CN107922368A - 新形式的螺螨酯,其制备方法及用途 - Google Patents
新形式的螺螨酯,其制备方法及用途 Download PDFInfo
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- CN107922368A CN107922368A CN201680047625.0A CN201680047625A CN107922368A CN 107922368 A CN107922368 A CN 107922368A CN 201680047625 A CN201680047625 A CN 201680047625A CN 107922368 A CN107922368 A CN 107922368A
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Abstract
具有式(I)之螺螨酯的新晶型、晶体制备方法、藉由各种分析方法对该晶体的分析和利用该晶体制备稳定的农用化学制剂。还描述了各种溶剂对晶型制备条件之用途。
Description
相关申请的交叉引用
本申请要求于2015年12月14日提交的第14/967,950号美国专利申请的优先权,其内容通过引用整体并入本文。
背景
技术领域
本公开内容涉及3-(2,4-二氯苯基)-2-氧代-1-氧杂螺[4.5]癸-3-烯-4-基-2,2-二甲基丁酸酯(螺螨酯(spirodiclofen))的晶型,其制备方法及其在农用化学品制剂中之用途。
现有技术
相关技术的说明
通用名为螺螨酯的3-(2,4-二氯苯基)-2-氧代-1-氧杂螺[4.5]癸-3-烯-4-基-2,2-二甲基丁酸酯是酮烯醇或特窗酸(tetronic acid)类化学品的成员。它是酮烯醇群组的具有独特中毒症状学和新颖生化作用模式的第一成员。它被用作广谱非系统性叶面杀虫剂和杀螨剂。它的杀有害生物作用模式为通过经由乙酰辅酶A羧化酶的抑制来抑制脂质合成,所述酶为脂肪酸生物合成中的关键酶。它通过干扰螨虫发育来控制有害生物,有害生物例如全爪螨属(Panonychus spp.)、皱叶刺节蜱属(Phyllocoptruta spp.)、短须螨属(Brevipalpus spp.)、刺瘿螨属(Aculus spp.)和叶螨属(Tetranychus spp.)。它控制柑橘类水果、葡萄、仁果类水果、核果类水果和树坚果作物中的螨虫和梨圆蚧(San Joe scale)。
螺螨酯的分子式为C21H24Cl2O4,其化学结构为
发明内容
可商购获得的螺螨酯(通常通过第5,262,383A号美国专利中所述方法生产,其出于所有目的通过引用方式而并入本文)以无定形状态存在,具有85℃至87℃的熔点。已发现无定形状态的螺螨酯因其在长期储存后的高聚集趋势而不适合制备成组合物或制剂。因此,需要开发表现出改进的储存稳定性的新形式的螺螨酯。
因此,本发明的实施方案提供了螺螨酯的新晶型,称为“结晶变体I”,和其制备方法,以及含有其的农用化学组合物,和在农用化学应用中使用其的方法,例如将其施用到植物、周围环境和植物部分的方法。已经发现新结晶变体I有利地具有改进的储存稳定性,在长期储存之后的聚集显著减少。
因此,本发明的实施方案还提供了用于控制不期望有害生物如螨虫有害生物的组合物,所述组合物包含螺螨酯的结晶变体I本身,作为与助剂和载体的混合物,以及作为与其他活性化合物的混合物。本发明的实施方案还提供了螺螨酯结晶变体I在控制不期望有害生物中的用途及其使用方法。
附图简述
可通过参考附图更清楚地理解本文公开的本发明实施方案的各种特征和方面,所述附图意在例证和说明而非限制本发明的范围,且其中:
图1为螺螨酯结晶变体I的实施方案之红外(IR)光谱;
图2为螺螨酯结晶变体I的实施方案之X射线粉末衍射图;
图3为螺螨酯结晶变体I的实施方案之差示扫描量热(DSC)热谱图;且
图4为无定形螺螨酯之X射线粉末衍射图。
具体实施方案之详细说明
可通过参考以下具体实施方案的详细说明更清楚地理解本发明,这些详细说明意在说明而非限制所附权利要求的范围。
已发现本发明的螺螨酯结晶变体I在其稳定性方面具有显著改进,在长期储存后未形成聚集。此外,发现与根据第5,262,383号美国专利的公开内容所制备的无定形螺螨酯相比,螺螨酯结晶变体I更易于过滤、粉碎和/或研磨。这允许制备商业制剂,如悬浮剂(SC)、油基悬浮剂(OD)、水分散粒剂(WG)和可溶粒剂(SG)。通过其高储存稳定性,螺螨酯结晶变体I赋予其制剂期望的长储存期。因此,可以制备呈结晶变体I的螺螨酯之任何制剂,其于下文中公开。
根据本发明的实施方案,提供了螺螨酯结晶变体I,其在利用Cu-Kα辐射在25℃下记录的X射线粉末衍射图中以任何组合呈现至少3个作为2θ值的如下反射:
2θ=11.322±0.2 (1)
2θ=14.858±0.2 (2)
2θ=15.382±0.2 (3)
2θ=17.184±0.2 (4)
2θ=19.617±0.2 (5)
2θ=21.739±0.2 (6)
2θ=22.784±0.2 (7)
2θ=23.840±0.2 (8)
2θ=25.725±0.2 (9)
2θ=28.195±0.2 (10)
2θ=30.974±0.2 (11)
本发明实施方案的螺螨酯结晶变体I通过具有上述反射中的至少三个(以其任何组合)的X射线粉末衍射图来表征。优选地,结晶变体I为具有上述反射中的至少四个、更优选所述反射中的至少五个、六个或七个、或八个(亦以其任何组合)的结晶变体。图2中示出螺螨酯结晶变体I的X射线粉末衍射图,其将在下文中详细说明。
根据优选实施方案,结晶变体I以任何组合呈现来自以下至少3个、4个、或5个或全部反射:
2θ=11.322±0.2 (1)
2θ=14.858±0.2 (2)
2θ=15.382±0.2 (3)
2θ=17.184±0.2 (4)
2θ=19.617±0.2 (5)
2θ=22.784±0.2 (7)
2θ=23.840±0.2 (8)
2θ=25.725±0.2 (9)
X射线衍射图如下测定:利用粉末衍射仪在25℃下,反射几何结构在3°-60°的范围内,增量为0.03°,利用Cu-Ka辐射。
在特别优选的实施方案中,螺螨酯结晶变体I呈现基本上与如图2中所示相同的X射线粉末衍射图案。
除X射线粉末衍射分析以外,螺螨酯结晶变体I还可通过IR光谱学来表征。以4cm-1的解析度和16的扫描次数测量纯化样品的IR光谱。可通过波数(cm-1,±0.2%)为约2971、2928、2854、1780、1749、1096、1061、862和819cm-1中的一个或更多个的特征官能团振动峰来鉴别螺螨酯结晶变体I,如图1中所示。
所有IR光谱都是利用以下采集参数获得:
FT-IR光谱仪 | 布鲁克滕瑟(Bruker Tensor)37 |
金刚石ATR单元 | 来自斯贝凯(Specac) |
波长范围 | 550-4000cm-1 |
解析度 | 4cm-1 |
扫描次数 | 16 |
根据本发明实施方案的螺螨酯结晶变体I可通过差示扫描量热法(DSC)进一步表征(图3)。图3中示出在约98.6℃下的吸热峰。本文所使用的术语“约98.6℃”指96℃至100℃的范围。
本领域中已知制备无定形螺螨酯的方法。无定形螺螨酯被生产并且可以商业规模使用。尤其适合用于制备无定形螺螨酯的方法描述于第5,262,383号美国专利中。
根据本发明的实施方案,螺螨酯结晶变体I可通过下面的方法获得:
将无定形状态的螺螨酯溶解,然后从溶剂中结晶。
在一个方面中,本发明的实施方案提供了用于制备螺螨酯结晶变体I的方法,所述方法包括以下步骤:
i)将无定形螺螨酯溶解在溶剂中;
ii)使溶解的化合物沉淀为具有式I的螺螨酯结晶变体I;以及
iii)分离沉淀的结晶变体I。
适合制备螺螨酯结晶变体I的溶剂包括:卤代烃(例如,氯苯、溴苯、二氯苯、氯甲苯、三氟甲苯和三氯苯)、醚类(例如,二乙醚、乙基丙基醚、正丁醚、苯甲醚、苯乙醚、环己基甲醚、二甲醚、二甲基乙二醇、二苯醚、二丙醚、二异丙醚、二正丁醚、二异丁醚、二异戊醚、乙二醇二甲醚、异丙基乙基醚、甲基叔丁醚、四氢呋喃、甲基四氢呋喃、二烷、二氯二乙醚、甲基-四氢呋喃、环氧乙烷和/或环氧丙烷的聚醚)、硝化烃(例如,乙腈、硝基甲烷、硝基乙烷、硝基丙烷、硝基苯、氯硝基苯、乙苯和邻硝基甲苯)、芳烃(异丙基甲苯、沸程从70℃至190℃的石油馏分、石油醚、轻石油、均三甲苯、苯、甲苯和二甲苯)、酯类(例如,丙二酸酯、乙酸正丁酯(acetic acidn-butyl ester,n-butyl acetate)、乙酸甲酯、乙酸乙酯、乙酸异丁酯、碳酸二甲酯、碳酸二乙酯、碳酸二丁酯和碳酸乙烯酯)和酮(例如,甲乙酮、丙酮)及其混合物。
优选的溶剂包括甲苯、二甲苯、苯、氯苯、二氯苯、乙苯、三氟甲苯、均三甲苯、硝基苯、醚、甲乙酮、丙酮和乙腈。本发明的实施方案还设想超过2或3或4种组分的溶剂混合物。
在本发明的实施方案中,优选地,溶剂为可任选地被一个或更多个可相同或不同、选自以下的取代基取代的芳烃:可任选地被一个或更多个可相同或不同的卤素进一步取代的烷基(例如低级烷基,如C1至C4烷基)、硝基和卤素;和酮。
在本发明的实施方案中,优选地,溶剂为甲苯和丙酮。
因此,根据优选实施方案,在步骤(i)中,将无定形螺螨酯溶解在包含甲苯或丙酮的溶剂中。在优选实施方案中,溶剂基本上由甲苯和/或丙酮组成。
根据步骤(i)的实施方案,通过从室温或环境温度加热至溶剂或溶剂混合物的回流温度或低于该回流温度,将无定形螺螨酯溶解在该溶剂或溶剂混合物中成为浓溶液。优选地,可在溶剂的回流温度下制备浓溶液。溶液的浓度取决于螺螨酯在相应溶剂或溶剂混合物中的溶解度。
然后将由此如步骤(i)中制备的浓均匀溶液冷却至室温或冷却至约0℃至20℃的温度,以使期望的结晶从该溶剂中结晶。螺螨酯结晶变体I也可通过以下方式结晶出来:通过借助或不借助施加真空将溶剂或溶剂混合物移除到一定体积,并且冷却至该溶剂或该溶剂混合物的回流温度以下来浓缩均匀溶液。
在另一个实施方案中,螺螨酯结晶变体I也可以通过在结晶期间将具有期望晶型的晶种加入步骤(i)中制备的溶液来实现,此举可促进或加速结晶。
基于用于制备步骤(i)中的浓溶液的螺螨酯的重量,添加至浓溶液中的晶种量螺螨酯典型地为按重量计0.001%至5%、通常为按重量计0.005%至0.5%。优选地,在低于相应溶剂或溶剂混合物的沸点的温度下将晶种添加至浓溶液中。
因此,本领域普通技术人员可实现使螺螨酯晶型I有效地从浓溶液沉淀。
通过常用的固体组分分离技术(如过滤、离心或倾析)从溶液中分离从步骤(ii)获得的经沉淀的螺螨酯结晶变体I。然后,用溶剂洗涤分离的固体沉淀一次或更多次。优选地,用于洗涤阶段的溶剂由用于制备步骤(i)中的浓溶液之溶剂或溶剂混合物的一种或多种组分组成,如前文所述。取决于晶体的溶解度,洗涤通常利用相应溶剂或溶剂混合物在室温与0℃之间进行,以尽可能地最小化或避免结晶材料在相应洗涤溶剂中的损失。
在一实施方案中,本发明还涉及包含螺螨酯结晶变体I的组合物。螺螨酯结晶变体I的量按组合物的重量计小于75%,优选按组合物的重量计小于50%,更优选按组合物的重量计小于30%,仍更优选按组合物的重量计约25%。
无定形螺螨酯作为杀昆虫剂和/或杀螨剂的用途在本领域中是已知的,且以商业规模使用。螺螨酯结晶变体I在控制例如如前文所述文献中所公开的诸如螨虫的不期望有害生物中亦具有活性。本发明的呈结晶变体I的螺螨酯可以类似于针对无定形螺螨酯所述的那些方式配制和施用。
因此,在又一个方面中,本发明的实施方案提供了包含如前文所定义的呈结晶变体I的螺螨酯的杀虫组合物。
因此,本发明的实施方案另外提供了利用螺螨酯结晶变体I制备用于控制不期望有害生物如螨虫的组合物的方法。
因此,本发明还提供了控制植物、植物部分和/或其周围环境中不期望有害生物的方法,所述方法包括向植物的叶子或果实、植物部分和/或植物的周围环境施用杀虫有效量的螺螨酯结晶变体I。
可利用适合的助剂、载剂和溶剂,以类似于已知用于无定形螺螨酯的方式将螺螨酯结晶变体I掺入常规制剂中,如悬浮剂(SC)、油基悬浮剂(OD)、可溶粒剂(SG)、可分散液剂(DC)、乳油(EC)、乳液拌种剂、悬浮液拌种剂、颗粒剂(GR)、微粒剂(MG)、悬乳剂(SE)和水分散粒剂(WG)。
在此背景下,螺螨酯结晶变体I可以按总混合物的重量计约0.1%至约75%的浓度,即呈足以达到所需剂量的量存在。例如通过在螺螨酯结晶变体I中掺入水、溶剂和载剂,如果合适的话,使用乳化剂和/或分散剂和/或其他助剂来制备制剂。
这些制剂通过混合螺螨酯结晶变体I与至少一种杀虫上可接受的助剂,例如表面活性剂、液体稀释剂、固体稀释剂、润湿剂、分散剂、增稠剂、消泡剂、防冻剂、防腐剂、抗氧化剂、固体附着剂、惰性填料和其他制剂成分来制备。
表面活性剂可为离子型或非离子型的乳化剂、分散剂或润湿剂。可使用的实例包括但不限于聚丙烯酸的盐、木质素磺酸的盐、苯磺酸或萘磺酸的盐、环氧乙烷与脂肪醇或与脂肪酸或与脂肪胺的缩聚物、经取代的苯酚(尤其是烷基酚)、磺基琥珀酸酯盐、牛磺酸衍生物(尤其是牛磺酸烷基酯)、或者聚乙氧基化酚或醇的磷酸酯。
液体稀释剂包括但不限于水,N,N-二甲基甲酰胺,二甲亚砜,N-烷基吡咯啶酮,乙二醇,聚丙二醇,碳酸丙烯酯,二元酯,石蜡,烷基苯,烷基萘,甘油,三醋精,橄榄、蓖麻、亚麻籽、芝麻、玉米、花生、棉籽、大豆、葡萄籽和椰子的油,酮类(如环己酮、2-庚酮、异佛尔酮和4-羟基-4-甲基-2-戊酮),乙酸酯(如乙酸己酯、乙酸庚酯和乙酸辛酯)和醇(如甲醇、环己醇、癸醇、苄醇和四氢糠醇、及其混合物。
固体稀释剂可为水溶性或水不溶性的。水溶性固体稀释剂包括但不限于盐类,如碱金属磷酸盐(例如,磷酸二氢钠),碱土金属磷酸盐,钠、钾、镁和锌的硫酸盐,氯化钠和氯化钾,乙酸钠,碳酸钠和苯甲酸钠;以及糖和糖衍生物,如山梨醇、乳糖、蔗糖和甘露醇。水不溶性固体稀释剂的实例包括但不限于黏土、合成和硅藻二氧化硅、硅酸钙和硅酸镁、二氧化钛、氧化铝、氧化钙和氧化锌及其混合物。
润湿剂包括但不限于磺基琥珀酸烷基酯、月桂酸酯、硫酸烷基酯、磷酸酯、炔属二醇、乙氧基氟化醇、乙氧基化硅酮、烷基酚乙氧基化物、苯磺酸酯、经烷基取代的苯磺酸酯、α-烯烃磺酸烷基酯、萘磺酸酯、经烷基取代的萘磺酸酯、萘磺酸酯和经烷基取代的萘磺酸酯与甲醛的缩合物、和醇乙氧基化物及其混合物。萘磺酸钠烷基酯对本发明组合物尤其有用。
分散剂包括但不限于木质素磺酸的钠盐、钙盐和铵盐(任选地被聚乙氧基化);马来酸酐共聚物的钠盐和铵盐;缩合苯酚磺酸的钠盐;和萘磺酸盐-甲醛缩合物。木质素磺酸盐如木质素磺酸钠对本发明组合物尤其有用。萘磺酸盐-甲醛缩合物如萘磺酸与甲醛和钠盐的聚合物对本发明组合物尤其有用。
增稠剂包括但不限于瓜尔胶、果胶、酪蛋白、角叉菜胶、黄原胶、藻酸盐、甲基纤维素、羟乙基纤维素、羟丙基纤维素和羧甲基纤维素及其混合物。合成增稠剂包括前面类别的衍生物,且还包括聚乙烯醇、聚丙烯酰胺、聚乙烯吡咯啶酮、各种聚醚、它们的共聚物以及聚丙烯酸和它们的盐及其混合物。烷基聚乙烯吡咯啶酮对本发明组合物尤其有用。
消泡剂包括正常地可以在农用化学组合物中用于此目的的所有物质。合适的消泡剂在本领域中是已知的,且为商业上可得。特别优选的消泡剂是聚二甲基硅氧烷和全氟烷基膦酸的混合物,如可从GE或康普顿(Compton)获得的硅酮消泡剂。
防腐剂包括正常地可以在这种类型的农用化学组合物中用于此目的的所有物质,并且也是本领域中熟知的。可提及的合适实例包括(来自拜耳公司(Bayer AG))以及(来自拜耳公司)。
抗氧化剂包括正常地可以在农用化学组合物中用于此目的的所有物质,如本领域中已知的。优选二丁基羟基甲苯。
固体附着剂包括有机黏合剂,包括增黏剂,如纤维素或经取代的纤维素,呈粉末、颗粒或晶格形式的天然及合成聚合物,以及无机黏合剂,如石膏、硅石或水泥。
惰性填料包括但不限于天然的地面矿物,如高岭土、氧化铝、滑石、白垩、石英、绿坡缕石、蒙脱石、和硅藻土;或合成地面矿物,如高度分散的硅酸、氧化铝、硅酸盐、以及磷酸钙和磷酸氢钙。用于颗粒的合适惰性填料包括例如,粉碎及分级的天然矿物(如方解石、大理石、浮石、海泡石、和白云石)、或者无机和有机研磨材料的合成颗粒,以及有机材料的颗粒(如锯屑、椰子壳、玉米芯、和烟草茎)。
其他制剂成分也可以用在本发明中,如染料、干燥剂等。这些成分是本领域技术人员已知的。
根据本发明实施方案的螺螨酯结晶变体I可以存在于制剂中和由这些制剂制备的其他形式中,以及作为与其他活性化合物(如引诱剂、消毒剂、杀菌剂、杀螨剂、杀线虫剂、杀真菌剂、生长调节物质、除草剂、安全剂、肥料、化学信息素和其他杀昆虫剂)或与用于改进植物性状的试剂之混合物存在。
当用作杀昆虫剂或杀螨剂时,根据本发明实施方案的螺螨酯结晶变体I可另外存在于制剂中和由这些制剂制备的其他形式中,以及作为与减少活性化合物在用于植物环境中、用在植物部分表面上或用在植物组织中后的降解的抑制剂之混合物存在。
所有植物、植物部分和其周围环境都可用根据本发明实施方案的螺螨酯结晶变体I处理。在当前背景下,植物应理解为意指所有植物和植物种群,诸如期望和不期望的野生植物或作物植物(包括天然存在的作物植物)。作物植物可以为可通过常规育种和优化方法、通过生物技术和基因工程方法、或通过这些方法的组合获得的植物,包括可以或不可以被植物育种者权利所保护的转基因植物和植物栽培品种。植物部分应理解为意指植物的所有地上和地下部分和器官,如芽、叶子、针叶、杆、茎、花、子实体、果实、种子、根、块茎以及根茎。还包括所收获的材料、以及营养性和生殖性繁殖材料,例如插条、块茎、分生组织、根茎、短匐茎、种子、单个及多个植物细胞及任何其他植物组织。
本文所用术语“约”在与数值量或范围连用时意指稍微大于或稍微小于所述数值量或范围,偏差为所述数值量或范围端值的±10%。
本文所用的术语“室温”指约20℃-26℃的温度范围。
本文所用的“周围环境”指植物生长的地方、植物的植物繁殖材料进行播种的地方或者植物的植物繁殖材料将会播种的地方。
用本发明的组合物或制剂对植物和植物部分进行的根据本发明的处理直接进行或通过常规处理方法使得组合物或制剂作用于它们的周围环境、栖息地或储存空间来进行。这些常规处理方法的实例包括浸渍、喷雾、汽化、雾化、撒播、涂刷(在繁殖材料的情况下)和施加一个或更多个涂层(尤其是在种子的情况下)。
当在种植诸如以下的有用植物作物中施用杀虫组合物来杀死有害生物如螨虫时,本发明的益处最大:玉米(maize,corn)(包括饲料玉米、爆粒玉米和甜玉米)、棉花、谷类、大麦、小麦、水稻、燕麦、马铃薯、甜菜、栽培作物(如香蕉、果树、橡胶树、树木苗圃)、树坚果作物、葡萄、柑橘类水果、仁果类水果、核果类水果、橄榄树、风景林、芦笋、灌木浆果(如蓝莓)、悬钩子、蔓越橘、亚麻、高粱、秋葵、薄荷、大黄、绿薄荷、草坪草和甘蔗。在本发明中,处理柑橘类水果、葡萄、仁果类水果、核果类水果和树坚果作物是尤其有益的。
除非另外指明,否则所有百分比都以重量%给出。
现将通过以下实施例说明本发明的实施方案,所述实施例只出于说明的目的而被提供,并不旨在限制本公开内容的范围。
实施例
实施例1:根据经修改的第5,262,383号美国专利的公开内容制备无定形螺螨酯。
1.己酯的制备:经修改的实施例1A(第125栏)
将0.1mol乙基-1-羟基环己烷羧酸酯引入200ml纯二氯甲烷中,添加0.12mol三乙胺(Et3N),并在0℃-10℃下逐滴添加0.1mol 2-(2,4-二氯苯基)乙酰氯在50ml纯二氯甲烷中的溶液。
在室温下搅拌该溶液16小时后,将它用柠檬酸水溶液和碳酸氢钠水溶液洗涤,并在硫酸钠上干燥有机相,并通过旋转蒸发进行蒸发。
2. 3-(2,4-二氯苯基)-4-羟基-5-环己烷-3-二氢呋喃-2-酮的制备:经修改的实
例1a-2(第90栏)
将90mmol氢化钠(80%)引入50ml纯甲苯中。这个过程在氩气气氛下进行。将混合物加热至回流温度。然后在回流条件下逐滴添加溶解在70ml纯甲苯中的60mmol己酯,并使混合物回流3小时。
在旋转蒸发器上蒸发溶液,并将残余物溶解在水中,并使溶液酸化。将这个过程中分离出的沉淀溶解在二氯甲烷中,并重复萃取含水母液。随后在硫酸钠上使萃取物干燥,并在旋转蒸发器上浓缩。
将产物悬浮在20ml热氯仿中,在回流条件下缓慢添加60ml正己烷,允许混合物缓慢冷却,并且借助抽吸滤出固体并干燥。
3.螺螨酯的制备:经修改的实例1b-1(第95栏)
将5mmol 3-(2,4-二氯苯基)-4-羟基-5-环己烷-3-二氢呋喃-2-酮引入20ml纯二氯甲烷中。向该混合物中添加6mmol三乙胺(Et3N),在0℃-10℃下添加6mmol 2,2-二甲基丁酰氯在5ml纯二氯甲烷中的溶液,并在室温下继续搅拌1小时。
用柠檬酸水溶液和碳酸氢钠水溶液洗涤溶液,在硫酸钠上干燥,并通过旋转蒸发进行蒸发。
方案1.螺螨酯的合成
螺螨酯结晶变体I的制备
实施例2-从甲苯中结晶
将如实施例1中制备的无定形螺螨酯样品(10g)连同甲苯(70mL)溶解在3颈圆底烧瓶中。将所得浆液加热至90℃,以得到均匀溶液。过滤均匀溶液来去除不溶性颗粒(如果有的话),并且使经过滤的溶液缓慢冷却至室温(rt)。在冷却时形成细晶,并在室温下搅拌所得不均匀混合物2小时。然后,过滤浆液,并用甲苯(3mL)洗涤。将经过滤的晶体在60℃下真空干燥,以从结晶产物中去除甲苯痕迹。由此获得的结晶产物具有98%的纯度。发现作为晶体回收的产物的收率为85%。
通过IR、粉末X射线和DSC分析分析所获得的晶体并且发现为螺螨酯结晶变体I,分别如图1、2和3中所示。
差示扫描量热(DSC)热谱图(图3)显示在约98.6℃下的吸热熔融峰。
螺螨酯的IR光谱显示在图1中的波数(cm-1,±0.2%)为约2971、2928、2854、1780、1749、1096、1061、862和819cm-1中的一个或更多个下的官能团特征振动峰。
晶体的X射线粉末衍射图在图2中显示出反射,并将值汇总在表1中。
表1.螺螨酯结晶变体I的X射线粉末衍射图反射
实施例3-从丙酮中结晶
将实施例1中制备的螺螨酯(5g)样品连同丙酮(35mL)溶解在3颈圆底烧瓶中,并将所得浆液加热至回流,以得到均匀溶液。过滤所得热溶液来去除不溶物(如果有的话),并使所得经过滤的溶液缓慢冷却至室温。产物在冷却期间作为细晶沉淀出,并在室温下搅拌混合物2小时。然后,过滤浆液,用丙酮(3mL)洗涤,并在40℃下真空干燥,以从晶体中去除丙酮痕迹。由此所获得的晶体具有98%的纯度,且产物的回收收率为85%。
利用IR光谱法、X射线衍射和DSC将晶体表征为螺螨酯结晶变体I,如实施例2中所述。
实施例4-制备无定形螺螨酯SC
均匀混合下表2中列出的所有组分,并用戴诺磨(Dyno-Mill)(由威利A.巴赫芬公司(Willy A.Bachofen AG)生产)研磨所得混合物,以获得悬浮剂。
表2
实施例5-螺螨酯结晶变体ISC的制备
均匀混合下表3中列出的所有组分,并用戴诺磨(由威利A.巴赫芬公司生产)研磨所得混合物,以获得悬浮剂。
表3
实施例6:储存稳定性的比较
将实施例4和5中制备的样品储存在54℃下1个月、3个月和6个月。过程遵循CIPACMT 46.3。在每个储存时间结束时通过HPLC测量螺螨酯的浓度。提供观察测量聚集。每种制剂中的螺螨酯的原始浓度为25%。结果列在表4中。
表4
备注:“+”意指少量聚集。“+++++”意指大量聚集。“-”意指无聚集。
Claims (16)
1.一种螺螨酯(3-(2,4-二氯苯基)-2-氧代-1-氧杂螺[4.5]癸-3-烯-4-基-2,2-二甲基丁酸酯)结晶变体I,其在利用Cu-Kα辐射在25℃下记录的X射线粉末衍射图中以任何组合呈现至少3个作为2θ值的如下反射:
2θ=11.322±0.2 (1)
2θ=14.858±0.2 (2)
2θ=15.382±0.2 (3)
2θ=17.184±0.2 (4)
2θ=19.617±0.2 (5)
2θ=21.739±0.2 (6)
2θ=22.784±0.2 (7)
2θ=23.840±0.2 (8)
2θ=25.725±0.2 (9)
2θ=28.195±0.2 (10)
2θ=30.974±0.2 (11)。
2.根据权利要求1所述的螺螨酯结晶变体I,其在利用Cu-Kα辐射在25℃下记录的X射线粉末衍射图中以任何组合呈现至少3个作为2θ值的如下反射:
2θ=11.322±0.2 (1)
2θ=14.858±0.2 (2)
2θ=15.382±0.2 (3)
2θ=17.184±0.2 (4)
2θ=19.617±0.2 (5)
2θ=22.784±0.2 (7)
2θ=23.840±0.2 (8)
2θ=25.725±0.2 (9)。
3.根据权利要求1所述的螺螨酯结晶变体I,其呈现特征官能团振动峰在约2971、2928、2854、1780、1749、1096、1061、862和819cm-1中的一个或更多个波数(cm-1,±0.2%)下的IR光谱。
4.根据权利要求1所述的螺螨酯结晶变体I,其呈现吸热熔融峰起始于约98.6℃的差示扫描量热(DSC)热谱图。
5.一种制备根据权利要求1所述螺螨酯结晶变体I的方法,其包括:
iii)将无定形螺螨酯溶解在溶剂中;
iv)使该溶解的化合物沉淀为式I的螺螨酯结晶变体I;以及
iii)分离该沉淀的结晶变体I。
6.根据权利要求5所述的方法,其中所述溶剂选自卤代烃、醚、硝化烃、芳烃、酯和酮及其混合物,优选芳烃和酮。
7.根据权利要求5所述的方法,其中所述溶剂选自酮和可任选地被一个或更多个取代基取代的芳烃,所述取代基可相同或不同且选自硝基、卤素和可任选地被一个或更多个可相同或不同的卤素进一步取代的烷基。
8.根据权利要求6所述的方法,其中所述溶剂选自甲苯、二甲苯、苯、氯苯、二氯苯、乙苯、三氟甲苯、均三甲苯、硝基苯、醚、甲乙酮、丙酮及其混合物。
9.根据权利要求5所述的方法,其中步骤ii)包括浓缩溶液,或将其冷却至室温,或冷却至约0℃至20℃,或添加所述螺螨酯结晶变体I的晶种。
10.一种结晶材料,其包含根据权利要求5所述方法获得的螺螨酯结晶变体I,且具有按重量计至少98%的螺螨酯结晶变体I含量的含量。
11.一种组合物,其包含根据权利要求1所述的螺螨酯结晶变体I和至少一种助剂。
12.根据权利要求11所述的组合物,其中所述助剂选自表面活性剂、稀释剂、润湿剂、分散剂、增稠剂、消泡剂、防冻剂、防腐剂、抗氧化剂、固体附着剂、惰性填料及其混合物。
13.根据权利要求11所述的组合物,所述组合物呈以下形式:悬浮剂(SC)、油基悬浮剂(OD)、可溶粒剂(SG)、可分散液剂(DC)、乳油(EC)、乳液拌种剂、悬浮液拌种剂、颗粒剂(GR)、微粒剂(MG)、悬乳剂(SE)或水分散粒剂(WG)。
14.根据权利要求13所述的组合物,其为悬浮剂(SC)形式。
15.一种控制不期望有害生物的方法,所述方法包括向植物、植物部分或所述植物的周围环境施用杀虫有效量的根据权利要求1所述的螺螨酯结晶变体I。
16.根据权利要求1-4中任一项所述螺螨酯结晶变体I或根据权利要求11-14中任一项所述组合物用于控制有害生物的用途。
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PCT/CN2016/097608 WO2017101515A1 (en) | 2015-12-14 | 2016-08-31 | Novel form of spirodiclofen, process for preparation and use thereof |
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Cited By (5)
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CN108658913A (zh) * | 2018-06-13 | 2018-10-16 | 石家庄市绿丰化工有限公司 | 一种合成农药螺螨酯关键中间体的方法 |
CN108840846A (zh) * | 2018-08-20 | 2018-11-20 | 山东康乔生物科技有限公司 | 一种螺螨酯及其中间体的制备方法 |
CN109053410A (zh) * | 2018-08-06 | 2018-12-21 | 兰博尔开封科技有限公司 | 一种合成1-羟基环己基甲酸的新工艺及应用 |
CN109369587A (zh) * | 2018-12-13 | 2019-02-22 | 新沂市永诚化工有限公司 | 一种高纯度高收率螺螨酯的生产工艺 |
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BR112017023291A2 (pt) | 2018-08-14 |
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US10005754B2 (en) | 2018-06-26 |
US20170166546A1 (en) | 2017-06-15 |
WO2017101515A1 (en) | 2017-06-22 |
MX2018005803A (es) | 2018-09-17 |
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