TW201323409A - 4,4-二氟-3,4-二氫異喹啉衍生物之製造方法 - Google Patents
4,4-二氟-3,4-二氫異喹啉衍生物之製造方法 Download PDFInfo
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Abstract
本發明提供大量地以簡便且有效率地製造4,4-二氟-3,4-二氫異喹啉衍生物之方法。一種以通式(1)表示之4,4-二氟-3,4-二氫異喹啉衍生物之製造方法,係使以通式(2)表示之化合物與氟化氫反應;□□
Description
本發明係關於4,4-二氟-3,4-二氫異喹啉衍生物之製造方法。
以防除農園藝用作物之病害為目的已有多數藥劑被提出。例如:專利文獻1及專利文獻2揭示含有以通式(1)表示之4,4-二氟-3,4-二氫異喹啉衍生物
(式中,R1及R2各自獨立地表示也可經取代之碳數1~6之烷基,或R1與R2與此等所鍵結之碳原子成為一體而形成也可經取代之碳數3~10之環烷基,X表示鹵素原子、也可經取代之碳數1~6之烷基、也可經取代之碳數1~6之烷氧基,n表示0~4之整數,Y表示鹵素原子、也可經取代之碳數1~6之烷基、也可經取代之碳數1~6之烷氧基,m表示0~6之整數。)者,該等已知作為農園藝用殺菌劑為有用。所以,以工業規模提供通式(1)表示之化合物之方法係為重要。
但前述專利文未記載上述通式(1)表示之4,4-二氟-3,4-二氫異喹啉衍生物之具體合成法。製造該等化合物群時,利用專利文獻1揭示之將通式(4)表示之異喹啉-4(3H)-酮衍生物之酮基予以脫氧氟化之方法為有效率的。
(式中,R1、R2、X、Y、n及m與前述為同義)。如比較例所示,使用脫氧氟化為代表性之試劑三氟化(二乙胺基)硫((diethylamino)sulfurtrifluoride(參照非專利文獻1)欲與通式(4)表示之化合物進行反應,結果反應進行慢,產率也只有28.9%。又,三氟化(二乙胺基)硫由於反應性高,會有於大量生產時之操作困難的缺點。
於如此的背景下,急切需要開發能簡便地合成4,4-二氟-3,4-二氫異喹啉衍生物且能以工業規模實施生產的製造方法。
【專利文獻1】國際公開第2005/70917號公報
【專利文獻2】國際公開第2011/77514號公報
【非專利文獻1】Journal of Organic Chemistry (J. Org. Chem.)、第40卷、574-578頁(1975)
提供以簡便且有效率製造4,4-二氟-3,4-二氫異喹啉衍生物之製造方法。
為了解決前述課題努力探討,結果發現:藉由使3,4-二氫異喹啉衍生物與溴化劑反應而變換為4,4-二溴-3,4-二氫異喹啉衍生物後,使該4,4-二溴
-3,4-二氫異喹啉衍生物與氟化氫反應,可製造目的之4,4-二氟-3,4-二氫異喹啉衍生物。該方法能簡便且有效率地供給4,4-二氟-3,4-二氫異喹啉衍生物,乃完成本發明。
亦即,本發明係:
[1]一種以通式(1)表示之化合物之製造方法,係使以通式(2)表示之化合物與氟化氫反應;
(式中,R1及R2各自獨立地表示也可經取代之碳數1~6之烷基,或R1與R2與此等所鍵結之碳原子成為一體而形成也可經取代之碳數3~10之環烷基,X表示鹵素原子、也可經取代之碳數1~6之烷基、也可經取代之碳數1~6之烷氧基,n表示0~4之整數,Y表示鹵素原子、也可經取代之碳數1~6之烷基、也可經取代之碳數1~6之烷氧基,m表示0~6之整數。)
(式中,R1、R2、X、Y、n及m與前述為同義。)。
[2]如[1]之以通式(1)表示之化合物之製造方法,其係使以通式(3)表示之化合物與溴化劑反應而得到以通式(2)表示之化合物;
(式中,R1、R2、X、Y、n及m與前述[1]為相同含意。)。
[3]如[1]之以通式(1)表示之化合物之製造方法,其中,R1及R2各自獨
立地表示也可經取代之碳數1~6之烷基,且n=0、m=0。
[4]如[2]之以通式(1)表示之化合物之製造方法,其中,R1及R2各自獨立地表示也可經取代之碳數1~6之烷基,且n=0、m=0。
依照本發明可提供大量製造4,4-二氟-3,4-二氫異喹啉衍生物之製造方法。又,由於能以簡便操作以良好效率製造目的之化合物,適於工業化製造方法。
以下針對實施本發明之形態詳細說明。
以下記載通式(1)之說明。
通式(1)中之R1及R2各自獨立,可為相同也可不同。
通式(1)中之R1及R2之也可經取代之碳數1~6之烷基中的取代基,係表示鹵素原子及碳數1~6之烷氧基。鹵素原子為氟、氯、溴、碘。碳數1~6之烷氧基,表示如甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、異丁氧基、第二丁氧基、第三丁氧基、戊氧基、異戊氧基、2-甲基丁氧基、新戊氧基、1-乙基丙氧基、己基氧基、4-甲基戊氧基、3-甲基戊氧基、2-甲基戊氧基、1-甲基戊氧基、3,3-二甲基丁氧基、2,2-二甲基丁氧基、1,1-二甲基丁氧基、1,2-二甲基丁氧基、1,3-二甲基丁氧基、2,3-二甲基丁氧基、2-乙基丁氧基之類之直鏈或分支之烷氧基。較佳為碳數1~4之烷氧基,更佳為甲氧基、乙氧基、丙氧基、異丙氧基。取代基之數目不特別限定,各取代基可為相
同也可相異。
通式(1)中之R1及R2之也可經取代之碳數1~6之烷基中之烷基,為如甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、第三丁基、戊基、異戊基、2-甲基丁基、新戊基、1-乙基丙基、己基、4-甲基戊基、3-甲基戊基、2-甲基戊基、1-甲基戊基、3,3-二甲基丁基、2,2-二甲基丁基、1,1-二甲基丁基、1,2-二甲基丁基、1,3-二甲基丁基、2,3-二甲基丁基、2-乙基丁基之類之直鏈或分支之烷基。較佳為碳數1~3之烷基,更佳為甲基或乙基。
通式(1)中之R1與R2與此等所鍵結之碳原子成為一體而形成之也可經取代之碳數3~10之環烷基中的取代基,與通式(1)中之R1及R2之也可經取代之碳數1~6之烷基中的取代基為相同含意。取代基之數目不特別限定,各取代基可為相同也可不同。
通式(1)中之R1與R2與此等所鍵結之碳原子成為一體而形成的也可經取代之碳數3~10之環烷基中之環烷基,為如環丁基、環戊基、環己基、環庚基、降莰基之類的碳數3~10的單環或多環環烷基。宜為環丁基、環戊基、環己基、環庚基,更理想為環戊基。
通式(1)中之X之鹵素原子,為氟、氯、溴、碘。
通式(1)中之X之也可經取代之碳數1~6之烷基,係與通式(1)中之R1及R2中之也可經取代之碳數1~6之烷基為相同含意。
通式(1)中之X之也可經取代之碳數1~6之烷氧基中之取代基,為鹵素原子,為氟、氯、溴、碘。取代基之數目不特別限定,各取代基可為相同或不同。
通式(1)中之X之也可經取代之碳數1~6之烷氧基中的烷氧基,表示如甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、異丁氧基、第二丁氧基、
第三丁氧基、戊氧基、異戊氧基、2-甲基丁氧基、新戊氧基、1-乙基丙氧基、己基氧基、4-甲基戊氧基、3-甲基戊氧基、2-甲基戊氧基、1-甲基戊氧基、3,3-二甲基丁氧基、2,2-二甲基丁氧基、1,1-二甲基丁氧基、1,2-二甲基丁氧基、1,3-二甲基丁氧基、2,3-二甲基丁氧基、2-乙基丁氧基之類的直鏈或分支之烷氧基。宜為碳數1~4之烷氧基,更佳為甲氧基、乙氧基、丙氧基、異丙氧基。
通式(1)中之n為0~4之整數。
通式(1)中之n為2以上時,X可為相同也可不同。
通式(1)中之Y之鹵素原子,與通式(1)中之X之鹵素原子為相同含意。
通式(1)中之Y之也可經取代之碳數1~6之烷基,與通式(1)中之X之也可經取代之碳數1~6之烷基為相同含意。
通式(1)中之Y之也可經取代之碳數1~6之烷氧基,與通式(1)中之X之也可經取代之碳數1~6之烷氧基為相同含意。
通式(1)中之m為0~6之整數。
通式(1)中之m為2以上時,Y可為相同也可不同。
通式(2)中之R1、R2、X、Y、n及m,與通式(1)為相同含意。
以下針對從通式(2)表示之化合物變換為通式(1)表示之化合物之方法說明。
反應使用之氟化氫,可單獨使用氟化氫也可使用如三氟化氫三乙胺、氟化氫吡啶、氟化氫1,3-二甲基-2-四氫咪唑酮之利用氫鍵予以安定化的試
劑。只要是含有氟化氫之試劑且能進行目的反應,其形態不特別限制。
氟化氫之使用量,相對於通式(2)表示之化合物為2當量以上即可,無特別限制,但從經濟性的觀點,為2當量以上20當量以下較佳。
反應時可使用溶劑。只要反應進行即可,無特別限制,但可使用甲苯、二甲苯、苯、氯苯、二氯苯等苯系溶劑、乙腈等腈系溶劑、乙酸乙酯、乙酸異丙酯、乙酸丁酯等酯系溶劑、N-甲基吡咯烷酮、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺等醯胺系溶劑、1,3-二甲基-2-四氫咪唑酮等脲系溶劑、吡啶、三甲基吡啶、三乙胺、三丁胺等鹼性溶劑、四氫呋喃、二乙醚、二異丙醚、甲基-第三丁醚等醚系溶劑、二氯甲烷、二氯乙烷、氯仿、四氯化碳等氯系溶劑、己烷、庚烷、環己烷、甲基環己烷等烴系溶劑等。又,可單獨使用也可將2種類以上以任意比例混用。
使用之溶劑量,只要反應可進行即不特別限定,但從經濟性的觀點,相對於通式(2)表示之化合物為2重量倍以上30重量倍以下較佳。
反應溫度只要反應進行即不特別限制,宜為30℃以上、120℃以下或溶劑之沸點以下。可於反應狀況適當設定。
就反應之後處理而言,可將反應混合物、與溶有氫氧化鉀、氫氧化鈉、碳酸鈉、碳酸鉀、碳酸氫鈉、碳酸氫鉀之鹼水溶液予以混合並進行分液操作。此時,視需要可追加甲苯、二甲苯、苯、氯苯、二氯苯等苯系溶劑、乙酸乙酯、乙酸異丙酯、乙酸丁酯等酯系溶劑、二乙醚、二異丙醚、甲基-第三丁醚等醚系溶劑、二氯甲烷、二氯乙烷、氯仿等氯系溶劑、己烷、庚烷、環己烷、甲基環己烷等烴系溶劑等與水不互溶的溶劑。又,該等溶劑可以單獨使用也可以2種以上以任意比例混合。分液之次數不特別限制,可因應目的之純度或產量實施。
前述獲得之含有化合物(1)之反應混合物,可以用硫酸鈉或硫酸鎂等乾
燥劑去除水分,但並非必要。
前述獲得之含有化合物(1)之反應混合物,在化合物不分解之限度內,可於減壓下將溶劑餾去。
溶劑餾去後獲得之含有化合物(1)之反應混合物,可利用適當溶劑以洗滌、再沉澱或再結晶予以精製。使用之溶劑,可列舉:水、或甲醇、乙醇、異丙醇等醇溶劑、甲苯、二甲苯、苯、氯苯、二氯苯等苯系溶劑、乙酸乙酯、乙酸異丙酯、乙酸丁酯等酯系溶劑、二乙醚、二異丙醚、甲基-第三丁醚等醚系溶劑、己烷、庚烷、環己烷、甲基環己烷等烴系溶劑等。此時,可使用單獨的溶劑或將2種以上以任意比例混合的溶劑。此外,也可利用管柱層析精製。因應目的之純度適當設定即可。
再者,含有化合物(1)之反應混合物,也可如通式(4)
(式中,R1、R2、X、Y、n及m與通式(1)為相同含意,Z表示酸,p為0.5~2。)表示之化合物之以通式(1)表示之化合物之鹽的形式取得。
通式(4)中之Z之酸,為鹽酸、硫酸、磷酸等無機酸、甲烷磺酸、對甲苯磺酸、草酸、琥珀酸等有機酸。
通式(4)中之p為0.5~2。
通式(4)表示之化合物,可藉由對於含有通式(1)表示之化合物之混合物加入適當溶劑後加入酸而製備。
製備通式(4)表示之化合物時之溶劑,可列舉水、或甲醇、乙醇、異丙
醇等醇溶劑、甲苯、二甲苯、苯、氯苯、二氯苯等苯系溶劑、四氫呋喃、二乙醚、二異丙醚、甲基-第三丁醚等醚系溶劑、乙酸乙酯、乙酸異丙酯、乙酸丁酯等酯系溶劑、己烷、庚烷、環己烷、甲基環己烷等烴系溶劑等。又,使用形態可單獨使用也可為將2種以上以任意比例混合之溶劑,不特別限定。
製備通式(4)表示之化合物時,酸之使用量只要是1當量以上即可,不特別限制,但從經濟的觀點,為1當量以上15當量以下。
獲得之鹽,於酸為1價之情形,p=1或2,為2價之情形,p=0.5或1。鹽形態可為單獨之鹽,也可為或單鹽與二鹽的混合物,不特別限制。
通式(4)表示之化合物可以用適當的溶劑予以洗滌、再沉澱或再結晶。使用之溶劑例如:水、甲醇、乙醇、異丙醇等醇溶劑、或甲苯、二甲苯、苯、氯苯、二氯苯等苯系溶劑、或四氫呋喃、二乙醚、二異丙醚、甲基-第三丁醚等醚系溶劑、乙酸乙酯、乙酸異丙酯、乙酸丁酯等酯系溶劑、己烷、庚烷、環己烷、甲基環己烷等烴系溶劑等。此時之溶劑可為單獨的溶劑或2種以上之混合溶劑,在能進行目的操作之限度內無限制。
通式(4)表示之化合物,可利用鹼性物質變換為通式(1)表示之化合物。鹼性物質,為氫氧化鉀、氫氧化鈉、碳酸鈉、碳酸鉀、碳酸氫鈉、碳酸氫鉀等,也可以將該等以溶於水之狀態使用。又,視需要,也可以用甲苯、二甲苯、苯、氯苯、二氯苯等苯系溶劑、乙酸乙酯、乙酸丁酯等酯系溶劑、二乙醚、二異丙醚、甲基-第三丁醚等醚系溶劑、二氯甲烷、二氯乙烷、氯仿等氯系溶劑、己烷、庚烷、環己烷、甲基環己烷等烴系溶劑等與水不互溶的溶劑萃取。分液之次數不特別限制,予以適當設定即可。獲得之通式(1)表示之化合物,可以用與前述反應後之後處理為相同之操作進行洗滌、再沉澱、再結晶、管柱層析等精製。可配合目的純度適當設定。
以下針對獲得通式(2)之方法說明。
通式(3)中之R1、R2、X、Y、n及m與通式(1)為相同含意。
溴化劑可列舉1,3-二溴-5,5-二甲基乙內醯脲或N-溴琥珀醯亞胺等。
通式(3)表示之化合物可參照專利文獻1合成。
將通式(3)表示之化合物以溴化劑變換為通式(2)表示之化合物時,需要過酸或偶氮化合物等自由基起始劑或光照射。
自由基起始劑,在目的之溴化會進行之限度內不特別限制,但宜以10小時半減期為90℃以下者較佳。
作為自由基起始劑之過酸,可列舉:過氧化二異丁醯、異丙苯基過氧化新癸酸酯、二正丙基過氧化二過氧化二碳酸酯、二異丙基過氧化二碳酸酯、二-第二丁基過氧化二碳酸酯、1,1,3,3-四甲基丁基過氧化新癸酸酯、二(4-第三丁基環己基)過氧化二碳酸酯、二(2-乙基己基)過氧化二碳酸酯、第三己基過氧化新癸酸酯、第三丁基過氧化新癸酸酯、第三丁基過氧化新庚酸酯、第三己基過氧化三甲基乙酸酯、第三丁基過氧化三甲基乙酸酯、二(3,5,5-三甲基己醯基)過氧化物、二月桂基過氧化物、1,1,3,3-四甲基丁基過氧化-2-乙基己酸酯、過氧化二琥珀酸、2,5-二甲基-2,5-二(2-乙基己醯基過氧化)己烷、第三己基過氧化-2-乙基己酸酯、二(4-甲基苯甲醯基)過氧化物、第三丁基過氧化-2-乙基己酸酯、二(3-甲基苯甲醯基)過氧化物與苯甲醯基(3-甲基苯甲醯基)過氧化物與二苯甲醯基過氧化物之混合物、二苯甲醯基過氧化物、1,1-二(第三丁基過氧化)-2-甲基環己烷、1,1-二(第三己基過氧化)-3,3,5-三甲基環己烷等。
作為自由基起始劑之偶氮化合物,可列舉:2,2’-偶氮雙異丁腈、2,2’-偶氮雙(4-甲氧基-2.4-二甲基戊腈)、2,2’-偶氮雙(2.4-二甲基戊腈)、二甲基2,2’-偶氮雙(2-甲基丙腈)、2,2’-偶氮雙(2-甲基丁腈)、1,1’-偶氮雙(環己烷-1-
甲腈)等。
自由基起始劑之使用量,在目的反應進行之限度內不特別限制。從經濟性的觀點,為0.001當量以上0.30當量以下為較佳。
溴化劑之使用量,在目的反應進行之限度內不特別限制,只要以溴原子換算為2當量以上即可。從經濟性的觀點,以溴原子換算為2當量以上4當量以下為較佳。
進行反應時可使用溶劑。溶劑例如氯苯、二氯苯等氯系苯溶劑或四氯化碳等鹵素系溶劑、己烷、庚烷、環己烷、甲基環己烷等烴系溶劑、乙酸乙酯、乙酸異丙酯、乙酸丁酯等酯系溶劑。
反應使用之溶劑之量,在反應進行之限度內不特別限制,但相對於通式(3)表示之化合物為3重量倍以上30重量倍以下為較佳。
反應溫度,配合自由基起始劑設定即可,為30℃以上150℃或溶劑之沸點以下。
作為反應之後處理,當從溴化劑產生之副產物(例如1,3-二溴-5,5-二甲基乙內醯脲之情形,為5,5-二甲基乙內醯脲)析出之情形,可利用過濾操作去除副產物。
通式(2)表示之化合物之反應混合物,可以用適當溶劑予以洗滌、再沉澱或再結晶。此時使用之溶劑,可列舉甲苯、二甲苯、苯、氯苯、二氯苯等苯系溶劑、乙酸乙酯、乙酸異丙酯、乙酸丁酯等酯系溶劑、二乙醚、二異丙醚、甲基-第三丁醚等醚系溶劑、二氯甲烷、二氯乙烷、氯仿等氯系溶劑、己烷、庚烷、環己烷、甲基環己烷等烴系溶劑等。又,該等溶劑可單獨使用,或將2種以上之溶劑以任意比例混合。此外,也可用管柱層析精製。配合目的純度適當實施即可。
通式(3)表示之化合物以溴化劑變換而得之通式(2)表示之化合物,可利用與氟化氫反應而變換為通式(1)表示之化合物。
利用以上可以良好效率製造4,4-二氟-3,4-二氫異喹啉衍生物。
以下利用實施例更詳細說明本發明,但本發明不限於該等實施例。3-(3,3-二甲基-3,4-二氫異喹啉-1-基)喹啉稱為化合物(I)、3-(4,4-二溴-3,3-二甲基-3,4-二氫異喹啉-1-基)喹啉稱為化合物(II)、3-(4,4-二氟-3,3-二甲基-3,4-二氫異喹啉-1-基)喹啉稱為化合物(III)、1,3-二溴-5,5-二甲基乙內醯脲稱為DBH、高速液體層析稱為HPLC。
於化合物(IV)4.57g與二氯甲烷5mL之混合物中加入三氟化(二乙胺基)硫20mL,進行13小時加熱回流。空冷後,將反應混合物以冰冷的飽和小蘇打水處理後以二氯甲烷萃取。將獲得之二氯甲烷層以飽和食鹽水洗滌,以硫酸鎂乾燥後,將溶劑減壓餾去,將獲得之殘渣以層析精製,獲得目的物(1.42g、產率28.9%)。同時回收原料(2.89g、回收率63.2%)。
將化合物(I)4.8g溶於氯苯48ml並升溫至93℃。加入DBH2.64g與2,2’-偶氮雙異丁腈(以下、AIBN)0.42g,攪拌5分鐘後,再度加入DBH2.64g與AIBN0.42g,攪拌2小時。冷卻至15℃並攪拌1小時後過濾。將濾液於減壓下餾去溶劑後,於殘渣加入乙酸乙酯與己烷之混合液(乙酸乙酯:己烷=4:1)5ml,於15℃攪拌再加入己烷15ml,於同溫攪拌1小時。濾取析出物,獲得之淡黃色固體6.68g為化合物(II)。純度為94.9%。
1H-NMR(CDCl3)δ:9.13(1H,d,J=2.0 Hz),8.38(1H,d,J=2.0 Hz),8.21(2H,t,J=8.1 Hz),7.89(1H,d,J=8.3 Hz),7.82-7.78(1H,m),7.62(2H,td,J=7.7,4.1 Hz),7.45-7.41(1H,m),7.24(1H,d,J=7.3 Hz),1.79(6H,br s)
於二甲苯30ml加入實施例1獲得之化合物(II)5.0g與三氟化氫三乙胺5.73g,於90℃反應4小時。其次於冰冷下滴加18%氫氧化鉀水溶液50g後,於室溫攪拌。將獲得之反應混合物分液,並將有機層於減壓下濃縮。於殘渣加入甲醇13ml並將其滴加到50%甲醇水溶液。再加入水26ml並攪拌。
過濾獲得之析出物,獲得淡黃色固體的標題化合物3.33g。產率為88%,本方法相較於比較例1可說是非常優異之方法。又,獲得之化合物與專利文獻1記載之1H-NMR數據一致。
於乙腈7.5ml加入三氟化氫三乙胺1.47g後,加入化合物(II)1.21g並於90℃反應4小時。以HPLC觀測此時之反應混合物,結果以反應產率90%生成了化合物(III)。冷卻至室溫後,將反應混合物加到氫氧化鉀水溶液中。其次,以乙酸乙酯萃取後以硫酸鎂乾燥。去除硫酸鎂後於殘渣加入甲醇水溶液並攪拌,濾取析出物。獲得之淡黃色固體0.67g為化合物(III)。產率80%。
於甲苯4ml加入三氟化氫三乙胺0.85g後,加入化合物(II)0.70g並於90℃反應4小時。以HPLC觀測此時之反應混合物,結果以反應產率96%生成了化合物(III)。冷卻至室溫後,於5%之氫氧化鉀水溶液中加入該反應混合物。分液後於減壓下將溶劑餾去。於獲得之殘渣中加入甲醇水溶液,濾取析出物。獲得之淡黃色固體0.43g為化合物(III)。產率84%。
於庚烷6ml加入三氟化氫三乙胺0.80g與化合物(II)1.0g,於90℃反應4小時。以HPLC觀測獲得之反應混合物,結果以反應產率93%生成了化合物(III)。
將庚烷改為乙酸丁酯,除此以外與實施例5同樣進行反應。以HPLC觀測獲得之反應混合物,結果以反應產率78%生成了化合物(III)。
於三乙胺4ml加入三氟化氫三乙胺0.88g後,加入化合物(II)0.72g並於90℃反應4小時。以HPLC觀測獲得之反應混合物,結果以反應產率82%
生成了化合物(III)。
將70%氟化氫吡啶0.43g與吡啶263mg加到甲苯6ml之後,裝入化合物(II)1.01g。其次於85℃攪拌4小時。將得到的反應混合物以HPLC分析,結果以反應產率87%生成了化合物(III)。
將裝有化合物(I)1g的氯苯10ml升溫到93℃。其次,加入N-溴琥珀醯亞胺1.40g與AIBN29mg,於同溫反應2小時。以HPLC觀測反應混合物,結果以反應產率90%生成了化合物(II)。
於含有化合物(I)21.73g的氯苯溶液483.87g中加入DBH26.0g及二(4-第三丁基環己基)過氧化二碳酸酯(純度93%)650.2mg,加熱至65℃。於6.5℃攪拌2.5小時後冷卻至45℃,於減壓下餾去一部分的氯苯。將獲得之該反應混合物213.7g過濾,獲得濾液223.4g。再於減壓下餾去氯苯,獲得82.91g之化合物(II)之氯苯溶液(37.97重量%、產率93.4%)。
於由上述反應獲得之化合物(II)之氯苯溶液82.77g中加入三氟化氫三乙胺5.10g,加熱至85℃並攪拌6小時。冷卻至60℃後,加入20%氫氧化鉀水溶液170.0g,冷卻至室溫後攪拌15分鐘。以分液操作獲得90.05g的有機層。以HPLC分析該有機層,結果確認以93.4%的產率生成化合物(III)。於減壓下濃縮反應液,獲得35.21g的黑色溶液。於獲得之溶液中加入乙醇189.11g及濃鹽酸12.94g,加熱至75℃並攪拌30分鐘。將溶液冷卻至2℃,攪拌3小時後,過濾析出物。獲得之淡黃色固體21.85g為化合物(III)之鹽酸鹽。純度97.4%、產率84%。
1H-NMR(DMSO-D6)δ:9.32(1H,d,J=1.8 Hz),9.04(1H,d,J=1.8 Hz),8.31(2H,dd,J=8.3,1.8 Hz),8.06(1H,dt,J=10.7,3.9 Hz),7.93(1H,d,J=7.6 Hz),7.88-7.82(2H,m),7.75(1H,t,J=7.5 Hz),7.57(1H,d,J=7.6 Hz),1.40(6H,s)
熔點188-191℃
C:66.8%、H:5.0%、N:7.8%、Cl:10%、F:11%
於10%氫氧化鈉水溶液28.00g中加入甲基-第三丁醚105.0g,邊攪拌邊加入前述化合物(III)之鹽酸鹽21.00g。於室溫攪拌30分鐘後分液,將獲得之有機層以水40g洗滌。於獲得之有機層中加入乙醇27.00g,加熱至59℃,並餾去甲基-第三丁醚。將溶液冷卻至10℃後加水84.0g,於室溫攪拌1小時。過濾析出的固體後乾燥,獲得18.79g的化合物(III)淡黃色固體(純度98.1%)。
使6-溴-3-(3,3-二甲基-3,4-二氫異喹啉-1-基)喹啉36.98g溶於氯苯740ml,加入DBH34.74g及二(4-第三丁基環己基)過氧化二碳酸酯(純度93%)4.33g,加熱至80℃。於80℃攪拌4小時後冷卻至18℃,過濾反應液。將濾液於減壓下餾去溶劑後,於殘渣中加入氯仿168g並加熱至60℃後,於同溫攪拌10分鐘。冷卻至20℃後於同溫靜置2小時。濾取析出物,獲得之固體36.03g為標題之化合物。產率68%。
1H-NMR(CDCl3)δ:9.13(1H,d,J=2.1 Hz),8.27(1H,d,J=2.1 Hz),8.22(1H,dd,J=7.8,1.1 Hz),8.05(2H,dd,J=3.1,1.5 Hz),7.85(1H,dd,J=9.2,2.1 Hz),7.64(1H,td,J=7.6,1.2 Hz),7.43(1H,td,J=7.6,1.2 Hz),7.21(1H,dd,J=7.6,0.9 Hz),1.65(6H,brs)
使6-溴-3-(4,4-二溴-3,3-二甲基-3,4-二氫異喹啉-1-基)喹啉35.93g溶於甲苯216ml,加入三氟化氫三乙胺36.54g,加熱至85℃並於同溫攪拌4小時。冷卻至30℃後,加入20%氫氧化鉀水溶液248.0g並攪拌30分鐘。將由分液操作獲得之有機層以水洗滌,並將有機層以硫酸鈉乾燥。過濾硫酸鈉後,將濾液於減壓下濃縮,獲得27.10g的褐色油。於獲得之褐色油中加入乙醇62.90g,加熱至70℃並攪拌10分鐘。將溶液冷卻至2℃,攪拌2小時後過
濾析出物。獲得之白色固體22.31g為標題之化合物。產率81%。
1H-NMR(CDCl3)δ:9.15(1H,d,J=2.1 Hz),8.30(1H,d,J=2.1 Hz),8.05-8.04(2H,m),7.88(1H,d,J=7.6 Hz),7.85(1H,dd,J=9.2,2.1 Hz),7.67(1H,td,J=7.5,1.0 Hz),7.55(1H,t,J=7.6 Hz),7.30(1H,dd,J=7.8,0.8 Hz),1.46(6H,s)
將6-溴-3-(3,3-二甲基-3,4-二氫異喹啉-1-基)喹啉替換為使用7-溴-3-(3,3-二甲基-3,4-二氫異喹啉-1-基)喹啉,除此以外與實施例11同樣進行,將製備的7-溴-3-(4,4-二溴-3,3-二甲基-3,4-二氫異喹啉-1-基)喹啉55.7mg溶於甲苯0.33ml並加入三氟化氫三乙胺60mg。加熱至95℃並於同溫攪拌4小時。冷卻至25℃後加入10%氫氧化鉀水溶液6.0g,攪拌1小時。加入甲苯6ml後,分液並將獲得之有機層以水6g洗滌,將有機層以硫酸鈉乾燥。將硫酸鈉過濾後,將濾液於減壓下濃縮並將獲得之殘渣以矽膠管柱層析精製。獲得之白色固體26.4mg為標題之化合物。產率62%。
1H-NMR(CDCl3)δ:9.14(1H,d,J=2.1 Hz),8.38-8.36(2H,m),7.88(1H,d,J=7.6 Hz),7.76(1H,d,J=8.6 Hz),7.71-7.65(2H,m),7.55(1H,t,J=7.6 Hz),7.31(1H,dd,J=7.6,0.6 Hz),1.45(6H,s)
使3-(3,3-二甲基-3,4-二氫異喹啉-1-基)-7-氟喹啉103.2mg溶於氯苯2ml,加入DBH116.3mg及二(4-第三丁基環己基)過氧化二碳酸酯(純度93%)7.3mg並加熱至75℃。於75℃攪拌3小時後冷卻至25℃,將反應液過濾。將濾液於減壓下餾去溶劑之後,將獲得之殘渣以矽膠管柱層析精製。獲得之固體109.6mg為標題之化合物。產率70%。
1H-NMR(CDCl3)δ:9.12(1H,d,J=2.1 Hz),8.37(1H,d,J=2.1 Hz),8.22(1H,dd,J=8.0,1.2 Hz),7.89(1H,dd,J=8.9,6.1 Hz),7.81(1H,dd,J=10.1,2.4 Hz),7.63(1H,td,J=7.6,1.2 Hz),7.45-7.39(2H,m),7.23(1H,dd,J=7.6,1.2 Hz),1.68(6H,br s)
使3-(4,4-二溴-3,3-二甲基-3,4-二氫異喹啉-1-基)-7-氟喹啉101.0mg溶於甲苯0.6ml,加入三氟化氫三乙胺60mg。加熱至90℃並於同溫攪拌4小時。冷卻至25℃後加入10%氫氧化鉀水溶液6.0g並攪拌1小時。加入甲苯6ml後,將由分液操作獲得之有機層以水6g洗滌,並將有機層以硫酸鈉乾燥。將硫酸鈉過濾後,將濾液於減壓下濃縮並將獲得之殘渣以矽膠管柱層析精製。獲得之無色油57.1mg為標題之化合物。產率77%。
1H-NMR(CDCl3)δ:9.15(1H,d,J=2.1 Hz),8.40(1H,d,J=2.1 Hz),7.91-7.87(2H,m),7.81(1H,dd,J=9.8,2.4 Hz),7.67(1H,t,J=7.5 Hz),7.55(1H,t,J=7.6 Hz),7.41(1H,td,J=8.6,2.7 Hz),7.33(1H,d,J=7.6 Hz),1.46(6H,s)
使3-(3-氯甲基-3-甲基-3,4-二氫異喹啉-1-基)喹啉651.0mg溶於氯苯13.35g,加入DBH696.2mg及二(4-第三丁基環己基)過氧化二碳酸酯(純度93%)87.0mg並加熱到65℃。於65℃攪拌5小時後冷卻至25℃,將反應液過濾。將濾液於減壓下餾去溶劑後,將殘渣以矽膠管柱層析精製。獲得之固體461.4mg為標題之化合物。產率48%。
1H-NMR(CDCl3)δ:9.16(1H,d,J=2.1 Hz),8.43(1H,d,J=2.1 Hz),8.20(2H,t,J=9.2 Hz),7.91(1H,dd,J=8.3,1.2 Hz),7.82(1H,m),7.66(1H,td,J=7.6,1.2 Hz),7.62(1H,m),7.47(1H,td,J=7.6,1.2 Hz),7.32(1H,dd,J=7.6,0.9 Hz),4.42(2H,br s),1.43(3H,br s)
使3-(4,4-二溴-3-氯甲基-3-甲基-3,4-二氫異喹啉-1-基)喹啉461.4mg溶於甲苯3ml,加入三氟化氫三乙胺520mg。加熱至90℃,並於同溫攪拌6小時。冷卻至25℃後,加入20%氫氧化鉀水溶液7.0g並攪拌30分鐘。加入乙酸乙酯後,將由分液操作獲得之有機層以硫酸鈉乾燥。過濾硫酸鈉後,將濾液於減壓下濃縮並將獲得之殘渣以矽膠管柱層析精製。獲得之固體332.2mg為標題之化合物。產率97%。
1H-NMR(CDCl3)δ:9.17(1H,d,J=2.1 Hz),8.43(1H,d,J=2.1 Hz),8.19(1H,d,J=8.6 Hz),7.90(2H,t,J=8.6 Hz),7.82(1H,m),7.69(1H,td,J=7.6,0.9 Hz),7.62(1H,m),7.58(1H,t,J=7.6 Hz),7.47(1H,dd,J=7.6,0.9 Hz),3.99(2H,s),1.48(3H,s)
依本發明,能以簡便操作及良好效率提供4,4-二氟-3,4-二氫異喹啉衍生物。再者,本發明由於在工業上也能有利地生產,故產業上利用價值高。
Claims (4)
- 一種以通式(1)表示之化合物之製造方法,其係使以通式(2)表示之化合物與氟化氫反應;
- 如申請專利範圍第1項之以通式(1)表示之化合物之製造方法,其係使以通式(3)表示之化合物與溴化劑反應而獲得以通式(2)表示之化合物;
- 如申請專利範圍第1項之以通式(1)表示之化合物之製造方法,其中,R1及R2各自獨立地表示也可經取代之碳數1~6之烷基且n=0、m=0。
- 如申請專利範圍第2項之以通式(1)表示之化合物之製造方法,其中,R1及R2各自獨立地表示也可經取代之碳數1~6之烷基且n=0、m=0。
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- 2012-09-28 CN CN201280045844.7A patent/CN103814023B/zh active Active
- 2012-09-28 RU RU2014117188A patent/RU2616608C2/ru active
- 2012-09-28 MY MYPI2014700760A patent/MY167697A/en unknown
- 2012-09-28 JP JP2013536426A patent/JP5993860B2/ja active Active
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AU2012317415A1 (en) | 2014-04-17 |
CN103814023B (zh) | 2015-09-23 |
WO2013047749A1 (ja) | 2013-04-04 |
HUE032086T2 (en) | 2017-09-28 |
EP2762473A1 (en) | 2014-08-06 |
CL2014000731A1 (es) | 2014-08-08 |
TWI530486B (zh) | 2016-04-21 |
CA2850337C (en) | 2018-04-24 |
IL231769A0 (en) | 2014-05-28 |
CN103814023A (zh) | 2014-05-21 |
MX2014003894A (es) | 2014-07-14 |
MY167697A (en) | 2018-09-21 |
AU2012317415B2 (en) | 2016-08-25 |
PL2762473T3 (pl) | 2017-02-28 |
RU2014117188A (ru) | 2015-11-10 |
ES2599752T3 (es) | 2017-02-03 |
KR20140079770A (ko) | 2014-06-27 |
IL231769A (en) | 2016-05-31 |
EP2762473A4 (en) | 2015-05-27 |
CO7020928A2 (es) | 2014-08-11 |
US20140235862A1 (en) | 2014-08-21 |
KR101961972B1 (ko) | 2019-03-25 |
CA2850337A1 (en) | 2013-04-04 |
BR112014007674A2 (pt) | 2017-04-18 |
JP5993860B2 (ja) | 2016-09-14 |
JPWO2013047749A1 (ja) | 2015-03-26 |
EP2762473B1 (en) | 2016-08-31 |
RU2616608C2 (ru) | 2017-04-18 |
US9150538B2 (en) | 2015-10-06 |
MX353553B (es) | 2018-01-17 |
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