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1.
6,7-Dimethoxy-2-phenyl-4-1,3-benzothiazine (1) and 6,7-dimethoxy-4-phenyl-2-1,3-benzothiazine (2) react with substituted acetyl chlorides to give linearly, and new angularly condensed β-lactam derivatives (4,5). Heating of the latter compounds with hydrogen chloride in anhydrous ethanol leads to the formation of the corresponding 4- and 2-1,3-benzothiazinium chloride, respectively. The configurations of these compounds (the mutual positions of the substituents relative to the β-lactam ring) were determined by 1H and 13C studies, also making use of the aromatic solvent-induced shifts. 相似文献
2.
Methods were developed to prepare 1 -methyl-, 3-methyl- and 4-0-methyl-ψ-isocytidine by selective methylation.35O-Tetraisopropyldisiloxanyl-ψ isocytidine (8) was trimethylsilylated and then treated with MeI and, after deprotection, 1 -methyl-ψ isocytidine (6) was obtained. The 2deoxy analog (7) was also prepared in a similar manner from the 2deoxy analog (10) of 8. Treatment of 8 with CH2N2 afforded the 3-methyl-ψ-isocytidine derivative (19) as the major product. Methylation with diazomethane also occurred mainly on N3 of the 2deoxy analog 10 to form 20. Removal of the 3 5O-protecting group from 19 and 20 afforded 3-methyl-ψ-isocytidine (14) and its 2-deoxy analog (15), respectively. 2-N-Acetyl- 35O-tetraisopropyldisiloxanyl-ψ-isocytidine (24), on the other hand, gave the 4-O-methyl derivative (25) as the major product upon CH2N2 treatment. Subsequent deprotection of 25 afforded 4-O-methyl-ψ-isocytidine (29). aiv51b1p33b 相似文献
3.
The enamino-thione, 1c, reacts with acrylonitrile and 2-chloroacrylonitrile at room temperature to give 3,4-dihydro-4-(1-pyrrolidinyl)-2-thiopyrans, 4 and 5, respectively. The reaction between 1-aryl-3-(1-pyrrolidinyl) (piperidino)-apropene-1-thiones, 1a-c (1d-f), and dimethyl acetylenedicarboxylate gives 4-(1-pyrrolidiny)(piperidino)-4-thiopyrans, 6a-c (6d-f). Compounds 1a-c (1d-f) and ethyl propiolate produce 2-(1-pyrrolidinyl) (piperidino)-2-thiopyrans, 8a-c (8d-f), and a new type of rearrangement is observed. The 2-thiopyran, 9, is formed from 1b and ethyl 3-propiolate, which elucidates the mechanism. 1H and 13C NMR data of 6 and 7 are discussed. 相似文献
4.
Enamino-thiones 1 prepared from the corresponding enaminones by thiation with Lawesson's Reagent, were allowed to react with 2-chloroacrylonitrile and dimethyl acetylenedicarboxylate giving dihydro-2-thiopyrans, 2, and 4-thipyrans, 3, respectively. The reaction of 1a with ethyl propiolate at room temperature afforded 4-thipyrans, 4a, which on standing rearranged to 2-thiopyran, 5a(1, 3 amide shift). The reaction of 1b with ethyl propiolate produced 4b and 5b. Some of the 13C NMR data are reported. 相似文献
5.
Shinichi Uesato Shinichi Ueda Koji Kobayashi Masao Miyauchi Hiroyuki Inouye 《Tetrahedron letters》1984,25(5):573-576
Administration of 2H- or 13C-labeled monoterpenes to f. cell suspension cultures demonstrated that iridoid glucosides of the suspension cultures are biosynthesized, after iridodial cation formation from 10-oxocitral (3), via 8-epiiridodial (13), 8-epiiridotrial (14), boschnaloside (8-epiiridotrial glucoside) (12) and dehydroiridotrial glucoside (8). In addition, the coexistence of a route via iridodial cation (4), dehydroiridodial (6), dehydroiridotrial (15) and dehydroiridotrial glucoside (8) is conceivable. 相似文献
6.
Photoisomerization of -benzocycloheptenone to benzocycloheptenone and its [4 + 2] cycloaddition with selected dienes is reported for the synthesis of fused benzobicyclo[5.3.0]decanes 10, 12 and benzobicyclo [5.4.0]undecanes 13, 15. 相似文献
7.
By an appropriate choice of cation, three of the four possible aldols from the reactions of the chiral α-silyloxy ketone 1 with aldehydes may be obtained. The , lithium enolate provides 6, the , boron enolate gives 7, and the magnesium enolate affords 8. 相似文献
8.
Hideo Nemoto Mitsuo Nagai Keiichiro Fukumoto Tetsuji Kametani 《Tetrahedron letters》1985,26(38):4613-4616
A stereoselective total synthesis of 19-nor-Δ9(10)-progesterone (14) was achieved through des-A B-aromatic steroid (3) which was obtained by an intramolecular cycloaddition of the -quinodimethane generated from the thermolysis of 3-isopropenyl-5-(4-metho-xybenzocyclobutenyl)pentan-2-one-2-ethylene ketal (2), and the compound (14) thus obtained was further converted into Δ9-progesterone (18). 相似文献
9.
The first asymmetric total synthesis of stoechospermol, a representative spatane diterpene having , , -tricyclo[5.3.0.02,6]decane ring system, was achieved. Using the intramolecular asymmetric (2+2) photocycloaddition reaction of the diastereomeric ester 11, the readily available butenolide 9 was transformed into the optically active dilactone 12a and 12b. Subsequent construction of tricyclic carbon ring system and introduction of substituents in a right stereochemistry gave rise to optically pure stoechospermol 1. 相似文献
10.
Spirophosphoranes with a P-OH bond have been prepared as free acid (compound 5c), triethylammonium salts (compounds 2c–6c), or adducts with DMF (compounds 5c and 6c). The ionic feature of triethylammonium salts of compounds 1c–6c, shows that these Spirophosphoranes are relatively strong Brønsted's acids. Tautomeric equilibrium phosphoric ester—phosphorane with a P-OH bond [Scheme 9), shown in many cases, has been studied by means of 31PN, MRspectroscopy. Influence of factors ruling this equilibrium is analysed. Some elements of dynamic stereochemistry are examined. 相似文献
11.
The efficient degradation of to the α-methylene ketone is described. Compound was then converted to the allylic alcohol - the precursor of vitamin D3 relatives. 相似文献
12.
13.
Jan A. Glinski Balawant S. Joshi Szu-yinq Chen S.William Pelletier 《Tetrahedron letters》1984,25(12):1211-1214
A novel C19-diterpenoid alkaloid designated as tatsinine has been isolated from the roots of and its structure (3) has been derived from 1H NMR and 13C NMR spectroscopic evidence. 相似文献
14.
H.W. Zandbergen 《Journal of solid state chemistry》1981,37(2):189-203
TlMnI3 and TlFeI3 are isostructural with NH4CdCl3. TlMnI3 has a spiral structure which can be described with an incommensurable vector k, in the direction of the b1 axis of length 0.3614(5)b1. The spins lie in the (0 0 1) plane. TlMnI3 exhibits antiferromagnetic behavior with a Néel temperature of 6.0(2) K. The exchange interaction was calculated to be being the number of nearest neighbors. Discontinuities in the magnetization are found for both the [1 0 0] and [0 1 0] directions at fields HaSF = 30.1(2) kOe and HbSF = 14.1(2) kOe. The magnetic structure of TlFeI3 consists of puckered ferromagnetic (1 0 0) planes, which are coupled antiferromagnetically. The magnetic moments are parallel to the b axis. The Néel temperature is 21.5(3) K. was found to be ?10(1) K with g = 2.68 and s = 2. The magnetic structures found for TlMnI3 and TlFeI3 are derived taking into account inter- and intra-double-chain interactions via two I? ions. 相似文献
15.
3-bromo-2-(tert-butylsulfonyl)-1-propene 1 reacts in good yields with various electrophiles (aldehydes, ketones, nitriles and alkynes) in the presence of zinc metal to give unsaturated sulfones of type 4. These compounds can further react with soft or hard nucleophiles (alkyl-, vinyl-, aryllithium compounds, a nitroparaffin or dimethylmalonate) to yield highly functionnalized sulfones of type 5 which can be readily transformed into enones or into a dienone. Thus sulfone 1 is a versatile multi-coupling reagent which is synthetically equivalent to the synthon 8 and to the synthons 9 and 10. 相似文献
16.
57Fe Mössbauer spectra have been obtained for Fe(p-CH3C6H4SO3)2 between 2.3 and 300 K in zero field, and at 2.3 and 4.2 K in longitudinal applied magnetic fields ranging from 1.1 to 5.6 T. The complex is a fast-relaxing paramagnet under all conditions studied and there is no evidence of antiferromagnetic exchange coupling. The FeO6 chromophore is distorted by a trigonal elongation and the orbital ground state is the [()|±2〉 ? ()|?1〉] doublet. The temperature dependence of the quadrupole splitting has been analysed via a crystal-field model to provide estimates of the axial field splitting parameter Ds = -93 cm-1, spin-orbit coupling constant λ = -70 cm-1, and fine structure constant Dσ = -28 cm-1. The magnetic properties of the complex are described by treating the ground state as a non-Kramers doublet with fictitious spin ? = . Five separate Mössbauer-Zeeman spectra can be fitted in this spin-hamiltonian approximation with identical values of the g- and A-tensor components, viz. g⊥ = 1.0, gu = 9.0; A⊥ ≈ 2.0 mm s-1. Au = -1.79 mm s-1. The trigonal z axis, the z axis of the electric field gradient tensor, and the easy axis of magnetisation are collinear, and the saturation value of the internal hyperfine field along this axis is +13.0 T. 相似文献
17.
18.
Cycloaddition reactions between vinyl ethers 3 and -quinone methides 2, thermally generated from 2-hydroxybenzyl alcohols 1, have been studied. The structure and conformational preferences of the 4-substituted 2-ethoxy-(2,3)-dihydro-2-benzopyrans 4–9 obtained, which show new interesting features, are discussed together with competitive kinetic data. The cycloaddition process is concerted and involves -quinone methides in the -configuration. The OEt- transition state seems to be preferred with ethyl vinyl ether and -1-propenyl ethyl ether, whereas with -1-propenyl ethyl ether the stereoselectivity of the cycloaddition process depends on substituents on the methylene group of the starting alcohol 1. These results are discussed in terms of and preference of the propenyl ether methyl group. 相似文献
19.
Lithiation of both ()- and ()-3-trimethylsilyl-2-propenyl ,-diisopropyl carbamate 2 affords the (2) -lithium compound 3. Aluminium- or titanium-mediated addition to aldehydes, 4 gives (1)-(3*4*)-enol carbamates 7. A stereospecific Peterson elimination (borontriflouride- or base-mediated) introduces the second double bond either with (3)- or with (3)-configuration. So just by reagent selection for each of the two steps, (1,3)-, (1,3)-, (1,3)-, or (1,3)- dienes 8 - 11, respectively, are prepared with stereoselectivities up to > 99.7% 相似文献
20.
2-Hydroxybenzoic acid heated with 2,4 - bis(4 - methoxyphenyl) - 1,3,2,4 - dithiadiphosphetane - 2,4 -disulfide, 1, gave 2 - (p - methoxyphenyl) - 4 - 1,3,2 - benzoxathiaphosphorin - 4 - one 2 - sulfide, 3, and its thio-analogue, 4, while its ethyl or phenyl esters gave 4 as the sole product. 2 - Mercaptobenzoic acid and its ethyl ester when heated with 1 produced 3 - 1,2 - benzodithiole - 3 - one, 8, 3 -1,2 - benzodithiole - 3 - thione, 9, and 2- (p - methoxyphenyl) - 4 - 1,3,2 - benzodithia - phosphorin - 4 - one 2 - sulfide, 10. The reaction of 2 -aminobenzoic acid with 1 gave 1,2 - dihydro - 2 - (p - methoxyphenyl) - 4 - 3,1,2 - benzoxaphosphorin - 4 - one 2 - sulfide, 12. Reactions of 1 with methyl 2 - aminobenzoate and 2 - aminobenzamides are described. Mechanistic considerations for the formation of the heterocyclic phosphorus compounds are presented. 相似文献