第五 六族元素的有机化合物在有机合成中应用的研究XXXI. 应用稳定胂叶立德合成β-酮酸酯和β-二酮的一种简便方法

本文报道一种在温和条件下使稳定胂叶立德(1)砷-碳键断裂的方法,从而合成了β-酮酸酯和β-二酮类化合物,特别是相应的含氟化合物,该方法操作简便,产物容易分离提纯,得率较好。     

第五、六族元素的有机化合物在有机合成中应用的研究 XVII.胂叶立德与氟代烯烃的反应

Reaction of perfluoropropylene (2a) with cyanomethylene- triphenylarsorane (1b) gave cyano-2, 3, 3, 3-tetrafluoropropionylmethylene-triphenylarsorane (4b), and with benzoylmethylene-(1c) and acetylmethylene-triphenylarsorane (1d) gave benzoyl-(3c) and acetyl-(trans-perfluoropropen-1-yl)- methylene-triphenylarsorane (3d), respectively 3c and 3d could be converted to benzoyl-(4c) and acetyl-2, 3, 3, 3-tetrafluoropropionyl -methylene triphenylarsorane (4d), respectively by refluxing with moist benzene. Reaction of carbomethoxymethylene- triphenylphosphorane (1e) with perfluoropropylene was similar to that of arsorane. However, benzoylmethylene-and acetylmethylene- triphenylphosphorane were unreactive towards perfluoropropylene. Reaction of carbomethoxymethylene-triphenylarsoraen (1a) with trifluorochloroethylene gave carbomethoxyfluoroacetylmenthylene- triphenylarsorane (4f) in low yield. when the residue was treated with methanol, difluorotriphenylarsorano and methyl- fluorochloroacetate (8) were obatined. The structures of the aforementioned products are ascertained by elemental analyses, IR, ^1H NMR, ^1^9F NMR and mass spectra.     

第五丶六族元素的有机化合物在有机合成中应用的研究 XXIII. 卤化烷氧羰基烷基三苯基 在N,N-二甲基甲酰胺中的分解反应

本文报道卤化烷氧羰基烷基三苯基在N,N-二甲基甲酰胺中, 100°C左右加热时所发生的分解反应. 当盐1的酯烷基R2 为甲基国, 生成产物为 有时也生成2和3的混合物. 当 盐1的酯烷基R2为乙基或正戊基时, 只生成产物2.     

第五、六族元素的有机化合物在有机合成中应用的研究 LII: 含氟烯醚的合成

含氟烯醚可作为亲偶极体进行偶极环加成反应. 某些含氟烯醚在亲核试剂作用下可作为烷基化试剂. 本文报导了Wittig反应通过芳氧.     

第五丶六族元素的有机化合物在有机合成中应用的研究 XVIII:氰基亚甲基三苯基胂与酮反应的立体化学以及几种吸电子基团取代的甲基三苯基 砷盐与酮的反应

The stereochemistry of carbonyl olefination reaction of cyanomethylene triphenylarsorane with ketones is reported. The thermodynamically stable E isomer of the products α, β unsaturated nitrile was formed predominantly. Under the experimental conditions we adopted, the reaction conditions had little effect on the E, Z ratio of the reaction products. However, the structure of the substrate showed profound effect. The results shown in Table 1 are similar to that of the reaction of carbomethoxymethylene triphenylarosorane reported in the previous paper. When methyl t-butyl ketone was used as the substrate and the reaction carried out in benzene solution, nearly pure E isomer was obtained. The reaction mechanism was proposed as shown in the previous paper. When Δ4-cholesten-3-one was used as the substrate, change of the solvents showed more prominent effect on the E, Z ratio of the reaction product. This paper also deals with the reaction of three electron-withdrawing group (CN, COOCH3, COCH3) substituted methyltriphenylarsonium salts with ketones in the presence of K2CO3, Na2CO3/benzo-15-crown-5, K2CO3/18-crown-6 or (C2H5)3N in CH3OH solution. The latter three gave satisfactory results (Table 2). The chromotographically pure products could be obtained from the crude products by passing through silica gel column. Its E, Z ratio is nearly the same as that of the crude product. This method seems to be a good one for preparing olefinic compounds in miligram scale.     

第五,六族元素的有机皂化合物在有机合成中应用的研究 XIX:全氟丁炔-[2]酸仲丁酯的合成及其化反应

The intramolecular Wittig Reaction has been applied to the synthesis of sec-butyl perfluorobutynoate. the saponification of the product with aqueous sodium hudroxide gave 3-sec-butoxy-4, 4, 4-trifluoro-(2) butenoic acid and 4, 4, 4-trifluoro-3-oxobutyric acid in 1:5 ration.     

第五 六族元素的有机化合物在有机合成中应用的研究 XXX。苯甲酰基亚甲基三苯基膦、胂与2-全氟炔酸甲酯的反应以及4-全氟烷基-6-苯基-2-吡喃酮的合成

苯甲酰基亚甲基三苯基膦、胂(1)与2-全氟炔酸甲酯(2)反应,生成主要产物3和少量4,总产率在95%左右,证明了3和4的结构,并推测了反应机理,胂化合物的3d～3f在含水甲醇中加热,发生砷-碳键断裂,生成4-全氟烷基-6-苯基-2-吡喃酮(7),产率40～83%。     

第五、六族元素的有机化合物在有机合成中应用的研究——ⅩⅤ.含氟膦叶立德的质谱研究

本文报道11个含氟膦叶立德的电子轰击(EI)质谱和化学电离(CI)正、负离子质谱。前者的断裂机理和一般膦叶立德相似,形成一系列骨架重排离子,而后者只出现(C₆H₅)₂离子。在1～11的CI正离子质谱中,基峰均为[M+H]⁺,在7～11中还观察到氧重排离子m/β279。CI负离子质谱出现稳定的[M-·C₆H₅]^-离子,化合物7～11的正、负离子质谱都出现特征的炔离子和炔基正离子。     

二茂钛含氟有机酸衍生物的质谱研究

本文研究了二茂钛含氟长链有机酸衍生物(1～3)和具有环状结构的新型二茂钛全氟有机酸(4～7)的电子轰击质谱(EIMS)和负离子化学电离质谱(NICIMS)。在EI谱中出现弱的或不出现M~+,1～7均以CpTiF_2离子为基峰。高质量区的主要特征碎片离子有[M-·cp]~+、[M-R]~+(1～3)和氟重排离子。在低质量区出现一系列二茂钛及茂钛氟重排离子。 1、4～7的NICI(CH_4)质谱中,4、5出现强的M~-离子峰,1出现[M-1]-离子峰,有两个钛的环状结构化合物6和7出现双电荷M~=离子峰,而不出现M~-。     

第五、六族元素的有机化合物在有机合成中应用的研究XXIX, 甲氧羰基亚甲基三苯基膦、胂与2-全氟炔酸甲酯的反应以及3-全氟烷基-戊烯二酸二甲酯的合成

甲氧羟基亚甲基三苯基膦(1a)、胂(1b)与2-金氟炔酸甲酯(2)在无水苯中迅速反应,生成高产率的加合物3. 3的结构通过元素分析、红外光谱、核磁共振谱和质谱予以鉴定,并证明了反应机理. 胂叶立德3d, 3e和3f在温和条件下水解,砷-碳键断裂,合成了高产率的3-全氟烷基-戊烯二酸二甲酯(7)。     

含氟膦、胂叶立德的质谱研究

本文报道37个含氟膦.胂羰基的叶立德衍生物的电子轰击(EI)和8个含氟胂羟基叶立德的甲烷化学电离(Cl)正.负离子质谱. 研究其断裂规律,氧和氟原子重排以及不同取代基对一些特征离子强度的影响.