2，6－二溴－1，5－二羟基萘的合成

以萘为原料，经磺化、羟基化、溴化反应合成了２，６二溴１，５二羟基萘，并对工艺条件进行了研究。其中磺化步１，５二磺化产物收率达７２６％，溴化步２，６二溴１，５二羟基萘收率达９３６％。     

1，5－二羟基萘的合成研究

以萘为原料，经磺化、碱熔反应合成１，５－二羟基萘，优化了反应条件。     

二异丙基萘合成新工艺

首次用天然硅铝酸合成二异丙基萘，生产过程简单、无腐蚀和废水污染。在１５０℃下，丙烯与萘的摩尔比为２：１、催化剂用量８％、反应时间６ｈ的条件下，二异丙基萘的单程收率为２３１％，单异丙基萘的单程收率为５８３％。     

1,5—二羟基萘的合成研究

以萘为原料，经磺化、碱熔反应合成１，５－二羟基萘，优化了反应条件。     

2—甲氧基—6—萘乙酮合成新工艺

本文报道了以２－萘酚为原料，采用溴保护法，经甲醚化，溴化，乙酰化，脱溴四步，合成２－甲氧基－６－萘乙酮，四步总收率达８３．４％（以２－萘粉汁），比文献收率５０％提高３３．４％，使产品成本大幅度下降。     

1,5-二羟基萘的合成

采用萘与 2 0 %发烟硫酸的磺化反应及 1 ,5-萘二磺酸钠与氢氧化钠水溶液的水解反应可合成1 ,5-二羟基萘。合成总收率达 49.9%。     

香兰素合成新工艺的改进

对以４ － 羟基苯甲醛为原料合成３ － 甲氧基－ ４ － 羟基苯甲醛的工艺进行了改进研究,其中包括以氯化溴代替溴素为溴化剂和以甲醇＋ ＤＭＦ（ 体积比甲醇∶ＤＭＦ＝ ６∶１） 代替ＤＭＦ 作为甲氧基化反应的溶剂,从而为降低生产成本提供了很好的条件。最后,溴化一步３ － 溴－ ４ － 羟基苯甲醛收率达９３ ．３ ％ ,甲氧基化一步３ － 溴－ ４ － 羟基苯甲醛转化率达９６ ．７ ％ 。     

新型阻燃剂TBT的合成

研究了新型阻燃剂５，６，７，８－四溴－１，２，３，４－四氢化萘（ＴＢＴ）的合成方法，并对工艺条件进行了研究。总收率可达５０．３％。     

高纯度1，5-二羟基萘的合成

以精萘为原料,通过磺化、碱熔制得高纯度的1,5-二羟基萘。最佳反应条件为磺化温度25℃,酸析pH=5~6,当精萘用量为10g时,溶剂1,2-二氯乙烷的用量45mL。在最佳反应条件下,碱熔收率达90.2%,产品纯度为99.3%。     

高附加值萘二酚类中间体的合成与应用进展

萘二酚类中间体的传统合成工艺具有操作简单和工业化程度高等优点，但存在废酸排放量大、后处理工艺复杂、成本高和环境污染严重等问题，近年来有被绿色合成工艺逐步替代的趋势。本文回顾了以磺化碱熔法和硝化还原法为主的传统合成方法；简述了用微藻类微生物、重组酵母以及多种结构的加氧酶代谢转化的生物转化法和以强酸、生物酶以及有机金属络合物作为催化剂的直接催化羟基化法等新兴绿色合成工艺。着重介绍了1,6-二羟基萘（又称为1,6-萘二酚）的合成工艺进展，特别是在过氧化氢存在下，采用酸催化剂，如用强酸氢氟酸和五氟化锑催化以及用氟锑磺酸、三氟化硼和氢氟酸等直接进行的催化羟基化反应。同时还综述了萘二酚化合物在染料、医药、催化及电池等领域的典型应用情况。最后指出了生物转化法及催化羟基化法制备萘二酚的改进方向是提高反应的收率及萘的转化率，以达到大规模工业化生产的水平；并对萘二酚类中间体应用领域的拓展进行了展望，指出其向精细化、高附加值的医药及材料方向发展的趋势。     

Synthesis and properties of 1,5- and 1,8-dichloro-substituted poly(9,10-dihydroanthracene-9,10-diylidene)s

Two new dichloro-substituted poly(9,10-dihydroanthracene-9,10-diylidene)s were prepared by self-condensation of 1,5-dichloroanthrone and 1,8-dichloroanthrone. The bromination and thermal and semiconductive properties were investigated.     

Studies on 2,4,6-Trinitrophenyl Substituted Naphthalenes. Part IV: Synthesis of Nitro- and Polynitro-Di-(2,4,6-trinitrophenyl)naphthalenes

The nitration of 1,4-di(2,4,6-trinitrophenyl)naphthalene and 1,5-di(2,4,6-trinitrophenyl)naphthalene and of mono- and dinitro-derivatives of these compounds has been studied with a view to obtaining heat resistant materials of high energy. A number of mono-, di- and tri-nitro derivatives of 1,4-di(2,4,6-trinitrophenyl) and 1,5-di(2,4,6-trinitrophenyl)naphthalenes have been prepared.     

Studies on 2,4,6-Trinitrophenyl Substituted Naphthalenes. Part II. Synthesis of nitro- and polynitro-1-(2,4,6-trinitrophenyl)naphthalenes

Mononitro-, dinitro-, trinitro- and tetranitro-derivatives of 1-(2,4,6-trinitrophenyl)naphthalene have been synthesised using a variety of nitration procedures. The mononitro- and dinitro-derivatives have also been synthesised from 1-bromonaphthalene and 1-nitronaphthalene via a combination of bromination, nitration and Ullmann reactions.     

1,5-萘二磺酸合成的研究

本文分别采用20％发烟硫酸磺化法及发烟硫酸有机溶剂磺化法合成了1，5－萘二磺酸，对影响反应的因素做了探讨。发烟硫酸浓度的增大、反应温度的提高、发烟硫酸与萘的配比的增大，都使得1，5－萘二磺酸收率降低。对两种方法合成1，5－萘二磺酸进行了比较，结果发现采用发烟硫酸有机溶剂磺化法产品收率高达76．5％，远高于20％发烟硫酸磺化法。     

Poly(naphthylenethiophene)s and poly(naphthylenevinylenephenylenevinylene)s: effect of naphthalene positional isomers on the light emitting properties of their polymers

Poly(naphthylenethiophene)s and poly(naphthylenevinylene-phenylenevinylene)s prepared from 1,5-dibromo-3,7-di-t-butylnaphthalene showed a significant blue shift in their UV-vis and photoluminescence spectra compared to copolymers derived from the 1,4-naphthylene system, both in solution and in thin film. This is correlated to a change in conjugation effect of the two positional isomers of naphthalene in the polymer backbone, where in 1,4-conjugation an aromatic sextet remains intact in one of the naphthalene rings whereas 1,5-conjugation involves the loss of resonance energy in the entire naphthalene unit. The series of poly(naphthylenevinylene-phenylvinylene)s emitted blue-green light with very high fluorescence quantum yields (80-95%) in solution. A fabricated device showed external quantum efficiency estimated at 0.2-0.4%, with a relatively high turn-on voltage at ∼7.0 V.     

Thioetherglycidyl resins. I. Products of condensation of 1-mercaptomethylnaphthalene and 1,4-, 1,5-di-(mercaptomethyl) naphthalene and their mixtures with epichlorohydrin

New thioetherglycidyl resins produced by condensation of 1-mercaptomethylnaphthalene, 1,4-di(mercaptomethyl)naphthalene, 1,5-di(mercaptomethyl)naphthalene, and their mixture of 1,4- and 1,5-di(mercaptomethyl)naphthalene with epichlorohydrin were obtained. The condensation was carried out in two ways. In the first way, potassium salt of mercaptans and epichlorohydrin were used. In the second, epichlorohydrin was added to mercaptans and then the obtained chlorohydrin thioether was dehydrohalogenated by the alkaline hydroxide in water and n-butanol or isopropyl alcohol solution. The method of heterogeneous condensation of dithiol with epichlorohydrin in water and isopropyl alcohol solution proved to be the most effective. Yield, the epoxide content, and the total chlorine content for all resins were found. The structure of thioetherglycidyl resins with the highest epoxide content was determined by elementary analysis, and infrared (IR) and NMR spectra. Thermal stability of resins was studied during long controlled heating at unchanged temperature and short heating carrying the thermal gravimetric analysis (TGA) mainly in air. As follows from the studies, thioetherglycidyl resins can be cured both chemically and thermally.     

Synthesis and Characterization of New Copoly(arylene ether)s Containing Naphthalene or Naphthalene/1,3,4-Oxadiazole Units

Summary Series of new copoly(arylene ether)s containing naphthalene or naphthalene/1,3,4-oxadiazole units have been obtained by polycondensation in solution starting from the following systems of monomers: 1,5 or 2,6-bis(4-fluorobenzenesulfonyl) naphthalene / 2,6-bis(4-fluorobenzoyl)naphthalene, 1,5 or 2,6-bis(4-fluorobenzen sulfonyl)naphthalene / 2,2-(oxydi-4,1-phenylene)bis[5-(4-fluorophenyl)-1,3,4- oxadiazole] and 2,6 bis-(4 fluorobenzoyl)naphthalene/2,2-(oxydi-4,1-phenylene)bis [5-(4-fluorophenyl)- 1,3,4-0xadiazole]. Hydroquinone and 4,4dihydroxy benzophenone have been used as aromatic dihydroxy compounds. The copolymers, obtained in quantitative yields, possessed inherent viscosities in the range 0.28-0.58 dl g^-1, had good thermal stability (10% weight loss temperatures were above 460°C both in nitrogen and air) and high glass transition temperatures (in the range 190-210°C). They have been characterized by infrared analyses, GPC and wide-angle X-ray diffraction. The copolymer property-structure relationships were studied and the properties have been compared with those of the corresponding homopolymers.     

Synthesis and properties of novel aromatic poly(ester–amide)s derived from 1,5‐bis(3‐aminobenzoyloxy)naphthalene and aromatic dicarboxylic acids

A new naphthalene‐ring‐containing bis(ester–amine), 1,5‐bis(3‐aminobenzoyloxy)naphthalene, was prepared from the condensation of 1,5‐dihydroxynaphthalene with 3‐nitrobenzoyl chloride followed by catalytic hydrogenation. A series of novel naphthalene‐containing poly(ester–amide)s was synthesized by direct phosphorylation polyamidation from this bis(ester–amine) with various aromatic dicarboxylic acids. The polymers were produced in high yields and had moderate inherent viscosities of 0.47–0.81 dL g^?1. The poly(ester–amide) derived from terephthalic acid was semicrystalline and showed less solubility. Other polymers derived from less rigid and symmetrical diacids were amorphous and readily soluble in most polar organic solvents and could be solution‐cast into transparent, flexible and tough films with good mechanical properties. The amorphous poly(ester–amide)s displayed well‐defined glass transition temperatures of between 179 and 225 °C from differential scanning calorimetry and softening temperatures of between 178 and 211 °C from thermomechanical analysis. These poly(ester–amide)s did not show significant decomposition below 400 °C in nitrogen or air. Copyright © 2004 Society of Chemical Industry