四氟乙烯齐聚体的反应 Ⅱ.四氟乙烯五聚体和烯丙醇的反应及反应产物的转化

全氟(3,4-二甲基-4-乙基己烯-[2])(1)虽早已合成,但有关它的反应至今报道不多。本文报道化合物1和烯丙醇在不同条件下的亲核取代反应和2-(1′-烯丙氧基四氟乙基)-全氟(3-甲基-3-乙基戊烯-[1])(2)的化学转化。1和烯丙醇的反应随溶剂和碱的变化而得到不同的产物。1和烯丙醇钠在FC-113中,于-40℃左右反应可得到2。若1与过量烯丙醇、三乙胺在35°～40℃反应40min,则得到2-烯丙氧基-全氟(3,4-二甲基-4-乙基已烯-[2])(3),但产率很低,绝大部分回收原料,并获得3-三氟甲基-3-五氟乙基-2,2-二氢五氟戊酸烯丙酯(5a)。若1与烯丙醇、碳酸钾在丙酮中于50～60℃反应,则主要产物为4和5a。以上化合物的结构均经~1HNMR,~(19)FNMR,IR和元素分析等证明。     

四氟乙烯齐聚体的反应——Ⅲ.四氟乙烯四聚体与脂族胺以及烷氧亲核试剂的反应

3,4-双(三氟甲基)-全氟己烯-[3](1)和仲胺(如二乙胺)反应得到末端烯胺2。它很易水解成相应的酰胺3.1和伯胺(如正丁胺)于40～50℃反应,主要产物为环状胺5;在-30～-40℃反应,则主要得到开链状不饱和胺4.1和烯丙醇钠反应得两种烯醚异构体6和7。     

四氟乙烯齐聚体的反应 Ⅵ.全氟-3,4-二甲基-4-乙基-2-已烯和脂族胺的反应及3-(N,N-二烷基胺基氟甲叉)-4-三氟甲基-4-五氟乙基-2-全氟已酮的~(19)F NMR研究

全氟-3,4-二甲基-4-乙基-2-己烯(1)和正丁胺(摩尔比1∶2)在乙醚中、三乙胺存在下于室温反应,主要得到2-N-正丁基亚胺基-3-N-正丁基亚胺基甲叉-4-三氟甲基-4-五氟乙基全氟己烷(2a)及少量2-N-正丁基亚胺基-3-羰基甲叉-4-三氟甲基-4-五氟乙基全氟己烷(3a).有水存在时则主     

四氟乙烯齐聚体的反应——Ⅴ.全氟3,4-二甲基-4-乙基-2-己烯和含硫亲核试剂的反应及其衍生物的转化

全氟3,4-二甲基-4-乙基-2-己烯(1)和含硫亲核试剂如苄硫酚、烯丙硫酚及苯硫酚等的反应及反应产物的转化可得四类异构体2,3,4,5;在-30～-60℃于乙醚中反应,得到动力学控制的产物2a～c。2a,2b与KF在DMF中,室温反应可转化为热力学稳定的产物3a,3b。在100～120℃,2a～c异构化为4a～c。后者在DMF-KF中室温反应,重排成5a～c。在DMF-NEt_3中2a再和苄硫酚反应得到连二苄硫醚(6)和含氢的端基烯7a及二取代产物8a,在乙醚-三乙胺中反应得到3a和9a。2a和甲醇反应,可得少量3a和10a。2b和二乙胺反应复杂,仅得少量3b和不饱和酰胺11。     

四氰乙烯齐聚体的反应;V.全氟3,4-二甲基-4-乙基-2-己烯和含硫亲核试剂的反应及其衍生物的转化

全氟3,4-二甲基-4-乙基-2-己烯(1)和含硫亲核试剂如苄硫酚、烯丙硫酚及苯硫酚等的反应及反应产物的转化可得四类异构体2,3,4,5;在-30～-60℃于乙醚中反应,得到动力学控制的产物2a～c.2a,2b与KF在DMF中,室温反应可转化为热力学稳定的产物3a,3b,在100～120℃,2a～c异构化为4a～c.后者在DMF-KF中室温反应,重排成5a～c.在DMF-NEt3中2a再和苄硫粉反应得到连二苄硫醚(6)和含氢的端基烯7a及二取代产物8a,在乙醚-三乙胺中反应得到3a和9a,2a和甲醇反应,可得少量3a和10a,2b和二乙胺反应复杂,仅得少量3b和不饱和酰胺11。     

亚磺化脱卤研究 X: 全氟及多氟溴代烷的反应研究

本文报道溴代全氟烷和α,ω-二溴代全氟烷在亚磺化脱卤反应体系中与烯烃的反应及其与相应的碘代全氟烷的区别. 合成了全氟仲溴代烷CF3CFBrOCF2CF(CF3)O(CF2)2SO2F(7), 它与烯烃反应可得到1:1的加成物. 7的水解产物CF3CFBrOCF2CF(CF3)O(CF2)2SO3Na(11)与连二亚硫酸钠反应只得到氢化脱溴产物. 多氟溴化物CF3CBr2X(13X=F; 14X=Cl; 15X=Br)经亚磺化脱溴可得到相应的亚磺酸钠盐CF3CBrXSO2Na(16X=F; 17X=Cl; 18X=Br), 其中间体多氟烷自由基可用烯烃捕集, 得到高产率的1:1加成产物.     

亚磺化脱卤研究 X: 全氟及多氟溴代烷的反应研究

本文报道溴代全氟烷和α,ω-二溴代全氟烷在亚磺化脱卤反应体系中与烯烃的反应及其与相应的碘代全氟烷的区别. 合成了全氟仲溴代烷CF3CFBrOCF2CF(CF3)O(CF2)2SO2F(7), 它与烯烃反应可得到1:1的加成物. 7的水解产物CF3CFBrOCF2CF(CF3)O(CF2)2SO3Na(11)与连二亚硫酸钠反应只得到氢化脱溴产物. 多氟溴化物CF3CBr2X(13X=F; 14X=Cl; 15X=Br)经亚磺化脱溴可得到相应的亚磺酸钠盐CF3CBrXSO2Na(16X=F; 17X=Cl; 18X=Br), 其中间体多氟烷自由基可用烯烃捕集, 得到高产率的1:1加成产物.     

四氟乙烯齐聚体的反应 VIII: 2-(1'-烯丙氧基)四氟乙基-3-三氟甲基-3-五氧乙基全氟-1-戊烯分子内[2+2]环化加成反应

研究了2-(1'-烯丙氧基四氟乙基)全氟-3-甲基-1-戊烯的分子内环加成反应, 反应温度低于100℃时, 未发现重排产物, 在140℃时发生分子内环加成, 得到1-(1'-三氟甲基1'-戊基氟乙基)-戊基氟丙基-2-三氟甲基-2-氟代-7,7-二氟代-3-氧杂二环庚烷[3,2,0]以及相应的二环庚烷[3,1,1]和分子间[2+2]环加成产品.     

水溶性铱—膦配合物催化烯烃加氢反应的研究

研究了两种水溶性铱—膦配合物IrCl(CO)(TPPTS)_2和HIr(CO)(TPPTS)_3[TPPTS=P(m-C_6H_4SO_3Na)_3]的合成和它们的组成与结构表征,在有机相和水相构成的两相催化反应体系中,评价了它们对烯烃的加氢活性.考察了反应温度(60～120℃),氢压(2～4MPa),两种相转移剂(CTAB和β-CD)浓度变化和反应时间等对烯烃转化率的影响,对1-己烯、环己烯和苯乙烯三种不同类型烯烃的加氢性能进行了对比.结果证明HIr(CO)(TPPTS)_3的加氢活性更佳,反应结束后催化剂与产物分离容易;CTAB是更有效的相转移剂,在所研究的条件下,三种类型烯烃的加氢活泼顺序为: 苯己烯>1-己烯>环己烯.     

羟甲基和碘甲基取代的3,4-亚乙基二氧噻吩衍生物及其选择性酯化与醚化

羟甲基或碘甲基取代的3,4-亚乙基二氧噻吩(EDOT)衍生物与含氰乙基或羧酸基的四硫代富瓦烯(TTF)衍生物通过酯化或醚化反应可生成EDOT-TTF类型的化合物.在此过程中发现,由3,4-二羟基噻吩-2,5-二羧酸甲酯(1)与环氧溴丙烷经醚化反应生成的关环产物是一个由3,4-二氧-羟甲基乙基噻吩-2,5-二羧酸甲酯(2)与3,4-二氧-2’-羟基亚丙基噻吩-2,5-二羧酸甲酯(2’)组成的混合物,两者很难用常规手段分离.由(2+2’)衍生的2,5-二羧酸甲酯-3,4-二氧-碘代甲基亚乙基噻吩(3)和3,4-二氧-碘代亚丙基噻吩-2,5-二羧酸甲酯(3’)以及3,4-二氧-羟甲基亚乙基噻吩(4)与3,4-二氧-2’-羟基亚丙基噻吩(4’)与2-氰乙基硫-3-甲基硫-6,7-二(正己基硫)-四硫代富瓦烯(TTF-1)或2-羧甲基硫-3-甲基硫-6,7-二(正己基硫)-四硫代富瓦烯(TTF-3)进行醚化或酯化反应表现出了高度的选择性,只有3能与TTF-1反应生成结构单一的EDOT-TTF 1.同样只有4能与TTF-3反应生成结构单一的EDOT-TTF 2.     

四氟乙烯齐聚体的反应: II.四氟乙烯五聚体和烯丙醇的反应及反应产物的转化

The reaction of perfluoro- (3, 4-dimethyl-3-ethylhexene-(2)) (1) with allyl alcohol under different conditions gave different products. Compound 1 reacted with sodium allyl alcoholate yielding 2-(1'-allyloxy-tetrafluoroethyl)-perfluoro(3-methyl-3-ethylpentene- (1))(2). In the presence of triethylamine, 1 reacted with allyl alcohol to give 2-allyloxy-perfluoro (3, 4-dimethy1-4-ethylhexene- (2))(3), and in the presence of acetone and K2CO3 to give compound 4. These reactions all gave allyl-3-trifluoromethyl-3- pentafluoroethyl-2,2-dihydro-pentafluorovalerate (5a) as byproduct. Compound 1 reacted with allyl alcohol in the presence of triethylamine at 20-22`C to give 2, at 30-35`C to give a mixture of 2 and 3 and at 35-40`C to give a mixture of 3 and 5a respectively. Compound 2 was transformed to compound 4 in acetone and in the psesence of K2CO3, \o\ compound 5a or 5b in the corresponding alcohol and to compound 6 on reacting with dimethylamine. Compound 2 as well as 3 was converted to perfluoro-(3-ethyl-2,3,4,5- tetramethyl-2,3-dihydrofuran) (7) by KF in sulpholane.     

几种新型苯甲酰基脲类几丁质抑制剂的合成(Ⅱ)

苯甲酰基脲类几丁质生物合成抑制剂以其独特的作用机制、高的环境安全性、对鳞翅目昆虫极佳的杀虫活性或生长调节作用。和不易产生抗药性且易于人工合成等传统农药无法比拟的优点,被誉为“21世纪农药”,自1973年开发出商品化的苯甲酰脲类化合物灭幼脲杀虫剂后,文献报道的苯甲     

Pyridazine Derivatives and Related Compounds,Part 1. Some Reactions with 4-Cyano-5,6-Diphenyl-2,3-Dihydropyridazine-3-One

4-Cyano-5,6-diphenyl-2,3-dihydropyridazine-3-onc 1 reacts with phosphorous oxychloride to give 70% of the corresponding 3-chloro derivative 2. Treating 2 with anthranilic acid in butanol, 4-cyano-2,3-diphenyl-10H-pyridazino[6,1-b]quinoxaline-10-one, 3 was obtained. Compound 1 reacts with phosphorous pentasulphide to give 3-mercapto derivative 4, which was converted by acrylonitrile to S-(2-cyanoethyl)pyridazine derivative 5. Compound 4 reacts with ethyl bromoacetate and with phenacyl bromide gave the corresponding thieno[2,3-c] pyridazine derivatives 8, 9, Alkylation of 1 with ethyl chloroacetate afforded 3-0-carbethoxymethyl derivative 10. Compound 10 reacts with amines (aniline, hydrazine) to give the corresponding amide and acid hydrazide 13, 12 respectively. Hydrolysis of 10 with sodium hydroxide gave the corresponding acid derivative 11. Treating 1 with methyl iodide, 3-0-methyl derivative 14 was obtained, which was converted by ammonium acetate/acetic acid to 3-amino-4-cyano-5,6-diphenyl pyridazine 15. Compound 1 reacts with methyl magnesium iodide gave 4-acetyl derivative 16, which was reacted with hydrazine, phenyl hydrazine and with hydroxylamine to give the substituted I H pyrazolo [3,4-c] pyridazine 17 a,b and isoxazolo [5,4-c] pyridazine 18 derivatives respectively.     

Reactions with dimethylformamide‐dimethylacetal: Synthesis and reactions of several new pyridine and pyrazolo[3,4‐b]pyridine derivatives

6‐Aminopyridine‐2(1H)‐thiones 1a,b reacted with dimethylformamide‐dimethylacetal (DMF‐DMA) to give the corresponding 6‐{[(N,N‐dimethylamino)methylene]amino}pyridine derivatives 2a,b . The latter compounds reacted with hydrazine hydrate to afford the 3,6‐diamino‐1H‐pyrazolo[3,4‐b]pyridine derivative 4 and 3‐amino‐5‐hydrazino‐1H‐pyrazolo[4′,3′:5,6]pyrido[2,3‐d]pyrimidine derivative 7 , respectively. Compound 4 condensed with DMF‐DMA to yield the 3,6‐bis{[(N,N‐dimethylamino)methylene]amino}‐1H‐pyrazolo[3,4‐b]pyridine derivative 10 , which reacted with malononitrile to give the corresponding pyridopyrazolopyrimidine derivative 15 . © 2007 Wiley Periodicals, Inc. Heteroatom Chem 18:399–404, 2007; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20312     

Synthesis and reactions of 3-thioxo[1,2,4]-triazino[3,2-b]quinazolin-10-ones

Thiation of [1,2,4]triazino[3,2-b]quinazoline-3,10-dione 1 proceeds selectively to give the 3-thioxo-analog 3 . The latter was converted to the corresponding 3-methylthio derivative 4 which was reacted with aniline and hydrazine to give the corresponding anilino- and hydrazino derivatives 5 and 7 . Compound 7 was converted to the hydrazones 8a,b and into the novel heterocyclic ring systems [1,2,4]triazolo[4′,3′:4,5][1,2,4]triazino-[3,2-b]quinazolin-7-ones 9, 10a,b and tetrazolo[1′,5′:4,5][1,2,4]triazino[3,2-b]quinazolin-7-one 11 .     

Enaminones as building blocks in heterocyclic synthesis: New syntheses of nicotinic acid and thienopyridine derivatives

Reacting 1,3‐diphenyl‐propan‐2‐one with equimolecular amount of dimethylformamide dimethylacetal afforded the enaminone 4. This when reacted with another equimolecular amount of dimethylformamide dimethylacetal afforded the dienaminone 5. Compound 4 condenses with cyanothioacetamide and with cyanoacetamide to yield 2‐thioxo‐ and 2‐oxo‐pyridine‐3‐carbonitrile derivatives 6a,b respectively. Compound 6a reacted with α‐chloroacetone 8 to yield the thieno[2,3‐b]pyridine derivative 10 that cyclized further into 4,7,8‐trisubstituted pyrido[2′,3′:2,3] thieno[4,5‐d]pyrimidine 12. Compound 4 also afforded 2,5,6‐trisubstituted nicotinic acid ethyl ester 13 by reaction with ethyl acetoacetate in acetic acid in the presence of ammonium acetate. The dienaminone 5 reacted with acetic acid, ammonium acetate/acetic acid, phenylhydrazine and 5‐amino‐3‐methylpyrazole yielding 3,5‐diphenyl‐pyran‐4‐one 15a , 3,5‐diphenyl‐1H‐pyridin‐4‐one 15b and 1,3,5‐trisubstituted pyridin‐4‐ones 16a‐b.     

An Approach to Polysubstituted Triazipines,Thiadiazoles and Thiazoles Based on Benzopyran Moiety Through The Utility of Versatile Hydrazonoyl Halides as In Vitro Monoamine Oxidase Inhibitors

The chromene compound 1 is used as a key intermediate for synthesis of new heterocyclic compounds, and it reacted with hydrazonoyl chlorides in presence of TEA to give the amidrazone derivatives 3a , 3b , 3c , 3d , 3e , 3f , 3g , 3h , which were cyclized to the corresponding triazepines 5a , 5b , 5c , 5d , 5e , 5f , 5g , 5h on boiling with sodium ethoxide. Conversion of compound 1 to the methylthiocarbamate derivative 6 was performed through its reaction with carbon disulfide and KOH followed by treatment with methyl iodide. Compound 6 reacted with hydrazonoyl chlorides in presence of TEA to give thiadiazoles 8a , 8b , 8c , 8d , 8e , 8f , 8g . In addition, chromene 1 combined with aminodithiocarbamic acid in DMF under reflux to furnish the thiosemicarbazide derivative 9 , which in turn interacted with several hydrazonoyl chlorides to give the thiazole derivatives 11a , 11b , 11c , 11d , 11e . The structures of the prepared compounds were confirmed from their spectroscopic data and elemental analysis. The synthesized compounds were tested against both monoamine oxidase (MAO)‐A and MAO‐B and corrected to analyses showed good inhibitory activities especially against MAO‐A.     

Synthesis and Antimicrobial Activity of Some Novel Substituted Bis‐Pyridone,Pyrazole, and Thiazole Derivatives

A variety of novel bis‐heterocyclic derivatives were synthesized via the reaction of bis‐cyanoacetanilide derivative 3 with various aromatic aldehydes (1:2 molar ratio), to give the corresponding bis‐arylidene derivatives 5a , 5b , 5c , 5d , 5e , 5f , 5g , 5h , 5i , 5j , 5k , 5l , 5m . On the other hand, reacting compound 3 with substituted 2‐hydroxybenzaldehydes 6a , 6b , 6c afforded 2‐iminochromene‐3‐carboxamides 7a , 7b , 7c . The reaction of compound 5 with malononitrile afforded the novel bis‐pyridones 9a , 9b , 9c , 9f , 9g , 9h . The reaction of 5 with hydrazine derivatives afforded pyrazoles 11a , 11b , 11c , 11d , 11e , 11f , respectively. Compound 3 reacts with phenyl isothiocyanate in the presence of potassium hydroxide at room temperature followed by addition of some different halo‐carbonyl compounds to afford bis‐poly‐functionalized thiazole derivatives 13a , 13b , 13c . The bis‐enamine derivative 15 reacts also with hydrazine hydrate, guanidine, and hydroxylamine to give bis‐pyrazole 17 , pyrimidine 19 , and isoxazole 21 derivatives, respectively. Some of the newly synthesized compounds show moderate to high antimicrobial activity.     

Utility of (p‐Sulfonamidophenyl)azomalononitrile,and Ethyl Acetoacetate in Synthesis of Fused Azole and Azines Derivatives II

[(p‐Sulfonamidophenyl)azo]malononitrile ( 1a,b ) reacted with N‐cyclohexanemethylidene‐2‐cyanoacetohydrazide, N'‐arylmethylidene‐2‐cyanoacetohydrazide ( 3a‐c ), S‐methylthiourea and hydrazine hydrate to afford [1,2,4]triazolo‐[1,5‐a]pyridinone derivatives ( 2a,b ) & ( 4a‐c ), substituted pyrimidines 5a,b and 6a,b. The corresponding pyridazinones 7a,b were synthesized from the reaction of 1c,d with ethyl cyanoacetate. Compound 7a,b reacted with elemental sulfur to yield 8a,b . Compound 6a underwent cycloaddition with α‐cinnamonitrile 9a‐e to yield 11a‐c, 14 and 15 . Also, compound 6a reacted with β‐ketoester and 1,3‐diketones to give 16, 17 and 18 .     

The reactions of tetrafluoroethylene oligomers: V. The reactions of perfluoro-3,4-dimethyl-4-ethylhexene-(2) with thionucleophiles and the chemical transformations of reaction products

The reactions of perfluoro-3,4-dimethyl-4-ethylhexene-(2) (1) with s-nucleophiles such as benzylthiol, allylthiol, phenylthiol and the chemical transformations of these reaction products were reported. 1 reacted with S-nucleophiles to give four types of isomeric products. At ?30～ ?60°C, in ether, kinetically controlled product 2 (a, b, c) were formed. Compound 2 might be converted directly into the thermodynamically stable products 3 (a, b,) in DMF-KF at r.t., At 100°C, 2 was converted to 4 (a, b, c) via intramolecular rearrangement. In KF-DMF at r.t., 4 was isomerized to 5 (a, b, c). 2a also reacted with another mole of thiol to give the corresponding disulfide 6 and hydrogen-containing olefin 7a as well as the disubstituted product 8a in DMF, but only give 3a and 9a in ether-Et₃N. The reaction of 2a with methyl alcohol gave only a small amounts of 3a and 10a. The reaction of 2b with dimethylamine was complex and 3b and 11 were obtained in low yield.