Tetrazolverbindungen. 2. (1-Aryl-1H-tetrazol-5-yl)-acetaldehyd-Derivate aus 1-Aryl-5-(2-dimethylamino-vinyl)-1H-tetrazolen

Tetrazole Compounds. 2. 1-Aryl-1H-tetrazole-5-acetaldehyde Derivatives from 1-Aryl-5-(2-dimethylamino-vinyl)-1H-tetrazoles 1-Aryl-5-(2-dialkylamino-vinyl)-1H-tetrazoles 2 , easily accessible by the reaction of 3-chloro-propeniminium salts 1 with excess sodium azide in refluxing alcohols, represent enamines of the hitherto unknown 1-aryl-1H-tetrazole-5-acetaldehydes 3 . Attempts to isolate the latter after acid-catalyzed hydrolysis of 2 were unsuccessful. However, generated in situ, they can be trapped by suitable aldehyde reagents. Thus, starting from 1-aryl-5-(2-dimethylamino-vinyl)-1H-tetrazoles 4 , the 4-nitrophenylhydrazones 5a--hyphen;i , 2,4-dinitrophenylhydrazones 5j--hyphen;r , and thiosemicarbazones 6 of the corresponding 1-aryl-1H-tetrazole-5-acetaldehydes 3 were obtained. Analogously, acid-catalyzed hydrolysis of 4 in the presence of 1,2-dianilinoethane resulted in 1-aryl-5-(1,3-diphenyl-2-imidazolidinylmethyl)-1H-tetrazoles 7 . --hyphen; The structure of the aldehyde derivatives 5 , 6 , and 7 was proved by ¹H n.m.r. spectroscopy.     

N1-(2-苯基-1,2,3-三唑-4-甲酰基)-吡唑类衍生物的合成

利用２－苯基－１,２,３－三唑－４－甲酰肼（１）分别与３－芳基偶氮乙酰丙酮（２）和３－芳基偶氮乙酰乙酸乙酯（３）在酸性条件下环化,制得１２个新的Ｎ１－（２－苯基－１,２,３－三唑－４－甲酰基（－３,５－二甲基－４－芳基偶氮吡唑（４）和Ｎ１－（２－苯革－１,２,３－三唑－４－甲酰基）－３－甲基－４－芳基偶氮－２－吡唑啉－５－酮（５）,用元素分析、ＩＲ、＾１ＨＮＭＲ和ＭＳ确定了它们的结构。     

Novel magnesium and zinc porphyrazines containing galactose moieties: Synthesis via click reaction and characterization

In this study, galactose conjugated new magnesium and zinc porphyrazines were synthesized by the cyclotetramerization reaction of 2,3-bis[1-(2,2,7,7-tetramethyltetra-hydro-bis[1,3]dioxolo[4,5-b;4′,5′-d]pyran-5,methyl)-1H-[1,2,3]triazol-4-yl methylsulfanyl]-but 2-enedinitrile. This substituted dicyano compound was prepared via two different routes. One started from cis-1,2-dicyano-1,2-ethylenedithiolate disodium, [1-(2, 2, 7,7-tetramethyltetrahydrobis[1,3]dioxolo[4,5-b;4′,5′-d]pyran-5-yl-methyl)-1H-[1,2,3]triazo-l-4-yl]methanol and ended in a multi-step reaction sequence via Click procedures. The other reaction was between 5-azidomethyl-2,2,7,7-tetramethyltetrahydro-bis[1,3]dioxolo[4,5-b;4′,5′-d]pyran and (2Z)-2,3-bis(prop-2-yl-1-yl-thio)but-2-enedinitrile. A very soluble galactose linked magnesium porphyrazine derivative in common polar solvents and water was achieved by the deprotected isopropylidene groups in TFA and water media. It is first time, zinc porphyrazine complex has been achieved at one-step reaction by using Zn(BuO)₂ as template agent. The new compounds have been characterized by a combination of elemental analysis, ¹H, ¹³C NMR, IR, UV–vis and MS spectral data.     

Synthesis and characterization of substituted 2-diazo-1 -oxo-1,2-dihydzonaphthalenes and their products of photolysis and thermolysis

Several 2-diazo-1-oxo-1,2-dihydronaphthalene{ ( 1 , 2 ) have been synthesized by reaction of selected hydroxy compounds and 2-diazo-1-oxo-1,2-dihydzonaphthalene-5- and -4-sulfonylchloride, respectively. Photolysis as well as thermolysis of 1 and 2 leads to final products, the nature of which depends on the position of substitution. So, reactions of 5-substituted derivatives ( 1 ) yield the corresponding indene-3-carboxylic acids 3 and their esters 5 , respectively. In contrast, reactions of 4-substituted derivatives ( 2 ) lead to the formation of the 1-sulfo-indene-3-carboxylic acid derivatives 4 and 6 . Prepared compounds have been characterized by means of mass, ultraviolet, infrared, ¹H-n.m.r. ind ¹³C-n.m.r. {pectroscopy.     

Orthoamide. L. Beiträge zur Chemie von Propiolaldehydaminalen – Synthesen und Umsetzungen zu Push–Pull-substituierten Buta-1,3-dienen,Cyclobutanen sowie vinylogen Amidiniumsalzen und 1,2,3-Triazolen

Orthoamides. L. Contribution to the Chemistry of Propiolaldehydaminales – Synthesis and Transformations to Push–Pull-substituted Buta-1,3-dienes, Cyclobutanes, Vinylogous Amidinium Salts and 1,2,3-Triazoles Tert-butylaminalester 5 reacts with terminal alkynes to give aminals of substituted propiolaldehydes 3c, d . The aminal 3a is accessible from N,N,N′,N′-tetramethylformamidinium chloride (7b) and sodium acetylide. The aminals 3b,c can also be prepared from bis(dimethylamino)acetonitrile 8 and terminal alkynes in the presence of sodium hydride. The nitrile 8 is also useful for the preparation of the bis-aminal of acetylenedialdehyde 6 . The aminal 3e can be transaminated by heating with secondary amines to give the aminals 3f–i . The aminals 3a–i react with strong CH₂-acidic compounds (pK_a between 9 and 14) to give the 1-dialkylamino-1,3-butadienes 10 . The isomeric 1-dialkylamino-butadienes 18 can be obtained from the condensation of the CH-acidic cinnamic acid derivatives 19 with dimethylformamidedimethylacetal. CH and NH-acidic compounds as cyanacetamide react with the aminals 3c,e exclusively with the acidic methylene group to produce the enamines 10h,t . The acylformamidine 21 can be obtained from 10t and tert-butylaminalester 5 . The pyridone 22 is accessible from the condensation product 10h by thermal cyclization. The pyrido[2,3-d]pyrimidine 26 is formed in the reaction of the 6-amino-uracile 23 with the aminal 3a . In an unexpected reaction the 1,2-bis(cyano-dialkylaminomethylene)-cyclobutanes 28a–d result from the action of trimethylsilylcyanide on the aminals 3e–h . The corresponding reaction with trimethylsilylisothiocyanate affords the vinylogous amidinium thiocyanates 34a, b . In the reaction of trimethylsilylazide and the aminals 3 are produced the 4-(dialkylaminomethylene)-4H-1,2,3-triazoles 38 .     

A novel synthesis of 1,3 Thiazetidine-2-one and 1,3-Oxazine-2-one Derivatives

In the reactions of acetylthioacetanilides ( 1a–c ) and diacetylthioacetanilides ( 3a–f ) with phosgene 1,3-thiazetidine-2-one ( 2a–c ) and 1,3-oxazine-2-one ( 5a–f ) were obtained respectively. The structures of new compounds were elucidated by elemental analyses, i.r., ¹H-n.m.r., m.s., for 1d–f by ¹⁹F-n.m.r. and for 2a and 5a by ¹³C-n.m.r. spectral data.     

Template synthesis and characterization of hexaaza macrocycles containing pyridine iron(II) complex nanoparticles dispersed within nanoreactors of zeolite-Y

Iron(II) complexes with 18- and 20-membered hexaaza macrocyclic ligands were entrapped in the nanoreactors of zeolite-Y by a two-step process in the liquid phase: (i) adsorption of [bis(diamine)iron(II)] (diamine = 1,2-diaminoethane, 1,3-diaminopropane, 1,2-diaminobenzene, 1,3-diaminobenzene); [Fe(N–N)₂]²⁺–NaY; in the nanoreactors of the zeolite, and (ii) template condensation of the iron(II) precursor complex with 2,6-diacetylpyridine.The mode of bonding and overall geometry of the complexes and new complex nanoparticles entrapped in the nanoreactor of zeolite-Y ([Fe([18 or 20]py₂N₄)]²⁺–NaY, [Fe(Bzo₂[18 or 20]py₂N₄)]²⁺–NaY) has been inferred through FT-IR, TGA, XRD, XPS spectroscopic techniques and elemental analysis as well as nitrogen adsorption.     

1,3-Diaza-2-azoniaallene Salts as Novel N3-Building Blocks: Preparation and cycloadditions to alkenes,alkynes, carbodiimides,and cyanamides

1,3-Diaza-2-azoniaallene salts R¹-NN⁺N R² 6 represent a new functional group. 1,3-Disubstituted triazenes 8 are oxidized with tert-butyl hypochlorite to stable open-chain N-chlorotriazenes R¹ NN NCl R² 9 , which at low temperatures with Lewis acids afford the reactive intermediates 6 . The salt 6a is stable below −50 °C and was characterized by spectroscopic and analytical data. Heterocumulenes 6 behave as positively charged 1,3-dipoles undergoing cycloadditions to many different multiple bonds to furnish 1,2,3-triazolium and tetrazolium salts, e.g. to both electron-rich and electron-deficient alkenes, alkynes, to one or both double bonds of 1,3-butadienes, to carbodiimides, and cyanamides (1,3-dipolar cycloaddition with inverse electron demand). With an allene, a butatriene and a pentatetraene the 4,5-dihydro-1H-1,2,3-triazolium salts 17–19 were obtained. The constitutions of four of the products were secured by X-ray structural analyses. 4,5-Dihydro-1H-1,2,3-triazolium salts 11 and 1H-1,2,3-triazolium salts 20 are aza analogues of Arduengo's and Wanzlick's nucleophilic carbenes.     

Direct Synthesis of Pyrazoles via reaction of C-ethoxycarbonyl-N-arylnitrilimines with benzalmalononitriles and some α-cyanocinnamic acid derivatives

Reaction of C-ethoxycarbonyl-N-arylnitrilimines ( 2a–d ) with α, β-disubstituted acrylonitriles ( 3a–f ) in refluxing benzene affords the corresponding substituted pyrazoles 5a–f and 6a–c respectively in good yield. However, reaction of 2a–e with 3g gives the 2-pyrazoline derivatives 7a–d . The assigned structures for the products 5–7 were confirmed by their spectra (i.r., ¹H-n.m.r.) and elemental analyses. Also the structures of the pyrazoles 5 were substantiated by comparison with their regioisomeres 8 .     

Strukturaufklärung von ausgewählten nitro- und sulfonsäuresubstituierten 1,2-Naphthochinon-2-diaziden

Structure Determination of Selected Nitro and Sulfonic Acid Substituted 1,2-Naphthoquinone-2-diazides Selected nitro derivatives of 1,2-naphtoquinone-2-diazide 2 and 5 have been synthesized, the position of the NO₂-group has been unambigously determined by means of ¹H and ¹³C n.m.r. spectroscopy, and the structure of these compounds has been comprehensively determined in relation to unsubstituted 1 and sulfonic acid substituted derivatives 3 , 3a , 4 and 4a . Furthermore, the spectroscopical behaviour, especially in the uv/vis region, was examined in correlation to quantum chemical calculations.     

Electrooxidation of bromoalkanes on platinum in liquid hydrogen fluoride. Selective displacement of bromine by fluorine

Carbon—bromine bond cleavage was investigated in HF as a privileged route to the formation of electrophilic carbon ions and subsequent obtention of alkyl fluorides.Nucleophilic attack of fluoride ions on electrochemically generated radical cations, R—Br⁺, or carbenium ions, R⁺, proved selective and quantitative in the case of bromomethane, 1,2-dibromoethane, 1,2-dibromopropane, 1,3-dibromo propane and 1,2,3-tribromopropane.For bromoethane, 1-(or 2-)bromopropane, 1-(or 2-)bromobutane, 1-bromo-2-methyl propane and 1-bromo-3-methyl butane, the observed lack of halogenation selectivity is discussed in terms of radical side reactions.     

Oxokohlenstoffe und verwandte Verbindungen. 27. Synthese von Dihydrocyclobuta[a]naphthalen-1,2-dionen und Cyclobuta[a]naphthalen-1,2-dionen durch Anellierung von Alkoxy-(1-alkenyl)benzolen mit 3-Chlor-3-cyclobuten-1,2-dion. Anwendungsbereich und Grenzen

Oxocarbons and Related Compounds. 27. Synthesis of Dihydrocyclobuta[a]naphthalene-1,2-diones and Cyclobuta[a]naphthalene-1,2-diones via Annulation of Alkoxy-(1-alkenyl)benzenes with 3-Chloro-3-cyclobutene-1,2-dione. Scope and Limitations The reaction of alkoxy-(1-alkenyl)benzenes with semisquaric chloride ( 3 ) has been investigated systematically. 1,2-Dialkoxy- and 1-alkoxy'-2-alkoxy″-4-(1-alkenyl)benzenes ( 6a–j ) and ( 11a–i ) react with 3 to give the 3,4-dihydrocyclobuta[a]naphthalene-1,2-diones ( 8a–j ) and ( 12a–i ). Treatment of the dihydrocyclobuta[a]naphthalene-1,2-diones with 1.2 equiv. bromine effects dehydrogenation and affords cyclobuta[a]naphthalene-1,2-diones ( 9a–e ) and ( 13b–f ). Any efforts to extend this annulation reaction to dimethoxy-(1-alkenyl)benzenes with the methoxy groups in other than the 1,2-positions, e. g. 14a, b, 16a, b have been unsuccessful. The reaction of 1,2,3-trimethoxy-4-(1-propenyl) [and 4-(1-butenyl)]-benzenes ( 18a ) and ( 18b ) with semisquaric chloride ( 3 ) leads to the elimination of HCl and CH₃OH and gives 5,6-dimethoxy-3-methyl [and 3-ethyl]-cyclobuta[a]naphthalene-1,2-diones ( 20a ) and ( 20b ). The reaction pathway of this novel annulation reaction is discussed.     

Synthese heterocyclisch substituierter 4-Piperidinyl-1,4-dihydropyridine durch Ringschlußreaktion an einer N-Acylthioamid- und N-Acylisothioamid-Seitenkette

Synthesis of Heterocyclically Substituted-4-Piperidinyl-1,4-dihydropyridines by Ring Closure Reactions at a N-Acylthioamide- or at a N-Acylisothioamide-Side-Group A series of 4-(2′-methylenepiperidin-4′-yl)-1,4-dihydropyridines [ 5–7 and 9–11 ] with a heterocyclic substituent at the methylene group is prepared by reaction of the nonsubstituted compound 1 with benzoylisothiocyanate or ethoxycarbonylisothiocyanate to the N-benzoylthioamide 2 or the N-ethoxycarbonylthioamide 3 , transformation of 2 into the isothioamide 4 by S-methylation, and subsequent ring closure of 2, 3 or 4 with hydrazine, methylhydrazine, phenylhydrazine, 1,2-diaminoethane, 1,2- and 1,3-diaminopropane, o-diaminobenzene and o-aminophenol.     

Reactions with β-ketodianilides. I. New synthesis of Pyrido[3,4-c]pyridine Derivatives

Acetonedicarboxylic acid dianiline reacted with malononitrile, ethyl cyanoacetate or benzoylacetonitrile to give (6-amino-5-cyano-1,2-dihydro-2-oxo-1-phenylpyrid-4-yl)-acetanilide ( 3 ), (3-cyano-2,6-dioxo-1-phenyl-1,2,5,6-tetrahydropyrid-4-yl)acetanilide ( 8 ) or (3-cyano-1,6-dihydro-1,2-diphenyl-6-oxopyrid-4-yl)acetanilide ( 9 ). Compounds 3 and 8 could be cyclised into 8-amino-1,6-diphenyl-1,2,4,5,6,7-hexahydro-7-iminopyrido[3,4-c]pyridine-2,5-dione ( 4 ) and 7-amino-1,2,3,5,6,8-hexahydro-1,6-diphenylpyrido[3,4-c]pyridine-2,5,8-trione ( 10 ) respectively by heating their solutions in dimethylformamide in the presence of triethylamine. Each of 3 and 4 coupled with arenediazonium chlorides to give the corresponding arylhydrazone derivatives ( 5a–d ) and ( 6a–c ), respectively. Condensation of 4 with p-nitrosodimethylaniline yielded 8-amino-4- (p-dimethylaminophenylimino)-1,6-diphenyl-1,2,4,5,6,7-hexahydro-7-iminopyrido[3,4-c]pyridine2,5-dione ( 7 ).     

Arsenical creosote. VI. Importance of the vicinal hydroxyls in the reaction of phenols with arsenic trioxide

Only those compounds with vicinal hydroxyls on the benzene ring reacted extensively with As₂O₃ when heated at 130–16° in high-temperature coke-oven creosote. About two moles of 1,2-dihydroxybenzene, 1,2-dihydroxy-3-methylbenzene and 1,2-dihydroxy-4-methylbenzene reacted with one mole of As₂O₃; for 1,2,3-trihydroxybenzene and 3,4-dihydroxybenzoic acid the ratio was about 2·7 and for 3,4,5-trihydroxybenzoic acid it was still higher. Similar reactions occurred in heavy petroleum, raw linseed, lubricant and paraffin oils. Arsenic derivatives have been synthesised either by gentle fusion of mixtures of the above compounds with As₂O₃, or by heating the reactants for 75 min in paraffin oil. The products, recrystallised from toluene, petroleum ether or toluene–ethanol are white, odourless, non-volatile and stable at temperatures of 150–200°.     

Synthesis,Thermal Stability and Impact Stability of Novel Tetranitro‐Dipyridotetraazapentalene Derivatives

The synthetic details for the construction of three new dipyridotetraazapentalene derivatives, 5H‐pyrido[3″,4″:4′,5′] [1,2,3]triazolo‐ [1′,2′:1,2][1,2,3]triazolo[5,4‐b]pyridin‐6‐ium inner salt ( 8 ), 5H‐pyrido[3″,2″:4′,5′] [1,2,3]triazolo[1′,2′:1,2] [1,2,3]triazolo[5,4‐b]‐pyridin‐6‐ium inner salt ( 15 ) and 5H‐pyrido[2″,3″:4′,5′] [1,2,3]‐triazolo[1′,2′:1,2][1,2,3]triazolo[4,5‐b]pyridin‐6‐ium inner salt ( 16 ) are presented. Nitration of ( 8 ) and ( 15 ) afforded the novel tetranitrodipyridotetraazapentalene derivatives, 2,4,8,10‐tetranitro‐5H‐pyrido[3″,4″:4′,5′][1,2,3]triazolo[1′,2′:1,2][1,2,3]‐triazolo[5,4‐b]‐pyridin‐6‐ium inner salt ( 3 ) and 2,4,8,10‐tetranitro‐5H‐pyrido[3″,2″:4′,5′][1,2,3]triazolo[1′,2′:1,2][1,2,3]‐triazolo[5,4‐b]‐pyridin‐6‐ium inner salt ( 4 ) in good yields. Both isomers, ( 3 ) and ( 4 ), exhibited high thermal stability (differential scanning calorimetric analysis and thermal gravimetric analysis) and were insensitive to impact (hammer/anvil test).     

Synthesis of 2,3-trans-3,4-cis- and 2,3-trans-3,4-trans-2,3,4-triphenyltetrahydrofurans

The synthesis of 2,3-trans-3,4-cis- and 2,3-trans-3,4-trans-2,3,4-triphenyltetrahydrofurans was undertaken because these compounds incorportae the essential structural features of certain 2,3-diphenyl-benzofurans and 1,2,3-triphenylalkanones reported earlier to have marked antifertility activity. The synthesis of the 2 tetrahydrofurans was achieved by the cyclization of corresponding 2,3,4-triphenylbutane-1,4-diols upon heating with dimethyl sulfoxide (DMSO). The butane 1,4-diols were in turn prepared either by direct litium aluminum hydride (LAH) reduction of methyl 3-benzoyl-2,3-diphenylpropionates or by conversion of these propionates to delta-3,4-butryrolactones followed by LAH reduction. The propionates were prepared from the Fiedel-Crafts reaction of 2,3-diphenylsuccinic anhydride with benzene. Tetrahydrofurans were tested for their antiimplantation activity in rats. 2,3-trans-3,4-cis-2,4-diphenyl-3-p -(beta-pyrrolidinoethoxy) phenyltetrahydrofuran oxalate was found to inhibit implantation completely at 50 mg/kg, but was inefective at a lower dose.     

Supported organometallic complexes. Part 37: synthesis and structures of diamine-bis(methoxyethyldimethylphosphine)ruthenium(II) complexes

The first two examples of diamineruthenium(II) complexes containing the hemilabile methoxyethyldimethylphosphine ligand, Cl₂Ru(en)(η¹-Me₂PCH₂CH₂OMe)₂ (2a) and Cl₂Ru[(R,R)-dpen](η¹-Me₂PCH₂CH₂OMe)₂ (2b) (en=1,2-diaminoethane, (R,R)-dpen=1R,2R-1,2-diamino-1,2-diphenylethane) have been synthesized and structurally characterized.     

Sensibilisierte Photooxidation von Butadien-(1,3)-sultamen-(1,4)

Sensitized Photooxidation of Butadiene-(1,3)-sultames-(1,4) The sensitized photooxidation of the butadiene-sultames 1a–d gives 2-aryl-3,5-dimethyl-5-hydroxy-1,1,6-trioxo-5,6-dihydro-2H-1,2-thiazines 2a–d in yields of 60%. The compounds 2a–d are instable against bases and acids. With triethylamine the N-aryl-5-hydroxypyrrolin-2-ones 5a–d are formed by SO₂-extrusion. With alkali 2b reacts to 5b and cis-β-acetyl-methacrylic acid 4 . ¹H- and ¹³C-n.m.r. spectroscopic data of 2 and 5 are given.     

Spiegelsymmetrische Hexahydro-1,2,4,5-tetrazine aus Pyrazolidon-(3)-N,N-betainen – ein Beitrag zur „thermischen Dimerisierung”︁ von 1,3-Dipolen

Mirror-symmetric Hexahydro-1,2,4,5-tetrazines from Pyrazolidine-3-one-N,N-betaines—a Contribution to the „Thermal Dimerization”︁ of 1,3-Dipoles Chemical reactions, i.r., ¹H-n.m.r., and ¹³C-n.m.r. data show that the “thermal dimers” of pyrazolidine-3-one azomethinimines 2 , which till now accidentally formed during the synthesis of 2 from pyrazolidine-3-ones 5 and aldehydes 6 , are 5,11-diaryl-perhydro-dipyrazolo[1,2-a; 1′,2′-d][1,2,4,5]-tetrazine-1,9-diones 3 , i.e. mirror-symmetric hexahydro-1,2,4,5-tetrazines with (C-5) and (C-11) placed on the mirror plane. From DREIDING models and from the nonequivalence, concerning ¹³C-n.m.r., of the pairs of carbon atoms in the o- resp. m-positions of the aryl substituent I at (C-5) of the “dimers” 3 is derived that the rotation of I is sterically hindered (ΔG = 16,3 kcal/mole for 3b ), and that the preferred arrangement of I is perpendicular to the plane of the hexahydrotetrazine ring. The “thermal dimerization” of the 1,3-dipoles 2 is a complex series of two addition and elimination steps proceeding in the presence of catalytical amounts of pyrazolidine-3-one 5 and of H^⊕. The mechanism is rationalized, consequences are suggested concerning known “dimerizations” of 1,3-dipoles.