Amines, acetylation alkylation

The quinaldine is separated from any unreacted aniline and from the alkyl-anilines by treatment with acetic anhydride, basified with sodium carbonate and steam distilled. Only the primary and secondary amines are acetylated the acetylated amines are now much less volatile so that separation from the steam-volatile quinaldine (a tertiary amine) is facile. 

Sulfur Substituents. Acetylation and alkylation of pyridinethiones usually take place on sulfur (39). An exception to this is 4-pyridinethione [19829-29-9] which is acetylated on nitrogen. Displacement of thioethers can be achieved with hydroxide or amines (eq. 13) (40). Thioether functional groups can also be removed by reduction (39). 

Amorphous (most likely atactic) 3,4-polyisoprene of 94—100% 3,4-microstmcture was prepared with a (C2H 3A1—Ti(0—/ -C Hy) catalyst (11). Crystalline 3,4-polyisoprene containing about 70% 3,4-units and about 30% i7j -l,4-microstmcture was prepared using a catalyst derived from iron acetyl acetonate, trialkyl aluminum, and an amine in benzene (37). However, this polyisoprene contained gel and was obtained in poor yield. Essentially gel-free crystallizable 3,4-polyisoprene of 70—85% 3,4-microstmcture with the remainder being cis-1,4 microstmcture was prepared in conversions of greater than 95% with a water-modified tri alkyl aluminum, ferric acetyl acetonate, and 1,10-phenanthroline catalyst (38). The 3,4-polyisoprene is stereoregular and beheved to be syndiotactic or isotactic. 

Purine, 6-bromo-9-/3-D-(2,3,5-tri-0-acetyl)ribofuranosyl-synthesis, 5, 598 Purine, 6-carboxy-reactions, 5, 549 Purine, 8-carboxy-reactions, 5, 549 Purine, 2-chloro-reactions, 5, 561 synthesis, 5, 597 Purine, 6-chloro-alkylation, 5, 529 glycosylation, 5, 529 oxidation, 5, 539 3-oxides reactions, 5, 554 synthesis, 5, 595 reactions, 5, 561, 595 with ammonia, 5, 562 with fluorides, 5, 563 with trimethylamine, 5, 562 9- -D-ribofuranoside synthesis, 5, 560 synthesis, 5, 597, 598 Purine, 8-chloro-amination, 5, 542 Purine, 6-chloro-8-ethoxy-synthesis, 5, 591 Purine, 6-chloro-9-ethyl-dipole moment, 5, 522 Purine, 6-chloro-2-fluoro-riboside... 

Purines, N-alkyl-N-phenyl-synthesis, 5, 576 Purines, alkylthio-hydrolysis, 5, 560 Mannich reaction, 5, 536 Michael addition reactions, 5, 536 Purines, S-alkylthio-hydrolysis, 5, 560 Purines, amino-alkylation, 5, 530, 551 IR spectra, 5, 518 reactions, 5, 551-553 with diazonium ions, 5, 538 reduction, 5, 541 UV spectra, 5, 517 Purines, N-amino-synthesis, 5, 595 Purines, aminohydroxy-hydrogenation, 5, 555 reactions, 5, 555 Purines, aminooxo-reactions, 5, 557 thiation, 5, 557 Purines, bromo-synthesis, 5, 557 Purines, chloro-synthesis, 5, 573 Purines, cyano-reactions, 5, 550 Purines, dialkoxy-rearrangement, 5, 558 Purines, diazoreactions, 5, 96 Purines, dioxo-alkylation, 5, 532 Purines, N-glycosyl-, 5, 536 Purines, halo-N-alkylation, 5, 529 hydrogenolysis, 5, 562 reactions, 5, 561-562, 564 with alkoxides, 5, 563 synthesis, 5, 556 Purines, hydrazino-reactions, 5, 553 Purines, hydroxyamino-reactions, 5, 556 Purines, 8-lithiotrimethylsilyl-nucleosides alkylation, 5, 537 Purines, N-methyl-magnetic circular dichroism, 5, 523 Purines, methylthio-bromination, 5, 559 Purines, nitro-reactions, 5, 550, 551 Purines, oxo-alkylation, 5, 532 amination, 5, 557 dipole moments, 5, 522 H NMR, 5, 512 pJfa, 5, 524 reactions, 5, 556-557 with diazonium ions, 5, 538 reduction, 5, 541 thiation, 5, 557 Purines, oxohydro-IR spectra, 5, 518 Purines, selenoxo-synthesis, 5, 597 Purines, thio-acylation, 5, 559 alkylation, 5, 559 Purines, thioxo-acetylation, 5, 559... 

At higher temperatures the mixture of 10 and methyl vinyl ketone yields the 1,4-carbocyclic compound as described previously. Methyl isopropenyl ketone (5), ethyl acetylacrylate (d), 2-cyclohexenone (21), and 1-acetyl-1-cyclohexene (22) also undergo this type of cyclization reaction with enamines at higher temperatures. This cycloalkylation reaction occurs with enamines made of strongly basic amines such as pyrrolidine, but the less reactive morpholine enamine combines with methyl vinyl ketone to give only a simple alkylated product (7). Chlorovinyl ketones yield pyrans when allowed to react with the enamines of either alicyclic ketones or aldehydes (23). 

The key to clinical agents in this series, the secondary amine, 65, is obtained by a sequence analogous to that used to obtain desmethymorphine. Thus, the phenol (63) is first acetyl-ated (64), and then demethylated by treatment with cyanogen bromide hydrolysis gives the desired aminophenol (65). Alkylation... 

Clerici and Porta reported that phenyl, acetyl and methyl radicals add to the Ca atom of the iminium ion, PhN+Me=CHMe, formed in situ by the titanium-catalyzed condensation of /V-methylanilinc with acetaldehyde to give PhNMeCHMePh, PhNMeCHMeAc, and PhNMeCHMe2 in 80% overall yield.83 Recently, Miyabe and co-workers studied the addition of various alkyl radicals to imine derivatives. Alkyl radicals generated from alkyl iodide and triethylborane were added to imine derivatives such as oxime ethers, hydrazones, and nitrones in an aqueous medium.84 The reaction also proceeds on solid support.85 A-sulfonylimines are also effective under such reaction conditions.86 Indium is also effective as the mediator (Eq. 11.49).87 A tandem radical addition-cyclization reaction of oxime ether and hydrazone was also developed (Eq. 11.50).88 Li and co-workers reported the synthesis of a-amino acid derivatives and amines via the addition of simple alkyl halides to imines and enamides mediated by zinc in water (Eq. 11.51).89 The zinc-mediated radical reaction of the hydrazone bearing a chiral camphorsultam provided the corresponding alkylated products with good diastereoselectivities that can be converted into enantiomerically pure a-amino acids (Eq. 11.52).90... 

In the study on tetrasubstituted [l,2,4]triazolo[l,5- ]pyrimidines 45, H and 13C NMR spectra of 35 different compounds have been recorded <1995JHC407>. Substituents in position 2 were various amines and sulfano groups, whereas the other substituents (Rs, R6, and R7) were alkyl, phenyl, and acetyl groups. 

The reaction of diethyl acetyl- and propionylmalonates with hydroxyl-amine hydrochloride or its N-methyl derivative in ethanol afforded the appropriate ethyl 3-alkyl-2,5-dihydro-5-oxo-4-isoxazolecarboxylate (88-TL6339). 

Nalorphine Nalorphine, N-allylnormorphine (3.1.75), is synthesized from morphine by its complete acetylation, i.e. by transformation into heroin (3.1.21), in order to temporarily protect the hydroxyl groups, and then by undergoing demethylation. In order to do this, heroin (3.1.21) is processed with cyanogen bromide. The resulting N-cyano derivative (3.1.73) is hydrolyzed by a solution of hydrochloric acid into the N-demethylated morphine, normorphine (3.1.74), whose secondary amine group undergoes alkylation with allylbromide to give desired nalorphine [47,48]. 

While reaction of the acetate 40 as well as the acetyl- and phthalimide derivatives of chiral amine (41b and 41c) proceeded with erythro diastereoselectivity (in accordance with the classical cis effect, minimization of 1,3-allyhc strain) (Table 6, entries 8, 10, 11), for the allylic alcohols 39, primary allyhc amine 41a, silyl enol ethers 42 and enol ether 43 threo selectivity was observed (Table 6, entries 1-7, 9, 12-14) (see also Scheme 24). For allyhc alcohols with an alkyl group R cis to the substituent carrying the hydroxyl group, diastereoselectivity was high (Table 6, entries 1-7) in contrast, stereoselection was low for allylic alcohols which lack such an R cis) substituent (substrates 39h and 39i, see Figure 4). 

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