Synthesis, structure and complexation of the fluorinated 1,3-enaminoketones containing at the nitrogen atom substituents with a terminal C≡C bond

The reaction of fluorinated lithium 1,3-diketonates with propargylamine hydrochloride and 1,1,1-trifluorpentane-2,4-dione or 1,1,1-trifluoro-4-methoxypent-3-en-2-one with propargylamine and 3-aminophenylacetylene were performed to obtain fluorinated 1,3-enaminones containing at a nitrogen atom substituents with terminal C≡C bonds: (Z)-1,1,1-trifluoro-4-(2-propynylamino)-3-pentene-2-one, (Z)-1,1,2,2-tetrafluoro-5-(2-propynylamino)-4-hexen-3-one, and 4-(3-ethynylphenylamino)-1,1,1-trifluoropentyl-3-en-2-one. Reactions of 4-(3-ethynyl-phenylamino)-1,1,1-trifluoro-pentyl-3-en-2-one with Cu(II) acetate or nanosized powder of copper or its oxides led to the respective chelate complex. The structure of (Z)-1,1,2,2-tetrafluoro-5-(2-propynylamino)-4-hexen-3-one and a copper complex of 4-(3-etinilphenylamino)-1,1,1-trifluoropenta-3-en-2-one was determined by XRD.     

Synthese von 3-Oxacholestanen

Successive treatment of 5α-cholestan-3-one ( 1 ) with O₂ under basic conditions and then NaBH₄ led to 5α-3-oxa-cholestan-2-one ( 5 ). Analogous reactions with 5β-cholestan-3-one ( 6 ) yielded 5α-4-oxa-cholestan-3-one ( 7 ) and 5 ξ-3-oxa-cholestan-4-one ( 8 ). 4-Cholesten-2-one ( 10 ), which was prepared starting from 4-cholesten-3-one, was isomerized by methanolic KOH to give a mixture of 5α-cholest-3-en-2-one ( 11 ) and 5β-cholest-3-en-2-one ( 12 ). 5β-Cholestane-2,3-dione ( 17 ) was synthesized from 4β-bromo-5β-cholestan-3-one ( 13 ). Ozonolysis of the dione 17 and subsequent NaBH₄ reduction of the oxidation product gave both 5β-2-oxa-cholestan-3-one ( 18 ) and 5β-3-oxa-cholestan-2-one ( 19 ).     

(5R,6R)-6-苯基-5-(苯磺酰基乙酰基)二环[2.2.1]-2-庚烯的合成及结构表征

报道了一种制备4-苯基-1-苯磺酰基-3-丁烯-2-酮的新合成方法. 4-苯基-3-丁烯-2-酮与溴化试剂Ph₃P^＋CH₂CH₂- COOHBr 作用, 得到1-溴-4-苯基-3-丁烯-2-酮, 不经分离直接与苯亚磺酸钠发生亲核取代反应, 得到4-苯基-1-苯磺酰基-3-丁烯-2-酮. 将此反应产物作为亲双烯体与环戊二烯在手性钛金属催化剂催化下进行不对称Diels-Alder反应, 得到了＞99% ee 的环加成产物(5R,6R)-6-苯基-5-(苯磺酰基乙酰基)二环[2.2.1]-2-庚烯. 用X衍射法对产物的晶体结构进行了测定, 讨论了反应机理, 通过元素分析, NMR, MS对产物的结构进行了表征.     

2-Aryl-4H-3,1-benzoxazin-4-ones nitration

2-(3-Nitrophenyl)-4H-3,1-benzoxazin-4-one is formed in the nitration of 2-phenyl-4H-3,1-benzoxazin-4-one, while 2-(2-tosylamino-5-nitrophenyl)-4H-3,1-benzoxazin-4-one is formed in the nitration of 2-(2-tosylaminophenyl)-4H-3,1-benzoxazin-4-one.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 908–909, July, 1974.     

Facile Regioselective Synthesis of Pyrano[3,2-c][1]benzo-thiapyran-5(2H)-one and 2-Methyl Furo[3,2-c][1] Benzothiapyran-4-one

The hitherto unreported title compounds were obtained in good yields by the application of [3,3]sigmatropic rearrangement on 4-]2′-propynyloxy] [1]benzothiapyran-2-one and 4-[2′-propenyloxy][1]benzothiapyran-2-one or 4-[2′-chloro-2′-propenyloxy][1]benzothiapyran-2-one respectively.     

Synthesis and pharmacological evaluation of some 3-(4-methoxyphenyl)-2-substitutedamino-quinazolin-4(3H)-ones as analgesic and anti-inflammatory agents

A variety of novel 3-(4-methoxyphenyl)-2-substitutedamino-quinazolin-4(3H)-ones were synthesized by reacting the amino group of 2-hydrazino-3-(4-methoxyphenyl)-quinazolin-4(3H)-one with a variety of alkyl and aryl ketones. The starting material 2-hydrazino-3-(4-methoxyphenyl)-quinazolin-4(3H)-one was synthesized from 4-methoxyaniline. The title compounds were investigated for analgesic, anti-inflammatory and ulcerogenic index activities. While the test compounds exhibited significant activity, compounds 2-(1-methylpropylidene)-hydrazino-3-(4-methoxyphenyl)-quinazolin-4(3H)-one (A1), 2-(1-ethylpropylidene)-hydrazino-3-(4-methoxyphenyl)-quinazolin-4(3H)-one (A2) and 2-(1-methylbutylidene)-hydrazino-3-(4-methoxyphenyl)-quinazolin-4(3H)-one (A3) showed moderately more potent analgesic activity and the compound 2-(1-methylbutylidene)-hydrazino-3-(4-methoxyphenyl)-quinazolin-4(3H)-one (A3) showed moderately more potent anti-inflammatory activity when compared to the reference standard diclofenac sodium. Interestingly the test compounds showed only mild ulcerogenic potential when compared to aspirin.     

Two new homoisoflavonoids from Caesalpinia pulcherrima

Two new homoisoflavonoids, (E)-7-methoxy-3-(4'-methoxybenzylidene)chroman-4-one (1) and (E)-7-hydroxy-3-(3',4',5'-trimethoxybenzylidene)chroman-4-one (5), along with three known homoisoflavonoids (Z)-7-hydroxy-3-(4'-methoxybenzylidene)chroman-4-one (isobon ducellin) (2), (E)-7-hydroxy-3-(4'-methoxybenzylidene)chroman-4-one (bonducellin) (3) and (E)-7-hydroxy-3-(2',4'-dimethoxybenzylidene)chroman-4-one (4) were isolated from the whole plant of Caesalpinia pulcherrima. The structures of these new compounds were elucidated by electron impact mass spectrometry (EI-MS) and 1D and 2D-NMR spectral studies. Antimicrobial activity of the new compounds was evaluated.     

Isolierung und Struktur von langkettigen Alkylphenolen und -pyrocatecholen aus Plectranthus albidus (Labiatae)

Isolation and Structure of Long-Chain Alkylphenols and -catechols from Plectranthus albidus (Labiatae) From the title plant, a series of even-numbered long-chain, phenol- or pyrocatechol-derived 1-arylalkan-5-ones was isolated by classical chromatography and preparative reversed phase HPLC. By chemical and spectroscopic methods, including coupled chromatographic techniques (GC/MS/FT-IR, HPLC/MS), their structures were established to be 1-(4′-hydroxyphenyl)tetradecan-5-one ( 2a ), 1-(4′-hydroxyphenyl)hexadecan-5-one ( 2b ), 1-(4′-hydroxyphenyl)octadecan-5-one ( 2c ), and (Z)-1-(4′-hydroxyphenyl)octadec-13-en-5-one ( 2d ); (E,E)-1-(3′,4′-dihydroxyphenyl)deca-1,3-dien-5-one ( 1a ), 1-(3′,4′-dihydroxyphenyl)dodecan-5-one ( 3a ), 1-(3′,4′-dihydroxyphenyl)-tetradecan-5-one ( 3b ), 1-(3′,4′-dihydroxyphenyl)hexadecan-5-one ( 3c ), 1-(3′,4′-dihydroxyphenyl)octadecan-5-one ( 3d ), 1-(3′,4′-dihydroxyphenyl)icosan-5-one ( 3e ), and (Z)-1-(3′,4′-dihydroxyphenyl)octadec-13-en-5-one ( 3f ). In vitro, the compounds show significant antioxidant activity, the inhibitory concentration of the most potent one, 1a , being slightly lower than for 2-(tert-butyl)-4-methoxyphenol (BHA) and 2,6-di(tert-butyl)-4-methylphenol (BHT) in the Fe²⁺-catalysed autooxidation of linoleic acid, whereas the acitivities of phenols 2a–d are in the same order of magnitude as α-tocopherol.     

4-(4-Acethylphenyl)-3-hydroxycoumarin in the Synthesis of Nitrogen-containing Heterocycles with a Neoflavonoid Moiety

Russian Journal of Organic Chemistry - 4-(4-Acetylphenyl)-3-hydroxy-2H-chromen-2-one has been prepared by the reaction of (4-acetylbenzene)diazonium chloride with 3-hydroxy-2H-chromen-2-one under...     

含肟醚的新型四唑啉酮衍生物的合成及除草活性研究

1-(4-氯苯基)-1,4-二氢-四唑-5-酮(1)与氯丙酮反应生成1-(4-氯苯基)-4-(2-氧代丙基)-1,4-二氢-四唑-5-酮(2). 中间体2、盐酸羟胺和卤化物通过三组分一锅法合成了目标化合物3. 初步生物活性测试结果表明: 目标化合物3具有较好的除草活性.     

The use of umbelliferone in the synthesis of new heterocyclic compounds

New coumarin derivatives, namely 7-[(5-amino-1,3,4-thiadiazol-2-yl)methoxy]-2H-chromen-2-one, 5-[(2-oxo-2H-chromen-7-yloxy)methyl]-1,3,4-thiadiazol-2(3H)-one, 2-[2-(2-oxo-2H-chromen-7-yloxy)acetyl]-N-phenylhydrazinecarbothioamide, 7-[(5-(phenylamino)-1,3,4-thiadiazol-2-yl)methoxy]-2H-chromen-2-one and 7-[(5-mercapto-4-phenyl-4H-1,2,4-triazol-3-yl)methoxy]-2H-chromen-2-one were prepared starting from the natural compound umbelliferone. The newly synthesized compounds were characterized by elemental analysis and spectral studies (IR, 1H-NMR and 13C-NMR).     

Regioselective alkylation of 2-alkyl-5,6,7,8-tetrahydro-3h-cycloheptimidazol-4-ones and 2-alkyl-3h-cycloheptimidazol-4-ones

Regioselective alkylation of 2-alkyl-5,6,7,8-tetrahydro-3H-cycloheptimidazol-4-one (1) and 2-alkyl-3H-cycloheptimidazol-4-one (2) was investigated. 3-[2'-(1-tert-Butyl-1H-tetrazol-5-yl)biphenyl-4-ylmethyl]-2-propyl-5,6,7,8-tetrahydro-1H-cycloheptimidazol-4-one (6) was preferentially obtained under the conditions by using NaH in DMF or THF. On the other hand, 3-[2'-(1-tert-butyl-1H-tetrazol-5-yl)biphenyl-4-ylmethyl]-2-propyl-5,6,7,8-tetrahydro-3H-cycloheptimidazol-4-one (5), the synthetic intermediate compound of Pratosartan, was obtained selectively in the presence of n-Bu(4)NBr in toluene by using aqueous sodium hydroxide as a base. In this reaction, it was found that the concentration of the alkaline solution influences its regioselectivity. This selectivity was observed even for aldehyde and ester derivatives.     

Synthese von Alkylphenolen und -pyrocatecholen aus Plectranthus albidus (Labiatae)

Synthesis of Alkylphenols and -catechols from Plectranthus albidus (Labiatae) In the preceding paper, we described the isolation and structure elucidation of a series of even-numbered phenol- or pyrocatechol-derived 1-arylalkane-5-ones. To establish the assigned structures unambiguously and to have larger quantities available for physiological testing, the following compounds were prepared: in the alkylphenol series, 1-(4′-hydroxyphenyl)tetradecan-5-one ( 2a ), 1-(4′-hydroxyphenyl)hexadecan-5-one ( 2b ), and 1-(4′-hydroxyphenyl)octadecan-5-one ( 2c ); in the alkylcatechol series, 1-(3′,4′-dihydroxyphenyl)decan-5-one ( 3a ; not isolated as a natural compound), 1-(3′,4′-dihydroxyphenyl)dodecan-5-one ( 3b ), 1-(3′,4′-dihydroxyphenyl)tetradecan-5-one ( 3c ), 1-(3′,4′-dihydroxyphenyl)hexadecan-5-one ( 3d ), 1-(3′,4′-dihydroxyphenyl)octadecan-5-one ( 3e ), and 1-(3′,4′-dihydroxyphenyl)icosan-5-one ( 3f ); in the alkenylphenol series, (Z)-1-(4′-hydroxyphenyl)octadec-13-en-5-one ( 4a ) and (E)-1-(4′-hydroxyphenyl)octadec-13-en-5-one ( 4b ); in the alkenylcatechol series, (E,E)-1-(3′,4′-dihydroxyphenyl)deca-1,3-dien-5-one ( 1 ) and (Z)-1-(3′,4′-dihydroxyphenyl)octadec-13-en-5-one ( 5 ). All compounds proved to be identical with the previously assigned structures. Compound 1 was synthesized by regioselective aldol condensation of heptan-2-one with (E)-1-(3′,4′-dimethoxyphenyl)prop-2-enal ( 6d ; Scheme 1), the phenols 2a–c and the catechols 3a–f by addition of the corresponding alkyl Grignard reagent to 5-(4′-methoxyphenyl)- or 5-(3′,4′-dimethoxyphenyl)pentanal ( 17c and 18c , resp.; Scheme 4), and the olefins 4a, 4b and 5 from 17c or 18c via the 9-O-silyl-protected 13-(4′-methoxyphenyl)- or 13-(3′,4′-dimethoxyphenyl)tridecanals ( 26 and 27 , resp.) and Wittig olefination as the key steps (Scheme 5).     

New sesquiterpenes and calebin derivatives from Curcuma longa

One novel sesquiterpene with new skeleton, (6S)-2-methyl-6-(4-hydroxyphenyl-3-methyl)-2-hepten-4-one (1), two new bisabolane sesquiterpenes, (6S)-2-methyl-6-(4-hydroxyphenyl)-2-hepten-4-one (2), (6S)-2-methyl-6-(4-formylphenyl)-2-hepten-4-one (3), and two calebin derivatives, 4'-(4'-hydroxyphenyl-3'-methoxy)-2'-oxo-3'-butenyl-3-(4'-hydroxyphenyl)-propenoate (4) and 4'-(4'-hydroxyphenyl)-2'-oxo-3'-butenyl-3-(4'-hydroxyphenyl-3'-methoxy)-propenoate (5) were isolated along with five known bisabolane sesquiterpenes from Curcuma longa. 1-4 were new compounds and 5 was a new natural product. Their structures were established by spectral methods.     

Condensation of Propan-2-one with Formaldehyde and Propane-2-thiol

Three-component condensation of propan-2-one with formaldehyde and propane-2-thiol in the presence of sodium hydroxide afforded 3-{[(propan-2-yl)sulfanyl)]methyl}but-3-en-2-one or 4-[(propan-2-yl)sulfanyl]-3-{[(propan-2-yl)sulfanyl]methyl}butan-2-one, depending on the amount of the base. The formation of 4-[(propan-2-yl)sulfanyl]-3-{[(propan-2-yl)sulfanyl]methyl}butan-2-one from 4-[(propan-2-yl)sulfanyl]butan-2-one involved aldol condensation of the latter with formaldehyde and subsequent nucleophilic addition of propane-2-thiol to the C=C double bond of intermediate 3-{[(propan-2-yl)sulfanyl]methyl}but-3-en-2-one in the presence of sodium hydroxide.     

Synthesis and mesomorphic properties of new liquid crystalline compounds with ß-hydroxy-, ß-chloroketone and a,ß-unsaturated ketone moieties in the terminal chains

The syntheses of new liquid crystalline compounds containing β-hydroxy-, β-chloroketone and α,β-unsaturated ketone moieties are described. The key intermediate 1-(4-hydroxyphenyl)-3-hydroxyoctan-1-one was obtained by the hydrogenolysis of the heterocycle in 3-(4-hydroxyphenyl)-5-pentyl-2-isoxazoline. Dehydratation of the intermediate β-hydroxyketone led to 1-(4-hydroxyphenyl)-oct-2-en-1-one. Reaction of 1-(4-hydroxyphenyl)-3-hydroxyoctan-1-one with hydrochloric acid yielded 1-(4-hydroxyphenyl)-3-chlorooctan-1-one. The target liquid crystalline compounds were synthesized by the esterification of these phenols with corresponding acids. The relationships between the moiety type in the terminal chain and the liquid crystalline properties are discussed.     

ortho-Directed electrophilic boronation of a benzyl ketone: the preparation, X-ray crystal structure, and some reactions of 4-ethyl-1-hydroxy-3-(4-hydroxyphenyl)-2-oxa-1-boranaphthalene

4-Ethyl-1-hydroxy-3-(4-hydroxyphenyl)-2-oxa-1-boranaphthalene (4) is formed in 78% yield from the reaction of 1-(4-methoxyphenyl)-2-phenylbutan-1-one with an of excess boron tribromide in dichloromethane followed by treatment with water. Reaction of 4 with iodine in aqueous sodium hydroxide gives a second oxaboracycle, 3-ethyl-1-hydroxy-3-(4-hydroxybenzoyl)-2,1-benzoxaborolane (5). The X-ray crystal structure determinations of both boron heterocycles are reported. Other new compounds reported are 1-(4-hydroxyphenyl)-2-(1-hydroxyphenyl)-butan-1-one (6), formed by reaction of 4 with alkaline hydrogen peroxide, and 1-(4-hydroxyphenyl)-2-(2-biphenyl)-butan-1-one (8), formed by coupling of 4 with bromobenzene in the presence of Pd(PPh₃) ₄.     

Synthesis and platelet aggregation-inhibitory activities of novel 3-(2-oxopropylidene)azetidin-2-one derivatives. I

Treatment of (E)-3-(2-hydroxypropylidene)-4-methyl-1-phenylazetidin-2-one (11) with 10% Pd/C gave (E)-(12), (Z)-3-(2-oxopropylidene)-4-methyl-1-phenylazetidin-2-one (13), 3,4-cis-(14a) and 3,4-trans-3-(2-oxopropyl)-4-methyl-1-phenylazetidin-2-one (14b). Among them, 12 and 13 were found to show potent inhibitory activities against rabbit platelet-rich plasma aggregation induced by adenosine diphosphate or collagen. Ring-expanded homologous derivatives and an acyclic analogue of 12 were also synthesized and tested for the biological activities. The azetidin-2-one skeleton bearing a 2-oxoalkylidene moiety at the 3 position was found to be essential for the platelet aggregation inhibitory activities of these compounds.     

无催化剂条件下4-羟基烷基-2-炔酸乙酯与N-杂环芳基甲基-N-2,2-二氟乙基-1-胺的串联反应

开发了无催化剂条件下4-羟基烷基-2-炔酸乙酯与N-杂环芳基甲基-N-2,2-二氟乙基-1-胺的串联反应.应用该反应在甲醇中回流,以39%~83%的收率合成了一系列4-(N-(2,2-二氟乙基)(N-杂环芳基甲基)氨基)-5,5-二取代呋喃-2(5H)-酮,其结构经1H NMR,13C NMR和HR-ESI-MS表征,并进一步通过3-氯-4-(N-2,2-二氟乙基)(N-嘧啶-5-基甲基胺基)-5,5-螺(4-甲氧基环己基)呋喃-2(5H)-酮(8)的晶体衍射间接证实.测试了所合成化合物的生物活性,结果表明,在600μg·mL^-1浓度时4-(N-2,2-二氟乙基)(N-6-氯吡啶-3-基甲基胺基)-5,5-二甲基呋喃-2(5H)-酮(3a)和4-(N-2,2-二.氟乙基)(N-6-氟吡啶-3-基甲基胺基)-5,5-二甲基呋喃-2(5H)-酮(3c)对桃蚜的死亡率均为100%.     

Polycyclic nitrogen compounds. Part II. Tricyclic quinoxalinones and their 4- or 6-aza analogues

1,2,3,3a-Tetrahydro-9-nitropyrrolo[1,2-α]quinoxalin-4-one and 7,8,9,10-tetrahydro-3-nitropyrido[1,2-α]quin-oxalin-6-one (V-VI) were reduced and deaminated to give new parent tricyclic quinoxalinone skeletons I-II. The latter compounds were identical with the tricycles obtained by an unambiguous independent synthesis. New 6-aza-1,2,3,3a-tetrahydropyrrolo[1,2-α]quinoxalin-4-one (III) and 4-aza-7,8,9,10-tetrahydropyrido[1,2-α]-quinoxalin-6-one (IV) were prepared by selective hydrogen transfer reductive cyclisation of esters of N-(2-nitro-3-pyridyl)pyrrolidine-2-carboxylic acid and N-(2-nitro-3-pyridyl)piperidine-2-carboxylic acid (Xb and XIb) respectively.