Potassium tris amine

The synthetic and industrial importance of this reaction lies in its generality, and the ease with which the amino substituent in the products can be subsequently transformed into other functionalities. Pyridine itself is more difficult to aminate than quinoline or isoquinoline, and it does not react with potassium amide in liquid ammonia even on prolonged treatment. However, pyridine is aminated in good yield by sodamide in toluene, and di- and tri-amination can be achieved with excess sodamide at higher temperatures. The 4-position is substituted last in triamination y-amination is very difficult indeed and only takes place when all a -positions are occupied. 

In the course of investigations involving the reaction of lithium triethylhydroborate with conjugated nitroalkenes (61),A -ethylamines (62) were consistently observed as by-products (equation 34). The intermediacy of nitroso compounds has been confirmed in this reaction which provides a useful method for the preparation of A -ethylated amine derivatives. These A -alkylated products are not produced when sterically demanding reagents, such as potassium tri-s-butylborohydride, are used. Apparently, the competition between reduction and alkylation of the nitroso group is sensitive to steric effects. 

An important mode of oxidation for -phenylenediamines is the formation of ben2oquinonediimines, easily obtained by oxidation with silver oxide in ether solution (17). DHmines undergo 1,4 additions with amines to generate tri- and tetraamines which readily oxidi2e in air to highly conjugated, colored products. An example of this is the formation of Bandrowski s base [20048-27-5] when -phenylenediamine is oxidi2ed with potassium ferricyanide (18). 

Strong bases, such as potassium acetate, potassium 2-ethylhexoate, or amine—epoxide combinations are the most useful trimerization catalysts. Also, some special tertiary amines, such as 2,4,6-tns(A7,A7-dimethylarninomethyl)phenol (DMT-30) (6), l,3,5-tris(3-dimethylaminopropyl)hexahydro-j -triazine (7), and ammonium salts (Dabco TMR) (8) are good trimerization catalysts. 

Potassium ferricyanide in oxidative decarboxylation, 40, 86 Potassium permanganate for oxidation of (trialkylmethyl)amines to tri-alkylnitromethanes, 43,87 Pregnenolone acetate, conversion to 3/3-acetoxyetienic acid, 42, 5 Propane, 2,2-dibotoxy-, 42,1 Propargylsuccinic anhydride, by-product in addition of maleic anhydride to allcne, 43, 27... 

The chemistry of the isocyanides began when, in 1859 Lieke formed allyl isocyanide from allyl iodide and silver cyanide, and when, in 1866 Meyer ° produced in the same way 1-isocyano-l-desoxy-glucose. In 1867, Gautier used this procedure to prepare alkylisocyanides, and Hofmann introduced the formation of isocyanides from primary amines, chloroform, and potassium hydro-xyde. Gautier also tried to prepare an isocyanide by dehydrating an amine formiate via its formylamine using phosphorus pentoxide, but this process produced no isocyanide. Gautier had not yet realized that acidic media destroyed the isocyanides. 

Preparative scale reduction of oximes at a mercury or lead cathode in acid solution has been used in the conversion of the carbonyl function to amine. Originally, 30-50% sulphuric acid was used as solvent [195] but ethanol with dilute hydrochloric acid is usually satisfactory. Aliphatic and aromatic oximes give amines in 64-86% yields [196]. Aromatic ketoximes are also reducible in alkaline solution and acetophenone oxime has been converted to 1-phenylethylamine in a tri-potassium orthophosphate solution [197], The reduction of oximes in acid solution is tolerant of many other substituents as indicated by a number of examples [198, 199, 200. Phenylglyoxa monoxime in acid solution is however reduced at both the carbonyl and the oxime centres by sodium amalgam to yield 2-amino-1-phenylethanol [201]... 

The reaction of tertiary formamides with sulfur tetrafluoride in the presence of potassium fluoride leads to replacement of both the carbonyl oxygen and formyl hydrogen atoms by fluorine. The formyl group is directly converted into the trifluoromethyl group to give N-(trifluoromethyl)amines which are isolated in almost quantitative yield (see Section 8.2.10.). Thus, dimethylformamide, diethylformamide, piperidinc-l-carbaldehyde, morpholine-1-carbaldehyde and ethyl(phenyl)formamide were converted into the corresponding A -(tri-fluoromethyl)amines 11.175... 

Lithium hexamethyldisilazide, 165 Potassium permanganate, 258 Trialkylaluminums, 21 Tris[2-(2-methoxyethoxy)ethyl]amine, 336... 

Vinyl iodides are considerably more reactive than bromides in the vinylations. It may be presumed that chlorides are not generally useful, with one exception noted below, since they have not been employed in the reaction. The bromides are usually reacted with a palladium acetate-triphenyl- or tri-o-tolyl-phos-phine catalyst at about 100 C. The reaction will occur without the phosphine if a secondary amine is present. Vinyl iodides will react in the absence of a phosphine even with only a tertiary amine present.48 37 The iodides are so reactive, in fact, that reactions occur even at room temperature if potassium carbonate is the base and tetra-zi-butylammonium chloride is used as phase transfer agent in DMF solution when palladium acetate is the catalyst.88... 

Starting with the tetraethyl ester of DOTA the potassium salt of the triester 31 has been obtained by a partial saponification. To the solution of this compound in anhydrous tetrahydrofuran dicyclohexylcarbodiimide and 1-hydroxybenzo-triazole has been added followed by tris(2-aminoethyl)amine. Subsequent hydrolysis of the ester groups yielded the nonaacid 32. 

A mixture of 66.13 g (0.159 mol) of methyl (R,S)-6-acetyl-3,4-dihydro-7-[5-[(methylsufonyl)oxy]pentyloxy]-2H-l-benzopyran-2-carboxylate, 30.99 g (0.159 mol) of l-[2,4-dihydroxy-3-propylphenyl)ethanone, 33.07 g (0.239 mol) of pulverized potassium carbonate, 5.16 g (15.9 mmol) of tris(3,6-dioxahepyl)amine in 900 mL of toluene was stirred under Ar at reflux for 6 h and then at room temperature overnight. The mixture was poured into 300 mL of water and the organic phase was separated, washed with brine, dried and evaporated to give 84.3 g of methyl (R,S)-6-acetyl-7-[5-(4-acetyl-3-hydroxy-2-propylphenoxy)pentoxy]-3,4-dihydro-2H-l-benzopyran-2-carboxilate. Crystallization from MeOH (0°C, 18 h) gave 66 g (81% yield), m.p. 77-80°C. 

The silyl enol ether may be obtained from the Fluka Chemical Corp., 255 Oser Avenue, Hauppauge, NY 11788. Alternatively, it may be prepared by the following modification of the procedure of Walshe and co-workers.2 The Walshe procedure is followed exactly with 36 g (0.30 mol) of acetophenone, 41.4 g (0.41 mol) of tri ethyl amine, 43.2 g (0.40 mol) of chlorotri-methylsilane, 60 g (0.40 mol) of sodium iodide, and 350 nt of acetonitrile. After extraction, the organic layer is dried over potassium carbonate and then concentrated with a rotary evaporator under reduced pressure. The crude product is a mixture of 97% of the desired silyl enol ether and 3% of acetophenone, as shown by gas chromatography. The crude product is distilled in a Claisen flask at a pressure of about 40 mm. After a small forerun (ca. 3... 

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