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PHOTOCYCLISATION OF KETO-LACTAMS. A NEW SYNTHESIS OF FUNCTIONALIZED 1-AZA-BICYCLO(X.Y.0.)ALKANES

A series of 1-azabicyclo(x.y.0)alkanes has been synthesized using an intramolecular photoreduction.The methodology consists of a regioselective abstraction of a hydrogen alpha to the nitrogen of an amide by the triplet T1(n, ?*) of a carbonyl derivative.

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Pyrroline – Wikipedia,
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Acetylcholinesterase inhibition by fused dihydroquinazoline compounds

A new type of dihydroquinazoline-based inibitor of acetylcholinesterase (AChE) is described. These compounds were designed to interact with the catalytic site of AChE in a manner similar to the known inhibitor tacrine. In a manner analogous to the potency enhancement obtained by addition of chlorine atoms to the tacrine molecule, a 3-chloro derivative of the parent hexahydroazepino[2,1-b]quinazoline structure was found to be about 8 times more potent as an AChE inhibitor than the unsubstituted compound.

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New method of preparation of C2F5Li and its reactions with cyclic imines and lactims: Synthesis of alpha-pentafluoroethyl proline

Addition of pentafluoroethyllithium to cyclic imines leads to pentafluoroethyl substituted pyrrolidines, piperidines and azepanes while reaction of cyclic lactims gives rise to 2-pentafluoroethyl imines. Oxidative cleavage of 2-furyl-2-pentafluoroethyl pyrrolidine has been found to be an effective method for the preparation of a racemic alpha-pentafluoroethyl proline.

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Evaluation of aroma components in Chinese southwest tobacco by headspace gas chromatography-mass spectrometry

In this paper, a simple method of headspace analysis (HSA) was applied to determine aroma components in Chinese southwest tobacco. Ninety-seven aroma compounds were extracted from tobacco under optimized experimental conditions. Meanwhile, it took 4 h for traditional method namely simultaneous distillation and extraction (SDE) for analysis, which is time-consuming and a waste of solvent. Compared with simultaneous distillation and extraction, headspace analysis is faster and more convenient in extracting tobacco aroma compounds. Moreover, six aroma compounds were first proposed in the research. The main aromatic components in tobacco detected by headspace can evaluate the tobacco quality and distinguish a specific variety from others. Headspace analysis method was proposed as an easy, rapid and environment-friendly method for the determination of aroma components in tobacco. The proposed method can not only enhance the extracting rate of aromas but meet the demand of qualitative analysis.

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Synthesis of 2-(omega-aminoalkyl)imidazolin-4-ones by ring chain transformation of lactam derivatives with alpha-aminoamides

Reaction of N-methylamides of biogenic (S)-alpha-aminoacids 3 with lactam acetals 1 or lactim ethers 2 gives three types of products, i.e. N-methyl-alpha-lactamiminoamides 5 by condensation, 2-(omega-aminoalkyl)imidazolin-5-ones 7 or 2-(omega-lactamiminoalkyl)imidazolin-4-ones 8 by ring chain transformation. All products represent novel optically active derivatives of biogenic alpha-aminoacids.

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N-heterocyclic carbene-catalyzed annulation of alpha-cyano-1,4-diketones with ynals

In this paper, the first stereoselective annulation reaction between r-cyano-1,4-diketones and ynals, mediated by catalytic amounts of a triazolium salt precatalyst and cocatalytic amounts of a weak carboxylate base, is disclosed. The title transformation proceeds smoothly under mild reaction conditions and generates three contiguous stereogenic centers, one of which is a quaternary acetal carbon. This reaction tolerates a wide variety of electronically distinct substituents on both reaction partners and affords privileged bicyclic scaffolds in 61-90% isolated yields and with up to 20:1 diastereomeric preference.

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Facile synthesis of 4H-1,2,4-benzothiadiazine-1,1-dioxides

o-Bromoarylsulfonylated amidines prepared either by acylation of amidine with o-bromoarylsulfonyl chloride or through the reaction of o-bromoarylsulfoamide with lactime ether underwent Cu(I)-catalyzed intramolecular cyclization to give 4H-1,2,4-benzothiadiazine-1,1-dioxides in good yield. By varying substituents on arylsulfonyl moieties, amidines, and lactime ethers, a small library of structurally diverse 4H-1,2,4- benzothiadiazine-1,1-dioxide derivatives was prepared.

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Absence of Stereoelectronic Control in Hydrolysis of Cyclic Amidines

According to Deslongchamps’ theory of stereoelectronic control, preferentioal cleavage of a tetrahedral intermediate occurs when there are two lone pairs antiperiplanar to the leaving group.For reasons presented (Perrin and Arrhenius, J.Am.Chem.Soc. 1982, 104, 2839), product studies of hydrolysis of cyclic amidines can test this theory, and initial results supported it.However, those results are ambiguous, owing to a mismatch of leaving abilities.We now find that hydrolysis of three six-membered ring amidines bearing matched leaving groups produces predominantly aminoamide, the product of ring cleavage, and only 3-9percent lactam, as expected from the theory.In contrast, hydrolysis of three five- or seven-membered ring amidines produces substantial (ca. 50percent) lactam.Despite attempts to accomodate these results to the theory, it is concluded that there is no general requirement for two lone pairs antiperiplanar to the leaving group and that stereoelectronic control, even in six-membered ring amidines, contributes less than 2 kcal/mol.

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Boric acid: a new regiospecific decarboxylating agent. Syntheses of cyclic imines, beta-enaminones, and beta-enaminodiketones from beta-enaminoesters

The synthesis of cyclic imines 2, beta-enaminones 6, and beta-enaminodiketones 7 is described.Regio- and stereospecific thermolysis of beta-enaminoesters 4 with boric acid permit these preparations in generally good yields. Key words: boric acid, cyclic beta-enaminoesters, decarboxylation, cyclic imines, cyclic beta-enaminones.

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Synthesis of 5-amino-4-(2-azacycloalkylidene)-2-phenyl-2,4-dihydro-3H- pyrazol-3-ones

The reaction 5-amino-2-phenyl-3,4-dihydro-3H-pyrazol-3-one with activated lactams (lactim ethers, lactam acetals, and methylthioalkylidene iminium salts) was investigated. It occurs on the active methylene group of 5-amino-2-phenyl-3,4-dihydro-3H-pyrazol-3-one to furnish cyclic enamines, 5-amino-4-(2-azacycloalkylidene)-2-phenyl-2,4-dihydro-3H-pyrazol-3-ones and 5-amino-4-(1-methyl-2-azacycloalkylidene)-2-phenyl-2,4-dihydro-3H-pyrazol-3- ones. Georg Thieme Verlag Stuttgart.

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Pyrroline – Wikipedia,
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