Reactions of 2,3-disubstituted 6,7-dihydro-5H-2a-thia(2a-SIV)-2,3,4a,7a-tetraazacyclopent[cd]indene-1,4(2H,3H)-dithiones with isothiocyanates and isocyanates

12π-Tetraazapentalenes, 2,3-disubstituted 6,7-dihydro-5H-2a-thia(2a-S^IV)-2,3,4a,7a-tetraazacyclopent-[cd]indene-1,4(2H,3H)-dithiones, 1 and 7 , reacted with excess alkyl or aryl isothiocyanates and isocyanates to afford mono- and di-alkyl or aryl substituted tetraazapentalene derivatives which have the thiocarbonyl and carbonyl groups.     

2-[3-(Trifluoromethyl)phenyl]furo[3,2-b]pyrroles: synthesis and reactions

The synthesis and reactions of methyl 2-[3-(trifluoromethyl)phenyl]-4H-furo[3,2-b]pyrrole-5-carboxylate (1a) are described. Upon reaction with methyl iodide, benzyl chloride, or acetic anhydride, this compound gave N-substituted products 1b-d. By hydrolysis of compounds 1a-c, the corresponding acids 2a-c were formed, or by reaction with hydrazine-hydrate, the corresponding carbohydrazides 3a-c were formed. By heating 2-[3-(trifluoromethyl)phenly]-4H-furo[3,2-b]pyrrole-5-carboxylic acid (2a) in acetic anhydride, 4-acetyl-2-[3-(trifluoromethyl)phenyl]furo[3,2-b]pyrrole (4) was formed. By hydrolysis of 4, 2-[3-(trifluoromethyl)phenyl]-4H-furo[3,2-b]pyrrole (5a) was formed, and reactions with methyl iodide or benzyl chloride gave N-substituted products 5b-c. The reaction of 4 with dimethyl butynedioate gave substituted benzo[b]furan 6. Compound 3a reacted with triethyl orthoesters giving 7a-c, which afforded with phosphorus (V) sulphide the corresponding thiones 8a-c. The thiones 8a-c reacted with hydrazine hydrate to form hydrazine derivatives 9a-c. The reaction of triethyl orthoformiate with compounds 9a-c led to furo[2′,3′: 4,5]pyrrolo[1,2-d][1,2,4]triazolo[3,4-f][1,2,4]triazines 10a-c. Hydrazones 11a-c were formed from 3a-c and 5-[3-(trifluoromethyl)phenyl]furan-2-carboxaldehyde. The effect of microwave irradiation on some condensation reactions was compared with “classical” conditions. The results showed that microwave irradiation shortens the reaction time while affording comparable yields.     

Facile Route for the Synthesis of Pyridazine Derivatives: Unexpected Pathway to Benzothiazole,Benzimidazole, and Triazole Derivatives

4‐Amino‐5‐arylmethylidene‐3‐phenyl‐pyridazin‐6‐ones 7 have been synthesized and reacted with selected nucleophile reagents such as phenyl hydrazine, semicarbazide, semithiocarbazide, cyanoacetohydrazide, 2‐aminothiophenol, and 2‐phenylenediamine in ethanol triethyl‐amine solution. An unexpected 1‐phenyl‐3‐arylaziridene 10, 3‐aryl‐5‐oxo(thio)‐1,2,4‐triazole 21, 4‐amino‐3‐aryl‐6‐hydroxy‐pridazine 27, 2‐arylbenzothiazole 30a–c, and 2‐arylbenzimidazole 30d–f have been obtained, respectively. Also, 2‐aminothiophenol and 2‐phenylenediamine were reacted with N‐phenylmethylidene‐2‐cyanoacetohydrazide 2, affording the new 1,4‐benzodiazepine derivatives 35.     

Composés sulfurés hétérocycliques. CII. Action de l'hydroxylamine sur les dihydro-1,2 benzothiazine-3,1 thiones-4

Hydroxylamine reacts with 1-alkyl-1,2-dihydro-3,1-benzothiazine-4thiones ( 1 ), giving 1-alky1-3-hydroxy-2,3-dihydro-1H-quinazoline-4-thiones ( 2 ). The same reagent, in neutral medium, converts 1-aryl-1,2-dihydro-3,1-benzothiazine-4-thiones ( 3 ) into 1-aryl-4-hydroxyimino-1,4-dihydro-2H-3,1-benzothiazines ( 4 ). In acidic medium, the same starting materials lead to 1-aryl-3-hydroxy-2-3-dihydro-1H-quinazoline-4-thiones ( 5 ). genrally with some quantity of the isomer 4 . Thiones 2 and 5 , as well as oximes 4 , heated at 200°, decomopose, yielding, in varying proportions, 1H-quinazoline-4-thiones ( 6 or 7 ), 1H-quinazoline-4-ones ( 9 ) and 2,3-dihydro-1H-quinazoline-4-thiones ( 11 ). Reacting with methyliodide, 1H-quinazoline-4-thiones ( 7 ) give 4-methylthioquinazolin-1-ium iodidies ( 12 ) which can be hydrolysed into 1H-quinazolin-4-ones ( 9 ). The latter are also obtained by reacting benzonitrile N-oxide with the corresponding thiones. 1-Aryl-1 H-quinazoline-4-thiones ( 7 ) react readily with nitrogen nucleophiles XNH₂ to give 1-aryl-4-imino-1,4-dihydro-quinazolines diversely substituted on the imino group. While thiones 7 are S- methylated by methyl iodide, the corresponding 1-aryl-1H-quinazolin-4-ones (9), with the same reagent, ungergo a N-methylation, yielding 1-aryl-3-methyl-4-oxo-3,4-dihydroquinazolin-l-ium iodides ( 18 ). Structure have been confirmed by uv, ir and nmr spectra.     

Preparation of Resin-Bound Bismethylene Cyclic Malonic Acid Ester and Facile Solid-Phase Synthesis of 2-Alkylthio-4(1H)-quinolone and 2-Alkyl-4(1H)-quinolone

Abstract

The resin-bound bismethylthiomethylene cyclic malonic acid ester 3 was built up efficiently. Resin 3 can react with arylamines and subsequent thermal cyclizations give 2-alkylthio-4-(1H)-quinolones. Furthermore, conjugate addition of Grignard reagents to the resin 3 forms the resin 6 which was reacted with aryl amines and subsequent thermal-cyclization-cleavages afford the 2-alkyl-4-(1H)-quinolones.     

Substituierte 5-Hydroxypyrimidine und ihre O,O-Diethylphosphorsäure-, O,O-Diethylthiophosphorsäure-und N,N-Dimethylcarbamidsäureester

4-Alkyl (or aryl)-6-chloro-5-hydroxy-2-methylpyrimidines5a–5e, 4-alkyl (or aryl)-5-hydroxy-2-methyl-1H-pyrimidin-6-ones5g–5k and 6-alkyl (or aryl)-5-hydroxy-1H,3H-pyrimidin-2,4-diones5l–5n were prepared and converted into O,O-diethylphosphoric acid esters7a–7e, O,O-diethylphosphorothioic acid esters7f–7i and N,N-dimethylcarbamic acid esters8.

     

Synthesis and Antifungal Activities of ω‐[4‐Aryl‐5‐(1‐phenyl‐5‐methyl‐1,2,3‐triazol‐4‐yl)‐1,2,4‐triazol‐3‐thio]‐ω‐(1H‐1,2,4‐triazol‐1‐yl)acetophenones

New 4‐aryl‐5‐(1‐phenyl‐5‐methyl‐1,2,3‐triazol‐4‐yl)‐1,2,4‐triazol‐3‐thiones 3 have been synthesized by the intramolecular cyclization of 4‐aryl‐1‐(1‐phenyl‐5‐methyl‐1,2,4‐triazol‐4‐formyl)thiosemicarbazides 2 with an 8% NaOH solution, and then 3 reacted with ω‐bromo‐ω‐(1H‐1,2,4‐triazol‐1‐yl)acetophenone to afford ω‐[4‐aryl‐5‐(1‐phenyl‐5‐methyl‐1,2,3‐triazol‐4‐yl)‐1,2,4‐triazol‐3‐thio]‐ω‐(1H‐1,2,4‐triazol‐1‐yl)‐acetophenones 4 . The preliminary biological test showed that the representative compounds possess some anti fungal activities.     

Vinylcyclopropanation of norbornadiene,norbornene, and dispiroheptadiene by methyl esters of 1-alkylcyclopropene-3-carboxylic acids

Methyl esters of 1-alkylcyclopropene-3-carboxylic acids (I) in the presence of CuCl·P(OPh)₃ cyclopropanate the intracyclic norbornene double bonds of norbornene, norbornadiene, and dispiroheptadiene to give the corresponding vinylcyclopropane adducts in yields up to 80%. 3,5-Dioxo-4-oxatricyclo[5.2.1. 0^2,6]dec-8-ene and 5-acetyl-7-oxabicyclo[2.2.1]hept-2-ene, which are heteroanalogs of dicyclopentadiene and norbornene, are inert relative to (I).Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 214–216, January, 1990.     

Iron Carbonyl Induced Reactions of Norbornene Derivatives with Substituted Acetylenes

Photochemical reactions of norbornadiene with substituted acetylenes in the presence of Fe(CO)₅ gave various products of different types, depending on the nature of the acetylene. The results are summarized in Table 1. The cyclopentanone 1 was always formed in these reactions. In the reaction of disubstituted acetylenes such as dimethyl acetylenedicarboxylate and ethyl phenylpropiolate, the cyclopentenones 2 and 5 were formed, respectively. By contrast, propiolic esters produced the cyclohexenones 3 and 4 , in which the ester group was attached on the β carbon with respect to the keto group. Plausible mechanisms for the formation of these products are shown in Schemes 7 and 8. The reaction of diphenylacetylene gave the cyclohexendione 7 as well as the cyclopentenone 6 . Two enedione products 8 and 9 were obtained from the reaction of phenylacetylene. Compound 9 was converted to the aromatic diacetate 13 by heating with acetic anhydride in pyridine. On irradiation in the presence of Fe(CO)₅ norbornene reacted similarly with dimethyl acetylenedicarboxylate and phenylacetylene to give the cyclopentenone 14 and the cyclohexenone 15 , respectively. Compound 15 , upon heating, isomerized to hydroquinone 16 , which on acetylation gave the diacetate 17 .     

Synthesis of (<Emphasis Type="Italic">S</Emphasis>)-(-)-1,4-diaryl-6-methyl-4-trifluoromethyl-3,4-dihydropyrimidine-2(1<Emphasis Type="Italic">H</Emphasis>)-thiones

(S)-(+)-4-Amino-4-aryl-5,5,5-trifluoropentan-2-one reacted with aryl isothiocyanates containing electron-withdrawing substituents to give (S)-(−)-1,4-diaryl-6-methyl-4-trifluoromethyl-3,4-dihydropyrimidine-2(1H)-thiones.     

Über die Synthese von Derivaten des Fluoreno[1,9-ef-1,4-diazepins

Zusammenfassung Beim Behandeln von1-Chloracetylaminofluoren-9-on-oxim (6) mit verd. KOH entsteht 3,4-Dihydro-2H-fluoreno[1,9-ef]-1,4-diazepin-3-on-1-oxid (7); durch Erhitzen von 1-Aminoacetyl-amino-fluoren-9-on (10) sowie durch Kondensation von 1-Aminofluoren-9-on mit Glycinesterhydrochlorid wird 3,4-Dihydro-2H-fluoreno[1,9-ef]-1,4-diazepin-3-on (11) erhalten. Es wird bewiesen, daß es sich bei7 und11 um Derivate des Fluoreno[1,9-ef]-1,4-diazepins (2) handelt und daß7 das 1-Oxid von11 ist. Die Synthesen weiterer Derivate von2 werden beschrieben.

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On treating the oxime of 1-chloroacetylaminofluoren-9-one (6) with dilute aqueous potassium hydroxide, 3,4-dihydro-2H-fluoreno[1,9-ef]-1,4-diazepin-3-one-1-oxide (7), is formed; heating of 1-aminoacetylaminofluoren-9-one (10) and condensation of 1-aminofluoren-9-one with glycine ester hydrochloride both yield 3,4-dihydro-2H-fluoreno[1,9-ef]-1,4-diazepin-3-one (11). It is shown that both7 and11 are derivatives of fluoreno[1,9-ef]-1,4-diazepine (2) and that7 is the 1-oxide of11. The syntheses of several other derivatives of2 are reported.

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Herrn Prof. Dr.F. Wessely zum 70. Geburtstag.     

烃基硅铜酸盐与2-芳基-2-环烯酮1,4-加成反应的立体选择性及2-取代- 3-硅基环烷酮的合成

研究了烷基苯基硅铜酸盐与2-环烯酮的1,4-加成反应的立体选择性, 并合成了一系列新的2-取代-3-硅基环烷酮. 结果表明, 在0 ℃下用饱和NH₄Cl溶液处理, 烷基苯基硅铜酸盐与2-芳基-2-环烯酮的1,4-加成反应的立体选择性不同程度地受芳基和环的大小影响, 得到顺、反两种产物; 并首次发现室温下用甲醇处理反应时, 其立体选择性不受或者很少受环大小、芳基的性质以及与硅原子相连的取代基的影响, 只得到反式产物. 芳基溴甲烷与由烷基苯基硅铜酸盐与2-环烯酮1,4-加成所得的烯醇盐反应时, 只得到反式产物. 合成产物的结构用IR, ¹H NMR, ¹³C NMR, MS和HRMS等进行了表征.     

Facile,Highly Stereoselective Synthesis of Cyclopropyl Benzoimidazoles via Cyclopropanation of Olefin with Arsonium Ylides

A facile and highly stereoselective methodology for the preparation of highly functionalized trans-1,2-cyclopropanes containing benzoimidazolyl, cyano, aryl, and carbonyl groups 3 is described. Arsonium bromides 2 reacted with electron-deficient olefins 1 in the presence of KF·2H₂O to provide 3 exclusively with high stereoselectivity in moderate to good yields.     

Protolytic and potential antithyroid properties of thioglycolurils and fused azolo-1,2,4-triazines

The protolytic properties and reactions with molecular iodine and blood serum proteins of 5,7-dimethyltetrahydro-1H-imidazo[4,5-e]-1,2,4-triazine-3,6(2H,4H)-dithione and (R)-1,3-dialkyl-4-[(2-hydroxybenzylidene)amino]-5-thioxohexahydroimidazo[4,5-d]imidazol-2(1H)-ones were studied. These compounds exhibit different chemical reactivities towards molecular iodine. The binding constants between these compounds and serum albumin attest to a considerable protein affinity of the compounds. The properties of the thiones make them promising as antithyroid agents.

     

Heteroleptic palladium(II) complexes containing N-heterocyclic carbenes and 4-phenyl-1H-1,2,3-triazole: Synthesis,characterization, and catalytic application

Abstract

Reaction of the dimeric N-heterocyclic carbene (NHC) palladium compounds [Pd(μ-Cl)(Cl)(NHC)]₂ with 4-phenyl-1H-1,2,3-triazole gave four mono- and dinuclear complexes 1–4. Mononuclear complexes 1 and 2 [(NHC)PdCl₂(4-phenyl-1H-1,2,3-triazole)] were obtained when the reactions were performed in CH₂Cl₂, whereas dinuclear complexes 3 and 4 [Pd₂(μ-Cl)(μ-4-phenyl-1H-1,2,3-triazole)Cl₂(NHC)₂] were obtained when the reactions were performed in THF in reflux with Et₃N as the base. Further explorations of the catalytic properties of 1–4 for Pd-catalyzed transformations have been performed and these complexes exhibited moderate to high catalytic activities for Suzuki–Miyaura coupling and arylation of benzoxazoles with aryl bromides.     

Eisenpentacarbonyl-induzierte Reaktionen von Norbornadien und substituierten Olefinen

Iron Pentacarbonyl Induced Reactions of Norbornadiene and Substituted Olefins The photochemical reaction of norbornadiene and α, β-unsaturated nitriles, esters and amides in the presence of Fe(CO)₅ was studied. Nitriles furnished the dinorbornenyl ketones 2a-c (Scheme 1). Esters led to an addition of a norbornene moiety to the double bond giving the substituted α, β-unsaturated esters 10a and 10b (Scheme 5). Methacrylamide and methyl β-aminocrotonate gave the cyclopentanone derivatives 14 and 17 , respectively (Schemes 7 and 8). The reaction was in all cases highly stereoselective with general exo-substitution on the norbornadiene. The attack on the unsymmetric olefins occurred regiospecifically at that point of the double bond which was furthest away from the functional group. A plausible mechanism for these reactions is suggested in Schemes 10 and 11 .     

Synthesis of New 1,4-Benzodioxanуl-1,2,4-triazole Derivatives

The reaction of 5-(1,4-benzodioxan-2-yl)-4H-1,2,4-triazole-3-thiol with N-substituted chloroacetic acid amides obtained by condensation of chloroacetyl chloride with various primary amines furnished a series of S-amidomethyl derivatives. The corresponding thiazolotriazolone prepared from 2-[5-(1,4-benzodioxan-2-yl)-4H-1,2,4-triazol-3-ylthio]acetic acid reacted with aromatic aldehydes to form arylidene derivatives.

     

An unusual way of the reaction of PI3 with norbornene and norbornadiene

The iodination of norbornene and norbornadiene with phosphorus triiodide in the presence and in the absence of weak electrophiles (arylsulfenamides orN-chloramines) and with elemental iodine was studied. Depending on the reaction conditions, the reactions resulted in mono- or diiodides of the norbornene and norbornadiene series. All the compounds obtained were characterized by¹H and¹³C NMR spectra.     

Photoaddition Reactions of Benzoxazole‐2(3H)‐thiones to Cycloalkenes and Heteroaromatics

Photoaddition reactions of benzoxazole‐2‐thiones 1 with cycloalkenes 2 and heteroaromatics 3 were examined. Irradiation of N‐acylbenzoxazole‐2‐thiones 1a and 1b , and 3‐(methoxycarbonyl)‐ and 3‐(phenoxycarbonyl)benzoxazole‐2(3H)‐thiones ( 1f and 1h , resp.) in the presence of cycloalkenes 2a – 2c , cyclohexa‐1,4‐diene ( 2d ), and indene ( 2e ) yielded 2‐substituted benzoxazoles 4 – 13, 18 and 19 , and iminothietanes 14 – 17 , by intramolecular trapping of the acyl or MeOCO and PhOCO groups by thiolate anion of the zwitterionic intermediate I and by the phenolate anion of the zwitterionic intermediate II , respectively, derived from the spirocyclic amino‐thietanes AT formed by [2+2] cycloaddition of the C?S bond of 1 and C?C bond of 2 . Irradiation of 1 in the presence of heteroaromatics 3 gave the 2‐substituted benzoxazoles 20 – 33 exclusively.     

Ultrasound-Mediated Synthesis of 3,4-Dihydropyrimidin-2-(1H)-Ones (or Thiones) with NaHSO4·H2O

Abstract

A fast and efficient Biginelli synthesis of 3,4-dihydropyrimidin-2-(1H)-ones (or thiones) by the reaction of aromatic aldehydes, β-dicarbonyls, and urea/thiourea using NaHSO₄·H₂O/ultrasound system is presented. The reactions were carried out in refluxing n-hexane/CH₃CN (2.5:0.5 mL) to afford the products in excellent yields.