Pyryliumverbindungen. XXI. Struktur und Tautomerie von Pseudobasen unsymmetrisch substituierter 2,4,6-Triarylpyryliumsalze

Pyrylium Compounds. XXI. Structure and Tautomerism of Pseudobases of Unsymmetrically Substituted 2,4,6-Triarylpyrylium Salts Hydrolytic ring opening of unsymmetrically substituted 2,4,6-triarylpyrylium salts 11 results in a mixture of two tautomeric pseudobases, the penten-1,5-diones 13 and 14 . In crystalline state as a rule one of these tautomers markedly predominates, whereas in solution a rapid equilibrium establishment occurs which can be followed by ¹H-n.m.r. and u.v. spectroscopy (equilibrium ratio nearly 1:1). The ¹H-n.m.r. spectroscopic structural assignment of the two isomeric forms was supported by u.v. spectroscopic studies using 1:1 mixtures of the chromophoric partial systems ArCOCHCHPh and ArCOMe or the pseudobases 10 of symmetrically substituted 2,4,6-triarylpyrylium salts 9 as reference systems. From the mass spectra of the pseudobases 10 and 13 / 14 follows that – if hydrolysis of 11 is performed in media containing H₂¹⁸O – mass spectrometric isotopic analysis of the resulting ¹⁸O-labelled pseudobases allows no information to be made about the regioselectivity of the ring opening. – Novel starting pyrylium salts of type 9 and 11 are characterized by u.v./vis data and by transformation into the corresponding pyridine derivatives.     

Pyryliumverbindungen. 30. C-Alkylierung von 1,3,5-Triaryl-penten-1,5-dion-Enolaten: Ein einfacher Zugang zu 3-alkylsubstituierten 2,4,6-Triaryl-pyryliumsalzen

Pyrylium Compounds. 30. C-Alkylation of 1,3,5-Triaryl-pentene-1,5-dione Enolates: A Simple Approach to 3-Alkylsubstituted 2,4,6-Triarylpyrylium Salts 1,3,5-Triaryl-pentene-1,5-dione enolates ( 10 ), obtainable in crystalline form from 2,4,6-triarylpyrylium pseudobases ( 9 ) and sodium methoxide in benzene/ether, react in dipolar aprotonic solvents (e.g. DMSO, DMF) with various types of alkyl iodides to give C-alkylation products ( 11 ) which afford 3-substituted 2,4,6-triarylpyrylium salts ( 12 ) on treatment with perchloric acid. This reaction sequence proved to be a convenient synthetic route to pyrylium salts ( 12 ) having 3-oriented substituents such as normal or branched alkyl groups C_nH_2n+1 (e.g.n = 1–5), isotopically modified alkyl groups (e.g. C[²H₃], C₂[²H₅]), allyl type substituents (e.g. CH₂CHCH₂, MeCHCHCH₂, CH₂, CH₂CMeCH₂) or benzyl groups (e. g. PhCH₂, 4-Br C₆H₄CH₂). Bifunctional alkylating agents (e.g. 1,4-diiodobutane, o-xylylenediiodide) resulted in a novel type of bispyrylium salts ( 14 ) with 3,3′-linkage. The pyrylium salts obtained were characterized by their ¹H-n.m.r. and u.v. spectra as well as, in most cases, by transformation into the corresponding pyridine derivatives ( 13 ) and bispyridines ( 15 ) respectively.     

Pyryliumverbindungen. 33 [1] 2-Dialkylamino-2H-thiopyrane aus 2,4,6-Triaryl-thiopyryliumsalzen

Pyrylium Compounds. 33. 2-Dialkylamino-2H-thiopyrans from 2,4,6-Triaryl-thiopyrylium Salts 2,4,6-Triaryl-thiopyrylium salts 7 react with dialkylamines in diethyl ether to give stable crystalline 2-dialkylamino-2H-thiopyrans 8 , the structure of which is in accordance with their u.v., n.m.r. and mass spectra. The chemical properties of 8 parallel those of structurally analogous 2-alkoxy- and 2-dialkylamino-2H-pyrans and 2-alkoxy-2H-thiopyrans. Thus, on heating 2-dimethylamino-2,4,6-triphenyl-2H-thiopyran ( 8a ) with methanol the corresponding 2-methoxy-2H-thiopyran 9 is formed. Nitromethane and ethyl cyanoacetate give rise to ring transformations yielding 1,3,5-triphenyl benzene ( 10 ) and 2,4,6-benzonitrile ( 11 ), respectively. From 8a electrophiles (e.g. mineral acids, methyl iodide, benzoyl chloride) regenerate the initial thiopyrylium system by taking over the dialkylamino group.     

Pyryliumverbindungen. 31 [1]. Reaktion 3-alkylsubstituierter 2,4,6-Triaryl-pyryliumsalze mit 1,3-Diketonaten: Ein Weg zur Darstellung 3-acylsubstituierter Benzophenone

Pyrylium Compounds. 31. Reaction of 3-Alkyl-2,4,6-triarylpyrylium Salts with 1,3-Diketonates: A Method for the Preparation of 3-Acylsubstituted Benzophenones Reaction of 3-alkyl-2,4,6-triarylpyrylium salts with 1,3-diketones in the presence of one equivalent of triethylamine or potassium tert-butoxide does not lead — as originally suspected — to the primary adducts of 2H-pyran structure 6 , but to the open-chain valence isomers 7 . Treatment of the latter with one equivalent of tert-butoxide in tert-butyl alcohol gives the same 3-alkyl-2,4,6-triarylacetophenones 9 which are obtained directly from 5 , 1,3-diketones and two equivalents of potassium tert-butoxide. However, on treating 7 with aqueous ethanolic sodium hydroxide 3-acylsubstituted benzophenones 10 are formed in good yields. The reaction sequence 5→7→10 can also be performed through a one-pot-procedure. — The i.r., u.v., n.m.r. and mass spectroscopic data of the novel products 7, 9 , and 10 are reported.     

Pyryliumverbindungen. 36. Substituierte Benzoesäureester aus 2,4,6-Triaryl-pyryliumsalzen und α-Ketocarbonsäureestern

Pyrylium Compounds. 36. Substituted Benzoic Acid Esters from 2,4,6-Triarylpyrylium Salts and α-Ketocarboxylic Acid Esters 2,4,6-Triarylpyrylium salts 1 react with α-ketocarboxylic acid esters 2 in the presence of two equivalents of an appropriate condensing agent (e.g. dialkylamine salts of weak acids, triethylamine/acetic acid, or sodium acetate) to give 2-aroyl-3,5-diarylbenzoic acid esters 3 . However, using only one equivalent of the condensing agent, the formation of 3,5-diarylbenzoic acid esters 5 predominates. Alkaline saponification of the new esters 3 and 5 yields the corresponding substituted benzoic acids 4 and 6 , respectively. – I.r., u.v., n.m.r. and mass spectroscopic data of the novel products 3 – 6 are reported.     

Pyryliumverbindungen. 42. Benzocycloalkenone und Dihydro-2H,7H-1-benzopyranone aus 2,4,6-Triaryl-pyryliumsalzen und Cycloalkan-1,2-dionen

Pyrylium Compounds. 42. Benzocycloalkenones and Dihydro-2H,7H-1-benzopyranones from 2,4,6-Triarylpyrylium Salts and Cycloalkane-1,2-diones 2,4,6-Triarylpyrylium salts 1 react with cycloalkane-1,2-diones 2 in the presence of an appropriate condensing agent to yield benzocycloalkenones 3 . Thus, sodium acetate and cyclo-hexane-1,2-dione ( 2a ) lead to the dihydro-2H-naphthalenones 3a – i , whereas with cycloheptane-1,2-dione ( 2b ) and piperidine acetate, triethylamine or sodium acetate the tetrahydro-5H-benzo-cyclohepten-5-ones 3j – r are formed. As shown for the example 3a, j → 4a, b , benzocycloalkenones of type 3 can be converted into phthalazines 4 on heating with hydrazine in ethanol. By reaction of the dione 2a and an equimolar mixture of triethylamine and acetic acid or morpholine acetate with the salts 1 5,6-dihydro-2H,7H-1-benzopyran-8-ones 5 are obtained as a result of a new type of ring transformation. The pyrans 5 can be cleaved with perchloric acid in ethanol to 5,6,7,8-tetrahydro-8-oxo-1-benzopyrylium perchlorates 6 . If the pyrans 5 are heated with sodium acetate in ethanol, a conversion to benzocycloalkenones 3 is achieved (cf. 5a → 3a ). The structure of the new compounds was established by spectroscopic methods.     

Pyryliumverbindungen. XXII. 1H-NMR- und UV-spektroskopische Untersuchungen zur Isomerisierung von Pseudobasen unsymmetrisch substituierter 2, 4, 6-Triarylpyryliumsalze

Pyrylium Compounds. XXII. ¹H-N.M.R. and U.V. Spectroscopic Investigations on the Isomerization of Pseudobases of Unsymmetrically Substituted 2, 4, 6-Triarylpyrylium Salts The kinetics and mechanism of the isomerization of the title compounds, the pentene 1,5-diones 2 and 3 , were studied by ¹H-n.m.r. and u.v. spectroscopy. The equilibrium constants measured vary little near 1, indicating the small influence of substituents on the equilibrium position. The mutual rearrangement 2 ⇄ 3 proved to be a base-catalized reaction which is characterized by strictly linear Hammett correlation between 1g k and Σσ_p. The results obtained suggest resonance-stabilized anions of type 4 as intermediates. - Pseudobases of 3-alkyl-2, 4, 6-triarylsubstituted pyrylium salts do not undergo a reversible isomerization.     

Anionen-Massenspektroskopie von Naturstoffen. VII. Vergleichende Anionen-kationenmassenspektroskopische Untersuchungen von Cumarin-Derivaten

Anion Mass Spectroscopy of Natural Products. VII. Comparative Anion-cation Mass Spectroscopic Investigations of Coumarin Derivatives Electron attachment mass spectra (2–4eV) of some simple coumarins and furanocoumarins have been studied in comparison with their respective cation mass spectra. The possibility of distinguishing of some isomeric pairs is discussed.     

Pyryliumverbindungen. XXIX [1] Substituierte Benzophenone aus 2,4,6-Triaryl-pyryliumsalzen und Methyl(en)ketonen

Pyrylium Compounds. XXIX. Substituted Benzophenones from 2,4,6-Triarylpyrylium Salts and Methyl(ene) Ketones In the presence of piperidine acetate (or similar salts of certain dialkylamines), 2,4,6-triarylpyrylium perchlorates 5 react with methyl(ene) ketones 6 to give benzophenones 7 , the structure of which was proved by spectroscopic methods as well as by independent synthesis. Besides acetone and other acyclic ketones (e. g. alkyl methyl ketones, phenylacetone, desoxybenzoin, dibenzyl ketone) cyclic ketones (e. g. cyclopentanone, cyclohexanone, cycloheptanone, acenaphthenone) can also be used as ketone component 6 ; acetophenones react differently leading to hydrocarbons of the 1,3,5-triarylbenzene type 15 . The varying efficiency of the diverse amine salts and the mode of incorporation of the unsymmetrically substituted ketones suggest the intermediate formation of enamines 10 as crucial step of the ring transformations observed. This assumption is supported by isolation of the iminium salt 18 on reacting 3,5-dimethyl-2,4,6-triphenylpyrylium perchlorate ( 16 ) with acetone/piperidine acetate.     

Pyryliumverbindungen. XXVII. Spezifisch deuterierte Carbo- und Heterocyclen via 2,4,6-Triaryl-[3,5-2H2]pyryliumsalze

Pyrylium Compounds. XXVIII. Specifically Deuterated Carbo- and heterocycles via 2,4,6-Triaryl[3,5-²H₂]pyrylium Salts On heating with catalytic amounts of bases(e.g. triethyl amine) in deuterated alcohols such as methan[²H]ol or ethan[²H]ol pseudobases of 2, 4, 6-triarylpyrylium salts 1 undergo fast¹H/²H isotopic exchange reaction affording 1, 3, 5-triaryl[2, 4, 4-²H₃]pent-2-ene-1,5-diones which with [²H] perchloric acid give highly deuterated 2, 4, 6-triaryl-[3, 5-²H] pyrylium perchlorates 8 . These salts are obtainable also directly from 1 through a one-pot procedure by ring opening of the latter with deuterium oxide under the above-mentioned¹H/²H isotopic exchange conditions followed by recyclization of the formed 1, 3, 5-triaryl[2, 4, 4-²H₃]pent-2-ene-1, 5-diones with [²H]ClO₄. Ring transformations of 2, 4, 6-triphenyl[3, 5-²H²]pyrylium perchlorate (8a) to 2, 4, 6-triphenyl[3, 5-²H₂]nitrobenzene (9) 2, 4, 6-triphenyl[3, 5-²H₂]pyridine (10) , 1, 2, 4, 6-tetraphenyl[3, 5-²H₂]pyrydinium perchlorate (11) , 2, 4, 6-triphencyl[3, 5-²H₂]thiopyrylium perchlorate (12) , 2-benzoyl-3, 5-diphenyl[4-²H]furan (13) , and 3, 5, 7-triphenyl-[4, 4, 6-²H₃]4H-1, 2-diazepin (14) demonstrate the usability of pyrylium salts of type 8 as starting materials for syntheses of specifically deuterated carbo- and hetrocycles.     

Pyryliumverbindungen. 44 [1]. 2-(2-Hydroxy-3-oxo-cycloalk-1-enyl)-2H-thiopyrane aus 2,4,6-Triaryl-thiopyryliumsalzen und Cycloalkan-1,2-dionen

Pyrylium Compounds. 44. 2-(2-Hydroxy-3-oxo-cycloalk-1-enyl)-2H-thiopyranes from 2,4,6-Triarylthiopyrylium Salts and Cycloalkane-1,2-diones 2,4,6-Triarylthiopyrylium salts 5 react with cyclopentane-1,2-dione ( 2a ) or cyclo-hexane-1,2-dione ( 2b ) in the presence of an appropriate acid binding agent (e.g. sodium acetate, piperidine acetate, triethylamine/acetic acid, triethylamine) to give the hitherto unknown 2-(2-hydroxy-3-oxo-cycloalk-1-enyl)-2H-thiopyranes 6 . – The structure of the novel compounds was established by n.m.r., i.r. and u.v. spectroscopic methods.     

Pyryliumverbindungen. 41. 7aH-Cyclopenta[b]pyran-7-one durch Ringtransformation von 2,4,6-Triaryl-pyryliumsalzen mit acyclischen 1,2-Diketonen

Pyrylium Compounds. 41. 7aH-Cyclopenta[b]pyran-7-ones by Ring Transformation of 2,4,6-Triarylpyrylium Salts with Acyclic 1,2-Diketones Reaction of 2,4,6-triarylpyrylium salts 1 with acyclic 1,2-diketones 2 (CH₃COCOR, R = Me, Ph) in the presence of an appropriate condensing agent (e.g. piperidine acetate, triethyl-amine/acetic acid, sodium acetate) yields the hitherto unknown 2,4,5,7a-substituted 7aH-cyclopenta[b]pyran-7-ones 3 as a result of a new type of ring transformation (2,5-[C₄O+C]/2,3-[C₂+C₃]). A characteristic feature of compounds 3 is their ability to undergo electrophilic substitutions. Thus, stepwise bromination of the 7a-methyl derivative 3a in acetic acid affords 6-bromo-7a-methyl-2,4,5-triphenyl-cyclopenta[b]pyran-7-one ( 4 ) and 3,6-dibromo-7a-methyl-2,4,5-triphenyl-cyclopenta[b]pyran-7-one ( 5 ); analogously, nitration of 3a leads to 7a-methyl-6-nitro-2,4,5-triphenyl-cyclopenta[b]pyran-7-one ( 6 ), indicating that position 6 is the favoured position for electrophilic substitutions. Contrary to the 3,5-unsubstituted pyrylium salts 1 , the 3,5-dimethyl-2,4,6-triphenyl-pyrylium perchlorate ( 13 ) reacts with 1,2-diketones 2 through a 2,6-[C₅+C] transformation to give arylsubstituted 1,2-diones 14 . The structure of the new compounds was determined by spectroscopic methods and by a single crystal X-ray analysis of the dibromo derivative 5 .     

O3/UV,O3/TiO2/UV,O3/VO2/TiO2降解磺基水杨酸

实验利用O3/UV,O3/TiO2/UV,O3/VO2/TiO2降解了磺基水杨酸.结果表明,在这三种高级氧化技术中,O3/VO2/TiO2的氧化效果最好,如在相同的条件下,30 min后取样表明三者COD的去除率分别为47%,55%和70%.在不同pH条件下研究表明O3/TiO2/UV对水体pH的影响较为敏感.通过加入自由基猝灭剂研究表明三者产生羟基自由基的活性顺序是O3/VO2/TiO2＞O3/TiO2/UV＞O3/UV.     

二氧化钛紫外光(UV/TiO2)降解2,4,6-三氯酚的多因素影响

采用UV/TiO2高级氧化技术对2,4,6-三氯酚(2,4,6-TCP)进行降解试验,结果表明,UV/TiO2高级氧化工艺能有效降解2,4,6-TCP,且符合准一级动力学模型,相关系数均在0.96以上.TiO2投加量、2,4,6-TCP初始质量浓度、紫外光照强度、pH、阴离子对UV/TiO2降解2,4,6-TCP速率均...