Preparation of substituted 4-(3-methyl-3-hydroxy-1-butynyl)-2-ethoxy-1,3-dioxolanes

A method has been developed for the preparation of 4-(3-hydroxy-1-alkynyl)-substituted 2-ethoxy-1,3-dioxolanes (which are novel flotation reagents for coal) based on the reaction between acetylene 1,2,5-triols and orthoformic ester in the presence of catalytic quantities of benzoic acid.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 770–771, June, 1987.     

Preparation of 7-ethoxy-3-hydroxy-6-methoxy-1-methyl-4-nitroisoquinoline

This paper reports the large scale preparation of 7-ethoxy-3-hydroxy-6-methoxy-1-methyl-4-nitroiso-quinoline (RWJ 19959, 2 ) from an available starting material, 4-ethoxy-3-methoxyphenylacetic acid ( 9 ). Previously 2 was prepared via a perchlorate salt which was found to decompose exothermically.     

5-Hydroxy-2,3-dihydrobenzofuran-derived polyfunctional antioxidants 3. Synthesis and antioxidant activity of 2-dodecylthiomethyland 2-dodecylselenomethyl-5-hydroxy-4,6,7-trimethyl-2,3-dihydrobenzofurans

New sulfur- and selenium-containing analogs of α-tocopherol, namely, 2-dodecylthiomethyl- and 2-dodecylselenomethyl-5-hydroxy-4,6,7-trimethyl-2,3-dihydrobenzofurans were synthesized from 4-ethoxy-3,5-dimethylphenol through intermediate 2-allyl-4-ethoxy-3,5,6- trimethylphenol, 2-iodomethyl-, 2-dodecylthiomethyl-, and 2-dodecylselenomethyl-5-ethoxy- 4,6,7-trimethyl-2,3-dihydrobenzofurans. The compounds terminated oxidation chains of AIBN-initiated oxidation of styrene at 50 °C with rate constant of 5.0?10⁶ mol L^–1 s^–1 and stoichiometric coefficients of 1.9±0.1. The O—H bond dissociation energies for obtained compounds (326.5 kJ mol^–1) are calculated based on the measured rate constants.     

2-Polyfluoroalkylchromones. 6. Synthesis of substituted 2-morpholino-2-trifluoromethylchroman-4-ones

Morpholine adds smoothly at the double bond of substituted 5- and 8-nitro-2-trifluoromethylchromones to form the corresponding 2-morpholino-2-trifluoromethylchroman-4-ones. 6-Methoxy-5-nitro-2-trifluoromethylchromone adds also benzylamine, whereas 7-methoxy-8-nitro-2-trifluoromethylchromone undergoes ring opening under the action of benzylamine to give 3-benzylamino-4,4,4-trifluoro-1-(2-hydroxy-4-methoxy-3-nitrophenyl)but-2-en-1-one.     

Investigations on 2, 1, 3-thia- and selenadiazoles

Nitration and nitrosation of 4-hydroxy-5-methyl-benzo-2, 1, 3-thiadiazole gives 4-hydroxy-5-methyl-7-nitro-and 4-hydroxy-5-methyl-7-nitrosobenzo-2, 1, 3-thiadiazoles. Oxidation of the latter, or of 4,7-diamino-5-methylbenzo-2,1,3-thiadiazole gives 5-methyl-4,7-dihydroxy-2, 1, 3-thiadiazole, forming derivatives with sodium bisulfite or hydroxylamine, and reduced by sodium dithionite to 5-methyl-4, 7-dihydroxybenzo-2, 1, 3-thiadiazole. The latter is also obtained by diazotizing 5-methyl-4-hydroxy-7-aminobenzo-2, 1, 3-thiadiazole, and decomposing the diazonium salt. Nitration of 4-ethoxybenzo-2, 1, 3-thiadiazole with sodium ethoxide gives 4-ethoxy-7-aminobenzo-2, 1, 3-thiadiazole, acetylated to 4-ethoxy-7-acetaminobenzo-2, 1, 3-thiadiazole.For Part XXXVII see [1].     

Iodine catalyzed synthesis of the chromene derivatives in one-pot

Iodine catalyzed one-pot reactions of salicylaldehyde and dimolecular 1 H-indene-1,3(2H)-dione,barbituric acids,4-hydroxycoumarin, or 4-hydroxy-6-methylpyran-2-one were performed and provided a rapid,convenient and general approach to synthesize the chromene derivatives.2-(11-Oxo-10,11-dihydroindeno[l,2-b]chromen-10-yl)-1H-indene-1,3(2H)-diones P1-P4 and 10-(4-hydroxy-6-methyl-2-oxo-2H-pyran-3-yl)-3-methylpyrano[4,3-6]chromen-1(10H)-ones P8-P9 were unprecedentedly prepared and structurally identified by NMR and Mass.The confirmation of structure by single crystal X-ray crystallography is reported for P3.     

2-羟基-4-(1′-甲庚氧基)苯烷酮肟的合成

具有邻位羟基的酮肟化合物(1)作为过渡金属螯合剂已在铜的萃取-电积工艺中得到广泛应用,如:LIX 64N(1a),LIX84(1b)及LIX 860(1c)。从萃取动力学行为来衡     

Synthesis of 4-chloro-7-ethoxy-2(3H)-benzoxazolone-6-carboxylic acid

As a part of metabolic studies of mosapride ( 1 ), a potential gastroprokinetic agent, the synthesis of 4-chloro-7-ethoxy-2(3H)-benzoxazolone-6-carboxylic acid ( 7 ) as a derivative of 4-amino-5-chloro-2-ethoxy-3-hydroxybenzoic acid ( 6 ), which has served a benzoic acid part of the metabolites 4 and 5 , is described. Treatment of methyl 3-amino-4-substituted amino-5-chloro-2-ethoxybenzoate derivatives 11a-c with sodium nitrate in acidic medium gave the benzotriazole derivatives 13x,y instead of the objective 3-hydroxy counterpart. The synthesis of 7 started from o-vanillin acetate ( 15 ) and proceeded through the intermediates 2-hydroxy-3-methoxy-4-nitrobenzaldehyde ( 18 ), methyl 4-amino-2,3-dihydroxybenzoate ( 23 ), and methyl 7-hydroxy-2(3H)-benzoxazolone-6-carboxylate ( 30 ). Compound 30 was alternatively prepared from 23 via methyl 4-ethoxycarbonylamino-2-ethoxycarbonyloxy-3-hydroxybenzoate ( 29 ), which is the product resulting from the migration of the ethoxycarbonyl group of methyl 4-amino-2,3-diethoxycar-bonyloxybenzoate ( 27 ).     

Reactions of substituted pyridines with electrophilic boranes

The lutidine derivative (2,6-Me(2))(4-Bpin)C(5)H(2)N when combined with B(C(6)F(5))(3) yields a frustrated Lewis pair (FLP) which reacts with H(2) to give the salt [(2,6-Me(2))(4-Bpin)C(5)H(2)NH][HB(C(6)F(5))(3)] (1). Similarly 2,2'-(C(5)H(2)(4,6-Me(2))N)(2) and (4,4'-(C(5)H(2)(4,6-Me(2))N)(2) were also combined with B(C(6)F(5))(3) and exposed to H(2) to give [(2,2'-HN(2,6-Me(2))C(5)H(2)C(5)H(2)(4,6-Me(2))N][HB(C(6)F(5))(3)] (2) and [(4,4'-HN(2,6-Me(2))C(5)H(2)C(5)H(2)(2,6-Me(2))N] [HB(C(6)F(5))(3)] (3), respectively. The mono-pyridine-N-oxide 4,4'-N(2,6-Me(2))C(5)H(2)C(5)H(2)(2,6-Me(2))NO formed the adduct (4,4'-N(2,6-Me(2))C(5)H(2)C(5)H(2)(2,6-Me(2))NO)(B(C(6)F(5))(3)) (4) which reacts further with B(C(6)F(5))(3) and H(2) to give [(4,4'-HN(2,6-Me(2))C(5)H(2)C(5)H(2)(2,6-Me(2))NO)B(C(6)F(5))(3)] [HB(C(6)F(5))(3)] (5). In a related sense, 2-amino-6-CF(3)-C(5)H(3)N reacts with B(C(6)F(5))(3) to give (C(5)H(3)(6-CF(3))NH)(2-NH(B(C(6)F(5))(3))) (6). Similarly, the species, 2-amino-quinoline, 8-amino-quinoline and 2-hydroxy-6-methyl-pyridine were reacted with B(C(6)F(5))(3) to give the products as (C(9)H(6)NH)(2-NHB(C(6)F(5))(3)) (7), (C(9)H(6)N)(8-NH(2)B(C(6)F(5))(3)) (8) and (C(5)H(3)(6-Me)NH)(2-OB(C(6)F(5))(3)) (9), respectively; while 2-amino-6-picoline, 2-amino-6-CF(3)-pyridine, 2-amino-quinoline, 8-amino-quinoline and 2-hydroxy-6-methyl-pyridine react with ClB(C(6)F(5))(2) to give the species (C(5)H(3)(6-R)NH)(2-NH(ClB(C(6)F(5))(2))) (R = Me (10), R = CF(3) (11)) (C(9)H(6)NH)(2-NH(ClB(C(6)F(5))(2))) (12), (C(9)H(6)N)(8-NH(2)ClB(C(6)F(5))(2)) (13) and (C(5)H(3)(6-Me)NH)(2-OClB(C(6)F(5))(2)) (14), respectively. In a similar manner, 2-amino-6-picoline and 2-amino-quinoline react with B(C(6)F(5))(2)H to give (C(5)H(3)(6-Me)NH)(2-NH(HB(C(6)F(5))(2))) (15) and (C(9)H(6)NH)(2-NH(HB(C(6)F(5))(2))) (16). The corresponding reaction of 8-amino-quinoline yields (C(9)H(6)N)(8-NHB(C(6)F(5))(2)) (17). In a similar fashion, reaction of 2-amino-6-CF(3)-pyridine resulted in the formation of (18) formulated as (C(5)H(3)(6-CF(3))N)(2-NH(B(C(6)F(5))(2)). Finally, treatment of 15 with iPrMgCl gave (C(9)H(6)N)(2-NH(B(C(6)F(5))(2))) (19). Crystallographic studies of 1, 2, 4, 6, 7, 10, 11, 12 and 15 are reported.     

1,2,4-三嗪类化合物的研究(ⅩⅩ)——利用波谱分析确定3-甲硫基-5-羟基-1,2,4-三嗪的取代苯磺酰化反应及其产物的结构

为寻找有效的抗肿瘤药物,作者对1,2,4-三嗪类化合物(6-氮杂尿嘧啶)的化学性质进行了研究,发现3-甲硫基-5-羟基-1,2,4-三嗪(1)在无水吡啶中与对甲苯磺酰氯发生不正常的对甲苯磺酰化反应,生成N-[6-(3-甲硫基-5-负氧基)-1,2,4-三嗪基]吡啶内鎓盐以及对甲苯磺酸对甲苯硫酚酯。为了研究其反应机理,把溶剂改为等摩尔NaOH的CH_3COCH_3-H_2O溶液,重复文献的实验。反应产物分离提纯后,确定其结构为3-甲硫基-4-对甲苯磺酰基-5-氧代-6-羟基-1,4,5,6-四氢-1,2,4-三嗪(2a)。此反应特点是:在1,2,4-三嗪环的4-氮上     

Synthesis and Crystal Structure of 4-Bromo-5-ethoxy-3-methyl-5- （naphthalen- 1-yl）- 1-tosyl- 1H-pyrrol-2（5H）- one

The title compound 4-bromo-5-ethoxy-3-methyl-5-(naphthalen-1-yl)-1-tosyl-1H- pyrrol-2(5H)-one 1 (C24H22BrNO4S, Mr = 500.40) has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/n with a = 8.8562(15), b = 18.118(3), c = 14.055(2) , β = 99.855(3)o, V = 2221.9(6) 3, Z = 4, Dc = 1.496 g/cm3, μ = 1.975 mm-1, λ = 0.71073 , F(000) = 1024, R = 0.0607 and wR = 0.1371.     

Reaction of trifluoromethyl-containing 1,3-dicarbonyl compounds with bis-hydrazides

Carbonic dihydrazide reacted with 2 equiv of trifluoroacetylacetone to give a compound containing 5-hydroxy-4,5-dihydropyrazole and keto enehydrazine fragments. Analogous 2 : 1 condensations of trifluoro-acetylacetone and 4-ethoxy-1,1,1-trifluorobut-3-en-2-one with oxalohydrazide and malonohydrazide afforded bis(5-hydroxy-4,5-dihydropyrazole) structures as two diastereoisomers.     

Crystal structure of phenylhydrazine with diacetyl substituted ketol of the cyclohexane series

The reaction of 2,4-diacetyl-5-hydroxy-5-methyl-3-phenylcyclohexanone-1 with phenylhydrazine is conducted, and the crystal structures of its products, 1-(6-hydroxy-3,6-dimethyl)-2,4-diphenyl-4,5,6,7-tetrahydro-2H-indazol-5-yl)ethane-1-one and 1-(2-hydroxy-2-methyl-6-phenyl-4-(2-phenylhydrazono)-5-(1-(2-henylhydrazono)ethyl)cyclohexyl)ethane-1-one, are determined by single crystal XRD.     

Synthesis of optically active seven-membered 1,5-anhydrocarbasugars and 1,4,5-tribenzoyloxy-2-ethoxy cycloheptanes via [5+2] cycloaddition

[5+2] Cycloaddition followed by asymmetric dihydroxylation procedure have been utilized to prepare novel cyclitols. Accordingly, rac-2α-hydroxy-6α-ethoxy-1,5-anhydro cyclohept-3-ene, 10 derived from [5+2] cycloaddition of 3-oxidopyrylium ylide and vinyl ether has been recognized as a seven-membered carbasugar equivalent and elaborated to 1,4,5-tribenzoyloxy-2-ethoxy cycloheptanes through a flexible, regio- and stereoselective strategy involving Sharpless asymmetric dihydroxylation conditions to resolve the compounds obtained. The structures and relative configurations of newly synthesized (+)-2α-acetoxy-6α-ethoxy-3β,4β-dihydroxy-1,5-anhydro cycloheptane ((+)-12)); (−)-1β,4β,5β-tribenzoyloxy-6α-ethoxy cycloheptane ((−)-17) and (+)-1α,4α,5α-tribenzoyloxy-6β-ethoxy cycloheptane ((+)-17) are unambiguously established by single crystal X-ray analysis and duly supported by ¹H and ¹³C NMR spectroscopy data.     

The stereochemical course of the catalytic hydrogenation of 3(2H)isoquinolinones

4-Benzylidene-1-phenyl-1,4-dihydro-3(2H)isoquinolinone ( 2 ), 4-benzyl-1-phenyl-3(2H)isoquino-linone ( 3 ) and 4-benzyl-3-ethoxy-1-phenylisoquinoline ( 6 ) have been hydrogenated on palladium-charcoal catalyst. The structure of the products and the ratio of the stereoisomers have been determined by nmr spectroscopy and by LIS measurements with Eu(dpm)₃.     

Thermal-Induced Dimerization Cyclization of Ethyl N-(Styrylcarbamoyl)acetates: Formation of 4-Hydroxy-2(1H)-pyridone-3- carboxamide Derivatives

Thermal-induced dimerization cyclization of ethyl N-(styrylcarbamoyl)acetate derivatives has been investigated, leading to 4-hydroxy-2(1H)-pyridone-3-carboxamide derivatives with good yields in diphenyl ether on 200–210 °C. Ethyl N-(styrylcarbamoyl)acetate derivatives readily provided the intermolecular cyclization products 4-hydroxy-2(1H)-pyridone-3-carboxylates on reflux in xylene. In addition, several related 3-acetyl-4-hydroxy-5-phenylpyridin-2(1H)-ones have been prepared. It provided an efficient preparation of 4-hydroxy-2(1H)-pyridone-3-carboxamide derivatives.     

Synthesis and Properties of Ammonium 5-Benzoyl-4-(2-chlorophenyl)-3-cyano-6-hydroxy-6-phenyl-1,4,5,6-tetrahydropyridine-2-thiolates

The reaction of 2-chlorobenzaldehyde with cyanothioacetamide and dibenzoylmethane in the presence of piperidine or N-methylmorpholine gave the corresponding 5-benzoyl-4-(2-chlorophenyl)-3-cyano-6-hydroxy-6-phenyl-1,4,5,6-tetrahydropyridine-2-thiolates, used in the synthesis of 1-alkylthio-4-benzoyl-1-benzoylamino-3-(2-chlorophenyl)-2-cyanobut-1-enes.     

2-苯甲酰基-N-芳基氨基脲的合成及抑菌活性

以N-取代三氯乙酰胺在碱催化下与苯甲酰肼反应,合成了8种2-苯甲酰基-N-芳基氨基脲3a～3h,其结构经元素分析、IR和1H NMR所表征;初步生物活性测定表明,部分化合物对大肠杆菌、枯草杆菌和金黄色葡萄球菌具有一定的抑菌活性.     

Electron Ionization Mass Spectra of Organophosphorus Compounds Part I: The Mass Fragmentation Pathways of Cyclic α-Aminophosphonates Monoester Containing 1,2,4-Triazinone Moiety

Abstract

The electron impact induced fragmentation reactions of 3-(4-chlorophenyl)-3,4- dihydro-2-ethoxy-2-oxido-7-methyl-2H,6H-[1,2,4]triazino[4,3-e][1,4,5,2]thiadiazaphosphin in-6-one (1), 3,7-dimethyl-2-ethoxy-2-oxido-1,2,3,4-tetrahydro-6H-[1,2,4]triazino[4,3-b][1,2,4,5]triazaphosphinin-6-one (2), and 9-amino-3,7-dimethyl-4-ethoxy-4-oxido-2,3,4,9-tetrahydro-8H-[1,2,4]triazino[3,2-c][1,2,4,5]triazaphosphinin-8-one (3) are presented and compared. The 1,2,4-triazine rings have almost identical fragmentation routes. The 1,2,4-triazine rings are rather stable relative to the phosphorus rings. Therefore, fragmentation of the phosphorus rings is more favorable for the compounds than the stable 1,2,4-triazine rings.     

Synthesis reactivity and electrochemical properties of substituted cyclopentadienyl cobalt (III) complexes

Cyclopentadienyl cobalt complexes (η⁵‐C₅H₄R) CoLI₂ [L = CO,R=‐COOCH₂CH=CH₂ (3); L=PPh₃, R=‐COOCH₂‐CH=CH₂ (6); L=P(p‐C₆H₄O₃)₃, R = ‐COOC(CH₃) = CH₂ (7), ‐COOCH₂C₆H₅ (8), ‐COOCH₂CH = CH₂ (9)] were prepared and characterized by elemental analyses, ¹H NMR, ER and UV‐vis spectra. The reaction of complexes (η⁵‐C₅H₄R)CoLI₂ [L= CO, R= ‐COOC(CH₃) = CH₂ (1), ‐COOCH₂C₆H₅(2); L=PPh₃, R=‐COOC (CH₃) = CH₂ (4), ‐COOCH₂C₆H₅ (5)] with Na‐Hg resulted in the formation of their corresponding substituted cobaltocene (η⁵‐C₅H₄R)₂ Co[R=‐COOC(CH₃) = CH₂ (10), ‐COOCH₂C₆H₅ (11)]. The electrochemical properties of these complexes 1–11 were studied by cyclic voltammetry. It was found that as the ligand (L) of the cobalt (III) complexes changing from CO to PPh₃ and P(p‐tolyl)₃, their oxidation potentials increased gradually. The cyclic voltammetry of α,α′‐substituted cobaltocene showed reversible oxidation of one electron process.