CYCLIC ORGANOPHOSPHORUS COMPOUNDS. PART XVI1. MASS SPECTROMETRIC FRAGMENTATION OF SOME 5,5-DIMETHYL-1,3,2-DIOXAPHOSPHORINAN 2-OXIDES AND 2-SULPHIDES

Abstract

The mass spectra of seventeen 5,5-dimethyl-1,3,2-dioxaphosphorinan 2-oxides and nineteen 5,5-dimethyl-1,3,2-dioxa-phosphorinan 2-sulphides, mostly with amino substituents on phosphorus, have been determined. In some cases, interpretation of the spectra was aided by accurate mass measurements and by the examination of deuterated compounds. For the 2-sulphides, sulphur is lost either as such or as the thiol radical, both processes often being of weak intensity, and the thiol hydrogen appears to be derivable from either a ring methylene group or a C-5 methyl group. Loss of S or HS occurs more strongly for the phosphoramidothionates which, together with the phosphoramidates, also fragment to an important extent in the amido substituent with retention of the dioxaphosphorinan ring; P[sbnd]N bond cleavage is also observed. For the 2-thiones, the ions at m/e 165 (14; R[dbnd]H) and 133 (15; R[dbnd]H) are characteristic.     

PHOSPHORUS-NITROGEN COMPOUNDS. PART 64.1 THE REACTIONS OF HEXACHLOROCYCLOTRIPHOSPHAZATRIENE WITH 2, 2-DIMETHYLPROPANE-1, 3-DIOL. NUCLEAR MAGNETIC RESONANCE STUDIES OF THE PRODUCTS

Abstract

The reactions of hexachlorocyclotriphosphazatriene, N₃ P₃ CI₆, with 2, 2-dimethylpropane-1, 3-diol yield monospiro-, N₃ P₃ Cl₄ [(OCH₂)₂ CMe₂, dispiro-, N₃ P₃ Cl₄((OCH₂)₂CMe₂|₂, and trispiroderivatives, N₃ P₃ ((OCH₂)₂, CMe₂]₃. An ansa, N₃ P₃ CI₄ [(OCH₂)₂ CMe₂]₂ and a spiro-ansa, N₃ P₃ Cl₂- ((OCH₂), CMe₂,]₂ and a doubly-bridged compound, (N₃ P₃ Cl₄,)₂[(OCH₂)]₂ were also isolated. Product types and relative yields were compared with those arising from propane-1, 3-diol. The yields of ansa products from the reactions of the dimethyl diol seem to be considerably enhanced relative to those of its unmethylated analogue. ³¹P and ¹H n.m.r. spectra are reported.     

8-喹啉偶氮显色剂QADCB的合成及其分析性能的研究

报道了8-喹啉偶氮显色剂2-(8-喹啉偶氮)-5-二羧甲氨基苯甲酸(QADCB)的合成、提纯与鉴定,研究了其与Co(Ⅱ)、Ni(Ⅱ)、Fe(Ⅲ)的显色反应,对QADCB与Co(Ⅱ)的显色反应作了研究。在pH5.9的缓冲体系中,试剂与Co(Ⅱ)形成棕红色配合物,其最大吸收波长位于650nm,表观摩尔吸光系数为4.2×104L.mol-1.cm-1,钴量在0~20μg/25mL范围内符合比耳定律。方法简便、快速,选择性较好,已用于纯铜、维生素B12中微量钴的测定,结果满意。     

A PETERSON OLEFINATION REACTION USING SILYL-SUBSTITUTED SULFONAMIDE CARBANIONS. SYNTHESIS OF VINYLIC SULFONAMIDES

Abstract

α-Trimethylsilyl-substituted sulfonamides RCH(SiMe₃)SO₂N(CH₃)₂ (3), (R[dbnd]H, CH₃ and C₆H₅) are synthetized in almost quantitative yields. Their lithium derivatives 4 undergo a smooth Peterson olefination reaction with nonenolisable carbonyl compounds to give good to excellent yields of vinylsulfonamides 6. With R[dbnd]H, the reaction is highly E-stereoselective. Moderate stereoselectivity is obtained in the cases of R[dbnd]CH₃ and R[dbnd]C₆H₅.     

IMPROVED SYNTHESIS OF DIALKYLTHIOXAPHOSPHORANESULFENYL CHLORIDES AND BROMIDES

Abstract

Dialkylthioxaphosphoranesulfenyl chlorides and bromides can be conveniently prepared in the reaction of the corresponding thioamides with hydrogen chloride generated in situ with trimethylsilyl chloride and ethanol. Stability of the chlorides and bromides obtained by this method is high and the yields are quantitative.     

NaCuO2及有关化合物的XPS研究

自从Muller等人发现高温超导体并提出超导机理可能与Cu~(3 )/Cu~(2 )混合价态有关以来,人们对三价铜的兴趣大大增加了。X射线光电子能谱(XPS)是研究原子价态的有效工具。但用XPS检测高温超导体中是否存在Cu~(3 )时得到了互相矛盾的结果。在这种情况下记录典型三价铜的XPS谱作为参照很有必要。但是到目前为止用XPS研究典型三价铜无机化合物的报导仅有少数几篇,而且文献[1]和[2]测得的Cu~(3 )-Cu~(2 )的Cu2p_(3/2)电子结合能位     

新试剂7-(苯并噻唑-2-偶氮)-8-羟基喹啉-5-磺酸的合成及与钴显色反应的研究

报道了新试剂7-(苯并噻唑-2-偶氮)-8-羟基喹啉-5-磺酸(BTHQSA)的合成方法,研究了该试剂与钴显色反应情况.结果表明,在pH3.94乙酸-乙酸钠、乳化剂OP存在下,Co-BTHQSA-OP配合物最大吸收波长为582nm,表观摩尔吸光系数ε_(582)=-5.7×10~4,钴的含量在0～12μg/25ml内,服从比耳定律.     

METALLOLES-14 CHEMISTRY

Abstract

In order to obtain β-functionalized 1-sila (or germa)-cyclopent-2-enes (M = Si, Ge; R¹, R² = Me or Ph; R³, R⁴ = H or Me) (I) various oxidation methods of metallacyclopent-3-enes have been examinated. The resulting metallacyclopent-4-ene-3-ols (I, X = OH) were converted into phenylcarbamates (I = OC(O)NHPh) or S-methylxanthates (I = OC(S)SMe) and their utility as intermediates in the synthesis of metalloles (siloles and germoles) was investigated.

Depending on the experimental conditions, catalytic dehydration of metallacyclopentenols or thermolysis of carbamates or xanthates give various dienes via four different reaction processes: i) β-elimination C-M; ii) β-elimination C-H; iii) isomerization of C-methylated metalloles; iv) catalytic demetallation.

The thermolysis of arylcarbamates is the best method for conversion of I to metalloles, specially for the synthesis of remarkably dimerization-stable 1,1-R¹R²-3,4-dimethylmetalloles (≥ 80% yield). A one pot synthesis of these stable metalloles from the corresponding alcohol and phenyl isocyanate is proposed.

Unstable monomeric metalloles are stabilized by transition metal complexes or trapped by a (4 + 2) cycloaddition.     

由丙酮还原偶联合成2,3—二甲基丁烯—2的研究

本文报道了利用ＭｃＭｕｒｒｙ反应，由丙酮还原偶联合成２，３—二甲基丁烯—２（ＤＭＢ—２）的实验结果。实验考察了镁粉还原四氯化钛的时间、丙酮与四氯化钛之比等因素对ＤＭＢ—２收率的影响。探讨了低价钛试剂活性物的价态与ＤＭＢ—２收率之间的关系。实验表明，大部分ＤＭＢ—２是在最初几分钟内生成的，每摩尔的低价钛试剂最多可转化９摩尔以上的丙酮。     

含亚甲基和双二氮杂萘酮结构的聚芳酮的合成与性能

聚芳醚酮是一类重要的具有优异综合性能的工程塑料 ,它具有高的热稳定性、尺寸稳定性、耐溶剂性、好的加工性能和电性能 ,因而它经常作为复合材料的基质、粘合剂等被广泛的应用于航空、航天和电子等领域 .近几十年来 ,人们付出了很大的努力去开发聚芳醚酮新品种[1,2 ] .本研究组以 4 (4′ 羟基苯氧基 ) 2 ,3 二氮杂萘 1 (2Ｈ) 酮为缩聚单体制备了一系列的性能优良的聚芳醚酮[3～ 6] ,在主链中引入高密度的氮杂萘酮结构是获得高热稳定性和良好溶解性的重要途径 .由单体中含有更多的氮杂萘酮结构获得可溶解且耐温等级更高的聚芳酮是人们期…     

STUDIES ON ORGANOPHOSPHORUS COMPOUNDS PART IX.1 THE ACTION OF Di-, TRIALKYL PHOSPHITES AND THIOL ACIDS ON SOME ENAMINOLACTONES

Abstract

Di-, and trimethylphosphites react with enaminolactone, 4, only in methanol to give N-benzoyl-3-phenyl-3-phosphonoalanine-trimethylester (7) in good yields. Diphenylphosphinodithioic acid also reacts with 4 to give N-benzoyl-3-phenylcysteine-methyl ester-diphenylphosphinodithioate (9). A mechanism is proposed to account for the formation of 7. Compatible analytical and spectroscopic results were obtained for the new compounds.     

希土高氯酸盐与N,N''''—二(2—吡啶亚甲基)—1,2—乙二胺配合物的合成及性质研究

自六十年代以来,希土离子与芳香胺及其衍生物的配合物研究受到人们的普遍重视。文献工作表明,N,N’-二(2-吡啶亚甲基)-1,2-乙二胺(简写为bpme)可与希土离子形成1:1型的配合物,但希土离子与该配体的1:2型固体配合物文献中尚未报道。为了探讨bpme与希土离子形成非1:1型配合物的可能性,我们在甲醇介质中合成出希土高氯酸盐与bpme的1:2型固体配合物,并对其性质进行了研究。     

大豆分离蛋白接枝氨基封端聚2-丙烯酰胺基-2-甲基丙磺酸的合成及溶液性质研究

用巯基乙胺为链转移剂,过硫酸铵为引发剂合成了氨基封端的聚2-丙烯酰胺基-2-甲基丙磺酸(H2N-PAMPS).再用1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐(EDC)和N-羟基琥珀酰亚胺(NHS)在室温下催化H2N-PAMPS的端氨基与大豆分离蛋白(SPI)的羧基反应形成酰胺键,得到接枝物SPI-g-NH-PAMPS.用1H-NMR、傅利叶红外光谱、13C-NMR对H2N-PAMPS和接枝物SPI-g-NH-PAMPS进行结构表征.用zeta电位仪、紫外可见光光谱,荧光光谱,动态激光光散射对SPI及其接枝物SPI-g-NH-PAMPS的水溶液性质进行了研究.结果表明,与SPI相比,SPI-g-NH-PAMPS的溶解性、表面疏水性、乳化性等有所改善,接枝物SPI-g-NH-PAMPS聚集体粒径增大,形成独特的核壳结构.     

新试剂2-(6-甲基-2-苯并噻唑偶氮)-5-二乙氨基酚与铂的显色反应及配合物结构研究

研究新试剂2-(6-甲基-2-苯并噻唑偶氮)-5-二乙氨基酚(MBTAE)与铂的显色反应。在1-羟基-2-萘甲酸(R)存在下,于pH 5．5的乙酸盐缓冲溶液中,形成配位比为PtMBTAER＝111的三元配合物,λmax＝592nm,表观摩尔吸光系数ε＝6．84×104L·mol-1·cm-1。通过配合物的紫外和红外光谱性质,研完了三元配合物的结构,方法应用于催化剂中铂的测定,结果满意。     

SYNTHESIS OF NOVEL BIDENTATE (Te,N) LIGANDS-2-ARYLTELLUROETHYLAMINES AND THEIR COMPLEXATION WITH MERCURY (II)

Abstract

Sodium aryltellurolate (ArTe^?Na⁺, where Ar = 4-MeOC₆H₄ or 4-EtOC₆H₄) reacts with 2- bromoethylamine resulting in the (Te, N) ligands 2-aryltelluroethylamine (ArTeCH₂CH₂NH₂, 1) which have been characterized by elemental analyses, molecular weight, IR, ¹H and ¹³C NMR spectra. With HgCI₂, they form HgC1₂·1 type of complexes. IR, ¹H and ¹³C NMR spectra of the complexes suggest that 1 ligates as a bidentate ligand with respect to Hg(II). Osmometric molecular weight measurements suggest that on heating the mercury complex HgCl₂·lb (Ar = 4-EtOC₆H₄) in solution, relatively less soluble species result. It seems to have two Hg atoms bridged by two (Te, N) ligands. The HgC₂·la (Ar = 4-MeOC₆H₄) has very low solubility in organic solvents and. therefore, seems to be dimerized or polymerized during the synthesis. Analysis of CH₂ rocking bands in IR spectra suggests that two CH₂ groups of the ligands are most probably in a gauche conformation in the mercury complexes.     

希土高氯酸盐与N,N''—二(2—吡啶亚甲基)—1,2—乙二胺配合物的合成及性质研究

自六十年代以来,希土离子与芳香胺及其衍生物的配合物研究受到人们的普遍重视。     

新试剂(2,6-二氯-4-硝基苯)-3-(4-硝基苯)-三氮烯的合成及其与汞的显色反应研究

合成了新试剂(2,6-二氯-4-硝基苯)-3-(4-硝基苯)-三氮烯(DCNPNPT),测定了试剂的亚氨基离解常数pKa＝9．2。在TritonX-100存在下,pH9．8～11．0范围内,试剂与Hg2+形成14黄色型配合物,用双波长法测得其表观摩尔吸光系数为2．27×105L·mol-1·cm-1。汞含量在0～10μg／25ml范围内符合比耳定律,用此法测定了天然水和实验室废水中微量汞含量,结果满意。     

9-(2-氨基苯胺基)吖啶的合成及其荧光光度法测定牛血清白蛋白

报道了荧光试剂9 (2 氨基苯胺基)吖啶(o APAA)的合成,产品经多次重结晶提纯,用IR、1HNMR和元素分析确证了结构,研究了它的荧光性质。拟定了一个测定牛血清白蛋白(BSA)的荧光光度法。在pH 2.4的H3PO4 KH2PO4 缓冲体系中,BSA与此试剂作用,产生荧光增敏,方法的检出限为0.015 mg·L-1,线性范围为0~5.0 mg·L-1。     

甲基丙烯酸2-(N-吖啶酮基)乙酯的合成及其敏化的烯类单体光聚合

我们曾报道过4-甲基丙烯酰氧基二苯甲酮(MABP)与甲基丙烯酸N,N-二甲氨基乙酯(DMAEMA)构成的氧化还原引发体系敏化丙烯腈的光聚合。由于MABP及DMAEMA是可聚合的二芳基酮和脂肪叔胺,因而既能参与引发又能参与聚合而进入聚合物链中。一般二苯甲酮要同三级胺,如三乙胺等一起在紫外光照条件下形成光氧化还原引发体系才能有较好的引发效果。同一分子中既含二苯甲酮基又含三级胺基的光敏剂,