从蒎烷合成二氢月桂烯醇的催化新技术

从顺式蒎烷裂解得二氢月桂烯，粗产物直接水合制二氢月桂烯醇。蒎烷的催化裂解明显优于热裂解。 当顺式蒎烷转化接近完全时，二氢月桂烯的选择性在50%以上，而热裂解则低得多。用固体酸催化二氢月桂烯直接水合反应的选择性可达80%以上，具有辅料少、生产周期短、消耗低、污染少等优点。     

蒎烷的制备及其下游产品开发应用综述

介绍了由蒎烯催化加氢合成顺式蒎烷的工艺，以及蒎烷在合成芳樟醇、香叶醇和二氢月桂烯及其下游萜类产品的应用。     

环氧蒎烷的合成研究与分析

综述了在各种反应条件下由α-蒎烯及β-蒎烯合成环氧蒎烷的研究现状，介绍了该课题组使用低浓度过氧乙酸由α-蒎烯合成2．3-环氧蒎烷的研究工作。     

蒎酸二酰基双去氢枞基双噁二唑的合成与表征

以歧化松香中提取的去氢枞酸为原料,经酰化得到去氢枞酸酰氯。以松节油的主要成分α-蒎烯为原料,经过蒎酮酸、蒎酸、蒎酸二乙酯得到蒎酸二酰肼。蒎酸二酰肼与去氢枞酸酰氯在相转移催化剂的作用下反应,得到N,N′-二去氢枞基取代蒎酸二酰肼,再经三氯氧磷脱水环合,得到蒎酸二酰基双去氢枞基双噁二唑。初步探讨合成条件,通过元素分析、IR、MS、1H NMR和13C NMR对所合成的化合物进行了结构表征。     

蒎烷空气氧化反应的研究

研究了蒎烷的氧化反应，实现了用空气代替纯氧气进行氧化以制备蒎烷氢过氧化物（PHP）的设想。蒎烷的空气氧化反应需要用催化剂；反应时间约在25h左右，比用纯氧氧化延长了3-5h；反应温度一般控制在110℃以内，与纯氧氧化温度类似。在空气氧化蒎烷得到的产物中，PHP含量一般可达45%-50%，与用纯氧氧化的结果相当。氧化产物进行常压催化加氢所得还原产物粗蒎醇用GC分析的结果表明，其蒎醇含量（超过38%）及主要产物组成与用纯氧氧化所得产物基本一致。在回收蒎烷中含较多反式蒎烷。实验结果表明，空气氧化工艺有可能代替纯氧氧化工艺应用于合成PHP的工业生产。     

4-异丙基-1,3-环己二烯酸酯衍生物的合成及其抑菌性能研究

以β-蒎烯为原料、碱性高锰酸钾为氧化剂合成了诺蒎酸,诺蒎酸酸性脱水并重排开环得到4-异丙基-1,3-环己二烯酸(二氢枯茗酸).二氢枯茗酸与氯化亚砜反应生成酰氯,再与各种醇反应生成了14个酯衍生物,通过IR、1H NMR、MS对产物进行了结构鉴定.通过抑菌环法测试探讨了化合物的抑菌活性,结果表明,256 mg/L时,除了...     

蒎烯分离技术的研究

用真空间歇精馏装置分离松节油中的α－蒎烯和β－蒎烯。在设计的日处理量为１ｔ和１．５ｔ松节油的两套网孔波纹填料塔中进行了生产性试验，在试验工艺条件下获得纯度为９９．２６％的α－蒎烯和纯度为９７．５％的β－蒎烯产品。     

-蒎烯合成诺蒎酸的反应条件研究

研究以松节油中的β-蒎烯为原料,通过KMnO4氧化合成诺蒎酸,并对氧化反应步骤中各因素对反应的影响进行了探讨。制备诺蒎酸的最佳条件为:β-蒎烯、KMnO4、NaOH的物质的量之比1∶2.5∶1,水为溶剂,温度25~30℃,反应时间4~5 h,得率达到35%。     

蒎酸基双硫脲类化合物的合成及生物活性研究

以α-蒎烯为原料,经过氧化和溴仿反应制备蒎酸,将其转化为双酰氯再与硫氰化钾反应得到蒎酸基双异硫氰酸酯。通过蒎酸基双异硫氰酸酯与苯胺类化合物的N-酰化反应,合成得到12个新型蒎酸基双硫脲类化合物。通过IR、1H NMR、13C NMR、MS和元素分析表征了目标化合物的结构。初步生物活性测试表明,目标化合物有一定的除草、杀菌和植物生长调节活性,其中在100 mg/L质量浓度下,化合物E1蒎酸基双苯基酰基硫脲对油菜胚根生长的抑制率为66.6%(达到B级活性水平)。     

二氢枯茗酰基硫脲的合成及抑菌活性研究

以β-蒎烯为原料、碱性高锰酸钾为氧化剂合成了诺蒎酸,诺蒎酸酸性脱水并异构开环得到二氢枯茗酸。二氢枯茗酸经过酰氯化、酯化,再与相应的胺反应得到了6种酰基硫脲化合物,通过IR,1H NMR,MS和元素分析对产物进行了结构鉴定,并通过抑菌环法对化合物的抑菌活性进行了测试。测试结果表明,化合物二氢枯茗邻甲苯酰基硫脲(Ⅵc),二氧枯茗间甲苯酰基硫脲(Ⅵd)对大肠杆菌的抑菌圈直径分别是11.33、11.00 mm,高于市售试剂新洁尔灭。     

Biochemical responses associated with induced resistance to Colletotrichum acutatum in Pinus radiata seedlings treated with methyl jasmonate and Trichoderma spp.

The effect of Trichoderma (T. atrobrunneumFCC320 and T. atrovirideLU633) and/or methyl jasmonate (MJ) on resistance to terminal crook (Colletotrichum acutatum) and on seedling biochemistry was investigated in radiata pine (Pinus radiata) seedlings. Seedlings were germinated and grown in Trichoderma‐amended or non‐amended media for 3 months and then sprayed with 2.25 mM MJ 1 week before inoculation with C. acutatum. The incidence and severity of terminal crook in the seedlings treated with MJ and Trichoderma+MJ were lower than in Trichoderma‐treated and Trichoderma‐untreated seedlings. The MJ‐induced resistance response was concomitant with an increase in the concentrations of the monoterpenes α‐pinene, β‐pinene, β‐phellandrene, camphene and myrcene in needles, and also α‐pinene, β‐pinene and camphene in stems. The concentrations of α‐pinene, β‐pinene and camphene were elevated from at least 1 week until 4 weeks after MJ application, compared with those in non‐MJ counterparts. Trichoderma alone did not affect monoterpenes, but the concentrations of α‐pinene, β‐pinene and camphene were greater in needles of Trichoderma+MJ than in MJ‐treated seedlings after 28 days. Total phenolic concentration in needles and peroxidase activity in stems were twofold greater in MJ‐treated seedlings than in non‐MJ seedlings over the same period. None of the treatments affected the activity of peroxidase in needles. It is proposed that the accumulation of monoterpene and phenolics and the induction of peroxidases contribute, in part, to MJ‐induced resistance to terminal crook in radiata pine seedlings.     

我国松节油的直接异构化

我国松节油含蒎烯90％以上,可用以直接异构化制备莰烯,现已用于工业生产。实践证明,工艺过程简便,莰烯得率达到83％以上,设备投资和生产费用低廉,动力消耗比用蒎烯异构时少,生产安全。     

高阿丁枫鲜叶精油化学成分

从云南乡土树种高阿丁枫鲜叶中提取精油，经ＧＣ／ＭＳ／ＤＳ定性、定量分析，鉴定了其中４０个化学成分，为精油总量的９３．４１％，主要成分为蒎烯和水芹烯。经评香鉴定，该精油有一定利用价值。     

A method for trapping hylobius abietis (L.) with a standardized bait and its potential for forecasting seedling damage

A method for trapping walking Hylobius abietis (L.) (Coleoptera: Curculionidae) was developed and evaluated. Synergism between α‐pinene and ethanol in attracting H. abietis was confirmed. The effects of varying release rates of these substances and of adding other host terpenes were studied. A simple bait was developed containing α‐pinene and ethanol released from separate vials. The correlation between trap catch and seedling damage was estimated during May, June, and August on 1‐, 2‐, and 3‐year‐old clear‐cuttings. In May and June, population levels were relatively high on all clear‐cuttings and no significant correlations were found. The August experiment showed a strong positive correlation between catch and damage. The percentage damaged seedlings per captured weevil was considerably higher in August than in May or June. Possibilities for developing a system for forecasting seedling damage using this trapping method are discussed.     

Essential oil composition and antioxidant activity of aerial parts of Grindelia robusta from Central Italy

The chemical composition of the essential oil obtained from Grindelia robusta aerial parts from central Italy was analyzed by GC and GC/MS and 45 components were identified. Borneol (15.2%), alpha pinene (10.3%), trans-pinocarveol (7.0%), bornyl acetate (4.5%), limonene (4.3%) were the main components. The antioxidant activity of the essential oil was evaluated using the DPPH and 5-lipoxygenase tests.     

蒎烯催化加氢催化剂研究进展

对贵金属和非贵金属催化作用下蒎烯的氢化反应进行了归纳总结.并主要介绍贵金属和非贵金属催化剂在均相或非均相的状态下,蒎烷总得率及顺式蒎烷选择性的差别.     

Terpene response of Picea abies and Abies alba to infection with Heterobasidion s.l.

The monoterpene composition of Picea abies and Abies alba resin was analysed in relation to growth by Heterobasidion spp. Fifteen‐year‐old P. abies and A. alba trees were inoculated on branches with three species of Heterobasidion annosum s.l. After 4 months of incubation, each host was colonized to a significantly greater degree by the pathogen specific to that host (H. parviporum on P. abies, H. abietinum on A. alba) than by the other fungi. Analysis of the enantiomeric monoterpene profiles in the spruce and fir showed that the response in terms of the relative proportions of the monoterpene compounds in the resin differed between tree species. Following challenge with Heterobasidion spp., A. alba trees did not show changes in monoterpene composition in addition to those in the wounding response (increase in (−)‐α‐pinene and (−)‐camphene, and decrease in β‐phellandrene). In P.abies, (−)‐α‐pinene, (+)‐α‐pinene and δ‐3‐carene increased following Heterobasidion attack but not after wounding alone.     

Antifungal properties of terpenoids in Picea abies against Heterobasidion parviporum

The antifungal properties of 14 major oleoresin‐constitutive terpenoids of Norway spruce (Picea abies) against Heterobasidion parviporum were evaluated in vitro at three gradient concentrations, 0.1, 0.2 and 0.4 μmol/cm², on potato dextrose agar medium. Eight monoterpene hydrocarbons (+)‐ and (?)‐α‐pinene, (?)‐β‐pinene, (+)‐3‐carene, myrcene, (+)‐ and (?)‐limonene, terpinolene; four oxygenated monoterpenes α‐terpineol, terpinen‐4‐ol, 1,8‐cineole, bornyl acetate; and two resin acids abietic acid and dehydroabietic acid were selected. Abietic and dehydroabietic acids showed the highest antifungal activities at all concentrations. Among oxygenated monoterpenes, bornyl acetate and α‐terpineol showed antifungal activity at the highest concentration. Among monoterpene hydrocarbons, (+)‐α‐pinene showed similar activity to terpinen‐4‐ol and 1,8‐cineole at the highest concentration; however, it was lower than α‐terpineol and bornyl acetate. Other monoterpene hydrocarbons inhibited mycelial growth by <10%. Re‐extraction of medium surfaces after the test period revealed that most α‐terpineol and terpinen‐4‐ol remained unchanged on the surface but monoterpene hydrocarbons completely disappeared. However, notable fungal transformed products were observed on surfaces applied with 1,8‐cineole and bornyl acetate. Thus, mycelial growth inhibition of monoterpenoids might be caused by complex functions such as biodegradation and/or detoxification by interaction between mycelium and compound. These results provide a basis for future studies considering the role of chemodiversity in the comprehensive chemical defence of P. abies.     

松褐天牛引诱剂Mat-1号的研究

以单萜烯类化合物为主要成份配制的松褐天牛ＭｏｎｏｃｈａｍｕｓａｌｔｅｒｎａｔｕｓＨｏｐｅ引诱剂Ｍａｔ—１号，主要对产卵期的松褐天牛起引诱作用。每个诱捕器在成虫出现期的诱捕量最高可达７４．３头，初诱日在５月２０日前后，终诱日在９月上旬。在离林缘３０ｍ、５０ｍ、１００ｍ、１５０ｍ、２００ｍ距离引诱到的松褐天牛百分比分别为５０％、２０．０％～２２．７％、１２．５％～１３．７％、９．１％～１０％、４．５％～７．５％，引诱的最远距离为２００ｍ