如本申請案中所用且除非另外指示，否則術語「除草劑」係指經生產、出售或用於田間以殺死或以其他方式抑制不需要之植物(例如(但不限於)有害或令人煩擾之雜草、闊葉植物、禾草及莎草)並可用於作物保護、大廈保護或草皮保護之組成混合物。術語「除草劑」包括最終使用之除草產品。此組合物可係純淨化合物、化學化合物之溶液、化學化合物之混合物、乳液、懸浮液、固-液混合物或液-液混合物。術語「除草劑」亦指經過商業渠道自製造商傳遞至終端使用者之產品，該終端使用者可將除草劑照所出售者或將其與其他賦形劑混合而施加至受影響之田間。 術語「雜草」意指並包括生長在不需要其處之任何植物，其包括自生作物植物或殺蟲劑抗性植物。 當關於除草劑使用時術語「有效」或「除草有效量」意指對不需要之植物生長產生可觀測到之除草效應所需之量，該等效應包括壞死、死亡、生長抑制、繁殖抑制、增殖抑制及去除、破壞或以其他方式減少不需要植物之出現及活性之效應中之一或多者。 術語「除草活性成份」意指在除草劑中導致除草劑防止、破壞、排斥或減少任何雜草之活性成份。作為非除草活性成份之除草劑之其他成份係輔助形成、儲存除草活性成份或將其遞送至靶標之賦形劑。 術語「除草組合物」之定義係指除草劑及此外包含除草活性成份之任何組合物。此組合物可係溶液或混合物。另外，術語「除草組合物」之定義亦指意欲用於製造中之產品或意欲調配或重新包裝成其他農用產品之任何產品。 如本文中所用術語「標記使用率」或「登記使用率」或「標記施加率」或「登記施加率」在應用於除草組合物時係指施加至含有作物及/或雜草之田間之比率，該比率如環境保護局(Environmental Protection Agency，EPA)規定中所反映已由農用化學行業確立適於控制所指雜草物種。登記使用率反映在適當標記中之商用調配物包裝上。 諸如PPO除草劑之速效性除草劑在萌後施加時對許多作物不安全。舉例而言，已知唑酮草酯會對禾榖引起損害。除草劑嗪草酸甲酯由於其對禾榖不安全而未在禾榖上標記。在此文件中，本發明者已證明安全劑/安全劑混合物之共同施加向禾榖提供安全性而免於該等除草劑之損害。另外，據信使用安全劑組合物與該等除草劑可擴大其對禾榖類作物之有用性。 在某些實施例中，可分開施加除草劑及安全劑。在其他實施例中，可施加包含除草劑及安全劑之混合物。 本發明之一個態樣係關於選擇性控制作物中之雜草之方法，其包含將除草有效量之包含速效性除草劑之除草組合物及有效量之安全劑組合物施加至作物雜草。 在實施例中，安全劑組合物包含一或多種選自由以下組成之群之安全劑：解草酯、吡唑解草酯、解草嗪、二氯丙烯胺、雙苯噁唑酸、環丙磺醯胺、解草啶、解草唑、氟草肟、萘二甲酸酐、解草安腈、解草腈、解草安、解草噁唑、殺草隆、苄草隆、哌草丹及增效磷。 在實施例中，速效性除草劑包含原紫質原氧化酶(PPO)抑制物、敵草快、巴拉刈、草銨膦及雙丙胺膦。 該等PPO抑制物之實例包括(但不限於)三氟羧草醚(acifluorfen)、三氟羧草醚鈉鹽(acifluorfen-sodium)、唑啶草酮(azafenidin)、治草醚(bifenox)、氟丙嘧草酯(butafenacil)、甲氧除草醚(chlomethoxyfen)、草枯醚(chlornitrofen)、氯氟草醚乙酯(ethoxyfen-ethyl)、三氟硝草醚(fluorodifen)、乙羧氟草醚(fluoroglycofen-ethyl)、氟除草醚(fluoronitrofen)、氟磺胺草醚(fomesafen)、呋氧草醚(furyloxyfen)、氟硝磺醯胺(halosafen)、乳氟禾草靈(lactofen)、除草醚(nitrofen)、三氟甲草醚(nitrofluorfen)、乙氧氟草醚(oxyfluorfen)、氟烯草酸(flumiclorac-pentyl)、丙炔氟草胺(flumioxazine)、氟唑草胺(profluazol)、雙唑草腈(pyrazogyl)、丙炔噁草酮(oxadiargyl)、噁草酮(oxadiazon)、環戊噁草酮(pentoxazone)、異丙吡草酯(fluazolate)、吡草醚(pyraflufen-ethyl)、雙苯嘧草酮(benzfendizone)、氟丙嘧草酯(butafenacil)、吲哚酮草酯(cinidon-ethyl)、炔草胺(flumipropyn)、夫波帕希(flupropacil)、嗪草酸甲酯(fluthiacet-methyl)、噻二唑草胺(thidiazimin)、唑啶草酮、唑草酮、唑酮草酯、甲磺草胺(sulfentrazone)、苯嘧磺草胺(saflufenacil)、氟噠嗪草酯(flufenpyr-ethyl)、ET-751、JV485、吡氯草胺(nipyraclofen)或其兩種或更多種之混合物。 本發明之另一態樣係關於選擇性控制作物中之雜草之方法，其包含將除草有效量之包含原紫質原氧化酶(PPO)抑制物之除草組合物施加至作物雜草並施加有效量之包含安全劑組合物之組合物。 本發明之另一態樣係關於選擇性控制作物中之雜草之方法，其包含將包含原紫質原氧化酶(PPO)抑制物及安全劑組合物之調配物施加至作物雜草。 在實施例中，安全劑可選自由以下組成之群：解草酯、吡唑解草酯、殺草隆、枯草酮、哌草丹、解草啶、解草唑、雙苯噁唑酸、環丙磺醯胺、解草嗪、二氯丙烯胺、解草噁唑、解草安、解草腈、解草安腈、萘二甲酸酐、增效磷、氟草肟及其混合物。在實施例中，安全劑較佳係解草酯、吡唑解草酯或其混合物。 在實施例中，PPO抑制物可選自由以下組成之群：唑草酮、唑酮草酯、甲磺草胺、嗪草酸甲酯、苯嘧磺草胺及其兩種或更多種之混合物。在實施例中，PPO抑制物較佳係唑酮草酯或嗪草酸甲酯。 在另一實施例中，原紫質原氧化酶(PPO)抑制物係選自二苯醚、噁二唑、環狀醯亞胺或吡唑。該等PPO種類之實例包括(但不限於)三氟羧草醚、三氟羧草醚鈉鹽、唑啶草酮、治草醚、氟丙嘧草酯、甲氧除草醚、草枯醚、氯氟草醚乙酯、三氟硝草醚、乙羧氟草醚、氟除草醚、氟磺胺草醚、呋氧草醚、氟硝磺醯胺、乳氟禾草靈、除草醚、三氟甲草醚、乙氧氟草醚、氟烯草酸、丙炔氟草胺、氟唑草胺、雙唑草腈、丙炔噁草酮、噁草酮、環戊噁草酮、異丙吡草酯、吡草醚、雙苯嘧草酮、氟丙嘧草酯、吲哚酮草酯、炔草胺、夫波帕希、嗪草酸甲酯、噻二唑草胺、唑啶草酮、唑草酮、唑酮草酯、甲磺草胺、苯嘧磺草胺、氟噠嗪草酯、ET-751、JV485、吡氯草胺或其兩種或更多種之混合物。 本揭示內容之除草組合物可呈任何習用農用形式，例如，呈雙組份或呈即用型調配物形式或呈桶混劑之形式。另外，活性化合物可以任何適當調配物類型供應(分開或預混合)，例如乳液濃縮物(EC)、懸浮液濃縮物(SC)、濃懸乳液(SE)、膠囊懸浮液(CS)、水可分散粒劑(WG)、可乳化粒劑(EG)、油包水乳液(EO)、水包油乳液(EW)、微乳液(ME)、油分散液(OD)、油懸劑(OF)、油溶性液體(OL)、可溶性濃縮物(SL)、超低容量懸浮液(SU)、超低容量液體(UL)、可分散性濃縮物(DC)、可濕粉末(WP)、CS及EW (ZW)之混合非均質調配物或任何其他技術上可行之調配物與農業上可接受之佐劑之組合。對於桶混合，在施加之前將PPO抑制物及安全劑之商用調配物在桶中以適當比率組合以提供活性成份之目標重量比。在某些實施例中，本揭示內容之除草組合物係桶混劑。在其他實施例中，本揭示內容之除草組合物係作為預混合可乳化濃縮物(EC)供應。 組合物或經桶混合單獨調配之活性成份之施加率將根據當時條件而變化，例如目標雜草、侵襲程度、天氣條件、土壤條件、作物物種、施加模式及施加時間。包含PPO抑制物及/或安全劑之組合物可以噴霧形式施加，例如水可分散濃縮物、可濕粉末或水可分散水可分散粒劑。 在實施例中，諸如除草劑或安全劑之每種活性成份(「ai」)之施加率可在作物之間變化。在實施例中，對於不同PPO抑制物除草劑可使用不同範圍之施加率。在實施例中，除草劑之施加率係約5 g活性成份/公頃(g ai/ha)至約420 g ai/ha。在實施例中，安全劑之施加率係約5 g ai/ha至約350 g ai/ha或約10 g ai/ha至約300 g ai/ha。在實施例中，安全劑與除草劑之間之比率以重量計係約10:1 (安全劑/除草劑)至約1:30 (安全劑/除草劑)。 在一個實施例中，本揭示內容闡述包含速效性除草劑及安全劑組合物之農用調配物或桶混劑。速效性除草劑可包括PPO。在實施例中，PPO抑制物係選自唑草酮、唑酮草酯、甲磺草胺、嗪草酸甲酯、苯嘧磺草胺或其兩種或更多種之混合物。在實施例中，PPO抑制物較佳係唑酮草酯或嗪草酸甲酯。在實施例中，安全劑包含解草酯、吡唑解草酯或其混合物。在實施例中，安全劑組合物及速效性除草劑係以重量計約10:1 (安全劑/除草劑)至約1:30 (安全劑/除草劑)之間之比率存在。在實施例中，該等可係在施加時經桶混合之商用調配物或呈適宜預混合調配物之形式。適宜預混合調配物包括(但不限於)懸浮液濃縮物(SC)及可乳化濃縮物(EC)。 在實施例中，作物可選自由以下組成之群：經遺傳修飾及未經修飾之草皮、小麥、大麥、玉米、稻、高粱、燕麥及黑小麥。 在實施例中，易感雜草物種可包括(但不限於)紅根藜、長芒莧、普通水麻、檾麻、牽牛花屬、龍葵屬、普通藜、野生薺菜、芹葉牻牛兒苗、敗醬草、普通錦葵、綠穗莧、匍匐藜、刺莧、大戟番荔枝、八仙草、蒼耳子、粟米草、鱧腸草、蔓陀羅、地膚草、燈籠草、多刺萵苣、水蒜芥籽、薺菜、俄國薊、油莎草、香附子、普通豚草、小白酒草、巨豚草、普通繁縷、耳菜草、粗毛牛膝菊、美國雛菊、火炭母草、洋甘菊、野生一品紅、普通馬齒莧、刺黃花穩、大馬唐草、滑葉馬唐草、牛筋草、果樹草、秋黍、茅草、大畫眉草、鬼針草、田旋花、野生蕎麥、蒲公英、匍匐紫菀、芥菜屬、加拿大薊、母豬薊、年生薊及刺薊。 本揭示內容之組合物及桶混劑可額外包含其他作物保護劑，其包括(但不限於)殺真菌劑、殺蟲劑、殺線蟲劑、植物生長調節劑、除PPO除草劑外之除草劑、肥料及其混合物。 在實施例中，雜草之控制在處理後有效至少約14天、較佳處理後至少約60天。 本揭示內容之組合物亦可包括防腐劑。適宜防腐劑包括(但不限於)苯甲酸C12
至C15
烷基酯、對羥基苯甲酸烷基酯、蘆薈萃取物、抗壞血酸、殺藻胺(benzalkonium chloride)、苯甲酸、C9
至C15
醇之苯甲酸酯、二丁基羥基甲苯、丁基羥基甲氧苯、第三丁基氫醌、蓖麻油、鯨蠟醇、氯甲酚、檸檬酸、可可脂、椰子油、雙烷基咪唑脲、己二酸二異丙酯、二甲基聚矽氧烷、DMDM乙內醯脲、乙醇、乙二胺四乙酸、脂肪酸、脂肪醇、十六烷基醇、羥基苯甲酸酯、丁基胺基甲酸碘代丙炔酯、異壬酸異壬酯、荷荷芭油、綿羊油、礦物油、油酸、橄欖油、對羥苯甲酸酯、聚醚、聚氧丙烯丁基醚、鯨蠟醇聚氧丙烯醚、山梨酸鉀、沒食子酸丙酯、聚矽氧油、丙酸鈉、苯甲酸鈉、亞硫酸氫鈉、山梨酸、硬脂脂肪酸、二氧化硫、維生素E、維生素E乙酸酯及其衍生物、酯、鹽及混合物。較佳防腐劑包括鄰苯基苯酚鈉、5-氯-2-甲基-4-異噻唑啉-3-酮、2-甲基-4-異噻唑啉-3-酮及1,2-苯并噻唑啉-3-酮。 本文件揭示為控制作物中之作物雜草提供效能之組合物及方法。現已證明添加諸如解草酯或吡唑解草酯之安全劑或諸如解草酯加吡唑解草酯之安全劑混合物可降低來自除草劑(例如，唑酮草酯及嗪草酸甲酯)之作物損害而不影響該等除草劑之效能。據信，安全劑/安全劑混合物與PPO除草劑之共同施加將容許除草劑對登記作物之較高施加率並擴大其對未經登記作物之使用。 以下實例僅用於說明本發明而不應理解為以任一方式限制本發明之範疇，此乃因由所揭示之本發明涵蓋之進一步修改將為熟習此項技術者所明瞭。將所有此等修改皆視為在如本說明書及申請專利範圍中所揭示之本發明之範疇內。 實例 實例1材料及方法
為研究一或兩種安全劑對作物之安全效應，將唑酮草酯以25 g ai/ha或50 g ai/ha或將嗪草酸甲酯以5.6 g ai/ha*或11.2 g ai/ha*與解草酯加吡唑解草酯、解草酯加萘二甲酸酐、吡唑解草酯加萘二甲酸酐、解草酯、吡唑解草酯或萘二甲酸酐組合施加。將安全劑解草酯、吡唑解草酯及萘二甲酸酐分別以6.6 g ai/ha、27.2 g ai/ha及74.1 g ai/ha施加。其他處理包括單獨施加唑酮草酯或嗪草酸甲酯。在所有唑酮草酯及嗪草酸甲酯處理中添加0.25% (v/v)之非離子型表面活性劑。種植10天後將唑酮草酯及嗪草酸甲酯處理施加至作物。使用metro-mix在3’’塑膠盆中種植小麥及雜草。處理係使用40 PSI之TeeJet 8001E噴嘴在30 GPA下使用壓縮氣動履帶噴霧室施加。在95%信賴區間下使用Minitab統計軟體分析數據。在95%信賴區間下，共用相同字母之小麥損害百分比之每個分級區間之含義無顯著差異。 在嗪草酸甲酯研究中不包括*萘二甲酸酐。 作物損害係藉由使用視覺分級方法評價。此方法係基於0%-100%之量表，其中0%意指無損害且100%意指植物完全死亡。表1顯示可用於評價雜草控制或作物受損之線性分級量表。(修改自Frans等人，1986)。認為小於或等於10%之作物損害在商業上可接受。小於或等於20%之損害分級指示作物不會顯著受到不利影響且會快速並完全恢復。商業上可接受之作物損害之程度在作物之間不同。任何大於20%之損害程度通常在商業上不可接受。 在本發明研究中，觀察到在安全劑/除草劑處理下作物損害自商業上不可接受至商業上可接受程度之降低。 表1
實例2 在溫室研究中，研究安全劑(解草酯或吡唑解草酯)及安全劑混合物(解草酯加吡唑解草酯)對小麥之安全效應。亦研究在安全劑或安全劑混合物存在下PPO抑制物除草劑之效能。為研究安全劑或安全劑混合物之安全效應，施加7.5% w/w之解草酯及3.39% w/w之吡唑解草酯與除草劑。以25 g ai/ha或50 g ai/ha施加唑酮草酯；以5.6 g ai/ha或11.2 g ai/ha施加嗪草酸甲酯。安全劑係以以下比率施加：解草酯為6.61 g ai/ha且吡唑解草酯為27 g ai/ha。所有處理(單獨、桶混合、預混合)皆係在作物苗期(種植後10天)施加。唑酮草酯或嗪草酸甲酯係單獨或與安全劑或安全劑混合物組合施加。 表2 當施加唑酮草酯與安全劑之不同組合時之小麥損害百分比(使用小麥物種「Yellowstone」)
在95%信賴區間下，共用相同字母之小麥損害百分比之每個分級區間之含義無顯著差異。 小麥損害係藉由使用上述視覺分級方法評價。小麥損害百分比係基於由PPO抑制物所致之小麥葉子之青銅化(bronzing)、黃化及壞死而分級。該等係PPO抑制物對敏感性植物之典型症狀(青銅化、黃化及壞死)。 在所有研究中，將處理與唑酮草酯單獨處理比較。此表及其他表中之數據指示在添加一或多種安全劑下對小麥之損害程度降低。舉例而言，在3 DAT (處理後之天數)時，與施加唑酮草酯與安全劑(例如，解草酯+吡唑解草酯)對小麥之損害小於或等於10%相比，以25 g ai/ha施加唑酮草酯係34%。 在3 DAT時，不管唑酮草酯比率如何，在安全劑存在下小麥損害低於或等於12%，只是在單獨萘二甲酸酐下損害大於25%。單獨唑酮草酯在25 g及50 g下分別引起34%及43%之損害(表2及表3)。 表3 當施加唑酮草酯與安全劑之不同組合時之小麥損害百分比(使用小麥物種「Yellowstone」)
在95%信賴區間下，共用相同字母之小麥損害百分比之每個分級區間之含義無顯著差異。 實例3 表4 當萌後10天施加唑酮草酯與單一安全劑或兩種安全劑時對小麥品種「Jagger」及「Yellowstone」之損害百分比
在95%信賴區間下，共用相同字母之小麥損害百分比之每個分級區間之含義無顯著差異。 所顯示之結果證明不管唑酮草酯比率及分級區間(3 DAT及7 DAT)如何，在解草酯加吡唑解草酯或單獨解草酯之存在下對兩種品種(Jagger及Yellowstone)之小麥損害皆係13%或更低(表4)。 在唑酮草酯+解草酯之預混合物下觀察到相似結果。施加50 g呈桶混劑或預混合物形式之吡唑解草酯及唑酮草酯對兩個品種皆引起大於20% 之損害(表4)。在25 g或50 g唑酮草酯而無安全劑下對兩個品種之損害分別＞35%或＞40% (表4)。 為便於參考，藉由與如上文所述及在下文中重現之0%至100%分級系統相似之方法測定雜草控制百分比。相同雜草控制分級系統亦可參見(例如) 「Research Methods in Weed Science」，第2版，B. Truelove編輯；Southern Weed Science Society
；Auburn University, Auburn, Ala., 1977。 表5
在7 DAT時，在所有處理下對檾麻及牽牛花之控制皆係100% (表6)。 表6 當萌後10天施加唑酮草酯與單一安全劑或兩種安全劑時之雜草控制百分比
在95%信賴區間下，共用相同字母之雜草控制百分比之每個分級區間之含義無顯著差異。 實例4 表7 當嗪草酸甲酯(F-M)與安全劑解草酯(C-M)或吡唑解草酯(M-D)以桶混劑形式組合或單獨施加時之小麥損害百分比
在表7中所顯示之兩個測試(1及2)中，單獨施加之嗪草酸甲酯在兩個比率下皆對小麥之Yellowstone品種損害(≥ 10%)，當單獨以5.6 g ai/ha施加嗪草酸甲酯時，Jagger小麥安全(≤ 10%損害)。在測試1中，在14 DAT時，當在嗪草酸甲酯與任一安全劑單獨或組合施加時，Yellowstone (1)及Jagger安全。在測試1中，在所有情形中皆控制檾麻及牽牛花(數據未顯示)。在測試2中，當以桶混劑形式施加5.6 g或11.2 g嗪草酸甲酯與解草酯加吡唑解草酯時，在14 DAT時Yellowstone (2)安全。在14 DAT時，5.6 g嗪草酸甲酯與任一安全劑對Yellowstone安全。 在本發明之特徵或態樣係按照馬庫什組(Markush group)或替代之其他分組闡述時，熟習此項技術者將認識到，本發明亦因此按照該馬庫什組或其他組之任何個別成員或成員之亞組來闡述。 除非指示相反之情形，否則本文中所述所有數字範圍包括範圍之所有組合及子組合及其中所涵蓋之特定整數。此等範圍亦在所述本發明之範疇內。 儘管本發明已參照具體實施例經闡述，但應理解，該等實施例僅說明本發明之原理及應用。因此，應理解，可在不背離如由以下申請專利範圍所界定之本發明之精神及範疇之情況下對說明性實施例進行眾多修改並可設計出其他配置。As used in this application and unless otherwise indicated, the term "herbicide" refers to a plant that is produced, sold, or used in the field to kill or otherwise inhibit unwanted plants (eg, but not limited to, harmful or Annoying weeds, broadleaf plants, grasses and sedges) and can be used as a mixture of crop protection, building protection or turf protection. The term "herbicide" includes the herbicidal product that is ultimately used. The composition may be a neat compound, a solution of a chemical compound, a mixture of chemical compounds, an emulsion, a suspension, a solid-liquid mixture or a liquid-liquid mixture. The term "herbicide" also refers to a product that is passed from the manufacturer to the end user through a commercial channel, and the end user can apply the herbicide to the affected field by mixing it with other excipients. The term "weed" means and includes any plant that grows where it is not needed, including authigenic crop plants or insecticide resistant plants. When used in relation to a herbicide, the term "effective" or "herbicidally effective amount" means the amount required to produce an observable herbicidal effect on unwanted plant growth, including necrosis, death, growth inhibition, reproduction inhibition, Proliferation inhibits and removes, destroys, or otherwise reduces one or more of the effects of unwanted plant appearance and activity. The term "herbicidal active ingredient" means an active ingredient which causes a herbicide to prevent, destroy, repel or reduce any weeds in a herbicide. Other ingredients which are herbicides other than herbicidal active ingredients are those which aid in the formation, storage or delivery of the herbicidal active ingredient to the target. The term "herbicidal composition" is defined to mean a herbicide and any composition further comprising a herbicidally active ingredient. This composition can be a solution or a mixture. In addition, the definition of the term "herbicidal composition" also refers to any product intended for use in the manufacture of a product or intended to be formulated or repackaged into other agricultural products. As used herein, the terms "marking usage rate" or "registration usage rate" or "marking application rate" or "registration application rate" when applied to a herbicidal composition refer to the ratio applied to fields containing crops and/or weeds. This ratio, as reflected in the Environmental Protection Agency (EPA) regulations, has been established by the agrochemical industry to control the weed species referred to. The registration usage rate is reflected on the commercial formulation package in the appropriate label. Fast-acting herbicides such as PPO herbicides are not safe for many crops when applied post-emergence. For example, oxazolone is known to cause damage to the pupa. The herbicide methyl oxalate is not labeled on the grass because it is unsafe for the grass. In this document, the inventors have demonstrated that the co-application of a safener/safener mixture provides safety to the weeds from damage by such herbicides. In addition, it is believed that the use of safener compositions with such herbicides can increase their usefulness to grass crops. In certain embodiments, the herbicide and safener can be applied separately. In other embodiments, a mixture comprising a herbicide and a safener can be applied. One aspect of the invention relates to a method of selectively controlling weeds in a crop comprising applying a herbicidally effective amount of a herbicidal composition comprising a quick-acting herbicide and an effective amount of a safener composition to the crop weed. In an embodiment, the safener composition comprises one or more safeners selected from the group consisting of: oxalate, pyrazolium, oxazin, dichloropropenylamine, dibenzoxazole, cyclopropane Sulfonamide, chlorpyrifos, oxazolidine, flufenacetin, naphthalic anhydride, oxalic acid nitrile, oxalic acid, chlorpyrifos, oxazolidine, chlorpyrifos, benzalkon, and piperacine And synergistic phosphorus. In an embodiment, the fast-acting herbicide comprises protopantinogen oxidase (PPO) inhibitor, diquat, paraben, glufosinate, and dipropylphosphine. Examples of such PPO inhibitors include, but are not limited to, acifluorfen, acifluorfen-sodium, azafenidin, bifenox, Butafenacil, chlomethoxyfen, chlornitrofen, ethoxyfen-ethyl, fluorodifen, flufenacetate (fluoroglycofen-ethyl), fluoronitrofen, fomesafen, furyloxyfen, halosafen, lactofen, herbicide ether Nitrofen), nitrofluorfen, oxyfluorfen, flumiclorac-pentyl, flumioxazine, profluazol, oxalox Pyrazogyl, oxadiargyl, oxadiazon, pentoxazone, fluazolate, pyraflufen-ethyl, diphenyl Benzfendizone, butafenacil, cinidon-ethyl, flumipropyn, fubopahi (flupropacil), fluthiacet-methyl, thiadiazimin, oxazolidine, oxazolone, oxazolone, sulfentrazone, saflufenazone (saflufenacil), flufenpyr-ethyl, ET-751, JV485, nipyraclofen or a mixture of two or more thereof. Another aspect of the invention relates to a method of selectively controlling weeds in a crop comprising applying a herbicidally effective amount of a herbicidal composition comprising a protophonoplast oxidase (PPO) inhibitor to crop weeds and applying An effective amount of a composition comprising a safener composition. Another aspect of the invention is directed to a method of selectively controlling weeds in a crop comprising applying a formulation comprising a propurinogen oxidase (PPO) inhibitor and a safener composition to crop weeds. In an embodiment, the safener may be selected from the group consisting of oxalate, pyrazolamide, chlorpyrifos, subtilisone, piperidin, chlorpyrifos, oxazolidine, dibenzoxazole, Cyclopropyl sulfonamide, oxacillin, dichloropropenylamine, oxazolidine, chlorpyrifos, oxalic acid, oxalic acid, naphthalic anhydride, synergistic phosphorus, flufenic acid and mixtures thereof. In an embodiment, the safener is preferably a herbicide, pyrazolam or a mixture thereof. In an embodiment, the PPO inhibitor may be selected from the group consisting of oxazinone, oxazolone, mesalamine, methyl oxazalamide, saflufenacil, and mixtures of two or more thereof. . In an embodiment, the PPO inhibitor is preferably oxazolone or methyl oxalate. In another embodiment, the propurinogen oxidase (PPO) inhibitor is selected from the group consisting of diphenyl ether, oxadiazole, cyclic quinone imine or pyrazole. Examples of such PPO species include, but are not limited to, acifluorfen, acifluorfen sodium, oxazolidin, herbicide, flufenic acid, methoxy herbicide, oxalic acid ether, Chlorfenamate, triflurane, flufenacetate, flufenic acid, flufenazone, furoxyl, flufenamide, flufenacil, herbicidal ether, trifluoro A herb, oxyfluorfen, flumethacic acid, propifluramide, fluoxetamine, oxazolidine, propargyl oxaloxone, oxadiazon, cyclopentazone, isopropylpyrazine Ester, pyriproxyfen, dipyrimazone, flumethicone, oxazolidine, ethinamide, fupoxil, methyl oxazinamide, thiadiazolamide, oxazinone, azole Oxalone, oxazolone, mesoxalam, saflufenacil, fluoxazine, ET-751, JV485, chlorhexidine or a mixture of two or more thereof. The herbicidal compositions of the present disclosure may be in any conventional agricultural form, for example, in the form of a two-component or ready-to-use formulation or in the form of a tank mix. In addition, the active compound may be supplied (separate or premixed) in any suitable formulation, such as emulsion concentrate (EC), suspension concentrate (SC), concentrated emulsion (SE), capsule suspension (CS), water. Dispersible granules (WG), emulsifiable granules (EG), water-in-oil emulsions (EO), oil-in-water emulsions (EW), microemulsions (ME), oil dispersions (OD), oil suspensions (OF) , oil soluble liquid (OL), soluble concentrate (SL), ultra low volume suspension (SU), ultra low volume liquid (UL), dispersible concentrate (DC), wettable powder (WP), CS and A combination of EW (ZW) mixed heterogeneous formulations or any other technically feasible formulation with an agriculturally acceptable adjuvant. For barrel mixing, commercial formulations of PPO inhibitors and safeners are combined in barrels at appropriate ratios to provide a target weight ratio of active ingredients prior to application. In certain embodiments, the herbicidal compositions of the present disclosure are tank mixes. In other embodiments, the herbicidal compositions of the present disclosure are supplied as a premixed emulsifiable concentrate (EC). The rate at which the composition or the active ingredient is separately formulated in a barrel mix will vary depending on the conditions at the time, such as target weeds, degree of attack, weather conditions, soil conditions, crop species, application mode, and application time. Compositions comprising PPO inhibitors and/or safeners can be applied in the form of a spray, such as a water dispersible concentrate, a wettable powder or a water dispersible water dispersible granule. In embodiments, the rate of application of each active ingredient ("ai"), such as a herbicide or safener, can vary from crop to crop. In embodiments, different ranges of application rates may be used for different PPO inhibitor herbicides. In an embodiment, the herbicide application rate is from about 5 g active ingredient per hectare (g ai/ha) to about 420 g ai/ha. In an embodiment, the rate of application of the safener is from about 5 g ai/ha to about 350 g ai/ha or from about 10 g ai/ha to about 300 g ai/ha. In the examples, the ratio between safener and herbicide is from about 10:1 (safener/herbicide) to about 1:30 (safener/herbicide) by weight. In one embodiment, the disclosure sets forth an agricultural formulation or tank mix comprising a quick-acting herbicide and a safener composition. Quick-acting herbicides can include PPO. In an embodiment, the PPO inhibitor is selected from the group consisting of oxazinone, oxazolone, mesalamine, methyl oxazalacetate, saflufenacil, or a mixture of two or more thereof. In an embodiment, the PPO inhibitor is preferably oxazolone or methyl oxalate. In an embodiment, the safener comprises oxalate, pyrazolium or a mixture thereof. In the examples, the safener composition and the quick-acting herbicide are present in a ratio of from about 10:1 (safener/herbicide) to about 1:30 (safener/herbicide) by weight. In embodiments, the may be in the form of a commercial formulation that is mixed in a barrel upon application or in a suitable premixed formulation. Suitable premix formulations include, but are not limited to, suspension concentrates (SC) and emulsifiable concentrates (EC). In an embodiment, the crop may be selected from the group consisting of genetically modified and unmodified turf, wheat, barley, corn, rice, sorghum, oats, and triticale. In an embodiment, the susceptible weed species may include, but is not limited to, red root mites, long awns, common marijuana, ramie, morning glory, genus Solanum, common carp, wild leeks, geranium geranium Miao, succulent, common mallow, green stalk, scorpion, hedgehog, sorghum, sage, stalk, corn, grass, mandala, grass, lantern grass, Spiny lettuce, water garlic mustard seeds, leeks, Russian oysters, oil sedge, fragrant aconite, common ragweed, small white wine grass, giant ragweed, common sorghum, earweed grass, rough hairy oxeye, American daisy, fire mother Grass, chamomile, wild poinsettia, common purslane, thorny yellow flower, big horse grass, stalk leaf horse grass, goose grass, fruit tree grass, autumn sorghum, thatch, big teff, snail grass, field flower, wild Buckwheat, dandelion, sable, mustard, canadensis, sow, annual cockroach and hedgehog. The compositions and tank mixes of the present disclosure may additionally comprise other crop protection agents including, but not limited to, fungicides, insecticides, nematicides, plant growth regulators, herbicides other than PPO herbicides , fertilizers and mixtures thereof. In embodiments, the control of the weeds is effective for at least about 14 days after treatment, preferably at least about 60 days after treatment. The compositions of the present disclosure may also include a preservative. Suitable preservatives include, but are not limited to, C 12 to C 15 alkyl benzoate, alkyl p-hydroxybenzoate, aloe extract, ascorbic acid, benzalkonium chloride, benzoic acid, C 9 to C 15 Alcoholic benzoate, dibutylhydroxytoluene, butylhydroxymethoxybenzene, tert-butylhydroquinone, castor oil, cetyl alcohol, chlorocresol, citric acid, cocoa butter, coconut oil, dialkyl Imidazolium urea, diisopropyl adipate, dimethyl polyoxyalkylene, DMDM carbendazim, ethanol, ethylenediaminetetraacetic acid, fatty acid, fatty alcohol, cetyl alcohol, hydroxybenzoate, Iodopropynyl butyl carbazate, isodecyl isononanoate, jojoba oil, lanolin, mineral oil, oleic acid, olive oil, paraben, polyether, polyoxybutyl butyl Ether, cetyl polyoxypropylene ether, potassium sorbate, propyl gallate, polyoxygenated oil, sodium propionate, sodium benzoate, sodium hydrogen sulfite, sorbic acid, stearic fatty acid, sulfur dioxide, vitamin E, Vitamin E acetate and its derivatives, esters, salts and mixtures. Preferred preservatives include sodium o-phenylphenolate, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, and 1,2-benzene. And thiazolin-3-one. This document discloses compositions and methods for providing efficacy in controlling crop weeds in crops. It has been demonstrated that the addition of a safener such as oxalate or pyrazolium to a safener mixture such as oxalate plus pyrazolamide can reduce herbicides (eg, oxazolone and methyl oxalate) Crop damage does not affect the efficacy of the herbicides. It is believed that the co-administration of a safener/safener mixture with a PPO herbicide will allow for a higher rate of application of the herbicide to the registered crop and expand its use of unregistered crops. The following examples are only intended to illustrate the invention and are not to be construed as limiting the scope of the invention, which is intended to be understood by those skilled in the art. All such modifications are considered to be within the scope of the invention as disclosed in the specification and claims. EXAMPLES Example 1 Materials and Methods To study the safety effects of one or two safeners on crops, oxazolone was 25 g ai/ha or 50 g ai/ha or methyl oxazinate was 5.6 g ai/ha* Or 11.2 g ai/ha* with oxalate plus pyrazole oxalate, oxalate plus naphthalic anhydride, pyrazolyl plus naphthalic anhydride, oxalate, pyrazole or naphthalene A combination of formic anhydride is applied. The safeners oxalate, pyrazolium and naphthalic anhydride were applied at 6.6 g ai/ha, 27.2 g ai/ha and 74.1 g ai/ha, respectively. Other treatments include the separate application of oxazolidine or methyl oxalate. 0.25% (v/v) of a nonionic surfactant was added to all of the oxazolidine and methyl oxalate. The oxazolone and methyl oxazinate treatment was applied to the crop after 10 days of planting. Use wheat-mix to grow wheat and weeds in 3'' plastic pots. The treatment was applied using a 40 PSI TeeJet 8001E nozzle at 30 GPA using a compressed pneumatic crawler spray chamber. Minitab statistical software analysis data was used under the 95% confidence interval. In the 95% confidence interval, there is no significant difference in the meaning of each grading interval for the percentage of wheat damage sharing the same letter. *Naphthalic anhydride was not included in the study of methyl oxalate. Crop damage is assessed by using a visual grading method. This method is based on a scale of 0% to 100%, where 0% means no damage and 100% means complete death of the plant. Table 1 shows a linear grading scale that can be used to evaluate weed control or crop damage. (modified from Frans et al., 1986). Crop damage of less than or equal to 10% is considered to be commercially acceptable. A damage rating of less than or equal to 20% indicates that the crop is not significantly adversely affected and will recover quickly and completely. The extent of commercially acceptable crop damage varies from crop to crop. Any degree of damage greater than 20% is generally commercially unacceptable. In the study of the present invention, a reduction in crop damage from commercial unacceptable to commercially acceptable levels under safe/herbicide treatment was observed. Table 1 Example 2 In a greenhouse study, the safety effect of a safener (a herbicide or pyrazolium) and a safener mixture (a solution of pyrethroid plus pyrazole) on wheat was investigated. The efficacy of PPO inhibitor herbicides in the presence of a safener or safener mixture was also investigated. To study the safety effect of a safener or safener mixture, 7.5% w/w of oxalic acid ester and 3.39% w/w of pyrazole oxalate and herbicide were applied. The oxazolone was applied at 25 g ai/ha or 50 g ai/ha; methyl oxalate was applied at 5.6 g ai/ha or 11.2 g ai/ha. The safener was applied at a ratio of 6.61 g ai/ha and pyrazolium to 27 g ai/ha. All treatments (individual, barrel mixing, premixing) were applied at the seedling stage (10 days after planting). The oxazolone or methyl oxalate is applied alone or in combination with a safener or safener mixture. Table 2 Percentage of wheat damage when different combinations of oxazolone and safener were applied (using the wheat species "Yellowstone") In the 95% confidence interval, there is no significant difference in the meaning of each grading interval for the percentage of wheat damage sharing the same letter. Wheat damage was assessed by using the visual grading method described above. The percentage of wheat damage is graded based on bronzing, yellowing and necrosis of wheat leaves caused by PPO inhibitors. These are typical symptoms of PPO inhibitors against sensitive plants (bronze, yellowing and necrosis). In all studies, treatment was compared to oxazolone alone. The data in this and other tables indicates a reduction in the degree of damage to wheat with the addition of one or more safeners. For example, at 3 DAT (the number of days after treatment), compared with the application of oxazolidine and a safener (eg, oxalate + pyrazolium), the damage to wheat is less than or equal to 10%, 25 g ai/ha was applied with oxazolone 34%. At 3 DAT, regardless of the oxazolidine ratio, the wheat damage was less than or equal to 12% in the presence of a safener, but the damage was greater than 25% under naphthalic anhydride alone. The oxazolone alone caused 34% and 43% damage at 25 g and 50 g, respectively (Table 2 and Table 3). Table 3 Percentage of wheat damage when different combinations of oxazolone and safener were applied (using the wheat species "Yellowstone") In the 95% confidence interval, there is no significant difference in the meaning of each grading interval for the percentage of wheat damage sharing the same letter. Example 3 Table 4 Percentage of damage to wheat varieties "Jagger" and "Yellowstone" when oxazolone was applied with a single safener or two safeners 10 days after the inoculation In the 95% confidence interval, there is no significant difference in the meaning of each grading interval for the percentage of wheat damage sharing the same letter. The results shown demonstrate that regardless of the ratio of oxazolone and the fractionation interval (3 DAT and 7 DAT), the two varieties (Jagger and Yellowstone) are present in the presence of chlorpyrifos plus pyrazole or individual oxalate. The wheat damage was 13% or less (Table 4). Similar results were observed with a premix of oxazolone + oxalate. The application of 50 g of pyrazolium and oxazolone in a tank mix or premix resulted in greater than 20% damage to both varieties (Table 4). Damage to both varieties at 25 g or 50 g of oxazolone and no safener was >35% or >40%, respectively (Table 4). For ease of reference, the weed control percentage is determined by a method similar to the 0% to 100% grading system as described above and reproduced below. The same weed control grading system can also be found, for example, in "Research Methods in Weed Science", 2nd edition, edited by B. Truelove; Southern Weed Science Society ; Auburn University, Auburn, Ala., 1977. table 5 At 7 DAT, control of castor and morning glory was 100% under all treatments (Table 6). Table 6 Percentage of weed control when oxazolone was applied 10 days after germination with a single safener or two safeners In the 95% confidence interval, there is no significant difference in the meaning of each grading interval for the percentage of weed control sharing the same letter. Example 4 Table 7 Percentage of wheat damage when methyl oxalate (FM) and safener herbicide (CM) or pyrazolium ester (MD) were combined in a tank mix or applied separately In the two tests (1 and 2) shown in Table 7, methyl oxalate methylate alone was damaged (≥ 10%) against the yellowstone variety of wheat at both ratios, when 5.6 g ai/ha alone Jagger wheat is safe (≤ 10% damage) when methyl oxalate is applied. In Test 1, at 14 DAT, Yellowstone (1) and Jagger were safe when methyl oxalate was applied alone or in combination with any safener. In Test 1, castor and morning glory were controlled in all cases (data not shown). In Test 2, Yellowstone (2) was safe at 14 DAT when 5.6 g or 11.2 g of methyl oxalic acid was added as a tank mix with oxalate plus pyrazole. At 14 DAT, 5.6 g of methyl oxalate was safe with either safener to Yellowstone. Insofar as the features or aspects of the invention are set forth in the Markush group or in other subgroups, those skilled in the art will recognize that the invention is therefore in accordance with the Markush group or any other group. Individual members or subgroups of members to elaborate. All numerical ranges recited herein are inclusive of all combinations and sub- These ranges are also within the scope of the invention as described. While the invention has been described with reference to the specific embodiments thereof, it is understood that Therefore, it is to be understood that various modifications may be made to the illustrative embodiments and other configurations may be made without departing from the spirit and scope of the invention as defined by the following claims.