二甲基二氯硅烷与二甲基环硅氧烷反应的研究

α,ω-二氯聚二甲基硅氧烷(1)是有机硅高分子制品的重要中间体,其n值的大小对有机硅高分子制品的性能有很重要的影响.因此,选用如下反应来制取中间物,是人们感兴趣的方法.其特点是C—Si在反应中不断裂,而Cl—Si和O—Si却在(CH_3)_2SiCl_2与-(CH_3)_2Si—O-间进行交换,以形成各种不同n值的α,ω-二氯聚二甲基硅氧烷.用精密分馏、气体色谱等方法定量地研究反应产物是不合适的,因为     

含5-氟脲嘧啶齐聚物的合成

<正> 5-氟脲嘧啶是用于治疗肺癌、肾癌、乳癌、结肠癌等癌变的药物。虽然5-氟脲嘧啶具有上述疗效,但在临床应用时,尚存在恶心,呕吐,腹泻,白细胞、血小板下降等副作用。更为严重的缺点,是既对肿瘤细胞有活性,同时也作用于正常细胞,为克服此缺点,将抗癌药物与低分子化合物结合,诸如激素、磺胺,这些是已知能集聚在一定组织内药物,但利用此法,迄今也很少获得成效。     

含5-氟脲嘧啶的聚硅氧烷的合成

5-氟脲嘧啶与α、ω双二乙胺基聚二取代基硅氧烷反应 可得含5-氟脲嘧啶的缩聚物。并以红外、核磁对缩聚物进行了研究。在室温将所得缩聚物在不同pH介质中,进行水解,以266.5nm处紫外吸收光度,定量测定所释放出来5-氟脲嘧啶。当缩聚物n值增大时,水解速度减慢,1、3结构则比2、4结构缩聚物为快。     

SYNTHESIS OF OLIGOMERS CONTAINING 5-FLUOROURACIL

The condensation oligomers of 5-fluorouracil were prepared by reaction of 2,4-bis-(trimethyl-silyloxy)-5-fluoropyrimidine) with various dicarboxylic chlorides, e.g.The structures of obtained oligomers were characterized by IR and the oligomers were then hydrolyzed in acid, alkaline and neutral media at room temperature respectively. The amount of 5-fluorouracil released was quantitated by measuring its UV absorbance at 265.5nm. However in the case of oligomers containing phenylene moiety, 5-fluorouracil was not detected when the hydrolysis was conducted in acid or neutral medium, while in the case of oligomers containing methylene moiety, hydrolysis proceeded easily in acid, alkaline and neutral media.     

甲基和苯基乙氧基硅烷的一步合成

溴甲烷或氯苯和金属镁作用于烃基三乙氧基硅烷可以一步合成二烃基二乙氧基硅烷,亦可作用于二烃基二乙氧基硅烷合成三烃基乙氧基硅烷.此法可不用乙醚,亦无需先制成Grignard试剂.操作方便,产率均在70%以上.     

SYNTHESIS AND CHARACTERIZATION OF POLYMER DERIVATIVES OF cis-PLATINUM COMPLEXES

Cis-platinum complexes used as antitumor drugs were attached onto preformed polymers toreduce the toxicity. Either alternating copolymer of styrene and maleic anhydride (CPSMA) orpolyacrylic acid (PAA) is readily dissolved in alkaline solution. The cis-platinum complexes areeasily converted into water soluble species when treated by silver nitrate in water. The expectedproducts could be obtained when the two aqueous solutions were brought together. The productswere characterized by elementary analysis, IR and XPS. The polymer derivatives could exchangeligands with nucleophilic groups in biological environment and also exhibit antineoplastic activity.     

低温辐射聚合制备聚合物药的慢释放研究

本文研究了低温辐射慢释放药的单体配比、药物含量及辐射刺量对药物释放速率的影响。结果表明,增加疏水性单体MMA,可以有效地控制大分子量药物消炎痛的释放速率;增加MMA及EDGMA,可以有效地控制小分子量药物5-Fu的释放速率;增加5-Fu的比例,可以降低5-Fu的释放速率;随辐照剂量的增加,聚合物药中5-Fu的释放量降低,二者之间成正比关系。     

关于原矽酸乙酯的制备

现行文献中所载原矽酸乙酯的制备法,其产率均不能使人满意。我们找出产率不高的主要原因是过量的醇和作用所发生的氯化氢生成了水,水引起了原矽酸乙酯的水解缩聚作用。这已经由实验证明。作用副产物亦经纯化鉴定,主要的是1,3-六乙氧基二矽氧烷和1,3,5-八乙氧基三矽氧烷。改进的制备法是将等作用量的四氯化矽和无水乙醇(克分子数比为1:4)同时滴入冷却的、受搅拌的原矽酸乙酯(作为稀释剂)中,经搅拌半小时,即徐徐加热以除去氯化氢,然后蒸馏。这样,原矽酸乙酯的产率达95%。这个方法并适用于连续操作。     

2,4,6-三甲基-2,4,6-叁(3′3′3′-三氟丙基)环三硅氧烷的简便制备法

2,4,6-三甲基-2,4,6-叁(3′3′3′-三氟丙基)环三硅氧烷(D_3~F)是合成氟硅橡胶的单体,一般以硅氢加于烯烃而制得:但因3,3,3-三氟丙烯的沸点为-22℃,需要在加压低温下操作,既不易纯化,又难以控制反应.我们以沸点102℃的甲基三甲氧基硅烷(1)、沸点45.5℃的1,1,1-三氟-3-氯丙烷(2)与镁屑在无溶剂常压下反应.这样既方便又安全,制得的3,3,3-三氟丙基     

SYNTHESIS AND CHARACTERIZATION OF TITANOCENE POLYMER DERIVATIVES

Titanocene polymer derivatives with potential antitumor properties were synthesized by interfacial condensation. The preformed polymers used are PAA (polyacrylic acid), CPSMA (1:1 alternating copolymer of styrene and maleic anhydride) and DVEMA (1:2 copolymer of divinyl ether and maleic anhydride). The ratio of practical and theoretical titanium content is 73.6%, 92.2% and 86.2% for PAA, CPSMA and DVEMA polymer derivatives respectively. The IR spectra of the polymer derivatives possess the characteristic absorptions of titanocene. XPS (X-ray photoelectron spectroscopy) of O_(1s) and Ti_(2p3/2) supports the existence of Ti-O bonding.