Umsetzungen mit 1,3-Dichlor-2-methylenpropan,III. Synthesen und Reaktionen von 1,3-Diamino-2-methylenpropanen

Reactions with 1,3-Dichloro-2-methylenepropane. III. Synthesis and Reactions of 1,3-Diamino-2-methylenepropanes 1,3-Bis(dialkylamino)-2-methylenepropanes are obtained by reaction of the chlorination product of isobutene with secondary amines. The synthesis of 1,3-diamino-2-methylenepropane succeeds by Gabrielsynthesis, by reaction of 1,3-diiodo-2-methylenepropane with liquid ammonia and by dehydration of 1,3-diamino-2-methyl-2-propanol, obtained from methallylchloride. The use of 1,3-diamino-2-methylenepropane as a C₃N₂-reagent for the synthesis of heteroalicycles is described.     

离子交换在1,3-丙二醇发酵液脱盐中的应用

针对1,3-丙二醇发酵液分离提取过程中的脱盐难点问题,采用离子交换方法对1,3-丙二醇发酵液的脱盐进行了研究。选用D001强酸性阳离子交换树脂及D354弱碱性阴离子交换树脂,进行了静态、动态及连续交换工艺的实验,并对阳、阴离子交换树脂交换顺序进行了考察。结果表明,离子交换方法用于发酵液的脱盐工艺具有良好的效果,阳、阴两种离子交换树脂的交换、再生性能稳定,交换后的料液完全能够满足后续工艺的要求,为生物法1,3-丙二醇发酵液分离提取提供了一个新的工艺手段。     

1,3-Dithienium- und 1,3-Dithioleniumsalze. IX. Reaktionen von 1,3-Dithian-2-ylium-tetrafluoroboraten mit C-Nucleophilen

1,3-Dithienium and 1,3-Dithiolenium Salts. IX. Reactions of 1,3-Dithiane-2-ylium Tetrafluoroborates with C-Nucleophiles 1,3-Dithian-2-ylium tetrafluoroborates ( 1 ), which can be easily obtained by variable methods, react in good to excellent yields with variable C-nucleophiles to new geminal disubstituted 1,3-dithianes. The latter compounds are potential precursors of interesting synthetic building blocks. Reactions are described with 2-lithio-1,3-dithianes 2 , sodium cyanide 4 , sodium salts of the nitro alkanes 7 and CH-acids of the type of the 1,3-dicarbonyl compounds 9 . The reduction of 3-oxo-2-(2-phenyl-1,3-dithian-2-yl)-ethoxybutanoat–following a diastereoselective pathway – leads to the Cram product 11 . Further presented is the crystal structure of 2-phenyl-1,3-dithiane-2-ylium tetrafluoroborate ( 1b ).     

1,3-二(二苯基氯硅烷基)-2,2,4,4-四苯基环二硅氮烷的合成及液晶性表征

用1,3-二(二甲基氯硅烷基)-2,2,4,4-四甲基环二硅氮烷与二苯基二氯硅烷反应,得1,3-二(二苯基氯硅烷基)-2,2,4,4-四苯基环二硅氮烷,用甲苯与正辛烷提纯化合物,熔点200～206℃,收率75%～78%。产品经IR和1H NMR确证了结构,用示差扫描量热法(DSC)与偏光显微镜分析,发现该化合物具有液晶性,属于热致型液晶,显示六方相。经教育部科技查新工作站(L03)2007年11月22日出具的第2007236号《科技查新报告》证实,在国内文献中未见关于1,3-二(二苯基氯硅烷基)-2,2,4,4-四苯基环二硅氮烷液晶性表征的相关报道。     

取代1,3-二苯基-1,3-丙二酮的合成与抗氧化性能

以取代芳酮和取代芳酯为原料,经克莱森反应合成了5个取代1,3-二苯基-1,3-丙二酮。采用正交实验优化1,3-二(4-甲氧基苯基)-1,3-丙二酮较佳的工艺条件:以甲苯为溶剂,NaNH2作催化剂,n(对甲氧基苯乙酮)∶n(对甲氧基苯甲酸甲酯)∶n(氨基钠)=1∶4∶5,微波辐射功率320 W,反应时间45 min,收率为72.1%。合成的产物结构经IR与1HNMR光谱进行了结构表征,用HPLC测定其含量。对UV光谱有良好的吸收及对猪油有较好的抗氧化作用。     

Zur Reduktion von 1,3-Thiaziniumsalzen; Synthese von 6,6′-Bi-1,3-thiazinylen und 6,6′-Bi-1,3-thiazinylidenen

On the Reduction of 1,3-Thiazinium Salts; Synthesis of 6,6′-Bi-1,3-Thiazinyls and 6,6′-Bi-1,3-Thiazinylidenes 1,3-Thiazinium perchlorates 1 are linked together in a reaction with zinc powder or at a cathode forming 6,6′-bi-1,3-thiazinyls 3 . This reaction proceeds via radical intermediates 2 . Evidence of the existence of the very short-lived radicals is given by means of ring-disk-voltammogrammes as well as by electrochemical luminescence excitation. The 6,6′-bi-1,3-thiazinyls 3 undergo the reverse fission at a platinum anode resulting in thiazinium salts 1 , whereas the dehydrogenation by chloranile yields the violet 6,6′-bi-1,3-thiazinylidenes 6 .     

1,3-丙二醇的生产与应用

1,3-丙二醇是合成聚对苯二甲酸丙二醇酯(PTT)的单体,PTT具有广泛应用领域,本文着重阐述1,3-丙二醇的性能、合成及几种生产方法的比较。     

2-甲基-1,3-氧硫杂环戊烷和2-丙基-1,3-氧硫杂环戊烷的合成

以对甲苯磺酸为催化剂 ,巯基乙醇与乙醛、丁醛 (量比为 1.0∶1.1)在苯中共沸脱水 ,合成两种目标产物 :2 甲基 1,3 氧硫杂环戊烷、2 丙基 1,3 氧硫杂环戊烷。其产率分别为 81%和 88% ,质量分数分别为 99%和 98%。经红外光谱、色谱、质谱、核磁共振谱检测 ,确证了产物结构。此方法简便易行 ,产率较高     

1，3-双亚氨基异吲哚啉的合成及分析

以硬脂酸和油酸为乳化剂、钼酸铵为催化剂,尿素和邻苯二甲酸酐经亚氨化,然后在硝酸铵存在下发生缩合反应得到1,3-双亚氨基异吲哚啉的硝酸盐,最后用氢氧化钠中和得到1,3-双亚氨基异吲哚啉。对反应路线及反应条件的选择进行了讨论,并采用高效液相色谱法测定了产物的纯度。     

Separation of ternary system (1,2-ethanediol + 1,3-butanediol +1,3-propanediol) by distillation

A study on separation of system (1,2-ethanediol (1,2-EG) + 1,3-butanediol (1,3-BD) + 1,3-propanediol (1,3-PG)) was conducted in the article. Vapor–liquid equilibria (VLE) behaviors of systems (1,2-EG + 1,3-BD), (1,2-EG +1,3-PG), (1,2-EG + 1,3-BD + 1,3-PG) were studied at 101.3 kPa . A two-column (column C1 and column C2) sequence distillation process at normal pressure was designed and optimized to separate the ternary mixture. The results have shown Wilson model is the most appropriate one to describe the ternary system; product amounts of 1,2-EG, 1,3-BD, and 1,3-PG can be up to 0.970, 0.945, and 0.980, respectively, under optimized conditions.     

Synthesis and Biological Application of Isosteviol-Based 1,3-Aminoalcohols

Starting from isosteviol, a series of diterpenoid 1,3-aminoalcohol derivatives were stereoselectively synthesised. The acid-catalysed hydrolysis and rearrangement of natural stevioside gave isosteviol, which was transformed to the key intermediate methyl ester. In the next step, Mannich condensation of diterpenoid ketone, paraformaldehyde, and secondary amines resulted in the formation of 1,3-aminoketones with different stereoselectivities. During the Mannich condensation with dibenzylamine, an interesting N-benzyl → N-methyl substituent exchange was observed. Reduction of 1,3-aminoketones produced diastereoisomeric 1,3-aminoalcohols. Alternatively, aminoalcohols were obtained via stereoselective hydroxy-formylation, followed by oxime preparation, reduction, and finally, reductive alkylation of the obtained primary aminoalcohols. An alternative 1,3-aminoalcohol library was prepared by reductive amination of the intermediate 3-hydroxyaldehyde obtained from isosteviol in two-step synthesis. Cytotoxic activity of compounds against human tumour cell lines (A2780, SiHa, HeLa, MCF-7 and MDA-MB-231) was investigated. In our preliminary study, the 1,3-aminoalcohol function and N-benzyl substitution seemed to be essential for the reliable antiproliferative activity. To extend their application, a diterpenoid condensed with 2-phenylimino-1,3-thiazine and -1,3-oxazine was also attempted to prepare, but only formation of thioether intermediate was observed.     

1,3-丙二醇生产技术及成本分析

介绍了三种已用于工业化生产的1,3-丙二醇的合成技术,对投资建设1,3-丙二醇生产装置的前景进行了对比、分析,指出开发1,3-丙二醇生产技术是当务之急。     

The thermodynamics and separation process design for the ternary system 1,3-propanediol + 1,3-butanediol + 2,3-butanediol

ABSTRACT

The isobaric vapor–liquid equilibrium (VLE) data at 101.3kPa for (1,3-propanediol(PG) + 1,3-butanediol(BD)), (1,3-PG+2,3-BD) and (1,3-BD+2,3-BD) and for the ternary system of (1,3-PG+1,3-BD+2,3-BD) have been measured. The thermodynamic properties of the non-ideal vapor phase have been considered with the EOS equation. The liquid activity coefficients have been calculated with Wilson, NRTL and UNIQUAC equations, and the binary interaction parameters were regressed by these models. The vapor composition of VLE data were calculated by the optimum parameter group and generated a good consistency to experimental values. Based on all the preceding results, a two-column distillation process was designed.     

Synthesis, characterisation and decomposition of 1,3-benzene disulfonyl azide; a cross-linking agent for polyolefins

We have studied the thermal decomposition of 1,3-benzenedisulfonyl azide (1,3-BDSA), and verified that sulfonyl nitrenes formed are able to cross-link polyolefins, including PP. The decomposition was studied with DSC, TGA, and the GC–MS analysis of gaseous products. Both the decomposition of pure 1,3-BDSA and 1,3-BDSA dissolved in a polyolefin were studied. Decomposition occurs by loss of nitrogen giving sulfonyl nitrenes. In the polyolefin nitrenes cross-links the carbon chains by C–H insertion. Cross-linking of PP was verified with SEC. SEC showed no signs of decomposition of PP. Decomposition in the polyolefin was a first order reaction with a half-life of 25.7 s at 200 °C. Hence, 1,3-BDSA is suited for processing with polyolefins. Decomposition of pure 1,3-BDSA is more complicated with unwanted products such as SO₂ and benzene being formed, thereby emphasising the need for good blending when used in polyolefins.     

Flüssigphasenoxidation von 1,3-Dioxolanen

Liquid Phase Oxidation of 1,3-Dioxolanes The oxidation rate and the kind of oxidation products in the oxidation reactions of the 1,3-dioxolanes ( 1a to 1f ) with molecular oxygen in liquid phase were investigated. The 2-methyl-substituted 1,3-dioxolane ( 1b ) has a lower, the 4-methyl-substituted 1,3-dioxolane ( 1d ) has a higher oxidation rate than the non-substituted 1,3-dioxolane ( 1a ). The 2,2-disubstituted 1,3-dioxolanes show no oxidation but a hydrolytic reaction. The main-products of the liquid-phase oxidation of the 1,3-dioxolanes 1a , 1b , 1d and 1e are the glycol-carbonic acid-monoesters 8 and the 2-oxo-1,3-dioxolanes 6 . Their formation is proved by gaschromatography, GC/MS-coupling, DC and ¹³C-n.m.r.-spectroscopy.     

1,3-双(二甲基羟基硅基)-2,2,4,4-四甲基环二硅氮烷的合成

通过1,3-双（二甲基氯硅基）-2,2,4,4-四甲基环二硅氮烷的水解反应合成了1,3-双（二甲基羟基硅基）-2,2,4,4-四甲基环二硅氮烷。初步探讨了反应的条件。产物收率达到92％。并经红外光谱和X射线衍射表征产物结构。     

硼酸催化合成N,N-二甲基-N′-月桂酰基-1,3-丙二胺及其同系物

以不同碳链长度的饱和脂肪酸、N,N-二甲基-1,3-丙二胺(DMAPA)为原料合成了N,N-二甲基-N′-月桂酰基-1,3-丙二胺(C12DMAPA)及其同系物。通过改变反应温度、调节酸胺的摩尔比和加入的硼酸的比例,探索反应的优化条件。在酰胺化反应中,最优条件为,n(脂肪酸)∶n(DMAPA)=1∶1.8,在110℃反应6～8h,加入催化量的硼酸(5mol%),收率为78%～90%。产物用IR表征鉴定。     

2-硝基-1,3-苯二甲醚的合成

采用间苯二酚为原料,经过磺化、硝化、水解合成2-硝基-1,3-苯二酚,再用硫酸二甲酯进行甲基化,得到2-硝基-1,3-苯二甲醚。重点讨论了2-硝基1,3-苯二酚及其甲醚化工艺条件,结果表明,使用质量分数20%发烟硫酸可使1,3-苯二酚全部二磺化从而使2-硝基1,3-苯二酚收率增至63.5%,色谱纯度达98.5%以上;在反应温度80℃,反应时间4 h,n(M e2SO4)∶n(2-硝基1,3-苯二酚)=2.2∶1.0时,2-硝基-1,3-苯二酚甲基化收率高达75.6%。     

1，3-丙二醇的生产和市场分析

介绍了1,3-丙二醇的国内外生产现状及生产技术进展,对国内1,3-丙二醇市场需求及消费进行了分析,并对其市场前景进行了预测。     

具有生物活性的1,3-环己二酮类化合物研究评述

综述了1,3-环己二酮类化合物作为杀虫、除草、杀菌和植物生长调节剂研究的进展情况,包括2-酰胺基-1,3-环己二酮类化合物、2-烷基(芳基)-1,3-环己二酮类化合物、乙酰辅酶A抑制剂类1,3-环己二酮化合物和2-酰基-1,3-环己二酮类化合物。