Anilines determination

Aniline, determination of impurities in 321 Aromatic hydrocarbons, determination of 343, 389, 394, 400... 

Two-colour photoionization spectroscopy of aniline cooled in a supersonic jet. Strong propensity for vertical (An = 0) ionization allows vibrational frequencies of CgHgNH2 ( B,) to be determined Two-colour photoacoustic and MPI spectra of aniline, determined as a function of time delay between the two laser pulses. Observed both ionization and dissociation t MPI/TOF mass spectrometric study of phenol. Mechanism of ionization and ion fragmentation t MPI/TOF mass spectrometric study of fragmentation patterns in benzaldehyde. Strong wavelength dependence observed at 266 and 355 nm. Results show operation of two different mechanisms at these excitation wavelengths... 

TABLE 1. Geometry of aniline determined using different levels of quantum chemical theory a and experiment... 

Figure 5 equally displays the localization domains of aniline determined using the electron localization function technique (ELF)12,64, which defines the electronic basins within a molecular system. The basins correspond to the domains where electrons are localized either in paired bonds or in nonbonding lone pairs. In such a way, the number and nature of bonds between atoms could be determined. The ELF r)(r) value varies from 0 to 1 (0 < rj(r) < 1), which is chosen to determine the isosurfaces of the domains. Basins can be classified according to their synaptic order, that is, monosynaptic basins belong to the cores (denoted by C) whereas disynaptic basins describe the valence regions (denoted by V). 

Properties of Aniline (SECTIONS 490, 494).—(a) Solubility of aniline.—Determine whether aniline is soluble in the following water, dilute sodium hydroxide, dilute hydrochloric acid, concentrated sulphuric acid, alcohol, and benzene. 

Allow the material to air-dry. Determine the weight of the crude product, and calculate the percent yield from aniline. Determine its melting point, and compare it to the reported value of 142-145 °C. 

Example 1.5.2 Aniline and hexane are completely miscible with each other at all temperatures higher than 59.6 °C, below which they separate into two immiscible phases. A uniform mixture of aniline and hexane containing 52 mole percent aniline is cooled in a closed vessel from 60 °C to 42 °C. At 42 °C, the hexane-rich layer has 83 mole percent hexane while the heavier and immiscible aniline-rich layer has 88 mole percent aniline. Determine the values of ai2 and f to indicate the separation that has been achieved compared to the original feed mixture. 

Most students will be familiar with simple distillation from their practical inorganic chemistry. Other students should determine the boiling-point of acetone (56°), using a water-bath and water-condenser, or of benzene (81 ), using a sand-bath and water-condenser, and finally of either aniline (184 ) or nitrobenzene (210 ), using for both these liquids a sand-bath and air-condenser. 

Anilides, (a) To 1 ml. of aniline in a small conical flask add very slowly and carefully about i ml. of acetyl chloride. A vigorous reaction occurs and a solid mass is formed. Add just sufficient water (about 15 ml.) to dissolve the solid completely on boiling. On cooling, crystals of acetanilide separate out filter and determine the m.p. 

Many chloroplatinates separate from aqueous solution with water of crystallisation. If this is suspected, the chloroplatinate should be dried to constant weight in the oven before analysis, to ensure elimination of water of crystallisation. Aniline, p-toluidine and pyridine all give anhydrous chloroplatinates, and can be conveniently used in the above determination no attempt should be made to recryrtallise their chloroplatinates. 

Vrocttd precisely as in the Determination of the Number of Hydroxyl Groups in Phenol, except that after weighing the flask A, run in about i ml. of pure aniline, and weigh again. Then continue exactly as before. The acetanilide which is formed usually remains in solution when the contents of the flask A are diluted with water for hydrolysis. 

The method can therefore be used to estimate the percentage of aniline hydrochloride in a crude sample, provided the impurities are not themselves salts of other similar amines. Alternatively, if aniline is known to be a monacidic base (forming therefore a mono-hydrochloride) the molecular weight of aniline can be determined, since the molecular weight of the aniline hydrochloride is clearly that weight which is neutralised by 1000 ml. of vl/.NaOH solution. 

Repeat the boiling point determination with the following pure liquids (a) carbon tetrachloride, A.R. (77°) (6) ethylene dibromide (132°) or chlorobenzene (132°) (c) aniline, A.R. (184-6°) and (d) nitrobenzene, A.R. (211°). An air condenser should be used for (c) and (d). Correct the observed boiling points for any appreciable deviation from the normal pressure of 760 mm. Compare the observed boiling points with the values given in parentheses and construct a calibration curve for the thermometer. Compare the latter with the curve obtained from melting point determinations (Section 111,1). 

Determination of boiling points. Distillation method (Fig. II, 12, 1) for carbon tetrachloride (25 nil. distillation flask and small water condenser), and SiwoloboflF s method (Fig. II, 12, 2) for carbon tetrachloride, aniline and nitrobenzene. Calibration curve for thermometer. Determination of b.p. of unknown liquid. 

Other analytical techniques ate also available for the determination of maleic anhydride sample purity. For example, maleic anhydride content can be determined by reacting it with a known excess of aniline [62-53-3] in an alcohol mixture (170). The solution is then titrated with an acid to determine the amount of unconsumed aniline. This number is then used to calculate the amount of maleic anhydride reacted and thus its concentration. Another method of a similar type has also been reported (171). 

Other terms relating to physical properties include viscosity refractive index pour point, ie, the lowest temperature at which the oil flows flash point, ie, the temperature at which the oil ignites and aniline point, ie, the minimum temperature at which equal volumes of oil and aniline are completely miscible. These are determined under defined conditions estabHshed by ASTM. 

Fig. 8. Pseudo-binary (solvent-free)jy-x phase diagrams for determining which component is to be the distillate where (—) is the 45° line, (a) No solvent (b) and (c) sufficient solvent to eliminate the pseudo-a2eotiope where the distillate is component 1 and component 2, respectively (51) and (d) experimental VLE data for cyclohexane—ben2ene where A, B, C, and D represent 0, 30, 50, and 90 mol % aniline, respectively (52).

Solubility of resins can be predicted in a similar way as for the solubility of polychloroprene rubbers in a solvent mixture (see Section 5.5) by means of solubility diagrams (plots of the hydrogen bonding index (y) against the solubility parameter (5). Another more simple way to determine the solubility of resins is the determination of the cloud point, the aniline and the mixed aniline points. 

Therefore it is possible to determine absorption spectra directly on the TLC plate by comparison with a substance-free portion of the layer. The wavelengths usually correspond to the spectra of the same substances in solution. However, adsorbents (silanols, amino and polyamide groups) and solvent traces (pH differences) can cause either bathochromic (ketones, aldehydes [60, 61], dyestuffs [62]) or hypsochromic (phenols, aniline derivatives [63]) shifts (Fig. 23). 

The vapour density of fieshly distilled aniline, b.p. 182 , may iDe determined, the temperatme of the air-bath being adjusted to about 240°. The adjustment is made by raising or loivermg the flame, or by altering the position of the movable ring burner. 

Diffusion-limited rate control at high basicity may set in. This is more eommonly seen in a true Br nsted plot. If the rate-determining step is a proton transfer, and if this is diffusion controlled, then variation in base strength will not affect the rate of reaction. Thus, 3 may be zero at high basicity, whereas at low basicity a dependence on pK may be seen. ° Yang and Jencks ° show an example in the nucleophilic attack of aniline on methyl formate catalyzed by oxygen bases. 

During the 1950s and 1960s Hafner used Konig salts, derived from the reaction of A -methyl aniline with Zincke salt 1, for azulene synthesis. The Zincke reaction also achieved prominence in cyanine dye synthesis and as an analytical method for nicotinamide determination. ... 

In summary, these results were interpreted to support rate-determining electrocyclization for the ring closure, starting from the all-trans iminium 11, via the cis conformation 13 of the neutral form, followed by fast proton transfer and elimination of aniline (Scheme 8.4.6). 

In 1883, Bottinger described the reaction of aniline and pyruvic acid to yield a methylquinolinecarboxylic acid. He found that the compound decarboxylated and resulted in a methylquinoline, but made no effort to determine the position of either the carboxylic acid or methyl group. Four years later, Doebner established the first product as 2-methylquinoline-4-carboxylic acid (8) and the second product as 2- methylquinoline (9). Under the reaction conditions (refluxing ethanol), pyruvic acid partially decarboxylates to provide the required acetaldehyde in situ. By adding other aldehydes at the beginning of the reaction, Doebner found he was able to synthesize a variety of 2-substituted quinolines. While the Doebner reaction is most commonly associated with the preparation of 2-aryl quinolines, in this primary communication Doebner reported the successful use of several alkyl aldehydes in the quinoline synthesis. 

In hydroxyUc solvents, the reaction with aniline follows a bi-molecular course but is complicated by competing solvolysis. This is a striking result when compared with the behavior of picryl chloride, which is much more selective with regard to the same reagents (aniline and alcohol), and has been interpreted to mean that bond-breaking has made appreciable progress in the rate-determining step of the reaction of phosphonitrilic chloride. Furthermore, the same indication is obtained from the fact that in the reactions of the halides, the fluorine chlorine ratios are less than one. ... 

Tamaoku and colleagues presented an efficient enzymatic photometric determination of hydrogen peroxide ffiat is essentially a color reaction resulting from the oxidative condensation of A/-ethyl-A/-(2-hydroxy-3-sulfopropyl)aniline derivatives wiffi 4-aminoantipyrine in the presence of hydrogen peroxide and peroxidase (82CPB2492). A similar calorimetric detection of hydrogen peroxide has been patented (83GEP3301470). 

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