4P-羟甲基-2,6,7-三氧杂-1,4-二磷杂双环[2.2.2]氯化辛烷的合成及波谱研究

Verkade等[1]首次合成具有新颖结构的双环(亚)磷酸,并发现其分子为一高度对称的笼状结构,它的衍生物不仅具有很强的生物活性,而且具有独特的生理作用机制.     

Increased stability of phosphite ozonides derived from 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane

Substituent changes at the hydroxyl group in the title compound affect the stability of the corresponding phosphite ozonides generated at the remote phosphorous atom. The benzoyl derivative was found to have a half-life > 100 minutes at 180°C and is at least 10 times more stable at that temperature than 1-phospha-2,8,9-trioxaadamantane ozonide.     

X-ray structural study of 1-oxo-4-isopropyl-and 1-thio-4-propyl-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octanes

Institute of Physiologically Active Substances, Academy of Sciences of the USSR. Translated from Zhurnal Strukturnoi Khimii, Vol. 30, No. 3, pp. 108–113, May–June, 1989.     

Complete transligation of (AcO)4Rh2 applied onto λ-Al2O3 with 4-ethyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane

Complete transligation of (AcO)₄Rh₂ with 4-ethyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane was conducted in the solid phase on λ-Al₂O₃. The reduction of Rh¹¹ to Rh^I on λ-Al₂O₃ at 130°C under the actionof the above-mentioned bicyclic phosphite is accompanied by the oxidation of the acetate anion to the acetoxyl radical. The oxidation products were detected by IR and ESR spectroscopy. 2,6-Di-tert-butyl-4-methylphenol was used as a “spin trap” to identify stable secondary radical cations. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2036–2038, October, 1998.     

CONDENSATION REACTION OF 1-OXO-4-CHLOROCARBONYL-1-PHOSPHA-2,6,7-TRIOXABICYCLO[2.2.2]OCTANE WITH N-t-BUTYL-N-BENZOYLHYDRAZINE

Abstract

1-Oxo-4-chlorocarbony1-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane (5) was obtained from phosphorus oxychloride. Benzyl chloroformate was synthesized by the reaction of benzyl alcohol and triphosgene in good yield for the first time. N-r-Butyl-N-benzoylhydrazine(II) was prepared in a new and convenivent procedure with good yield. The reaction of 5 and II proceeded smoothly in the presence of sodium carbonate and afforded the desired compound 13 in good yield, while in the presence of triethylamine, the elimination of butyl was observed and afforded the compound 12.     

Synthesis And Biological Activities of 4-Neoalkyl-2,6,7-Trioxa-1-PhosphabicycIo[2.2.2] Octanes

4-Alkyl derivatives of 2,6,7-trioxa-1-phosphabicyclo[2.2.2] octanes are extensively used for spectroscopic studies and are candidates for use as flame retardants, vinyl resin stabilizers and antioxidants^[1-4]. Bicyclic phosphates are antagonist of GABA receptor, further research show that these compounds act on the chloride ion channel connecting with GABA receptor. So bicyclic phosphate can act as drugs to probe the Cl^- channel. Our preliminary pharmacological results indicate that these bicyclic phosphorus compounds should be handled with great care because of their high toxicity to mammals. Some derivatives of bicyclic phosphates have been prepared in our laboratory.     

1-硫代-1-磷杂-2,6,7-三氧杂双环[2,2,2]辛烷-4-甲撑烷氧基硫代磷酰胺的合成

以三氯硫磷、高位阻醇A等为原料,通过三步反应合成了化合物1-硫代-1-磷杂-2,6,7-三氧杂双环[2,2,2]辛烷-4-甲撑烷氧基硫代磷酰胺.研究了化合物的31P NMR和MS.产物的结构经元素分析和核磁共振等证实.     

N－（1－氧代－1－磷杂－2，6，7－三氧杂双环［2．2．2］－辛烷－4－羰基）－N＇－芳（烷）基硫脲的合成及结构研究

首次合成了酰基异硫氰酸酯４，并将其与各种芳胺、脂肪胺和肼衍生物加成，得到了２２种未见文献报道的含双环笼状磷酸酯结构的酰基硫脲化合物（５ａ－５ｘ）。４与丁胺反应未得到预期的加成产物，而得到相应的取代产物６。研究了５的结构。     

Cationic polymerization of 1-phenyl-4-ethyl-2,6,7-trioxabicyclo[2.2.2]octane

Cationic polymerization of bicyclo ortho ester, 1-phenyl-4-ethyl-2,6,7-trioxabicyclo[2.2.2]octane, was carried out with Lewis acids and cation sources to obtain the polyether containing ester group in the side chain. It was found that boron trifluoride etherate was the most active initiator in the Lewis acids. Magnesium perchlorate and triphenylcarbenium tetrafluoroborate, which have lower nucleophilic counter ions, initiated effectively the polymerization of bicyclo ortho ester.     

Synthesis of triethylammonium l,4-diphenyl-3-o-hydroxyphenyl-2,8,9-trioxa-1-borata-4-phospha-6,7-benzenobicyclo[3.3.1]nonane

Conclusions The reaction of phenylphosphine with salicylaldehyde and phenylboric acid anhydride in the presence of triethylamine proceeds with the formation of triethylammonium 1,4-diphenyl-3-o-hydroxypheny1-2,8,9-trioxa-1-borata-4-phospha-6,7-benzenobicyclo[3.3.1]nonane.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2118–2120, September, 1987.     

双环笼状磷酸酯衍生物的研究Ⅵ:4-取代-2,6,7-三氧杂-1-磷杂双环[2.2.2]辛烷的反应研究

双环笼状亚磷酸酯类衍生物由于其笼状结构所引起的张力及高位阻性 ,使得它同一般直链亚磷酸酯类化合物相比,在亲核取代反应性等方面有关明显的不同.本文用化合物1分别同SO~2Cl~2,Cl~2, Br~2, PCl~5等反应,结果表明,1均发生了类Arbuzov反应,生成具有相同立体构型的开环产物.本文还对化合物2的磷酰化反应进行了研究,发现在这类高位阻性的双环笼状亚磷酸酯衍生物的磷酰化反应中,DMAP是一个较有效的催化剂.     

Electron impact induced fragmentation of 4-alkyl derivatives of 2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane and the corresponding 1-oxides, 1-sulfides and 1-selenides

The electron impact fragmentations of several derivatives of 2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane have been examined by means of high resolution and metastable ion analysis. The principal fragmentation route for bicyclophosphites, phosphates and phosphorothionates involves a loss of formaldehyde, followed by a loss of the PO₂X and HPO₂X groups (X = -, O, S). The behaviour of phosphoroselenates is quite different, due partly to the favoured loss of selenium from the molecular ion before further fragmentation. Fragmentation through C? O bond breaking and a rearranged molecular ion is dependent on the exocyclic chalcogen atom (-, O, S, Se) on phosphorus. The reactions have been rationalized in terms of 1- and 4-substitutions.     

1-硫代-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷基-4-亚甲基硫醚及其亚砜的合成

本文通过Williamson反应,合成了9个双环笼状硫代磷酸酯的硫醚衍生物3a～i。以3b,3c为例研究了硫醚衍生物的还原性,并合成相应的亚砜化合物4b,4c。讨论了亚砜化合物的立体化学。     

1-氧代-1-磷杂-2, 6, 7-三氧杂双环[2.2.2]-4-含硫取代基辛烷 的合成

本文利用中间体1-氧代-1-磷杂2,6,7-三氧杂双环[2.2.2]-4-羟甲基辛烷(1)和1-氧代-1-磷杂-2,6,7-三氧杂双环[2.2.2]-4-氯甲酰基辛烷(3)分别与RSH或取代硫醇按步骤反应得到了相应的4-亚甲基硫醚(5a～f)、4-亚甲基亚砜(6a～f)、4-(氯代乙硫基)甲酰基(7)及4-(β-烷硫基)-α-硫代酯基(8a～i)的双环笼状磷酸酯新衍生物共22个。所有的化合物经元素分析、IR和^1HNMR得到了证实。