CN100494179C - 脱水啶酰菌胺的新晶型 - Google Patents
脱水啶酰菌胺的新晶型 Download PDFInfo
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- WYEMLYFITZORAB-UHFFFAOYSA-N boscalid Chemical class C1=CC(Cl)=CC=C1C1=CC=CC=C1NC(=O)C1=CC=CN=C1Cl WYEMLYFITZORAB-UHFFFAOYSA-N 0.000 title abstract description 4
- 239000013078 crystal Substances 0.000 claims description 48
- 150000001875 compounds Chemical class 0.000 claims description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 229940031815 mycocide Drugs 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 229940084434 fungoid Drugs 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- 229960003966 nicotinamide Drugs 0.000 claims description 4
- 239000011570 nicotinamide Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 3
- 241000233866 Fungi Species 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 2
- 230000000855 fungicidal effect Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 125000006850 spacer group Chemical group 0.000 claims description 2
- 239000003880 polar aprotic solvent Substances 0.000 claims 3
- 125000003158 alcohol group Chemical group 0.000 claims 1
- 239000000155 melt Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000005740 Boscalid Substances 0.000 description 22
- 229940118790 boscalid Drugs 0.000 description 22
- -1 boscalid amine Chemical class 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 16
- 238000005755 formation reaction Methods 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 230000018044 dehydration Effects 0.000 description 12
- 238000006297 dehydration reaction Methods 0.000 description 12
- 239000008187 granular material Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
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- 238000006703 hydration reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical compound NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000005152 nicotinamide Nutrition 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000004546 suspension concentrate Substances 0.000 description 1
- 239000004548 suspo-emulsion Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/81—Amides; Imides
- C07D213/82—Amides; Imides in position 3
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
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- Agronomy & Crop Science (AREA)
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- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
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- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Health & Medical Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pyridine Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Centrifugal Separators (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
熔点147-148℃、结构式I的单斜晶2-氯-N-(4′-氯代联苯-2-基)-烟酰胺及其制备方法。
Description
本发明涉及熔点147-148℃、结构式I的单斜晶2-氯-N-(4′-氯代联苯-2-基)-烟酰胺。
本发明进一步涉及所述化合物的制备。
熔点144-145℃、结构式I的单斜晶2-氯-N-(4′-氯代联苯-2-基)烟酰胺在EP-A-545 099及PCT/EP02/10320中叙述,并以通用名称啶酰菌胺(boscalid)已知。PCT/EP02/10320叙述了脱水啶酰菌胺、水合啶酰菌胺,及从啶酰菌胺脱水化物制备啶酰菌胺水合物。
本申请中,已知的脱水啶酰菌胺称为晶型I,而权利要求1的脱水啶酰菌胺称为晶型II。
为了从脱水啶酰菌胺制备水性悬浮浓液(aqueous suspensionconcentrate)(SC)或悬浮乳液(suspoemulsion)(SE),根据PCT/EP02/10320,首先需要制备水合啶酰菌胺,然后在水和其它助剂的存在下,将所述水合啶酰菌胺粉碎得非常细。这对于脱水啶酰菌胺是不可能的,因为当其与助剂在水中粉碎时,会形成壤质固体从而阻碍进一步的粉碎。
根据PCT/EP02/10320,通过将晶型I的脱水啶酰菌胺溶于水溶性溶剂,然后加入水以沉淀出水合物,可以制备晶型I的水合啶酰菌胺。
固体制剂,例如水中可分散的喷雾干燥式或挤出式粒剂,可以直接从晶型I的脱水啶酰菌胺制备,而无须提前转化为水合物。
若随后将上述水中可分散的粒剂用水稀释,并与含溶剂的植保制剂,例如乳液浓液(emulsion concentrate)(EC)混合,则形成啶酰菌胺晶体,可阻塞使用设备中的过滤器,从而可能会在使用中出现问题。
本发明的目的之一就是消除所述的水中可分散粒剂的不足。
我们已经发现,通过提供熔点147-148℃、晶型II的结构式I的单斜晶脱水啶酰菌胺可以达到上述目的。令人惊讶的是,已经发现晶型II形式的结构式I的脱水啶酰菌胺在溶剂存在下几乎不显示晶体成长。
EP-A-545 099及PCT/EP02/10320中叙述了晶型I的结构式I的脱水啶酰菌胺的制备。
本发明进一步涉及晶型II的脱水啶酰菌胺的制备方法。
在一例实施方案(方法1)中,所述方法包括以下步骤:
a)将晶型I的结构式I的脱水化合物溶于极性有机溶剂或芳烃中,
b)通过冷却所述溶剂,沉淀出晶型II的结构式I的脱水化合物。
适合的极性溶剂为醇、二醇、酮、醚、酯、酰胺、二甲基亚砜或这些溶剂的混合物。芳烃更适合。
醇的实例为甲醇、乙醇或丙醇。特别优选甲醇。
适合的二醇为,例如乙二醇及二甘醇。
适合的酮为,例如丙酮及环己酮。
适合的醚为,例如二噁烷及四氢呋喃。
适合的酯为,例如乙酸乙酯。
适合的酰胺为,例如二甲基甲酰胺。
适合的芳烃溶剂为,例如苯、甲苯及二甲苯。
阶段a)中晶型I的结构式I的脱水化合物的溶解在20~150℃,优选40~115℃,特别优选50~95℃实现。
阶段b)中晶型II的结构式I的脱水化合物的沉淀通过将阶段a)得到的溶液冷却至0~30℃,优选10~25℃,特别优选20~25℃温度实现。沉淀进行1-24小时,优选2-20小时。
阶段b)中加入晶型II的结构式I的脱水化合物的晶种是特别有利的,可以显著加速沉淀。
在另一例实施方案(方法2)中,所述方法包括以下步骤:
a)将晶型I的结构式I的脱水化合物加热至150℃以上直至每种成分均熔融,
b)在加入晶型II的结构式I的脱水化合物的晶种的条件下,冷却所述熔融物。
阶段b)中晶种加入量为0.01~20重量%(重量百分比),优选0.05~5重量%。
所述方法优选在适合的不锈钢容器中进行。晶型I的结构式I的脱水化合物到晶型II的转化定量地发生。
本发明还涉及杀真菌剂,包含结构式I的化合物及惰性添加剂。
优选地,所述杀真菌剂包含0.1~95重量%的结构式I的化合物。
本发明还涉及控制有害真菌的方法,其中使用杀真菌量的结构式I的化合物或包含结构式I的化合物的杀真菌剂处理有害真菌、其生长环境或待抑制所述真菌的植物、区域、物质或场所。
表1中比较了结构式I的脱水化合物的两种晶型的物理性质:
表1
性质 | 脱水化物,晶型I | 脱水化物,晶型II |
分子量[g/mol] | 342 | 342 |
熔点[℃](DSC) | 144.8 | 147.2 |
熔化热[J/g](DSC) | 85 | 106 |
密度[g/cm<sup>3</sup>] | 1.399 | 1.457 |
IR特征带[cm<sup>-1</sup>] | 924,1310,1650 | 868,917,1675 |
表2中显示了使用西门子公司(Siemens)的单晶衍射仪对晶体进行检测得到的晶胞参数:
表2
参数 | 脱水化物,晶型I | 脱水化物,晶型II |
分类 | 单斜晶 | 单斜晶 |
空间群 | P21/c | P21/c |
a | 1479.2(3)pm | 1162.5(6)pm |
b | 1157.67(19)pm | 1134.2(4)pm |
c | 1872.1(3)pm | 1283.2(5)pm |
α | 90° | 90° |
β | 91.993(17)° | 114.52(4)° |
γ | 90° | 90° |
体积 | 3.2038(9)nm<sup>3</sup> | 1.5390nm<sup>3</sup> |
Z | 8 | 4 |
密度(计算值) | 1.423Mg/m<sup>3</sup> | 1.481Mg/m<sup>3</sup> |
R<sup>1</sup>,wR<sup>2</sup> | 0.1036;0.1699 | 0.0489;0.1264 |
所示参数具有以下含义:
a,b,c=单位晶胞的边长(edge length)
α,β,γ=对应的角度(corresponding angles)
Z=单位晶胞内的分子数
实施例1:
晶型II的结构式I的脱水化合物的制备:
首先将30g的甲醇加入具有玻璃磨口接头的锥形瓶中。然后加入5g晶型I的结构式I的脱水化合物,混合物在水浴中边搅拌边加热至55℃直至每种成分均溶解(约10分钟)。然后移去锥形瓶的水浴,环境温度下(约20℃)冷却18小时。结晶出晶型II的结构式I的脱水化合物。熔点147.2℃。
实施例2:
在不锈钢容器中将200g晶型I的结构式I的脱水化合物加热至160℃。然后边搅拌边冷却熔融物。150℃时,用晶型II的结构式I的脱水化合物的晶体实现接晶种(seeding),继续冷却。得到晶型II的结构式I的脱水化合物。
实施例3:
晶型I或II的结构式I的脱水化合物的水中可分散粒剂的制备:
组成:
组分 | 浓度 |
啶酰菌胺(活性成分) | 30-60% w/w |
分散剂(木素磺酸盐) | 10-20% w/w |
润湿剂(萘磺酸提浓物盐) | 5-10% w/w |
消泡剂(硅油) | 0.5-1% w/w |
标准化剂(standardizing agent)(硫酸钠) | 至100% |
制备方法:
制备合适浓度的悬浮液,并用破碎机(pearl mill)将其粉碎至所需的颗粒尺寸(50%<2μm)。然后在喷雾塔内干燥所述悬浮液。
罐混合相容性(tank mixing compatibility)比较:
为此目的,制备了上述组成的、包括晶型I的结构式I的脱水化合物的水中可分散粒剂(制剂A),及包括晶型II的结构式I的脱水化合物的水中可分散粒剂(制剂B)。
然后用CIPACD水(Ca++/Mg++(4:1))分别制备两种水中可分散粒剂的浓度5%的悬浮液,所述CIPACD水的硬度为342ppm、pH值6.0~7.0。然后将悬浮液与1%的Solvesso 200(芳烃混合物)混合,所述Solvesso200为含溶剂的液体制剂(例如EC)的一种常用溶剂。然后将相应的喷雾液(spr ayliquor)在某一温度下储存一段时间。储存后由75μm筛测定固体残余物,以评价其质量。
结果
制剂 | 储存时间 | 储存温度 | 75μm筛残余物 |
A | 24小时 | 20℃ | 13.0% w/w |
A | 24小时 | 30℃ | 14.3% w/w |
A | 7天 | 20℃ | 16.8% w/w |
A | 7天 | 30℃ | 19.3% w/w |
B | 24小时 | 20℃ | 0.1% w/w |
B | 24小时 | 40℃ | 痕量 |
B | 7天 | 20℃ | 痕量 |
B | 7天 | 40℃ | 0.1% w/w |
Claims (12)
1.熔点147-148℃且具有以下参数的结构式I的单斜晶2-氯-N-(4′-氯代联苯-2-基)-烟酰胺
2.制备权利要求1的化合物I的方法,其中
a)将熔点144-145℃、结构式I的2-氯-N-(4′-氯代联苯-2-基)-烟酰胺溶于极性质子溶剂或芳烃中;并且
b)冷却后从溶剂中结晶出。
3.权利要求2的制备化合物I的方法,其中所用极性质子溶剂为醇、酮、醚、酯、酰胺、二甲基亚砜或它们的混合物。
4.权利要求3的制备化合物I的方法,其中所述醇为甲醇、乙醇、丙醇或二醇。
5.权利要求4的制备化合物I的方法,其中所述二醇为乙二醇或二甘醇。
6.权利要求3的制备化合物I的方法,其中所用极性质子溶剂为醇、酯或酮。
7.权利要求6的制备化合物I的方法,其中所用醇为甲醇或乙醇。
8.权利要求2的制备化合物I的方法,其中阶段a)中结构式I的化合物在20~150℃溶解。
9.权利要求2的制备化合物I的方法,其中阶段a)中结构式I的化合物在40~115℃溶解。
10.杀真菌剂,包含权利要求1的结构式I的化合物及惰性添加剂。
11.权利要求10的杀真菌剂,所述杀真菌剂包含0.1~95重量%的权利要求1的结构式I的化合物。
12.控制有害真菌的方法,其中使用杀真菌量的权利要求1的结构式I的化合物或权利要求10的包含权利要求1的结构式I的化合物的杀真菌剂处理有害真菌、其生长环境或待抑制所述真菌的植物、区域、物质或场所。
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DE10307751A DE10307751A1 (de) | 2003-02-14 | 2003-02-14 | Neue kristalline Modifikation des Anhydrates von Boscalid |
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UA90035C2 (ru) | 2005-11-10 | 2010-03-25 | Басф Се | Фунгицидная смесь, которая содержит боскалид и пириметанил и способ борьбы с фитопатогенными грибами |
ATE505083T1 (de) * | 2007-08-09 | 2011-04-15 | Basf Se | Fungizide mischungen |
JP2013510113A (ja) | 2009-11-06 | 2013-03-21 | ビーエーエスエフ ソシエタス・ヨーロピア | 4−ヒドロキシ安息香酸及び選択された殺有害生物剤の結晶複合体 |
CN103338642A (zh) | 2010-09-09 | 2013-10-02 | 桑科能源股份有限公司 | 协同作用的石蜡油和啶酰菌胺杀真菌剂 |
CN102217604B (zh) * | 2011-04-16 | 2013-11-06 | 陕西汤普森生物科技有限公司 | 一种含啶酰菌胺与三唑类化合物的杀菌组合物 |
CN102860307B (zh) * | 2012-09-13 | 2014-04-02 | 倪烈 | 一种含井冈霉素与啶酰菌胺的复配农药及其应用 |
CN103348982B (zh) | 2013-07-15 | 2016-06-15 | 江苏龙灯化学有限公司 | 一种杀真菌混合物 |
CN103980192B (zh) * | 2014-01-20 | 2016-02-17 | 泰州百力化学股份有限公司 | 一种选择性合成不同晶型啶酰菌胺的方法 |
CN104016915B (zh) * | 2014-06-27 | 2016-03-30 | 重庆工商大学 | 一种啶酰菌胺的制备方法 |
CN104920366A (zh) * | 2015-05-14 | 2015-09-23 | 京博农化科技股份有限公司 | 一种啶酰菌胺制剂的加工方法 |
GB2539022B (en) * | 2015-06-04 | 2018-02-07 | Rotam Agrochem Int Co Ltd | Process for preparing boscalid |
GB2536979B (en) * | 2015-06-04 | 2019-03-13 | Rotam Agrochem Int Co Ltd | Process for preparing boscalid |
GB2550138B (en) | 2016-05-09 | 2019-06-12 | Rotam Agrochem Int Co Ltd | Process for preparing boscalid |
GB2552694B (en) * | 2016-08-04 | 2020-03-04 | Rotam Agrochem Int Co Ltd | A Synergistic fungicidal composition and use thereof |
GB2552696B (en) * | 2016-08-04 | 2020-03-04 | Rotam Agrochem Int Co Ltd | Process for preparing boscalid |
GB2552699B (en) * | 2016-08-04 | 2021-03-10 | Rotam Agrochem Int Co Ltd | Process for preparing boscalid |
GB2552697B (en) * | 2016-08-04 | 2021-03-10 | Rotam Agrochem Int Co Ltd | Process for the preparation of boscalid |
GB2552695B (en) * | 2016-08-04 | 2020-03-04 | Rotam Agrochem Int Co Ltd | A synergistic fungicidal composition |
EP3519388B1 (en) * | 2016-09-28 | 2023-03-29 | UPL Limited | Process for preparation of boscalid anhydrate form i and boscalid anhydrate form ii |
CN115536581A (zh) * | 2022-10-08 | 2022-12-30 | 河北兰升生物科技有限公司 | 高纯度啶酰菌胺晶型i的制备方法 |
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CH657129A5 (en) | 1983-12-20 | 1986-08-15 | Sandoz Ag | Process for preparing N-thienylchloroacetamides |
CA2081935C (en) | 1991-11-22 | 2004-05-25 | Karl Eicken | Anilide derivatives and their use for combating botrytis |
TW431861B (en) | 1997-12-18 | 2001-05-01 | Basf Ag | Fungicidal mixtures based on amide compounds and azoles |
WO2003029219A1 (de) * | 2001-09-25 | 2003-04-10 | Basf Aktiengesellschaft | Kristalline hydrate von nicotinsaeurenilid- und benzoylanilid-derivaten |
DK2308304T3 (da) * | 2002-03-21 | 2012-11-05 | Basf Se | Fungicide blandinger |
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