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1.
Simon S. Jones Colin B. Reese Samson Sibanda Aiko Ubasawa 《Tetrahedron letters》1981,22(47):4755-4758
The protection of uracil and 2--acyl guanine residues with 4--phenyl [or 4--(2,4-dimethylphenyl)] and 6--(2-nitrophenyl) groups as in [or ] and , respectively, is described. These -aryl protecting groups, which appear to withstand the usual conditions of oligonucleotide synthesis, may readily be removed by treatment with 2-nitrobenzaldoximate ions. 相似文献
2.
Starting from the aldehydes and the acetylene is prepared via the borane by means of a combined Wittig reaction-hydroboration reaction sequence. may be converted into the (E)-6,(Z)-11-hexadecadienylacetate () and the corresponding aldehyde . The synthetic route proceeds with high stereospecifity (isomeric purity of and ? 97%). 相似文献
3.
Furan-, thiophene- and -methylpyrrole-2-carboxaldehydes may be transformed into the corresponding ,'-dimethylimidazolidines in a reaction not requiring acid catalysis. The resulting furan and thiophene (but not -methylpyrrole) derivatives may be metallated in high yields [predominantly at the 5 (α-) positions of the heteroaromatic rings] and the carboxaldehyde functionality regenerated under very mild conditions. Treatment of the aldehydoketone 2-acetyl-5-formylthiophene with ,'-dimethylethylenediamine gives the product of reaction at the aldehyde function thus establishing this methodology as a potentially valuable method for the protection of an aldehyde in the presence of a ketone. 相似文献
4.
A series of phenoxathiins () were produced by the reaction between spiroepoxy-2,4-cyclohexadienones () and the pentachlorothiophenolate anion. The spiroepoxycyclohexadienones () may be regarded as polarity-reversed masked phenols in these reactions. 相似文献
5.
A short and efficient synthesis of the 4-oxo-1,2,3,4-tetrahydro-2-naphthalenecarboxylic acid derivative () is described. This synthon may be converted to the dihydronaphthacenone derivative () in a regiocontrolled manner in only two steps using condensation with 2,5-dimethoxybenzaldehyde followed by intramolecular acylation. The enol form of the dihydronaphthacenone, () corresponds to a derivative of 11-deoxypretetramide. 相似文献
6.
Felix H. Cano Concha Foces-Foces Manuel Bernabe Jesus Jimenez-Barbero Manuel Martin-Lomas Soledad Penades-Ullate 《Tetrahedron》1985,41(18):3875-3886
X-Ray and 1H N.M.R. studies on pyranoid rings 1,2--fused to dioxolane rings in acetylated -gluco- and --galactopyranose derivatives demonstrate that the configuration of the dioxolane ring influences the conformation of the pyranoid ring in the -gluco but not in the -galactopyranose series. The crystal structure of 3,4,6-tri--acetyl-1,2--(R)--(l-cyano-ethylidene)-α--glucopyranose () and 3,4,6-tri--acetyl-1,2--()-(1-cyano-ethylidene)-α--galactopyranose ()have been determined by X-ray analysis. Lattice parameters for are a=20.6021 (11), b=8.0438 (2), c=5.5541 (1) Å and β= 95.588 (3)° for a cell with P21 symmetry. These parameters for are a=20.3361 (7), b=10.0907 (2), c=18.9115 (5) Å, β =112.399 (2)°, C2, with two crystallographycally independent molecules. The conformation of the pyranoid ring in both compounds can be described as flattened 4C1 and that of the dioxolane ring as distorted E1. The importance of the torsion angles for describing problems of configuration is remarked and the use of relative configurational angles is stressed. The 1H N.M.R. spectra of and and 3,4,6-tri--acetyl-1,2-O-(S)- and (R)-ethylidene-α--glucopyranose ( and ), 3,4,6-tri-O-acetyl--1,2-O-(S)- and ()-ethylidene-α--galactopyranose ( and ), and 3,4,6-tri--acetyl-1,2--()-and ()-benzylidene-α--glucopyranose ( and ) have been analyzed by using iterative computer methods and N.O.E. measurements. The results indicate that the major solution conformation of the pyranoid ring of the derivatives in the -gluco series , and may be described as flattened 4C1 and that of and as 25. The major solution conformation of the pyranoid ring in all compounds in the -galacto series (,,,) may be described as flattened 41. 相似文献
7.
Erythrinin A () has been synthesised by the oxidative rearrangement of dihydropyranochalcone with thallium(III) nitrate (TTN) in trimethyl orthoformate (TMOF) to the dimethyl acetal , followed by cyclisation to , demethylation to and dehydrogenation. Compound could also be obtained from chalcone on similar rearrangement followed by cyclisation, demethoxymethylation and dehydrogenation. In another route, chalcone was oxidatively rearranged with TTN in TMOF, to which on treatment with HCl yielded . 相似文献
8.
Lutz-F. Tietze Karl-Heinz Glüsenkamp Klaus Harms Gert Remberg George M. Sheldrick 《Tetrahedron letters》1982,23(11):1147-1150
2-Formyl-malondialdehyde () reacts at 22°C in a type of Diels-Alder reaction with reversed electron demand with the enol-ethers () – () and () – () within a frew hours to give the dihydropyrans () – () and () – (). Thio-enol-ethers may also be employed in this cycloaddition. 相似文献
9.
4-Dimethylamino--triphenylmethylpyridinium chloride () reacts with primary but not secondary alcohols to produce trityl ethers in good yield; in addition, amines may be selectively - tritylated witth in the presence of alcohols. 相似文献
10.
Di--alkylamines can be synthesized efficiently by a three-step process: (1) oxidation of a -alkylamine to a -alkylnitroso compound with peracetic acid in ethyl acetate (2) conversion of the -alkylnitroso compound to a tri--alkylhydroxylamine by successive trapping of two -butyl radicals and (3) sodium naphthalide reduction to the di--alkylamine. 相似文献
11.
Cyclisation of readily available diary1-1,2 ethanes proceeds in SbF5,-HF at 0°C to yield tricyclic phenanthrenones , , and bearing an angular methyl group. This process implies the electrophilic attack of the more basic aromatic ring, reacting through its diprotonated form (on the oxygen and the meta carbon atom) on the second aromatic ring. Isomerization of these primary products may be observed to give ketones , , from and from ) and it has been demonstrated by the use of specifically deuterated that it involves stereospecific 1,2 hydride (or deuteride) shifts, without exchange. 相似文献
12.
Experimental details are provided to support a previous report that α-methylenetriphenylphosphorane () may be activated for reaction with unreactive substrates such as epoxides and hindered ketones by α-metallation to . 相似文献
13.
John F. Blount Glenna D. Gray Karnail S. Atwal Thomas Y.R. Tsai Karel Wiesner 《Tetrahedron letters》1980,21(46):4413-4416
The α,β-unsaturated ketone yields with allene the photocycloadduct predicted by our empirical photoaddition rule and the byproduct 7. The formation of this material may be rationalized by the sequence → → → → . The isomeric ketone is unreactive under the same conditions, since α addition is prohibited by the rule and β addition is severely blocked. 相似文献
14.
The structures and syntheses of prenylhydroquinone (), 6-hydroxy-2,2-dimethylchromeme (), and prenylquinone (), which are natural products isolated from the marine colonial tunicate , are described. Prenylhydroquinone shows activity against P388 lymphocytic leukemia (T/C=138). Both and significantly inhibit the mutagenic effects of benzo(a)pyrene, aflatoxin B1 and ultraviolet light on , and may be cancer protective agents. 相似文献
15.
Jean-Paul Behr Cynthia J. Burrows Richard Heng Jean-Marie Lehn 《Tetrahedron letters》1985,26(2):215-218
A pathway yielding both and -functionalized macrocycles derived from bis-tartaro-18-crown-6 (1) as well as a selective route to compounds have been developed and applied to the synthesis of new macrobicyclic polyether cryptands (2) and (3), which may also be obtained by direct bridging of the dianhydride (4). 相似文献
16.
Flow vacuum thermolysis (FVT) of thiophene-2,3-dicarboxylic anhydride () in the presence of 2,3-dimethylbutadiene () gives, in addition to 5,6-dimethylthianaphthene (). small quantities of a dihydrodimethylthianaphthene () and another dimethylthianaphthene () which is probably also formed by dehydrogenation of with chloranil. The partial structures of these minor products are consistent with their being formed by a [2+2]-cycloaddition between and an intermediate aryne, 2,3-didehydrothiophene (), followed by a rearrangement of the resulting adduct and dehydrogenation. FVT of in the presence of 2,5- () or 3,4-dimethylthiophene () also gave a mixture of the dimethylthianaphthenes (, ) which can be rationalized as arising by a [4+2]- and two [2+2]-cycloadditions of the aryne to the thiophenes with subsequent desulfurization. The lack of equilibration of the products , and , was demonstrated and their origin as a function of the structure and reactivity of the aryne discussed. 相似文献
17.
Herbert Muffler Guenter Siegemund Werner Schwertfeger 《Journal of fluorine chemistry》1982,21(2):107-132
4.5-Perfluoro-1.3-dioxolanes are available by reaction of 2(α-chloroalkoxy)perfluoro-carbonyl halides or -ketone with fluoride ions. A mechanism for the intramolecular ring- closure-reaction is proposed. Hydrogen atoms at C-2 in can be exchanged photochemically by chlorine. Starting from the 2-monochloro-derivatives the 2-monofluoro-4.5-perfluoro- 1.3-dioxolanes are formed by reaction with triethylamine- hydrofluoride. 相似文献
18.
Reactive 1,6-disubstituted perfluorohexanes have been prepared the reaction of 1,6-(dimethylhydrosilyl)-perfluorohexanes with alkyllithium and Grignard reagents. The resulting species may be derivatized in the same manner as organolithium reagents, but are appreciably more stable than the 1,6-dilithioperfluorohexane which is presumably generated by the halogen-metal exchange between an alkyllithium reagent and Br(CF2)6Br. 1,6-bis(Bromomagnesium)-perfluorohexane was also prepared in good yield by a halogen-metal exchange reaction. 相似文献
19.
The addition of phenylhydrazine to phenylazo-alkenes yields α-(1-phenylhydrazino)-phenylhydrazones . The reaction of phenylhydrazine with α-halogenated carbonyl compounds affords either or the isomeric α-(2-phenylhydrazino)-phenylhydrazones . Structures and (>N-NH2 and-NH-NH- groups, respectively) can be differentiated by 1H NMR in DMSO-D6 solution. Possible pathways of the reactions leading to either or are discussed. Compounds are found to be precursors of phenylosazones . 相似文献
20.
Trifluoroethyl cyclohexyl ketone () is prepared by acylation of difluoroethylene () with cyclohexanecarboxylic acid chloride (), followed by Cl→F exchange with potassium fluoride in the presence of triethylbenzyl- ammonium chloride. Bayer-Villiger oxidation of ketone () with trifluoroperacetic acid gives cyclohexyl trifluoropropionate (). 3,3,3-trifluoropropionic acid () is obtained by treatment of () with trimethylsilyl iodide. Condensation of 2,2,2-trifluorodiazoethane () with ethyl glyoxylate () gives mainly ethyl 4,4,4-trifluoro-2-ketobutyric acid ester () which leads after hydrolysis to the corresponding acid (). 相似文献