in Germany). Production of MTBE in Western Europe exceeded 600,000 tons in 1990. 

FIG. 23-3 Temperature and composition profiles, a) Oxidation of SOp with intercooling and two cold shots, (h) Phosgene from GO and Gfi, activated carbon in 2-in tubes, water cooled, (c) Gumene from benzene and propylene, phosphoric acid on < uartz, with four quench zones, 260°G. (d) Mild thermal cracking of a heavy oil in a tubular furnace, hack pressure of 250 psig and sever heat fluxes, Btu/(fr-h), T in °F. (e) Vertical ammonia svi,ithesizer at 300 atm, with five cold shots and an internal exchanger. (/) Vertical methanol svi,ithesizer at 300 atm, Gr O -ZnO catalyst, with six cold shots totaling 10 to 20 percent of the fresh feed. To convert psi to kPa, multiply by 6.895 atm to kPa, multiply by 101.3. 

Esterification and etherification may be catalyzed by mineral acids or BF3. The reaction of isobutylene with methanol to make MTBE is catalyzed by a sulfonated ion exchange resin. 

Deuteration of 3 -Hydroxy-5a-androstan-7-one at C-6 and C-8 by Exchange with Deuterium Oxide-5% Sodium Deuterioxide in Methanol-OD... 

Deuteration of 5a.-Pregn-9-en-12-one at C-8 and C-11 by Exchange with Deuterium Oxide-20% Sodium Deuterioxide in Methanol- OD... 

The dimethyl acetal (94) is readily prepared from the 22-aldehyde (93) by direct reaction with methanol in the presence of hydrogen chloride. Ena-mines (95) are formed without a catalyst even with the poorly reactive piperidine and morpholine.Enol acetates (96) are prepared by refluxing with acetic anhydride-sodium acetate or by exchange with isopropenyl acetate in pyridine.Reaction with acetic anhydride catalyzed by boron trifluoride-etherate or perchloric acid gives the aldehyde diacetate. 

Exchange with deuterium oxide-10% deu-teriosulfuric acid in methanol-OD deuteration of estradiol at C-2 and C-4, 157... 

Tiazofurine (142) is an antimetabolite with antineoplastic activity. It preferentially affects leukemic lymphocytes over normal cells due to selective activation by formation of its adenine dinucleotide by transformed cells. Of the syntheses available, one starts by conversion of iniidate 138 to methyl 2,5-anhydroallonothioate (139). Next, condensation with ethyl 2-amino-2-cyanoac-etate leads to the thioamide which undergoes thiol addition to the nitrile function to produce the amminothiazolecarboxyester system of 140 directly. Sodium nitrite in aqueous hypophosphorus acid eliminates the superfluous amino group via the diazonium transformation to give 141. This synthesis of tiazofurine (142) concludes by ester amide exchange in methanolic ammonia [48]. 

Active fractions are combined and concentrated in vacuo to about 5 liters. The concentrate is then adjusted to a pH of 8.0 with 6N sulfuric acid and passed through a column packed with 1 liter of an anion exchange resin, Dowex 1X2 (OH form). The column is washed with about 5 liters of water and the effluent and the washings containing active substance are combined and are concentrated to 1/15 by volume. The concentrate is adjusted to a pH of 10.5 with 6N sodium hydroxide and 5 volumes of acetone is added thereto. The resultant precipitate is removed by filtration and the filtrate is concentrated to 500 ml. The concentrate is adjusted to a pH of 4.5 with 6N sulfuric acid and 2.5 liters of methanol is added thereto. After cooling, a white precipitate Is obtained. The precipitate is separated by filtration and washed with methanol. After drying in vacuo, about 300 g of white powder is obtained. 

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