一种萘并吡喃化合物的合成及其工艺研究

本文以4,4'-二甲氧基二苯甲酮、苯乙酮和呋喃甲醛为原料,采用新的路线,6步反应合成了一种新型萘并吡喃类化合物,借助核磁共振、质谱等检测手段对最终产物的结构进行了结构表征,并对其反应条件进行优化,提高了反应收率,最后应用紫外-可见吸收光谱对目标产物在不同溶剂中的光致变色性质进行了初步探索研究。     

KF/Al_2O_3催化下4-芳基-9,10-二氢萘并[2,1-b]-4H-吡喃衍生物的合成

在KF/Al2O3催化下,α,β-不饱和腈或α,β-不饱和羧酸酯和7-甲氧基-1,2,3,4-四氢-2-萘酮反应,生成了一系列4-芳基-9,10-二氢萘并[2,1-b]-4H-吡喃衍生物.产物的结构通过红外光谱和核磁共振氢谱进行表征,并通过X单晶衍射分析进一步证实产物的结构.     

萘并吡喃类固态光致变色化合物的合成及性能研究

合成了化合物 ２,２－二芳基萘并吡喃（２ａ－２ｐ）,产物结构和组成通过１Ｈ ＮＭＲ, ＭＳ和元素分析证实．测定了化合物光照前后的紫外可见吸收光谱．部分化合物表现出良好的固态光致变色性能,分析了它们的结构与光致变色性能间的关系．     

微波辐射下吡喃并[3,2-c]吡啶酮和吡喃并[4,3-b]吡喃酮类化合物的高效绿色合成

对离子液体介质中微波辐射下芳香醛、吡啶(喃)酮和丙二腈的三组分缩合反应的研究发现,该反应可快速完成,无需使用催化剂,并以较高的收率生成相应的吡喃并[3,2-c]吡啶酮和吡喃并[4,3-b]吡喃酮类化合物。与文献方法相比,该方法具有反应速度快、效率高、原料易得、对环境友好等优点。另外,该方法已成功地应用于吡喃并[3,2-c]吡啶酮和吡喃并[4,3-b]吡喃酮-嘧啶核苷杂化体的合成中。     

2,2-二芳基取代萘并吡喃类光致变色化合物的合成与性能研究

从光消色速度和最大吸收强度两个角度出发, 用Grignard试剂和萘并吡喃-2|酮合成了一系列2,2-二芳基取代萘并吡喃类光致变色化合物, 并用 1H NMR, IR, MS和元素分析确定其结构. 研究了其紫外-可见光谱, 并探讨了紫外-可见光谱和光致变色性能之间的关系, 分析了其结构和光消色速度之间的关系, 初步探索到光消色速度快慢和取代基位置之间的规律, 为实用化的有机光致变色化合物的合成提供了有价值的参考依据.     

Ring-opened Crystal Structure and Photochromism of 2,2-Bis（4-tertiary butyl phenyl）-3H-naphtho[2,1-b]pyran

The title compound, 2,2-bis（4-tertial butyl phenyl） naphthopyran, has been prepared and characterized by means of IR, ^1H NMR and elemental analysis, and its crystal structure was determined with X-ray diffraction in the ring-opened form after hydrolyzation. It belongs to monoclinic, space group P21/c, with a = 14.358（3）, b = 7.6725（15）, c = 24.470（5） А, β= 97.147（4）°, C_33H_36O2, Mr=464.62, V= 2674.8（9）А^3, Z = 4, Dc = 1.154 g/cm^3,μ= 0.070 mm^-1, F（000） = 1000, the final R = 0.0514 and wR = 0.1272 for 5444 observed reflections （I 〉 2σ（I））. X-ray analysis revealed that the C（13）-O（1） bond of the title compound cracks after UV irradiation, the six-membered heterocycles are destroyed, and zwitterionic intermediates come into being. The molecular structure in the ring-opened form is obtained after hydrolyzation. It is infrequent that the single-crystal structure is determined in a ring-opened form. A two-dimensional framework is formed by O-H…O and CAr-H…O hydrogen bonds. The UV-vis spectra show that the title compound exhibits excellent photochromic properties in solutions and polymers.     

2-氨基-3-氰基-4-芳基-6-甲氧基-1,4,9,10-四氢萘并[2,1-b]吡喃衍生物的一步合成

以芳醛、丙二腈和7-甲氧基-1,2,3,4-四氢萘-2-酮为原料,在六氢吡啶催化下以乙醇为溶剂,在室温合成了一系列新的2-氨基-3-氰基-4-芳基-6-甲氧基-1,4,9,10-四氢萘并[2,1-b]吡喃衍生物,反应条件温和,产率较高,并通过IR,1H NMR和元素分析表征产物的结构,还通过单晶X射线衍射分析确证产物的构象.     

含苯氧基萘并萘醌和偶氮苯双变色基化合物的合成和性质

通过６－氯－５，１２－萘并萘醌与４－羟基偶氮苯及其衍生物的反应合成了３种含苯氧基萘并萘醌和偶氮苯光致变色基的双变色基化合物，６－［４－（苯偶氮基）苯氧基］－５，１２－萘并萘醌（５），６－［４－（ｐ－乙氧基苯偶氮基）苯氧基］－５，１２－萘并萘醌（６）和６－［４－（ｐ－硝基苯偶氮基）苯氧基］－５，１２－萘并萘醌（７）．这些化合物的苯氧基萘并萘醌变色基的ＵＶ诱导光致变色性较弱；基于氨与苯氧基萘并萘醌ａｎａ显色体的不可逆反应，化合物５和６ＤＭＳＯ溶液在３６５ｎｍ紫外光辐照光稳态（ＰＳＳ）下的ａｎａ醌式摩尔分数估计分别为２２％和１７％．这些结果说明，苯偶氮基对苯氧基萘并萘醌变色基的光致变色性质有着极强的影响．另一方面，与４－羟基偶氮苯母体不同，这些双变色基化合物在ＤＭＳＯ中偶氮苯变色基的顺式异构体是相对稳定的     

KF-Al2O3催化下二-γ-吡喃并[2,3-a;2'''',3''''-f]萘衍生物的合成

以芳醛、氰乙酸酯和1,5-萘二酚为原料,以乙醇为溶剂,在80℃以KF/Al2O3为催化剂合成了一系列的2,8-二氨基-4,10-二芳基-4H,10H-二-γ-吡喃并[2,3-a;2',3'-f]萘-3,9-二羧酸酯衍生物,该反应具有反应条件温和、产率良好、操作方便等优点.产物的结构通过IR,1HNMR和元素分析表征,并进一步通过X射线衍射分析确证4h的结构.     

Synthesis of 6H-Naphtho[1,2,3-cd]indol-6-ones

S,S-Dimethyl-and S-methyl-S-phenyl-N-(9,10-anthraquinon-1-yl)sulfoximides are converted into 6H-naphtho[1,2,3-cd]indol-6-ones on heating in polar aprotic solvents.     

Synthesis of 3a,6,6,9a-tetramethyl-trans-perhydronaphtho [2,1-b]furan and 4a,7,7,10a-tetramethyl-trans-perhydronaphtho [2,1-b]pyran

The compounds 3a,6,6,9a-tetramethyl-trans-perhydronaphtho[2,1-b]furan (ambrox or ambroxide) and 4a,7,7,10a-tetramethyl-trans-perhydronaphtho[2,1-b]pyran (homofixator) — substances important in the perfume industry — have been synthesized by superacid cyclization of E,E-homofarnesol and E,E-bishomofarnesol or mixtures of the isomeric bicyclohomofarnesenes or bicyclobishomofarnesenols. Superacid cyclization of these alcohols was shown to be an effective structurally selective and stereospecific method of obtaining ambroxide and homofixator.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 896–901, July, 1990.     

Synthesis of 3-aryl-3a-phenylindano[2,1-d]-oxazolidine-2,4-diones

2-Phenylindan-1,3-dione reacts with aryl isocyanates in benzene in the presence of catalytic amounts of triethylamine with the formation of 3-aryl -3a-phenylindano-[2,1-d]oxazolidine-2,4-diones. In pyridine, this reaction leads to 2-arylcarbamoyl-2-phenylindan-1,3-dione.Translated from Khimiya Geterotsklicheskikh Soedinenii, No. 5, pp. 612–615, May, 1985.     

3-Chloro-6-alkylisoindolo[2,1-a]quinazol-5-ones

3-Chloro-11H-isoindolo[2,1-a]quinazol-5-one was obtained by condensation of o-chloromethylbenzonitrile with 5-chloroanthranilic acid, and its alkylation, electrophilic substitution, and addition reactions were studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1129–1131, August, 1977.     

纳米TiO_2催化一锅法合成喹唑啉酮并酞嗪酮及3-酰胺基异吲哚酮并喹唑啉酮类化合物

以纳米TiO_2为催化剂,靛红酸酐、2-甲酰基苯甲酸、不同芳香肼或酰肼类化合物为原料,在乙醇/水溶液为溶剂的条件下一锅法合成,高产率得到6个喹唑啉酮并酞嗪酮类化合物及10个3-酰胺基取代的异吲哚酮并喹唑啉酮类化合物.该方法简洁高效,反应条件温和,为喹唑啉酮并杂环类化合物的合成提供了一条新途径.     

Solid-phase synthesis of 7-substituted 3H-imidazo[2,1-i]purines

A method for solid-supported synthesis of N,N-disubstituted (3H-imidazo[2,1-i]purin-7-yl)methyl amines has been developed. The key features of this library synthesis are: (i) immobilization of commercially available N6-benzoyl-5'-O-(4,4'-dimethoxytrityl)-2'-deoxyadenosine 3'-(2-cyanoethyl N,N-diisopropylphosphoramidite) by phosphitylation to a hydroxyl-functionalized support, (ii) quantitative conversion of the deprotected adenine base to 3H-imidazo[2,1-i]purine-7-carbaldehyde with bromomalonaldehyde in DMF in the presence of formic acid and 2,6-lutidine, (iii) reductive amination of the formyl group followed by N-alkylation or N-acylation, and (iv) release from the support by acidolytic cleavage of the N-glycosidic bond. Steps (ii) and (iii) have been optimized in some detail by using (adenin-9-yl)acetic acid anchored to a Phe-Wang resin as a model compound.