Amines results

Alkali moderation of supported precious metal catalysts reduces secondary amine formation and generation of ammonia (18). Ammonia in the reaction medium inhibits Rh, but not Ru precious metal catalyst. More secondary amine results from use of more polar protic solvents, CH OH > C2H5OH > Lithium hydroxide is the most effective alkah promoter (19), reducing secondary amine formation and hydrogenolysis. The general order of catalyst procUvity toward secondary amine formation is Pt > Pd Ru > Rh (20). Rhodium s catalyst support contribution to secondary amine formation decreases ia the order carbon > alumina > barium carbonate > barium sulfate > calcium carbonate. 

Varying the fatty acid portion of the surfactant can have an effect on antistatic performance. In the example given in Table 5, ethoxylated coconut amine results in the shortest static decay time, whereas ethoxylated stearyl amine results in the longest static decay time (135). 

In Robinson s now well-known suggestions, regarding the processes by which alkaloids may be produced in plants, two main reactions are used j the aldol condensation and the similar condensation of carbinol-amines, resulting from the combination of an aldehyde or ketone with ammonia or an amine, and containing the group. C(OH). N., with substances in which the group, CH. CO. is present. By these reactions it is possible to form the alkaloid skeleton, and the further necessary changes postulated include oxidations or reductions and elimination of water for the formation of an aromatic nucleus or of an ethylene derivative. 

The acid-catalyzed reaction of acetophenone with acyclic secondary amines results in the formation of the expected enamine and a rearrangement product. The latter product arises from the transfer of one of the amino N-alkyl groups to the cnamine s carbon to produce a ketimine (53a). 

Alkaline hydrolysis of 6-methoxy- 4-methoxycarbonyl-2-methyl-tbiopyrimidine leaves unaffected only the methylthio group which can then be hydrolyzed in acid. 9-Alkylthioacridines are hydrolyzed by acid less readily than the corresponding alkoxy compounds and more readily than alkylamino derivatives. Peculiarly, a better yield of the amine results from 4-thioxo than from 4-methylthio-quinazoline on heating with primary amines. Displacement in 2-methylthio-quinolinium and 3-methylthiopyridazinium compounds (137) proceeds readily with the carbanion of diethylmalonate or the zwitterion of 2-methylbenzothiazolinium derivatives. 

Similarly, indole itself could be converted by 2-methylsulfanyl-l,3-dithiolium iodide to its 3-dithiolium derivative, which gave 27 quantitatively with DBU. However, treatment of indoles, which bear the benzo-dithiolium moiety in the 2-position with tertiary amines, resulted in a black reaction mixture. All attempts to isolate the o-quinoid compound 28 failed (Scheme 7). 

The reaction of the fervenulin 1-oxides 100 with secondary amines results in contraction of the 1,2,4-triazine ring to form 2-amino-5,7-dimethylimidazo[4,5-e] pyrimidine-4,6(5/7,7//)-diones 101. The reaction of the same fervenulin 1-oxides 100 with ammonia leads to the 1,2,4-triazine ring cleavage product, 1,3-dimethyl-5-imino-6-isonitrosouracil 102 (94KGS1253). 

Ammonia and other amines are good nucleophiles in SN2 reactions. As a result, the simplest method of alkylamine synthesis is by Sn2 alkylation of ammonia or an alkylamine with an alky) halide. If ammonia is used, a primary amine results if a primary amine is used, a secondary amine results and so on. Even tertiary amines react rapidly with alkyl halides to yield quaternary ammonium salts, R4N+ X-... 

Ketenes react with tertiary allylic amines in the presence of Lewis acids to give zwitterionic intermediates which undergo [3,3]-sigmatropic rearrangement [119]. Photolysis of chromium carbene complexes in the presence of tertiary amines results in similar chemistry [120]. Cyclic (Table 21) and strained allylic amines (Eq. 34) work best, while acylic amines are less reactive (Eq. 35). 

The use of microwave irradiation for this reaction, compared to conventional thermal heating, was investigated. Chloroform used as solvent under the conventional heating did only allow a temperature of 60 °C and a direct comparison between the two methods is therefore somewhat unfair imder these circumstances. Nevertheless, the microwave-assisted method is attractive and proved useful for both primary and secondary amines resulting in highly substituted pyrazolo ring-fused pyridones 40 in 68-86% yields within only 10 min. 

The reaction of EPM-g-MA with primary aliphatic amines results in amide acids, which at elevated temperature convert to imides [12] (Figure 13.6). The reaction of EPM-g-MA with alcohols yields... 

The silylation-amination of 5,10-dihydroxy-l,4-dioxo-l,2,3,4-tetrahydroben-zo[g]phthalazine 281 for 27 h at 170 °C with excess N(2-aminoethyl)piperidine 282 and HMDS 2 proceeds with catalytic amounts of Ts0H-H20 to afford, via the activated persilylated intermediate in which the sensitive phenolic hydroxy groups are protected, the 1,4-bis-amine 283 in 67% yield. All conventional efforts with POCI3, PCI5, or SOCI2 to convert 281 into the corresponding 1,4-dichloro compound, to be followed by amination, resulted in failure [86] (Scheme 4.35). 

Safe" secondary amines resulting in non-carcinogenic N-nitroso compounds after nitrosation (German Patent Application No P 3029 318 6)... 

The 1,3,4-substituted benzene is reacted with an N,N-disubstituted-N -methyl-amine resulting in transfer of the methyl group to the 2-position of the aromatic ring, thereby creating a crowded 1,2,3,4-substituted aromatic [127]. No details on the nature of the substituents and the presence of a solvent are given, as the process is proprietary. The temperature in the micro reactor was set to 0 °C. 

Similar reactions with primary and secondary amines result in the formation of 3-aUcylamino- or 3-dialkylamino-l-butyne in 30-80% yield (TON = 3-9) [243-247]. In one example, the TOP could be estimated as 0.2 h" [246]. Enamines were proposed as reaction intermediates. It was later shown that enamines effectively react with terminal aUcynes, including acetylene, to afford the expected aminoalkynes without catalyst or, more rapidly, sometimes exothermically, in the presence of CujCf [248]. Aromatic amines do not react under the same conditions. However, in the presence of organic acids, e.g. acetic acid, 3-arylamino-l-butynes can be isolated in moderate yields (Eq. 4.59) [246, 247, 249]. 

The reaction of 2,2 -dithiodibenzaldehyde with Ni11 complexes containing coordinated primary amines results in Schiff base condensation and cleavage of the disulfide bond to form a chelating... 

The addition of ammonia to excess methyl acrylate (a linear monomer), followed by amidation with excess ethylenediamine afforded the resultant cascade molecule, and thus Tomalia [37] created the commercially available PAMAM starburst series of dendrimers (2, Fig. 2). Related core molecules such as ethylenediamine and aminoalcohols and other functionalizable groups such as thiol moieties were used to prepare similar dendrimers [38]. This methodology is applicable to most primary amines, resulting in a 1 —> 2 branching pattern. Recently, examples of related Si-, [39] P-, [40] and metallo systems [41], which follow this linear monomer protocol have been reported. 

The reaction of the epoxide with a thiol group yields a thioether linkage, whereas reaction with a hydroxyl gives an ether and reaction with an amine results in a secondary amine bond. The relative reactivity of an epoxy group is thiol > amine > hydroxyl, and this is reflected by... 

Amines resulting from the reaction of an amino group (-NIL), with naphthalene they are used as rubber antioxidants. See PAN, PBN. 

However, reaction of C02 with a tertiary amine results in the formation of bicarbonates ... 

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