Methyl, alcohol pyridines

Chromium tetraphenyl hydrogen oxanilate,1 (C6H6)4Cr.02C. C0.NH.C6H5.C6H5.NH.C0.C02H, from the pentaphenyl base and oxanilic acid, yields orange-red needles, M.pt. 1-11° C., very soluble in methyl alcohol, pyridine or chloroform, sparingly soluble in ethyl alcohol, insoluble in benzene. 

A method of estimating small amounts of water in organic liquids (and also in some inorganic salts) is that of Karl Fischer. The substance is titrated with a mixture of iodine, sulphur dioxide and pyridine dissolved in methyl alcohol. The essential reaction is ... 

Typically in such a process the bis-phenol A is dissolved in about ten times its weight of pyridine and vigorously stirred at 25-35°C. Phosgene is then bubbled into the solution and in a few minutes the pyridine hydrochloride starts to precipitate. As polymer is formed the viscosity of the solution increases and eventually becomes too great for stirring. The polymer is then recovered by the addition of a solvent such as methyl alcohol which dissolves the pyridine hydrochloride but precipitates the polymer. 

Bebeerine, CjjHjgOjNj. This alkaloid has been described imder various names, pelosine, chondrodendrine, chondodendrine and curine (Z-form) whose origin is described elsewhere (pp. 363 and 374). It crystallises with one molecule of benzene, m.p. 161°, or 213° (solvent-free) or from methyl alcohol, m.p. 214°, and has [ajn 298° (EtOH) for the d- or Z-form (Scholtz ). Spath et recorded m.p. 221-221-5° (vac.) for both forms and + 332° and — 328° for the d- and Z-forms, in pyridine. 

When yohimbine is heated with potash solution it is eonverted into potassium yohimbate, from which yohimbic acid (the forms yohimboie and yohimboaic are also used and noryohimbine), C20H24O3N2. H2O, is liberated by acetie acid it crystallises from water in lustrous prisms, m.p. 269° or 299° (dry, dec.), [ajo 138-8° (pyridine), and, on esterification with methyl alcohol and its homologues, reproduces yohimbine and its homologues, analysis of which by Field confirmed the view that yohimbine is methyl yohimbate, and has the formula assigned to it by Fourneau and Page. ... 

In presence of platinum oxide as catalyst in methyl alcohol, it hydrogenates to dihydrowogermine, which darkens >265° and melts at 277-8° (dec.) [a]n ° — 61° (pyridine). The dihydro-base still contains eight... 

The combined liquors, which comprise an aqueous hydrochloric acid solution of 3-amino-methyl-pyridine hydrochloride, are then heated to a temperature of 60° to 65°C, and ethyl nitrite gas is passed into the heated solution. The ethyl nitrite is generated by placing 20 liters of 90% ethyl alcohol in a suitable vessel, diluting with 200 liters of water, and, while stirring, adding to the dilute alcohol 18.3 kg of nitrosyl chloride at the rate of 2.25 kg per hour. (The process using methyl nitrite is carried out by substituting a stoichiometrically equivalent quantity of methyl alcohol for the ethyl alcohol.)... 

Inulin Acetate. Stir 100 g. of inulin in 1,000 ml. of pyridine at 80° for forty-five minutes. Cool, while continuing the stirring, and to the clear solution add dropwise 180 ml. of acetic anhydride. After six hours more of stirring, pour the clear solution into 10 liters of water. The inulin acetate separates as a white solid. Filter and wash repeatedly with distilled water to remove the pyridine and acetic anhydride. Purify the dried crude product by dissolving in ten times its weight of hot methyl alcohol and filtering. Inulin acetate separates from the cold solution as a fine white powder [ajj20 = — 34° (c = 1.5, chloroform), [o ]d20 = — 43° (c = 1.8, acetic acid). 

They prepared the acetate by means of acetic anhydride in dry pyridine and purified it by separation from an acetic acid solution to which warm methyl alcohol had been added n ]n2 = — 22.70° (c = 10, acetic acid), m. p. 206-208°. In the presence of barium hydroxide irisin formed an insoluble product whose composition was represented by 6(C6Hi0O6)-Ba(OH)2. In contrast to inulin, these authors found that Takadiastase at pH 5 to 5.5 did not hydrolyze irisin. 

In a i-l. three-necked flask fitted with a fetirrer and thermometer are placed 93 g. (0.5 mole) of dodecanol (Note 1) and 158 g. (2 moles) of pyridine. The flask is surrounded by a water bath sufficiently cold to lower the temperature of the mixture to io°. At this temperature 105 g. (0.55 mole) of />-toluenesul-fonyl chloride is added in portions over a twenty- to thirty-minute period, or at such a rate that the temperature does not exceed 20° at any time. The mixture is then stirred for three hours at a temperature below 20°, after which it is diluted with 300 cc. of hydrochloric acid (sp.gr. 1.19) in 11. of ice water. The ester which crystallizes is collected on a chilled Buchner funnel and sucked as dry as possible. The solid is transferred to a 600-cc. beaker, 250--300 cc. of methyl alcohol is added, and the mixture is warmed on the steam bath until the ester melts. It is then cooled in a freezing mixture while being stirred continuously the ester separates in a fairly fine state. It is then collected on a chilled funnel and allowed to dry in the air, preferably at a temperature, below 20°. The yield of ester is 152-156 g. (88-90 per cent of the theoretical amount based upon the dodecanol used). It melts at 20-250 (Note 2) and is sufficiently pure for most purposes. 

The solvents most commonly employed are water, ethyl and methyl alcohol, ether, benzene, petroleum ether, acetone, glacial acetic acid also two or three solvents may be mixed to get the desired effect as described later. If you still cannot dissolve the compound, try some of these chloroform, carbon disulfide, carbon tetrachloride, ethyl acetate, pyridine, hydrochloric acid, sulfuric acid (acids are usually diluted first), nitrobenzene, aniline, phenol, dioxan, ethylene dichloride, di, tri, tetrachloroethylene, tetrachloroethane, dichloroethyl ether, cyclohexane, cyclohexanol, tetralin, decalin, triacetin, ethylene glycol and its esters and ethers, butyl alcohol, diacetone alcohol, ethyl lactate, isopropyl ether, etc. 

The following abbreviations are used W (water), M (methyl alcohol), E (ethyl alcohol), A (acetone), C (chloroform), P (pyridine), EA (ethyl acetate), and B (benzene). 

Limitations and interferences. The Karl Fischer reagent is composed of pyridine, sulfur dioxide, and iodine dissolved in either methyl alcohol or ethylene glycol monomethyl ether. Substances which react with any of these components will interfere. For example, Karl Fischer reagent will react with aldehydes or ketones in the presence of Methyl alcohol. 

Similarly with the raising of the b.p. in violet or reddish-violet soln. of iodine in benzophenone, carbon disulphide, ethyl chloride, chloroform, carbon tetrachloride, ethylene chloride or benzene or in brown soln. of ethyl alcohol, methyl alcohol, thymol, ethyl ether, methylal, or acetone. The values for the last three solvents were rather low, presumably because of the chemical action of solute on solvent. High values with benzene are attributed to the formation of a solid soln. of solvent and solid. Confirmatory results were found by J. Hertz with naphthalene, and by E. Beckmann and P. Wantig with pyridine. The results by I. von Ostromisslensky (o-nitrotoluene), by G. Kriiss and E. Thiele (glacial acetic acid), and by H. Gautier and G. Charpy indicate polymerization, but they are not considered to be reliable. 

D. L. Chapman, for potassium tri-iodide. 0. Gropp measured the effect of temp, on the conductivity of solid and frozen soln. of sodium iodide. For the effect of press, on the electrical properties, vide alkali chlorides. A. Reis found the free energy for the separation of the ions of K1 to be 144 lrilogrm. cals, per mol. for iN al, 158 Lil, 153 and for HI, 305. S. W. Serkofi 35 measured the conductivity of lithium iodide in methyl alcohol P. Walden, of sodium iodide in acetonitrile P. Dutoit in acetone, benzonitrite, pyridine, acetophenone. J. C. Philip and H. R. Courtman, B. B. Turner, J. Fischler, and P. Walden of potassium iodide in methyl or ethyl alcohol J. C. Philip and H. P. Courtman in nitromethane P. Dutoit in acetone. H. C. Jones, of rubidium iodide in formamide. S. von Lasczynsky and S. von Gorsky, of potassium and sodium iodides in pyridine. A. Heydweiller found the dielectric constants of powdered and compact potassium iodide to be respectively 3 00 and 5 58. 

Nitroglycerine is readily dissolved in most organic solvents and itself behaves as a good solvent. Thus, it is completely miscible in all proportions at room temperature with the following liquids methyl alcohol, ethyl acetate, anhydrous acetic add, benzene, toluene, xylenes, phenol, nitrobenzene, nitrotoluenes, pyridine, chloroform, dichloroethane, dichloroethylene, and the like. 

The residue is dissolved in fifteen to twenty times its weight of methyl alcohol (Note 6), filtered and an excess of pyridine (Note 7) is added. The free amino acid separates on standing overnight. It is collected on a Buchner funnel, washed thoroughly with methyl alcohol and dried. The yield is 92-102 g. (30-33 per cent of the theoretical amount). If a pyridine-free product is desired, it is dissolved in 200 cc. of warm water, filtered and the filtrate poured into 2 1. of methyl alcohol (Note 8). There is less than 10 g. of product in the mother liquors. It may be isolated by evaporating to dryness, washing with methyl alcohol and purifying by reprecipitation in the same way. 

In a 5-I. flask fitted with a downward condenser, are placed 340 g. of methylene aminoacetonitrile (p. 47) and 2500 g. of 48 per cent hydrobromic acid (Note 1). The mixture is heated on the steam bath for three hours (Note 2). The pressure in the apparatus is then reduced and dilute acid and formaldehyde are distilled into a water-cooled receiver until the separation of ammonium bromide from the reaction mixture causes bumping. This occurs when approximately half of the liquid has been distilled over. The ammonium bromide is filtered from the hot liquid and washed with a small amount of cold water the filtrates are returned to the flask and distillation continued as nearly as possible to dryness (Note 3). The residue is dissolved in 2 1. of cold methyl alcohol and filtered to the filtrate is added 350 cc. of pyridine, with vigorous shaking (Note 4). 

A further small quantity of impure glycine can be isolated by concentrating the filtrates obtained on recrystallization. The liquors from the first precipitation, containing ammonium bromide, pyridine hydrobromide, excess pyridine, and alcohol-soluble by-products, may be treated as follows The mixture is first acidified with mineral acid and the methyl alcohol recovered by distillation with a column. The residue is rendered strongly alkaline and the bulk of the ammonia removed by boiling under a reflux condenser wet pyridine can be recovered by downward distillation and treatment of the distillate with solid sodium hydroxide. 

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