酰氧基

A selective and mild PS-DIB/ionic-liquid immobilized 2, 2, 6, 6-tetramethyl-piperidin-4-ol-N-oxyl catalytic oxidation procedure of alcohols to the corresponding aldehydes and ketones in ionic liquid BF4 at room temperature was developed. The oxidant PS-DIB was prepared via the iodation and acetylation of polystyrene resin. For the preparation of the ionic-liquid immobilized TeMPO catalyst, 4-(2, 2, 6, 6-Tetramethyl-1-oxyl-4-piperidoxyl)butyl bromide was first synthesized from TeMPO and 1, 4-dibromobutane.

将聚苯乙烯树脂先碘化再乙酰基化，制得了负载型二乙酰氧碘苯作为氧化剂。2， 2， 6， 6-四甲基－N-氧自由基哌啶醇与1， 4-二溴丁烷反应生成4-溴丁氧基－2， 2， 6， 6-四甲基－哌啶－1-氧化物，再与N-甲基咪唑发生季铵化反应，生成的溴化季铵盐与四氟硼酸钠进行离子交换制得氟硼酸型2， 2， 6， 6-四甲基－N-氧自由基哌啶负载离子液体。

A selective and mild PS-DIB/ionic-liquid immobilized TEMPO catalytic oxidation procedure of alcohols to the corresponding aldehydes and ketones in ionic liquid BF4 at room temperature was developed. The oxidant PS-DIB was prepared via Iodation and acetylation of polystyrene resin. For the preparation of the ionic-liquid immobilized TEMPO catalyst, 4-(2,2,6,6-Tetramethyl-1-oxyl-4-piperidoxyl)butyl bromide was first synthesized from 2,2,6,6-tetramethyl-piperidin-4-ol-N-oxyl and 1,4-dibromobutane.

将聚苯乙烯树脂先碘化再乙酰基化，制得了负载型二乙酰氧碘苯(diacetoxyiodo polystyrene，PS-DIB)作为氧化剂。2，2，6，6-四甲基-N-氧自由基哌啶醇(2，2，6，6-tetramethyl-piperidin-4-ol-N-oxyl，TEMPO)与1，4-二溴丁烷反应生成4-溴丁氧基-2，2，6，6-四甲基-哌啶-1-氧化物，再与N-甲基咪唑发生季铵化反应，生成的溴化季铵盐与四氟硼酸钠进行离子交换制得氟硼酸型2，2，6，6-四甲基-N-氧自由基哌啶负载离子液体TEMPO-IL。

They are 4-(2- hydroxy-3-butynlenoxy) benzoic acid (1, WA), 5-chloro-7, 8-dihydroxy-7-methyl- 6-oxo-3- [ -3, 4-dihydroxy-3, 5-dimethyl-l-heptylene] -1H-8, 8a-dihydrobenzo [2, 3-c] pyran (2, WB),-2-(2-methyl-2-dibutene diamido)-2-butenoic acid (3, B5262), 3, 4-dihydro-9, 10-dihydroxy-7-methoxy-3-methyl-1H-naphtho [2, 3- c] pyran-1-one (4, A73 semi-Vioxanthin), 8, 8'-bis (6, 9-dioxo-3,4-dihydro-10- hydroxy-7-methoxy-3-methyl-1H-naphtho [2, 3-c] pyran-1-one)(5, A122 Xanthomegnin), 2, 5-dioxo-3a-hydroxymethyl-3, 3a, 6, 6a-tetrahydro-furo [2, 3-b] furan (6, 1003-2), 7-acety1-5-chloro-6, 8-dioxo-7-methyl-3- [ -3, 5-dimethyl-1, 3- diheptylene] -4aH-benzo [2, 3-c] pyran (7, M2-2 sclerotiorin), respectively.

它们分别被命名为4-（2-羟基-3-丁炔氧基）苯甲酸（1，WA）、5-氯-7，8-二羟基-7-甲基-6-氧代-3-[-3，4-二羟基-3，5-二甲基-1-庚烯基]-1H-8，8a-二氢苯并[2，3-c]吡喃（2，WB）、-2-（2-甲基-2-丁烯二酰亚胺基）-2-丁烯酸（3，B5262）、3，4-氢-9，10-二羟基-7-甲氧基-3-甲基-1H-萘并［2，3-c］吡喃-1-酮（semi-Vioxanthin，4，A73）、8，8'-双（6，9-二氧代-3，4-二氢-10-羟基-7-甲氧基-3-甲基-1H-萘并［2，3-c］吡喃-1-酮）（Xanthomegnin，5，A122）、2，5-二氧代-3a-羟甲基-3，3a，6，6a-四氢-呋喃并［2，3-b］呋喃（6，1003-2），7-乙酰基-5-氯-6，8-二氧代-7-甲基-3-［-3，5-二甲基-1，3-庚二烯基］-4aH-苯并2，3-c］吡喃（Sclerotiorin，7，M2-2）。

The bay area has no substituent and has electron-withdrawing groups,such as bromine atom,cyano-group and 4-formyl phenoxy group compounds have strong absorption in 525 nm,when excitated them,they have strong yellow and salmon pink luminescence bettwen 538 and 566 nm.When introduce electron-donating substituents,such as phenoxy group,morpholinyl,piperidinyl and n-butylamino group,the absorption bathochromic shift while the electron-donating ability is improved,bettwen 536 and 692 nm have strong absorption,reach to the near-infrared region. When excitated them,only the phenoxy group compound has strong salmon pink luminescence in 572 nm,the others have no fluorescence.

其中，港湾位无取代的以及含吸电基团(—Br、—CN、对甲酰基苯氧基)化合物在525 nm左右处均有很强的吸收ε＞10~4M~(-1cm~(-1)，当光激发时，港湾位无取代、溴代和氰基取代物发出538～547 nm的强烈黄色荧光，对甲酰基苯氧基取代物则发出566 nm的强烈橙红色荧光；含供电基团(苯氧基、吗啉基、哌啶基、正丁氨基)化合物随着供电子能力的增强，吸收发生红移，在536～692 nm处均有很强的吸收ε＞10~4M~(-1cm~(-1)，达到了近红外区，当光激发时，只有苯氧基取代物发出572 nm的强烈橙红色荧光，而含氮供电基取代物均发生了荧光淬灭。

Spiral Spirobifluorene acetylated is oxidated by m-chloroperoxybenzoic acid and hydrolyzed by sodium hydroxide ,obtaining 2,2 '- dihydroxy -9,9'- spiral Spirobifluorene .Through nitrification,Reduced by hydrazine hydrate, we may get the 2,2 '- diamino -9,9'- spiral Spirobifluorene which are characterizated by IR, 1H-NMR !

L-酒石酸和乙醇酯化得到酒石酸二乙酯，将保护羧基保护起来，然后用碘甲烷在2，3-位上两个甲基，得到2，3-二甲氧基-酒石酸二乙酯，再用氢氧化钠将其水解，得到2，3-二甲氧基-酒石酸，用五氯化磷将羧基酰化，得到2，3-二甲氧基- 1，4-丁二酰氯，经过与二环己胺反应，得到拆分配体2，3-二甲氧基–N，N，N'，N'-四环己丁二酰胺。

In this Ph. D. dissertation, reverse microemulsion method was fully used infabricating and modifying polyacrylamide with functional and high-relative moleculeweight. The copolymerization of 2-acrylamide-2-methylpxopanesulfonic acid, fluorescent monomer 4-methoxy-N-(2-N\', N\'-dimethylamino ethyl)naphthalimide alkyl chloride quaternary ammonium salt, fluorescentmonomer 4-(N\'-methyl-1-piperazinylallyl)-N-butyl-naphthalimide chloride quaternaryammonium salt, Cationic monomer dimethylethylammonium bromide and hydrophobical monomer octadecylacrylate with acrylamide and properties of the copolymers werestudied. The interaction between five polymers and Al_2O_3(012) crystal surface have beensimulated by Materials Studio 3.0 program package, binding energies and non-bondinteraction energies and deformation energies have also been acquired.

本文以制备具有较高相对分子质量和功能型PAM为研究目的，将反相微乳液法运用到其制备及改性的有关环节，通过反相微乳液聚合工艺，将几种改性功能单体2-丙烯酰胺基-2-甲基-丙磺酸、荧光单体2-(4-甲氧基-1，8-萘二甲酰亚胺基)-乙基二甲基烯丙基氯化铵、荧光单体4-(N'-甲基-1-哌嗪基)-N-丁基-1，8-萘烯丙氯季铵盐、阳离子单体丙烯酰氧乙基-二甲基-乙基溴化铵和疏水单体丙烯酸十八酯与AM共聚，制备AMPS改性PAM、荧光示踪型PAM、阳离子单体DMB改性PAM和OA改性PAM等四类不同功能单体改性PAM，并研究其应用性能。

As for the ester exchange reaction on phosphorus, it was found that N-phosphoryl histidine the fastest one among all of the N-phosphoryl aminoacids. The results studied by MNDO method indicate that due to theparticipation of imidazole group, the formation of hexa-coordinatephosphorus intermediate made the iso-propoxyl which is opposite toimidazole group more active than the other ones and much easier to leave.When iso-propoxyl left, a new penta-coordinate phosphorus intermediate wasformed, and it is sterically favorable to be attacked by an alcohol from theopposite direction of imidazole.

对于磷上酯交换反应，实验中发现N-磷酰组氨酸反应速度明显高于其它N-磷酰氨基酸，理论研究表明，侧键咪唑基参与下六配位磷中间体形成后，位于咪唑基对面的异丙氧基反应活性大大提高，即从咪唑基的对面位置发生异丙氧基的离去和另一分子醇的进攻，在能量上和空间上都是有利的。N-磷酰丝氨酸的磷上酯交换反应有着类似的特点。

To study the relationship between the "tail" structure and the characteristics of Gemini surfactants, a new gemini surfactant CH(subscript 2s)-αω-Bis (dehydroabietyihydroxypropyltetramethylethyldiammonium Chloride) here s=2, has been synthesized. Dehydrogenated rosin as hydrophobic "tails" in the structure. The affections of reacttants ratio, reaction temperature and time on the yield of aimed compound have been discussed.

研究了Gemini表面活性剂中疏水&尾巴&结构对性质的影响，以脱氢松香酸和环氧氯丙烷为原料合成了中间体3-脱氢松香酰氧－2-羟丙基氯，再与四甲基乙二胺反应，得到1种以脱氢松香酰基为疏水链&尾巴&的对称Gemini型双季铵盐阳离子表面活性剂：二氯化－N，N'-二（3-脱氢松香酰氧－2-羟丙基）四甲基乙二胺。

To study the relationship between the hydrophobic "tail" structure and thecharacterizations of Gemini surfactants, a new gemini surfactant CsH2s-α,ω-bis(dehydroabietylhydroxypropylteteramethylethylammonium Chloride),here s=2, wassynthesized. Dehydrogenated rosin as hydrophobic "tails" in the structure. The impact factorsin the two steps are discussed.

为研究gemini表面活性剂中疏水&尾巴&结构对性质的影响，本论文以脱氢松香酸和环氧氯丙烷为原料合成了中间体3-脱氢松香酰氧-2-羟丙基氯，再与四甲基乙二胺反应，得到一种以脱氢松香酰基为疏水链&尾巴&的对称gemini型双季铵盐阳离子表面活性剂：二氯化-N，N′-二(3-脱氢松香酰氧-2-羟丙基)四甲基乙二胺。

First, by using p-methoxybenzaldehyde , p-hydroxybenzaldehyde and pyrrole as raw materials, 5-(p-hydroxyphenyl)-10,15,20-tri(p-methoxyphyenyl)porpyrin was prepares under acidity condition and the let reacted with benzoyl chloride, o-nitrobenzoyl chloride, m- nitrobenzoyl chloride and p- nitrobenzoyl chloride respectively under alkalinity condition with DMF as solvent.

以对-甲氧基苯甲醛、对-羟基苯甲醛和吡咯为原料，在酸性条件下合成了5-对羟苯基10，15，20-三对甲氧苯基卟啉，再以该化合物为原料分别与苯甲酰氯、邻-硝基苯甲酰氯、间-硝基苯甲酰氯和对-硝基苯甲酰氯反应，在碱性条件下以DMF为溶剂合成了四种目前尚未见文献报道的对-甲氧基卟啉硝基苯甲酸酯类化合物。

We have no common name for a mime of Sophron or Xenarchus and a Socratic Conversation; and we should still be without one even if the imitation in the two instances were in trimeters or elegiacs or some other kind of verse--though it is the way with people to tack on 'poet' to the name of a metre, and talk of elegiac-poets and epic-poets, thinking that they call them poets not by reason of the imitative nature of their work, but indiscriminately by reason of the metre they write in.

索夫农 、森那库斯和苏格拉底式的对话采用的模仿没有一个公共的名称；三音步诗、挽歌体或其他类型的诗的模仿也没有——人们把&诗人&这一名词和格律名称结合到一起，称之为挽歌体诗人或者史诗诗人，他们被称为诗人，似乎只是因为遵守格律写作，而非他们作品的模仿本质。

The relationship between communicative competence and grammar teaching should be that of the ends and the means.

交际能力和语法的关系应该是目标与途径的关系。