全氟碘烷烃的合成和应用

1 前言在40年代末获得了第一批CF3I和C2F6I全氟碘烷烃(ИПФА),目的是利用它们来合成有机汞化合物。从此开始了对全氟碘烷烃进行大规模的研究。ИПФА在合成有机和     

全氟碘烷的应用现状分析

全氟碘烷是有机氟精细化工生产过程中的关键中间体,分析了其应用领域,并着重介绍了其衍生产品的合成工艺和最新进展。     

全氟碘代烷调聚工艺研究

全氟碘代烷(CF3（CF2）nI)是合成氟表面活性剂、疏水疏油织物整理剂和其他含氟精细化学品的重要原料，主要由低级全氟碘代烷和全氟烯烃以调聚法合成，工艺复杂，链长难以控制。国内无全氟碘代烷的生产，严重制约了有机氟精细化学品的发展。本文较为全面地介绍了全氟碘代烷调聚反应的机理、评价指标以及国外调聚工艺的研究现状。     

全氟己基乙酸的合成研究

针对当前广泛使用的全氟辛酸及其盐类(PFOA)等含有C8全氟链段的化合物因对环境和人体健康存在潜在危害等问题,以全氟己基乙基碘为原料出发进行了温和条件下合成其替代品的研究。结果表明,第1步取代反应,当全氟己基乙基碘、H2O与NMP的摩尔比为1:3:22时,可以以86.2%的最高收率得到全氟己基乙醇;第2步氧化反应,当滴加时间和反应时间分别为1 h时,可以以91.3%的最高产率得到全氟己基乙酸。目标化合物的总收率为78.7%。该合成方法具有条件温和、收率高、反应路线短等特点,适用于工业化生产。     

全氟碘烷应用技术与市场开发前景

简要介绍了全氟碘烷在生物活性物质、含氟织物整理剂、含氟表面活性剂等方面的应用,并对其合成技术和市场情况作了简单的介绍。     

全氟碘烷应用技术与市场开发前景

简要介绍了全氟碘烷在生物活性物质、含氟织物整理剂、含氟表面活性剂等方面的应用,并对其合成技术和市场方面的情况作了简单的介绍。     

催化调聚法生产全氟碘辛烷的研究与改进

全氟碘代烷是生产含氟整理剂、含氟表面活性剂及其他含氟精细化学品的关键中间体,我国也因国外的垄断而几乎完全依赖进口,严重制约了我国有机氟精细化工的发展。对国外生产全氟碘代烷的方法进行分析,通过对已有催化调聚法的研究,提出了合理化的改进措施和合成工艺。     

TFE调聚法合成全氟烷基乙基丙烯酸酯工艺研究综述

通过四氟乙烯(TFE)调聚法合成全氟烷基碘,进而合成全氟烷基乙基丙烯酸酯工艺分析,介绍了全氟烷基乙基丙烯酸酯的合成概况,并对其反应及应用进行了详细综述。     

全氟丁二烯的合成条件研究及机理探讨

在原来全氟丁二烯的合成研究基础上,从工业化制备的角度出发,优化以1,4-二碘全氟丁烷为原料制备全氟丁二烯的工艺,得到适宜的反应条件:由溴苯在乙醚溶剂中制备的格氏试剂与1,4-二碘全氟丁烷在四氢呋喃溶剂中,加料速度为20 mL·min-1、真空度为6.7 kPa的条件下进行反应,目标产物收率最佳可达到87.32％.同时根据产物的分布对该反应的反应历程进行推导,指出该反应为E2消除过程.     

四取代全氟辛基金属酞菁的合成

以邻苯二甲酰亚胺为起始原料,在30%的发烟硫酸条件下经碘化得到3-碘邻苯二甲酰亚胺,氨解、脱水得到3-碘邻苯二甲腈,并与全氟辛基碘在铜粉催化作用下,生成3-全氟辛基邻苯二甲腈,选用DBU合成法得到了标题化合物。对3-碘邻苯二甲酰亚胺的合成条件进行考察,得到了最佳反应条件:反应温度为60℃,n(邻苯二甲酰亚胺)∶n(单质碘)=1∶1,反应时间为12 h。目标产物结构经1HNMR和HRMS确认。     

Host selection behavior of bark beetles (Coleoptera: Scolytidae) attackingPinus ponderosa,with special emphasis on the western pine beetle,Dendroctonus brevicomis

Detection of weakened hosts from a distance by bark beetles through olfaction was investigated in field experiments. No significant numbers of Scolytidae were attracted to anaerobically treated pine bolts, stem disks, or sugar and ponderosa pine bark including phloem. Treatment of living trees with cacodylic acid induced attacks byDendroctonus brevicomis, D. ponderosae, Ips latidens, Gnathotrichus retusus, andPityophthorus scalptor, beginning two weeks after treatment. There was no significant difference between landing rates ofD. brevicomis andD. ponderosae on screened treated trees and screened controls. There was a significant increase in landing rates ofG. retusus andI. latidens, because both species had penetrated the screen and produced pheromones. Tree frilling alone did not increase the landing rate of bark beetles. Freezing of the lower trunk with dry ice did not increase significantly the landing rate ofD. brevicomis, D. ponderosae, G. retusus, orI. latidens on screened trees, whereas unscreened frozen trees were attacked by all four species. There was no significantly higher landing rate byD. brevicomis, D. ponderosae, I. paraconfusus, I. latidens, G. retusus, orHylurgops subcostulatus on screened trees evidencing symptoms of severe infection by the root pathogenVerticicladiella wagenerii, than on symptornless trees. These experiments show thatD. brevicomis, D. ponderosae, I. paraconfusus, I. latidens, andG. retusus land, apparently indiscriminately, on healthy and stressed hosts. Thus, in these species host discrimination must occur after landing and prior to sustained feeding.These studies were supported in part by the U.S.D.A. Forest Service, Cooperative State Research Services (2598-RRF.W-1 10) and the National Science Foundation and Environmental Protection Agency through a grant (NSF GB-34719/BM575-04223) to the University of California; and by the Canada Department of the Environment. The findings, opinions and recommendations are not necessarily those of the University of California or the funding agencies.From a thesis submitted by H.A. Moeck to the University of California, Berkeley, in partial fulfillment of the requirements for the degree Doctor of Philosophy in Entomology.     

Defensive strategy of twoHypselodoris nudibranchs from Italian and Spanish coasts

Hypselodoris nudibranchs from different geographic areas (Spain and Italy) have been studied in order to investigate their general defensive strategy. Longifolin (1) and nakafuran-9 (2) are the main ichthyodeterrent allomones used by the mollusks to avoid predation. Evidence of their dietary origin is presented and the very effective strategy against predators, which includes secretion of allomones into the mucus and their storage into specific mantle dermal formations (MDFs), is also discussed.F.P.I.-M.E.C. Spanish fellowship (University of Barcelona) at the I.C.M.I.B.     

Olfactory-based behavioral interactions among five species in the southern pine bark beetle group

Olfactory-mediated behavioral interactions were investigated among the five scolytid species comprising the southern pine bark beetle group. Behavioral response, as determined from field trap catch data, showed that each species was attracted in greatest numbers to the pheromonal blend produced by conspecifies. Interspecifically,D. frontalis displayed no cross-attractancy toIps pheromonal blends, but was weakly attracted to the pheromonal blend of femaleD. terebrans. ThreeIps species displayed varying degrees of cross-attraction as well as to theDendroctonus pheromonal blends. More specifically,I. calligraphus was attracted toI. avulsus and, to a very limited extent, also to the maleD. terebrans pheromonal blend.I. avulsus was somewhat more cross-attractive thanI. calligraphus and showed attraction to the pheromonal blends of femaleD. frontalis, male and femaleD. terebrans, maleI. calligraphus, and maleI. grandicollis. I. grandicollis showed the greatest degree of cross-attraction, particularly in response to theDendroctonus pheromonal blends.Research support in part by CSRS grant 86-CRCR-1-2270, NATO grant CRG.0710/86 and Texas Agricultural Experiment Station project MS1525 (while M.T.S. and T.L.P. were with Texas A&M University). The findings, opinions, and recommendations expressed herein are those of the authors and not necessarily those of the U.S. Department of Agriculture.     

Density-Dependent Reduction and Induction of Milkweed Cardenolides by a Sucking Insect Herbivore

The effect of aphid population size on host-plant chemical defense expression and the effect of plant defense on aphid population dynamics were investigated in a milkweed-specialist herbivore system. Density effects of the aposematic oleander aphid, Aphis nerii, on cardenolide expression were measured in two milkweed species, Asclepias curassavica and A. incarnata. These plants vary in constitutive chemical investment with high mean cardenolide concentration in A. curassavica and low to zero in A. incarnata. The second objective was to determine whether cardenolide expression in these two host plants impacts mean A. nerii colony biomass (mg) and density. Cardenolide concentration (microgram/g) of A. curassavica in both aphid-treated leaves and opposite, herbivore-free leaves decreased initially in comparison with aphid-free controls, and then increased significantly with A. nerii density. Thus, A. curassavica responds to aphid herbivory initially with density-dependent phytochemical reduction, followed by induction of cardenolides to concentrations above aphid-free controls. In addition, mean cardenolide concentration of aphid-treated leaves was significantly higher than that of opposite, herbivore-free leaves. Therefore, A. curassavica induction is strongest in herbivore-damage tissue. Conversely, A. incarnata exhibited no such chemical response to aphid herbivory. Furthermore, neither host plant responded chemically to herbivore feeding duration time (days) or to the interaction between herbivore initial density and feeding duration time. There were also no significant differences in mean colony biomass or population density of A. nerii reared on high cardenolide (A. curassavica) and low cardenolide (A. incarnata) hosts.     

Ancestral semiochemical attraction persists for adjoining populations of siblingIps bark beetles (Coleoptera: Scolytidae)

Three species ofIps pine bark beetles in Hopping's group IX (S.L. Wood'sgrandicollis group),Ips confusus, I. lecontei, andI. paraconfusus, are parapatrically distributed in the American Southwest. They share post-Pleistocene altitudinal ecotones with their host pines. Adjacent to these areas of host overlap, we tested the hypothesis that aggregation pheromones produced by male beetles and/or host volatiles are sufficient to elicit the speciesspecific colonization behaviors typical of these threeIps species in nature. A more distantly related species,I. pini (Hopping's group IV, S.L. Wood'spini group) was used for outgroup comparison. Under the influence of pheromone, males ofI. confusus andI. paraconfusus do not discern among unin-fested log bolts of host and nonhost pine prior to bark contact. Males responding to pheromones emanating from infested bolts are similarly undiscriminating. Females ofI. confusus andI. lecontei olfactorily discern the combination of conspecific males in host pine from other possible beetlepine combinations; females ofI. paraconfusus do not. FemaleI. pini discerned conspecific pheromone from that ofI. lecontei. The bark beetle predator,Enoclerus lecontei, is attracted by, but does not discriminate among, the male-produced volatiles of these Group IXIps species. These results support a hypothesis that divergence in pheromonal responses by these group IXIps species has evolved following their speciation, having been manifested first in the female sex. Evolutionarily, the derived pheromonal messages have preceded their behavioral discrimination by these beetles. Additional speciesspecific cues may operate between the sexes in the field that may preclude heterospecific pairings.     

Cuticular Hydrocarbons as Chemotaxonomic Characters of Pine Engraver Beetles (Ips spp.) in the grandicollis Subgeneric Group

Cuticular hydrocarbons were extracted, identified, and evaluated as chemotaxonomic characters from all species of adult Ips pine engraver beetles in the grandicollis subgeneric group. The grandicollis group consists of Ips grandicollis (Eichhoff), I. cribricollis (Eichhoff), I. lecontei Swaine, I. montanus (Eichhoff), I. paraconfusus Lanier, I. confusus (LeConte), and I. hoppingi Lanier. In order to provide outgroups for a phylogenetic analysis, cuticular hydrocarbons were also analyzed from Orthotomicus caelatus (Eichhoff), I. latidens (LeConte) (latidens subgeneric group), and I. pini (Say) (pini subgeneric group). Two hundred forty-eight hydrocarbon components were identified by gas chromatography–mass spectrometry. The members of the grandicollis group provided 206 of these compounds. The components represented eight classes: n-alkanes, alkenes, alkadienes, terminally branched methylalkanes, internally branched methylalkanes, dimethylalkanes, trimethylalkanes, and tetramethylalkanes. Different populations of O. caelatus, I. grandicollis, I. lecontei, I. montanus, I. paraconfusus, I. confusus, and I. hoppingi provided no evidence for interpopulational variation in cuticular hydrocarbons. Single populations only were analyzed for I. latidens, I. pini, and I. cribricollis. Sexual dimorphism in cuticular hydrocarbons occurred only in I. lecontei where females produced eight unique components with a pentatriacontane parent chain. Several phylogenetic analyses based on hydrocarbon phenotypes agreed in general with the established morphologically based system of relatedness and with published phylogenies reconstructed from protein and nucleic acid characters. Nearly all hydrocarbon analyses suggested a close relationship between I. grandicollis and I. cribricollis; between I. lecontei and I. montanus; and among the sibling species I. paraconfusus, I. confusus, and I. hoppingi. The presence or absence of specific n-alkanes (n-docosane, n-triacontane); certain dimethylalkanes (terminally branched with octacosane and triacontane parent chains and internally branched with heptacosane, hentriacontane, and docotriacontane parent chains); and 3,7,11-; 3,7,15-trimethylheptacosane permit facile discrimination of I. paraconfusus, I. confusus, and I. hoppingi. These three sibling species are difficult to resolve by external morphology. These data support the species status of I. hoppingi rather than it being considered a host race of the I. confusus complex. They also support the species status of I. cribricollis rather than it being considered part of I. grandicollis. In contrast to other published phylogenies reconstructed from molecular data, phylogenies reconstructed from cuticular hydrocarbons repeatedly place I. lecontei as an integral part of the grandicollis subgeneric group. Thus, cuticular hydrocarbon and pheromone alcohol composition of I. lecontei support its inclusion in the grandicollis subgeneric group.     

Extracts of Flourensia cernua (L): Volatile Constituents and Antifungal, Antialgal, and Antitermite Bioactivities

The chemical components of tarbush (Flourensia cernua) leaves were fractionated by extracting successively with hexanes, diethyl ether, and ethanol. Volatile profiles of each fraction were identified by using GC-MS. The hexanes fraction contained mostly monoterpenoids, while the ethanol fraction volatiles were primarily sesquiterpenoids. Crude fractions were tested for activity against fungi, algae, and termites. Application of as little as 1 g of the essential oil from the hexanes fraction was sufficient to provide visible antifungal activity in bioautography assays. The diethyl ether fraction showed selective activity against the cyanobacterium responsible for the 2-methylisoborneol-induced off-flavor sometimes associated with catfish farming operations. All three fractions exhibited a high degree of antitermite activity.     

A Simulation Model for Heat Pump Dryer Plants for Fruits and Roots.

Dryer design requires food properties, drying rate and mass-heat transfer coefficients. These values change continuously during drying due to changes in food fractions, particularly the water fraction. The high energy demand and costs allied to inefficient devices, creates a great need for new processing equipment. Along these guide-lines, several heat pump drying research projects were established at the Norwegian University of Science and Technology. The heat pump dryer provides high quality final product as its drying conditions can be controlled. Its efficiency and non-polluting operation come from closed air-refrigerant circuits and from its ability to fully recover the latent heat of moist air as it exits the drying chamber. Most of the above features are quite the opposite of the conventional dryer characteristics. Several experiments were made on heat pump drying of fruits and roots at temperatures from -22.5 to 40°C to obtain data and correlations on thermophysical properties, specific enthalpy and rehydration. Also, tests were done on drying rate, moisture content, drying constant, effective mass diffusivity and heat and mass transfer equations. The next important phase is the development of a simulation model to predict the performance and characteristics of the heat pump dryer plant. The objectives of the present work are to develop and lo test a heat pump dryer simulation model. The simulation provides results on the characteristics of both plant and components which are integrated by heat and mass transfer equations. The program has menus with click-on icons, input and output pop-up dialogue boxes. The usual commands such as, file-open, file-save, edit-delete are available in this program simply called Hpdryer. The model contains moist air psychrometric. natural and conventional refrigerant property libraries. Ammonia is a time-tested, self-alarming and natural refrigerant. It has been used extensively in the past, and it has better thermodynamic and transport properties than halocarbons. Safety is easily attained by design and its restrictive standards have helped increase its use in several countries. There are 36 ammonia installations in Norway and in the United Kingdom, including a drying plant. Ammonia has zero Odp, zero Gwp and the recent R&D has led to viable small-sale heat pump plants. Ammonia and dichlarodifluoromethane refrigerants were used in the test cases simulated by Hpdryer madel.     

Recognition of aphid parasitoids by honeydew-collecting ants: The role of cuticular lipids in a chemical mimicry system

The aphidiid waspLysiphlebus cardui parasitizes in ant-attendedAphis fabae cirsiiacanthoidis colonies without causing aggressive behavior in the antLasius niger. By contrast,Trioxys angelicae, another aphidiid parasitoid of aphids, is rapidly recognized and vigorously attacked by the ants.L. niger workers also responded differently to dead individuals ofL. cardui andT. angelicae. DeadL. cardui parasitoids were often ignored when encountered byL. niger, whereas deadT. angelicae individuals were immediately grasped by ants that discovered them. However, hexane-washed parasitoids caused a similar reaction pattern in the ants, in that both aphidiid species were tolerated in the aphid colony. Lure experiments demonstrated that chemical stimuli on the cuticle are major cues for the ants to distinguish between the parasitoids. The hexane extract ofL. cardui transferred to washed individuals ofT. angelicae resulted in ant responses characteristic towardsL. cardui, andL. niger workers displayed the typical removal pattern they normally showed towardsT. angelicae whenT. angelicae extract was applied toL. cardui individuals. Both parasitoid species treated with the hexane extract ofA. fabae cirsiiacanthoidis were similarily treated by the ants as were aphid control individuals. The suggestion that the aphidiid waspL. cardui uses chemical mimicry is discussed.     

国外生物降解聚合物的种类及主要组分

据１９９６～１９９８年国外有关文献的汇集,由美,日,德等国主要研制,生产的生物降解聚合物种类为：１,单一型生物降解聚合物;（１）合成酯（酸）类;（２）淀粉基材料;（３）天然高分子材料;２、复合型生物降解聚合物;（１）不同种类的烃基互聚物;（２）烃酯（酸）／聚酯（３）脂肪族聚酯／芳香族聚酯共聚物;（３）淀粉基复合型,（５）光／生物降解聚合物;３、可生物降解水溶性聚合物。