4‐Substituted 2,3‐Dihydroisoxazoles as Masked Azomethine Ylides: Access to Pyrrole Derivatives by 1,5‐ and 1,7‐Dipolar Electrocyclizations of Enynyl Derivatives

The enynyl‐substituted 2,3‐dihydroisoxazoles (‘isoxazolines') 9 – 14 were prepared by highly (Z)‐selective Peterson olefination reaction from the corresponding carbaldehydes 6 – 8 . On short‐time thermolysis (280 – 406°/10 s) the TMS derivatives 9 – 11 give rise to the annulated pyrrolines 18 – 20 , which, in some cases, suffer CH₄ elimination affording the pyrroles 15 – 17 . In contrast, thermolysis of the terminal alkyne derivatives 12 – 14 leads to the bicyclic compounds 21 – 23 . The reaction pathways are discussed on the basis of the formation of conjugated azomethine ylides as key intermediates, which either undergo a 1,5‐cyclization to 18 – 20 or a 1,7‐ring‐closure affording cycloallene intermediates of type V , which are further transformed into the azepino pyrroles 21 – 23 .     

Neue β-Lactam-Antibiotika. Über Derivate der 3-Hydroxy-7-amino-ceph-3-em-4-carbonsäure. Modifikationen von Antibiotika, 10. Mitteilung [1]

3-Hydroxy-ceph-3-em-esters 5 a – c , versatile intermediates for the preparation of new β-lactam antibiotics, were obtained by ozonolysis of the corresponding 3-methylidene-esters 3 a – c . Reduction and elimination gave the 3-unsubstituted ester 13 ; derivatives 16 a – c and 20 – 22 resulted from O-alkylation. The 3-methoxy-esters 16 a – c were converted into the corresponding acids 23 a – d . Several other transformations of the β-ketoester system are described.     

Efficient Synthesis of α‐Benzylidene‐γ‐methyl‐γ‐butyrolactones

A concise synthesis of α‐benzylidene‐γ‐methyl‐γ‐butyrolactones 5a – g from substituted benzaldehydes is described. Compounds 1a – g on reaction with phosphorane 2 , provide the pentenoates 3a – g , which can be hydrolyzed to the acids 4a – g . The latter are cyclized to the corresponding butyrolactones 5a – g in excellent yields. The pentenoates 3a – g , on acid catalyzed cyclization, also provide 5a – g in very high yields.     

Ein neuer Reaktionsweg zu 1, 3-Dicarbonylderivaten. Modelluntersuchungen am A/B-Teil von 3-Oxo-5α-steroiden

A New Route to 1, 3-Dicarbonyl Derivatives, Model Investigations on the A/B-Part of-3-Oxo-5α-steroids Starting from 1 the 1, 3-dicarbonyl compounds 4a – d were synthetized via the enynes 2a – e and the relatively unstable epoxides 3a – d . The latter were reacted with 95% formic acid to gave 4a – d ; small amounts of the furane derivatives 5a – c were identified as by-products in this last step. In the presence of catalytic amounts of HgSO₄ the epoxides 3a – c yielded with 95% formic acid the furanes 5a – c , but no detectable amounts of 4a – c .     

Regioselective 1,3‐Dipolar Cycloadditions of (1Z)‐1‐(Arylmethylidene)‐5,5‐dimethyl‐3‐oxopyrazolidin‐1‐ium‐2‐ide Azomethine Imines to Acetylenic Dipolarophiles

The 5,5‐dimethylpyrazolidin‐3‐one ( 4 ), prepared from ethyl 3‐methylbut‐2‐enoate ( 3 ) and hydrazine hydrate, was treated with various substituted benzaldehydes 5a – i to give the corresponding (1Z)‐1‐(arylmethylidene)‐5,5‐dimethyl‐3‐oxopyrazolidin‐1‐ium‐2‐ide azomethine imines 6a – i . The 1,3‐dipolar cycloaddition reactions of azomethine imines 6a – h with dimethyl acetylenedicarboxylate (=dimethyl but‐2‐ynedioate; 7 ) afforded the corresponding dimethyl pyrazolo[1,2‐a]pyrazoledicarboxylates 8a – h , while by cycloaddition of 6 with methyl propiolate (=methyl prop‐2‐ynoate; 9 ), regioisomeric methyl pyrazolo[1,2‐a]pyrazolemonocarboxylates 10 and 11 were obtained. The regioselectivity of cycloadditions of azomethine imines 6a – i with methyl propiolate ( 9 ) was influenced by the substituents on the aryl residue. Thus, azomethine imines 6a – e derived from benzaldehydes 5a – e with a single substituent or without a substituent at the ortho‐positions in the aryl residue, led to mixtures of regioisomers 10a – e and 11a – e . Azomethine imines 6f – i derived from 2,6‐disubstituted benzaldehydes 5f – i gave single regioisomers 10f – i .     

Syntheses of the Macrocyclic Spermine Alkaloids (±)‐Budmunchiamine A – C

The syntheses of four macrocyclic spermine alkaloids, (±)‐budmunchiamine A – C ( 1a – c ) and (±)‐budmunchiamine L4 ( 1 ), were accomplished by Michael addition of spermine to the α,β‐unsaturated esters 3a – d , followed by cyclization of the resulting α,ω‐tetraamino esters 4a – d with triethoxyantimony; N‐methylation of the amino lactams 6a – c yielded the budmunchiamines A – C ( 1a – c ).     

Acid/Alkali Gated Photochromism of Diarylethenes with Quinoline Derivatives

Three new diarylethenes 1 – 3 combined with quinoline derivatives have been synthesized. Through controlled chemical condition of deprotonation/protonation, they presented some new irreversible photochromic phenomenons under UV/Vis light irradiation in chloroform solution. It was found that 1 – 3 had well photoisomerization upon UV/Vis light irradiation in neutral chloroform solution. Addition of acid to the solution of the ring‐opening isomers of 1 – 3 produced 1oa – 3oa , which performed reversible photochromic behavior under UV/Vis light irradiation and reversed back to 1 – 3 under neutralizing with adding lewis base. However, addtion of base to neutral soluton of the ring‐opening isomers of 1 – 3 produced 1ob – 3ob , which could not change to the deprotonated ring‐closing isomers under UV light irradiation.     

Selectively C‐Deuterated Indigotins

Selectively C‐deuterated indigotins were synthesized from halogenated indigotins 1a – c as precursors. The described reactions – used already by the ancient purple dyers – allowed the introduction of D‐atoms at defined positions of the indigo molecule. The exchange of halogen atoms by D‐atoms was induced by UV irradiation of the leuco compounds 2a – c and 3a – c in D₂O. The resulting leuco forms 4a – c were oxidized to the deuterated indigotins 5a – c . Some conclusions were drawn as to the kinetics of the reaction. The physical properties of the new compounds were determined.     

Addition von Aldehyden an aktivierte Doppelbindungen,XXXIV1). Addition von Aldehyden an cyclische α-Methylenketone

Addition of Aldehydes to Activated Double Bonds, XXXIV¹⁾. Addition of Aldehydes to Cyclic α-Methylene Ketones The thiazolium salt-catalyzed addition of aldehydes to the cyclic α-methylene ketones 3, 4, 7, 8, 48 , and 49 leads to γ-diketones 9 – 22, 50 – 53 ; some of them were converted into unsaturated ketones 23 – 28 , pyrroles 29 – 34, 37 – 43 , and furans 35, 36, 44 – 46 . The α-methylene ketones were synthesized by retro Diels-Alder reaction of the corresponding norbornene compounds 1, 2, 5, 6, 47 .     

Preparation of optically active cyclohexenones: Chirons for the lipophilic moiety of flowery- and woody-like odorant ketones

Optically active 2,5,6,6- and 2,4,4,5-tetraalkylcyclohex-2-en-1-ones ((+)- 2a – d and (?)- 5a – d ), important building blocks for flowery- and woody-like odorants, have been prepared. Compounds (+)- 2a – d and (?)- 5a – d were obtained by ozonolysis of the corresponding cyclopentenic precursors, followed by intramolecular aldol condensation. Alternatively, enones (+)- 2a – d were reduced to the corresponding allylic alcohols ad converted to enones (-)- 5a – d via acidic isomerization and oxidation. ¹³C-NMR assignments are presented.     

Cycloaddition von Heterocumulenen an CN-Bindungssysteme. 1. Mitteilung. Perhydro-s-triazindione und Perhydro-s-triazinyl-harnstoffe aus N,N,N′-trisubstituieten Formamidinen und Isocyanaten

The addition of methyl isocyanate to N,N-dimethyl-N′-arylformamidines 4d – 4r leads to the perhydro-s-triazine-diones 5d – 5o and to the s-triazinylureas 10a – 10k . The mechanism of formation is discussed. The addition of the arylisocyanates 18a – 18p to the N,N,N′-trialkylformamidines 9 and 27a – 27i furnishes the expected 1,4-cycloaddition products 26 and 27 in good yields. The N,N-di-isopropyl-N′-alkylformamidines 27j – 271 , however, do not undergo 1,4-dipolar cycloadditions and react with the arylisocyanate 18b to yield the alkyl isocyanates 31a – 31c and N,N-diisopropyl-N′-(p-chlorphenyl)-formamidine 32 exclusively.     

Laser-Induced Hydrogen Radical Removal in UV MALDI-MS Allows for the Differentiation of Flavonoid Monoglycoside Isomers

Negative-ion matrix-assisted laser desorption/ionization (MALDI) time-of-flight mass spectra and tandem mass spectra of flavonoid mono-O-glycosides showed the irregular signals that were 1 and/or 2 Da smaller than the parent deprotonated molecules ([M – H]^–) and the sugar-unit lost fragment ions ([M – Sugar – H]^–). The 1 and/or 2 Da mass shifts are generated with the removing of a neutral hydrogen radical (H*), and/or with the homolytic cleavage of the glycosidic bond, such as [M – H* – H]^–, [M – Sugar – H* – H]^–, and [M – Sugar – 2H* – H]^–. It was revealed that the hydrogen radical removes from the phenolic hydroxy groups on the flavonoids, not from the sugar moiety, because the flavonoid backbones themselves absorb the laser. The glycosyl positions depend on the extent of the hydrogen radical removals and that of the homolytic cleavage of the glycosidic bonds. Flavonoid mono-glycoside isomers were distinguished according to their TOF MS and tandem mass spectra.

Photochemische Umwandlungen, 42 [1] Photoisomerisierungen im 5-Isopropyliden-tetracyclo-[4.3.0.02,4.03,7]non-8-en-System. Vorläufige mitteilung

Direct photochemical excitation of the tetracyclo[4.3.0.0.^2,4.0^3,7]non-8-enes 7a – d leads to a mixture of the isomers 8a – d and 10a – d , with the former being the main products. On sensitization by acetone the formation of 10a – d is clearly favored. The cis-bishomobenzenes 9a – d are the postulated intermediates. Spectral data and some thermal reactions are described.     

7-Halogenated 7-Deaza-2′-deoxyinosines

The synthesis of the 7-deaza-2′-deoxyinosine derivatives 3a – c with chloro, bromo, and iodo substituents at position 7 is described. Glycosylation of the 7-halogenated 6-chloro-7-deazapurines 4a – c or of the 7-halogenated 6-chloro-7-deaza-2-(methylthio)purines 9a – c with 2-deoxy-3,5-di-O-(4-toluoyl)-α-D -erythro-pentofuranosyl chloride ( 5 ) furnished the intermediates 7a – c and 11a – c , respectively, which gave, upon deprotection, the desired nucleosides 3a – c .     

Mass spectrometry of 3-substituted 4-hydroxyisoquinolines and their derivatives

Under electron impact, 3-aryl-4-hydroxyisoquinolines form [M – H]⁺, [M – CO]⁺ and [M – H – CO]⁺ ions with a subsequent elimination of HCN or CH₃CN. A cyclic structure for the [M – H]⁺ ion is suggested. The primary act of fragmentation of the corresponding methyle ether derivatives is the loss of CH₃?, as well as H?; the further fragmentatio is similar to that described above. It has been established that the unusual [M – H]⁺, [M – OH]⁺ and [M – CH₅?]⁺ ions are formed when 8 fragments. Fragmentation schemes for all compounds are proposed based upon high resolution mass spectra and deuterated analogues.     

Triarylborane-Appended Anils and Boranils: Solid-State Emission,Mechanofluorochromism, and Phosphorescence

Herein, the design, synthesis, optical properties, and mechanofluorochromism characteristics of a series of conjugates having covalently linked triarylborane (TAB) and anil/boranil units (TAB-anil: 1 a – 3 a and TAB-boranil: 1 – 3 ) are reported. The electronic interactions between TAB and anil/boranil in 1 a – 3 a and 1 – 3 were fine-tuned by changing the boryl moiety's position on the phenyl spacer connecting the BMes₂ (Mes=mesityl) and anil/boranil units. A boryl moiety at the meta position ( 1 a ) of the phenyl spacer stabilizes the enolic form (E-OH), whereas a boryl moiety at the para position ( 2 a and 3 a ) stabilizes the keto form (Z-NH) in the solid state. However, in solution 1 a , 2 a , and 3 a exhibit keto–enol tautomerism in both ground and excited states. Compounds 1 a – 3 a and 1 – 3 show red-shifted absorption compared with 4 a and 4 , which are devoid of TAB moieties, which indicate effective participation of an empty p orbital on the boron center in 1 a – 3 a and 1 – 3 . Compounds 1 and 2 showed fluorescence variations in response to external stimuli such as mechanical grinding. Long phosphorescence lifetimes of 18–46 ms were observed for compounds 1 – 3 . The observed optical properties of 1 a – 3 a and 1 – 3 are rationalized in the context of quantum mechanical calculations.     

Identification of the aromatic hydroxylamine group by mass spectrometry

The mass spectra of aromatic hydroxylamines are diagnostic; [M], [M – 2], [M – 16] and, in most instances, [M – 17] ions are observed.     

Selective Synthesis of [2＋2] Macrocyclic Schiff Bases from Chiral 1,4-Diamines

[2＋2] macrocyclic Schiff bases of three kinds have been synthesized from chiral 1,4-diamines by use of different methods. Macrocyclic Schiff bases 1a-1c have been selectively obtained based on a non-templated dilution method from chiral 1,4-diamines a-c and dialdehyde DA1, whereas macrocycles 2a-2c have been selectively produced from reaction of diamines a-c and dialdehyde DA2 in the presence of boric acid as templates. Macrocyclic Schiff bases 3a-3c have been afforded in high selectivity from diamines a-c and dialdehyde DA3 by means of sodium-template. All the titled compounds have been confirmed by ^1H NMR and ESI-MS analyses.     

The chemistry and physics of zinc oxide surfaces

Metal oxides are virtually everywhere – only gold has the property not to form an oxide on its surface when exposed to the ambient. As a result, understanding the physics and chemistry of oxide surfaces is a topic of pronounced general interest and, of course, also a necessary prerequisite for many technical applications. The most important of these is certainly heterogeneous catalysis, but one has to realize that – under ambient conditions – virtually all phenomena occurring at liquid/metal and gas/metal interfaces are determined by the corresponding oxide. This applies in particular to friction phenomena, adhesion and corrosion. A necessary – but not necessarily sufficient – condition for unravelling the fundamentals governing this complex field is to analyze in some detail elementary chemical and physical processes at oxide surfaces. Although the Surface Science of metal surfaces has seen a major progress in the past decades, for oxides detailed experimental investigations for well-defined single crystal surfaces still represent a formidable challenge – mostly because of technical difficulties (charging), but to some extent also due to fundamental problems related to the stabilization of polar surfaces. As a result, the amount of information available for this class of materials is – compared to that at hand for metals – clearly not satisfactory. A particular disturbing lack of information is that about the presence of hydrogen at oxide surfaces – either as hydroxy-species or in form of metal hydrides.In the present review we will summarize recent experimental and theoretical information which has become available from single crystal studies on ZnO surfaces. While the number of papers dealing with another oxide, rutile TiO₂, is significantly larger (although titania does not exhibit a polar surface), also for zinc oxide a basis of experimental and theoretical knowledge as been accumulated, which – at least for the non-polar surfaces – allows to understand physico-chemical processes on an atomic level for an increasing number of cases. In particular with regards to the interaction with hydrogen a number of – often surprising – observations have been reported recently. Some of them carry implications for the behaviour of hydrogen on oxide surfaces in general. We will present the currently available information for both, experiment and theory, and demonstrate the rather large variety of this material’s surface properties.     

Synthesis of Some Novel Pyrido[2,3‐d]pyrimidine and Pyrido[3,2‐e][1,3,4]triazolo and Tetrazolo[1,5‐c]pyrimidine Derivatives as Potential Antimicrobial and Anticancer Agents

A novel series of pyrido[2,3‐d]pyrimidines 3a – d , 4a – d , 5a – d , 6a – d , and 7a – d ; pyrido[3,2‐e][1,3,4]triazolo; and tetrazolo[1,5‐c]pyrimidines 10a – d and 11a – d was synthesized through different chemical reactions starting from 2‐amino‐3‐cyano‐4,6‐diarylpyridines. The newly synthesized heterocycles were characterized by elemental analysis, IR, ¹H‐NMR, ¹³C‐NMR, and mass spectral data. Compounds have been screened for their antibacterial and antifungal activities. The data showed that the presence of electron‐donating group such as p‐methoxyphenyl increases the antimicrobial activity. Also, the compounds have shown anticancer activity for colon and liver cancer cells.