Methanol, Anhydrous

By increasing the molar proportion of the monocarboxylic acid, the yield of (II) is improved. Thus electrolysis of a mixture of decanoic acid (n-decoic acid capric acid) (V) (2 mols) and methyl hydrogen adipate (VI) (1 mol) in anhydrous methanol in the presence of a little sodium methoxide gives, after hydrolysis of the esters formed, n-octadecane (VII), tetradecanoic or myristic acid (VIH) and sebacic acid (IX) ... 

Indane-1 3-dione (1 3-diketohydrindene). Method A. To a solution of sodium methoxide, prepared from 6 1 g. of sodium and 200 ml. of anhydrous methanol, add 15 g. of phthalylacetic acid and allow to stand for 1 hour at room temperature collect the yellow precipitate by suction filtration. Mix the yellow solid with 150 ml. of 10 per cent, sulphuric acid, heat on a steam bath until no more carbon dioxide is evolved (15-20 minutes), filter the hot solution and allow to cool. Collect the yellow crystals by filtration at the pump, wash with a httle water and dry at 100°. The yield of crude 1 3-indanedione, m.p. 125-126°, is 7 g. RecrystaUise from hght petroleum, b.p. 80-100°, and thus obtain the pure product, m.p. 129-130°. 

Organic compounds normally cause Htde or no corrosion of magnesium. Tanks or other containers of magnesium alloys are used for phenol [108-95-2] methyl bromide [74-96 ] and phenylethyl alcohol [60-12-8]. Most alcohols cause no more than mild attack, but anhydrous methanol attacks magnesium vigorously with the formation of magnesium methoxide [109-88-6]. This attack is inhibited by the addition of 1% ammonium sulfide [12135-76-1] or the presence ofwater. 

Sodium cyanide is soluble in Hquid ammonia. At temperatures below —31°C, sodium cyanide pentaammoniate [69331-34-6] NaCN-5NH3, separates in large flat crystals. At 15°C, 100 g anhydrous methanol dissolves 6.44 g anhydrous sodium cyanide at 67.4°C, it dissolves 4.10 g. Sodium cyanide hemihydrate [69331 -35-7] NaCNO.5 H2O, has been obtained by recrystaUization from cold 85% alcohol. The system NaCN—NaOH—H20 has been studied (48,49). Sodium cyanide is slightly soluble in formamide, ethanol, methanol, SO2, furfural, and dimethylformamide. 

Sodium methoxide was prepared just prior to use from 23.0 g (1.0 g-atom) of sodium metal and 400 mL of anhydrous methanol (distilled from magnesium turnings), then cooled to room temperature. 

Tetra-n-butylammonium iodide [311-28-4] M 369.4, m 146". Crystd from toluene/pet ether (see entry for the corresponding bromide), acetone, ethyl acetate, EtOH/diethyl ether, nitromethane, aq EtOH or water. Dried at room temperature under vac. It has also been dissolved in MeOH/acetone (1 3, lOmL/g), filtered and allowed to stand at room temperature to evaporate to ca half its original volume. Distilled water (ImL/g) was then added, and the ppte was filtered off and dried. It was also dissolved in acetone, ppted by adding ether and dried in vac at 90" for 2 days. It has also been recrystallised from CH2Cl2/pet ether or hexane, or anhydrous methanol and stored in a vacuum desiccator over H2SO4. [Chau and Espenson J Am Chem Soc 108 1962... 

The checkers used commercial "anhydrous methanol without further drying. 

Cinnamaldehyde dimethylacetal is prepared by the method used to prepare the corresponding diethylacetal. A mixture of 66.0 g. (0.5 mole) of Aldrich Chemical Company, Inc.), 100 g. (1.06 mole) of trimethyl orthoformate (Eastman Organic Chemicals), 450 ml. of anhydrous methanol (J. T. Baker Chemical Company), and 0.5 g. ofp-toluenesulfonic acid monohydrate (Fisher Scientific Company) is stirred at room temperature for 24 hours. At the end of this time the alcohol is removed with a rotary evaporator and the residue is distilled to give 81-83 g. (91-93%) of cinnamaldehyde dimethylacetal, b.p. 93—96° (0.2 mm.). 

Chaput, Jeminet and Juillard measured the association constants of several simple polyethylene glycols with Na", K", Cs", and Tl". Phase transfer catalytic processes and most biological processes are more likely to involve the first two cations rather than the latter two, so we will confine the discussion to these. Stability constants for the dimethyl ethers of tetra-, penta-, hexa-, and heptaethylene glycols were determined poten-tiometrically in anhydrous methanol solution and are shown in Table 7.1. In the third column of the table, the ratio of binding constants (Ks/K s) is calculated. Note that Simon and his coworkers have referred to this ratio as the selectivity constant. ... 

Table 7.1. Stability constants for several open-chained polyethers in anhydrous methanol at 25...

Oxidation of 20-keto-21-hydroxy steroids with oxygen in aqueous methanol or in anhydrous methanol in the presence of cupric acetate has been reported to give good yields of the corresponding 21-aldehydes. 

Tricyano-s-triazine (322) is mono-substituted very rapidly with anhydrous methanol (20°, few min) and with water di- and trisubstitution products also result under mild conditions (65°, one min, and 65°, several hr, respectively, for methanol). 

The pharmacological versatility of this general substitution strategy is further illustrated by diazonium coupling of 14 with 2-nitrobenzenediazonium chloride to produce biarylal-dehyde 18. Formation of the oxime with hydroxylamine is followed by dehydration to the nitrile. Reaction with anhydrous methanolic hydrogen chloride leads to imino ether and addition-elimination of ammonia leads to the antidepressant amid-ine, nitrafudam (20). ... 

Step C Preparation ofthebase-A 300 ml one-necked, round-bottomed flask, equipped with a water-cooled condenser, calcium chloride tube and magnetic stirrer is charged with anhydrous methanol (150 ml) and sodium metal (5.75 g,0.25 g atom). When the reaction is complete, the solution is treated with dry guanidine hydrochloride (26.3 g, 0.275 mol) and stirred for 10 minutes. The sodium chloride that forms is removed by filtration. The solution is concentrated in vacuo to a volume of 30 ml and the residue treated with the product of Step B, heated one minute on a steam bath and kept at 25°C for 1 hour. The product is filtered, washed well with water, dissolved In dilute hydrochloric acid and the free base precipitated by addition of sodium hydroxide to give the amllorlde product base, a solid which melts at 240.5°-241.5°C. 

N-methyl-4-piperidyl benzilate methobromide To a suspension of 0.15 mol of freshly prepared silver bromide in 300 ml of anhydrous methanol is added a solution of 0.1 mol of quaternary iodide obtained as above. The mixture is stirred and refluxed for several hours after which time transhalogenation is complete. The mixture is cooled, the insoluble silver... 

For the determination of small amounts of water, Karl Fischer (1935) proposed a reagent prepared by the action of sulphur dioxide upon a solution of iodine in a mixture of anhydrous pyridine and anhydrous methanol. Water reacts with this reagent in a two-stage process in which one molecule of iodine disappears for each molecule of water present ... 

When hemin (1) is treated with gaseous hydrogen chloride in anhydrous methanol/pyridine in the presence of iron(II) sulfate, protoporphyrin dimethyl ester (2), the metal-free ligand of hemin. is produced in almost quantitative yield. This compound is quite sensitive to oxygen... 

It is difficult to estimate the magnitude of the error due to insufficiently low humidity when distillation methods are used with organic liquids such as toluene (6, 28), xylene (6, 28), or chloroform (12). With organic liquids essentially immiscible with water and of high boiling point the error is probably very small. When methanol is used as an extraction solvent, as in the Fischer reagent method, the amount of unextracted water is undoubtedly some function of the concentration of water in the alcohol, but the error might be small because of substitution of adsorbed water by adsorbed alcohol (23, 34). This seems to be borne out by experiments of Schroeder and Nair (31), who deliberately added water to the alcohol to form a 0.5% water solution and found that the results of their moisture determinations were essentially the same as with anhydrous methanol, which contained about 0.05% water. 

B. Method for determining the number of —COOH groups in a molecule The TMS derivative of an acid can be converted to the methyl ester using anhydrous methanolic HQ. 1 2 3 Obtain a mass spectrum of the TMS derivative of the acid, and then evaporate the TMS reaction mixture with clean, dry nitrogen. Add 250 pd of anhydrous methanolic HC1 (Pierce cat. no. 33050) and heat at 60° for 20 min. Many TMS derivatives of acids are converted to methyl esters at room temperature after 20 min. If the sample is rerun as the methyl ester, the number of carboxyl groups can be determined by the mass differences before and after making the methyl ester from the TMS derivative. 

The beads prepared above (11.58 g.) are suspended in 175 ml. of boiling absolute ethanol, and 0.94 g. (0.0159 mole) of aqueous 85% hydrazine monohydrate is added with stirring. The resulting mixture is refluxed for 10 hours, after which the polymer is collected by filtration and washed with 150-ml. portions of ethanol, aqueous 0.2A sodium hydroxide, distilled water, and anhydrous methanol. After vacuum drying at 60° for four hours, the yield of polymeric benzylamine is 10.38 g. 

Hydrochloric acid in anhydrous methanol (1 4 volume ratio) has been used to desilylate the trimethylsilyl derivatives of ferrocene, ruthenocene, and os-mocene, the rate coefficients (lO5 ) being ferrocene (5.60, 4.08), ruthenocene (261, 182), and osmocene (104, 80.2) for 0.596 M and 0.477 M hydrochloric acid, respectively, (temperature not quoted)690. 

It was reported earlier that even dialkyl sulphides are efficiently oxidized to sulphoxides without a concomitant C—S bond cleavage by NBS or N-chlorosuccinimide (NCS) when the reaction is performed in anhydrous methanol at low temperature103. iV-Chloro-Nylon-6,6 in methanol-water or dioxane-water104 and iV-bromo- -caprolactam in water or alcohols105 were also used successfully for oxidation of sulphides. 

Commercially available anhydrous methanol was used without further treatment. 

Synthesis of N,N -bis(p-carbomethoxybenzoyl) butanediamine (T4T-dimethyl). Dimethyl terephthalate (DMT) (275 g, 1.42 mol) is dissolved at 65°C in a mixture of 1100 mL anhydrous toluene and 85 mL anhydrous methanol in a 2-L flask equipped with a stirrer, condenser, calcium chloride tube, and nitrogen inlet. When all the DMT is dissolved, 15 mL lithium methoxide (1.25 M) is added. 1,4-Butanediamine (BDA) (34 mL, 0.34 mol), dissolved in 150 mL anhydrous toluene and 10 mL anhydrous methanol, is added dropwise in 4-6 h while the nitrogen flow is stopped. Three hours after the start of the BDA addition, the temperature is gradually increased up to 90°C (5°C/h) while the methanol is stripped off. After a total reaction time of 24 h the reaction is stopped. The white... 

Phenyl-2(lH)Pyridone Sodiim Salt. A solution of sodium metal (0.25 g, 11.3 mmol) and anhydrous methanol (10 mL) was allowed to react to form sodium methoxide. Pyridone IV (1.88 g, 11 mmol) was added to the solution and allowed to stand at room temperature for 24 h. The methanol was removed under reduced pressure and the residue was extracted with hot benzene 3 times and dried in the Abderhalden drying pistol for 30 min. The yield was 1.7 g (82%). 

Substances 5-(Dimethylamino)-naphthalene-l-sulfonyl chloride Sodium carbonate, anhydrous Methanol Ethanol (96< 7o)... 

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