201036967 六、發明說明： 本發明係關於。塞美索森（thiamethoxam )之新賴共晶體 及其於殺昆蟲組成物、特別是農業化學組成物中之用途。 °塞美索森為一種新類尼古丁（ ne〇nic〇tin〇id )殺見蟲劑 且被認為藉由影響昆蟲中樞神經系統十之突觸而起作用。 噻美索森係用於例如菜類作物、葉果蔬菜、馬鈐薯、水稻、 〇 棉花、落葉果樹、柑橘、煙草等之葉面及土壤處理中且用 作玉米、高粱、穀物、蓁菜、油菜、棉花、豌豆、蠶豆、 向日葵、水稻及馬鈐薯之種子拌藥（seed dressing )，來控 . 制諸如蚜蟲、粉虱、薊馬、稻飛蝨、稻椿象、粉蚧、蜻螬、 科羅拉多馬鈐薯甲蟲（C〇i〇rad〇 p0tat〇 beetle )、跳甲、線 蟲、地面曱蟲、潛葉蟲及一些鱗翅目物種之多種病原體。 噻美索森亦被用作種子處理。噻美索森可購得且描述於 -The Pesticide Manual»[The Pesticide Manual - A World 〇 C〇mpendium;第 13 版；編輯：C. D. S. Tomlin; The British Crop Protection Council]中。 儘管噻美索森已用於商業調配物中，但仍始終需要具 有改良物理特性之改良組成物。舉例而言，改變熔點、相 變溫度或於水或其他溶劑中之溶解度可導致活性成份更易 製備' 調配及處理及/或導致改良之生物特性，諸如土壤淋 >谷降低及田間持久性增加。 因此，本發曰月提供嘆美索森之新賴共、结晶形式，其與 201036967 此殺昆蟲劑之市售形式相比具有改良之特性。 詳言之，本發明提供噻美索森與2胺基苯并噻唑之共 晶體。 噻美索森與2-胺基苯并噻唑之共結晶形式的特徵可由 曰曰體形癌（在單位晶胞方面描述）或以在2 0角方面所表示 之粉末X射線繞射圖之選定峰描繪。 在一具體實例中，噻美索森與2胺基苯并噻唑之共晶 體形式的特徵係、由在20角方面所表示之粉末χ射線繞射 圖描繪，其中該粉末Χ射線繞射圖包含至少三個選自包含 以下之群組之20角值：（a) 14〇至144、25 3至257及 26.4 至 26.8 或（b) 6.9 至 7.3、13.4 至 13.8、14.2 至 14.6、 至 18.0、19.6 至 20.0、21.0 27.2、29.4 至 29.8 及 32.4 14.5 至 14.9、17.1 至 17.5、17.6 至 21.4、25.5 至 25.9、26.8 至 至32.8。粉末χ射線繞射圖更佳包含至少三個選自包含以 下之群組之2Θ角值：（a) 14.2、25 5及2“或（b)7i、 29‘6及32.6。粉末X射線繞射圖更佳包含所有角值（ 或:（b)《（C)。該等2Θ角值係源自可完全歸於共晶體之 私末X射線繞射圖之彼等峰；表i包含該等2 ^值以及在嗟 美索森及/或2-胺基苯并嗟唾以及共晶體之粉末χ射線繞射 圖^出現的其他峰值。在-具體實例中…塞美索森與厂胺 基笨并噻唑之共晶體形式的特徵係由在角方面所表示 之粉末X射線繞射圖描繪1中粉末χ射線繞射圖包含表 1中列出之所有2 Θ角值’亦即粉末χ射線繞射圖包含“) 201036967 ‘ 5.9 至 6.3、11.8 至 12.2、14.0 至 14.4、15.0 至 15.4、18.1 至 18.5 、 20.8 至 21.2 、 21,7 至 22.1 、 22.8 至 23.2 、 25.3 至 25.7、 26.4 至 26.8 及 27.5 至 27.9 或（b) 6.9 至 7.3、13.4 至 13.8 、 14.2 至 14.6 、 14.5 至 14.9 、 17.1 至 17.5 、 17.6 至 18.0、19.0 至 19.4、19.6 至 20.0、21.0 至 21.4、22.0 至 22.4、 23.8 至 24.2、24.7 至 25」、25.5 至 25.8、26.9 至 27.2、28.4 至 28.8、28.8 至 29.2、29.4 至 29.8 及 32.4 至 32.8 之 20 角 值’且更佳包含（a) 6.1、12.0、14.2、15.2、18.3、21.0、 〇 21.9、23.0、25.5、26.6 及 27.7 或（b) 7.1、13.6、14.4、 14.7、 17.3、17.8、19.2、19.8、21.2、22.2、24.0、24·9、 25.7、 27.0、28.6、29.0、29.6 及 32.6 之 2 0 角值。所有該 等峰均源自使用實施例la( 2Θ ( a))及實施例lb( 20 ( b)) 之方法所獲得的噻美索森-2-胺基苯并噻唑共晶體之粉末X 射線繞射圖。表1亦列出該等峰之強度（強（S )、中等（Μ ) 或弱（W))。所有該等峰位置所來源之繞射圖展示於圖1 (2 Θ (a))及圖 2(20 ( b))中。 201036967201036967 VI. INSTRUCTIONS: The present invention relates to. The new eutectic crystal of thiamethoxam and its use in insecticidal compositions, particularly agrochemical compositions. ° Samesone is a new class of nicotine (ne〇nic〇tin〇id) insecticides and is thought to act by affecting the synapses of the insect central nervous system. Thiomesone is used in foliar and soil treatments such as vegetable crops, leafy vegetables, horse yam, rice, glutinous cotton, deciduous fruit trees, citrus, tobacco, etc. and is used as corn, sorghum, cereals, leeks Seed dressing of rapeseed, cotton, peas, broad beans, sunflower, rice and horseshoe, etc., such as aphids, whiteflies, thrips, rice planthoppers, rice blasts, whiteflies, crickets , Colorado horseshoe beetle (C〇i〇rad〇p0tat〇beetle), jumping armor, nematodes, ground locusts, leaf miner and some lepidopteran species of various pathogens. Thiomesone is also used as a seed treatment. Thimesolone is commercially available and described in -The Pesticide Manual»[The Pesticide Manual - A World 〇 C〇mpendium; 13th edition; edit: C. D. S. Tomlin; The British Crop Protection Council]. Although thimethacone has been used in commercial formulations, there is always a need for improved compositions with improved physical properties. For example, changing the melting point, phase transition temperature or solubility in water or other solvents can result in easier preparation of the active ingredient's formulation and treatment and/or resulting in improved biological properties such as soil drenching > valley reduction and field persistence. . Therefore, this release provides a new form of crystallization of the sigh, which has improved properties compared to the commercially available form of the insecticide 201036967. In particular, the present invention provides a eutectic of thimetreson with 2-aminobenzothiazole. The co-crystallized form of thimetreson and 2-aminobenzothiazole may be characterized by a squamous carcinoma (described in terms of unit cells) or a selected peak of a powder X-ray diffraction pattern expressed at 20 degrees Depiction. In one embodiment, the characteristic form of the eutectic form of thimesole and 2-aminobenzothiazole is depicted by a powder χ ray diffraction pattern represented by the 20-angle aspect, wherein the powder Χ ray diffraction pattern comprises At least three values selected from the group consisting of: (a) 14〇 to 144, 25 3 to 257, and 26.4 to 26.8 or (b) 6.9 to 7.3, 13.4 to 13.8, 14.2 to 14.6, to 18.0, 19.6 to 20.0, 21.0 27.2, 29.4 to 29.8 and 32.4 14.5 to 14.9, 17.1 to 17.5, 17.6 to 21.4, 25.5 to 25.9, 26.8 to 32.8. Preferably, the powder xenon diffraction pattern comprises at least three angles selected from the group consisting of: (a) 14.2, 25 5 and 2" or (b) 7i, 29'6 and 32.6. Powder X-ray winding Preferably, the map contains all angular values (or: (b) "(C). These 2 Θ angle values are derived from the peaks of the private X-ray diffraction pattern that can be completely attributed to the eutectic; Table i contains such 2 ^ value and other peaks appearing in the powder χ ray diffraction pattern of 嗟 索 索 森 and / or 2-aminobenzo benzopyrene and eutectic. In the specific example ... simesumson and plant amine The eutectic form of stupid and thiazole is characterized by a powder X-ray diffraction pattern represented by the angle 1 in which the powder χ ray diffraction pattern contains all the 2 Θ angle values listed in Table 1 'ie powder χ ray The diffraction pattern contains ") 201036967 ' 5.9 to 6.3, 11.8 to 12.2, 14.0 to 14.4, 15.0 to 15.4, 18.1 to 18.5, 20.8 to 21.2, 21, 7 to 22.1, 22.8 to 23.2, 25.3 to 25.7, 26.4 to 26.8 and 27.5 to 27.9 or (b) 6.9 to 7.3, 13.4 to 13.8, 14.2 to 14.6, 14.5 to 14.9, 17.1 to 17.5, 17.6 to 18.0 , 19.0 to 19.4, 19.6 to 20.0, 21.0 to 21.4, 22.0 to 22.4, 23.8 to 24.2, 24.7 to 25", 25.5 to 25.8, 26.9 to 27.2, 28.4 to 28.8, 28.8 to 29.2, 29.4 to 29.8 and 32.4 to 32.8 20 angular value 'and more preferably (a) 6.1, 12.0, 14.2, 15.2, 18.3, 21.0, 〇21.9, 23.0, 25.5, 26.6 and 27.7 or (b) 7.1, 13.6, 14.4, 14.7, 17.3, 17.8, 19.2 2 0 angle values of 19.8, 21.2, 22.2, 24.0, 24·9, 25.7, 27.0, 28.6, 29.0, 29.6, and 32.6. All of these peaks are derived from powder X-rays of the thimetsone-2-aminobenzothiazole cocrystal obtained using the method of Example la (2 (a)) and Example lb (20 (b)). Diffraction pattern. Table 1 also lists the intensity of these peaks (strong (S), medium (Μ) or weak (W)). The diffraction patterns from which all of these peak positions are derived are shown in Figure 1 (2 Θ (a)) and Figure 2 (20 (b)). 201036967
峰 2Θ (a) 2Θ (b) 強度Τϊ!~~~ 1 6.1 __W 7.1 Μ 2 12.0 __W 13.6 L_ W ' 3 14.2 --1 ,— Μ 14.4 S 4 15.2 "------ W 14.7 卜 w 5 18.3 Μ 17.3 Μ 6 21.0 ------ Μ 17.8 -------- Μ 7 21.9 W 19.2 S 8 23.0 Μ 19.8 S — 9 25.5 _ Μ 21.2 S — 10 26.6 Μ 22.2 W ' 11 27.7 ----^ Μ 24.0 S- 12 ------ 24.9 一 Μ 13 ------ 25.7 w 14 27.0 s' 15 28.6 一 Μ 16 ------ 29.0 s- 17 29.6 s 18 1 32.6 Μ ----- 已發現噻美索森與2-胺基苯并噻唑之共晶體與噻美索 森相比，展示降低之水溶性（參見實施例3)。就這一點而 淪，其提供與噻美索森本身相比改良之生物特性，諸如降 低之土壤淋溶及增加之田間持久性。 奸、， +代坑签秀茱森與2- "本开喧唾之共晶體用於㉟昆蟲組成4勿中以_低嘆美索 淋溶至土壤t及/或增加麵索森之田間持久性的用途'。、 、體實例中’本發明提供降低錢索森淋溶至土壤 = 美索森之間持久性的方法，其包含⑴形 併^ 胺基苯并°塞°坐之共晶體，（U)將該等共晶 i开=昆蟲組成物中，&(-)用殺昆蟲有效量之殺昆蟲 成物處理植物或植物繁殖材料。 201036967 ΟPeak 2Θ (a) 2Θ (b) StrengthΤϊ!~~~ 1 6.1 __W 7.1 Μ 2 12.0 __W 13.6 L_ W ' 3 14.2 --1 , — Μ 14.4 S 4 15.2 "------ W 14.7 w 5 18.3 Μ 17.3 Μ 6 21.0 ------ Μ 17.8 -------- Μ 7 21.9 W 19.2 S 8 23.0 Μ 19.8 S — 9 25.5 _ Μ 21.2 S — 10 26.6 Μ 22.2 W ' 11 27.7 ----^ Μ 24.0 S- 12 ------ 24.9 One Μ 13 ------ 25.7 w 14 27.0 s' 15 28.6 One Μ 16 ------ 29.0 s- 17 29.6 s 18 1 32.6 Μ ----- It has been found that the eutectic of thimeson and 2-aminobenzothiazole exhibits reduced water solubility compared to thimesole (see Example 3). In this regard, it provides improved biological properties compared to thimetreson itself, such as reduced soil leaching and increased field persistence.奸,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, Persistent use'. In the present invention, the present invention provides a method for reducing the persistence of Qiansson's leaching to soil = masonsen, which comprises (1) a compound of a benzophenone and a co-crystal, (U) In the eutectic = insect composition, & (-) treats the plant or plant propagation material with an insecticidally effective amount of an insecticide. 201036967 Ο
Q 如本文中所用’「共晶體」意謂包含兩種或更多種化 學計量比之獨特組份的結晶物質，該等組份各具有不同的 物理特性’諸如結構、熔點及熔融熱。如本文t所用，共 晶體不同於結晶鹽’因為其係由t性組份組成，而不是: I中土現由帶電荷之組份組成。共晶體可經由若干種分 子識別模式建構，包括氫鍵結、n (pi)堆疊、客體主體 複合及凡得瓦爾（Van_Der_Waals)相互作用。在上文列出 之相互作用中，氫鍵結為共晶體形成中之主要相互作用， 藉以在部分之—之氫鍵供體與另—部分之氫鍵受體之間形 成非共價鍵。本發明之較佳共晶體為在2_胺基苯并噻唑與 σ塞美索森之間發生鱼鍵纟士的丘曰缺 奴土軋埏、，'口的共日日體。注意到晶體中可形成 多點接觸。舉例而言’兩個分子之噻美索森可肖2_胺基苯 并噻唑上之不同官能基形成接觸，或實際上，在單一噻美 索森分子與單-2·胺基苯#㈣分子之間可存在多點接 觸。 咸注意到氫鍵結可導致若干種不同的分子間組裝，且 就這點而論，本發明之共晶體可以一或多種多晶型形式存 在。多晶型共晶體可含有任何莫耳比之錢索森：2_胺基苯 并㈣，但典型地將在5: i至！ ： 5範圍内。各多晶型形 式可由-或多種固態分析技術界定，包括單晶體χ射線繞 射、粉末X射線繞射、DSC、拉曼（Raman)光|#術或紅外 光譜術。 共晶體中噻美索森與2-胺基笨并噻唑之莫耳比適宜在 5M至5範圍内。共晶體中錢索森與2_胺基苯并嘆嗤 之比率更適宜在4: i至丨：4範圍内。^索森與2_胺基 7 201036967 苯并料之比率甚至更適宜在2:1至1:1範圍内，且最 適宜為1 : 1。 本發明之共晶體係藉由使噻美索森與2_胺基苯并噻唑 接觸而形成。此可藉由以下步驟進行：（i)將兩種固體一 起研磨（11)使一種或兩種組份熔融且使其再結晶，（iH) 使售美索森溶解或部分溶解且添加2胺基苯H坐，或（iv) 使2-胺基苯并心溶解或部分溶解且添加錢索森。亦可 能使嗟美索森溶解或部分轉於2_胺基料㈣中，或反 之使2胺基苯并^溶解或部分溶解於嗟美索森中。隨後 在適合條件下使結晶發生。舉例而言，結晶可能需要改變 溶液性質（諸如pH值或溫度）且可能需要通常藉由移除溶 劑且典型地藉由乾燥溶液來濃縮溶質。溶劑移除導致噻美 索森之濃度隨時間增加以促進結晶。在一些情況下，可使 用微波轄射及/或音波處理來促進結晶。—旦形成包含任何 晶體之固相’則可如本文中所述對其進行測試。 因此’本發明提供製備本發明之共晶體的方法， 含： ，、匕 …）使塞美索森與2_胺基苯并ag哇—起研磨、加熱或 以溶液接觸’其在結晶條件下以形成固相； 〜 (b )分離包含噻美索森及2·胺基苯 可藉由此項技藝中已知之習知方…广、曰曰體。 ^ ^ 〇知之^知方法進行檢定固相中嚏 ^與2·胺基苯并°塞唾之共晶體的存在。舉例而言，便 利的常規方法是使用粉末χ射線繞射技術來評估共晶體之 可藉由比較噻美索森、2-胺基苯并噻唑及假定的共 晶體之繞射圖以確定是否已形成真正的共晶體來實現。以 201036967 類似方式使用之其他技術包括差示掃描熱量測定（DSC)、 熱重分析（TGA )及拉曼光譜術或紅外光譜術、NMR、氣 相層析或HPLC。單晶體X射線繞射尤其適用於鑑別共晶體 結構。本發明之共晶體可由習知方式容易地併入殺昆蟲組 成物（包括農業化學組成物）中。因此，本發明亦提供包 含如上文所定義之本發明共晶體的殺昆蟲組成物。在一具 體實例中，殺昆蟲組成物為農業化學組成物。 包3本發明共晶體之農業化學組成物可用於控制多種 植物物種上之昆蟲。因此，本發明亦提供預防/控制植物或 植物繁殖材料上之昆蟲的方法，其包含用殺昆蟲有效量之 本發明農業組成物處理植物或植物繁殖材料。「植物繁殖 材料」意謂所有種類之種子（果實、塊莖、球莖、穀粒等）、 插條、伐條（cut sh〇〇t)及其類似物。 詳σ之本發明之農業化學組成物可用於控制例如辑 蟲、粉虱、15馬、稻飛兹、稻椿象、粉汾、蜡增、科羅拉 多馬铃箸甲蟲、跳甲、線蟲、地面曱蟲、潛葉蟲及-些鱗 本發月之辰業化學組成物適用於控制多種植物 殖材料上之, 蟲包括（但不限於）以下目標作物：穀物 C小麥、大虫 田+ 、…麥、燕麥、玉米（包括飼料玉米、爆玉 米及甜玉米彳 碌土 )、水稻、高粱及相關作物）；甜菜（茱荽乃 飼用甜菜）.邱木、忝杲及 料植物蠢豆、扁豆、婉豆、大豆）；油 甜瓜） 介采、向日葵）；黃瓜植物（萌蘆、黃瓜、 甘藍菜、胡蘿蔔、茄子、洋蕙 胡椒 菜、葛苣、、植物（棉花、亞麻、大麻、黃麻）；蔬菜（緩 ° 、簏筍 9 201036967 番茄、馬鈐薯、紅辣椒、秋葵）；種植作物（香蕉、果樹、 ，膠樹、遠圃樹）、觀賞植物（花、灌木、闊葉樹及常綠 树諸如針葉樹）；以及其他植物，諸如藤、唐棣屬植物 (諸如越桔）、蔗莓（caneberry)、蔓越莓 '胡椒薄荷、 大κ綠薄荷、甘蔗及草皮草，包括（但不限於）冷季型 草皮草（例如，藍草（野生早熟禾屬（z ))，諸如肯 塔基藍草（Kentucky biuegrass )(草地早熟禾（ .))、粗莖藍草（粗莖早熟禾（ρ⑽如L ))、加 拿大藍草（扁杯早熟禾（— m以a l))及一年生藍 草（一年生早熟禾（Ρ⑽細⑽L ));小糠草（翦股賴屬 (々⑽…L.))’諸如葡句性小糠草（㈣翦股顆（处⑽出 ㈣伽Η_.))、瘦民地小糠草（細弱翦股穎（々⑽沿 ㈣-sibth.))、絨毛小糠草（絨毛翦股賴（知⑽a __ L.))及紅頂草（小糖草（知⑽沿[ η ;牛毛草（羊 茅屬（—·））’諸如高牛毛草（葦狀羊茅（F— ㈣W⑽Schreb.))、草地牛毛草（草地羊茅㈤⑽ e/an’or L.))及細牛毛箪，铋 早 渚如匍匐性紅牛毛草（紫羊茅 (L.))、邱氏车 、卞七旱（chewings fescue )(細 羊茅（尸esiMca rMra var , ^ r. c〇mmutata ））、綿羊牛毛 草（羊茅（芦eWwcfl 〇W«a L Ή » r» 止 〇)及硬牛毛草（長葉羊茅 longifolia)).，及黑參萆 “、、1草屬（ZWwm L.))，諸 如多年生黑麥草（多年生黑麥草 ^ ^ folium perenne L.))及 一年生（義大利）黑麥草（客r 匕…、麥車 Q Lolium multiflorumQ As used herein, "eutectic" means a crystalline material comprising two or more unique components of a stoichiometric ratio, each of which has a different physical property' such as structure, melting point and heat of fusion. As used herein, the eutectic is different from the crystalline salt 'because it consists of t-components, rather than: The soil in I is now composed of charged components. Co-crystals can be constructed via several molecular recognition modes, including hydrogen bonding, n (pi) stacking, guest host complexing, and Van_Der_Waals interactions. In the interactions listed above, hydrogen bonding is the primary interaction in eutectic formation whereby a non-covalent bond is formed between a portion of the hydrogen bond donor and another portion of the hydrogen bond acceptor. A preferred eutectic of the present invention is a succulent sulcata, which is formed by a fish bond between a 2-aminobenzothiazole and σ-Semisson. It is noted that multiple points of contact can be formed in the crystal. For example, 'two molecules of thimesen succinyl 2_aminobenzothiazole on different functional groups form a contact, or indeed, in a single thiomethyst molecule with a single -2 -amino benzene # (four) There may be multiple points of contact between the molecules. It is noted that hydrogen bonding can result in several different intermolecular assemblies, and as such, the eutectic of the present invention can exist in one or more polymorphic forms. Polymorphic co-crystals can contain any molar ratio of Watson: 2_Aminobenzo (4), but typically will be at 5: i to! : 5 range. Each polymorphic form may be defined by one or more solid state analytical techniques, including single crystal xenon ray diffraction, powder X-ray diffraction, DSC, Raman light, or infrared spectroscopy. The molar ratio of thimesen to 2-amino benzothiazole in the cocrystal is suitably in the range of 5M to 5. The ratio of Qiansuosen to 2-amino-benzopyrene in the eutectic is more suitably in the range of 4: i to 丨: 4. ^Soyson and 2_Amine 7 201036967 The ratio of benzoate is even more suitable in the range of 2:1 to 1:1, and most preferably 1:1. The eutectic system of the present invention is formed by contacting thimetreson with 2-aminobenzothiazole. This can be done by (i) grinding the two solids together (11) to melt and recrystallize one or both components, (iH) dissolving or partially dissolving Messon and adding 2 amines. The base benzene H sits, or (iv) dissolves or partially dissolves the 2-aminobenzene and adds Qiansson. It is also possible to dissolve or partially transfer the indomethacin to the 2_amine base (4), or to dissolve or partially dissolve the 2 aminobenzene in the samuelson. Crystallization then takes place under suitable conditions. For example, crystallization may require changes in solution properties (such as pH or temperature) and may require concentration of the solute, typically by removing the solvent and typically by drying the solution. Solvent removal results in an increase in the concentration of thimetsone over time to promote crystallization. In some cases, microwave catalysis and/or sonication can be used to promote crystallization. Once a solid phase comprising any crystal is formed, it can be tested as described herein. Thus, the present invention provides a process for the preparation of the eutectic of the present invention comprising: , hydrazine...) to cause the mesexone to be ground, heated or contacted with a solution of the 2-amino benzo-ag w'. To form a solid phase; ~ (b) Separation comprising thimethacone and 2-aminobenzene can be carried out by the conventional methods known in the art. ^ ^ The method of knowing is to verify the presence of eutectic crystals in the solid phase of 嚏^ and 2·amino benzophenanthene. For example, a convenient conventional method is to evaluate the eutectic by using powder enthalpy diffraction techniques by comparing the diffraction diagrams of thimesen, 2-aminobenzothiazole and the hypothetical eutectic to determine if Form a true eutectic to achieve. Other techniques used in a similar manner to 201036967 include differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and Raman spectroscopy or infrared spectroscopy, NMR, gas chromatography or HPLC. Single crystal X-ray diffraction is especially useful for identifying eutectic structures. The co-crystals of the present invention can be readily incorporated into insecticidal compositions (including agrochemical compositions) by conventional means. Accordingly, the present invention also provides an insecticidal composition comprising a eutectic of the invention as defined above. In a specific example, the insecticidal composition is an agrochemical composition. Package 3 The agrochemical composition of the eutectic of the invention can be used to control insects on a variety of plant species. Accordingly, the present invention also provides a method of preventing/controlling insects on a plant or plant propagation material comprising treating the plant or plant propagation material with an insecticidally effective amount of the agricultural composition of the invention. "Plant propagation material" means all kinds of seeds (fruits, tubers, bulbs, grains, etc.), cuttings, cut sh〇〇t and the like. The agrochemical composition of the present invention can be used to control, for example, worms, whiteflies, 15 horses, rice worms, rice blasts, white mites, wax mites, Colorado horse mites, beetles, nematodes, ground mites , leaf miner and some scales of the hair industry chemical composition is suitable for controlling a variety of plant materials, including but not limited to the following target crops: grain C wheat, large worm field +, ... wheat, oats , corn (including feed corn, popcorn and sweet corn glutinous rice), rice, sorghum and related crops; beet (茱荽 饲 feed beet). Qiu wood, 忝杲 and plant plants stupid beans, lentils, kidney beans , soybeans; oil melons), cucumber plants; cucumber plants (sweet, cucumber, cabbage, carrots, eggplant, artichoke pepper, chicory, plants (cotton, flax, hemp, jute); vegetables (slow °, 簏 9 9 201036967 tomato, horse yam, red pepper, okra); planting crops (banana, fruit trees, gum trees, distant eucalyptus), ornamental plants (flowers, shrubs, broadleaf trees and evergreen trees such as conifer); And other plants, such as vines, tangs (such as bilberry), caneberry, cranberry, peppermint, glutamate, sugar cane and turf, including but not limited to cold season grass Fur (for example, bluegrass (wild blue (z)), such as Kentucky biuegrass (bluegrass (.)), crude stem bluegrass (grassgrass (ρ(10) such as L)), Canada Bluegrass (bluegrass (-m to al)) and annual bluegrass (annual bluegrass (Ρ(10)fine (10)L)); small alfalfa (翦股赖(々(10)...L.))) such as Portuguese Small sedge ((4) 翦 颗 ( (10) (4) Η Η 、 、 瘦 瘦 瘦 瘦 瘦 瘦 瘦 瘦 瘦 瘦 瘦 瘦 瘦 瘦 瘦 瘦 瘦 瘦 瘦 瘦 瘦 瘦 瘦 瘦 瘦 瘦 瘦 瘦 瘦 瘦 瘦 瘦 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( (Knowledge (10)a __ L.)) and red top grass (small sugar grass (known as (10) along [ η ; cattle grass (Shem's (—·))' such as high cattle grass (苇-like fescue (F-(four) W(10) Schreb.) ), grassland cattle grass (grass fescue (five) (10) e/an'or L.)) and fine cattle hairy, early in the morning, such as scorpion red cow hair grass (Zi fescue (L.)), Qiu's car, 卞 seven drought (chewings fes Cue ) (seed fescue ( esiMca rMra var , ^ r. c〇mmutata )), sheep cattle grass (feather grass (reeWwcfl 〇W«a L Ή » r» 〇) and hard cattle grass (long leaf sheep) Long longifolia))., and black ginseng ",, 1 genus (ZWwm L.)), such as perennial ryegrass (perennial ryegrass ^ ^ folium perenne L.) and annual (Italian) ryegrass (guest r匕..., 麦车 Q Lolium multiflorum
Lam.))) ’及溫季型草古苴 (例如，百慕達草（狗牙根 屬（L. C. Rich)) , ’包括雜交及常見百慕達草； 201036967 結縷草（結縷草;I ( ☆州α的⑹））；冑奥古斯丁草（认 Augustinegrass) ( 1¾ ^ ^ ( Stenotaphrum secundatum (Walt.) Kuntze));及假儉草（窮人草（心⑽咖扣__化 (Munro.)Hack.) ) ) 〇Lam.))) 'and the warm-season grass sorghum (for example, Bermuda grass (LC Rich), 'including hybrid and common Bermuda grass; 201036967 Zoysia (Knots; I ( ☆ state alpha (6))); 胄 Augustine grass (Augustinegrass) ( 13⁄4 ^ ^ ( Stenotaphrum secundatum (Walt.) Kuntze)); and false 俭 grass (poor grass (heart) (10) __ (Munro. )Hack.) ) ) 〇
另外，「作物」應理解為包括由於習知育種或基因工 程方法而已變成耐受害蟲及農藥（包括除草劑或除草劑種 類）之作物。對例如除草劑之耐受性意謂與習知作物品種 相比對由特定除草劑造成之損害的敏感性降低。作物可經 改良或育種以财受例如HPPD抑制劑（諸如硝草_ (mesotrione ))或EPSPS抑制劑（諸如草甘膦 (glyphosate) ) ° 本發明農業化學組成物之施用率將取決於待控制昆蟲 之特定類型、所需控制程度及施用時序及方法，且可容易 地由熟習此項技藝者確定。一般而言’以組成物中活性殺 昆蟲劑之總量計，本發明組成物可以介於0 005公斤/公頃 (kg/ha)與約1.0 kg/ha之間的施用率施用。介於約〇 〇1 〇 kg/ha與約0.5 kg/ha之間的施用率較佳，而介於約〇 〇1 kg/ha 與0.2kg/ha之間的施用率尤佳。 實際上，包含本發明共晶體之農業化學組成物係以含 有工業中已知或使用之各種佐劑及載劑之調配物施用。其 因此可經調配成顆粒、可濕性粉末、可乳化濃縮物、懸浮 濃縮物（包括油分散液）、粉末或粉劑、可流動物、溶液、 懸浮液或乳液、懸浮-乳液或控制釋放（諸如微囊）。本發 明農業化學組成物可適宜調配成懸浮濃縮物、懸浮-乳液戍 濕顆粒。該等調配物更詳細地描述於下文且可含有少至約 11 201036967 0.5重量％至多至約95重量％或更多之呈共晶體形式的活性 成份。最佳量將視調配物、施用設備及待控制昆蟲之性質 而定。 可濕性粉末呈細粉狀粒子形式，其容易分散於水或其 他液體載劑中。該等粒子含有保持於固體基質中之活性成 份。典型固體基質包括漂白土（fuller,s earth)、高嶺土、 矽石及其他易濕性有機或無機固體。可濕性粉末通常含有 約5%至約95%之活性成份以及少量濕潤劑、分散劑或乳化 劑0 可乳化濃縮物為可分散於水或其他液體中之均質液體 組成物且可完全由活性化合物與液體或固體乳化劑組成， 或亦可含有諸如二曱苯、重芳族石腦油、異佛爾酮 (is〇ph〇rone)及其他非揮發性有機溶劑之液體載劑。在使 用中’該等濃縮物經分散於水或其他液體中且通常以嗔霧 施用至待處理之區域。活性成份之量可在濃縮物之約〇外 至約95%範圍内。 懸浮濃縮物為活性化合物之細粉狀固體粒子穩定懸浮 之調配物。該等固體粒子可懸浮於水溶液或油（呈油分散 液）中。該等調配物包括防沈劑及分散劑且可進一步包括 用於增強活性之濕潤劑以及消泡劑及晶體生長抑制劑。在 使用中’該等濃縮物經稀釋於水中且通常以喷霧施用至待 處理之區域。活性成份之量可在濃縮物之約0.5%至約95% 範圍内。 顆粒調配物包括播屮私^ & μ ^ ^， 微出物與相對粗糙粒子，且可不經稀 釋即施用於需要控制昆蟲夕p ^ + ’ 匕蟲之£域或例如在施用前分散於噴 12 201036967 霧罐1ί7。顆粒調配物之典型載劑包括沙、、、φ /示白土、鎮銘海 泡石黏土、膨潤土、微晶兩嶺石黏土、. ^ . 、珍珠岩、碳 酸約、碑、浮石、葉蠛石、高嶺土、白雲石、熟石膏 屑、經研磨玉米穗軸、經研磨花生殼、糖、& 藏•化納、硫酸 納、矽酸鈉、硼酸鈉、氧化鎂、雲母、 〆, 乳化鐵、氧化鋅、 氧化鈦、氧化銻、冰晶石、生石膏、石夕荡 喿土、硫酸鈣及其 他吸收活性化合物或可經塗佈活性化合物之有機或益機材 Ο Ο 料。不經稀釋即使用之顆粒調配物通常含有約5%至約25% 之活性成份，其可包括表面活性劑，諸如重芳族石腦油、 煤油及其他石油餾份，或植物油；及/或黏著劑，諸如糊精、 膠或合成樹脂。當顆粒在施用前欲分散於喷霧罐中時，活 性成份含量可增加至80%« ' ，粉劑為活性成份與充當分散劑及載劑之細粉狀固體 (諸如滑石、黏土、粉（flour)及其他有機及無機 的自由流動混合物。 微囊典型地為活性成份之液滴或顆粒封閉於惰性多孔 殼中，該毅允許所封閉的材料以受控速率逸出至周圍環境 中。囊封液滴之直徑典型地為約1微米至50微 體典型地佔微囊重量之約50%至95%且除活性化合物之外 亦可包括溶劑。囊封顆粒一般為由多孔膜密封顆粒孔開 口、將液體形式之法4 y I1生物種保邊在顆粒孔内部之多孔顆 粒。顆粒+直徑典型地在1毫米至1公分範_且㈣為i 顆粒係藉由擠出、黏聚或製粒形成，或係天然 存在。§亥等材料之實例為虫至石、燒結黏土、高嶺土、鎮銘 海泡石黏土、鑛屬及碳粒。殼或膜材料包括天然及合成橡 13 201036967 膠、纖維素材料、苯乙烯-丁二烯共聚物、聚丙烯腈、聚丙 烯酸酯、聚酯、聚醯胺、聚脲、聚胺酯及黃原酸殿粉。 其他適用於農業化學應用之調配物包括活性成份於溶 劑中之簡單溶液，在該溶劑中活性成份在所需濃度下完全 可溶’諸如丙酮、院基化萘、二甲苯及其他有機溶劑。亦 可使用加壓喷霧器，其中活性成份由於低沸點分散性溶劑 載劑汽化而以細粉形式分散。 如上所述之許多調配物包括濕潤劑、分散劑或乳化 劑。實例為烷基及烷基芳基磺酸酯及硫酸酯及其鹽、多元 醇；聚乙氧基化醇、酯及脂肪胺。當使用時，該等試劑通 常佔調配物之0.1重量％至40重量％。 適用於將本發明組成物調配成上文所述之調配物類型 的適合農業佐劑及載劑為熟習此項技藝者所熟知。不同類 別之適合實例見於下文非限制性清單中。 可使用之液體載劑包括水、甲苯、二甲苯、石腦油、 作物油、丙酮、曱基乙基酮、環己酮、乙酸酐、乙腈、苯 乙酮、乙酸戊酯、2-丁酮、氣苯、環己烷、環己醇、乙酸烷 酯、二丙酮醇、1，2-二氣丙烷、二乙醇胺、對二乙基苯、二 乙二醇、松脂酸二乙二醇酯、二乙二醇丁醚、二乙二醇乙 醚、二乙二醇甲醚、N，N-二甲基甲醯胺、二甲亞諷、l4-二腭烷、二丙二酵、二丙二醇甲醚、二苯曱酸二丙二醇酯、 二丙二醇（diproxitol )、烧基〇比洛咬鲷、乙酸乙酯、2-乙 基己醇、碳酸伸乙酯、1，1，1-三氯乙烷、2-庚酮、α蒎烯、 d-檸檬烯、乙二醇、乙二醇丁醚、乙二醇甲醚、r-丁内s旨、 甘油、二乙酸甘油酯、單乙酸甘油酯、三乙酸甘油醋、十 14 201036967 六烷、己二醇、乙酸異戊酯、乙酸異冰片酯、異辛烷、異 佛爾酮、異丙基苯、肉豆蔻酸異丙酯、乳酸、月桂胺、異 亞丙基丙酮（mesityl oxide )、甲氧基-丙醇、甲基異戊其 酮、曱基異丁基酮、月桂酸曱酯、辛酸曱酯、油酸甲醋、 二氣曱烷、間二甲苯、正己烷、正辛胺、十八酸、辛基胺 乙酸酯（octyl amine acetate )、油酸、油胺、鄰二甲苯、 酌、聚乙二醇（PEG400 )、丙酸、丙二醇、丙二醇單甲喊、 對一甲苯、曱苯、磷酸三乙酯、三乙二醇、二甲笨磺酸、 〇 石壌、礦物油、三氯乙烯、全氣乙烯、乙酸乙酯、乙酸戊 酯、乙酸丁酯、曱醇、乙醇、異丙醇，及諸如戊醇、四氫 糠醇、己醇、辛醇等、乙二醇、丙二醇、甘油之高分子量 醇、N-曱基-2-吡咯啶酮，及其類似物。一般選擇水作為稀 釋濃縮物之載劑。 適合固體載劑包括滑石、二氧化鈦、葉蠟石黏土、矽 石、鎂鋁海泡石黏土、矽藻土（ kieselguhr )、白垄、石夕藻 土（ diatomaxeous earth)、石灰、碳酸鈣、膨潤土漂白 〇 土、棉花籽殼、小麥粉、大豆粉、浮石、木粉、胡桃殼粉、 木質素及其類似物。 多種表面活性劑宜用於該等液體及固體組成物中，尤 其彼等經設計成在施用前用載劑稀釋之組成物。該等表面 活性劑可性質上為陰離子型、陽離子型、非離子型或聚合 型且可用作乳化劑、濕潤劑、懸浮劑或用於其他目的。血 型的表面活性劑包括烷基硫酸鹽，諸如月桂基硫酸二乙醇 銨；烷基芳基磺酸鹽，諸如十二烷基苯磺酸鈣；烷基酚-伸 烷基氧化物加成產物’諸如壬基酚_Cis乙氧基化物；醇-伸 15 201036967 烷基氧化物加成產物，諸如十三醇_Ci0乙氧基化物；皂，諸 如硬脂酸鈉；烷基萘磺酸鹽，諸如二丁基萘磺酸鈉，·磺基 丁二酸二烧醋鹽，諸如二（2-乙基己基）續基丁二酸納；山梨 醇酯，諸如山梨醇油酸酯；四級胺，諸如氣化月桂基三甲 銨，脂肪酸聚乙二醇酯，諸如硬脂酸聚乙二醇酯；氧化乙 烯與氧化丙烯之嵌段共聚物；以及單烷基磷酸酯及二烷基 鱗酸醋之鹽。 農業組成物中常用之其他佐劑包括結晶抑制劑、黏度 調節劑、懸浮劑、喷霧液滴調節劑、顏料、抗氧化劑、發 /包齊丨阻光劑、相谷劑、消泡劑 '螯合劑、中和劑及緩衝 劑、腐蝕抑制劑、染料、氣味劑、展布劑、穿透助劑、微 量營養素、柔軟劑、潤滑劑、黏著劑及其類似物。 另外，進一步，其他殺生物活性成份或組成物可與本 發明之農業化學組成物組合。舉例而言，該等組成物可含 有其他殺昆蟲劑、除草劑 '殺真菌劑、殺細菌劑、殺蟎劑、 殺線蟲劑及/或植物生長調節劑，以拓寬活性範圍。 各上述調配物可製成含有殺昆蟲劑以及其他調配物 (稀釋劑、乳化劑、界面活性劑等）成份之包裝。亦可藉 由槽混方法製備調配物，其中成份係分別獲得且於生長物 之處合併。 該等調配物可藉由習知方法施用至需要控制之區域。 J而。了藉由使用動力撒粉機、掃帚及手動噴霧器及 噴霧撒粉機施用粉劑及液體組成物。亦可自飛機以粉劑或 噴霧或藉由繩芯施用（rope wick appHcati〇n)來施用調配 物。固體與液體調配物均亦可施用至待處理植物所在地之 16 201036967 土壤，使得活性成份通過根部擴散於植物。本發明之調配 物亦可用於對植物繁殖材料之拌藥應用，以提供保護二免 植物繁殖材料上之昆蟲感染以及以免土壤中存在之昆蟲。 適宜地，可藉由以殺昆蟲齊丨之液體調配物浸潰植物繁殖材 料（詳言之，種子）或將植物繁殖材料（詳言之，種子） 塗以固體調配物來將活性成份施用至待保護之植物繁殖材 料。在特殊情況下，其他類型之施用亦為可能，例如，充 當繁殖作用的植物插條或嫩枝之特殊處理。 宜在昆蟲侵襲之前施用纟發明 < 農業化學組成物及調 配物。調配物之使用比率及頻率為此項技藝中所習用之比 率及頻率且將視受昆蟲侵襲之風險而定。. 現將藉由以下非限制性實施例及圖式來描述本發明。 實施例 la.藉由熟化製備噻美索森共晶體 Ο 將力20 mg °塞美索森稱入1 5 mi小瓶中。將約丄當量 (以質量計）t 2-胺基苯并㈣添加至嚷美索森中。添加 250 μΐ乙腈且以8小時溫度循環（自室溫加熱至5代歷時* 小時且隨後再經四小時冷卻至室溫）使所得聚料熟化7天。 隨後在室溫下在真空烘箱中將樣品乾燥隔夜。 lb.藉由熟化製備噻美索森共晶體（2) 將約索森稱人小瓶中n515g2胺基笨并 !，添力:至嗟美索森中。添…乙猜且以8小時溫度猶 々自至/皿加熱至5(TC歷時4小時且隨後再經四小時冷卻 至室溫）使所得毁料熟化7 A。隨後在 中將樣品乾燥隔夜。 隹具工烘相 17 201036967 2.共晶艘之分析 藉由上文詳述之方法製備之後，棄去任何所得油狀物 及膠狀物。隨後藉由粉末Χ射線繞射對樣品進行分析。使 用實施例U及lb之方法所獲得之晶體的粉末χ:線繞射 圖分別展示於圖i及圖2中。該等粉末χ射線繞射跡線明 確顯示產物共晶體與其構成相無類似之處，表明已形成新 的固體。該等晶體之粉末χ射線繞射圖之選定峰位置的2 0值展示於表1中。 藉由DSC進-步分析共晶體。圖3為2胺基笨并嗟唾 之D S C跡線。 3·噻美索森-2-胺基苯并噻唑共晶體於水中之溶解度 ，使噻美索森（對照物）及藉由實施例lb之方法製得的 噻美索森-2 -胺基苯并喔唾共晶體在水中變成焚料隔夜且隨 後使用0.2 μηι過濾器過濾。隨後用8〇 : 2〇乙腈：〇 1 % H3p〇4 之儲備溶液將過濾後之溶液稀釋至約100 ppm。接著藉由 HPLC進行溶解度量測。測得a塞美索森於水中之溶解^為 〇.3%/〇 ( w/w)且共晶體之溶解度為〇 2料％ ( W&)，因此 顯示溶解度明顯降低。 曰儘&已參考本發明之較佳具體實例及實施例描述本發 j 本發明之範嘴並非僅限於;皮等所述具體實例。如熟 習此項技藝者將容易認識到’可在不障離本發明之精神及 ，的It況下對上述發明作出修部及修改，本發明之精神 範11係由&附申請專利範圍界定及限制。本文中所引用 之所有公開案係出於所有目的以全文引用的方式併入本文 中其引用的程度如同各個別A開案被特定地且個別地指 18 201036967 出以引用的方诖广 々汗入一般。 圖1展示（a )使用實施例1 a中所述之技術獲得之噻美 索森_2_胺基笨并噻唑共晶體、（b) 2-胺基苯并噻唑及（c) 噻美索森的粉末χ射線繞射圖。 圖2展示（a ) 2-胺基苯并噻唑、（b )使用實施例lb中 所述之技術獲得之噻美索森-2-胺基苯并噻唑共晶體及（c) 噻美索森的粉末χ射線繞射圖。 圖3展示（a) 2_胺基苯并噻唑、使用實施例lb中 所述之技術獲得之噻美索森-2-胺基苯并噻唑共晶體及（c ) 養美索森的DSC跡線。 【主要元件符號說明】 無 〇 19In addition, "crop" should be understood to include crops that have become resistant to pests and pesticides (including herbicides or herbicides) due to conventional breeding or genetic engineering methods. Tolerance to, for example, herbicides means reduced sensitivity to damage caused by specific herbicides compared to conventional crop varieties. Crops may be modified or bred to benefit, for example, HPPD inhibitors (such as mesotrione) or EPSPS inhibitors (such as glyphosate). The rate of application of the agrochemical composition of the present invention will depend on the rate to be controlled. The particular type of insect, the degree of control desired, and the timing and method of administration can be readily determined by those skilled in the art. In general, the compositions of the present invention can be applied at an application rate between 0,005 kg/ha (kg/ha) and about 1.0 kg/ha, based on the total amount of active insecticide in the composition. An application rate of between about 〇1 〇 kg/ha and about 0.5 kg/ha is preferred, and an application rate between about kg1 kg/ha and 0.2 kg/ha is particularly preferred. In fact, the agrochemical compositions comprising the eutectic of the present invention are applied as a formulation containing various adjuvants and carriers known or used in the industry. It can therefore be formulated into granules, wettable powders, emulsifiable concentrates, suspension concentrates (including oil dispersions), powders or powders, flowables, solutions, suspensions or emulsions, suspension-emulsions or controlled release ( Such as microcapsules). The agrochemical composition of the present invention can be suitably formulated into a suspension concentrate, a suspension-emulsion 戍 wet granule. Such formulations are described in more detail below and may contain as little as about 11 201036967 0.5% by weight up to about 95% by weight or more of the active ingredient in co-crystal form. The optimum amount will depend on the formulation, the application equipment and the nature of the insect to be controlled. The wettable powder is in the form of finely powdered particles which are readily dispersed in water or other liquid carriers. The particles contain active components that are retained in a solid matrix. Typical solid substrates include fuller, s earth, kaolin, vermiculite, and other wettable organic or inorganic solids. The wettable powder usually contains from about 5% to about 95% of the active ingredient and a small amount of wetting agent, dispersing agent or emulsifier. The emulsifiable concentrate is a homogeneous liquid composition which can be dispersed in water or other liquid and can be completely active. The compound is comprised of a liquid or solid emulsifier, or may also contain a liquid carrier such as diterpene, heavy aromatic naphtha, isopranone, and other non-volatile organic solvents. In use, the concentrates are dispersed in water or other liquids and are typically applied to the area to be treated by mist. The amount of active ingredient may range from about 5% to about 95% of the concentrate. The suspension concentrate is a stable suspension of fine powdered solid particles of the active compound. The solid particles may be suspended in an aqueous solution or oil (in an oil dispersion). The formulations include anti-settling agents and dispersing agents and may further comprise wetting agents for enhancing activity as well as antifoaming agents and crystal growth inhibitors. In use, the concentrates are diluted in water and are typically applied as a spray to the area to be treated. The amount of active ingredient may range from about 0.5% to about 95% of the concentrate. The granule formulation comprises sputum sputum & μ ^ ^, micro-equivalent and relatively coarse particles, and can be applied to the field of insect itch p ^ + ' aphids without dilution or dispersed, for example, prior to application. 12 201036967 The fog tank 1 ί7. Typical carriers for particle formulations include sand, , φ / ash clay, Zhenming sepiolite clay, bentonite, microcrystalline two-stone clay, . . . , perlite, carbonic acid, monument, pumice, ochre , kaolin, dolomite, cooked gypsum crumb, ground corn cob, ground peanut shell, sugar, & Tibetan • sodium, sodium sulphate, sodium citrate, sodium borate, magnesium oxide, mica, strontium, emulsified iron, Zinc oxide, titanium oxide, cerium oxide, cryolite, gypsum, sulphate, calcium sulphate and other organic or absorbing materials which can be coated with the active compound. Granule formulations for use without dilution typically contain from about 5% to about 25% active ingredient, which may include surfactants such as heavy aromatic naphtha, kerosene and other petroleum distillates, or vegetable oils; and/or Adhesives such as dextrin, glue or synthetic resin. When the granules are intended to be dispersed in a spray can before application, the active ingredient content can be increased to 80% « ', and the powder is the active ingredient and a fine powdery solid (such as talc, clay, powder (flour) acting as a dispersing agent and carrier. And other organic and inorganic free-flowing mixtures. The microcapsules are typically encapsulated in an inert porous shell of droplets or particles of the active ingredient which allows the enclosed material to escape to the surrounding environment at a controlled rate. The diameter of the droplets is typically from about 1 micron to about 50 micrometers, typically from about 50% to about 95% by weight of the microcapsules and may include a solvent in addition to the active compound. The encapsulated particles are typically sealed by a porous membrane. The liquid form method 4 y I1 biological species is preserved in the porous particles inside the particle pores. The particle + diameter is typically in the range of 1 mm to 1 cm _ and (4) is the i particle system by extrusion, cohesion or granulation Formed, or naturally occurring. Examples of materials such as hai and hai to stone, sintered clay, kaolin, Zhenming sepiolite clay, mineral and carbon particles. Shell or membrane materials including natural and synthetic rubber 13 201036967 glue, fiber Material, styrene Alkene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamines, polyureas, polyurethanes, and xanthate powders. Other formulations suitable for agrochemical applications include active ingredients in solvents. A simple solution in which the active ingredient is completely soluble at the desired concentration, such as acetone, anhydride-based naphthalene, xylene, and other organic solvents. A pressurized sprayer can also be used, in which the active ingredient is dispersed due to low boiling point. The solvent carrier is vaporized to be dispersed as a fine powder. Many of the formulations described above include wetting agents, dispersing agents or emulsifiers. Examples are alkyl and alkyl aryl sulfonates and sulfates and salts thereof, polyols; Polyethoxylated alcohols, esters, and fatty amines. When used, such agents typically comprise from 0.1% to 40% by weight of the formulation. Suitable for formulating the compositions of the present invention to the type of formulation described above. Suitable agricultural adjuvants and carriers are well known to those skilled in the art. Suitable examples of different classes are found in the non-limiting list below. Liquid carriers that can be used include water, toluene, xylene, naphtha, Oil, acetone, mercaptoethyl ketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, benzene, cyclohexane, cyclohexanol, alkyl acetate, diacetone alcohol 1,2-dipropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol rosinate, diethylene glycol butyl ether, diethylene glycol ether, diethylene glycol methyl ether , N,N-dimethylformamide, dimethyl sulphate, l4-dioxane, dipropylene glycolate, dipropylene glycol methyl ether, dipropylene glycol dipropylene glycol, dipropxitol, decyl hydrazine Bilo biting, ethyl acetate, 2-ethylhexanol, ethyl carbonate, 1,1,1-trichloroethane, 2-heptanone, α-decene, d-limonene, ethylene glycol, B Glycol butyl ether, ethylene glycol methyl ether, r-butane s, glycerin, diacetin, monoacetin, triacetin, dec 14 201036967 hexaane, hexanediol, isoamyl acetate, Isobornyl acetate, isooctane, isophorone, cumene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxy-propanol, methyl Isova , mercaptoisobutyl ketone, decyl laurate, decyl octoate, methyl oleic acid, dioxane, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate (octyl Amine acetate ), oleic acid, oleylamine, o-xylene, discretion, polyethylene glycol (PEG400), propionic acid, propylene glycol, propylene glycol monomethyl, p-toluene, toluene, triethyl phosphate, triethylene glycol , dimethyl sulfonate, vermiculite, mineral oil, trichloroethylene, total ethylene, ethyl acetate, amyl acetate, butyl acetate, decyl alcohol, ethanol, isopropanol, and such as pentanol, tetrahydrogen Sterols, hexanol, octanol, etc., ethylene glycol, propylene glycol, high molecular weight alcohols of glycerol, N-mercapto-2-pyrrolidone, and the like. Water is generally selected as the carrier for the dilute concentrate. Suitable solid carriers include talc, titanium dioxide, pyrophyllite clay, vermiculite, magnesium aluminum sepiolite clay, kieselguhr, white ridge, diatomaxeous earth, lime, calcium carbonate, bentonite bleaching Bauxite, cotton seed hulls, wheat flour, soy flour, pumice, wood flour, walnut shell powder, lignin and the like. A wide variety of surfactants are suitable for use in such liquid and solid compositions, especially those designed to be diluted with a carrier prior to application. These surfactants may be anionic, cationic, nonionic or polymeric in nature and may be used as emulsifiers, wetting agents, suspending agents or for other purposes. Blood group surfactants include alkyl sulfates such as diethanol ammonium lauryl sulfate; alkyl aryl sulfonates such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products' Such as nonylphenol_Cis ethoxylate; alcohol-extension 15 201036967 alkyl oxide addition product, such as tridecyl alcohol _Ci0 ethoxylate; soap, such as sodium stearate; alkylnaphthalene sulfonate, Such as sodium dibutylnaphthalenesulfonate, sulfosuccinate diacetate, such as sodium di(2-ethylhexyl) succinate; sorbitol, such as sorbitol oleate; quaternary amine , such as gasified lauryl trimethylammonium, fatty acid polyethylene glycol esters, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and monoalkyl phosphates and dialkyl citrate Salt. Other adjuvants commonly used in agricultural compositions include crystallization inhibitors, viscosity modifiers, suspending agents, spray droplet regulators, pigments, antioxidants, hair/packaging agents, phase granules, defoamers' Chelating agents, neutralizing agents and buffers, corrosion inhibitors, dyes, odorants, spreaders, penetration aids, micronutrients, softeners, lubricants, adhesives and the like. Further, further, other biocidal active ingredients or compositions may be combined with the agrochemical compositions of the present invention. For example, the compositions may contain other insecticides, herbicides "fungicides, bactericides, acaricides, nematicides and/or plant growth regulators" to broaden the range of activity. Each of the above formulations may be packaged with an insecticide and other ingredients (diluent, emulsifier, surfactant, etc.). Formulations can also be prepared by tank mixing methods in which the ingredients are separately obtained and combined at the growth site. The formulations can be applied to the area to be controlled by conventional methods. J and. The powder and liquid compositions are applied by using a power duster, a broom and a hand sprayer, and a spray duster. Formulations may also be applied from the aircraft by powder or spray or by rope wick appHcati(R). Both solid and liquid formulations can also be applied to the soil of the 16 201036967 where the plant is to be treated so that the active ingredient diffuses through the roots to the plant. The formulations of the present invention can also be used in the dosing of plant propagation materials to provide protection against insect infections on plant-free material and to prevent the presence of insects in the soil. Suitably, the active ingredient can be applied by impregnating the plant propagation material (in particular, the seed) with an insecticidal liquid formulation or by applying the plant propagation material (in particular, the seed) to a solid formulation. Plant propagation material to be protected. Other types of application are also possible in special cases, for example, special treatments for plant cuttings or shoots that are effective for reproduction. It is preferred to apply the invention <agrochemical composition and formulation prior to insect attack. The ratio and frequency of use of the formulation are the ratios and frequencies conventionally used in the art and will depend on the risk of attack by the insect. The invention will now be described by the following non-limiting examples and drawings. Example la. Preparation of thimescen co-crystals by aging Ο A force of 20 mg ° Semensson was weighed into a 15 5 vial. About about the equivalent weight (by mass) of t2-aminobenzobenzoic acid (tetra) was added to imemisone. The resulting polymer was aged for 7 days by adding 250 μM acetonitrile and circulating at 8 hours (from room temperature to 5 generations for *hours and then four hours to room temperature). The samples were then dried overnight in a vacuum oven at room temperature. Lb. Preparation of thimetsone co-crystals by aging (2) Josson said that the n515g2 amine group in the vial is stupid! Adding force: to 嗟美索森. Add... B guess and cure the resulting residue by 7 A at a temperature of 8 hours until the dish is heated to 5 (TC lasts for 4 hours and then cooled to room temperature over four hours). The samples were then dried overnight in the middle.隹Working bake phase 17 201036967 2. Analysis of eutectic vessels After preparation by the method detailed above, any resulting oils and gums are discarded. The sample was then analyzed by powder enthalpy diffraction. The powder enthalpy:line diffraction patterns of the crystals obtained by the methods of Examples U and lb are shown in Figures i and 2, respectively. These powder enthalpy diffraction traces clearly show that the product eutectic has no resemblance to its constituent phase, indicating that a new solid has formed. The 20 values of the selected peak positions of the powder χ ray diffraction patterns of the crystals are shown in Table 1. The eutectic was analyzed by DSC. Figure 3 is a D S C trace of a 2-amino stupid. 3. The solubility of the thimetsone-2-aminobenzothiazole co-crystal in water, thimesen (control) and the thimesen-2 -amine group prepared by the method of Example lb The benzopyrene eutectic was turned into a fuel in water overnight and then filtered using a 0.2 μηι filter. The filtered solution was then diluted to about 100 ppm with a stock solution of 8 Torr: 2 acetonitrile: 〇 1 % H3p 〇4. The dissolution metric was then performed by HPLC. The dissolution of acerexin in water was measured as 〇.3%/〇 (w/w) and the solubility of the eutectic was 〇2% (W&), thus indicating a significant decrease in solubility. DETAILED DESCRIPTION OF THE INVENTION The present invention has been described with reference to preferred embodiments and examples of the present invention. The present invention is not limited to the specific examples described herein. It will be readily appreciated by those skilled in the art that the invention may be modified and modified without departing from the spirit and scope of the invention, and the spirit of the invention is defined by & And restrictions. All publications cited herein are hereby incorporated by reference in their entirety for all of their entireties in the extent of the disclosures in the the the the the the . Figure 1 shows (a) a thimetsone 2 -amino benzothiazole cocrystal obtained using the technique described in Example 1 a, (b) 2-aminobenzothiazole, and (c) thiram Mori's powder χ ray diffraction pattern. Figure 2 shows (a) 2-aminobenzothiazole, (b) thimesen-2-aminobenzothiazole co-crystal obtained using the technique described in Example lb, and (c) thimetreson Powder χ ray diffraction pattern. Figure 3 shows (a) 2-aminobenzothiazole, thiamethoxol-2-aminobenzothiazole co-crystal obtained using the technique described in Example lb, and (c) DSC trace of Yangsson line. [Main component symbol description] None 〇 19