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1.
L. V. Klyba N. A. Nedolya O. A. Tarasova E. R. Zhanchipova O. G. Volostnykh 《Russian Journal of Organic Chemistry》2010,46(7):1038-1048
The mass spectra of previously unknown 1-alkyl(cycloalkyl, aryl)-3-alkoxy(aryl)-2-methylsulfanyl-1H-pyrroles were studied. Fragmentation of all 3-alkoxy-substituted pyrroles under electron impact (70 eV) follow both ether
and sulfide decomposition paths; In particular, 1-R-substituted 3-methoxy-2-methylsulfanyl-1H-pyrroles (R = Me, Et, i-Pr, s-Bu, cyclo-C5H9, cyclo-C6H11, Ph) lose methyl radical group from both methoxy and methylsulfanyl groups. The mass spectra of 1-sec-butyl- and 1-cycloalkylpyrroles also contained a strong peak (10–49%) from odd-electron [M — C
n
H2n
]+· ion formed via cleavage of the N-R bond with synchronous hydrogen transfer. Cleavage of the O-Alk bond in the fragmentation
of 3-alkoxy-1-isopropyl-2-methylsulfanyl-1H-pyrroles (Alk = Et, i-Pr, t-Bu) was accompanied by rearrangement process leading to the corresponding alkene and odd-electron 1-isopropyl-2-methylsulfanyl-1H-pyrrol-3-ol ion. The main fragmentation path of 1-alkyl-2-methylsulfanyl-3-phenyl-1H-pyrroles (Alk = Me, i-Pr) under electron impact involves dissociation of the S-Me bond with formation of rearrangement 1H-[1]benzothieno[2,3-b]pyrrol-8-ium ion. 相似文献
2.
L. V. Klyba N. A. Nedolya O. A. Tarasova E. R. Sanzheeva 《Russian Journal of Organic Chemistry》2014,50(1):35-44
Fragmentation patterns of 5-methylsulfanyl-1-vinyl-1H-pyrrol-2-amines under electron impact (70 eV) and chemical ionization (methane as reactant gas) were studied for the first time. The electron impact mass spectra of all the examined compounds contained a strong peak of molecular ion which decomposed along four pathways. Two pathways involved cleavage of the C-S bonds with elimination of methyl (major) and MeS radicals (minor), and the two others, decomposition of the pyrrole ring. The chemical ionization mass spectra displayed strong molecular, [M + H]+, and odd-electron [M + H ? SMe]+ ion peaks. N,N-Dimethyl-5-methylsulfanyl-4-phenyl-1-vinyl-1H-pyrrol-2-amine under chemical ionization with methane as reactant gas characteristically decomposed with formation of [M ? C4H9N]+ as the only fragment ion. 相似文献
3.
P. V. Savitskii R. I. Vas’kevich Yu. L. Zborovskii V. I. Staninets S. A. But A. N. Chernega 《Russian Journal of Organic Chemistry》2008,44(3):402-406
1-(Benzothiazol-2-yl)-4-phenylthiosemicarbazide reacted with methyl iodide in the presence of sodium acetate in boiling ethanol to give 2,2′-dithiobis[N-(5-methylsulfanyl-4-phenyl-4H-1,2,4-triazol-3-yl)-benzenamine]. The reaction of the title compound with dimethyl acetylenedicarboxylate in dioxane led to the formation of methyl 3-(benzothiazol-2-yl)-2-(2-methoxy-2-oxoethyl)-2,3-dihydro-1,3,4-thiadiazole-2-carboxylate. 相似文献
4.
L. V. Klyba N. A. Nedolya N. I. Shlyakhtina E. R. Zhanchipova 《Russian Journal of Organic Chemistry》2005,41(10):1544-1550
Previously unknown 5-(1-ethoxyethoxy)-2-methoxy-6-methylsulfanyl-2,3-dihydropyridine, 3-(1-ethoxyethoxy)-2-methylsulfanylpyridine, and 2-methylsulfanylpyridin-3-ol were synthesized from α-lithiated 1-(1-ethoxyethoxy)allene, methoxymethyl isothiocyanate, and methyl iodide, and their fragmentation under electron impact was studied. At ionizing electron energies of 12 and 60 eV in the temperature range from 50 to 250°C, the molecular ions derived from 5-(1-ethoxyethoxy)-2-methoxy-6-methylsulfanyl-2,3-dihydropyridine and 3-(1-ethoxyethoxy)-2-methylsulfanylpyridine decompose along two main pathways: rupture of the C-O bond in the acetal moiety to give oxonium ions with m/z 73 (in the two cases) and 168 (pyridine derivative) and unexpectedly facile McLafferty rearrangement with elimination of ethoxyethene molecule to produce fragment ions with m/z 173 and 141, respectively. The latter pathway was not observed previously for dihydropyridines and acetals, and it predominates in the fragmentation of 3-(1-ethoxyethoxy)-2-methylsulfanylpyridine. Expulsion of methanol molecule from the molecular ion of 5-(1-ethoxyethoxy)-2-methoxy-6- methylsulfanyl-2,3-dihydropyridine occurred only above 170°C. 相似文献
5.
Previously it was shown that condensation of dimethyl N-cyanodithioimidocarbonate ( 1a ) with methylhydrazine gave predominantly 1-methyl-5-methylthio-1H-,2,4-triazol-3-amine ( 2 ), which was initially identified erroneously as the regioisomer l-methyl-3-methylthio-1H-1,2,4-triazol-5-amine ( 3 ). We have found that reaction of dimethyl N-cyanoimidocarbonate ( 1b ) with methyl hydrazine affords a high yield of 3-methoxy-1-methyl-1H-1,2,4-triazol-5-amine ( 4 ) rather than the regioisomer 5-methoxy-1-methyl-1H-1,2,4-triazol-3-amine ( 5 ). The structure assignment of 4 was confirmed by X-ray crystallographic analysis of the benzenesulfonyl isocyanate adduct 7 . Triazole 5 was obtained after reacting dimethyl N-cyanothioimidocarbonate ( 1c ) with methylhydrazine. 相似文献
6.
The four stereoisomers of 3-isopropyl-5-methoxy-6-ketoheptanoic acid methylester and those of 2-methoxy-4-isopropylhexandioic acid methylester were synthesized from R(?)- and S(+)-carvone. The combined data given provide a basis for specific enantiomer assignment to natural product degradation materials. 相似文献
7.
A DMAP (4-dimethylaminopyridine) catalyzed cyclization of methyl 2-alkynylbenzimidates has been developed, which affords 3-methoxy-1-methyleneisoindoles with excellent Z-stereoselectivity under mild and transition-metal-free conditions. The (Z)-3-methoxy-1-methyleneisoindole products can be converted to corresponding 3-amino-1-methyleneisoindoles, 3-methoxy-isoindoles, 3-methyleneisoindolinones and isoindolinones with high efficiency. 相似文献
8.
P. P. Mukovoz A. V. Gorbunova P. A. Slepukhin O. S. El’tsov I. N. Ganebnykh A. N. Sizentsov I. V. Korobova 《Russian Journal of General Chemistry》2017,87(8):1695-1701
Reactions of methyl 3,4,6-trioxoalkanoates (3,4-dihydroxy-6-oxo-2,4-alkadienoates) with mixtures of aromatic aldehydes and arylamines or with the corresponding N-(arylmethylidene)anilines afforded methyl (4-alkanoyl-1,5-diaryl-2-hydroxy-3-oxo-2,3-dihydro-1H-pyrrol-2-yl)acetates. The product structure was discussed on the basis of their IR, 1H NMR, and mass spectra and X-ray diffraction data, and their antimicrobial activity against Staphylococcus aureus P-209 and Escherichia coli M17 was evaluated. 相似文献
9.
N. I. Makarova E. N. Shepelenko A. V. Metelitsa V. A. Bren’ V. I. Minkin 《Russian Chemical Bulletin》2013,62(11):2424-2429
Novel asymmetric dihetarylethenes, viz., 3-(1-isopropyl-5-methoxy-2-methyl-1H-indol-3-yl)-4-(3-thienyl)furan-2,5-dione and 1-alkyl/aryl-3-(1-isopropyl-5-methoxy-2-methyl-1H-indol-3-yl)-4-(3-thienyl)-1H-pyrrole-2,5-diones, were obtained. These dihetarylethenes exhibit photochromism in solutions. Replacement of the N-methyl group in the indole fragment by the N-isopropyl group imparts photochromic properties to the resulting furan-2,5-dione derivative. The open forms of (N-isopropylindol-3-yl)pyrrole-2,5-diones are characterized by lower quantum yields of fluorescence, and their cyclic forms are thermally more stable. 相似文献
10.
The asymmetric synthesis of the potent selective NOP agonist 2-(3-{1-[3-(5-methoxy-2-methyl-phenoxy)-4-methyl-pentyl]-piperidin-4-yl}-2-oxo-2,3-dihydro-benzimidazol-1-yl)-N-methyl-acetamide and analogues was developed. The key step, chiral reduction of methyl isobutyryl acetate, was achieved using a mild Noyori-type asymmetric hydrogenation. 相似文献
11.
The oxidation of methyl 6-methyl-2-methylsulfanyl-4-oxo-3,4-dihydro-3-pyrimidinylacetate by reagents which oxidized the SMe
group to SO2Me gave the products of the further transformation of the corresponding 2-methylsulfonyl-substituted ester obtained: methyl
5,5-dichloro-6-methoxy-6-methyl-2,4-dioxohexahydro-3-pyrimidinylacetate (using Cl2 in 70 or 50% MeOH), its mixture (about 1:10) with methyl 6-methyl-2,4-dioxo-1,2,3,4-tetrahydro-3-pyrimidinylacetate (Cl2 in 30% MeOH) or only to the latter compound (Cl2 in H2O, m-ClC6H4CO3H in CHCl3, H2O2 in MeOH). The reaction did not take place with NaOCl in DMF.
__________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 901–905, June, 2006. 相似文献
12.
《Tetrahedron: Asymmetry》2005,16(15):2559-2568
Enantioresolution of 3-octanol, 6-methyl-5-hepten-2-ol (sulcatol), and 1-octen-3-ol was conducted using (S)-(+)-2-methoxy-2-(1-naphthyl)propionic acid (MαNP acid) and (S)-(+)-2-methoxy-2-(9-phenanthryl)propionic acid (M9PP acid). In each case, the diastereomeric esters obtained were readily separated by HPLC. The stereochemistry of the esters could be assigned from their respective 1H NMR analyses. Solvolyses of the esters gave enantiopure alcohols and acids. MαNP and M9PP acids displayed almost equivalent properties in 1H NMR anisotropy. The chiral resolving ability of M9PP acid was slightly superior to that of MαNP acid in HPLC. 相似文献
13.
Ke Cheng 《Tetrahedron》2005,61(40):9594-9599
The aza-Diels-Alder reaction of trans-1-methoxy-2-methyl-3-trimethylsiloxybuta-1,3-diene with N-benzhydryl imines in the presence of Yb(OTf)3 in toluene at room temperature gave the corresponding 2,5-disubstituted 2,3-dihydro-4-pyridones in high yields. This reaction can also be carried out with diene, aldehydes, and amine in a three-component one-pot reaction manner in moderate to high yields under solvent-free conditions. The relationship between Lewis acids and activity, solvents and catalyst loading were studied. Some investigation towards the reaction mechanism was discussed. 相似文献
14.
Yu. M. Sadykova N. V. Dalmatova A. R. Burilov M. A. Pudovik A. B. Dobrynin 《Russian Chemical Bulletin》2011,60(10):2078-2080
Condensation of 2-ethoxyvinylphosphonic dichloride with 3-methoxy-2-methylphenol in dioxane in the presence of trifluoroacetic acid results in 5,13-dimethoxy-4,14-dimethyl-1-phospha-2,16-dioxatetracyclo[7.7.1.03,8.010,15]heptadeca-3,5,7,10,12,14-hexaene 1-oxide and 2-hydroxy-7-methoxy-8-methyl-2-oxobenzo[e]-1,2-oxophosphorine. 相似文献
15.
Utilizing the MP2/6-31G(d,p) method a quantum-chemical investigation was performed of thermally induced formation of pyrrole and/or 2,3-dihydropyridine structures from methyl N-methyl-2-methoxy- and 2-(methylsulfanyl)buta-2,3-dienimidothioates (1-aza-1,3,4-trienes). According to calculations the pyrrole and dihydropyridine cyclization of a methoxy-substituted 1-aza-1,3,4-triene is both kinetically and thermodynamically virtually equally probable with a little prevalence of the first pathway. The main direction of the structural reorganization of methylsulfanyl-substituted 1-aza-1,3,4-triene is the kinetically controlled formation of the dihydropyridine ring. 相似文献
16.
《Tetrahedron》2009,65(45):9103-9115
3-Alkyl/aryl-3-amino-1H,3H-quinoline-2,4-diones react with alkyl/aryl isothiocyanates to give 3a-alkyl/aryl-1,2,3,3a-tetrahydro-9b-hydroxy-2-thioxo-5H-imidazo[4,5-c]quinolin-4(9bH)-ones in high yields. These compounds rearrange in boiling acetic acid or concd hydrochloric acid to give novel 4-(2-aminophenyl)-1H-imidazole-2(3H)-thiones, 1,3-bis(2-(2,3-dihydro-2-thioxo-1H-imidazol-5-yl)phenyl)ureas and minor N-(2-(2,3-dihydro-2-thioxo-1H-imidazol-4-yl)phenyl)acetamides. In the presence of ethanol, the starting compounds rearrange in boiling acetic acid to give ethyl 2-(2,3-dihydro-2-thioxo-1H-imidazol-4-yl)phenylcarbamates. All compounds were characterized by their 1H, 13C, IR and MS spectra and some of them also by 15N NMR data. The structures of two compounds were supported by single-crystal X-ray diffraction. 相似文献
17.
Beata Orlińska Zbigniew Stec Jan Zawadiak 《Monatshefte für Chemie / Chemical Monthly》2012,9(4):295-301
Abstract
Aerobic oxidation of 2-methoxy-6-(1-methylethyl)naphthalene to hydroperoxide, alcohol, and ketone, is reported. These compounds, particularly 2-acetyl-6-methoxynaphthalene, are important intermediates in naproxen synthesis. N-Hydroxyphthalimide is shown here to be an efficient catalyst for oxidation to the hydroperoxide, 2-methoxy-6-(1-hydroperoxy-1-methylethyl)naphthalene, with a yield of 87%. However, the ketone and alcohol were obtained with lower yields, with a maximum yield of 13% for the ketone and 27% for the alcohol, using N-hydroxyphthalimide and Cu(II) acetylacetonate as a catalyst. The synthesis of the products 2-acetyl-6-methoxynaphthalene and 2-methoxy-6-(1-hydroxy-1-methylethyl)naphthalene via an initial oxidation step to the hydroperoxide followed by a hydroperoxide decomposition step is shown to be more efficient; the ketone and alcohol were obtained from 2-methoxy-6-(1-methylethyl)naphthalene with yields of 40 and 56%, respectively. 相似文献18.
At low temperature in trifluoromethanesulfonic acid, 1-benzylamino-1-methylthio-2-nitroethene derivatives form hydroxynitrilium ions (or O-protonated nitrile oxides) observed by NMR. Quenching with water leads to the formation of a reactive nitrile oxide, dipole which undergoes an unexpected INOC reaction leading to new 3-methylsulfanyl-8a,8b-dihydro-5H-1-oxa-2,4-diazaacenaphthylenes. 相似文献
19.
L. V. Klyba N. A. Nedolya O. A. Tarasova E. R. Zhanchipova O. G. Volostnykh 《Russian Journal of Organic Chemistry》2010,46(2):218-225
Mass spectra were investigated for the first time of four structural isomers of heterocycles, formerly inavailable 7-methyl-2-(methylsulfanyl)-3-(1-ethoxyethoxy)-4,5-dihydro-3H-azepine, 2,2-dimethyl-6-(methylsulfanyl)-5-(1-ethoxyethoxy)-2,3-dihydropyridine, 1-isopropyl-2-(methylsulfanyl)-3-(1-ethoxyethoxy)pyrrole,
and N-isopropyl-N-methyl-3-(1-ethoxyethoxy)-2-thiophenamine prepared from a single linear precursor, adduct of α-lithiated 1-(1-ethoxyethoxy)allene
and isopropyl isothiocyanate. All compounds formed a molecular ion (I
rel
1–6%) whose primary fragmentation at the electron impact (70 eV) occurs in two principal directions related to the cleavage
of the C-O bonds in the 1-ethoxyethoxy-substituent: with a simple rupture of the bonds C-OEt and C-O(heterocycle) and with
the elimination of an ethoxyethene molecule. In the spectra of 4,5-dihydro-3H-azepine and 2,3-dihydropyridine the first fragmentation
channel of [M]+· dominates. The second direction prevailes at the fragmentation of pyrrole and thiophene molecular ions leading to an odd-electrons
ion with m/z 171. Further fragmentation of this ion is characteristic of each isomer and resulted in the formation of diagnostic
ions providing a possibility of identification of these isomers by mass spectrometry. 相似文献
20.
Irum Shahzadi Ameer F. Zahoor Azhar Rasul Nasir Rasool Zohaib Raza Shahla Faisal Bushra Parveen Shagufta Kamal Muhammad Zia-ur-Rehman Faisal M. Zahid 《Journal of heterocyclic chemistry》2020,57(7):2782-2794
Theophylline-7-acetic acid (acefylline) ( 3 ) and its derivatives are pharmacologically active compounds and generally recognized as bronchodilators for the treatment of respiratory diseases like acute asthma for over 70 years. In this article, synthesis of 2-((5-((1,3-dimethyl-2,6-dioxo-2,3-dihydro-1H-purin-7(6H)-yl)methyl)-1,3,4-oxadiazol-2-yl)thio)-N-arylacetamides ( 10a-j ) has been reported. All the synthesized derivatives ( 10a-j) were structurally verified by FT-IR, 1H NMR, 13C NMR and evaluated for their anti-cancer (using MTT assay), hemolytic and thrombolytic potential. N-(4-Chlorophenyl)-2-(5-((1,3-dimethyl-2,6-dioxo-2,3-dihydro-1H-purin-7(6H)-yl)methyl)-1,3,4-oxadiazol-2-ylthio)acetamide ( 10g ) was found to be the most active against human liver cancer cell lines (Huh7) having cell viability 53.58 ± 1.28 using 100 μg/mL concentration of compound which was further in-silico modelled to describe the possible mechanistic insights for its anti-proliferative activity. The results of hemolytic and thrombolytic activities indicated that these derivatives were less toxic and hold considerable potential as a drug candidate. 2-(5-((1,3-Dimethyl-2,6-dioxo-2,3-dihydro-1H-purin-7(6H)-yl)methyl)-1,3,4-oxadiazol-2-ylthio)-N-(2-fluorophenyl)acetamide ( 10c ) of the series was found to be least toxic with 0.1% hemolysis relative to ABTS (95.5%) as positive control. 2-(5-((1,3-Dimethyl-2,6-dioxo-2,3-dihydro-1H-purin-7(6H)-yl)methyl)-1,3,4-oxadiazol-2-ylthio)-N-(tetrahydro-2H-pyran-4-yl)acetamide ( 10j ) exhibited potent clot lysis activity (90%) as compared to negative control DMSO (0.57%). 相似文献