1,4-双正丙氧基柱[7]芳烃的合成及主客体化学

我们以1,4-二正丙氧基-2,5-双甲氧甲基苯为原料用对甲苯磺酸为催化剂在二氯甲烷中制备了1,4-双正丙氧基柱[5]芳烃, 1,4-双正丙氧基柱[6]芳烃和1,4-双正丙氧基柱[7]芳烃. 我们用氢谱, 碳谱和质谱对它们进行了表征. 它们有不同的氢谱却有相似的碳谱. 对比它们的空腔尺寸, 柱[5]的内径大约是4.6 Å, 与葫芦脲[6]及α-环糊精类似. 柱[6]的内径大约是6.7 Å, 与葫芦脲[7]及β-环糊精类似. 柱[7]的内径大约是8.7 Å, 与葫芦脲[8]及γ-环糊精类似. 我们用正辛基三乙基六氟磷酸铵盐作为模型客体研究了它们之间的主客体络合. 柱[5]与之有微弱的络合, 柱[6]显示了良好的络合, 而柱[7]与之没有络合.     

内-α-甲基-α-取代双环[2·2·2]-5-辛烯(辛烷)-2-基甲醇的合成及香气

合成了内 -α-甲基 -α-取代双环 [2· 2· 2 ]-5 -辛烯 -2 -基甲醇和内 a-甲基 -α-取代双环 [2· 2· 2 ]辛烷 -2 -基甲醇共 2 0个化合物 ,其中 1 8个未见报道。通过 IR、1HNMR、对 MS碎片解析并配合气相色谱测定纯度确证了它们的结构 ,请评香专家评定了它们的香气 ,并讨论了化合物结构和香气之间的关系。     

内-α,α-二取代双环[2.2.1]-5-庚烯-2-甲醇的合成及其香气

文献[1]报道了一系列a-甲基-a-取代双环[2.2.1]-5-庚烯-2-甲醇类化合物的合成,并评定了它们的香气。我们以环戊二烯和丙烯酸甲酯为原料,经Diels-Alder反应和Grignard反应,合成了九个标题化合物(2a～i)。除2a外,其余均为新化合物。     

1-(3-芳亚甲基氨基)丙基-2,8,9-三氧杂-5-氮杂-1-硅杂双环[3,3,3]十一烷金属络合物的合成及其抗肿瘤活性研究

我们曾对1-亚甲基氨基烷基-2,8,9-三氧杂-5-氮杂-1-硅杂双环[3,3,3]十一烷的合成及其抗肿瘤活性作过研究,发现1-[3-(2-羟基苯亚甲基氨基)丙基]-2,8,9-三氧杂-5-氮杂-1-硅杂双环[3,3,3]十一烷和1-[3-(2,4-二羟基苯亚甲基氨基)丙基]-2,8,9-三氧杂-5-氮杂-1-硅杂双环[3,3,3]十一烷具有较好的抗肿瘤活性。已知亚甲胺类(Schiff碱)化合物与某些金属离子形成络合物后,能提高它们的抗肿瘤活性。为此,我们进一步研究了这两种亚甲胺衍生物的合成及其抗肿瘤活性。     

对叔丁基杯[6]-1,4-2,5-双冠醚的合成、构象及其对阳离子的识别性能研究

采用分步法高产率地合成了系列新型对叔丁基杯[6]双冠醚，并得到了除杯式与1，2，3－交替式构象之外的第3种稳定构象的杯[6]衍生物：1，4－交替式杯[6]-1,4-2,5-双冠醚。研究了它们对碱金属及脂肪胺离子的两相萃取性能，发现杯[6]双冠醚具有与杯[6]单冠醚不同的识别能力。     

环氧丙基杯[6]-1,4-冠-4聚合物的合成与吸附性能

通过具有稳定锥式构象的杯[6]-1,4-冠-4与环氧氯丙烷反应,再与多乙烯多胺开环聚合,合成了一系列具有稳定构象的新型含氮杯[6]芳烃冠醚聚合物(3a-3c)。并研究了它们对阳离子的吸附性能,结果表明,其吸附选择性较没有稳定构象的类似杯[6]芳烃聚合物好,聚合物3b和3c对Cu^2 表现较好的选择性吸附能力。     

某些内-双环[2.2.2]辛烯(或辛烷)基-2-甲醛缩醛的合成及香气

合成了16个内-双环[2.2.2]辛烯(或辛烷)基-层-甲醛缩醛类化合物。用Ms, IR和HNMR测定了它们的结构。双环[2.2.2]辛烯基缩醛的质谱断裂途径被确定了, 对这些化合物的香气进行了评定, 讨论了香气和结构的关系。     

α-单取代环十二酮构象的研究

利用分子力学计算，单晶X射线分析和~1H NMR技术研究了α-单取代环十二酮 的构象。结果表明，它们的优势构象的环骨架仍是[3333]构象，而羰基则在2-C位 置上。在晶体中，它们的优势构象为α－角顺取代[3333]-2-酮构象，而在溶液中 则取α－角顺取代和α－边外取代[3333]-2-酮两种构象，且两种构象处于动力学 平衡之中，以α－边外取代[3333]-2-酮构象占优势。     

酰氨基硫脲及其相关杂环衍生物的研究II.1-[5-(α-萘)-2H-四唑-2-乙酰[-4-苯基氨基硫脲及其相关环衍生物的合成

本文合成了1-[5-(α-萘)-2-H-四唑2-乙酰]-4-苯基氨基硫脲5,以及由5衍生的环化产物3-[5-(α-萘)-2H-四唑2-甲撑]-4-苯基-1,2,4-三咪啉-5-硫酮6,2-苯胺基-5-[5-(α-萘)-2H-四唑-2-甲撑]-1,3,4-噻二唑7及2-苯胺基-5-[5-(α-萘)-2H-四唑-2-甲撑]-1,3,4-二唑8.它们的结构均通过元素分析,红外光谱,核磁共振及质谱鉴定.其药理实验正在进行中.初步实验表明,5及6对小麦生长有较强的促进作用.     

内-α-取代-α-甲基双环[2,2,1]庚烷-2-基甲醇的合成及其结构与香气的关系

合成了18种内-α-取代-α-甲基双环[2,2,1]庚烷-2-基甲醇(Ⅰ)。测定了所有化合物的折光率(或熔点)、质谱、红外光谱、~1H核磁共振谱、气相色谱的保留时间和薄层色谱的比移值。评定了它们的香气,并与相应的内-α-取代-α-甲基双环[2,2,1]-5-庚烯-2-基甲醇(Ⅱ)系列化合物的香气进行了比较,初步探讨了结构与香气的关系。     

Synthesis and stereochemical assignment of exo- and endo-7-methyl-7-azabicyclo[2.2.1]heptan-2-ol

[formula: see text] The syntheses of both exo and endo stereoisomers of 7-methyl-7-azabicyclo[2.2.1]heptan-2-ol were achieved in straightforward fashion. Alternatively, the intramolecular cyclization of syn-4-N-methylaminocyclohexane 1,2-epoxide was found to give exo-7-methyl-7-azabicyclo-[2.2.1]heptan-2-ol as the sole product. The stereochemistry of the exo isomer was unequivocally confirmed by X-ray crystallography.     

Zur Chemie von Polyhalocyclopentadienen, 22. Mitt.: Über die Herstellung von 1,4,5,6,7,7-Hexachlorbicyclo[2.2.1]hepten-(5)-bishydroxymethylen-(2,3)

Zusammenfassung 1,4,5,6,7,7-Hexachlor-bicyclo[2.2.1]hepten-(5)-bis-hydroxymethylen-(2,3) (I) läßt sich sowohl durch direkte Umsetzung von Hexachlorcyclopentadien (II) und Buten-(2)-diol-(1,4) (III) wie auch durch LiAlH₄-Reduktion von 1,4,5,6,7,7-Hexachlor-bicyclo[2.2.1]hepten-(5)-dicarbonsäure-(2,3) (IV), IV-Anhydrid oder IV-Estern in guter Ausbeute gewinnen.Auf Wunsch der Autoren erscheint diese Abhandlung erst im Herbst 1961.21. Mitt., Dtsch. Bund. Pat. 1 081 886 vom 2. 5. 1958.     

新的手性β-亚磺酰亲双烯体用于不对称Diels-Alder反应

手征性cis-β-亚磺酰丙烯酸酯可从(1R, 2S, 3R)-3-巯基-1,7,7-三甲基二环[2.2.1]庚-2-醇制备, 它与环戊二烯的反应得Diels-Alder加成物, 并具有相当高的端基差向异构选择性。     

Synthesis of 2-substituted (+/-)-(2r,3r,5r)-tetrahydrofuran-3,5-dicarboxylic acid derivatives

An efficient synthesis of 2-substituted (+/-)-(2R,3R,5R)-tetrahydrofuran-3,5-dicarboxylic acid derivatives has been developed. Starting from 5-norborne-2-ol, the key intermediate (+/-)-methyl 5,6-exo,exo-(isopropylidenedioxy)-2-oxabicyclo[2.2.1]heptane-3-exo-carboxylate (15) was synthesized in an efficient six-step sequence. The key transformation is the base-catalyzed methanolysis-rearrangement of (+/-)-6,7-exo,exo-(isopropylidenedioxy)-4-exo-iodo-2-oxabicyclo[3.2.1]octan-3-one (14). Further manipulation of the 3-substituent of (+/-)-methyl 5,6-exo,exo-(isopropylidenedioxy)-2-oxabicyclo[2.2.1]heptane-3-exo-carboxylate (15) followed by deprotection of the diol moiety and ring opening catalyzed by RuCl(3)/NaIO(4) gave the title compounds in good yield.     

Rationalization of enantioselectivities in dialkylzinc additions to benzaldehyde catalyzed by fenchone derivatives

Three (-)-fenchyl alcohol derivatives, ?(1R,2R,4S)-exo-(2-Ar)-1,3, 3-trimethylbicyclo[2.2.1] heptan-2-ol, Ar = o-anisyl (2), 2-N-methylimidazolyl (3), 2-N,N-dimethylbenzylamine (4)? were synthesized, characterized by X-ray analyses, and employed as precatalysts in diethyl zinc additions to benzaldehyde. Directions and relative degrees of enantioselectivities are rationalized by QM/MM ONIOM computations of mu-O transition structure models. Enantioselectivities arise from repulsive interactions between "transferring" or "passive" alkyl groups at the zinc centers and the substituents at donor groups or the bicyclo[2.2.1]heptane moieties. These results enable predictions for ligand-tuning to improve catalyst efficiency of fenchone-based ligands in dialkylzinc additions to aldehydes.     

Synthesis and Dehydration of endo-2-(3-R-Isoxazol-5-yl)-1,7,7-trimethylbicyclo[2.2.1]heptan-exo-2-ols

endo-2-Ethynyl-1,7,7-trimethylbicyclo[2.2.1]heptan-exo-2-ol reacts with nitrile oxides, yielding endo-2-(3-R-isoxazol-5-yl)-1,7,7-trimethylbicyclo[2.2.1]heptan-exo-2-ols. Treatment of the latter with methanesulfonyl chloride in pyridine leads to dehydration and formation of mixtures of the corresponding 1-(3-R-isoxazol-5-yl)-3,3-dimethyl-2-methylenebicyclo[2.2.1]heptanes and 2-(3-R-isoxazol-5-yl)-1,7,7-trimethylbicyclo[2.2.1]hept-2-enes at a ratio of 2:1.     

Mass spectrometry in stereochemical problems. 6 — The case of mono and di-substituted norbornanes

The mass spectrometric behaviour of pairs of stereoisomeric mono- and di-substituted norbornanes, namely bicyclo[2.2.1]heptane-2-endo- and -exo-carboxylic acid, methyl bicyclo[2.2.1]heptane-2-endo- and -exo-carboxylate, 2-exo-acetamidobicyclo[2.2.1]heptane-2-endo- and 2-endo-acetamidobicyclo[2.2.1]heptane-2-exo-carboxylic acid and methyl 2-exo-acetamidobicyclo[2.2.1]heptane-2-endo- and 2-endo-acetamido-bicyclo[2.2.1]heptane-2-exo-carboxylate was studied in detail with particular emphasis on characterization of the stereoisomers. The fragmentation patterns, studied with the aid of mass-analysed ion kinetic energy spectrometry, were supported by semi-empirical MO–SFC calculations, performed using the AM1 method included in the AMPAC program.     

The Quantum Yield of Singlet Oxygen in Thermal Degradation of Alcohol Hydrotrioxides

The yield of singlet oxygen (¹О₂) in the decomposition of a number of hydrotrioxides of alcohols (cyclobutanol, cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol, L-menthol, 1,7,7-trimethylbicyclo[2.2.1]heptan-2-ol, 1,3,3-trimethylbicyclo[2.2.1]heptan-2-ol, heptan-4-ol, propanol-2, and 1-cyclopropylethanol) has been determined using the IR chemiluminescence technique. It has been shown that cyclopentanol, 1,3,3-trimethylbicyclo[2.2.1]heptan-2-ol and 1-cyclopropylethanol hydrotrioxides are efficient sources of singlet oxygen; the yield of ¹О₂ reaches up to 58%.     

对映体纯1-甲基-7-氧杂双环[2.2.1]庚烷-2-酮的制备

1-甲基 - 7-氧杂双环 [2 .2 .1 ]庚烷 - 2 -酮 ( 1 )是萜类天然产物全合成中的重要中间体 ,能被广泛地应用于多种桉烷 ( Eudesmane)、沉香呋喃 ( Agarofuran)和降胡萝卜素 ( Norcarotenoids)等倍半萜天然产物的全合成[1,2 ] .我们以对映体纯化合物 1为原料 ,实现这类天然产物的不对称全合成 [3～ 6 ] .消旋的化合物 (± ) - 1可以 2 -甲基呋喃和 2 -氯丙烯腈为原料 ,经 3步反应得到 [2 ] .但对映体纯化合物 1的制备尚未见报道 .本文用化学拆分方法 ,成功地制备了对映体纯的 ( + ) - 1和 ( - ) - 1 ,并确定了其绝对构型 .1　结果与讨论为减…     

Monooxygenase stereoselectivity in the biosynthesis of stereoisomeric spiroacetals in the cucumber fly,Bactrocera cucumis

[reaction: see text] The stereoselectivity of hydroxylation of alkyltetrahydropyran-2-ols (or their biological equivalents) in the formation of stereoisomers of 2,8-dimethyl-1,7-dioxaspiro[5.5]undecanes in male Bactrocera cucumis has been investigated. Racemic, (6R)-, and (6S)-6-methyl-2-[5-(2)H(1)]-n-pentyltetrahydropyran-2-ol was administered under an [(18)O(2)]-enriched atmosphere. The stereochemistry and isotopic composition of generated spiroacetals were monitored by combined enantioselective GC-MS. The monooxygenase(s) strongly prefers the (6S)-substrate and furnishes predominantly the (S)-alcohol and then the (2S,6R,8S)-2,8-dimethyl-1,7-dioxaspiro[5.5]undecane. The (2S,6S,8R) and (2R,6S,8S) (E,Z)-isomers appear to be derived in vivo predominantly from (R)-hydroxylation of the (6S)-tetrahydropyranol.