Umsetzung von 3-(Dimethylamino)-2H-azirinen mit 1,3-Oxazolidin-2-thion zu 3-(2-Hydroxyethyl)-2-thiohydantoinen

Reaction of 3-(Dimethylamino)-2H-azirines with 1,3-Oxazolidine-2-thione to 3-(2-Hydroxyethyl)-2- thiohydantoins The reaction of 3-(dimethylamino)-2H-azirines 1 and 1,3-oxazolidine-2-thione ( 6 ), in MeCN at room temperature, yields, after hydrolytic workup, 3-(2-hydroxyethyl)-2-thiohydantoins 7 (Scheme 2). In the case of the spirocyclic 1c , crystallization of the crude reaction mixture leads to spiro [cyclopentane-1, 7′(7′aH)-imidazo [4, 3-b] oxazole] -5′-thione 8c . The mechanism is discussed.     

Facile one-pot three-component synthesis of 4,6-diaryl-3,4-dihydropyrimidine-2(1H)-thiones under ultrasonic irradiation

Abstract

We developed a facile one-pot procedure for the synthesis of 4,6-diaryl-3,4-dihydropyrimidine-2(1H)-thione under ultrasonic irradiation. The method is based on a three components reaction of aldehydes, ketones, and thiourea under basic conditions affording isolated yields of up to 95% within a reaction time of 30–90?min.     

Convenient synthesis of 4H-chromenyl-tetrahydro-2H-pyrancarboxylates and cleavage of chromone and pyran rings leading to 5-(2-hydroxybenzoyl)-2-(trifluoromethyl)-1,2-dihydropyridine-3-carboxylates

4H-Chromenyl-tetrahydro-2H-pyrancarboxylates 3a–k have been conveniently prepared by the reaction of 3-formylchromones 1a–k and ethyl 4,4,4-trifluoro-3-oxobutanoate 2a with good yields. Thus obtained 4H-chromenyl-tetrahydro-2H-pyrancarboxylates 3a–k were reacted with amines 4a–e to provide series of 5-(2-hydroxybenzoyl)-2-(trifluoromethyl)-1,2-dihydropyridine-3-carboxylates 5a–o. The reaction proceeded via Michael addition (C-N bond formation) and followed by cleavage of chromone and pyran rings (C-O bond cleavage) in one pot.     

Base-mediated one-pot synthesis of 3,4,5,6-tetrahydro-4-substituted benzo[h]quinazoline-2(1H)-thione derivatives and evaluation of their antioxidant activity

One-pot three-component Beginelli-like reactions of a ketone 1, an aryl aldehyde 2, and thiourea 3 in the presence of sodium hydroxide are described. In this reaction, 3,4,5,6-tertrahydro-4-substituted quinazoline-2(1H)-thione derivatives 4a–h were obtained in good yields (73–85%). The compound 4a has been characterized by single crystal X-ray analysis. All the synthesized compounds 4a–h and 5a–b were screened for their in vitro antioxidant activity. Compounds 4c, 4e, and 4h have exhibited an excellent than the standard ascorbic acid. Compounds 4d, 4f, and 4g have also shown good activity. Remaining compounds show moderate antioxidant activity.     

Sodium bis(2-methoxyethoxy)aluminum hydride in reactions with 3-cyano-6-methylpyridine-2(1H)-thione and 3-cyano-6-methyl(4,6-dimethyl)-2-methylthiopyridines

The reactions of sodium bis(2-methoxyethoxy)aluminum hydride with 3-cyano-6-methylpyridine-2(1H)-thione and 3-cyano-6-methyl-2-methylthiopyridine afforded 3-aminomethyl-6-methylpyridine-2(1H)-thione and azomethine of the pyridine series, respectively. The corresponding reaction with 3-cyano-4,6-dimethyl-2-methylthiopyridine gave rise to azomethine, substituted 3-aminomethylpyridine, and substituted dipyridylmethane.     

Über die Umsetzung von 2-Methyl-2,5-diphenyl-imidazolin-4-thion und 2-Methyl-2,5-diphenyl-4-chlor-2H-imidazol mit aliphatischen und aromatischen Aminen,Alkoholen und Phenolen

Zusammenfassung Aliphatische Amine bzw. Alkohole reagiren (in Gegenwart von PbO) mit 2-Methyl-2,5-diphenyl-imidazolin-4-thion (1) glatt zu 4-Alkylamino-2H-imidazolen (2 a-f, 7) bzw. 4-Alkoxy-2H-imidazolen (9 a-g). Die Darstellung von 4-Arylamino-2H-imidazolen (4 a-j) bzw. 4-Aroxy-2H-imidazolen (10 a-t) gelingt in guten Ausbeuten durch Umsetzung von 2-Methyl-2,5-diphenyl-4-chlor-2H-imidazol (3) mit aromatischen Aminen in siedenden Lösungsmitteln (Petroläther, Aceton) bzw. mit Phenolen in siedendem Aceton in Gegenwart von HCl-Acceptoren (K₂CO₃, Dabco). Die Umsetzung von3 mit Anthranilsäure liefert in 83proz. Ausbeute 1-Methyl-1,3-diphenyl-1H, 9H-imidazo[5,1-b]chinazolin-9-on (6). Aus3 und Thiophenol erhält man glatt 2-Methyl-2,5-diphenyl-4-phenylthio-2H-imidazol (11).

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On the reaction of 2-Methyl-2,5-diphenyl-imidazoline-4-thione and 2-Methyl-2,5-diphenyl-4-chloro-2H-imidazole with aliphatic and aromatic amines, alcohols and phenols (joint action of elemental sulfur and gaseous ammonia upon ketones, LXXVI

Aliphatic amines and alcohols (in the presence of PbO) easily react with 2-methyl-2.5-diphenyl-imidazoline-4-thione (1) to 4-alkylamino-2H-imidazoles (2 a-f, 7) and 4-alkoxy-2H-imidazoles (9 a-g), resp. 4-arylamino-2H-imidazoles (4 a-j) are prepared in good yields by the reaction of 2-methyl-2.5-diphenyl-4-chloro-2H-imidazole (3) with aromatic amines under reflux in light naphtha or acetone; in the same manner 4-aroxy-2H-imidazoles (10 a-t) are obtained from3 and phenols in boiling acetone in the presence of HCl-acceptors (K₂CO₃, Dabco). Reaction of3 with anthranilic acid leads to1-methyl-1.3-diphenyl-1H.9H-imidazo[5.1-b]chinazoline-9-one (6) in 83% yield. By reaction of thiophenol with3 2-methyl-2.5-diphenyl-4-phenylthio-2H-imidazole (11) is easily obtained.

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Herrn Prof. Dipl.-Ing., Dr. techn., Dr. e. h.Otto Kratky zum 70. Geburtstag herzlichst gewidmet.

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Teil der DiplomarbeitJ. Gräber, Techn. Hochschule Aachen, 1970.

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Teil der DiplomarbeitU. Lames, Techn. Hochschule Aachen, 1971.     

KF-alumina 催化下2-氨基-4-芳基-5,6-二氢化-4H-吡喃[3,2-c]喹啉-5-酮-3-羧酸酯衍生物的一步合成

以芳醛、氰乙酸酯和4-羟基喹啉-2-酮为原料, 乙醇为溶剂, 在KF-Al₂O₃催化下80 ℃, 一步合成了2-氨基-4-芳基-5,6-二氢化-4H-吡喃[3,2-c]喹啉-5-酮-3-羧酸酯衍生物, 和其它方法相比, 具有反应条件温和, 容易操作和产率高等优点, 产物4a的结构通过X单晶衍射分析确证.     

Notiz zur Struktur des Umsetzungsproduktes von 4-Isothiocyanato-4-methyl-2-pentanon mit Hydrazin —Über das 2,4,5,6-Tetrahydro-5,5,7-trimethyl-3H-1,2,4-triazepin-3-thion

On reaction of 4-isothiocyanato-4-methyl-2-pentanone (1) with hydrazine 2,4,5,6-tetrahydro-5,5,7-trimethyl-3H-1,2,4-triazepine-3-thione (4 a) is formed not 1-aminodihydro-2(1H)-pyrimidinethione (3 a) [1-aminodihydro-2-pyrimidinethiol (2 a)].     

Zur Umsetzung des 3,4,5,6-Tetrahydro-6-hydroxy-4,4,6-trimethyl-1,3-thiazin-2-thions mit primären Aminen

Tetrahydro-6-hydroxy-4,4,6-trimethyl-1,3-thiazine-2-thione (1 a) reacts with methyl-, ethyl- and n-butylamine to the corresponding 1-alkyl-6-alkylaminotetrahydro-2(1H)-pyrimidinethione12 but withi-propylamine to tetrahydro-6-isopropylamino-1,3-thiazine-2-thione (6 d). On treatment withDCC,6 d is rearranged to dihydro-4-isopropylamino-2(1H)-pyridinethione (8 d), and 6-amino-tetrahydro-1,3-thiazinethione (6 a) to dihydro-4,4,6-trimethyl-2(1H)-pyrimidinethione (10 a). The reaction of 6-aminothiazinethiones6 a, d and 6-(4-morpholinyl)-thiazinethione13 resp., with methylamine leads to 1-methyl-6-methylamino-pyridinethione12 b. 1-Alkyl-6-alkylamino-tetrahydro-2(1H)-pyrimidinethiones (12) react at reflux temperature to dihydro-1-alkylpyrimidinethiones10. With methylamine only 6-methylamino-3,4,4,6-tetramethyl-1,3-thiazine-2-thione (6 f) is formed from tetrahydro-6-hydroxy-tetramethyl-1,3-thiazine-2-thione (1 b).     

Unusual behavior of 3-(dimethylamino)-1-(2-hydroxyphenyl)prop-2-en-1-one towards some phosphorus reagents: Synthesis of novel diethyl 2-phosphonochromone,diethyl 3-phosphonopyrone and 1,3,2-oxathiaphosphinines

The chemical reactivity of 3-(dimethylamino)-1-(2-hydroxyphenyl)prop-2-en-1-one (1) towards some phosphorus reagents was studied. The enaminone 1 was cyclized into diethyl 2-phosphonochromone 2 via its treatment with diethyl phosphite in basic medium. However, its reaction with triethoxy phosphonoacetate gave the substituted pyrone phosphonate 3. In addition, two novel examples of 4-(dimethylamino)-6-(2-hydroxyphenyl)-2-sulfido-4H-1,3,2-oxathia-phosphinines 6 and 7 were obtained from treatment of enaminone 1 with O,O-diethyl dithiophosphoric acid and Lawesson’s reagent. When enaminone 1 was also treated with phosphorus decasulfide, it was turned into 4H-thiochromene-4-thione while its treatment with phosphorus tribromide, phosphorus oxychloride, or phenylphosphonic dichloride, 4H-4-oxo-chromene was isolated in all cases. The possible reaction mechanisms of the formation of these products were discussed. The structures of newly isolated products were established by elemental analysis and spectral tools.     

A 2-D nickel coordination polymer with an unsymmetric ligand, 5-(3-pyridyl)-1,3,4-oxadiazole-2-thione

A new nickel coordination polymer was obtained from an unsymmetric building block 5-(3-pyridyl)-1,3,4-oxadiazole-2-thione (HL6) and Ni(NO₃)₂ · 6H₂O-afforded [Ni(L6)₂(H₂O)₂] _n (1) with a (4,4) network. Complex 1 exhibits moderate antimicrobial activity against Bacillus subtilis ATCC 6633 and Candida albicans ATCC 90028. Thermogravimetric data and magnetic moments for 1 have been investigated.     

Synthesis of 3-aminothiophene-2-thioamides

Summary 4-Dimethylamino-5,6-dihydro-2H-thiopyran-2-thiones (1) were alkylated to N,N-dimethyl-6-methylthio-2H-thiopyran-4(3H)-iminiumiodides (2). Aminolysis of the latter with ammonia led to 6-dimethylamino-2H-thiopyran-4(3H)-iminiumiodides (3) which were hydrolyzed to 3-amino-N,N-dimethyl-2,4-pentadienthioamides (4). Ring closure with sulfur gave 3-aminothiophene-2-thioamides (5). The configurations of the pentadienthioamides (4) have been investigated by NOE experiments. The structures of the thiophene-2-thioamides (5) were established by means of two-dimensional NMR techniques.

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Synthese von 3-Aminothiophen-2-thiocarboxamiden

Zusammenfassung 4-Dimethylamino-5,6-dihydro-2H-thiopyran-2-thione (1) wurden zu N,N-Dimethyl-6-methylthio-2H-thiopyran-4(3H)-iminiumiodiden(2) alkyliert. Die Umsetzung mit Ammoniak führte zur Bildung von 6-Dimethylamino-2H-thiopyran-4(3H)-iminiumiodiden (3). Diese wurden zu 3-Amino-N,N-dimethyl-2,4-pentadienthioamiden (4) hydrolysiert. Beim Erhitzen mit Schwefel erfolgte Cyclisierung zu 3-Aminothiophen-2-thiocarboxamiden (5). Die Konfiguration der Pentadienthioamide (4) wurde mit NOE-Messungen untersucht, die der Thiophen-2-thiocarboxamide (5) mit Hilfe zweidimensionaler NMR-Methoden aufgeklärt.

     

Simple Synthesis of Stable Phosphorus Ylides Derived from Imidazolidine-2-Thione. Efficient One-Pot Synthesis of α-Amino Esters with β-Phosphorus Substituents

Crystalline phosphorus ylides are obtained in nearly quantitative yields from the addition reaction between triphenylphosphine, dialkyl acetylenedicarboxylates, and imidazolidine-2-thione. A dynamic NMR effect is observed in the ¹ H NMR spectrum of the stabilized ylide obtained from dimethyl acetylenedicarboxylate (Δ G ^≠ = 66.6 kJmol^?1 ) and is attributed to restricted rotation around the carbon–carbon partial double bond resulting from the conjugation of the ylide moiety with the adjacent carbonyl group.     

Reactions of substituted furo[3,2-<Emphasis Type="Italic">b</Emphasis>]pyrrole-5-carboxhydrazides and their biological activity

The reactions of substituted furo[3,2-b]pyrrole-5-carboxhydrazides 1 with 5-arylfuran-2-carboxaldehydes 2, 4,5-disubstituted furan-2-carboxaldehydes 3 and thiophene-2-carboxaldehyde 4 has been studied. The advantage of microwave irradiation on some of these reactions was reflected in the reduced reaction time and increased yields. Reactions of 1 with 4-substituted 1,3-oxazol-5(4H)-ones 11 led to diacylhydrazines 13 or to imidazole derivatives 14 depending on the temperature. 1,2,4-Triazole-3-thione 17 was synthesized by two-step reaction of 1 with phenylisothiocyanate and subsequent base-catalyzed cyclization of thiosemicarbazide 16. The effects of hydrazones 5–10 on inhibition of photosynthetic electron transport in spinach chloroplasts and chlorophyll content in the antialgal suspensions of Chlorella vulgaris were investigated.     

Synthesis and characterization of complexes of organotin(IV) with 2-thiazoline-2-thione

The reaction of 2-thiazoline-2-thione (TZDSH) with SnR₂Cl₂ (R=Ph 1, Me 2, Bu 3) in dry ethanol in the presence of sodium ethoxide leads to [SnR₂(C₃H₄NS₂)₂] (1, 2, and 3), respectively. Reaction between TZDSH and SnPh₂Cl₂ in dichloromethane and dry ethanol in an inert atmosphere produces [SnPh₂Cl₂(C₃H₅NS₂)₂] (4). The yields of the products were over 80%. These new complexes have been characterized by IR, UV-Vis, multinuclear (¹H, ¹³C, and ¹¹⁹Sn) NMR spectroscopy, and mass spectrometry, as well as elemental analysis.     

H6P2W18O62·14H2O as an efficient catalyst for the green synthesis of α-aminophosphonates from α-amino acids

Abstract

A simple, efficient and eco-friendly protocol has been described for the synthesis of α-aminophosphonates via Kabachnik-Fields reaction, catalyzed by H₆P₂W₁₈O₆₂·14H₂O as a reusable catalyst. The reaction was realized by condensation of amino acids, various aromatic aldehydes and triethylphosphite under solvent-free conditions, the corresponding α-aminophosphonates were formed in good yields. All the new products were characterized by IR, ¹H, ¹³C and ³¹P-NMR analyses. This method offers advantages such as simplicity workup with the green aspects, good yields and short reaction times.     

Synthesis of 2-oxo and 2-thioxo-3(2H)-benzothiazoleethanimic acid anhydride with acetic acid and related products

The reaction of the appropriate 2-benzothiazolinone with 2-chloroacetamide under basic conditions afforded the 2-oxo-3(2H)-benzothiazolineacetamides 6–9. The 2-thioxo-3(2H)-benzothiazolineacetamide ( 10 ) was prepared by the reaction of 3-(carbethoxymethyl)benzothiazoline-2-thione with ammonium hydroxide. The reaction of acetamides 6–10 with the appropriate anhydride containing a catalytic amount of the sodium salt of the acid corresponding to the anhydride afforded the titled compounds 11–18 in excellent yields. The omission of the catalyst in the same reaction furnished a mixture containing 57% of the titled compound, 37% of the nitrile and 6% of an unknown. Possible mechanism and supporting nmr, ir and mass spectral data are discussed.     

Zur Einwirkung von Schwefel und Aminen auf Dihydro-2(1H)-pyrimidinone bzw.-thione

Zusammenfassung Dihydro-4,4,6-trimethyl-2(1H)-pyrimidinone (1) bzw.-thione reagieren mit Schwefel und Morpholin zu Tetrahydro-2-oxobzw.-2-thiono-4,4-dimethylpyrimidin-6-thiocarbonsäuremorpholiden (3); mit Schwefel in Dimethylformamid bzw. Tetramethylharnstoff bilden sich Dihydro-3-thiono-3H-1,2-dithiolo-[4,3—d]pyrimidin-5(4H)-one (5) bzw.-3,5-dithione. Das Dihydro-6-methyl-4-phenyl-2(1H)-pyrimidinon2 bzw.-thion geben mit Schwefel und Tetramethylharnstoff das Dihydro-1-methyl-2-oxo-bzw.-2-thiono-4-phenylpyrimidin-6-trimethylcarboxamidin (7). Methylheterocyclen, wie Chinaldin, werden bei analoger Behandlung in Chinolin-2-thiocarbonsäuredimethylamid usw. übergeführt.

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Reaction of sulfur + amines with dihydro-2 (1H)pyrimidinones and-thiones

Dihydro-4,4,6-trimethyl-2(1H)-pyrimidinones (1) and-thiones react with sulfur and morpholine to tetrahydro-2-oxo- and-2-thiono-4,4-dimethylpyrimidine-6-thiocarboxylic acid morpholides (3); with sulfur inDMF or tetramethylurea (TMU) the formation of dihydro-3-thiono-3H-1,2-dithiolo[4,3—d]pyrimidin-5(4H)-ones (5) or-3,5-dithiones, resp. was observed. Dihydro-6-methyl-4-phenyl-2(1H)-pyrimidinone (2) (-thione) with sulfur andTMU yields dihydro-1-methyl-2-oxo- and-2-thiono-4-phenylpyrimidin-6-trimethyl-carboxamidine (7). Methyl substituted heterocycles e.g. quinaldine, are converted under analogous conditions to quinoline-2-thiocarboxylic acid dimethylamide and corresponding compounds. *** DIRECT SUPPORT *** A3615139 00018

     

Synthese von 4H-Pyrano[2,3-d]pyrimidinen

Summary Good yields of substituted 5-(5R-2-furyl)-4H-pyrano[2,3-d]pyrimidines4 were obtained in the reaction of 2-ethoxymethyleneamino-3-cyano-4H-pyranes2 with ammonia. Compounds2 were prepared by the condensation of the starting 2-amino-5-acetyl-3-cyano-6-methyl-4H-pyranes1 with ethyl orthoformate. Spectral properties of the bicyclic system4 in relation to compounds3 are discussed.

     

Unprecedented Multicomponent Reaction of Indoles,CS2 and Nitroarenes: Stereoselective Synthesis of (Z)-3-((Arylamino)methylene)indoline-2-thiones

An efficient method for the stereoselective synthesis of (Z)-3-((arylamino)methylene)indoline-2-thiones have been developed via a novel multicomponent reaction of indoles, CS₂ and nitroarenes. A range of functionalized indoline-2-thiones were prepared in moderate to good yields from easily available starting materials. The indoline-2-thione products can be easily derivatized to give biologically active thieno[2,3-b]indole and thiopyrano[2,3-b]indole skeletons in high yields.