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.

     

Synthesis and antimicrobial activity of some 2-alkyl-2H-1,4-benzothiazin-3(4H)-ones and 2-alkylbenzo[d]imidazolo[2,1-b]-thiazolidin-3-ones

Summary Sodium 2-aminothiophenoxide (1) reacts with ethyl 2-bromoalkanoates (2) under direct cyclization to form 2-alkyl-2H-1,4-benzothiazin-3(4H)-ones (3). Reaction of the sodium salt of 2-mercaptobenzimidazole (4) with2 or 2-bromoalkanoic acids (5) affords only S-alkylated products (6 or7, respectively). The cyclization products — 2-alkylbenzo[d]imidazolo[2,1-b]thiazolidin-3-ones (8) — can be obtained only from the corresponding 2-(2-benzimidazolylthio)alkanoic acids (7) by the action of acetic anhydride. Both compounds3 and8 exhibit only moderate antimicrobial activity against some gram-positive bacteria.

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Synthese und antimikrobielle Wirkung von einigen 2-Alkyl-2H-1,4-benzothiazin-3(4H)-onen und 2-Alkylbenzo[d]imidazolo[2,1-b]thiazolidin-3-onen

Zusammenfassung Bei der Reaktion von Natrium-2-aminothiophenolat mit 2-Bromoalkansäure-ethylestern (2) entstehen als Cyclisierungsprodukte 2-Alkyl-2H-1,4-benzothiazin-3(4H)-one (3). Die Umsetzung von Natriumbenzimidazol-2-thiolat mit2 oder mit 2-Bromoalkansäuren (5) liefert nur S-Alkylierungsprodukte (6 oder7). Die Cyclisierungsprodukte — 2-Alkylbenzo[d]imidazolo[2,1-b]thiazolidin-3-one (8) — sind nur durch Umsetzung von entsprechenden 2-(2-Benzimidazolylthio)-alkansäuren (7) mit Acetanhydrid erhältlich. Die Verbindungen3 und8 weisen nur mäßige antimikrobielle Wirkung gegen einige gram-positive Bakterien aus.

     

Natural product chemistry,part 137: Oxidation of acridone alkaloids: Synthesis of 5-methoxyacronycine

Summary Epoxidation of the acridone alkaloid acronycine (1) resulted in hydroxylation at the aromatic ring giving 5-hydroxyacronycine (3). The same reaction on 1,3-dimethoxy-10-methyl-9(10H)-acridinone (5) gave 1,3-dimethoxy-2-hydroxy-10-methyl-9(10H)-acridinone (6), 1,3-dimethoxy-2-hydroxy-4-peroxy-10-methyl-9(10H)-acridinone (8), and 1,3-dimethoxy-2,4-diperoxy-10-methyl-9(10H)-acridinone (9).

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Naturstoffchemie, 137. Mitt.: Oxidierung von Acridonalkaloiden: Synthese des 5-Methoxyacronycins (Kurze Mitt.)

Zusammenfassung Die Epoxidierung des Acridonalkaloids Acronycin führte zu einer Hydroxylierung des aromatischen Rings, wobei 5-Hydroxyacronycin (3) entstand. Die gleiche Reaktion mit 1,3-Dimethoxy-10-methyl-9(10H)acridinon (5) ergab 1,3-Dimethoxy-2-hydroxy-10-methyl-9(10H)acridinon (6), 1,3-Dimethoxy-2-hydroxy-4-peroxy-10-methyl-9(10H)acridinon (8) und 1,3-Dimethoxy-2,4-diperoxy-10-methyl-9(10H)acridinon (9).

     

Zur Synthese der 4-Dialkylamino-5,6-dihydro-2(1H)-pyridinthione sowie entsprechender 4-Alkylamino- bzw. 4-Arylaminoverbindungen

The rearrangement of 1-alkyl- and 1-aryldihydro-6-methyl-2(1H)-pyrimidinethiones (1 a) or-ones (1 b) and of methylene compounds (2a, 2b) resp., to 4-alkylamino- and 4-arylaminodihydro-2(1H)-pyridinethiones (4 a) or-ones (4 b) takes place via the corresponding 3-alkylamino- and 3-aryl-amino-3-butenylisothiocyanates (3 a) or-isocyanates (3 b). Dialkylamino-dihydro-2(1H)-pyridinethiones (10) are formed by heating dihydro-6-methyl-2(1H)-pyrimidinethiones (6 a) and 3,4-dihydro-6-methyl-1,3-thiazin-2-thiones (6 b) with dialkylformamides and by the reaction of secondary amines with tetrahydro-6-hydroxy-6-methyl-1,3-thiazin-2-thiones (5 a), with N,N-dialkyl-N-(3-oxobutyl)-thioureas (7) and 3-oxobutyl isothiocyanates (8). A general method for the preparation of10 is the reaction of dialkylammoniumrhodanides12, N,N-dialkylthioureas13 and dialkylammonium chlorides and KCNS, resp., with 3-alken-2-ones14 and 4-hydroxy-2-alkanones15, resp. Methyl ketones such as acetone, which readily undergo the aldol condensation, behave analogously. The reactions described take place via the intermediate aminoalkenyl isothiocyanates (9).     

(±)-Shegansu B,Gnetuhainin F, (±)-Maackin A与(±)-Cassigarol E的全合成

对四种天然二聚二苯乙烯类化合物Shegansu B (1), Gnetuhainin F (1a), Maackin A (2)以及Cassigarol E (3)的全合成进行了研究. 以3,5-二羟基苯甲酸(4)为起始原料, 经六步反应制得异丹叶大黄素(13)和白皮杉醇(14), 在HRP/H₂O₂酶催化氧化体系中, 13和14分别进行自身的氧化偶联得到各自的二聚产物. 首次完成了1a, (±)-2和(±)-3的全合成, 并以较文献报道为高的氧化偶联产率合成了(±)-1.     

OPTICAL ISOMERS OF 2,2′-DIAMINOBIPHENYLBIS(ETHYLENEDIAMINE) COBALT(III) CHLORIDE AND ITS RELATED COMPLEXES1

Abstract

Several cobalt(III) complexes incorporating 2,2′-diaminobiphenyl(dabp) and other 2(2N)- or 4N-type ligands were prepared and resolved by chemical and chromatographic methods: (1) [Co(en)₂(dabp)]Cl₂2H₂O, (2) [Co(l-pn)₂(dabp)] (ClO₄)₃4H₂O, (3) [Co(l-chxn)₂(dabp)](ClO₄)₃3H₂O, (4) α-[Co(trien)(dabp)](ClO₄)₃, (5) α-[Co(2S,9S-dimetrien)(dabp)] (ClO₄)₃ 2H₂O, (6) α-[Co(3S,8S-dimetrien)(dabp)] (ClO₄)₃3H₂O, (7 [Co(tren)(dabp)]Cl₃5H₂O, (8) [Co(bpy)₂(dabp)] Cl₃3H₂O. The complexes (1), (4) and (8) gave one pair of enantiomers, Δ(Λ) and Λ(δ), and the complexes (2) and (3) gave only one Δ-isomer. The absolute configuration of the complexes (5) and (6) was found to be Λ, and that of (7) was not determined because of unsuccessful resolution. The three geometric isomers of the complex (2) were separated and their structures assigned.     

Studies on Phosphonium Ylides,XXIV: Reactions of Phosphorus Ylides with 1,2,3,4-Tetrahydro1-Naphthylidene-Malononitrile

1,2,3,4-tetrahydro-1-naphthylidene-malononitrile (1) reacts with carbethoxymethylene and carbmethoxymethylene- triphenylphosphoranes (2a, 2b) to give the new phospho-ranylidenecyclopentaylidene products (4a, 4b, and 5), respectively. The treatment of (1) with phosphorus ylide 2c afforded the new phosphonium ylide 6. Moreover, the application of reagent (2d) on (1) renders compound 7. On the other hand, when N-phenyliminotriphenylphosphorane (3) reacts with (1), the corresponding adduct (8) was obtained together with triphenylphosphine. Mechanisms accounting for the formation of new products are discussed, and probable structures of products are presented based on analytical and spectroscopic data.     

Über das 4-Hydroxy-6,6-dimethyl-5,6-dihydro-2(1H)-pyridinthion bzw.-on und die entsprechenden Tautomeren

The tautomers, 4-hydroxy-5,6-dihydro-6,6-dimethyl-2(1H)-pyridinethione (1) and 6,6-dimethyl-2-thioxo-4-piperidone (2) resp., and 4-hydroxy-5,6-dihydro-6,6-dimethyl-2(1H)-pyridone (9) and 6,6-dimethyl-2,4-piperidinedione (10) resp. were synthesized by hydrolysis of 4-amino-5,6-dihydro-6,6-dimethyl-2(1H)-pyridinethiones (4, 5) and-ones (11, 12).1, 2 and9, 10 undergo an aminolysis in amines to the corresponding 4-aminodihydro-2(1H)-pyridinethiones4, 5 and-ones11, 12 resp.

     

利用甾体皂甙元氧化降解废弃物(R)-4-甲基-δ-戊内酯合成松叶蜂主要性信息素(2S,3S,7S)-3,7-二甲基-2-十五醇乙酸酯和丙酸酯

首次利用甾体皂甙元氧化降解废弃物(R)-4-甲基-δ-戊内酯合成了松叶蜂性信息素(2S,3S,7S)-3,7-二甲基-2-十五醇乙酸酯(2)和丙酸酯(3). 甾体皂甙元氧化降解废弃物(R)-4-甲基-δ-戊内酯首先被转化成为性质稳定易保存的(R)-5-溴-4-甲基戊酸甲酯(5), 化合物5经过偶联、还原、溴代、环氧加成开环和酰化反应给出目标分子. 本研究结果不仅为松叶蜂性信息素化合物2和3提供了一个简洁有效的合成方法, 同时也丰富了资源化学(即基于资源性化合物合理利用的有机合成化学)的内涵.     

Formation of Chromene Analogs of Homophthalates: Investigation of Condensation Products Derived from 2-Hydroxybenzaldehydes and Diethyl 2-Pentenedicarboxylates

Condensation of substituted 2-hydroxybenzaldehyde derivatives (1a-1) with diethyl 2-pentenedicarboxylate (2) in the presence of piperidine gave coumarin and / or chromene derivatives. Attempted reaction of 4-N,N-diethylamino-2-hydroxybenzaldehyde (1a) and 2-hydroxy-3-nitrobenzaldehyde (1i) with diethyl 3-phenyl-2-pentenedicarboxylate (5) led to formation of no coumarin or chromene derivative.     

Diisophorone and related compounds. Part 12 Synthesis of 4-bromodiisophorones and their reactions with nucleophiles

4-Bromodiisophor-2(7)-en-1-ol-3-one (2) is accessible by the action of hydrobromic acid on 2,7-epoxydiisophoran-1-ol-3-one (1), and is convertible into the corresponding 1-carboxylic acid (9) by theKoch-Haaf reaction. Nucleophilic substitution displaces the halogen in both the 4-bromoketol (2) and the 4-bromoketo-acid (9). Amongst the products thus obtained, 4-hydroxy-1-carboxydiisophor-2(7)-en-3-one (11) is of special interest as a source of the 3,4-diketo-1-carboxylic acid (13).

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Diisophoron und verwandte Verbindungen, 12. Mitt.: Synthese von 4-Bromdiisophoronen und ihre Reaktion mit Nucleophilen

Zusammenfassung 4-Bromdiisophor-2(7)-en-1-ol-3-on (2) ist durch Einwirkung von Bromwasserstoffsäure auf 2,7-Epoxydiisophoran-1-ol-3-on (1) erhältlich und wird mittels derKoch-Haaf-Reaktion zur entsprechenden 1-Carbonsäure (9) umgesetzt. Durch nucleophile Reagenzien wird das Halogen sowohl im 4-Bromketol (2) als auch in der 4-Bromoketosäure (9) substituiert. Unter den so erhältlichen Produkten ist das 4-Hydroxy-1-carboxydiisophor-2(7)-en-3-on als Ausgangsmaterial für die 3,4-Diketo-1-säure (13) von zusätzlichem Interesse.

     

Titanium-dioxide-mediated photocatalysed reaction of selected organic systems

The photocatalysed reaction of four selected organic systems, namely dichlone (1), 2-amino-5-chloropyridine (2), benzoyl peroxide (3) and 3-chloro perbenzoic acid (4), has been investigated in an acetonitrile/water mixture in the presence of titanium dioxide and oxygen. An attempt has been made to identify the products formed during the photo-oxidation process using the GC/MS analysis technique. The photolysis of dichlone (1) leads to the formation of phthalic anhydride (11) and 1H-indene-1,2,3-trione (10), whereas 2-amino-5-chloropyridine (2) gave rise to 2,2′-diamino bipyridyl (14), 2-pyridinamine (16), 2-hydroxy-5-chloropyridine (18), bipyridyl (19) and 2-amino bipyridyl (21). The photolysis of benzoyl peroxide (3) yielded a mixture of products such as benzoic acid (24), biphenyl (27), biphenyl-4-carboxylic acid (29) and benzoic acid phenyl ester (30). Two intermediate products, as 3-chlorobenzaldehyde (35) and hydroxyl added 3-chlorobenzaldehyde (33), have been identified in the case of 3-chloro perbenzoic acid (4). The products have been identified by comparing the molecular ion and mass fragmentation peaks of the products with those reported in the GC-MS library. A probable mechanism for the formation of the products has been proposed.     

Acetylene chemistry,part 32: Alkinylation and cyclic rearrangement of theophylline with unsaturated alcohols by Mitsunobu reaction

Summary The reaction of theophylline (1) with 2-methyl-3-butyn-2-ol and 1-butyn-3-ol under Mitsunobu conditions gave the respective 9-substituted derivatives 9-[2-(2-methyl-3-butynyl)]-theophylline (2) and 9-[2-(3-butynyl)]-theophylline (3). On reaction with 2-methyl-3-buten-2-ol, theophylline yielded in addition to the 9-[2-(2-methyl-3-butenyl)]-theophylline (4), two more cyclic products, identified as 1,5,5a,8-tetrahydro-1,3,8,8-tetramethyl-2H-pyrrolo[1,2-e]purine-2,4(3H)-dione (5) and 8a,9-dihydro-1,3,6,6-tetramethyl-1H-pyrrolo[2,1-f]purine-2,4(3H,6H)-dione (7).

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Acetylenchemie, 32. Mitt.: Alkinylierung und cyclische Umlagerung von Theophyllin mit ungesättigten Alkoholen mittels Mitsunobu-Reaktion

Zusammenfassung Die Reaktion von Theophyllin (1) mit 2-Methyl-3-butin-2-ol und 1-Butin-2-ol unter Mitsunobu-Bedingungen führte zu den 9-substituierten Derivaten 9-[2-(2-Methyl-3-butinyl)]-theophyllin (2) bzw. 9-[2-(3-Butinyl)]-theophyllin (3). Bei der Reaktion mit 2-Methyl-3-buten-2-ol ergab Theophyllin außer 9-[2-(2-Methyl-3-butenyl)]-theophyllin (4) noch zwei weitere cyclisierte Produkte, die als 1,3,8,8-Tetramethyl-1,5,5a,8-tetrahydro-pyrrolo[1,2-e]purin-2,4(3H)-dion (5) und 1,3,6,6-Tetramethyl-8a,9-dihydro-1H,6H-pyrrolo[2,1-f]purin-2,4-dion (7) identifiziert wurden.

     

Oxazepines and thiazepines,XXIV synthesis of optically active 2,3-dihydro-2-methyl-1,5-benzoxazepin-4(5H)-ones

Summary 2,3-Dihydro-2(R)-methyl-1,5-benzoxazepin-4(5H)-one [(R)-3] and its enantiomer (S)-3 have been synthesized via the optical resolution and subsequent chemical transformations of (±)-3-(2-nitrophenoxy)butyric acid (1). Compounds (R)-3 and (S)-3 were converted into optically active 1,5-benzoxazepines (R)-7–(R)-14 and (S)-15–(S)-32.

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Oxazepine und Thiazepine, XXIV: Darstellung optisch aktiver 2,3-Dihydro-2-methyl-1,5-benzoxazepin-4(5H)-one

Zusammenfassung 2,3-Dihydro-2(R)-methyl-1,5-benzoxazepin-4(5H)-on [(R)-3] und sein Enantiomeres (S)-3 wurden durch Racemattrennung und weitere chemische Umsetzungen von (±)-3-(2-Nitrophenoxy)buttersäure (1) dargestellt. Die Verbindungen (R)-3 und (S)-3 wurden in die optisch aktiven 1,5-Benzoxazepine (R-7 bis (R)-14 und (S)-15 bis (S)-32 übergeführt.

     

Synthesen von Heterocyclen, 105. Mitt.: Über Synthesen mit Kohlensuboxid

Die bei der Einwirkung von Kohlensuboxid auf Benzoylaceton sowie auf 4-Hydroxy-5-acetyl-6-phenyl-pyron-(2) (2) und 4-Hydroxy-5-benzoyl-6-methyl-pyron-(2) (3) entstehenden Produkte werden als Pyrono-pyrone (4, 5 und6) erkannt.The reaction of carbon suboxide with benzoyl acetone (1) and 5-acetyl-4-hydroxy-6-phenyl-pyron-(2) (2) and 5-benzoyl-4-hydroxy-6-methyl-pyron-(2) (3) yields the pyrono-pyrones4, 5 and6.     

4-溴-2-环戊烯砜酯化衍生物的合成

以3,4-二溴环戊砜(1)为原料, 在无水吡啶作用下发生消除反应, 得到反应中间体4-溴-2-环戊烯砜(2), 再分别与一系列取代苯甲酸盐3a～3c以及茜素黄GG (3d)发生酯化反应, 合成出4种新环戊烯砜衍生物4a～4d, 并用IR, ¹H NMR, MS, 元素分析等表征了它们的结构.     

Synthesis of 4-thia analogues of isoquinoline alkaloids

Summary (±)-4-Thiacarnegin (3) was synthesized by reaction of 6,7-dimethoxy-3-methyl-2H-1,3-benzothiazinium iodide (2) with methyl magnesium iodide, thereby opening a new synthetic route to 4-substituted dihydro-2H-1,3-benzothiazines. Compound3 was also obtained by reduction of 6,7-dimethoxy-3,4-dimethyl-2H-1,3-benzothiazinium iodide (5). In a similar way, reduction of the quaternary salts9 a–c afforded the (±)-4-thia analogues of cryptostilin-I, -II and -III (10 a–c). The isomers of the former compounds (12 a–c) were also synthesized by reduction of the 4H-1,3-benzothiazinium salts11 a–c.

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Synthese von 4-Thiaanalogen von Alkaloiden mit Isochinolingerüst

Zusammenfassung Aus 6,7-Dimethoxy-3-methyl-2H-1,3-benzothiaziniumjodid (2) wurde mit Methylmagnesiumjodid (±)-Thiacarnegin (3) dargestellt. Diese Reaktion bietet ein neues Verfahren für die Synthese von 4-substituierten Dihydro-2H-1,3-benzothiazinen.3 wurde auch durch Reduktion von 6,7-Dimethoxy-3,4-dimethyl-2H-1,3-benzothiaziniumjodid (5) erhalten. Die Reduktion der quartären Ammoniumsalze9 a–c ergab ebenfalls die Cryptostillin I-, II-, III-(±)-4-thiaanalogen Verbindungen (10 a–c). Reduktion der 4H-1,3-Benzothiazinium-Salze11 a–c lieferte die entsprechenden Isomeren12 a–c der obengenannten Verbindungen.

     

Supramolecular assemblies tailored by dipyridyl-1,2-4-thiadiazoles: influence of the building blocks in the predictability of the final network

ABSTRACT

Coordinatively unsaturated dithiophosphato complex [Cd((MeO)₂PS₂)₂] (1) was reacted with the bifunctional ligands 3,5-di-(4-pyridyl)-1,2,4-thiadiazole (L1) and 3,5-di-(3-pyridyl)-1,2,4-thiadiazole (L2) to give the helicoidal coordination polymer (1·L1)_∞ and the paddle-wheel dimer (1·L2)₂, both characterised by single-crystal X-ray diffraction. A comparison of the structures with the different supramolecular constructs obtained by reacting L1 and L2 with differently P-substituted dithiophosphoric Ni^II complexes allowed to evaluate the role of the metal ion for the predictable assembly of this class of coordination polymers.     

A study of the Claisen rearrangement of 7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one derivatives

Summary The Claisen rearrangement of 7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one (2 a) gave 7-hydroxy-8-(1-phenyl-2-propenyl)-3-phenyl-(4H)-1-benzopyran-4-one (3 a) and 2,3-dihydro-2,6-diphenyl-3-methyl-(7H)furo[2,3-h]-1-benzopyran-7-one (7 a). 2-Methyl-7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one (2 b) afforded4 b and7 b. 8-Methyl-7-(3-phenyl-2-propenyloxy)-3-phenyl-(4H)-1-benzopyran-4-one (12) gave only the alkali soluble product 7-hydroxy-8-methyl-6-(1-phenyl-2-propenyl)-3-phenyl-(4H)-1-benzopyran-4-one (13).3 a,4 b, and13 were further cyclized in acidic medium to9 a,10 b, and14 followed by dehydrogenation.This paper is dedicated to Dr. F. M. Dean, Department of Organic Chemistry, Robert Robinson Laboratories, University of Liverpool, Liverpool, U. K., on his retirement     

Polycondensation of Tris(Trimethylsilylseleno)Phosphane

Abstract

Tris-(trimethylsilyl)phosphane and their organo substituted derivatives (Me₃Si)_3?nP(Me₃C)_n (n: 0, 1, 2) (la-c) had been found suitable for the insertion of selenium into the phosphorus-silicon bond. At deep temperatures all silylselenophosphanes of the series (Me₃SiSe)_3?nP(Me₃C_n) (2a-c) are formed in a nearly quantitative reaction, if no excess selenium is present. (Me₃C)(Me₃SiSe)₂P=Se (3b) and (Me₃C)₂(Me₃SiSe)P=Se (3c) are detectable in small quantities as the only by-products of the reaction of (Ib-c), whereas (la) end in the formation of (2a) and traces of the dimer (Me₃SiSe)₂P-P(SeSiMe₃)₂ (4). On exposure to light or at elevated temperatures (2a) undergoes a disproportionation, forming Se=P(SeSiMe₃)₃ (3a), and the heterocycles P₃Se₄(SeSiMe₃) (5) and α-P₄Se₃(SeSiMe₃)₂ (6). (Me₃Si)₂Se is spUt off as a condensation product. After further irradiation or prolonged standing at room temperature, an insoluble oligomer is formed. The constitutions of (2-6) were determined by the analysis of their ³¹P- and ⁷⁷Se-nmr spectra.