Amines diethylamine

B) SECONDARY AMINES, (i) Aromatic amines. RjNH. Monomethyl- and monoethylaniline, diphenylamine. (ii) Aliphatic and other amines. Diethylamine, di-n-propylamine, di-isopropylamine. Also Piperidine, piperazine diethylene diamine). 

Experiments designed to clarify the situation were carried out by Wittig and Mayer (40). It was shown that changing the molar ratio of amine (diethylamine, di- -butylamine, or diisobutylamine) to -butyraldehyde from 1 1 to 2 1 did not affect the yield of enamine (53- 64%, based on the aldehyde). Contrariwise, changing the ratio of amine (morpholine, piperidine, or pyrrolidine) to n-butyraldehyde from 1 1 to 2 1 boosted the yields from 52-57 % to 80-85 %. The authors interpret these data as indicating that the cyclic amines form aminals with n-butyraldehyde, while the open-chain do not. Infrared evidence is stated as having shown that the aminal originates not from attack of excess amine on the enamine, which is stable under the conditions of the reaction, but from the N-hemiacetal (17). 

A direct conversion of RPOCl3 complexes can only be carried out with secondary amines. Diethylamine reacts with the ethyl phosphorus oxydichloride... 

Isomerization of the epoxide (IV) with pyrrolidine was carried out as described by Sih (8) and consistently gave yields of 35-60% rather than the 73% reported. Changes in experimental conditions including longer reaction times at lower temperatures, use of freshly distilled pyrrolidine, use of NaOH dried pyrrolidine, and use of distilled epoxide (IV) had little effect on the yield. The only variation that improved the yield was to allow the reaction to proceed at ambient temperature for a longer period of time than the recommended 3 hours. Allowing the reaction to proceed for 40 hours provided a maximum 67.5% yield. Other bases such as sodium carbonate, tri ethyl amine, diethylamine l,5-diazabicyclo[4.3.0]non-5-ene(DBN), and sodium methoxide all gave lower yields of distilled product than pyrrolidine. It is important to use the hydroxyaldehyde (V) as soon as possible since it is a very unstable material. 

The benzotriazole derivatives 111, obtained from benzotriazole, ethyl glyoxylate and secondary amines (diethylamine, pyrrolidine, piperidine or morpholine), furnish the amino esters 112 by the action of organozinc reagents R2ZnX (R2 = Me, Bu, PhCH2 or Ph)120. 

Trichlorosilane reacts with secondary amines (diethylamine, pyrrolidine, piperidine, morpholine and 1-methylpiperazine) to give the corresponding tris(diaLk ylamino)silanes HSi(NR2)3289. 

In aliphatic amines (diethylamine or triethylamine) the intramolecular hydrogen abstraction is quenched almost completely. Instead, smooth photoreduction of the nitro group without participation of the side chain is observed with 1,3,5-tri-fezf-butyl-2-nitrobenzene (5) and 14, R = C(CH3)3 ). Products derived from the respective phenylhydroxylamines were isolated in both cases. Again, an electron transfer, which does not seem to suffer from steric restrictions, is operative (see also Section A. 1.3). 

Amines aniline, cyclic amines, diethylamine, dimethylforamine, EDTA, propanediamine, -propylamine... 

Available chemistry quaternary amine, diethylamine, ethylenediamine, ethyl, butyl, hydroxyl, sulfonyl, carboxymethyl, epoxy, protein A, protein G, IDA, revered phase. ... 

Success was obtained with Ru3(CO)i2 as catalyst precursor [6], but the most efficient catalysts were found in the RuCl2(arene)(phosphine) series. These complexes are known to produce ruthenium vinylidene spedes upon reaction with terminal alkynes under stoichiometric conditions, and thus are able to generate potential catalysts active for anti-Markovnikov addition [7]. Similar results were obtained by using Ru(r]" -cyclooctadiene)(ri -cyclooctatriene)/PR3 as catalyst precursor [8]. (Z)-Dienylcarba-mates were also regio- and stereo-selectively prepared from conjugated enynes and secondary aliphatic amines (diethylamine, piperidine, morpholine, pyrrolidine) but, in this case, RuCl2(arene) (phosphine) complexes were not very efficient and the best catalyst precursor was Ru(methallyl)2(diphenylphosphinoethane) [9] (Scheme 10.1). 

Secondary amines (diethylamine, piperidine, or morpholine) attack the l,3-thiazine-2,6-dithiones (211) at C-2 (Scheme 85) [80JCR(S)148],... 

The sensor did not respond to volatile compounds such as acetic acid, ethyl alcohol, and amines (diethylamine, propylamine, and butylamine) or to nonvolatile nutrients such as glucose, amino acids, and metal ions (potassium and sodium ions). Therefore, the selectivity of this microbial sensor was satisfactory in the presence of these different substances. The current output of the sensor was almost constant for more than 21 days and 400 assays. The microbial sensor can be used to assay sodium nitrite for a long period. In the same experiments the concentration of sodium nitrite was determined by both the sensor proposed and the conventional method (dime-thyl-a-naphtylamine method). A good correlation was obtained between the sodium nitrite concentrations determined by the two methods (correlation coefficient 0.99). 

The reactions of nucleophilic substitution with participation of reactive clathrochelates are very sensitive to the donor properties of an attacking amine. With aromatic amines, as well as secondary and primary sterically hindered amines in acceptor solvents, and hexachloride precursors, the reaction stops with the formation of disubstituted products. When secondary and sterically hindered primary aliphatic amines are used in donor solvents and sterically unhindered primary aliphatic amines in acceptor solvents, the reaction terminates at trisubstituted products. In the case of sterically unhindered aliphatic amines, tetrasubstituted clathrochelates are formed. With dichloride precursor FeBd2(C12Gm)(BF)2, the primary aliphatic amines in donor solvents form diamine clathrochelates, whereas the secondary amines (diethylamine or piperazine) give only monoamine complexes both in acceptor and donor solvents. 

The secondary amines, diethylamine and methylaniline, were amongst the first materials to be studied in combination with COF,. The reactions, using an excess of COFj, take place readily at room temperature, according to [589] ... 

Formaldehyde la and the secondary amine diethylamine 2b equilibrate with the a-arai- noalkylation 5a and the OH-anion 6b, which can form the a-adduct 15a of the isocyanide 13b whose OH rearranges into its NH-product 18a. Since its OH-anion 6a comes from water 4, it became clear that this reaction was not a 3CR a la HO-3CR, but that a 4CR took place. 

Zollinger s group (Szele et al., 1983 a) studied the reactions of such an alkenedi-azonium salt with O-nucleophiles (ethers, alcohols, water, 2-naphthol) and with a secondary amine (diethylamine), since, in the latter reaction, the cyclization of Scheme 9-46 would not be possible. 

Aldehydes and ketones react with primary amines to give imines. The imin-ium salt intermediate 80 immediately precedes the imine product, and it has an acidic proton that is lost from the nitrogen to form the imine. When a secondary amine (HNR2) reacts with an aldehyde or a ketone, rather than a primary amine, the course of the reaction is identical until the iminium salt intermediate is formed. In a typical experiment, 3-pentanone (69) reacts with the secondary amine diethylamine (Et2NH) and an acid catalyst however, the isolated product is not an imine with a C=N unit, but rather a mixture of compounds that have an amine group attached to a C=C unit. Such products are enamines, and 83 is formed in 86% yield along with 14% of 84. Note that enamine 83 is an E-isomer and 84 is a Z-isomer. 

Nitrogen bases having an ionization constant > 10 , such as N-butyl-amine, diethylamine, piperidine and triethylamine, are reported to suppress the hydroformylation completely [130]. 

The second version of the Gewald s process is the most elegant and consist of the one-pot reaction of three components - or-methylene earbonyl eompound 5b, a-activated acetonitrile 6 and sulfur at temperature not exceeding 45 °C in ethanol or methanol. In this case the base, mainly secondary amine (diethylamine, morpholine), is used in 0.5-1.0 molar equivalent amounts. Reaction towards substituted 2-aminothiophenes with an electron-withdrawing substituent in position C-5 (R ) occurs within three base-promoted steps condensation of starting substrates 5b and 6 - addition of sulfur to a y unsaturated nitrile 9 - ring-closure of the ylidene-sulfur adduet 10 (Seheme 4) [17, 26,34],... 

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