首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 31 毫秒
1.
Abstract

The photolysis of diphenyl sulfone in neat pyridine or pyridine diluted with the organic solvent, with a high-pressure mercury arc lamp, was studied. The presence of acetone in the reaction system remarkably promoted photochemical conversion of the sulfone. The isomer distribution ratios (β > α > γ) of phenylpyridines produced during the reaction were clearly different from those (α > β > γ) so far reported for a free-radical phenylation of pyridine. Benzenesulfinic acid produced in the reaction was separated from the product mixture and identified as its S-benzylthiuronium derivative.  相似文献   

2.
Abstract

Reduction of sulfimides and sulfoximides with p-toluenesulfonyl nitrite, a new nitrosating agent, gave nearly quantitatively the corresponding deimination products, sulfides and sulfoxides, respectively. In the reaction of dialkyl and aryl alkyl sulfoximides with t-butyl thionitrate, N-t-butylthiosulfoximides were obtained besides the usual deimination products, although diaryl sulfoximides were readily deiminated to the corresponding sulfoxides in good yields in the same treatment. t-Butyl thionitrate was also found to deiminate diphenyl sulfimide to give diphenyl sulfide in good yield. Sulfoximides reacted sluggishly with t-butyl thionitrite, however, eventually affording a small amount of sulfoxides.  相似文献   

3.
Abstract

The reaction of potassium isopropyl dithiocarbonate with 4-chloro-3,5-dinitrobenzotrifluoride in dimethylformamide at 25–30°C afforded the titled phenothiazine (1) and sulfide (2). The reaction of bis(2,6-dinitro-4-trifluoromethylphenyl)-sulfide or the above halogen compound with sodium hydrosulfide in the same solvent at 80–90°C furnished 1. At 25–30°C the latter reaction afforded the titled disulfide (3). Possible mechanisms and supporting nmr, ir and mass spectral data are discussed.  相似文献   

4.
The cobalt species PPh4[CoIII(TAMLred)] is a competent and stable catalyst for the sulfimidation of (aryl)(alkyl)-substituted sulfides with iminoiodinanes, reaching turnover numbers up to 900 and turnover frequencies of 640 min−1 under mild and aerobic conditions. The sulfimidation proceeds in a highly chemoselective manner, even in the presence of alkenes or weak C−H bonds, as supported by inter- and intramolecular competition experiments. Functionalization of the sulfide substituent with various electron-donating and electron-withdrawing arenes and several alkyl, benzyl and vinyl fragments is tolerated, with up to quantitative product yields. Sulfimidation of phenyl allyl sulfide led to [2,3]-sigmatropic rearrangement of the initially formed sulfimide species to afford the corresponding N-allyl-S-phenyl-thiohydroxylamines as attractive products. Mechanistic studies suggest that the actual nitrene transfer to the sulfide proceeds via (previously characterized) electrophilic nitrene radical intermediates that afford the sulfimide products via electronically asynchronous transition states, in which SET from the sulfide to the nitrene radical complex precedes N−S bond formation in a single concerted process.  相似文献   

5.
The stepwise decomposition of carbonyl diisocyanate, OC(NCO)2, has been studied by using IR spectroscopy in solid argon matrices at 16 K. Upon irradiation with an ArF laser (λ=193 nm), carbonyl diisocyanate split off CO and furnished a new carbonyl nitrene, OCNC(O)N, in its triplet ground state. Two conformers of the nitrene, syn and anti, that were derived from the two conformers of OC(NCO)2 (62 % synsyn and 38 % synanti) were identified and characterized by combining IR spectroscopy and quantum chemical calculations. Subsequent irradiation with visible light (λ>395 nm) caused the Curtius rearrangement of the nitrene into OCNNCO. In addition to the expected decomposition products, N2 and CO, further photolysis of OCNNCO with the ArF laser yielded NOCN, through a diazomethanone (NNCO) intermediate. To further validate our proposed reaction mechanism, ArF‐laser photolysis of the closely related NNNNCO and cyclo‐N2CO in solid argon matrices were also studied. The observations of NOCN and in situ CO‐trapped product OCNNCO provided indirect evidence to support the initial generation of NNCO as a common intermediate during the laser photolysis of OCNNCO, NNNNCO, and cyclo‐N2CO.  相似文献   

6.
Abstract

Photochemical reactions of elemental sulfur with several olefins were studied. Irradiation of a mixture of elemental sulfur and norbornylene with 3500 Å light afforded 3,4,5-trithiatricyclo[5.2.1.0]decane (1) and 2,3-epithionorbornane (2). Similarly, several thiane derivatives (4–6) were found to be formed by the photolysis of a mixture of cyclohexene and sulfur.  相似文献   

7.
Reactions of trifluoromethanesulfonamide with divinyl sulfone, divinyl sulfoxide, divinyl sulfide, diphenyl sulfide, vinyl allyl and diallyl ethers was investigated in the presence of oxidation system t-BuOCl + NaI. The reaction with divinyl sulfone afforded a product of 1,5-heterocyclization, 2,6-diiodo-4-[(trifluoromethyl) sulfonyl]thiomorpholine 1,1-dioxide. The same product was obtained in the reaction with divinyl sulfoxide apparently due to its preliminary oxidation to sulfone. In reactions with divinyl sulfide and unsaturated ethers only the oxidation of substrates was observed accompanied with strong tarring; the products of a reaction with trifluoromethanesulfonamide were absent. With diphenyl sulfide a product was formed resulting from the oxidation at the sulfur atom [S(II) → S(IV)], N-(diphenyl-λ4-sulfanylidene)trifluoromethanesulfonamide.  相似文献   

8.
The molecular and crystal structures of 4-amino-2,6-diazido-3,5-dichloropyridine and 6-amino-2,4-diazido-1,3,5-triazine, as well as the paramagnetic photolysis products of their crystals at 77 K, were studied using X-ray diffraction analysis and ESR spectroscopy. Triplet nitrenes generated during the photolysis of diazidopyridine form triplet—triplet nitrene pairs, whose ESR spectrum corresponds to the quintet spin state. The high-spin state (S = 2) results from the exchange interaction between two triplet molecules with the zero-field splitting parameters |D| = 1.0280 cm−1 and |E| = 0.0038 cm−1 and the γ angle between two C—N nitrene bonds equal to 133°. This angle is close to an angle of 136.2° between the C-N bonds of two adjacent molecules in the crystal structure. No formation of the triplet—triplet nitrene pairs is observed during the photolysis of crystalline diazidotriazine, whose molecules lie in the parallel planes. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 513–520, March, 2008.  相似文献   

9.
The kinetics of the reactions of diphenylcarbonyl oxide with dimethyl, di-n-hexyl, diphenyl, dibenzyl, andn-hexylbenzyl sulfoxides in acetonitrile was studied by flash photolysis at 295 K. The oxidation of sulfoxide affords the corresponding sulfone as the main reaction product, and diphenyl sulfide also forms in the case of Ph2SO. Solvent effect on the reaction kinetics and the composition of the reaction products was studied. The reaction mechanism is discussed, which includes two parallel pathways: the nucleophilic attack of carbonyl oxide at the sulfur atom of sulfoxide and the formation of the cyclic sulfurane intermediatevia the electrophilic 1,3-cycloaddition of Ph2COO at the S=O bond. The sulfurane undergoes fragmentationvia parallel channels to form sulfone or sulfide. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1504–1509, September, 2000.  相似文献   

10.
Abstract

The mechanism of the reactions of diphenyl N-bromosulfilimine (I) with such nucleophiles as sulfides, phosphines and tertiary amines was investigated. In the presence of water, (I) reacts with sulfides or phosphines to afford the corresponding sulfoxides or the phosphine oxides in moderate yields; however, the reaction with tertiary amine gave only the N-t-aminosulfilimine derivative. The effect of ring size in the reaction with cyclic sulfides suggests that the reaction proceeds via initial bromine transfer from the nitrogen atom to the sulfur atom of the cyclic sulfides followed by SN2 type substitution of bromide on the sulfur atom of the cyclic sulfide with the sulfilimino group. The phosphine oxide obtained in the reaction of (I) with optically active methyl n-propyl phenyl phosphine was racemized but retained a small portion of the optical activity. In the case of tertiary amines, even 1,4-diazabicyclo-(2,2,2)-octane (DABCO), in which the back side of the nitrogen atom is blocked, reacted smoothly to afford the corresponding ammonium salts, suggesting the reaction to be of SN2 type on the nitrogen atom of the sulfilimine.  相似文献   

11.
N-t-Butylbenzamidines 1 reacted with diphenyl phenylmalonate or diphenyl methylmalonate to give 6-hydroxypyrimidin-4(3H)-ones 4 or 5. Amidines 1 on reaction with diphenyl imidodicarboxylate afforded 1,3,5-triazine-2,4(1H, 3H)-diones 8.  相似文献   

12.
The singlet—triplet energy splitting (ΔE ST = E S E T ) was calculated for formylnitrene (5) and for the syn- and anti-rotamers of carboxynitrene HOC(O)N (6) by the CCSD(T) method. Extrapolation of ΔE ST to a complete basis set was calculated to be negative for 5 and strongly positive for 6. Similar results were obtained by the G2 procedure. The reason for the dramatic stabilization of the singlet state appeared to be a special bonding interaction between the nitrogen and oxygen atoms, which results in the structure intermediate between those of nitrene and oxazirene. It was found that the B3LYP/6-31G(d) method overestimates ΔE ST by ∼9 kcal mol−1 for 5 and by ∼7 kcal mol−1 for 6. Taking into account this overestimation and the results of DFT calculations, it was concluded that benzoylnitrene has a singlet ground state. It was proved experimentally using photolysis of benzoyl azide in an argon matrix at 12 K that benzoylnitrene has a singlet ground state and its structure is similar to that of oxazirene. Nevertheless, these singlet intermediates have low barrier to the aziridine formation, which is traditionally considered to be a typical singlet nitrene reaction.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 519–526, March, 2005.  相似文献   

13.
The reaction of bis(hydroxymethyl)phenylphosphine with 4,4"-diaminodiphenylmethane in DMF afforded 1,1",5,5"-bis[methylenedi(p-phenylene)]di(3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) (1) whose structure was established by X-ray diffraction analysis. Sulfurization and oxidation of macrocyclic tetraphosphine 1 gave rise to products 2 and 3, respectively, compound 3 being obtained as a stable hexahydrate. The reaction of bis(hydroxymethyl)phenylphosphine with bis(4-N-methylaminophenyl)methane in DMF followed by sulfurization yielded monocyclic bis{methylenedi[p-phenylene(N-methyl)aminomethyl]}di(P-phenyl)phosphine sulfide (4).  相似文献   

14.
In photolysis of 4-azidoquinoline N-oxide azoxy compound was isolated as the final reaction product. This result may be ascribed to the dimerization of the intermediate nitrene to azo compound followed by oxidation of the latter with air oxygen. The initially arising nitrene is stabilized by resonance conjugation involving the aromatic system and the N-oxide group. The rate constants of 4-azidoquinoline N-oxide photolysis were measured in various solvents and the values of spin density and bond lengths in the formed nitrene were calculated.  相似文献   

15.
Condensation of 4‐acetyl‐5,6‐diphenyl‐2,3‐dihydropyridzin‐3‐one (1) with dimethylformamide dimethylacctal (DMFDMA) afforded the enaminone 2. This could be converted into the pyrazolylpyridazine derivative 4 on reaction with hydrazine hydrate and into pyridazinylpyridazinone 7a,b via coupling with aromatic diazonium salts and subsequent treatment with active methylene compounds. The reaction of 6 with dimethyl acetylenedicarboxylate in the presence of triphenylphosphine afforded the pyridazinylpyridazine derivative 8. Compound 1 converted into 9 upon reflux in acetic acid in the presence of ammonium acetate and afforded 10 on reflux in acetic acid.  相似文献   

16.
Abstract

Photopolymerization of styrene in the presence of diphenyl diselenide proceeded smoothly. The polymer yields and the number average molecular weight (Mn) of the polymers increased with reaction time. Further, a linear relationship was found for a plot of Mn for polystyrene versus polymer yield. These results indicate that this polymerization proceeds through a living radical mechanism. Photopolymerization of styrene with bis(p-tertbutylphenyl) diselenide afforded a telechelic polystyrene with terminal arylseleno groups. The resulting polymer underwent the reductive elimination of terminal seleno groups by the reaction with tri-n-butyltin hydride. Moreover, this telechelic polymer was treated with hydrogen peroxide to afford polystyrene with carbon-carbon double bonds at both chain ends.  相似文献   

17.
5-Azido-8-alkoxy psoralens were synthesized. Laser flash photolysis (LFP: XeF, 351 nm, 55 mJ, 17 ns) of the azides in acetonitrile or benzene solution produces the triplet nitrene and a small amount of ketenimine. Laser flash photolysis of the azides in methanol or aqueous solution cleanly produces the triplet nitrene. In aqueous solution containing highly polymerized calf thymus DNA, LFP produces a mixture of triplet nitrene and ketenimine corresponding to photolysis of free and bound psoralen, respectively. The two transients decay slowly but at different rates. Assignment of the transient spectra were secured by matrix EPR and UV-visible spectroscopy. The triplet nitrene lifetime is the same in buffer and in the presence and absence of calf thymus DNA. The results explain why psoralen azides are unable to efficiently nick plasmid DNA pBR322 upon UV activation.  相似文献   

18.
New mesoionic amides 4 and 5 with novel tricyclic ring systems have been synthesized by the photolysis of a 5‐azido‐1‐mesityl‐3‐phenyltetrazolium salt 1c via the corresponding triplet nitrene inter mediate. The structure of 5 has been determined by X‐ray crystallography.  相似文献   

19.
    
3-[4-(Azidocarbonyl)]phenylsydnone (2) obtained from 3-(4-hydrazinocarbonyl) phenylsydnone (1) on Curtius rearrangement with alcohols, water and amines afforded the corresponding carbamates (3a-h), 4,4′-(sydnone-3-yl) diphenyl urea (4) and 4-(heterocyclyl)phenyl ureas (5a-l). Compounds (5a-l) on one-pot ring conversion yielded the 1,3,4-oxadiazolin-2-one derivatives (6a-l), which on reaction with N2H4 gave the 4-amino-1,2,4-triazolin-3-ones (7a-l). All these compounds exhibited moderate antimicrobial activity against the few microbes tested. The carbamates have been found to be more toxic against fourth instar larvae ofAedes aegypti, in particular, then-butyl derivative (3e).  相似文献   

20.
A new type of sulfoxide, 4-(2-(2-(methylsulfinyl) ethyl)-4-nitrophenyl)- morpholine (I), was designed and prepared in good yield. Upon the combination of I and bis(trichloromethyl)carbonate, the Swern oxidation of primary and secondary alcohols was significantly promoted under mild conditions, which afforded the corresponding aldehydes or ketones in good yields. It is noteworthy that the reoxidation of the isolated by-product sulfide V could be further recycled in Swern oxidation.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号