顺,顺,顺-3,6,9-二十碳三烯及顺,顺,顺-3,6-9-二十一碳三烯的合成

由于昆虫信息素研究的需要,我们曾于1979年合成了顺、顺、顺-3,6,9-二十碳三烯(1)和顺、顺、顺-3,6,9-二十一碳三烯(2),最近Conner等报道,1和2为鳞翅目昆虫信息素组分,并发表了以亚麻油酸及亚麻油醇为原料的合成路线。本文报道我们的合成路线,以丙炔醇为原料,经2-戊炔醇-[1](3),1-溴-2-戊炔     

10-Alkenylphenothiazines. 2. Synthesis and mechanism of acidic hydrolysis of cis- and trans-10-2-phenylvinyl)phenothiazines

The addition of phenothiazine to phenylacetylene in super-base media proceeds regio- and stereoselectively and leads to the predominant formation of cis-10-(2-phenylvinyl)phenothiazine, which is completely converted to its trans-isomer at 200C. Kinetic analysis of the acidic hydrolysis of the cis- and transisomers has allowed us to assign to it an AS_E2 reaction mechanism, similar to the mechanism of hydrolysis of vinyl alkyl ethers.For Communication No. 1, see [1].Translated from Khimiya Geterotsicheskikh Soedinenii, No. 10, pp. 1420–1424, October, 1986.     

Synthesis of cis,cis,cis-tetrasubstituted cyclobutanes. Trapping of tetrahedral intermediates in intramolecular nucleophilic addition

The intramolecular [2 + 2] photocycloaddition of bismaleimides leads to cage diimides 2. Nucleophilic addition on these compounds (NaBH4, RLi, or MeONa) gives rise to various diazatetracyclic 4 and 11 or oxadiazapentacyclic 3 "bowl shaped" alcohols. X-ray analyses of 3c and 11a provide definite structural data concerning these two highly functionalized compounds.     

N-hetarylethylenes. 1. Synthesis and isomerization of 10-allyland 10-propenylphenoxazines

Alkylation of phenoxazine with allyl bromide has given 10-allylphenoxazine. The prototropic isomerization of 10-allylphenoxazine in DMSO on treatment with t-BuOK, KOH, and NaOH has been examined. At elevated temperatures, mixtures of cis- and trans-10-propenylphenoxazines are formed, but at room temperature in the presence of t-BuOK isomerization proceeds stereoselectively to give cis-10-propenylphenoxazine. The influence of temperature and reaction times on the isomeric composition of the 10-propenylphenoxazines has been studied. The cis-propenylphenoxazine obtained in the kinetically controlled reaction isomerizes under the reaction conditions to the equilibrium mixture of cis- and transisomers of 10-propenylphenoxazine.For preceding communication, see [1]. The series N-Hetarylethylenes comprises 9-alkenyl-carbazoles, 10-alkenylphenothiazines, and 10-alkenylphenoxazines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12,. pp. 1674–1678, December, 1988.     

Stereospecific Synthesis and Acylation of cis 1-Halo 2-Trimethylsilyl Ethylenes

Several routes to 1-halo 2-trimethylsilyl ethylenes have been previously proposed ^1-6: from ethyn7yltrimethylilane (addition of HBr^1,2), ethyltrichlorosilane (addition H by C1, followed by dehydrohalogenation and further methylation of th Si-C1 bonds)³ or by other ways ^4,5, especially by reaction of (2-trimethylsilyl) vinyl lithium with dibromoethane⁶.     

Synthesis of cis,syndiotactic ROMP polymers containing alternating enantiomers

Ring-opening metathesis polymerization (ROMP) of rac-endo,exo-5,6-dicarbomethoxynorbornene (inter alia) yields a cis,syndio,alt-polymer, one in which the sequential units in the cis,syndiotactic polymer consist of alternating enantiomers. Cis selectivity arises through addition of the monomer to produce an all-cis-metallacyclobutane intermediate, while syndioselectivity and alternating enantiomer structures arise as a consequence of inversion of configuration at the metal center with each metathesis step.     

1,3-Oxazolidin-4-ones. Synthesis and configuration of cis and trans isomers

Mixtures of cis and trans 1,3-oxazolidin-4-ones were obtained by cyclodehydration, in the presence of p-toluenesulfonic acid or boron trifluoride etherate, of lactamide and N-methyl-lactamide with aromatic and aliphatic aldehydes. The products were separated by column (silica) chromatography and their configurations were determined.     

10,10-二吡啶甲基-9,10-二氢蒽的合成研究

蒽酮1和氯甲基吡啶盐酸盐2在甲苯中回流反应生成10,10-二吡啶甲基-9(10H)蒽酮(3),收率63％～68％;3用硼氢化钠还原生成10,10-二吡啶甲基-9,l0-二氢蒽-9-醇(4),收率87％～90％;蒽醇4在酸催化下发生歧化反应,得到还原产物10,10-二吡啶甲基-9,10-二氢蒽(5)和氧化产物蒽酮3.该歧化反应受催化剂、溶剂和反应温度等影响.当蒽醇4用三氟化硼为催化剂、甲苯为溶剂、回流反应,5的收率达到74％.所合成的新化合物都经1H NMR,13C NMR,MS和元素分析表征确认.     

Technology for the identification of unusual cis, cis octadecadienoic fatty acids.

In this article methods are presented for the separation and identification of unusual cis, cis dienoic and polygnoic long chain fatty acids. Special emphasis has been laid on the identification of cis, cis octadecadienoic acids. The steps followed are: after transesterification the fatty acid methyl esters are separated by preparative gas chromatography according to chain length followed by argentation chromatography on thin-layer plates. After hydroxylation of the double bonds with osmium tetroxide the polyhydroxy compounds are derivatized to the per-O-trimethylsilyl-ethers. Separation and identification of individual compounds are achieved by combined gas chromatography-mass spectrometry using SCOT columns and low ionization energy.