Diethylamine, reaction with anhydrides

Rhoda.mines, Rhodamines are commercially the most important arninoxanthenes. If phthalic anhydride is used in place of formaldehyde in the above condensation reaction with y -dialkylarninophenol, a triphenyknethane analogue, 9-phenylxanthene, is produced. Historically, these have been called rhodamines. Rhodamine B (Basic Violet 10, Cl45170) (17) is usually manufactured by the condensation of two moles of y -diethylaminophenol with phthahc anhydride (24). An alternative route is the reaction of diethylamine with fluorescein dichloride [630-88-6] (3,6-dichlorofluoran) (18) under pressure. 

To synthesize new surfactants, having incorporated both structural elements, the known siloxanyl modified halogenated esters and ethers of dicyclopentadiene [5] were treated with different amines according to the reaction scheme. Triethylamine yielded quaternary ammonium salts directly. Alternatively, after reaction with diethylamine or morpholine, the isolated siloxanyl-modified tertiary amines were also converted to quaternary species. To obtain anionic surfactants, the halogenated precursors were initially reacted with n-propylamine. In subsequent reaction steps the secondary amines formed were converted with maleic anhydride into amides, and the remaining acid functions neutralized. Course and rate of each single reaction strongly depended on the structure of the initial ester or ether compound and the amine applied. The basicity of the latter played a less important role [6]. 

Two years later, the same group reported a formal synthesis of ellipticine (228) using 6-benzyl-6H-pyrido[4,3-f>]carbazole-5,ll-quinone (6-benzylellipticine quinone) (1241) as intermediate (716). The optimized conditions, reaction of 1.2 equivalents of 3-bromo-4-lithiopyridine (1238) with M-benzylindole-2,3-dicarboxylic anhydride (852) at —96°C, led regioselectively to the 2-acylindole-3-carboxylic acid 1233 in 42% yield. Compound 1233 was converted to the corresponding amide 1239 by treatment with oxalyl chloride, followed by diethylamine. The ketone 1239 was reduced to the corresponding alcohol 1240 by reaction with sodium borohydride. Reaction of the alcohol 1240 with f-butyllithium led to the desired 6-benzylellipticine quinone (1241), along with a debrominated alcohol 1242, in 40% and 19% yield, respectively. 6-Benzylellipticine quinone (1241) was transformed to 6-benzylellipticine (1243) in 38% yield by treatment with methyllithium, then hydroiodic acid, followed... 

The corresponding imides (1.40), called fulgimides, are most readily synthesised by conversion of the fulgide into the succinamic acids by reaction with amines, followed by dehydration. Functionalisation of the anhydride can also be achieved by reaction of the fulgides with malononitrile in the presence of diethylamine and subsequent recyclisation with acetyl chloride to give (1.41) from the corresponding E-fulgide and (1.42) from the Z-isomer. 

Nitrogenous bases useful in my process include ammonia, either as liquid ammonia or as ammonium hydroxide, and hydrazine primary amines, such as ethylamine, glycine, propylamine, aniline, and the like, secondary amines, such as morpholine, diphenylamine, methylaniline, diethylamine, and the like aminoalcohols, such as 2-aminopropan-l-ol, isovalinol, ephedrine, 2-(N-benzylamino)-propan-l-ol, and the like. A specific aminoalcohol, l-(+)-2-aminopropan-l-ol, is especially usefully employed in my invention since its reaction with the mixed anhydride of d-lysergic and sulfuric acids produces the pharmacologically active... 

DIETHYLAMINE or N,iV-DIETHYLAMINE (109-89-7) Forms explosive mixture with air (flash point — 18°F/—28°C). A strong organic base. Reacts violently with oxidizers. Violent reaction with acids, mercury. Incompatible with alcohols, acrylates, aldehydes, alkali metals, alkylene oxides, caprolactam solution, cellulose nitrate, cresols, epichlorohydrin, glycols, isocyanates, ketones, organic anhydrides, phenols, substituted allyls, vinyl acetate. Attacks aluminum, copper, lead, tin, zinc, and their alloys. Flow or agitation of substance may generate electrostatic charges due to low conductivity. 

Diazene 19 was synthesized in the manner portrayed below. Thus, treatment of anhydride 20 with sodium borohydride selectively reduces one carbonyl to a methylene unit. Reduction of the resulting lactone with DIBAL followed by a Wittig reaction and oxidation with PCC afforded aldehyde 22. When treated with cyclopentadiene in the presence of diethylamine in methanol, 22 undergoes a smooth and efficient conversion to fulvene 23. Diels-Alder cycloaddition to the azodicarboxylate 24 proceeded rapidly, a characteristic of reactions with this electron deficient chlorinated dienophile [8]. Selective reduction of the endocyclic n bond using diimide generated in situ, followed by the electrochemical reductive cleavage of the biscarbamate led to diazene 19 [6]. 

Anhydrides can be converted to ra-amino acids via reaction with amines and reduction of the resultant imide or acyclic amide product. When succinic anhydride was treated with two equivalents of diethylamine. amido acid 2.37 was produced. ... 

The frustrating and sometimes capricious nature of simple reactions of 2-amino-4(5H)-oxazolones is exemplified in the following reports. Ramsh and co-workers acetylated 68 with acetyl chloride in benzene but isolated both a poor yield and a poor mass balance of 131 together with dehydroacetic acid 132. Attempts to transaminate 131 with diethylamine in the absence of a solvent or with aniline in benzene failed. The authors recovered 68, which is in stark contrast to an earlier report from Hansen and Masch that acetylation of 68 with acetic anhydride gave 131 in 87% yield. In addition, these same authors reported that reaction of 131 with diethylamine at room temperature gave 134 in excellent yield (Scheme 6.35). 

A new approach to the synthesis of annulated sulfur heterocycles based on triflic anhydride-promoted electrophilic cyclization of the hetaryl-containing alkyl sulfides, including 1409, was elaborated <2003S1191>. The proposed method includes intermediate formation of sulfonylsulfonium salts 1410 followed by electrophilic attack on the aromatic ring (Scheme 271). Smooth demethylation of initially formed cyclic sulfonium salts 1411 by treatment with EtsN afforded a number of five- 1412 and six- 1413 membered fused sulfur heterocycles. Unexpected ring opening with formation of compound 1414 took place in the reaction of diethylamine with five-membered sulfonium salt 1411. 

Amino groups have also been acetylated with acetic anhydride in dimethylacetamide. Diethylamine was added, and the excess amine was titrated potentiometrically. The sequence distribution of an aromatic polyamide terpolymer prepared under various reaction conditions was determined by nuclear magnetic resonance spectrometry. Infrared spectroscopy and mass spectrometry have been used to estimate the degree of conversion of polyimides, ie. the extent of polyamic acid ring closure. 

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