膦、胂叶立德的化学与应用26: 含全氟烷基胂叶立德的合成及 水解反应研究

报道溴化α-呋喃甲酰基)甲基三苯基申(1)在无水碳酸钾存在下,以无水二氯甲烷作溶剂,保持0-5℃下与2-全氟炔酸甲酯(2)反应,高产率地得到加合产物4-(α-呋喃甲酰基)-2-三苯基胂基-3-全氟烷基-3-丁烯酸甲酯(3)。加合产物3在V(甲醇):V(水)=9:1溶液中分别于室温、回流和封管120℃三种条件下反应,高产率地得到4-全氟烷基-6-(α-呋喃基)-2-吡喃酮(4)和4-(α-呋喃甲酰基)-3-全氟烷基-3-丁烯酸甲酯(5)。化合物4和5可以通过柱层析分离;化合物5为一对Z,E异构体,它们不能通过柱层析分离,但其比例可以由^1HNMR估算得到。研究还发现硅胶对该反应具有催化作用,提出并讨论了反应机理。     

膦、胂叶立德的化学与应用ⅩⅩⅥ.含全氟烷基胂叶立德的合成及水解反应研究

报道溴化(α-呋喃甲酰基)甲基三苯基钟(1)在无水碳酸钾存在下,以无水二氯甲烷作溶剂,保持0～5℃下与2-全氟炔酸甲酯(2)反应,高产率地得到加合产物4-(α-呋喃甲酰基)-2-三苯基胂基-3-全氟烷基-3-丁烯酸甲酯(3).加合产物3在V(甲醇):V(水)=9:1溶液中分别于室温、回流和封管120℃三种条件下反应,高产率地得到4-全氟烷基-6-(α-呋喃基)-2-吡喃酮(4)和4-(α-呋喃甲酰基)-3-全氟烷基-3-丁烯酸甲酯(5).化合物4和5可以通过柱层析分离;化合物5为一对Z,E异构体,它们不能通过柱层析分离,但其比例可以由1HNMR估算得到.研究还发现硅胶对该反应具有催化作用,提出并讨论了反应机理.     

膦、胂叶立德的化学与应用(ⅩⅩⅠⅩ)——含全氟烷基胂叶立德水解合成2-吡喃酮衍生物

在无水碳酸钾存在下,以无水二氯甲烷作溶剂,室温下将溴化(2-萘甲酰基)甲基三苯基(1)与2-全氟炔酸甲酯(2)反应,高产率地得到加合产物4-(2-萘甲酰基)-2-三苯基胂基-3-全氟烷基-3-丁烯酸甲酯(3)和少量4-(2-萘甲酰基)-4-三苯基胂基-3-全氟烷基-2-丁烯酸甲酯(4). 加合产物3在9∶1的甲醇-水溶液中在一定温度下反应,高产率地得到4-全氟烷基-6-(2-萘基)-2-吡喃酮(5). 研究发现硅胶对该反应具有催化作用. 提出并讨论了反应机理.     

膦、胂叶立德的化学与应用(ⅩⅩⅨ)──含全氟烷基胂叶立德水解合成2-吡喃酮衍生物

在无水碳酸钾存在下,以无水二氯甲烷作溶剂,室温下将溴化(2－萘甲酰基)甲基三苯基鉮(1)与2－全氟炔酸甲酯(2)反应,高产率地得到加合产物4-(2－萘甲酰基)－2－三苯基胂基－3－全氟烷基－3－丁烯酸甲酯(3)和少量4－(2－萘甲酰基)－4－三苯基胂基－3－全氟烷基－2－丁烯酸甲酯(4).加合产物3在9:1的甲醇－水溶液中在一定温度下反应,高产率地得到4-全氟烷基－6－(2－萘基)－2－吡喃酮(5).研究发现硅胶对该反应具有催化作用.提出并讨论了反应机理.     

膦、胂叶立德的化学应用与应用（XXIX）：——含全氟烷基胂叶立德水解合成2—吡喃酮衍生物

在无水碳酸钾存在下，以无水二氯甲烷作溶剂，室温下将溴化（2－萘甲酰基）甲基三苯基Shen（1）与2－全氟炔酸甲酯（2）反应，高产率地得到加合产物4－（2－萘甲酰基）－2－三苯基胂基－3－全氟烷基－3－丁烯酸甲酯（3）和少量4－（2－萘甲酰基）－4－三苯基胂基－3－全氟烷基－2－丁烯酸甲酯（4），加合产物3在9：1的甲醇－水溶液中在一定温度下反应，高产率地得到4－全氟烷基－6－（2－萘基）－2－吡喃酮（5），研究发现硅胶对该反应具有催化作用，提出并讨论了反应机理。     

第五、六族元素的有机化合物在有机合成中应用的研究 XXXIII: 氰基亚甲基三苯基膦、胂与2-全氟炔酸甲酯的反应以及3-全氟烷基-4-氰基-3-丁烯酸甲酯的立体选择性合成

氰基亚甲基三苯基胂(1)与2-全氟炔酸甲酯(2)反应,生成加合产物2-三苯胂基-3-全氟烷基-4-氰基丁烯-3-酸甲酯(3)通过3的水解,立体选择性地合成了3-全氟烷基-4-氰基-3-丁烯酸甲酸甲酯[5(Z),6(E)],Z:E约为95:5.氰基亚甲基三苯基膦(7)与2亦可反应,生成加合产物2-三苯基膦叉-3-全氟烷基-4-氰基丁烯-3-酸甲酯的顺式和反式异构体(8)和(9).总产率在90%左右.8与9的比例受反应介质极性的影响,若溶剂极性增大,则有利于8的生成.     

第五、六族元素的有机化合物在有机合成中应用的研究 ⅩⅩⅩⅢ.氰基亚甲基三苯基膦、胂与2-全氟炔酸甲酯的反应以及3-全氟烷基-4-氰基-3-丁烯酸甲酯的立体选择性合成

氰基亚甲基三苯基胂(1)与2-全氟炔酸甲酯(2)反应,生成加合产物3.通过3的水解,立体选择性地合成了3-全氟烷基-4-氰基-3-丁烯酸甲酯[5(Z),6(E)],Z:E约为95∶5。氰基亚甲基三苯基膦(7)与2亦可反应,生成加合产物8和9,总产率在90%左右。8与9的比例受反应介质极性的影响,若溶剂极性增大,则有利于8的生成。     

膦、胂叶立德的化学与应用 XII. 对硝基苯基亚甲基三苯基膦、胂与2-全氟炔酸甲酯的反应以及(Z)3-全氟烷基 4-对硝基苯基-3-丁烯酸甲酯的立体专一性合成

溴化对硝基苄基三苯基 (1a)、 (1b)在碳酸钾存在下与2-全氟炔酸甲酯(2)在常温下反应, 生成加合物3(当M=As时)或3和4的混合物(当M=P时), 其中3的含量随反应温度升高而增加, 当反应温度为90℃时, 产物全部为3。4c加热时转化为3c。膦加合物3或4在甲醇-水中于封管内150℃加热, 发生P-C键断裂。两者都立体专一性地生成(Z)3-全氟烷基-4-对硝基苯基-3-丁烯酸甲酯(5)。胂加合物3在甲醇-水中回流, 发生As-C键断裂, 生成(Z)-5。对水解机理进行了研究。     

膦、胂叶立德的化学与应用 XII. 对硝基苯基亚甲基三苯基膦、胂与2-全氟炔酸甲酯的反应以及(Z)3-全氟烷基 4-对硝基苯基-3-丁烯酸甲酯的立体专一性合成

溴化对硝基苄基三苯基 (1a)、 (1b)在碳酸钾存在下与2-全氟炔酸甲酯(2)在常温下反应, 生成加合物3(当M=As时)或3和4的混合物(当M=P时), 其中3的含量随反应温度升高而增加, 当反应温度为90℃时, 产物全部为3。4c加热时转化为3c。膦加合物3或4在甲醇-水中于封管内150℃加热, 发生P-C键断裂。两者都立体专一性地生成(Z)3-全氟烷基-4-对硝基苯基-3-丁烯酸甲酯(5)。胂加合物3在甲醇-水中回流, 发生As-C键断裂, 生成(Z)-5。对水解机理进行了研究。     

膦、胂叶立德的化学与应用 Ⅻ.对硝基苯基亚甲基三苯基膦、胂与2-全氟炔酸甲酯的反应以及(Z)3-全氟烷基4-对硝基苯基-3-丁烯酸甲酯的立体专一性合成

溴化对硝基苄基三苯基鏻(1a)、鉮(1b)在碳酸钾存在下与2-全氟炔酸甲酯(2)在常温下反应,生成加合物3(当M=As时)或3和4的混合物(当M=P时),其中3的含量随反应温度升高而增加,当反应温度为90℃时,产物全部为3.4c加热时转化为3c.膦加合物3或4在甲醇-水中于封管内150℃加热,发生P—C键断裂.两者都立体专一性地生成(Z)3-全氟烷基-4-对硝基苯基-3-丁烯酸甲酯(5).胂加合物3在甲醇-水中回流,发生As—C键断裂,生成(Z)-5.对水解机理进行了研究.     

Counter-current chromatographic estimation of hydrophobicity of Z-(cis) and E-(trans) enalapril and kinetics of cis/trans isomerization

The kinetics of Z-(cis)/E-(trans) isomerization of enalapril was investigated by reversed phase high-performance liquid chromatography (RP-HPLC) using a monolith ODS column under a series of different temperature and pH conditions. At a neutral pH 7, the rate (k(obs)) of Z-(cis)/E-(trans) isomerization of enalapril at 4 degrees C (9.4 x 10(-3)min(-1)) is much lower than at 23 degrees C (1.8 x 10(-1)min(-1)), while the fractional concentration of Z-(cis) isomer is always higher than that of E-(trans) isomer in the pH range 2-7. The fractional concentration of the E-(trans) isomer becomes a maximum (about 40%) in the pH range 3-6, where enalapril exists as a zwitterion. The hydrophobicity (logP(O/W)) of both isomers was estimated by high-speed counter-current chromatography (HSCCC). Normal phase HSCCC separation using a tert-butyl methyl ether-acetonitrile-20mM potassium phosphate buffer (pH 5) two-phase solvent system (2:2:3, v/v/v) at 4 degrees C was effective in partially separating the isomers, and the partition coefficient (K) of each isomer was directly calculated from the retention volume (V(R)). The logP(O/W) values of Z-(cis) and E-(trans) isomers were -0.46 and -0.65, respectively.     

Phosphonium and arsonium ylides. XVII. A facile synthesis of methyl 2,6-bisperfluoroalkylbenzoates via acyclic precursors

The title compounds 6a—6f were prepared with high yield via intramolecular Wittig reaction of methyl 3-perfluoroalkyl-6-peifluoroacyl-2-triphenylphosphoranylidenchex-3,5-dienoates (5a—5i) which were obtained from the reaction of 3-perfluoroacylprop-2-enylidenetriphenylphosphoranes (3a—3c) with methyl perfluoroalkynoates (4a—4c).     

Halogenation of unsaturated esters—III : Reactions of bromine chloride with chlorinated methyl 2-butenoates

Additions of Cl₂, Br₂; and BrCl to methyl Z-2-chloro-2-(1), E-3-chloro-2-(2), Z-3-chloro-2-(3) and E-4-chloro-2-butenoates (4) in CCl₄ both in the dark and light have been investigated. The product compositions are compared with those reported previously for methyl monochloropropenoates. The chlorine substitution was found to affect the product distributions in the reactions with the BrCl reagent. Under the ionic conditions Br₂ adducts were the main products from 1 and 2, whereas 3 reacted like methyl Z-3-chloropropenoate giving only negligible amount of the Br₂ addition. The Cl₂ addition amounted, as in the reactions of methyl monochloropropenoates, to only a few percent. Compared with the parent esters the chlorine substitutions in 2, 3 and 4 also affected the regiochemistry of the BrCl addition. The main regioisomer in the dark, i.e. the 2-bromo-3-chloro adduct, was obtained from 3, as from methyl Z-3-chloropropenoate, with almost complete regioselectivity. Compound 4 also showed greater regioselectivity than methyl E-2-butenoate. Substrate 2 was, however, found to produce more 3-bromo-2-chloro adduct than the unchlorinated parent ester. Mechanisms presented for the additions of BrCl to methyl 3-chloropropenoates are reconsidered on the basis of the results from the present study.     

Alkenylation by 5-hexen-2-one oxime: Prototropic isomerization under trofimov reaction conditions

From 5-hexene-2-one oxime (I) and acetylene in KOH/DMSO, 2-methyl-3-(2-propenyl)pyrrole (II), E- and Z-2-methyl-3-(1-propenyl)pyrroles (III), and E- and Z-1-vinyl-2-methyl-3-(1-propenyl)pyrroles (V) were synthesized. The isomerization of the alkenyl radical of pyrroles II was studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 477–480, April, 1992.     

(Butadiene)metallocene/B(C6F5)3 pathway to catalyst systems for stereoselective methyl methacrylate polymerization: evidence for an anion dependent metallocene catalyzed polymerization process

The ansa-zirconocene dichlorides [Me(2)Si(C(5)H(4))(3-R-C(5)H(3))]ZrCl(2) 7a-e (R = H, CH(3), cyclohexyl, -CHMe(2), -CMe(3)) were reacted with butadiene-magnesium to yield the respective (eta(4)-butadiene)metallocenes 17a-e. The chiral examples give a mixture of two s-cis and two s-trans diastereomers. The strong Lewis acid B(C(6)F(5))(3) adds selectively to a terminal butadiene carbon atom to yield the (butadiene)metallocene/B(C(6)F(5))(3) betaine complexes 18a-e. Initially, the formation of the Z-18 isomers is preferred. These consecutively rearrange to the thermodynamically favored isomers E-18. The dipolar systems 18 are active single component metallocene catalysts for the stereospecific polymerization of methyl methacrylate. With increasing steric bulk of the attached single alkyl substituent an increasingly isotactic poly(methyl methacrylate) is obtained. A similar trend is observed in the methyl methacrylate polymerization at the [Me(2)Si(C(5)H(4))(3-R-C(5)H(3))]ZrCH(3)(+) catalysts (9a-e) that were conventionally prepared by methyl abstraction from the corresponding ansa-zirconocene dimethyl complexes by treatment with B(C(6)F(5))(3). A comparison of the poly(methyl methacrylates) obtained at these two series of catalysts has revealed substantial differences in stereoselectivity that probably originate from an influence of the respective counteranions. An initial reactive intermediate of methyl methacrylate addition to the dipolar single component metallocene catalyst E-18a was experimentally observed and characterized by NMR spectroscopy at 253 K. The subsequently formed series of [PMMA-C(4)H(6)(-)B(C(6)F(5))(3)](-) anion oligomers (at the catalyst 18c) was monitored (after quenching) and characterized by electrospray mass spectrometry.     

Syntheses of highly unsaturated isocyanides via organometallic pathways

The carbon carbon coupling reaction by nucleophilic attack of (CO)(5)Cr(CN-CF=CF(2)) 1 by lithium or Grignard compounds 2a-i yields the isocyanide complexes (CO)(5)Cr(CN-CF=CF-R) 3a-i (a R = CH=CH(2), b R = CH=CF(2), c R = C≡CH, d R = C≡C-SiMe(3), e R = C≡C-Ph, f R = C≡C-C(6)F(4)OMe, g R = C≡C-C(6)H(3)(CF(3))(2), h R = C(6)F(5), i R = C(6)H(3)(CF(3))(2)) as mixtures of E and Z isomers. The dinuclear complexes 5a-c are obtained from the reaction of 1 with the dilithio or dimagnesium compound 4a-c as the Z,Z-, E,Z- and E,E-isomers, respectively. (CO)(5)Cr(CN-CF=CF-C≡C-C≡C-CF=CF-NC)Cr(CO)(5)7 is obtained as a mixture of Z,Z-, Z,E- and E,E-isomers from (CO)(5)Cr(CN-CF=CF-C≡C-H 3d by Eglington-Glaser coupling. (CO)(5)Cr(CN-CF=CF-C≡C-CF=CF-NC)Cr(CO)(5)6 and (CO)(5)Cr(CN-CF=CF-C=C-C≡C-CF=CF-NC)Cr(CO)(5)7 react with octacarbonyldicobalt forming the cluster compounds Z,Z-[{η(2)-μ(2)-(CO)(5)Cr(CN-CF=CF-C≡C-CF=CF-NC)Cr(CO)(5)}Co(2)(CO)(6)] Z,Z-8, E,Z-[{η(2)-μ(2)-(CO)(5)Cr(CN-CF=CF-C≡C-CF=CF-NC)Cr(CO)(5)}Co(2)(CO)(6)] E,Z-8 and E,E-[{η(2)-μ(2)-(CO)(5)Cr(CN-CF=CF-C≡C-CF=CF-NC)Cr(CO)(5)}Co(2)(CO)(6)] E,E-8 and Z,Z-[{η(2)-μ(2)-(CO)(5)Cr(CN-CF=CF-C≡C-C≡C-CF=CF-NC)Cr(CO)(5)}{Co(2)(CO)(6)}(2)] Z,Z-9, E,Z-[{η(2)-μ(2)-(CO)(5)Cr(CN-CF=CF-C≡C-C≡C-CF=CF-NC)Cr(CO)(5)}{Co(2)(CO)(6)}(2)] E,Z-9 and E,E-[{η(2)-μ(2)-(CO)(5)Cr(CN-CF=CF-C≡C-C≡C-CF=CF-NC)Cr(CO)(5)}{Co(2)(CO)(6)}(2)] Z,Z-9, respectively. The crystal and molecular structures of E-3d, Z-3h, Z,Z-8, E,Z-8 and Z,Z-9 were elucidated by single-crystal X-ray crystallography.     

Enantiomer analysis of E- and Z-10-hydroxyamitriptyline in human urine

E- and Z-10-hydroxyamitriptyline (E- and Z-10-OH-AT) are racemic alcoholic metabolites of the antidepressant amitriptyline. Their enantiomers were separated by high-performance liquid chromatography as diastereomeric derivatives using R-(+)-alpha-methoxy-alpha-trifluoromethylphenylacetyl chloride (Mosher's reagent). Although E-10-hydroxyamitriptyline excreted in patient urine in free form or as the O-glucuronide consisted primarily of the (-)-enantiomer, the N-glucuronide contained similar amounts of the two enantiomers. Z-10-OH-AT was analysed in one patient and an excess of the (+)-isomer was found in the unconjugated, total conjugated and N-glucuronidated metabolite. The specific optical rotation of (-)-E-10-OH-AT was determined.     

由有机硼烷立体选择合成(Z)、(E)链烯-1-醇乙酸酯类昆虫性信息素

等摩尔的甲硼烷甲硫醚(H₃B·SMe₂)与四溴化碳在60℃下反应20h,定量得到一溴硼烷甲硫醚。从链端烯烃、一卤硼烷甲硫醚和2-[7-辛炔-1-氧基]四氢吡喃及其8-溴代衍生物出发,经硼氢化反应和Zweifel的顺-,反-烯烃合成法,立体选择地合成了鳞翅目昆虫性信息素:(Z)-7-十四烯-1-醇乙酸酯9a、(Z)-7-十六烯-1-醇乙酸酯9b、(E)-7-十四烯-1-醇乙酸酯12及其相应的醇13。产物经GC分析和MS、¹H及¹³C NMR数据证实了它们的纯度和几何构型。