金刚烷基甜菜碱型和季铵盐阳离子型表面活性剂的合成研究

以金刚烷胺为起始反应物,首先在过量甲酸存在下,与甲醛发生埃斯韦勒-克拉克甲基化反应合成了N,N-二甲基金刚烷叔胺,在此基础上通过N,N-二甲基金刚烷叔胺与氯乙酸钠、溴代正丁烷、溴代正辛烷、溴代十二烷、溴代十六烷等一系列季铵化试剂的季铵化反应,分别合成了N,N-二甲基金刚烷甜菜碱型表面活性剂及N-(1-金刚烷基)-N,N-二甲基正丁基溴化铵、N-(1-金刚烷基)-N,N-二甲基辛基溴化铵、N-(1-金刚烷基)-N,N-二甲基十二烷基溴化铵、N-(1-金刚烷基)-N,N-二甲基十六烷基溴化铵等金刚烷季铵盐阳离子型表面活性剂,产率分别为75%,75%,61%,44%,54%.采用元素分析,IR,1H NMR等分析手段对5种产物进行了结构鉴定,测试了各种金刚烷表面活性剂水溶液的表面张力.     

新型金刚烷基杂双子表面活性剂的合成及其表面活性

以1-金刚烷甲酸为原料,经酰化,取代和还原反应制得N,N-二甲基-1-金刚烷基甲胺(1);1与双子季铵盐(2)在无水乙醇中反应合成了一种新型的金刚烷基杂双子表面活性剂——1-(N,N-二甲基-1-金刚烷甲基溴化铵)-6-(N,N-二甲基-十二烷基溴化铵)-己烷(3),总收率30.9%,其结构经1H NMR和元素分析表征。采用表面张力法研究了3的表面活性。结果表明:3具有较强的聚集能力和界面吸附能力,其cmc,γcmc,p C20,Γmax,Amin分别为1.18 mmol·L-1,35.5 m N·m-1,0.48,2.63μmol·m-2和0.63 nm2。     

(乙烯基咔唑-甲基丙烯酸金刚烷酯)共聚物的制备与光致发光性能

以1-金刚烷醇和甲基丙烯酰氯为原料,经酯化反应合成甲基丙烯酸金刚烷酯单体。然后通过甲基丙烯酸金刚烷酯与N-乙烯基咔唑进行共聚反应合成了乙烯基咔唑-甲基丙烯酸金刚烷酯共聚物。采用1H-NMR、FI-IR和元素分析等表征了共聚产物的结构,通过凝胶渗透色谱仪和荧光光谱仪考察了金刚烷基团对共聚物结构与荧光性能的影响。     

N-叔丁氧羰基-3-羟基-1-金刚烷基甘氨酸的合成

以金刚烷甲酸(1)为起始原料,经过酰化,取代,脱羧三步反应一锅法制得金刚烷甲基酮(2),然后氧化甲基得到1-金刚烷基乙醛酸(3),将3与盐酸羟氨反应得到1-金刚烷乙醛酸肟(4),还原4并用BOC酸酐保护氨基得到N-叔丁氧羰基-1-金刚烷基甘氨酸(5),最后经高锰酸钾氧化得到DPP-IV抑制剂沙格列汀中间体N-叔丁氧羰基-3-羟基-1-金刚烷基甘氨酸(6),总收率28%。     

具有阳离子表面活性ATRP引发剂的合成

以2-溴异丁酰溴、2-溴乙醇、6-氯-1-己醇及N,N-二甲基正十二烷基胺为主要原料,分别通过两步或三步反应合成了具有阳离子表面活性的原子转移自由基聚合(ATRP)引发剂——N-[2-(2-溴-2-甲基丙酰氧基)乙基]-N,N-二甲基正十二烷基溴化铵或N-[6-(2-溴-2-甲基丙酰氧基)己基]-N,N-二甲基正十二烷基碘化铵,其结构经1H NMR,13C NMR,IR和元素分析表征。     

双烷链阳离子表面活性剂的合成与定量分析

以N,N-二甲基烷基叔胺和α，ω-二溴烷烃为原料，无水乙醇为溶剂合成阳离子型Gemini表面活性剂。反应产物以混合剂乙酸乙酯/乙醇重结晶纯化后，用红外光谱和核磁共振进行结构分析；以溴酚蓝为指示剂、二氯乙烷为分散相的两相化学滴定法测定其含量。结果表明：7种已合成的阳离子型Gemini的活性物含量均在97.5％以上。     

氨甲酰基硅烷与酮反应合成α-硅氧基酰胺衍生物

N,N-二甲基氨甲酰基三甲基硅烷与一系列芳基酮、不饱和芳基酮在无水无氧、105℃、甲苯作溶剂的条件下反应,合成了α-三甲基硅氧基酰胺衍生物,收率60%~89%,其结构用元素分析、1H NMR、13C NMR和IR等方法进行了表征.烷基烷基酮、烷基芳基酮、烷基不饱和芳基酮与N,N-二甲基氨甲酰基三甲基硅烷不反应.通过研究反应的影响因素发现,反应底物酮中与羰基相连的芳环上取代基的电子效应是该加成反应的重要影响因素,芳环上取代基的给电子能力越強,反应越慢.     

新型季铵化多羟基Gemini表面活性剂的合成及其表面性能

2-甲氨基乙醇和二乙醇胺分别与十二烷基溴经取代反应制得叔胺(2a和2b);2a,2b及N,N-二甲基十二烷基叔胺分别与1,3-二溴丙烷反应合成了Gemini表面活性剂(3a~3c),其中3a和3b为新化合物,其结构经1H NMR表征。表面活性测试结果表明,3a~3c的CMC分别为0.859 4 mmol·L-1,0.769 1 mmol·L-1和0.962 9 mmol·L-1,呈随羟基数量的增加而降低趋势。     

季铵盐和叔胺协同催化一步酯交换法合成碳酸二甲酯的研究

以不同季铵盐和叔胺为催化剂,考察了它们各自和协同催化甲醇、CO2和环氧丙烷(PO)或环氧氯丙烷(ECH)一步法合成碳酸二甲酯(DMC)的催化性能。结果表明,季铵盐对一步法合成DMC中第一步反应(即CO2和PO环加成反应生成环状碳酸酯)的催化性能较好,而叔胺对一步法合成DMC中第二步反应(即环状碳酸酯与甲醇反应生成DMC)的催化效果较好。其中,以双十六烷基二甲基溴化铵(DHDMAB)和N,N-二烯丙基甲基胺(MDAA)分别为季铵盐和叔胺的协同催化性能最佳,其DMC产率达35.2%。此外,以PO为环氧化合物的DMC产率远高于ECH。     

含胺基功能性单体的聚合研究 XIV.含二甲氨基丙烯酰类衍生物与过硫酸钾引发体系引发的丙烯酰胺聚合

N-(N′,N′-二甲氨基亚甲基)甲基丙烯酰胺、甲基丙烯酸N,N二甲氨基乙酯、可聚合叔胺、氧化还原引发体系、超高分子量聚丙烯酰胺     

Reaction of acetic anhydride with monoterpene amine oxides possessing the 2,7-dimethyloctane skeleton

Under the conditions of the Polonovsky reaction, N-(2,7-dimethyl-2,7-octadienyl)-N,N-dimethylamine oxide gives 2,7-dimethyl-2,7-octadienal and N-(2,7-dimethyl-2,7-octadienyl)-N-methylacetamide. Under the same conditions, N-(2,7-dimethyl-2,7-octadienyl)-N,N-dietnylamine oxide dihydrate does not undergo the Polonovsky reaction and gives the rearrangement product, O-(1-isopropenyl-5-methyl-5-hexenyl)-N,N-diethylhydroxylamine, and the hydration product, O-[1-(1-hydroxy-1-methyl)ethyi-5-methyl-5-hexenyl]-N,N-diethylhydroxylamine.The work was accomplished under the financial support of the Russian Fund for the Fundamental Research (93-03-4219).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1588–1590, September, 1993.     

C-hydroxyalkylation of N-adamantylanilines by hexafluoroacetone and methyl trifluoropyruvate

N-(1-Adamantyl)-4-(1-hydroxy-1-trifluoromethyl- 2,2,2- trifluoroethyl)aniline (III) and N-(1-adamantyl)-4-(1-hydroxy-1-methoxycarbony 1-2,2,2-trif luoroethyl) aniline (IV) were obtained by the reaction of N-(1-adamantyl)aniline with ketone (I) and ketoester (II). Analogous procedures gave N-(2-adamantyl)- 4- (1-hydroxy- 1-trifluoromethyl- 2, 2,2-trifluoroethyl)aniline (V) and N-(2-adamantyl)-4-(1-hydroxy-1-methoxycarbonyl-2,2,2-trifluoroethyl)aniline (VI). The action of hydrogen peroxide on (III) in the presence of sodium tungstenate gave N- (1- adamantyl)- 4- (1- hydroxy- 1- trifluoromethyl- 2,2,2- trifluoroethyl)aniline N-oxide (VII).Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2348–2350, October, 1989.     

Synthesis of 1,8-di(1-adamantyl)naphthalenes as single enantiomers stable at ambient temperatures

Single enantiomers of 1,8-di(1-adamantyl)naphthalenes were synthesized by the [4+2]cycloaddition reaction of 6-adamantylbenzyne and 2-adamantylfuran. The enantiomers were resolved by conversion into diastereomeric ketopinic acid esters. The absolute configuration was determined by X-ray analysis. Kinetic studies by CD revealed an enantiomerization barrier of 29 kcal mol(-1) for 1,8-(1-adamantyl)naphthalenes.     

Synthesis of β-Aminoketones of the Adamantane Series

4-(1-Adamantyl)-1-aminobutan-3-one hydrochlorides were synthesized by the Mannich reaction of (1-adamantyl)acetone with paraformaldehyde and secondary amine hydrochlorides (diethylamine, dibenzylamine, piperidine). Analogous reactions of 1-adamantyl(methyl)amine with acetone, p-hydroxyacetophenone, and methyl 2-thienyl ketone gave 1-[(1-adamantyl)methylamino]propan-3-one hydrochlorides.     

N-(4-氯-3-三氟甲基苯基)-N′-(对取代苯基)脲的合成

以4-氯-3-三氟甲基苯胺、固体光气、对取代苯胺为原料,采用一锅法合成了N-(4-氯-3-三氟甲基苯基)-N-′(对甲基苯基)脲和N-(4-氯-3-三氟甲基苯基)-N-′(对溴苯基)脲,其结构经1H NMR,IR和元素分析表征。     

Synthesis and spectroscopic studies of novel mononuclear and binuclear ruthenium(III) complexes with bidentate and tridentate acyclic hydrazones

Nine novel acyclic hydrazone ligands, FINH?=?N-(furylidene)-N′-isonicotinoylhydrazine, FNH?=?N-(furylidene)-N′-nicotinoylhydrazine, PINH?=?N-(pyrienylidene)-N′-isonicotinoylhydrazine, PNH?=?N-(pyrienylidene)-N′-nicotinoylhydrazine, TINH?=?N-(thienylidene)-N′-isonicotinoylhydrazine, TNH?=?N-(thienylidene)-N′-nicotinoylhydrazine, FSH?=?N-(furylidene)-N′-salicyloylhydrazine, PSH?=?N-(pyrienylidene)-N′-salicyloylhydrazine and TSH?=?N-(thienylidene)-N′-salicyloylhydrazine, have been synthesized. Their corresponding mononuclear and binuclear ruthenium(III) complexes have been prepared by the reaction of the ligand with RuCl₃·3H₂O in 1?:?2 and 2?:?2 molar ratio and are characterized by elemental analyses, thermogravimetric analyses (TGA and DTG), IR, electronic, magnetic susceptibility and electrical conductance measurements. Electronic spectra and magnetic susceptibility measurements of the solid complexes (both mono- and binuclear) indicate an octahedral geometry around ruthenium(III). Particular emphasis is given to the binuclear complexes in which FSH, PSH and TSH behave as tridentate ligands and chloride bridges the Ru(III) ions. Conductance measurements show the mononuclear complexes are electrolytic and binuclear complexes are of non-electrolytic. The fungicidal activities of the ligands and metal complexes against Fusarium oxysporium and Aspergillus niger are described.     

Synthesis and Properties of N,N′-Disubstituted Ureas and Their Isosteric Analogs Containing Polycyclic Fragments: II. N-(4-Oxoadamantan-1-yl)-N′-[fluoro(chloro)phenyl]ureas

Russian Journal of Organic Chemistry - A series of N-(4-oxoadamantan-1-yl)-N′-[fluoro(chloro)phenyl]ureas have been synthesized in 27–73% yields by reaction of...     

Synthesis and Some Chemical Transformations of Adamantyl-Substituted Pyrazolones

1-Substituted 3-(1-adamantyl)-4,5-dihydro-1H-pyrazol–5-ones and 3-(1-adamantyl)-4,5-dihydroiso-xazol-5-one were synthesized by reaction of ethyl 3-(1-adamantyl)-3-oxopropanoate with various hydrazine derivatives and hydroxylamine hydrochloride. Nitrosation of adamantyl-substituted pyrazolones with sodium nitrite in acetic acid gave the corresponding 4-hydroxyimino derivatives. Reactions of 3-(1-adamantyl)-4,5-di-hydro-1H-pyrazol–5-ones and 3-(1-adamantyl)-4,5-dihydroisoxazol–5-one with aromatic and heterocyclic aldehydes led to the formation of condensation products at position 4 of the heteroring.     

Separation of brompheniramine enantiomers by capillary electrophoresis and study of chiral recognition mechanisms of cyclodextrins using NMR-spectroscopy, UV spectrometry, electrospray ionization mass spectrometry and X-ray crystallography

Opposite migration order was observed for the enantiomers of brompheniramine [N-[3-(4-bromphenyl)-3-(2-pyridyl)propyl]-N,N-dimethylamine] (BrPh) in capillary electrophoresis (CE) when native beta-cyclodextrin (beta-CD) and heptakis(2,3,6-tri-O-methyl)-beta-CD (TM-beta-CD) were used as chiral selectors. NMR spectrometry was applied in order to obtain information about the stoichiometry, binding constants and structure of the selector-selectand complexes in solution. The data were further confirmed by UV spectrometry and electrospray ionization mass spectrometry. The structure of the complexes in the solid state was determined using X-ray crystallography performed on the co-crystals precipitated from the 1:1 aqueous solution of selector and selectand. This multiple approach allowed an elucidation of the most likely structural reason for a different affinity (binding strength) of BrPh enantiomers towards beta-CD and TM-beta-CD. However, the question about a force responsible for the opposite affinity pattern of BrPh enantiomers towards these CDs could not be answered definitely.