Amine 4- morpholine

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). 

Primary and secondary aliphatic amines, morpholine and 2-methylaziridine and aniline and even the sterically hindered 2.2,6,6-tetramethylpiperidine readily react with 6-bromo-trithiadiazepine 7, in certain cases in the presence of /V./V-diisopropylethylamine, at room temperature by substitution of the bromine atom ammonia, for example, yields trithiadiazepin-6-amine 22 (R1 = R2 = H). There is compelling evidence that these reactions proceed by an elimination-addition mechanism via the heteroaryne, trithiadiazepyne 21.391... 

Direct GC Injection of Amines. Morpholine, 2,6-dimethyl-morpholine, or pyrrolidine in methanol (2.6 to 2.8 g/ml) solutions were injected directly into the GC inlet at 210 C. Portions of these solutions were exposed to ultraviolet radiation (366 nm) for 16 hours prior to injection. 

Hydroamination of activated alkenes has been reported with complexes 91-93 (Fig. 2.15). For example, 91 catalyses the hydroamination of methacrylonitrile (X = CN in Scheme 2.13) by a range of secondary amines (morpholine, thiomorpholine, piperidine, iV-methylpiperazine or aniline) in good to excellent conversions (67-99%) and anfi-Markovnikov regioselectivity (5 mol%, -80°C or rt, 24-72 h). Low enantioselectivies were induced ee 30-50%) depending on the amine used and the reaction temperature [79]. 

Ethylene- diamine Mono- ethanol- amine Morpholine... 

Good results were obtained for a wide range of substrates with stoichiometric amounts of Nb(OEt)s as the Lewis acid the amines used also included a secondary amine, morpholine, which gave results similar to benzylamine. 

Aminocarbonylation has also been applied to the synthesis of unsymmetrical ferrocene-1,1 -bis-carboxamides. Ferrocene-based chiral ligands are very useful in asymmetric catalysis, and enantiomerically pure ferrocenyl ligands can be obtained by optical resolution of unsymmetrically substituted ferrocenes. However, the synthesis of such unsymmetrical ferrocenes is not an easy task. The use of aminocarbonylation gave a solution to this challenge. For example, the Pd-catalyzed reaction of symmetrical ferrocenyl diiodide 144 with two different amines, morpholine and diethylamine (5 equiv. each) under 39.5 atm of CO, gave the desired unsymmetrically disubstituted ferrocene-biscarboxamide 145 in 85% yield (Equation (11)). ... 

The reaction of norbomadiene and secondary amines (morpholine, piperidine, pyrrolidine, N- methylbutylamine) results in the formation of interesting aminated products 593... 

The Heck-type reaction of vinylic bromides with alkenes in the presence of nucleophiles such as stabilized enolates or secondary amines (morpholine or piperidine) are efficient three-component reactions that were developed in the late 1970s... 

The enamine 102, made with the cyclic secondary amine morpholine 101, does the job admirably.20 The immediate product is the conjugated enamine 103 rather than an imine, but this is easily hydrolysed to the enone 99 with aqueous acid. 

The Buchwald-Hartwig reaction was performed under a variety of conditions starting with the model compounds and leading up to target substrate. The results are shown in Table 3. There was a 70 % yield obtained in the reaction of triflate 35 with the cyclic secondary amine morpholine using condition A (entry l),32 however the reaction fails with diphenethylamine (entry 2). Changing the base to sodium tert-butoxide (condition B) or the catalyst to Pd2(dba)3 and ligand (condition C) also resulted in no reaction (entries 3 and 4). 

The Swiss chemist Oppolzer used just such a reaction. He first prepared an acid chloride from cyclopentadiene, and the enamine from cyclopentanone and the secondary amine morpholine. 

When piperidine was used for the formation of the enamine of l-methyl-3-phosphola-none 1-oxide, the saturated amine was obtained, thus confirming the reductive properties of secondary amines, morpholine excluded212 (Scheme 141). 

TFA catalysis accelerated the reaction, which reached 90% conversion after 15 min. Secondary alcohols were considerably less reactive (with z-PrOH 92% of 623 remained after 1 h) and tertiary alcohols showed the lowest reactivity (with /-BuOI I 98% of 623 remained after 1 h). Dioxocindione 623 reacted with BuNH2 to give 650a in 70% yield after 24 h. More sterically hindered amines such as 1-phenethylamine furnished 650b after 10 d in 50% yield. The secondary amine morpholine converted 623 into 650c after 6 d in 94% yield (Scheme 129) <199514CA1525>. 

Isocyanat 1,1-Dipropyl-butyl- E4, 763 (R-CO-NH-C1 4- Amin) Morpholin 2-Cyclohexyl-3-methyl-VI/4, 542... 

Aryl-3-chloro-l,2-dithiolium ions react with various secondary amines (morpholine, A-alkylanilines, diarylamines) to give 3-amino-5-aryl-l,2-dithiolium ions (41) which may also be considered as iminium derivatives (42). ... 

Dichloro- and trichloro-nitrobenzenes also react with Et2NH and cyclic amines (morpholine, pyrrolidine) at 0.6 GPa pressure to give mono-, di-, and trisubstitution products. For example, 2,3-dichloronitrobenzene (116a) and 2,5-dichloronitrobenzene (116b) reacted with these amines to give the... 

Acrylonitrile and the anion of 58 (formed by KOH-MeOH) give the bis-cyanoethyl adduct 117.74- The cyclic amide bond in compound 58 was slowly cleaved by amines morpholine at elevated temperatures affords the sulfonamide-carboxamide 118.46 Pyrrolidine reacts similarly.40... 

Proline is a highly effective hgand for the Cul-catalysed displacement of bromine in 3-bromopyridines, 2-bromothiazoles and 5-bromo-l-phenylsulfonylindole by primary amines, morpholine and pyrazole. ... 

The alkylation reaction in a two-phase system was extended to various heteronucleophiles [12], Secondary amines (morpholine, benzylmethylamine, etc.) as well as primary amines (n-butylamine, 2,2-diethylpropargylamine, cydohexylamine, a-methylbenzylamine, etc.) reacted for example with (E)-cinnamyl acetate to give only the monoalkylation product in quite good yields (Eq. 4). Even the bis(N,0-boc)-... 

A greater array of amine substrates has also been explored for this reaction utilizing the 4-fluorobromobenzene as the fluoroarene. The results (Table 1) show excellent yields (85 - 93 %) for the primary (7) and secondary (8, 9) amines. Although no reaction was observed with aniline, 93 % yield was obtained with N-methylaniline (8). Derivatives prepared from the cyclic amines, morpholine (10) and piperidine (11), were also obtained in excellent yields of 82 - 98 %. A preliminary attempt at a disubstitution reaction using two equiv of piperazine Avith one equiv of 4-bromofluorobenzene gave the disubstituted product (12) in only 35 % yield. However, it is likely that this yield could be improved using an excess of... 

NITROCARBOL (75-52-5) Forms explosive mixture with air (flash point 95°F/35°C). Thermally unstable. Shock, friction, pressure, or elevated temperature above 599°F/315°C can cause explosive decomposition, especially if confined. Violent reaction with strong oxidizers, alkyl metal halides, diethylaluminum bromide, formic acid, methylzinc iodide. Contact with acids, bases, acetone, aluminum powder, amines, bis(2-aminoethyl)amine, haolforms make this material more sensitive to explosion. Reacts, possibly violently, with ammonium hydroxide, calcium hydroxide, calcium hypochlorite, 1,2-diaminomethane, formaldehyde, hexamethylbenzene, hydrocarbons, hydroxides, lithium perchlorite, m-methyl aniline, nickel peroxide, nitric acid, metal oxides, potassium hydride, potassium hydroxide, sodium hydride. Mixtures with ammonia, aniline, diethylenetriamine, metal oxides, methyl amine, morpholine, phosphoric acid, silver nitrate form shock-sensitive compounds. Forms high-explosive compound with urea perchlorate. Mixtures with hydrocarbons and other combustible materials can cause fire and explosions. Attacks some plastics, rubber, and coatings. 

Analysis of enone (77) reveals a condensation between an aldehyde and the enol of a less reactive ketone, easily achieved by first making the enamine of the ketone—the cyclic secondary amine morpholine (78) is often used. 

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