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1.
The 4-(α-hydroxyalkylidene)-Δ2-5-isoxazolones2 exist in the β-ketoenol form (“vinyloge car☐ylic acids”),2a,c react with guanidine and amidines to give only the enolates4, whereas they react both with hydrazines and 1,2-diamines to form the enamines6 and9 (“vinyloge amids”). The 4-(α-ethoxyalkylidene)-Δ2-5-isoxazolones 7 (“vinyloge esters”) condense with guanidine, benzamidine, and urea to affort the enamines8. Attempted ring-opening by bases failed whilst catalytic hydrogenation of the enamines6 and8 yielded the pyrazoles10,11 and diazepines12. The structures of the compounds have been elucidated by NMR and IR-spectra. 相似文献
2.
Victor M. Karpov Vyacheslav E. Platonov Tatjana V. Rybalova Yuri V. Gatilov Makhmut M. Shakirov 《Journal of fluorine chemistry》2006,127(7):936-942
Acetic acid-catalyzed condensation of 2-amino-3-(1-imino-2,2,2-trifluoroethyl)-1,1,4,5,6,7-hexafluoroindene (1b) with acetone and cyclopentanone gives 5,6,7,8,9,9-hexafluoro-2,2-dimethyl-4-trifluoromethyl-2,3-dihydro-1,3-diazafluorene (2a) and 5,6,7,8,9,9-hexafluoro-4-trifluoromethyl-2,3-dihydro-1,3-diazafluorene-2-spiro-1′-cyclopentane (3a) together with small amounts of 5,6,7,8,9,9-hexafluoro-2,2-dimethyl-4-trifluoromethyl-1,2-dihydro-1,3-diazafluorene (2b) and 5,6,7,8,9,9-hexafluoro-4-trifluoromethyl-1,2-dihydro-1,3-diazafluorene-2-spiro-1′-cyclopentane (3b), respectively. When acted upon by (CH3)2SO4 compounds 2, 3 were converted into corresponding fluorine-containing 1-methyl-1,2-dihydro-1,3-diazafluorenes 6, 7. 4a-Chloro-5,6,7,8,9,9-hexafluoro-2,2-dimethyl-4-trifluoromethyl-2,4a-dihydro-1,3-diazafluorene (8) has been synthesized by the interaction of compound 2 with SOCl2. Solution of compound 2 as well as 8 in CF3SO3H-CD2Cl2 generated 5,6,7,8,9,9-hexafluoro-2,2-dimethyl-4-trifluoromethyl-1,2,3,4-tetrahydro-1,3-diazafluorene-4-yl cation (2c). The structures of compounds 2, 3, 6-8 have been determined by single crystal X-ray diffraction. 相似文献
3.
John W. Barton Michael C. Goodland Ken J. Gould John F.W. Mcomie W.Roderick Mound Sadiq A. Saleh 《Tetrahedron》1979,35(2):241-247
As possible routes to 1,4-diazabiphenylene and its 2,3-disubstituted derivatives we have studied the condensation of benzocyclobutene-1,2-dione (BBD) with various 1,2-diamines. Instead of giving the 1,4-diazabiphenylene ring system, BBD reacted with ethylenediamine, diaminomaleonitrile, 4,5-diaminopyrimidine, 2-aminopyridine, also 2,3- and 3,4-diaminopyridine to give, respectively, 2-o-carboxyphenylimidazolidinium acetate 4, 3,4-dicyano-2,5-dihydro[2,5]benzodiazocine-1,6-dione 10, 4-amino-5a,9b-dihydro-5-,9b-dihydroxybenzo [3',4']cyclobuta[1',2'-4,5]imidazo[1,2-c]pyrimidine 14, 5a,9b-dihydro-5a,9b-dihydroxybenzo[3',4']cyclobuta[1',2'-4,5] imidazo[1,2-a]pyridine 17, the 4-amino derivative 16 of the latter, and the zwitter ion 18 of 4-amino-3(2-carboxy-benzylideneamino) However, BBD reacted with 4,5-diaminobenzotriazole to give the expected 1,2,3,6,11-penta-aza-1-H-indeno [4,5-b]biphenylene 20, which, on amination followed by oxidation, gave a very low yield of cis-2-cyano-3-(2'-cyanovinyl)-1,4-diazabiphenylene 3. In model experiments, 7,8-diphenylfurazano [3,4-f]quinox-aline 28 was reduced to 2,3-diamino-5,6-diphenyl quinoxaline 29, which on oxidation, gave a mixture of cis- and trans-2-cyano-3-(2'-cyanovinyl)5,6-diphenylpyrazine, 30 and 31. The pentacyclic compounds, 1,3,6,II-tetra-aza-2-oxa-2H-indeno [4,5-b]biphenylene 23 and 1,3,5,10-tetra-aza-1-H-indeno[5,6-b] biphenylene 25, were formed from BBD and the appropriate 1,2-diamines but the 5-membered heterocyclic rings could not be cleaved by reduction and hydrolysis respectively) to give tetracyclic diamines which might have undergone oxidation to give derivatives of 1,4-diazabiphenylene. Compounds 14, 16, 20, 23, 25 and 28 are derivatives of new heterocyclic systems. 相似文献
4.
A. Z. Zandersons V. K. Lusis é. é. Liepin'sh D. Kh. Mutsenietse E. L. Khanina G. Ya. Dubur 《Chemistry of Heterocyclic Compounds》1988,24(8):936-941
Derivatives of 2-thiono-5-oxo-2,3,4,5-tetrahydroindeno[1,2-d] pyrimidine and 5-oxo-1,2,4,5-tetrahydroindeno [1,2-d] [3,1] thiazine are formed in the cyclocondensation of 2-arylideneindan-1,3-diones with thiourea and N-monomethylthiourea, while only derivatives of indeno [1,2-d]-pyrimidine are formed in the reaction with N,N-di-methylthiourea. S- and N(3)-Alkylation occur in the alkylation of 2-thiono-4-pheny1-5-oxo-2,3,4,5-tetrahydroindeno[1,2-d]pyrimidine, while only the N-methyl derivative is formed in the alkylation of 2,5-dioxo-4-phenyl-1,2,4,5-tetrahydroindeno [1,2-d] [3,1]thiazine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1136–1141, August, 1988. 相似文献
5.
The reaction of triallylborane (All3B, 1) with various 1-alkynylsilanes of the type Me3Si–CCR1 [R1=H (2a), Me (2b), Ph (2c), CC–SiMe3 (2d), SiMe3 (2e)], Ph3Si–CCPh (3) MeCC–SiMe2SiMe2–CCMe (4) and Me2Si(Cl)–CCPh (5) was studied. Triallylborane 1 turned out to be much more reactive than other triorganoboranes R3B (e.g. R=Et, Ph). In the cases of 2 and 5, the products are organometallic-substituted alkenes 6 and 11, respectively, with the boryl and silyl group in cis-positions as the result of selective 1,1-allylboration (via cleavage of the Si–C bond) or mixtures of such and other alkenes 7 or 8 because of competition between 1,1- and 1,2-allylboration (the composition of these mixtures depends on the polarity of the solvent). In the case of 4, the 1,2-dihydro-1,2-disilaborepine derivative 12 is formed selectively (twofold 1,1-allylboration). The alkyne 3 did not react with 1. The products were characterised by 1H-, 11B-, 13C- and 29Si-NMR spectroscopy. 相似文献
6.
2-Amino-and 2-hydrazino-5-(3 or 4-pyridyl)-1, 3, 4-oxadiazoles [IIi-k] have been prepared by racting 2-chloro derivatives with the corresponding amines or hydrazines, the 2-hydrazino (IIi-k) compounds that obtained were heated with carbon disulphide and alcoholic potassium hydroxide where 5-(3 or 4-pyridyl)-1,3,4-oxadiazolo (2,3-C)-1,2,4-triazole 5-thione (IIIa-c) were obtained, the given structures were biologically screened. 相似文献
7.
Junes Ipaktschi Katja Reimann Michael Serafin Ansgar Dülmer 《Journal of organometallic chemistry》2003,670(1-2):66
Treatment of the η1-acetylide complex [(η5-C5H5)(CO)(NO)W---CC---C(CH3)3]Li (4) with 1,2-diiodoethane in THF at −78 °C, followed by the addition of Li---CC---R [R=C(CH3)3, C6H5, Si(CH3)3, 6a–6c] or n-C4H9Li and protonation with H2O, afforded the corresponding oxametallacyclopentadienyl complexes (η5-C5H5)W(I)(NO)[η2-O=C(CC---R)CH=CC(CH3)3] (7a–7c), 8c and (η5-C5H5)W(I)(NO)[η2-O=C(n-C4H9)CH=CC(CH3)3] (9). The formation of these metallafuran derivatives is rationalized by the electrophilic attack of 1,2-diiodoethane onto the metal center of 4 to form first the neutral complex [(η5-C5H5)(I)(CO)(NO)W---CC---C(CH3)3] (5). Subsequent nucleophilic addition of Li---CC---R 6a–6c or n-C4H9Li and a reductive elimination step followed by protonation leads to the products 7a–7c and 9. One reaction intermediate could be trapped with CF3SO3CH3 and characterized by a crystal structure analysis. The identity of another intermediate was established by infrared spectroscopic data. The oxametallacyclopentadienyl complex 10 forms in the presence of excess 1,2-diiodoethane through an alternative pathway and crystallizes as a clathrate containing iodine. 相似文献
8.
A general synthetic route to 3'-deoxy-3'-dihydroxyphosphinylmethyl ribonucleosides 3 the isosteric phosphonate analogs of nucleoside 3'-phosphates, is described. This involved alkylation of 1,2;5,6-di-O-isopropylidene-α-D-ribo-hexofuranose-3-ulose 7) with tetraethyl methylenediphosphonate 6, followed by stereoselective catalytic reduction and cleavage of C6 to generate 3-deoxy-3-diethoxyphosphinylmethyl-1,2-O-isopropylidene-α-D 12a. Benzoylation followed by acetolysis then generated the key crystalline intermediate 1,2-di-O-acetyl-5-O-benzoyl-3-deoxy-3-diethoxyphosphinylmethyl-β-D-ribofuranose 13, This compound, or the related glycosyl chloride, was condensed with several purine and pyrimidine bases and all protecting groups were removed by mild alkaline treatment via a series of intramolecular cyclizations and hydrolysis. In this manner the phosphonate analogs of nucleoside 3'-phosphates derived from adenine, 6-dimethylaminopurine, uracil, thymine, and cytosine were prepared. 相似文献
9.
Pradeep Mathur Vidya D. Avasare Shaikh M. Mobin 《Journal of organometallic chemistry》2004,689(7):1325-1327
Molybdenum dithiopropiolato complexes, [(η5-C5R4R′)Mo(CO)2(η2-S2CCCPh)] (R=H, R′=Me 1a, R=R′=H 1b; R=R′=Me 1c) react with trimethylamine-N-oxide (TMNO · 2H2O) under mild thermolysis to form 5-phenyl-1,2-dithiole-3-thione (2). The reaction proceeds through the formation of the oxo-complexes, [(η5-C5R4R′)Mo(O)(η3-S2CCCPh)] (R=H, R′=Me 3a, R=R′=H 3b; R=R′=Me 3c). Direct reaction of 3a-c with TMNO · 2H2O under thermolysis also results in formation of 2. 相似文献
10.
8,2'-O-Cycloadenosine was protected at 3' and 5'-OHs with acetyl groups and cleaved using liq. H2S. Subsequent dethiolation and mesylation gave 2'-O-mesyl-3',5'-di-O-acetyl-arabinosyladenine (6). When 6 or its deacetylated parent compound (7) was heated with sodium azide in DMF, 3'-azido-3'-deoxyxylofuranosyladenine (9) was the only product. The cyclonucleoside was then protected with tetrahydropyranyl groups and subjected to a similar series of reactions as above to give 2'-O-mesyl-3',5'-di-O-tetrahydropyranylarabinosyladenine (14). The compound 14 was heated with sodium azide after which acidic deprotection afforded 2'-azido-2'-deoxyadenosine (16). Hydrogenation of 16 gave 2'-amino-2'-deoxyadenosine (18). 2'-Chloro-2'-deoxyadenosine (19) was also obtained by treatment of 14 with lithium chloride and subsequent deprotection. UV, IR and NMR spectral data of these compounds are described. 相似文献
11.
Lidia S. Konstantinova 《Tetrahedron letters》2007,48(33):5851-5854
Reaction of 4-isopropylamino-5-chloro-1,2-dithiole-3-ones 3 and S2Cl2 in acetonitrile gave selectively 3-oxo-bis[1,2]dithiolo[1,4]thiazine-5-thiones 1 by the addition of triethylamine and bis[1,2]dithiolo[1,4]thiazine-3,5-diones 5 under the action of formic acid. 3,5-Diones 5 were also obtained by intramolecular cyclization of N,N-bis(5-chloro-3-oxo[1,2]dithiol-4-yl)amines 6 with S2Cl2 in the presence of Et3N. 相似文献
12.
Addition of the internal alkyne, 2-butyne, to nido-1,2-(Cp*RuH)2B3H7 (1) at ambient temperature produces nido-1,2-(Cp*Ru)2(μ-H)(μ-BH2)-4,5-Me2-4,5-C2B2H4 (2), nido-1,2-(Cp*RuH)2-4,5-Me2-4,5-C2B2H4 (3), and nido-1,2-(Cp*RuH)2-4-Et-4,5-C2B2H5 (4), in parallel paths. On heating, 2, which contains a novel exo-polyhedral borane ligand, is converted into closo-1,2-(Cp*RuH)2-4,5-Me2-4,5-C2B3H3 (5) and nido-1,6-(Cp*Ru)2-4,5-Me2-4,5-C2B2H6 (6) the latter being a framework isomer of 3. Heating 2 with 2-butyne generates nido-1,2-(Cp*RuH)2-3-{CMeCMeB(CMeCHMe)2}-4,5-Me2-4,5-C2B2H3 (7) in which the exo-polyhedral borane is triply hydroborated to generate a boron bound ---CMeCMeB(CMeCHMe)2 cluster substituent. Along with 3, 4, 5, 6, and 7, the reaction of 1 with 2-butyne at 85 °C gives closo-1,7-(Cp*Ru)2-2,3,4,5-Me4-6-(CHMeCH2Me)-2,3,4,5-C4B (8). Reaction of 1 with the terminal alkyne, phenylacetylene, at ambient temperature permits the isolation of nido-1,2-(Cp*Ru)2(μ-H)(μ-CHCH2Ph)B3H6 (9) and nido-1,2-(Cp*Ru)2(μ-H)(μ-BH2)-3-(CH2)2Ph-4-Ph-4,5-C2B2H4 (11). The former contains a Ru---B edge-bridging alkylidene fragment generated by hydrometallation on the cluster framework whereas the latter contains an exo-polyhedral borane like that of 2. Thermolysis of 11 results in loss of hydrogen and the formation of closo-1,2-(Cp*RuH)2-3-(CH2)2Ph-4-Ph-4,5-C2B3H3 (12). 相似文献
13.
Richard D. Adams Burjor Captain Jack L. Smith Jr. 《Journal of organometallic chemistry》2004,689(1):65-70
Diacenaphtho[1,2-c:1′,2′-e]-1,2-dithiin 2 was synthesized in 23% yield by the reaction of acenaphthylene with elemental sulfur at 120 °C. This reaction also afforded either diacenaphtho[1,2-b:1′,2′-d]thiophene 1 or diacenaphtho[1,2-b:1′,2′-e]-dihydro[e]-1,4-dithiin 3 depending on the reaction time. Compound 2 was desulfurized and converted to 1 under UV-vis irradiation in a benzene solution. Reaction of 2 with Pt(COD)2 yielded the complex Pt(COD)(C24H12S2) 4 (COD=1,5-cyclooctadiene) by insertion of a Pt(COD) group into the S-S bond of 2. When heated, 4 was desulfurized and converted to 1 by elimination of a (COD)PtS grouping. Compounds 1-4 were characterized crystallographically. 相似文献
14.
An efficient synthesis is reported for 4,5-dibromo-[1,3]dithiole-2-thione (1) and 4-bromo-1,3-dithiole-2-thione (7) by bromination of lithiated vinylene trithiocarbonate. Compound 1 acts as a convenient precursor to a number of asymmetric electron donors. This is exemplified by the formation of 4,5-dibromo-4′,5′-bis(2′-cyanoethylsulfanyl)TTF (3) by cross-coupling methodology and subsequent conversion into 4,5-dibromo-4′,5′-ethylenedithioTTF (4) by reaction with caesium hydroxide and 1,2-dibromoethane. The new donor 4,5-dibromo-4′,5′-ethylenedithiodiselenadithiafulvalene (5) was prepared by cross-coupling of 1 and 4,5-ethylenedithio-1,3-diselenol-2-one (6). The X-ray structures of 3 and 5 are reported. 相似文献
15.
Thermal decomposition of the sodium salts of benzocyclobutenone tosylhydrazone and 2-methylbenzocyclobutenone tosylhydrazone in benzene affords 9a,10-dihydrobenz[α]azulene 4 and trans-10-methyl-9a, 10-dihydrobenz[α]azulene 3, respectively. A mechanism involving initially the addition of the carbene benzocyclobutenylidene, or its 2-Me derivative, to the benzene ring is postulated. A proposed intermediate in the reaction, spiro [benzocyclobutene 1,7' cyclohepta-1',3',5'-triene] 12 has been synthesised, and shown to give rise to 4 under the reaction conditions. The rate of rearrangement of 12 → 4 has been measured, and the activation energy determined: Ea = 125.9 ± O.8 KJmol?1 and A = 1.38 × lO14sec?1. The mechanism for the rearrangement must involve ring opening of the benzocyclobutene moiety of 12 to give an o- xylylene intermediate which is postulated to possess considerable diradical character. At 71.8 °, this ring opening is 2.7 × 106 times faster than the ring opening of the parent benzocyclobutene molecule. The decomposition of the sodium salt of 2-(7' -cyclohepta-1',3',5' trienyl)benzaldehyde tosylhydrazone has also been investigated and is shown to yield 4a,10-dihydrobenz[α]azulene, 9,10-dihydrobenz[α]azulene and 8,9-benzotricyclo [5.3.0.02.10]deca-3,5,8-triene. A mechanism involving intramolecular 1,3-dipolar addition of a diazo grouping to a cycloheptatriene Π-bond, followed by decomposition of the resulting pyrazoline intermediate, is proposed. 相似文献
16.
Evgeny G. Rys Peter Lnnecke Sven Stadlbauer Valery N. Kalinin Evamarie Hey-Hawkins 《Polyhedron》2009,28(16):3467-3472
When rac- or meso-1,2-bis(tert-butylchlorophosphino)-1,2-dicarba-closo-dodecaborane(12) (1a or 1b) is reacted with [M(CO)4(NBD)] (M = Cr, Mo, NBD = norbornadiene), [Mo(CO)4(EtCN)2] or [W(CO)6], rac-[Cr(CO)4{1,2-(PtBuCl)2C2B10H10}] (2), rac- or meso-[Mo(CO)4{1,2-(PtBuCl)2C2B10H10}] (3a or 3b) and rac-[W(CO)4{1,2-(PtBuCl)2C2B10H10}] (4) could be isolated as pure diastereomers. UV irradiation of 1 with [Cr(CO)6] in moist THF proceeds with hydrolysis and formation of [Cr(CO)4{1,2-(P(OH)tBu)2C2B10H10}] (5) which contains the metal complex-stabilized phosphinous acid. Compounds 2–5 were characterized spectroscopically (1H, 31P, 11B, 13C NMR), by mass spectrometry and by X-ray structure determination. 相似文献
17.
Treatment of solutions of 1,3-thiazole-5(4H)-thiones 1 in CH2Cl2 at room temperature with BF3⋅Et2O and 1,2-epoxycyclohexane (7-oxabicyclo[4.1.0]heptane; 2a ) or 1,2-epoxycyclopentane (6-oxabicyclo[3.1.0]hexane; 2b ) yielded mixtures of diastereoisomeric spirocyclic 1,3-oxathiolanes ( 3 / 4 and 8 / 9 , respectively). In addition, the corresponding 1,3-dithiolane 6 was formed as a minor product in the reaction of 4,4-dimethyl-2-phenyl-1,3-thiazole-5(4H)-thione ( 1a ) with 2a . The structures of the different types of products have been established by X-ray crystal-structure analysis. An ionic two-step mechanism via nucleophilic ring-opening of the complexed oxirane by the attack of the thiocarbonyl S-atom is proposed. This proposal is supported by the formation of the propellane 10 with a Wagner-Meerwein rearrangement as the key step. 相似文献
18.
Sergey N. Tverdomed Gerd-Volker Röschenthaler Nataliya Kalinovich Alla V. Dogadina 《Tetrahedron》2008,64(22):5306-5313
Carbocyclic 1,2-diphosphonates (1a, 1b) are prepared by the Diels-Alder reaction of classical donor alka-1,3-dienes (isoprene and 2,3-dimethyl-1,3-butadiene) with tetraethyl acetylene bisphosphonate. Their aromatization by the KMnO4-Al2O3 system affords 4-methyl and 4,5-dimethylbenzene-1,2-diphosphonates (2a, 2b), used as precursor for the generation of benzyl-type carbanions (3a, 3b) by lithiation with lithium isopropylamide in THF at −80 °C. The carbanions react with electrophilic reagents (chlorotrimethylsilane, p-fluorobenzaldehyde, and ethyl trifluoroacetate) in situ to form corresponding α-substituted monoalkyl- and dialkylbenzenediphosphonates in good yields. 相似文献
19.
L. S. Konstantinova A. A. Berezin K. A. Lysov O. A. Rakitin 《Russian Chemical Bulletin》2006,55(1):147-151
A number of 4-dialkylamino-5-mercapto-1,2-dithiole-3-thiones were synthesized by reactions of alkyl(diisopropyl)amines with
S2Cl2. Their reactions with S2Cl2—DABCO unexpectedly gave 5-chloro-4-dialkylamino-1,2-dithiol-3-ones.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 143–147, January, 2006. 相似文献
20.
Unsubstituted and alkyl- or cyanosubstituted lactones such as dihydro-2(3 H)-furanone, dihydro-5-methyl-2(3 H)-furanone, dihydro-5,5-dimethyl-4-propyl-2(3 H)-furanone and tetrahydro-2,2-dimethyl-5-oxo-3furan-carbonitrile react with the dimer of p-methoxyphenylthionophosphine sulfide, 1, in anhydrous xylene or toluene to give the corresponding thionolactones, 3a-d, in good yields. Dihydro-2(3 H)-thiophenone and 1 produce dihydro-2(3 H)-thiophenthione. Aromatic lactones such as 2 H-1-benzopyran-2-one give the corresponding 2-thione. 1-Oxa-4-thiaspiro[4,5]decan-2-one, when treated with 1 at 120-125°, gave 1,4-dithiaspiro[4,5]decan-2-one and 1,4-dithias-piro[4,5]decan-2-thione. Tetrahydro-5,5-dimethyl-2-oxo-4-propyl-3-furancarboxylic acid ethyl ester reacted with 1 at 110° giving the corresponding 2-thione and 5,5-dimethyl-4-propyl-4,5-dihydrothieno[2,3-c]-1,2-dithiole-3-thione. 相似文献