本发明提供一种从楝树（Azadirachta indica Juss）籽萃取和纯化杀虫物质的新方法，含此类萃取物的组合物和作为杀虫剂的使用方法。 The present invention provides a method from the neem tree (Azadirachta indica Juss) seed extract, and the new method for purifying insecticidal materials, compositions containing such extracts and methods of use as insecticides.

鉴于希望化合物具有较高的杀虫活性、较好的选择性、对环境损害低、生产成本低和对许多公知杀虫剂具有抗药性的昆虫是有效的这样一些因素的考虑，所以仍在继续寻找具有综合性能（如杀虫活性优异、对动植物的毒性低）好的组合物。 Given hope compounds having high insecticidal activity, better selectivity, low environmental damage, low production cost and many well known insecticide resistance in insects is effective so a number of elements, it continues Looking for a good composition has overall performance (such as excellent insecticidal activity and low toxicity to plants and animals).

由于楝树以其防治或杀虫性著称，所以它的各个部分长期以来一直在印度使用。 Due to its control or neem insecticidal known, so it has long been used in the various parts of India. 这种亚热带树产于印度、巴基斯坦、斯里兰卡及部分东南亚和非洲的干燥地区。 This subtropical tree produced in the dry regions of India, Pakistan, Sri Lanka and parts of Southeast Asia and Africa.

虽然楝树的各个部分都似乎具有天然的抗病虫害性能，但是其种籽的抗病虫害性最高。 While various parts of the neem tree seems to have a natural resistance to pests performance, but its highest pest-resistant seeds. 楝树籽的制剂和萃取物对柿毛虫、日本甲虫、蚜虫、烟草芽虫和棉子象鼻虫等多种植物的害虫业已呈现出抗虫效果，例如参见Chem and Engineering News，May 27，1985，PP.46-51和USDep，Agric.Rev.Man.，ARM-NE-4，认为楝树籽取物是一种广谱杀虫剂。 Preparations and extracts of neem seed caterpillar pests persimmon, Japanese beetle, aphids, tobacco budworm and cotton seed weevils and other insect-resistant plants already showing results, see for example Chem and Engineering News, May 27,1985 , PP.46-51 and USDep, Agric.Rev.Man., ARM-NE-4, considered neem seed extract is a broad-spectrum insecticide.

印苦楝子素和楝子树籽的其他杀虫活性成分可用水、甲醇、乙醇等级性溶剂从研磨的楝树籽中萃取出来。 Other insecticidal active ingredient azadirachtin prime and sub-tree seeds of neem with water, methanol, ethanol grade solvent extracted from ground neem seeds. 按干重基计算，此种萃取物含印苦楝子素的量一般低于5%。 By dry weight based calculation, the amount of such extracts containing azadirachtin factors generally less than 5%. 由于活性成分的分解，这种萃取物作为杀虫剂的效力就迅速降低了。 Due to the decomposition of the active ingredient, such as the effectiveness of insecticides extracts were quickly lowered. 这样，此类楝树籽萃取物作为一种有益的植物保护物质的利用就受到了严重限制。 Thus, this type of neem seed extract as a beneficial use of plant protection substances is severely restricted.

正如U.S4，556，562中所述，把粗萃取物配制为一般含0.3%左右的印苦楝子素的稀的醇溶液，且把此种萃取物的pH调至3.5-6左右，可以获得较长时期的贮存稳定性。 As U.S4,556,562 described, the crude extract was formulated as a dilute alcohol solution typically contains about 0.3% of azadirachtin pigment, and the pH was adjusted to about 3.5-6 such extract can obtain a longer period of storage stability. 此外，U.S4，946，681中也记载了用分子筛除水来稳定楝树籽的醇萃取物的办法。 In addition, U.S4,946,681 also recorded using a molecular sieve to remove water to stabilize alcohol neem seed extract solution.

还有一些获得高纯度（一般含印苦楝子素10-100%的）萃取物的公知技术。 There are a number of high purity (typically containing azadirachtin prime 10-100%) extract of known techniques. 这些技术的共同特点是，要用诸如醇类极性溶剂来获得粗萃取物，而从此萃取物中分离出印苦楝子素要用液-液萃取、相分离、溶剂反萃、有时还需用硅胶进行色谱分离这样一连串的操作步骤。 Common feature of these techniques is to use polar solvents such as alcohols to obtain a crude extract, and isolated from this extract azadirachtin hormone use liquid - liquid extraction, phase separation, solvent stripping, and sometimes need to use silica gel chromatography such a series of steps. 一般而言，用己烷等非极性溶剂对干粗萃取物或对溶于50-100%甲醇水溶液中的粗萃取物进行萃取便能除去大部分诸如甘油三酯一类的疏水杂质（Journal of Liquid Chromatography，10（6），1151（1087））。 Generally the non-polar solvent, such as hexane with dry crude extracts or dissolved in 50-100% aqueous methanol crude extract was able to remove most of the extraction, such as triglycerides, a class of hydrophobic materials (Journal of Liquid Chromatography, 10 (6), 1151 (1087)). 接着将此萃取物分配于水和如乙酸乙酯等同水不混溶的有机溶剂间，对有机相进行反萃便可获得含印苦楝子素一般为15-25%以下的半纯的萃取物，其贮存稳定性是有限的。 Subsequently this extract was partitioned between water and ethyl acetate as equivalents between a water-immiscible organic solvent, back extraction of the organic phase can be obtained is generally 15 to 25% or less semi-pure extract containing azadirachtin prime , its storage stability is limited. 为获得高纯度的印苦楝子素组合物，一般还需进行硅胶色谱，、florasil等分离。 In order to obtain high purity azadirachtin prime compositions generally need to silica gel chromatography, etc ,, florasil separation.

由于需要处理大量的（相对于回收的印苦楝子素的量）可燃性溶剂，所以当此种公知技术用于大规模生产时既不适用，成本又高。 The need to handle a large number of (relative to the recovery of azadirachtin prime amount) flammable solvents, so when such a well-known technique is neither suitable for mass production, the cost is too high. 由于甲醇一类极性有机溶剂要萃取许多伴随的杂质，为防止此萃取物中的印苦楝子素的迅速分解随后即需对这些杂质进行分离，基于此，所以问题更加严重。 Due to a class of polar organic solvents methanol To extract many incidental impurities, in order to prevent rapid decomposition of this extract of Azadirachta prime then that these impurities need to be separated, based on this, so the problem is more serious.

如用水代替醇进行萃取，那么对许多疏水杂质的可萃取性则会大大降低，当然燃烧性的问题也消除了。 Such as water instead of alcohol extracted, then for many hydrophobic impurities will greatly reduce the extractability, of course flammability problems are eliminated. 但是，尽管知道水能从研磨的楝树籽中萃取印苦楝子素，但并未公开利用这一事实的方法。 However, despite knowing that the water from the ground seeds of the neem extract azadirachtin factors, but did not disclose the fact that the use of this method. 其原因是，如采用惯常的过滤方法，从萃取的楝树饼中分离出干净的萃取水液十分缓慢。 The reason is that the use of usual filtration method such as, from the extracted neem cake isolated clean aqueous extract is very slow. 此外，也进行了种种尝试来用极性有机溶剂（如乙酸乙酯）从水滤液中萃取出印苦楝子素，但是由于形成了稳定的难于破坏的乳液，所以这些尝试均告失败。 Also, try to make all sorts of polar organic solvents (such as ethyl acetate) to extract the azadirachtin prime filtrate from the water, but is difficult due to the formation of a stable emulsion damage, so these attempts were unsuccessful.

因此，仍需一种能制备其中印苦楝子素的量超过15%的无溶剂组合物的经济、实用、能大规模生产的方法。 Therefore, still need a way to mass production can be prepared in which the amount of azadirachtin prime no more than 15% of solvent composition of economic, practical. 这样的组合物将具有足够的稳定性以使之能用于各杀虫用途，如有需要还可用简单的化学方法使之进一步稳定。 Such a composition will have sufficient stability to enable it to be used for each pesticidal uses, if needed, by simple chemical methods make further stabilized.

业已发现，水或醇的楝树萃取物可吸附于大分子聚合物吸附剂上，此后再用溶剂解吸，所以本发明提供了一种可获得其中印苦楝子素的浓度在15%以上的无溶剂组合物的实用、可大规模生产的、经济的方法。 It has been found in water or alcohol extract of neem macromolecular polymers can be adsorbed onto the adsorbent, then followed by a solvent desorption, the present invention provides a method wherein the concentration of available prime azadirachtin in no more than 15% Practical solvent composition can be mass-produced, economical method.

把经研磨的楝树籽或脱油楝树饼同水一起搅拌，离心分离除去液相，便可从含印苦楝子素的楝树籽中得到干净的水萃取物。 The milled neem seeds or deoiled neem cake is stirred together with water, centrifuged to remove liquid, you can get clean water extracts from neem seeds containing azadirachtin in prime. 把经澄清的水楝树籽萃取物同大孔聚合物吸附剂接触即能从此澄清的水萃取物中得到富印苦楝子素馏分。 To get rich in azadirachtin prime distillate water neem seed extract was clarified with the macroporous polymeric adsorbent that is able to extract from this clear water. 本文所说的大孔聚合物吸附剂包括：如按Meitzner等人在US4，256，840中披露的方法，在沉淀剂存在下制备的大孔或大网络树脂共聚物，和如其中的大孔穴是用其他方法（如US3，122，514中的）得到的共聚物。 Referred to herein macroporous polymeric adsorbent comprising: a macroporous e.g. by Meitzner et al. In US4,256,840 disclose a method of, in the presence of precipitating agent prepared or macroreticular resin copolymer, and as one of the large cavities with other methods (e.g. US3,122,514) to afford the copolymer. 二乙烯苯聚合物、二乙烯苯/苯乙烯共聚物、丙烯酸（酯）聚合物、苯酚/甲醛共聚物等则是大孔聚合物吸附剂的例子。 Divinylbenzene polymer, divinyl benzene / styrene copolymer, acrylic acid (ester) polymer, phenol / formaldehyde copolymers are examples of macroporous polymeric adsorbents. 然后用甲醇等醇、乙酸乙酯等酯、甲异丁酮等酮、其他极性有机溶剂（如N，N-二甲基甲酰胺（DMF）和二甲基亚砜（DMSO））、甲苯等芳烃、水和其混合物等溶剂把含印苦楝子素的萃取物从树脂上解吸下来，按此操作步骤得到的萃取物所含的印苦楝子素超过15%。 Then alcohol such as methanol, esters such as ethyl acetate, methyl isobutyl ketone and other ketone, other polar organic solvents (e.g. N, N- dimethylformamide (DMF) and dimethyl sulfoxide (DMSO)), in toluene and other aromatic solvents, water and mixtures thereof, such as the extract containing azadirachtin prime desorption from the resin, extracts press procedure was contained Azadirachta prime more than 15%.

优选的解吸溶剂为醇类、酯类或酮类和其混合物。 Preferred desorption solvents are alcohols, esters or ketones and mixtures thereof. 更优选的溶剂为乙酸乙酯。 More preferred solvent is ethyl acetate.

如用柱子进行操作，使约20-25柱体积的水以每小时6个相柱体积的速度流过柱子以除去解吸的溶剂即可使柱再生。 As with the column is operated so that about 20 to 25 column volumes of water per hour with 6 column volumes of flow rate through the column to desorb the solvent was removed so that the column can be regenerated. 如用乙酸乙酯作解吸溶剂，此再生步骤使洗涤水中乙酸乙酯的水低于100ppm（到能足以开始下一个新的循环）。 Such as using ethyl acetate as the desorption solvent, this regeneration step of the washing water is lower than the water with ethyl acetate 100ppm (next to be sufficient to start a new cycle).

具体讲，把经从粉碎的楝树籽进行机械榨油所得的楝树籽饼研磨后按饼/水＝1/6（重量计）的比例同水一起搅拌，利用离心分离从重固相（湿饼）分去轻液相。 Specifically, the press cake / water = 1/6 (weight) ratio was stirred together with water from the neem seeds were crushed neem seed oil extraction cake obtained after mechanical polishing, the heavy solid phase by centrifugation (wet cake) points to the light phase. 湿饼可再按湿饼/水＝约1/3（重量计）的比例用更多的水使此湿饼再浆化，按前述方式分离轻液相。 The wet cake can then wet cake / water = 1/3 (weight) ratio with more water so that this wet cake was repulped, light liquid phase separated as previously described manner. 使合并后的一般每升含印苦楝子素低于0.6g的干净水萃取物以每小时约10个柱（床）体积的速度通大孔聚合物吸附剂柱，最后须让树脂饱和（印苦楝子素），所说吸附剂为：聚二乙烯苯合成的树脂，如Amberlite So that the consolidated general azadirachtin per liter of clean water concentrations less than 0.6g of extract per hour to about 10 column (bed) volume velocity through macroporous polymeric adsorbent column, the last to be let resin saturation (India Azadirachtin), said adsorbent is: Poly divinylbenzene synthetic resins such as Amberlite

XAD-16树脂，A mberlite XDA-4树脂，Amberchrom XAD-16 resin, A mberlite XDA-4 resin, Amberchrom

CG-161树脂，Amberchrom CG-162树脂;二乙烯苯/苯乙烯共聚物合成的树脂，如Amberlite XAD-2树脂、Duloite CG-161 resin, Amberchrom CG-162 resin; divinylbenzene / styrene copolymer synthetic resins such as Amberlite XAD-2 resin, Duloite

S-861树脂;丙烯酸（酯）聚合物合成的树脂，如Amberlite XAD-7树脂，Amberchrom CG-71树脂;苯酚/甲醛共聚物合成的树脂，如Duolite XAD-761树脂等。 S-861 resin; an acrylic (ester) polymer synthetic resins, such as Amberlite XAD-7 resin, Amberchrom CG-71 resin; phenol / formaldehyde copolymer synthetic resin, such as Duolite XAD-761 resin. 1升树脂Amberlite XAD-16能约吸附20-40g印苦楝子素。 1 liter resin Amberlite XAD-16 adsorption capacity of about 20-40g azadirachtin factors. 饱和后，以每小时约3个柱体积的速度让约3个柱体积的如乙酸乙酯的溶剂通过树脂。 Saturated to about 3 column volumes per hour, the speed so that approximately three column volumes of a solvent such as ethyl acetate through the resin. 必要时，干燥溶剂相，减压除去溶剂，得到其中印苦楝子素超过15%的富印苦楝子素萃取物。 If necessary, dry solvent phase, the solvent removed under reduced pressure, in which the rich get prime azadirachtin azadirachtin extract more than 15% of prime.

需要的话，可用过氧化氢碱溶液、过氧烷基醚（如过氧二正丁基醚）、酸的过氧化物（过苯甲酸，过碳酸钠）等温和氧化剂作进一步处理即可使富印苦楝子素萃取物的稳定性进一步提高。 Desired, an alkaline solution of hydrogen peroxide can be used, peroxy alkyl ethers (e.g. peroxy di-n-butyl ether), acid peroxide (perbenzoic acid, sodium percarbonate), and other mild oxidizing agent for further treatment so that the rich Stability azadirachtin prime extract further improved. 用于此反应的优选溶剂有如乙酸乙酯或乙酸丁酯等极性有机溶剂。 Preferred solvents for this reaction are ethyl acetate or butyl acetate and like polar organic solvents. 优选的氧化剂为过氧化氢。 The preferred oxidizing agent is hydrogen peroxide. 同过氧化氢一道使用的优选碱为饱和碳酸氢钠溶液。 Used in conjunction with hydrogen peroxide is preferably the base is saturated sodium bicarbonate solution.

在本发明的另一实施方案中，用水把按本领域内公知方法所得的楝树籽的粗甲醇萃取物稀释到水/甲醇的最终比例为55/45至95/5左右（体积计），优选65/35左右。 In another embodiment of the present invention, the crude methanol extract was washed with water according to methods known in the art resulting neem seed diluted to a final ratio of water / methanol is about 55/45 to 95/5 (by volume), preferably from about 65/35. 然后使清洁的液相通过聚合物树脂（如Amberlite XAD-16树脂等聚二乙烯苯合成的树脂）柱，再按上述方法进行解吸，需要的话，可用上述的温和氧化剂作进一步处理以使所得的富印苦楝子素萃取物的稳定性进一步提高。 Then, the cleaning liquid through the polymer resin (such as Amberlite XAD-16 resin, poly-divinylbenzene synthetic resin) column, then the method described above desorption, if desired, the above-described soft oxidant available for further processing such that the resulting Stability prime azadirachtin rich extract further improved.

所得萃取物含印苦楝子素约为1-80%，一般约为15-45%。 The resulting extract containing azadirachtin prime about 1-80%, typically about 15-45%.

用本发明方法所得的萃取物也可方便地用于制备制剂和组合物。 The combined extracts were obtained by the method of the present invention may also be conveniently used for the preparation of formulations and compositions. 在美国化学协会出版物“Pesticidal Formulation Research”（1969），Advances in Chemistry Series，86和“Pesticide Formulations”（1973）（Wade Van Valkenburg编辑）上可以找到制备组合物和制剂的例子。 In the American Chemical Society publication "Pesticidal Formulation Research" (1969), Advances in Chemistry Series, 86 and "Pesticide Formulations" (1973) (Wade Van Valkenburg editor) can find examples on the preparation of the compositions and preparations. 对于这些组合物和制剂而言，把活性物质和农学上可接受的（即适宜于植物的和/或对杀虫剂是惰性的）本领域内众所公知的适用于惯常组合物或制剂的稀释剂或固形填料进行混合。 For these compositions and formulations, the active substance and agronomically acceptable (i.e., suitable for the plant and / or pesticidally inert) As is well known in the art suitable for the composition or formulation of the usual solid diluents or fillers were mixed. 如需要的话，还可加入表面活性剂、稳定剂、抗泡剂和抗漂浮剂等辅助剂。 If desired, a surfactant may be added, stabilizers, anti-foam agents and anti-floating agents adjuvant.

本发明的组合物和制剂剂形的例子是本领域普通技术人员所知道的，它们有液剂和液分散剂、油剂和油分散剂、糊剂、撒粉剂、可湿性粉剂、乳油、悬浮剂、粒剂、铒剂、逆乳剂、气雾剂和熏蒸蜡烛剂。 Examples of compositions and formulations of the present invention dosage forms are those of ordinary skill know, they have a liquid, and a liquid dispersing agent, oil and oil dispersions, pastes, dusting powders, wettable powders, emulsifiable concentrates, suspensions , granules, erbium agent, inverse emulsions, aerosols and fumigating candles agent.

本发明的组合物和制剂是按本领域的普通技术人员所知道的方法制备的。 Compositions and formulations according to the present invention is of ordinary skill in the art known prepared. 例如，把活性化合物同可分散的惯常液形填料载体和/或可分散的固形载体进行混合。 For example, the active compound may be dispersed with the usual liquid-packings carriers and / or dispersible solid carriers are mixed. 如有必要，可用载体助剂，如惯常的表面活性剂，其中包括乳化剂和/或分散剂，如用水作稀释剂，可用有机溶剂作为助溶剂。 If desired, carrier vehicle assistants such as conventional surface-active agents, including emulsifying agents and / or dispersing agents, such as water as a diluent, organic solvents can be used as auxiliary solvents.

对于粉剂、粒剂和胶乳剂剂形而言可把羧甲基纤维素及天然和合成的聚合物，如阿拉伯树胶，聚乙烯醇、聚乙烯纤维素和聚乙酸乙烯酯用于制剂以改进杀虫剂的粘附性。 For powders, granules and latex emulsion dosage form may be in terms of the carboxymethylcellulose and natural and synthetic polymers, such as gum arabic, polyvinyl alcohol, polyvinyl cellulose and polyvinyl acetate used in the formulation to improve the kill pesticides adhesion. 硬脂酸钙或硬脂酸镁等润滑剂可加到可湿润的粉中或将予造粒的混合物中。 A lubricant such as magnesium stearate or calcium stearate, can be added to a wettable powder or a mixture to be granulated in.

需要的话，本发明的萃取物可以单独使用和/或同固形和/或液形载体和/或同其他已知的可相容的活性成分一道使用，特别是同下述植物保护剂一道使用：如其他杀虫剂，杀节枝动物剂（arthropodicides）、杀线虫剂、杀真菌剂、杀细菌剂、杀鼠剂、除草剂、肥料、生长调节剂、增效剂等，或将其用于配制特殊用途特殊剂量的便于使用的制剂剂形，如液剂、乳剂、悬浮剂、粉剂、糊剂和粒剂。 Desired, the extract of the invention may be used alone and / or with the solid and / or liquid form carrier and / or used in conjunction with other known compatible active ingredients, in particular the use of a plant protection agents with the following: such as other insecticides, animal section sticks agent (arthropodicides), nematicides, fungicides, bactericides, rodenticides, herbicides, fertilizers, growth regulators, synergists, etc., or use it for preparation of special purpose special dosage formulation easy to use dosage form, such as solutions, emulsions, suspensions, powders, pastes and granules.

就制造商业上销售的制剂而言，这些制剂一般将为含载体组合物混合物，其中经稳定的萃取物的存在量基本介于0.1-99%（混合物重量计）间，优选1-75%左右。 Sold commercially to manufacture formulations, these preparations generally will contain a carrier composition mixtures in which the stabilized by the presence of an amount of extractables of between 0.1 to 99% of basic (mixture weight) between, preferably about 1-75% .

可能由于分散、防潮和防阳光照射等原因，某些制剂能对所配剂形中的印苦楝子素起到稳定的效果。 May be due to dispersion, moisture and sunlight proof and other reasons, certain formulations can be shaped for the formulation of azadirachtin factors play a stabilizing effect.

萃取物制剂可用公知方法进行喷雾施用，如惯常的高加仑量液压喷雾、低加仑量的喷雾、超低量喷雾、鼓风喷雾、飞机喷雾和撒粉。 The extract formulations can be spray application known methods such as conventional high-gallonage hydraulic sprays, low gallonage sprays, ultra low volume sprays, blast spray, aerial sprays and dusts.

而且，本发明提供的选择性杀害、防治有害生物的方法包括相当防治或中毒量（即有效防治或杀虫量）的经稳定的本发明化合物单独或同上述的载体（组合物或制剂）一起同昆虫接触。 Moreover, selective killing of the present invention provides a method of controlling pests comprising relatively prevention or toxic amount (i.e., prevention or insecticidally effective amount) of the stabilized compounds of the invention alone or with the above-described carrier vehicle (composition or formulation) together contact with the insects. 这里所用术语“接触”意为仅把本发明的活性化合物、作为组合物或制剂成分的本发明的活性化合物或作为含其他杀虫剂或杀真菌剂的组合物或制剂的成分的本发明的活性化合物至少施于（a）和（b）中的一种情形：（a）害虫;（b）其相应的栖息地（即要予保护的场所，如植物生长地或将为作物生长的区域）。 As used herein, the term "contact" means only the active compounds of the invention, the active compound as a composition or formulation or composition of the present invention as a component containing other insecticides or fungicides compositions or formulations of the present invention. (b) the corresponding habitat (that is, to be protected location, such as plant growth or crop area will grow; (a) pests: at least one case the active compound is applied to (a) and (b) of the ).

当然，用于载体混合物中的具体的萃取物浓度取决于许多因素，例如所用设备类型、施用方法、要予处理的区域、要予防治的有害生物的类型和侵染的程度。 Of course, the specific concentrations of the extract for the carrier mixture depending on many factors, such as the type and degree of infestation of the device type, application method, the region to be treated, to be prevention of pests. 除上述成分外，本发明的制剂还可含一般用于此种制剂中的其他物质。 In addition to the aforementioned ingredients, the formulations of the present invention may further contain generally used in such formulations other substances.

下面的实施例是用于说明本发明的，不能认为是对本发明范围的限制。 The following examples are intended to illustrate the present invention, can not be considered as limiting the scope of the invention. 另有说明除外，所有份数和百分数均是按重量计的。 Unless otherwise indicated, all parts and percentages are by weight.

实施例1：萃取物1（40%印苦楝子素）把1282kg楝树籽部分去皮并用一般的机械方法（如机械榨油法）进行脱油。 Example 1: 1 extract (40% azadirachtin hormone) to 1282kg part of neem seed oil, peeled and de-general mechanical methods (such as mechanical crushing method). 用3150kg水对586kg脱油的楝树籽饼进行研磨，用离心沉淀分去湿饼。 586kg off the water with 3150kg of neem seed oil cake is ground with a centrifugal decanter cake dehumidification. 用2100kg水对湿饼进行再浆化，重复分离步骤，过滤使合并的液相3618kg再予澄清并以每小时600kg的速度流经含60升AmberliteXAD-16树脂的不锈钢柱。 With 2100kg water wet cake repulped, repeating the separating step, the combined filtering the re-clarified liquid 3618kg and 600kg of 60 liters per hour flow through containing resin AmberliteXAD-16 stainless steel column. 随后用180升乙酸乙酯对柱中的树脂进行淋洗，把乙酸乙酯相减压浓缩到25kg。 Followed by 180 liters of ethyl acetate resin column leaching, the ethyl acetate phase was concentrated under reduced pressure to 25kg. 55℃下，把乙酸乙酯浓缩物同10kg饱和碳酸氢钠水溶液和300ml30%过氧化氢一起搅拌20分钟。 At 55 ℃, the ethyl acetate concentrate was 10kg with a saturated aqueous sodium bicarbonate and 300ml30% hydrogen peroxide was stirred together for 20 minutes. 分去上部有机相，Na2SO4干燥，过滤并反萃除去乙酸乙酯得到4.25kg萃取物1（含印苦楝子素40%）。 Points to the upper organic phase, Na2SO4 dried, filtered and stripped to remove the ethyl acetate extract to obtain a 4.25kg (including azadirachtin prime 40%).

实施例2：萃取物2（印苦楝子素27%）用新制的甲醇（每份200升）连续萃取脱油楝树饼（200kg）三次制备144kg含印苦楝子素的粗甲醇萃取物，合并甲醇萃取物并进行部分反萃，向所得浓缩物中加入280kg水，除沉淀，让所得甲醇水萃取物以每分2升的速率流过Amberlit XAD-16树脂（30升）柱，然后用90升甲醇淋洗树脂，解吸甲醇，把所得残余物放于乙酸乙酯中，按实施例1的方法，用含过氧化氢的饱和碳酸氢钠水溶液进行处理得到含印苦楝子素27%的萃取物2（1.66kg）。 Example 2: Extract 2 (Azadirachta prime 27%) with fresh methanol (per 200 liters) continuously extracting crude methanol extract deoiled neem cake (200kg) of three preparation 144kg containing azadirachtin prime merger Methanol extracts and partially stripping, the resulting concentrate was added to 280kg of water, in addition to precipitation, the resulting aqueous methanol extract to a rate of 2 liters per minute flow through Amberlit XAD-16 resin (30 l) column, followed by 90 L of methanol was rinsed resin, desorption of methanol, and the resulting residue was placed in ethyl acetate, according to the method of Example 1, treated with saturated aqueous sodium bicarbonate-containing hydrogen peroxide-containing azadirachtin of 27% of the extracted pigment was 2 (1.66kg).

实施例3：生物活性实验实施例制得的含印苦楝子素40%的萃取物的生物活性。 Example 3: containing azadirachtin biotin activity obtained in Experimental Example 40% of extract of biological activity.

此实验中，用实验溶液对2-3周龄的利马豆植物（phaseolus limensis var.woods prolific）进行喷药，干后，离脱去经处理的叶并用Mexican豆科甲虫（MBB：Epilachna Varivestis）的第二龄期幼虫和Southern粘虫（SAW：Spodophtera eridania）进行感染（剂量为20，10，5和2，5ppm，每剂5个昆虫），在3天和6天时测定百分死亡率。 This experiment, a test solution of 2-3-week-old plants lima beans (phaseolus limensis var.woods prolific) were spraying, dry, leaves stripped from the treated and legumes with Mexican beetle (MBB: Epilachna Varivestis ) and second instar larvae of Southern armyworm (SAW: Spodophtera eridania) were infected (at a dose of 20,10,5 and 2,5ppm, 5 insects per dose), Percent mortality was determined at 3 days and 6 days .

所得结果列于下表百分死亡剂量ppm MBB MBB SAW SAW(3天) (6天) (3天) (6天) The results obtained are shown in the following (6 days) (3 days) (6 days) Table percentage mortality dose ppm MBB MBB SAW SAW (3 days)

20 23 67 100 10010 6 73 93 735 15 46 93 932.5 6 46 53 60当然，本说明书及其实施例是用于说明的，而不是用于限制的，可对其作各种修改和变更，但这些并不背离本发明的精神和不超出本发明申请待批的权利要求所限定的范围。 20 23 67 100 1,001,067,393,735,154,693 932.5 6465360 Of course, the present description and examples are intended to be illustrative, and not for purposes of limitation, and that various modifications can be made thereto changes, but these without departing from the spirit of the invention and claimed in the present invention without departing from the requirements of the copending application range defined.