C．I．酸性蓝264及N-甲基-N-（4′-氨基苄基）-4-氨苯磺酰胺的合成

N-甲基-N-（4′-氨基苄基）-4-甲苯磺酰胺的合成包括三步反应,首先由对甲苯磺酰氯与甲胺反应得到N-甲基-4-甲基苯磺酰胺,再与对硝基苄基溴反应引入苄基,然后在铁催化剂存在下用水舍肼将硝基还原,得到N-甲基-N-（4′-氨基苄基）-4-甲苯磺酰胺;该工艺重现性好,三废少,三步反应总收率81％。得到的N-甲基-N-（4′-氨基苄基）-4-甲苯磺酰胺与溴胺酸反应即得C．I．酸性蓝264,该染料染色时对染浴的pH不敏感、竭染率高、水洗牢度好。     

新型含吡啶基N-苄基磺酰胺的合成

通过N-苄基对甲苯磺酰胺和N-苄基邻硝基苯磺酰胺分别与三个氯甲基吡啶(2-氯甲基吡啶,3-氯甲基吡啶和4-氯甲基吡啶)盐酸盐在碳酸钾作用下室温反应数天,合成了六个新的含吡啶基的N-苄基-N-吡啶亚甲基磺酰胺衍生物,收率为59.1%～82.4%。全部结构经1HNMR和13CNMR确认。     

N-二甲氨基丙基-N-三乙氧基硅甲基全氟辛基磺酰胺的合成

全氟辛基磺酰氟与N,N-二甲基-1,3-丙二胺在甲苯中反应,得到N-3-二甲氨基丙基全氟辛基磺酰胺;再与氯甲基三乙氧基硅烷在乙醇中反应,制得N-二甲氨基丙基-N-三乙氧硅基甲基全氟辛基磺酰胺,产率达84%.通过红外光谱、核磁共振谱对目标产物进行了结构表征,测得该化合物在乙醇-水溶液中的表面张力为17.3 mN/m.     

新型除草剂苯嘧磺草胺的合成研究

以2-氯-4-氟苯甲酸为起始原料,经硫酸和硝酸硝化,氯化亚砜酰化后与N-甲基-N-异丙基磺酰胺反应得到化合物N-(2-氯-4-氟-5-硝基苯甲酰)-N′-异丙基-N′-甲基磺酰胺;制得N-(2-氯-4-氟-5-硝基苯甲酰)-N′-异丙基-N′-甲基磺酰胺经钯碳加氢硝基还原,然后与氯甲酸乙酯反应得到化合物N-[2-氯-4-氟-5-{(乙氧基羰基)氨基}苯甲酰]-N′-异丙基-N′-甲基磺酰胺;N-[2-氯-4-氟-5-{(乙氧基羰基)氨基}苯甲酰]-N′-异丙基-N′-甲基磺酰胺与3-甲基氨基-4,4,4-三氟丁烯酸乙酯进行环化,得到目的产物苯嘧磺草胺。总收率68.0%(以2-氯-4-氟苯甲酸计)。经核磁谱图分析,所得化合物与目的产物苯嘧磺草胺结构一致。     

2-甲基-5-(4-甲氧基苯磺酰胺)萘并[1,2-b]呋喃-3-羧酸乙酯的合成

乙酰乙酸乙酯与对甲苯胺、磷酸二氢钾反应得到3-(对甲苯氨基)-2-丁烯酸乙酯(化合物3);4-氨基-1-萘酚盐酸盐与甲氧基苯磺酰氯反应得到4-甲氧基-N-(4-羟基萘)苯磺酰胺(化合物6),之后经高碘酸钠氧化得到4-甲氧基-N-(4-氧代萘)苯磺酰胺(化合物7);中间体3和7发生环化得到目标物2-甲基-5-(4-甲氧基苯磺酰胺)萘并[1,2-b]呋喃-3-羧酸乙酯(化合物8),其结构经1H NMR、13C NMR和HRMS确证.对中间体3、中间体7以及目标物8的合成条件进行优化,滴加原料对甲苯胺、使用KH2PO4作为催化剂时,可在较低温度下顺利得到中间体3;控制氧化剂用量、使用乙醇含量高的水溶液作为溶剂有利于中间体7的生成和后处理;在反应体系中加入少量水,可减少化合物8的副产物生成.该方法为N-(萘并[1,2-b]呋喃-5-基)苯磺酰胺类化合物的合成提供了参考.     

N-(4-氨基苄基)-N,4-二甲基苯磺酰胺的环保型合成方法探索

本文以对甲苯磺酰氯、甲胺、对硝基溴苄为基本原料,对N-(4-氨基苄基)-N,4-二甲基苯磺酰胺的合成方法进行了探索,得出一条既经济、方便,又环保的合成工艺,具有很强的技术价值.一缩合反应温度在70～80℃,物料配比为1:1.05,pH=7～8,产品收率可达95%以上,产品纯度可达99%以上.二缩合采用酒精为溶剂,采用液碱为缚酸剂,避免了资料上使用的氢氧化钾为缚酸剂,解决了废水污染问题.还原反应采用以骨架镍为催化剂的加氢还原反应,对环境无污染问题,而且收率高,品质好,操作方便.     

超声波促进3-(4-苯磺酰基-3-甲基-2-丁烯基)-4,5,6-三甲氧基-2-甲基苯基苄基醚的合成

以3,4,5-三甲氧基甲苯(Ⅰ)为原料,经过Vilsmeier-Haack反应合成了6-甲基-2,3,4-三甲氧基苯甲醛(Ⅱ),收率94.1,Ⅱ经过Dakin反应得到2,3,4-三甲氧基-6-甲基苯酚(Ⅲ),收率96.2,用溴化苄对Ⅲ进行酚羟基保护得到2,3,4-三甲氧基-6-甲基苯基苄基醚(Ⅳ),收率95.0,Ⅳ在有机碱作用下发生溴代反应,得到6-甲基-5-溴-2,3,4-三甲氧基苯基苄基醚(Ⅴ),收率92.2,Ⅴ在超声波作用下制成格氏试剂(Ⅵ),再与4-溴-2-甲基-1-苯磺酰基-2-丁烯发生格氏偶联反应得到辅酶Q10的关键中间体3-(4-苯磺酰基-3-甲基-2-丁烯基)-4,5,6-三甲氧基-2-甲基苯基苄基醚(Ⅶ),收率72.0,五步反应总收率为57.1,产物经FTIR和1H NMR确定结构。     

2,2,2-三氟-1-苯基-1-胺类化合物的合成

以卤代苯甲醛与叔丁基亚磺酰胺为原料,在钛酸异丙酯催化下合成中间体1(E)-N-(4-卤苄基)-2-甲基丙烷-2-亚砜酰胺(1a-1b);然后在TBAF引发下,与TMSCF3反应得到中间体2a-2b N-(1-(4-卤苯基)-2,2,2-三氟乙基)-2-甲基丙烷-2-亚磺酰胺;最后经酸水解得到2,2,2-三氟-1-苯基-1-胺类化合物(3a-3b)。所有化合物结构经红外、核磁、质谱对其进行表征。     

芳硝基物水合肼催化氢转移还原研究

采用自制廉价催化剂、水合肼为清洁还原剂研究了不同结构芳硝基物的水合肼催化氢转移还原反应,发现取代基的性质及位置对水合肼还原反应均有影响,苯环上吸电子基的存在有利于硝基还原;水合肼还原法不还原蒽醌结构中的醌式羰基。在水合肼用量接近理论量的前提下,N-甲基-4-硝基苯胺、N-甲基-N-(4'-硝基苄基)-4-甲基苯磺酰胺、4,4'-二硝基二苯砜的水合肼还原产品收率分别达到99%、97%、92%。实验中以高效液相色谱对还原反应过程进行跟踪分析,分别采用大气压离子化质谱(APCI-MS)、核磁共振谱及红外光谱对还原产物的结构进行了表征。     

拉科酰胺的合成工艺改进

以丙烯酸为起始原料与苄胺缩合得到N-苄基丙烯酰胺(4),收率由70%提高至83%,4与NBS通过烯烃双键双官能团化用二氯甲烷和甲醇混合溶剂得到N-苄基-3-甲氧基-2-溴丙酰胺(5)收率由70%提高至76%,5与叠氮钠反应得到N-苄基-2-叠氮基-3-甲氧基丙酰胺(6),6经钯碳加氢得到2-氨基-N-苄基-3-甲氧基丙酰胺(7)两步收率达到83.6%,7经乙酰化得到2-乙酰胺基-3-甲氧基-N-苄基丙酰胺(8),8经SFC色谱柱手性拆分得到拉科酰胺(1)(拆分收率47.6%),总收率22.8%(以2计)。拉科酰胺结构经~1CNMR、~1HNMR及MS确证。     

Novel polymeric photoinitiators bearing side-chain α-aminoacetophenone moieties for ultraviolet-curable pigmented coatings

New polymeric photoinitiators with pendant α-aminoacetophenone moieties, such as the homopolymers of 1-(4-morpholinophenyl)-2-benzyl-2-[N-methyl-N-(3-methacryloyloxypropyl)]aminopropan-1-one and of 1-(4-morpholinophenyl)-2-benzyl-2-[N-methyl-N-(3-methacryloyloxypropyl)]aminobutan-1-one have been prepared and fully characterized. Their photoinitiation activity has been also checked in the ultraviolet cure of a standard acrylic mixture, under irradiation over 380 nm, thus simulating the absorption conditions of a TiO₂-pigmented coating formulation. The results have been compared with those found by using the corresponding low-molecular-weight structural models, purposely synthesized. The activity data obtained are discussed and related to the structural requirements of the above systems. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 2237–2246, 1997     

Copolymeric systems bearing side-chain thioxanthone and α-aminoacetophenone moieties as photoinitiators for ultraviolet-curable pigmented coatings

Copolymers of 1-(4-morpholinophenyl)-2-benzyl-2-[N-methyl-N-(3-meth-acryloyloxy propyl)]aminopropan-1-one and of 1-(4-morpholinophenyl)-2-benzyl-2-[N-methyl-N-(3-methacryloyloxypropyl)]aminobutan-1-one with 1-[(2-methacryloyloxy)ethoxycarbonyl]thioxanthone were prepared and structurally characterized. The above systems were also checked in the ultraviolet cure of an acrylic mixture upon irradiation over 380 nm, thus simulating the conditions of a TiO₂-pigmented formulation. The curing results were compared with those obtained in the presence of the mixtures of the corresponding homopolymers as well as of their low-molecular-weight models. The copolymeric systems display synergistic effects of activity with respect to the structural models but show lower photoinitiation efficiency against the homopolymers mixtures. These data are discussed and interpreted in terms of structural requirements and photochemical mechanistic aspects of the above systems. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 2247–2258, 1997     

Surface active agents from isopropenyl esters: Acylation of isethionic acid and N-methyltaurine

Acylation of sodium isethionate with isopropenyl stearate at 200 C for 30 min gave a 95% yield of sodium 2-sulfoethyl stearate, acetone being the only byproduct. Acylation of N-methyltaurine at 200 C for 90 min gave a 95% yield of N-methyl-N-(2-sulfoethyl) stearamide sodium salt. Corresponding surface active derivatives were also prepared from pelargonic, lauric, myristic, palmitic, oleic, phenylstearic and hydrogenated tallow fatty acids from their respective isopropenyl esters. Detergency, foam height, wetting time, lime soap dispersing power, critical micelle concentration and other surfactant properties were evaluated. Optimum properties were found at the C₁₄−C₁₈ fatty acid chain length. Unsaturation or branching increased solubility. The 2-sulfoethyl esters were similar to the N-methyl-N-(2-sulfoethyl) amides in foam height, wetting ability and lime soap dispersing power, superior to the N-methyl-N-(2-sulfoethyl) amides in detergency, but inferior in calcium stability and less stable to acid and alkali. Both compounds are readily biodegraded. The fatty isopropenyl ester synthesis has an advantage in yield and purity of the product and could increase the utilization of the 2-sulfoethyl esters and N-methyl-N-(2-sulfoethyl) amides in many applications. Presented at the ISF-AOCS Meeting in Chicago, September 1970. Deceased. E. Mark. Nutr. Res. Div., ARS, USDA.     

电解氧化4-甲基吡啶合成异烟酸

以Ti基PbO2 为阳极 ,Cu或Ni为阴极 ,在硫酸介质中 ,电解氧化 4 甲基吡啶合成了异烟酸。经过实验确定的最佳合成条件为 :c(硫酸 ) =4 6 0mol/L ,c(4 甲基吡啶 ) =0 6 0mol/L ,电解电流密度i=6 0mA/cm2 ,t=6 0℃。在此条件下 ,异烟酸的收率为 6 4 6 % ,电流效率为 6 7%。同时还研究了电解过程中反应物转化率、电流效率、槽压的变化规律。经示波极谱、红外光谱和熔点测定法证明电合成的物质为异烟酸 ,质量分数为 97 7%。     

4-(4-甲酯基苯基)丁醛的合成

以对溴苯甲酸为原料,经酯化后与3-丁烯-1-醇偶联,再与亚硫酸氢钠反应形成磺酸钠盐,经盐酸酸化后得4-(4-甲酯基苯基)丁醛。总收率可达37.3%。     

New polymer syntheses: 59. Homo-and copolyesters of 4-(4′-hydrophenoxy)benzoic acid

The homopolyester of 4-(4′-hydroxyphenoxy)benzoic acid (poly(4-HPBA)), was prepared under two different reaction conditions and compared with a sample provided by another research group. Depending on the synthetic route, different melting points, d.s.c. traces and crystal lattices were found. However, after repeated heating and cooling, one thermodynamically stable modification with a melting point of 370–375°C can be obtained. Copolyesters of 4-hydroxybenzoic acid and 4-(4′-hydroxyphenoxy)benzoic acid were prepared with various molar ratios either in the melt (condensation in bulk) or in solution. These copolyesters were characterized by elemental analyses, ¹H n.m.r. spectroscopy, d.s.c. measurements, wide-angle X-ray scattering measurements at various temperatures, and optical microscopy. Whereas copolyesters prepared in solution do not melt below 500°C, those prepared by polycondensation in bulk show melting points down to approximately 260°C and form a nematic melt.     

4-(4-氯苯基)环己醇及4-(4-氯苯基)环己酮的合成研究

以氯苯、环己烯、乙酰氯为原料,通过Friedel-Crafts反应、Baeyer-Villiger反应、水解反应得到4-(4-氯苯基)环己醇。通过正交试验得到Friedel-Crafts反应和Baeyer-Villiger反应优化后的工艺条件。4-(4-氯苯基)环己醇总收率达12.9%,较文献收率提高了6%以上。所得醇经次氯酸钠氧化,得到4-(4-氯苯基)环己酮,氧化收率87%,产品的结构经1HNMR、GC-MS鉴定。     

Phenanthrene Metabolites from a New Polycyclic Aromatic Hydrocarbon-Degrading Bacterium Aeromonas salmonicida subsp. Achromogenes Strain NY4

A new polycyclic aromatic hydrocarbon (PAH)-degrading Gram-negative bacterium Aeromonas salmonicida subsp. achromogenes strain NY4 was isolated from coking wastewater sludge. Strain NY4 could not grow on1-hydroxy-2-naphthoic acid, hexadecane or hexanol as sole carbon source but phenanthrene. This strain was able to utilize several known microbial metabolites of PAHs, including catechol, protocatechuic acid, salicylic acid, and phenol as sole carbon source. The mixture of the acidic and neutral fraction, acidic fraction alone and neutral fraction alone of phenanthrene metabolites were prepared and analyzed by GC-MS. A total of at least 27 metabolites were identified as the degradation products of phenanthrene by strain NY4. Among them, 1-hydroxy-α-oxo-2-naphthaleneacetic acid, 2-hydroxy-α-oxo-1-naphthaleneacetic acid, 2-hydroxy-1-(1-hydroxy-2-naphthalenyl)-ethanone, 1,2-dihydro naphtha [2,1-b] furan-2-ol and 2,3-dihydro naphtha [1,2-b] furan-2-ol have not been reported as the metabolites of phenanthrenes so far. The accumulation patterns of phenanthrene metabolite accumulation by strain NY4 depended on the incubation time, inoculum size and concentration of phenanthrene. Based on the degradation metabolites of phenanthrene by strain NY4, degradation pathways are proposed. This is the first report of PAH degradation in Aeromonas salmonicida, which lay the foundation for recognition and further characterization of PAH degradation metabolites and pathways in Aeromonas salmonicida strains.