2.6- diethylaniline

Diethyloniline is a light-yellow, oily, toxic liquid with a pungent odor. It is soluble in ethyl alcohol, ethyl ether, and carbon tetrachloride, but only very slightly soluble in water. It is used in the preparation of dyes, pharmaceuticals, and other organic compounds. 

5-95% within 3.5 C Boiling range ineludea 216.3 C Light yellow 0.2% max. 

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Phosphorus trichloride reacts readily with three equivalents of an alcohol e.g, ethanol, in the presence of a tertiary amine such as pyridine, dimethyl-aniline, or diethylaniline, to form triethyl phosphite and hydrogen chloride, the latter being immediately neutralised by the tertiary amine. 

Diethylaniline. Use 28 g. of pure aniline and 36 g. (34 ml.) of purified ethyl phosphate, and proceed exactly as described for dimethylaniline. The reaction is not so vigorous initially. Separation into two layers occurs after 30 to 90 minutes. The yield of diethylaniline, b.p. 215-216°, is 41-5 g. 

Pure diethylaniline from commercial diethylaniline. Use 50 g. (53-5 ml.) of a good commercial specimen of diethylaniline and 25 g, (23 ml.) of acetic anhydride, and reflux for 4 hours. Distil and collect the pure diethylaniline at 216-217° as a pale yellow liquid. The yield is 30-40 g. 

A mixture of 0.30 mol of the tertiairy acetylenic alcohol, 0.35 mol of acetyl chloride (freshly distilled) and 0.35 mol of /V/V-diethylaniline was gradually heated with manual swirling. At 40-50°C an exothermic reaction started and the temperature rose in a few minutes to 120°C. It was kept at that level by occasional cooling. After the exothermic reaction had subsided, the mixture was heated for an additional 10 min at 125-130°C, during which the mixture was swirled by hand so that the salt that had been deposited on the glass wall was redissolved. After cooling to below 50°C a mixture of 5 ml of 36% HCl and 200 ml of ice-water was added and the obtained solution was extracted with small portions of diethyl ether. The ethereal solutions were washed with water and subsequently dried over magnesium sulfate. The solvent was removed by evaporation in a water-pump vacuum... 

Other catalysts that can be used are boron trifluoride (5), copper—chromium oxides (6), phosphoric acid (7), and siUca-alurnina (8). Under similar conditions, ethanol yields /V-ethylaniline [103-69-5] and /V,/V-diethylaniline [91-66-7] (9,10). 

V-Alkylation can also be carried out with the appropriate alkyl haUde or alkyl sulfate. Reaction of aniline with ethylene, in the presence of metallic sodium supported on an inert carrier such as carbon or alumina, at high temperature and pressure yields V/-ethyl- or /V,/V-diethylaniline (11). At pressures below 10 MPa (100 atm), the monosubstituted product predominates. 

N,N- diethylaniline CioHisN [91-66-7] pale yellow Hquid 215-21 alkylating agent... 

In contrast to electrophilic reagents, the highly -tt-deficient character of the pteridine nucleus is responsible for its vulnerability towards nucleophilic attack by a wide variety of reagents. The direct nucleophilic substitution of pteridine itself in a Chichibabin-type reaction with sodamide in diethylaniline, however, was unsuccessful (51JCS474). Pteridin-6-one, on the other hand, yielded pteridine-6,7-dione under the same conditions, via a still unknown reaction mechanism. 

Butyl acrylate has been prepared by direet esterifieaLion/ by debromination of -butyl ,/3-dibromopropionate with zinc, by treatment of either butyl /3-chloropropionate or butyl /3-bromopropionate with diethylaniline, and by the pyrolysis of butyl (3-acetoxypropionated Direct esterification and alcoholysis of methyl or ethyl acrylate have been recommended for the preparation of the higher alkyl acrylates. ... 

Ethoxy-7V,7V-diethylaniline [1846-92-2] M 193.3, b 141-142 /15mm pK st 6-l- Refluxed for 3h with acetic anhydride, then fractionally distilled under reduced pressure. 

Boron triiodide rapidly cleaves methyl ethers of o-, m-, or / -substituted aromatic aldehydes (0°, 25° 0.5-5 min 40-86% yield)." BI3 complexed with A/,A-diethylaniline is similarly effective, but benzyl ethers are converted to the iodide... 

Beside metal salts, a variety of other modifiers, which include amines, chlorobenzene, hydroxides (S2,S2a), and sulfur compounds, have been used. Among amines used are quinoline (SJ0J7,S4), pyridine (29,33,50,60,64), piperidine, aniline, and diethylaniline. The reduction may be quite sensitive to these modifiers for instance, one drop of quinoline was sufficient to cause hydrogenation to come to an abrupt stop after absorption of I mol of hydrogen (2a). 

On the other hand, Davies5 , studying the reaction of adipic add with 1,5-pentanediol in diphenyl oxide or diethylaniline found an order increasing slowly from two with conversion. From this result he concluded that Flory s1,252-254> and Hinshelwood s240,241 interpretations are erroneous. Two remarks must be made about the works of Davies5 experimental errors relative to titrations are rather high and kinetic laws are established for conversions below 50%. Under such conditions the accuracy of experimental determinations of orders is rather poor. 

Reaction is brought about thermally usually at around 200 °C either in an inert solvent (diphenyl ether, cyclohexane and diethylaniline have been used) or in the absence of a solvent. If the ortho positions in the aromatic ether are blocked (as in LXXVII) then rearrangement to the para position LXXVIII occurs, viz. 

Oxa-7,7-dichloronorcarane, 41, 76 Oxalyl chloride, condensation, with N,N-diethylaniline, 41, 3 with N,N-dimethylaniline, 41, 1 with N,N-di- -propylaniline, 41, 3... 

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