- A general and efficient method for the synthesis of 9-trifluoromethylated [1,2,4]triazolo[1,5-a]azepine derivatives
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(1-Chloro-2-trifluoromethylcyclohexyl)azo compounds 3a - d, prepared by oxidation of the hydrazones 2a - d of 2-trifluoromethylcyclohexanone (1) with a slightly excess amount of tert-butyl hypochlorite, react with antimony pentachloride and a nitrile to afford the respective 2,3-disubstituted-9-trifluoromethyl-6,7,8,9-tetrahydro-5H-[1,2,4]triazolo [1,5-a]azepinium hexachloroantimonates 6a - j. The reaction mechanism comprises of the initial cycloaddition of the in situ generated 1-aza-2-azoniaallene salts 4 to the triple bond of nitrile, giving the spiro-substituted 5a - j, followed by rearrangement and concomitant ring enlargement. From 3a - c where R1 = aryl, the salts 6a - h are isolated in high yields. However, if ethyl (1-chloro-2-trifluoromethyl)azocarboxylate (3d) is employed, the neutral N(3)-unsubstituted analogues 7a and 7b are obtained and after usual basic work-up, are converted to picrates 8a and 8b respectively. For one compound 6f, the X-ray diffraction analysis has been carried out in order to confirm the structural assignment. A practical modified procedure for preparation of the crucial starting ketone 1 is also described.
- Ding, Zongbiao,Xia, Shijing,Ji, Xiaojun,Yang, Haiyan,Tao, Fenggang,Wang, Quanrui
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Read Online
- Pyridone derivative and application thereof in preparation of medicine for preventing and/or treating tuberculosis caused by Mycobacterium tuberculosis
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The invention provides a pyridone derivative and application thereof in preparation of a medicine for preventing and/or treating tuberculosis caused by mycobacterium tuberculosis, which belong to the field of pharmacy. The structure of the pyridone derivative is shown as a formula (I). Experimental results show that the pyridone derivative provided by the invention can specifically inhibit the activity of mycobacterium tuberculosis, has small toxic and side effects, can be used for preparing a medicine for resisting mycobacterium tuberculosis, can also be used for preparing a medicine for preventing and/or treating tuberculosis, and a new choice is provided for medicines for treating tuberculosis (especially drug-resistant tuberculosis).
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Paragraph 0085-0089
(2021/07/01)
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- 1 microwave-induced montmorillonite-mediated facile synthesis of enamines
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Montmorillonite clay-mediated simple and high yielding protocol for the synthesis of various enamines with secondary amines and ketones is developed under microwave condition. This protocol is very convenient to accesses the enamines from cyclic amines with various carbonyl compounds in high yield under mild reaction conditions with short reaction time.
- Yadav, Ram Naresh,Banik, Indrani,Srivastava, Ashok Kumar,Ramos, Katherine,Banik, Bimal Krishna
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p. 249 - 254
(2020/01/08)
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- Synthesis and Cytotoxic Evaluation of Novel 1,2,3-Triazole-4-Linked (2E,6E)-2-Benzylidene-6-(4-nitrobenzylidene)cyclohexanones
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This work describes the synthesis of novel 1,2,3-triazole-4-linked (2E,6E)-2-benzylidene-6-(4-nitrobenzylidene)cyclo-hexanones starting from cyclohexanone. 1-(Cyclohex-1-en-1-yl)piperidine, the enamine from cyclohexanone and piperidine, reacted with 4-nitrobenzaldehyde to obtain 2-(4-nitrobenzylidene)cyclohexanone. Condensation of the latter compound with (prop-2-yn-1-yloxy)benzaldehyde derivatives under acidic conditions gave (4-nitrobenzylidene)-[(prop-2-yn-1-yloxy)-benzylidene]cyclohexanones. Finally, 'click reaction' of these derivatives and various organic azides led to the title compounds. All compounds were examined by MTT assay for cytotoxic activity in one human breast cancer cell line, MDA-MB-231.
- Mahdavi, Mohammad,Akhbari, Maryam,Saeedi, Mina,Karimi, Maryam,Foroughi, Niloufar,Karimpour-Razkenari, Elahe,Alinezhad, Heshmatollah,Foroumadi, Alireza,Shafiee, Abbas,Akbarzadeh, Tahmineh
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p. 175 - 180
(2016/04/19)
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- DICARBOXYLIC ACID HAVING CYCLIC ALKYLENE GROUP
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PROBLEM TO BE SOLVED: To provide especially dicarboxylic acid useful as electrolyte for an electrolytic capacitor among polycarboxylic acids, an electrolyte for electrolytic capacitor and an electrolytic capacitor using the same. SOLUTION: The problem is solved by novel dicarboxylic acid containing a cyclic structure represented by the formula (1). (1), where R1 to R5 and Z represents each specific group, n represents the number of methylene groups in a specific range and the total carbon atom number of the dicarboxylic compound is 10 to 50. COPYRIGHT: (C)2015,JPOandINPIT
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Paragraph 0058
(2017/01/02)
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- New nucleophilic rearrangement in the mechanism of the three-component domino cyclisation affording fluoroalkylated (pyrrolo)quinazolines
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The following mechanism steps were verified for the three-component domino cyclisation affording (pyrrolo)quinazolines from 2-(aminomethyl)aniline, a very reactive oxo compound and "usual" oxo compound. The first step was a rapid reaction of very reactive oxo compound (trifluoropyruvate or hexafluoroacetone) with benzylic amino group to form hemiaminal, but not imine; the second step was the reaction of oxo compound with aromatic amino group to form imine (Schiff base) being in equilibrium with its enamine form; the third step was an intramolecular attack of the hemiaminal carbon by the enamine carbon followed by a new nucleophilic rearrangement to form tetrahydropyrimidine cycle; the forth step was closure of the lactam ring, if ester group was available as in trifluoropyruvate.2013 Elsevier B.V. All rights reserved.
- Paleta, Old?ich,Dolensky, Bohumil,Pale?ek, Ji?í,Kví?ala, Jaroslav
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supporting information
p. 1 - 11
(2014/01/06)
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- The hit-to-lead optimization of 1,2,3,4,4a,9a-hexahydro-1H-xanthenes as glucocorticoid receptor antagonists
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The structure-activity relationship (SAR) study of a 1,2,3,4,4a,9a- hexahydro-1H-xanthene series of selective, human glucocorticoid receptor α (hGRα) antagonists is reported. Compounds were screened using hydroxyapatite-based GR binding and MMTV-Luc co-transfection reporter gene assays. Four different regions of the scaffold were modified to assess the effects on hGRα antagonism and related potency. Compound 8d exhibits an 8-fold better bioactivity than the original hit 1a, as well as an improved chemical stability, which make it a promising lead for the subsequent optimization.
- Zhu, Yan-Hui,Zhang, Meng,Li, Qun-Yi,Liu, Qing,Zhang, Jie,Yuan, Yun-Yun,Nan, Fa-Jun,Wang, Ming-Wei
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supporting information
p. 693 - 698
(2014/06/09)
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- Colloid and nanosized catalysts in organic synthesis: IX hydrogenation of enamines with hydrogen at atmospheric pressure
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Hydrogenation of enamines with hydrogen at atmospheric pressure was performed using nickel nanoparticles as a catalyst. The reaction may be used to produce tertiary amines under mild conditions using an accessible catalyst.
- Mokhov,Popov,Nebykov
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p. 2073 - 2075
(2015/02/02)
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- Hydrogen activation by 2-boryl-N,N-dialkylanilines: A revision of Piers' ansa-aminoborane
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Two 2-[bis(pentafluorophenyl)boryl]-N,N-dialkylanilines reported here exemplify a new class of intramolecular frustrated B/N Lewis pairs. A structure closely related to this class structure was synthesized in 2003 by Piers et al. but was unable to activate H2. The new aminoboranes can activate hydrogen at near ambient conditions; besides, one of them can hydrogenate imines and enamines in a catalytic fashion demonstrating the validity of the original Piers' approach to hydrogen activation with ansa-aminoboranes.
- Chernichenko, Konstantin,Nieger, Martin,Leskelae, Markku,Repo, Timo
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supporting information; body text
p. 9029 - 9032
(2012/09/08)
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- Synthesis, structure and thermal decomposition of cycloalkanone enamine peroxides
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Reactions of cycloalkanone enamines with H2O2 gave bis(1-morpholinocyclopent-1-yl)- and bis(1-morpholinocyclohex-1-yl)-peroxides, which were studied by NMR spectroscopy and X-ray diffraction. Thermolysis of bis(1-morpholinocyclohex-1-yl)-peroxide in n-hexane resulted in two major products, viz., cyclohexanone and morpholine.
- Starostin, Evgenii K.,Khrustalev, Victor N.,Antipin, Mikhail Yu.,Lalov, Andrei V.
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body text
p. 334 - 336
(2010/01/18)
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- Base-promoted reactions of dichlorocarbene adducts of cyclic enamines: A new route to annulated pyrroles
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Treatment of the gem-dihalogenocyclopropanes 1-5 with potassium tert-butoxide or LDA results in the formation of the corresponding and annulated pyrroles 13-17, respectively.
- Bissember, Alex C.,Phillis, Andrew T.,Banwell, Martin G.,Willis, Anthony C.
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p. 5421 - 5424
(2008/09/17)
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- Novel and convenient aldolization of methyl 3,3,3-trifluoropyruvate using enamines instead of ketones
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Piperidine enamines derived from acetone, acetophenone, cyclopentanone and cyclohexanone react easily in minutes with methyl 3,3,3-trifluoropyruvate (1) to afford products of the aldol condensation in high yields at room temperature, which is in contrast to the direct aldolization of 1 with the ketones.
- Palecek, Jiri,Paleta, Oldrich
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p. 521 - 524
(2007/10/03)
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- Rigid phencyclidine analogues. Binding to the phencyclidine and σ1 receptors
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Three phencyclidine (PCP) analogues possessing a highly rigid carbocyclic structure and an attached piperidine ring which is free to rotate were synthesized. Each analogue has a specific fixed orientation of the ammonium center of the piperidinium ring to the centrum of the phenyl ring. The binding affinities of the rigid analogues 1-piperidino-7,8- benzobicyclo[4.2.0]octene (14), 1-piperidinobenzobicyclo[2.2.1]heptene (16), and 1-piperidinobenzobicyclo[2.2.2]octene (13) for the PCP receptor ([3H]TCP) and σ-receptor (NANM) were determined. The three analogues show low to no affinity for the PCP receptor but good affinity for the σ-receptor and can be considered σ-receptor selective ligands with PCP/σ ratios of 13, 293, and 368, respectively. The binding affinities for the σ-receptor are rationalized in terms of a model for the σ-pharmacophore.
- Moriarty, Robert M.,Enache, Livia A.,Zhao, Lei,Gilardi, Richard,Mattson, Mariena V.,Prakash, Om
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p. 468 - 477
(2007/10/03)
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- Clay catalyzed synthesis of imines and enamines under solvent-free conditions using microwave irradiation
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The reactions of primary and secondary amines with aldehydes and ketones, respectively, are accelerated by microwaves under solvent-free conditions in the presence of montmorillonite K 10 clay to afford a high yield synthesis of imines and enamines.
- Varma, Rajender S.,Dahiya, Rajender,Kumar, Sudhir
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p. 2039 - 2042
(2007/10/03)
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- Microwave-Assisted Facile Synthesis of Imines and Enamines using Envirocat EPZGR as a Catalyst
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In a simple microwave-assisted and environmentally benign approach, aldehydes and ketones react readily with primary and secondary amines to afford imines and enamines, respectively, under solvent-free conditions using Envirocat EPZGR as a catalyst.
- Varma, Rajender S.,Dahiya, Rajender
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p. 1245 - 1246
(2007/10/03)
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- Synthesis of Enamines from Cycloalkanones and Secondary Cyclic Amines using K-10 Montmorillonite Clay
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The synthesis of enamines from cycloalkanones and secondary cyclic amines has been carried out in 85-95percent yield in the presence of K-10 montmorrilonite clay and with azeotropic removal of the water formed in the condensation.
- Dewan, Sharwan K.,Varma, Urmila,Malik, Shiv Darshan
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- Chemically Labile Stannylene-Nitrogen Bonds. The Chemoselective and Stereoselective Synthesis of N,N-Bis(trimethylsilyl)enamines and N,N-Dialkylenamines
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The chemoselective reaction of Sn2 with primary aldehydes leads to the stereoselective synthesis of trans-N,N-bis(trimethylsilyl)enamines.More reactive Sn(NR2)2 (R = Et, iPr, or piperidine) can be generated in situ and then treated with aldehydes or ketones to give trans enamines.
- Burnell-Curty, Cynthia,Roskamp, Eric J.
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p. 5063 - 5064
(2007/10/02)
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- Studies on the Oxidation of Enamines with Molecular Oxygen. I. Oxidation of Some Piperidino Alkenes
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In the autoxidation of 1-piperidinocyclohex-1-ene (1), 1-piperidinobut-1-ene (2), 3-piperidinopent-2-ene (3), and 1-piperidino-2-methyl-prop-1-ene (4) only products of an oxidative attack at the C=C-double bond are formed.Both α-aminoketones, the products of the rearrangement of primarily formed epoxides, and products of the oxidative scission of the C=C double bond are obtained.As a side reaction some hydrolysis of the starting enamines takes place.This hydrolysis proves that some water must be formed during the enamine oxidation.
- Blau, Karla,Voerckel, V.
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p. 285 - 292
(2007/10/02)
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- SYNTHESIS ODS PERFLUOROCHEMICALS FOR USE AS BLOOD SUBSTITUTES. PART IV. ALACTROCHEMICAL FLUORINATION OF N-CYCLOALKYL-PYRROLIDINES AND -PIPERIDINES
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Electrochemical fluorination of N-cyclopentylpyrrolidine gave the corresponding F-amine together with a ring-opened compound N-(F-pentyl)-F-pyrrolidine in the ratio of 1 to 1, in 55 percent yield.N-cyclohexylpyrrolidine, N-cyclopentylpiperidine and N-cyclohexylpiperidine were also electrochemically fluorinated in the same manner to give the corresponding F-amines, their isomers with rearranged structures, and ring-opened ones, in the ratio of ca. 4:2:1, 2:1:1, and 2:1:1, respectively in 51 to 53 percent yields.Supporting spectral data are presented.
- Ono, Taizo,Inoue, Yoshihisa,Arakawa, Yoshio,Naito, Youichiro,Fukaya, Chikara
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- THE REACTION OF TRICHLOROSILANE WITH ENAMINES
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A previously unknown reaction of trichlorosilane with enamines has been discovered and a preliminary study done on the possible mechanism.The products of the reaction are a regiospecific trichlorosilyl adduct resulting from addition of the trichlorosilane to the enamine unsaturation and the amine corresponding to simple reduction of the double bond.The addition of the trichlorosilane requires no catalyst and the relative percentages of the products varies in a generally inverse fashion depending on the exact structure of the enamine.Evidence is given to support the assigned structure of the trichlorosilyl species and mechanisms are hypothesized to explain the formation of both products from a common intermediate.Steric rather than electronic factors are suggested as responsible for the observed balance between them.
- Snyder, Dudley C.
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p. 137 - 144
(2007/10/02)
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- Reaction of Enamines with Acetals or Trialkyl Orthoformates Activated by Lewis Acids
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Enamines, prepared readily from various carbonyl compounds, react with acetals or trialkyl orthoformates in the presence of Lewis acids such as BF3.OEt2 to give corresponding β-alkoxy carbonyl compounds or α-dialkoxymethyl carbonyl compounds in good yields.The reaction of dienamines with acetals or trialkyl orthoformates also selectively gives corresponding β,χ-unsaturated α-(α-alkoxyalkyl) carbonyl compounds or β,χ-unsatureted α-dialkoxymethyl carbonyl compounds in good yields.
- Takazawa, Osamu,Kogami, Kunio,Hayashi, Kazuo
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p. 1876 - 1881
(2007/10/02)
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- Electrophilic Substitution in Indoles. Part 11. The Mechanism of Substitution in 5-Methoxyindoles
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Deuterium labelling experiments show that the boron trifluoride-catalysed cyclisation at 90 deg C of 4-(5-methoxyindole-3-yl)butanol (1e) to 6-methoxytetrahydrocarbazole (11a) occurs by two simultaneous pathways.The main route (83.5percent) involves initial cyclisation at the 3-position of (1e) to give an intermediate spirocyclic indolenine which then rearranges to the tetrahydrocarbazole.The minor pathway (16.5percent) involves direct attack at the 2-position.A similar duality of mechanism of substitution applies to the 6-methoxy-, 4,6-dimethoxy-, and 5,6-dimethoxy-indole analogues for which the extent of substitution at the 2-position can be correlated with the calculated change in ?-electron density at the 2- and 3-positions for a series of methoxy-substituted 3-methyl-indoles.These calculations do not, however, fit the experimental findings for the 5-methoxy-derivative which appears to be anomalous, showing an unexpectedly high percentage of direct substitution at the 2-position.A possible explanation of this result is advanced.
- Clack, Denis W.,Jackson, Anthony H.,Prasitpan, Noojaree,Shannon, Patrick V. R.
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p. 909 - 916
(2007/10/02)
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- BICYCLIC 1,2-OXAZINE N-OXIDES. DIFFERENT BEHAVIOUR IN RING FISSION BETWEEN SYSTEMS DERIVED FROM 5- AND 6-MEMBERED RING CYCLIC ENAMINES
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1,2-Oxazine N-oxides derived from aminocyclohexenes open into the corresponding nitroalkylated trisubstituted enamines, whereas those derived from aminocyclopentenes give stable tetrasubstituted enamines.Both open-chain systems are easily hydrolyzed to the corresponding χ-nitrocycloalkanones.
- Daneo, S.,Pitacco, G.,Risaliti, A.,Valentin, E.
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p. 1499 - 1504
(2007/10/02)
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