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1.
5H-1,2,4-oxathiazoles were efficiently synthesized from 6H-1,3,5-oxathiazine S-oxides by thermal cycloreversion of the substrates and the products were effectively converted into 1,2,4-thiadiazoles. © 2004 Wiley Periodicals, Inc. Heteroatom Chem 15:175–186, 2004; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20004  相似文献   

2.
Heating of 6H-1,3,5-oxathiazine S-oxides efficiently afforded 1,2,4-oxathiazoles through the mechanism involving thermal cycloreversion of the substrates and the subsequent ring closure of the intermediary 1,3-thiaza-1,3-butadiene S-oxides.  相似文献   

3.
Oxidation of 5-hydroxy-5, 6-dihydro-4H-1, 2, 5-oxadiazines leads to the formation of 6H-1,2, 5-oxadiazine-5-oxides. Acid treatment of 5, 6-dihydro-4H-1, 2, 5-oxadiazines and 6H-1, 2, 5-oxadiazine-5-oxides results in heterocyclic-ring contraction with the formation of imidazole 3-oxides and 1-hydroxyimidazole 3-oxides. The structures of the products are established by their spectral properties and confirmed by independent synthesis.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1264–1266, September, 1970.  相似文献   

4.
A series of novel 6H‐1,3,5‐oxathiazine S,S‐dioxides were synthesized by the m‐CPBA oxidation (2.2 equiv) of 6H‐1,3,5‐oxathizines. The synthetic utilities of the newly synthesized cyclic sulfones were investigated. In a thermal condition, compounds 6H‐1,3,5‐oxathiazine S,S‐dioxides were found relatively stable, but Lewis acid‐induced thermal reaction afforded the corresponding amides. The plausible pathway to amides from 6H‐1,3,5‐oxathiazine S,S‐dioxides was also discussed in this account.  相似文献   

5.
O-(Trimethylsiloxy)alkyl S-trimethylsilyl aryldithiophosphonates 7a–d were obtained by the reaction of 2,4-diaryl-1,3,2,4-dithiadiphosphetane-2,4-disulfides 5a,b with disilyl derivatives of glycols 6a,c and salicyl alcohol 6b . The reactions of mixed O,S-bis(trimethylsilyl) 2,4-di(3,5-di-tert-butyl-4-hydroxyphenyl)dithiophosphonate 1 and S-silyl aryldithiophosphonates 7a,b with S,S-diethyldithiodiphenylgermane 2 , dichlorodiphenylgermane 8a , and dichlorodiphenylstannane 8b were studied. The structure of hexaphenyl-2,4,6,1,3,5-trithiatrigerminane 11 was established by X-ray single crystal diffraction. © 2004 Wiley Periodicals, Inc. Heteroatom Chem 15:225–232, 2004; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20009  相似文献   

6.
1,2-Dithiolopyrrolones and their heterologues of type 1 are resonance stabilized systems displaying a high dipole moment. Upon oxidation with organic peracids compounds 2 , 5 , 15a, 16a, 20a and 25a gave the corresponding S(2)-oxides and, depending on substituents, in some cases the S(2)- and S(1)-dioxides. The S(2)-monoxides showed a proclivity to disproportionation and were easily reduced to dithioles with symme trical dimethylhydrazine. From S(2)-oxides and several primary amines bicyclic isothiazole-S-oxides were obtained (S/N-exchange reaction). From the N-unsubstituted isothiazole S-oxide 10e the N-hydroxyisothiazole 9d was synthesized by an aza-Pummerer-type rearrangement. The assumption is made that S(2)-oxides may be biologically important as active metabolites of pyrrothines and analogues of type 1 in their action as antibacterials and antimycobacterials.  相似文献   

7.
An efficient synthesis of N-substituted dihydro-4H-1,3,5-dithiazines is described. N,N-Bis(benzotriazolylmethyl)alkylamines 1 smoothly under go cyclisation reaction in the presence of formaldehyde and hydrogen sulfide to give 5-substituted dihydro-4H-1,3,5-dithiazines 2.  相似文献   

8.
An analysis of the PMR spectra of 2H, 6H-2, 6-dimethyl-4-amino-1,3,5-dithiazine, its acyl derivatives, and 2H, 3H, 6H-2, 6-dimethyl-4-amino-1,3,5-thiadiazine in various solvents and in the presence of Eu(FOD)3 [tris(1,1,1,2,2,3,3-heptafluoro-7,7-dimettyl-4,6-octanedionato)3 europium] confirms the structure assigned to it and makes it possible to prefer a cis orientation of the methyl substituents in the half-chair conformation.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 485–487, April, 1981.  相似文献   

9.
Four 6-phenyl-5,6,7,8-tetrahydro-4H-1,3,2,6-dioxathiazocine 2-oxides were synthesized by the reaction of the corresponding N,N-bis(2-hydroxyethyl)aniline with thionyl chloride in the presence of triethylamine.  相似文献   

10.
The mass spectral fragmentation patterns of a series of thienopyridine N-oxides, S-oxides, and S,S-dioxides were elaborated as a means of structural determination. Observation of a significant (M-16) peak is diagnostic for the presence of either an N-oxide or an S-oxide function (indistinguishable from one another by this method) but does not occur for an S,S-dioxide function. For a substituted thieno[2,3-b]pyridine 7-oxide, structural rearrangement to a pyridone (followed by emission of carbon monoxide or formyl radical) or side-chain fission may be competitive with de-N-oxygenation. For two tricyclic parent S-oxides, rearrangement and de-S-oxygenation are competing initial processes. For parent S,S-dioxides structural rearrangement precedes fragmentation, wherein the oxygen is ejected in such forms as sulfur monoxide, carbon monoxide, formyl or cyanate radicals, and ketene.  相似文献   

11.
The syntheses of 2H-1,2,4,6-thiatriazin-3(4H)-one 1-oxides and 1,1-dioxides is described. The reaction of 1-carbamoyl-2-methylisothioureas 2 with thionyl chloride gave 2H-1,2,4,6-thiatriazin-3(4H)-one 1-oxides 3 in high yields. The treatment of 3 with either diazomethane or O-(2,4-dinitrophenyl)hydroxylamine furnished regioselectively N4-methylated and N4-aminated 2H-1,2,4,6-thiatriazin-3(4H)-one 1-oxides, respectively. Subsequent dimethylamination of 4 followed by oxidation with m-chloroperoxybenzoic acid led to 2H-1,2,4,6-thiatriazin-3(4H)-one 1,1-dioxides 6a-c .  相似文献   

12.
The reactions of 1,4,5-trisubstituted imidazole 3-oxides 1a – k with cyclobutanethiones 5a , b in CHCl3 at room temperature give imidazole-2(3H)-thiones 9a – k in high yield. The second product formed in this reaction is 2,2,4,4-tetramethylcyclobutane-1,3-dione ( 6a ; Scheme 2). Similar reactions occur with 1 and adamantanethione ( 5c ) as thiocarbonyl compound, as well as with 1,2,4-triazole-4-oxide derivative 10 and 5a (Scheme 3). A reaction mechanism by a two-step formation of the formal cycloadduct of type 7 via zwitterion 16 is proposed in Scheme 5. Spontaneous decomposition of 7 yields the products of this novel sulfur-transfer reaction. The starting imidazole 3-oxides are conveniently prepared by heating a mixture of 1,3,5-trisubstituted hexahydro-1,3,5-triazines 3 and α-(hydroxyimino) ketones 2 in EtOH (cf. Scheme 1). As demonstrated in the case of 9d , a `one-pot' procedure allows the preparation of 9 without isolation of the imidazole 3-oxides 1 . The reaction of 1c with thioketene 12 leads to a mixture of four products (Scheme 4). The minor products, 9c and the ketene 15 , result from an analogous sulfur-transfer reaction (Path a in Scheme 5), whereas the parent imidazole 14 and thiiranone 13 are the products of an oxygen-transfer reaction (Path b in Scheme 5).  相似文献   

13.
A series of 1,3-thiasilacycloalkanes and their S-oxides, S,S-dioxides, and sulfonium salts were studied by the DFT (B3LYP/6-31G*) method. In six-membered sulfoxides, the oxygen atom preferentially occupies the axial position, whereas in the corresponding sulfonium salts the S-alkyl group occupies the equatorial position. The calculation results explain the lower hydrolytic stability of the five-membered rings compared to the six-membered analogs and the lower stability of sulfoxides compared to sulfones.  相似文献   

14.
The mass spectral fragmentation of 4-, 5-, and 4,8-disubstituted derivatives of 6-aryl-5,6,7,8-tetrahydro-4H-1,3,2,6-dioxathiazocine 2-oxides is reported.  相似文献   

15.
Catalytic hydrogenation of o-nitrophenylbenz[a], benz[c], dibenz[a,h] and dibenz[a,g]acridinones using Pd/C as catalyst, at 60 psi of pressure, gave the hiterto unknown benzoquinoacridine N-oxides and benzo-pyranonaphthyridine N-oxides. The structure of all products was corroborated by ir, 1H- and 13C-nmr and mass spectra data.  相似文献   

16.
Alkoxy-λ6-sulfanenitriles were found to be versatile alkylating reagents toward various nucleophiles bearing at least one proton such as methanol, phenol, thiophenols, carboxylic acids, p-toluenesulfonic acid, hydrochloric acid, and primary and secondary amines. Reactivity of the alkoxy group of the λ6-sulfanenitriles showed an opposite trend to the usual SN2 character, i.e. Me ( 1a ), Pr ( 1b ), and Bu ( 1d ) ≪ i-Pr ( 1c ). In the presence of p-TsOH, alkyl tosylates were predominantly formed instead of the alkylation products of nucleophiles. In addition, even a sterically hindered substrate, neopentyloxy-λ6-sulfanenitrile, was found to undergo an SN2 reaction toward thiophenol without any rearrangement product to give neopentyl phenyl sulfide in good yield. © 2004 Wiley Periodicals, Inc. Heteroatom Chem 15:193–198, 2004; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20006  相似文献   

17.
The reaction of 3-mercapto-4-arylideneamino-1,2,4-triazoles 2b-d , 3a-d with ethyl bromoacetate and/or phenacyl bromide in hot DMF and triethylamine affords the stereochemically pure 7-acyl-6-aryl-6,7-dihydro-5H-1,2,4-triazolo[3,4-b][1,3,4]thiadiazines 4b-d , 5a-d , 6b , d in which the consecutive hydrogen atoms N(5)H-C(6)H-C(7)H are cis to each other. This stereochemistry was determined by 1H NMR spectroscopy and confirmed by comparison with the spectrum of 3,6-diphenyl-6,7-dihydro-5H-1,2,4-triazolo[3,4-b][1,3,4]thiadiazine 10 . The latter was prepared by NaBH4 reduction of 3,6-diphenyl-5H-1,2,4-triazolo[3,4-b][1,3,4]thiadiazine 9 . The reported reactions offer two interesting stereospecific syntheses of the condensed heterocyclic compounds.  相似文献   

18.
3,4-Dihydro-2H-1,3,5-thiadiazines substituted at the 3 and 6 positions were synthesized by treatment of N-substituted N,N-bis(1H-1,2,3-benzotriazol-1-ylmethyl)-amines with thioamides and zinc bromide in dry CH(2)Cl(2) at room temperature for 48-60 h in 48-80% yields.  相似文献   

19.
The alkylation of salicylaldehyde and o-hydroxyacetophenone with 2-amino-4-arylamino-6-chloromethyl-1,3,5-triazines is accompanied by intramolecular condensation and affords 2-aryl-4-arylamino-6-benzo[b]furan-2-yl-1,3,5-triazines.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2758–2759, December, 2004.  相似文献   

20.
ABSTRACT

3-Methyl-1-phenyl-2-phospholene and 1-phenyl-2-phospholene 1-oxides were converted into 2-bromo-3-hydroxy-3-methyl-1-phenylphospholane and 2-bromo-3-hydroxy-1-phenylphospholane 1-oxide (1-bromo-1,3,4-trideoxy-1,4-C-[(R, S)-phenylphosphinylidene]-glycero-tetrofuranose) by the action of bromine in aqueous medium. The bromo substituent of the phospholane was substituted by treatment with amines or an azide anion to afford novel glycoside derivatives of phosphanyl sugar analogs such as 2-amino-3-hydroxy-1-phenylphospholane (3,4-dideoxy-1,4-C-[(R, S)-phenylphosphinylidene]-glycero-tetrofuranosylamine) and 2-azido-3-hydroxy-3-methyl-1-phenylphospholane 1-oxides with retention of the configuration. The 1,3-dipolar cycloaddition of the 2-azido derivative of the phospholane with alkynes gave 3-hydroxy-3-methyl-1-phenyl-2-(triazol-1′-y1)phospholane 1-oxides as a novel triazole-derived nucleoside of phosphanyl sugar analogs. The structure of the glycoside and nucleoside derivatives of the phosphanyl sugar analogs prepared was deterimined from IR, NMR, and X-ray crystallography analysis.  相似文献   

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