TWI668201B - １－二氫茚醇類及１－胺基二氫茚類之製備方法 - Google Patents

１－二氫茚醇類及１－胺基二氫茚類之製備方法 Download PDF

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TWI668201B
TWI668201B TW104102456A TW104102456A TWI668201B TW I668201 B TWI668201 B TW I668201B TW 104102456 A TW104102456 A TW 104102456A TW 104102456 A TW104102456 A TW 104102456A TW I668201 B TWI668201 B TW I668201B
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馬克 福特
尚皮耶 沃斯
奧利維 伯多因
賽門 加諾迪
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德商拜耳作物科學股份有限公司
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Abstract

揭示一種1-二氫茚醇類及1-胺基二氫茚類之製備方法，其係經由鈀-催化之芳基化反應，及使用其作為合成精緻化學品與活性農用化學品成分之中間物。

Description

1-二氫茚醇類及1-胺基二氫茚類之製備方法
本發明係有關1-二氫茚醇類及1-胺基二氫茚類之製備方法，其係經由鈀-催化之芳基化反應，及使用其作為合成精緻化學品與活性農用化學品成分之中間物。
式(I)之1-二氫茚醇類及1-胺基二氫茚類，其中Y是經取代之羥基或胺基，構成在許多農用活性物質之重要的結構單元，如揭示在，例如WO 2004/069814 A1及WO 2007/112834 A1。
J.A.Pincock等人："The Photochemistry of Conformationally Rigid Benzylic Esters：2,2-Dimethyl-1-indanyl Acetates and Pivalates",The Journal of Organic Chemistry 1995,13,4067，揭示經由還原相關之1-二氫茚酮類，以製備1-二氫茚醇類。
Hui Fang等人："Rapid Catalyst Screening by a Continuous-Flow Microreactor lnterfaced with Ultra-High-Pressure Liquid Chromatography",The Journal of Organic Chemistry 2010,16,5619，揭示由相關之3-(3,4-二甲氧基苯基)-2,2-二甲基丙腈或自一種醯基胺縮醛類前驅物開始合成胺基二氫茚。
從C.Pierre,O.Baudoin,Org.Lett. 2011,13,1816及N.Martin,C.Pierre,M.Davi,R.Jazzar,O.Baudoin,O.Chem.-Eur.J. 2012,18,4480，鈀(0)-催化2-鹵化酮類(IIa)或2-鹵化合物(IIb)之芳基化反應係已知。在兩個實例起始化合物(IIa)及(IIb)，化合物其在苯環中相對於鹵原子，在2-位置有一個碳原子，其不帶有氫原子(C=O在式IIa及CRY，R及Y個別均非氫，在式IIb)：
然而，在這些文獻中詳述製備1-二氫茚醇類及1-胺基二氫茚類的方法，都限制在實驗室批量的成果，因為它們有一些缺點，所以無法用於工業上的生產。在已知先前技藝的方法，目前已被揭示2-鹵化合物經由鈀-催化之芳基化反應，有一個更重要的缺點是，是僅能從(IIa)及(IIb)作為起始化合物，其在苯環中相對於鹵原子，在2-位置有一個碳原子，其不帶有氫原子，所以生成之1-二氫茚醇類及1-胺基二氫茚類(Ia)，其中R不是氫。
然而，要製備前述農用活性物質，式(I)之1-二氫茚醇類及1-胺基二氫茚類，是最佳的中間物，即，那些碳原子被Y取代基取代，仍帶有氫原子。
本發明之目的在提供一種製備1-二氫茚醇類及1-胺基二氫茚類之方法，其可克服先其技藝中已知方法的缺點。
已發現1-二氫茚醇類及1-胺基二氫茚類可經由鈀-催化1-(2-鹵苯基)烷-1-醇類或1-(2-鹵苯基)烷-1-胺類之芳基化反應以高產率製備。
依本發明提供製備通式(I)1-二氫茚醇類及1-胺基二氫茚類之方法，其包括在升溫，鈀催化，於膦配位子、鹼，及溶劑存在下，反應1-(2-鹵苯基)烷-1-醇類或1-(2-鹵苯基)烷-1-胺類(II)。
且其中取代基、符號及指數之定義如下：Y 係NR1R2或OR3，R1 係氫或COR4，R2係COR4，或R1及R2一起形成COCH2CH2CO或CO-伸苯基-CO，R3 係Si(R5)3或三甲基乙醯基(2,2-二甲基丙醯基)，R4 係(C1-C6)-烷基或苯基，R5 係(C1-C6)-烷基或苯基，Hal 係氯、溴或碘，R 係氟、(C1-C3)-烷基或(C1-C3)-烷氧基，X1 係氫或(C1-C6)-烷基，X2 係氫或(C1-C6)-烷基，X3 係氫或(C1-C6)-烷基，X4 係氫或(C1-C6)-烷基，或X1及X2，或X3及X4，或X1與X3 一起與其鍵結之碳原子形成一3-至7-員之飽和環，或 Y與X1 一起與其鍵結之碳原子形成一5-至7-員之飽和環，m 係0、1、2或3。
適當的鈀催化劑係，例如，Pd(OAc)2、Pd2dba3(三(二亞芐丙酮)二鈀(0))、PdCl2及PdBr2，較佳的是用Pd(OAc)2。鈀催化劑之習用量是0.1至10莫耳%，較佳地1至10莫耳%，更佳地1至5莫耳%，以化合物(II)計。
適當的膦配位子係，例如，三烷基膦，三環烷基膦如三環己基膦，三芳基膦如三苯基膦、三-正-甲苯基膦、三(4-二甲基胺基苯基)膦，及烷基二芳基膦如丁基二苯基膦，特別佳是使用三苯基膦。膦亦可使用鹽類型式，例如HBF4。膦配位子之習用量是0.1至10莫耳%，較佳地1至10莫耳%，更佳地1至5莫耳%，以化合物(II)計。
鈀催化劑及膦配位子可使用不同的化合物，或通常地以預成錯合物型式-例如，如四(三苯基膦基)鈀，其是特別佳的。
適當的鹼係，例如，碳酸鹽、氫碳酸鹽、磷酸鹽、烷氧化物，及鹼金屬羧酸鹽，如Li2CO3、Na2CO3、K2CO3、NaHCO3、KHCO3、K3PO4、K2HPO4、NaOMe、NaOEt、NaOiPr、NaOtBu、KOMe、KOEt、KOiPr、KOtBu、NaOAc、KOAc、NaOPiv(三甲基乙酸鈉)、KOPiv、NaOCOPh及KOCOPh或這些鹼之混合物。較佳的是碳酸鹽與羧酸鹽混合物。特別佳的是K2CO3與KOPiv混合物。
鹼的習用量是1-至5-莫耳比，以化合物(II)計。
適當的溶劑係，例如，芳香族類如甲苯、二甲苯、氯苯及甲氧苯；醚類如二丁基醚、二苯基醚，及聚乙二醇醚類；酯類如乙酸丁酯及乙酸異丙酯；醯胺類如二甲基乙醯胺、二甲基甲醯胺及二丁基甲醯胺，或其混合物。特別佳的是芳香族溶劑如二甲苯。
本發明之製備方法習用地是在超過100℃升溫至高達所用溶劑的沸點下進行。較佳的是自120至150℃之範圍。問題是所用之溶劑的沸點可能低於此，有用的是在超大氣壓力下進行。
較佳地方法是以前揭詳細說明之結構式化合物進行，其中取代基、符號及指數之定義如下： Y 係NR1R2或OR3，R1 係氫或COR4，R2 係COR4，R3 係Si(R5)3或2,2-二甲基丙醯基，R4 係第三丁基，R5 係異丙基，Hal 係溴或碘，R 係氟、甲基或甲氧基，X1 係氫或甲基，X2 係氫或甲基，X3 係氫或甲基，X4 係氫或甲基，或X1及X2，或X3及X4，或X1與X3 一起與其鍵結之碳原子形成一3-至7-員之飽和環，或Y與X1 一起與其鍵結之碳原子形成一5-至7-員之飽和環，m 係0、1、2或3。
在式(I)及所有化學式其依照，烷基具有超過兩個碳原子，可為直鏈或支鏈。烷基係例如甲基、乙基、正-或異丙基、正-、異-、第三或2-丁基、戊基、及己基，如正己基、異己基及1,3-二甲基丁基。
下列實施例例示本發明。
本文所用縮寫是：
一般操作說明：
在惰性氣體下，導入鈀催化劑(0.015毫莫耳，5莫耳%)、任意地膦配位子(0.03毫莫耳，10莫耳%)，及鹼，如三甲基乙酸鉀(0.030毫莫耳，10莫耳%)及K2CO3(0.3毫莫耳，1.0當量)，並加入溶劑(3毫升二甲苯)及式(II)化合物(0.3毫莫耳，1.0當量)。而後混合物在室溫下攪拌10分鐘，並加熱至140℃，而後在這個溫度攪拌16小時。反應混合物冷卻至室溫並過濾，去除溶劑，殘餘物以色層分析法純化。
實施例1：從[1-(2-溴苯基)-2,2-二甲基丙氧基](三異丙基)矽烷製備2,2-二甲基-2,3-二氫-1H-茚-1-基)氧基)三異丙基矽烷
反應依照一般操作指引進行，使用5莫耳%之Pd(PPh3)4，得到產率89%。
1H NMR(300MHz,CDCl3,293 K)δ 1.01(s,3H),1.06-1.25(m,24H),2.60(d,J=15.2Hz,1H),2.75(d,J=15.2Hz,1H),4.93(s,1H),7.11-7.22(m,3H),7.29-7.38(m,1H).
實施例2：從[1-(2-溴苯基)-環丙乙氧基](三異丙基)矽烷製備((2',3'-二氫螺旋[環丙烷-1,1'-茚]-3'-基)氧基)三異丙基矽烷
反應依照一般操作指引進行，使用5莫耳%之Pd(PPh3)4，得到產率69%。
1H NMR(300MHz,CDCl3,293 K)δ 0.70-0.82(m,1H),0.85-0.96(m,1H),1.00-1.27(m,23H),2.31(d,J=7.2Hz,2H),5.60(t,J=7.2Hz,1H),6.67-6.76(m,1H),7.17-7.27(m,2H),7.39-7.46(m,1H).
實施例3：從[1-(2-溴-4,5-二甲氧基苯基)-2,2-二甲基丙氧基](三-第三丁基)矽烷製備((5,6-二甲氧基-2,2-二甲基-2,3-二氫-1H-茚-1-基)氧基)三異丙基矽烷
反應依照一般操作指引進行，使用5莫耳%之Pd(PPh3)4，得到產率84%。
1H NMR(300MHz,CDCl3,293 K)δ 1.02(s,3H),1.06-1.25(m,24H),2.53(d,J=15.0Hz,1H),2.69(d,J=15.0Hz,1H),3.85(s,6H),4.86(s,1H),6.69(s,1H),6.89(s,1H).
實施例4：從[1-(2-溴-5-甲氧基苯基)-2,2-二甲基丙氧基](三-第三丁基)矽烷製備((6-甲氧基-2,2-二甲基-2,3-二氫-1H-茚-1-基)氧基)三異丙基矽烷
反應依照一般操作指引進行，使用5莫耳%之Pd(PPh3)4，得到產率81%。
1H NMR(300MHz,CDCl3,293 K)δ 0.98(s,3H),1.05-1.28(m,24H),2.54(d,J=14.8Hz,1H),2.65(d,J=14.8Hz,1H),3.79(s,3H),4.90(s,1H),6.73(dd,J=2.5,8.1Hz,1H),6.89(d,J=2.5Hz,1H),7.04(d,J=8.1Hz,1H).
實施例5：從[1-(2-溴-5-氟苯基)-2,2-二甲基丙氧基](三-第三丁基)矽烷製備((6-氟-2,2-二甲基-2,3-二氫-1H-茚-1-基)氧基)三異丙基矽烷
反應依照一般操作指引進行，使用5莫耳%之Pd(PPh3)4，得到產率84%。
1H NMR(300MHz,CDCl3,293 K)δ 1.00(s,3H),1.06-1.26(m,24H),2.55(d, J=15.0Hz,1H),2.68(d,J=15.0Hz,1H),4.90(s,1H),6.87(ddd,J=2.5,8.1,9.2Hz,1H),7.00(dd,J=2.5,8.7Hz,1H),7.07(dd,J=5.2,8.1Hz,1H).
實施例6：從1-(2-溴苯基)-2,2-二甲基丙基2,2-二甲基丙酸酯製備2，2-二甲基-2,3-二氫-1H-茚-1-基2,2-二甲基丙酸酯
反應依照一般操作指引進行，使用5莫耳%之Pd(PPh3)4，得到產率95%。
1H NMR(300MHz,CDCl3,293 K)δ 1.09(s,3H),1.16(s,3H),1.21(s,9H),2.69(d,J=15.3Hz,1H),2.87(d,J=15.3Hz,1H),5.81(s,1H),7.09-7.29(m,4H).
實施例7：從1-(2-溴基-5-甲氧苯基)-2,2-二甲基丙基2,2-二甲基丙酸酯製備6-甲氧基-2,2-二甲基-2,3-氫-1H-茚-1-基2,2-二甲基丙酸酯
反應依照一般操作指引進行，使用5莫耳%之Pd(PPh3)4，得到產率88%。
1H NMR(300MHz,CDCl3,293 K)δ 1.09(s,3H),1.16(s,3H),1.22(s,9H),2.63(d,J=15.3Hz,1H),2.80(d,J=15.3Hz,1H),3.77(s,3H),5.79(s,1H),6.77-6.84(m,2H),7.05-7.12(m,1H).
實施例8：從1-(2-溴-5-氟苯基)-2,2-二甲基丙基2,2-二甲基丙酸酯製備6-氟-2,2-二甲基-2,3-二氫-1H-茚-1-基2,2-二甲基丙酸酯
反應依照一般操作指引進行，使用5莫耳%之Pd(PPh3)4，得到產率76%。
1H NMR(300MHz,CDCl3,293 K)δ 1.08(s,3H),1.16(s,3H),1.22(s,9H), 2.65(d,J=15.4Hz,1H),2.81(d,J=15.4Hz,1H),5.76(s,1H),6.87-6.99(m,2H),7.08-7.15(m,1H).
實施例9：從5-(2-溴苯基)-4,4-二甲基二氫呋喃-2(3H)-酮製備(3aR*,8bS*)-3a-甲基-3,3a,4,8b-四氫-2H-茚酮[1,2-b]呋喃-2-酮
反應依照一般操作指引進行，使用5莫耳%之Pd(PPh3)4，得到產率88%。
1H NMR(300MHz,CDCl3,293 K)δ 1.34(s,3H),2.45(d,J=17.8Hz,1H),2.51(d,J=17.8Hz,1H),2.87(d,J=16.4Hz,1H),3.00(d,J=16.4Hz,1H),5.32(s,1H),7.13-7.29(m,3H),7.36(d,J=7.2Hz,1H).
實施例10：從2-[1-(2-溴苯基)-2-甲基丙基]-1H-異吲哚-1,3(2H)-二酮製備2-(2-甲基-2,3-二氫-1H-茚-1-基)異吲哚啉-1,3-二酮
反應依照一般操作指引進行，使用5莫耳%之Pd(PPh3)4，得到產率88%之反式異構物。
1H NMR(300MHz,CDCl3,293 K)δ 1.27(d,J=6.8Hz,3H),2.65(dd,J=8.6,15.6Hz,1H),3.00-3.18(m,1H),3.37(dd,J=8.2,15.6Hz,1H),5.43(d,J=8.2Hz,1H),7.01(d,J=7.6Hz,1H),7.11-7.19(m,1H),7.20-7.30(m,2H),7.70-7.79(m,2H),7.82-7.91(m,2H).
實施例11：從2-[1-(2-溴苯基)-2,2-二甲基丙基]-1H-異吲哚-1,3(2H)-二酮製備2-(2,2-二甲基-2,3-二氫-1H-茚-1-基)異吲哚啉-1,3-二酮
反應依照一般操作指引進行，使用5莫耳%之Pd(PPh3)4，得到產率86%。
1H NMR(300MHz,CDCl3,293 K)δ 0.64(s,3H),0.83(s,3H),2.34(d,J=15.6Hz,1H),2.87(d,J=15.6Hz,1H),4.9(s,1H),6.66-6.77(m,2H),6.80-6.89(m,2H),7.16-7.33(m,3H),7.42-7.49(m,1H).
實施例12：藉由2-[(1R,2S)-2,6-二甲基-2,3-二氫-1H-茚-1-基]-1H-異吲哚-1,3(2H)-二酮，從2-[1-(2-溴-5-甲基苯基)-2-甲基丙基]-1H-異吲哚-1,3(2H)-二酮製備(1R,2S)-2,6-二甲基二氫茚-1-胺
反應開始依照一般操作指引進行，使用5莫耳%之Pd(PPh3)4，得到產率55%之初級產物。
1H NMR(300MHz,CDCl3,293 K)δ 1.24(d,J=7.0Hz,3H),2.25(s,3H),2.58(dd,J=8.0,15.7Hz,1H),2.97-3.15(m,1H),3.32(dd,J=8.2,15.7Hz,1H),5.37(d,J=8.2Hz,1H),6.80(s,1H),7.03(d,J=7.5Hz,1H),7.14(d,J=7.5Hz,1H),7.70-7.78(m,2H),7.80-7.90(m,2H).
而後，在1毫升甲醇及1毫升THF中之0.17毫莫耳2-(2,6-二甲基-2,3-二氫-1H-茚-1-基)異吲哚啉-1,3-二酮溶液，在0℃下與1.7毫莫耳之聯胺水合物混合。而後混合液在室溫攪拌12小時。過濾混合液並濃縮。殘留物在DCM 與水之間分離，分離出有機層並以飽和NaHCO3沖洗。在MgSO4下乾燥並濃縮，得到產率98%之固體產物。
1H NMR(300MHz,CDCl3,293 K)δ 1.25(d,J=6.7Hz,3H),1.68(s,2H),1.90-2.08(m,1H),2.35(s,3H),2.44(dd,J=9.5,15.3Hz,1H),2.99(dd,J=7.7,15.3Hz,1H),3.76(d,J=8.3Hz,1H),7.01(d,J=7.5Hz,1H),7.08(d,J=7.5Hz,1H),7.13(s,1H).
實施例13：從[1-(2-溴苯基)-2-甲基丙氧基](三異丙基)矽烷製備三異丙基((2-甲基-2,3-二氫-1H-茚-1-基)氧基)矽烷
反應在不同鈀催化劑、膦配位子及不同量之鹼下進行。這些在不同條件達成之實驗結果，以表格顯示。
順式異構物：1H NMR(300MHz,CDCl3,293 K)δ 0.99(d,J=6.9Hz,3H), 1.08-1.25(m,21H),2.56-2.68(m,2H),2.92(dd,J=7.1,15.7Hz,1H),5.29(d,J=5.8Hz,1H),7.17-7.25(m,3H),7.35-7.43(m,1H).
反式異構物：1H NMR(300MHz,CDCl3,293 K)δ 1.05-1.31(m,24H),2.34-2.57(m,2H),3.10-3.33(m,1H),4.98(d,J=5.0Hz,1H),7.19-7.28(m,3H),7.37-7.46(m,1H)

Claims (11)

  1. 一種製備通式(I)1-二氫茚醇類及1-胺基二氫茚類之方法，其包括在升溫，使用鈀催化劑，於膦配位子、鹼及溶劑存在下，反應1-(2-鹵苯基)烷-1-醇類或1-(2-鹵苯基)烷-1-胺類(II)， 且其中取代基、符號及指數之定義如下：Y 係NR1R2或OR3，R1 係氫或COR4，R2 係COR4，或R1及R2一起形成COCH2CH2CO或CO-伸苯基-CO，R3 係Si(R5)3或2,2-二甲基丙醯基，R4 係(C1-C6)-烷基或苯基，R5 係(C1-C6)-烷基或苯基，Hal 係氯、溴或碘，R 係氟、(C1-C3)-烷基或(C1-C3)-烷氧基，X1 係氫或(C1-C6)-烷基，X2 係氫或(C1-C6)-烷基，X3 係氫或(C1-C6)-烷基，X4 係氫或(C1-C6)-烷基，或X1及X2，或X3及X4，或X1與X3 一起與其鍵結之碳原子形成一3-至7-員之飽和環，或 Y與X1 一起與其鍵結之碳原子形成一5-至7-員之飽和環，m係0、1、2或3。
  2. 如請求項1之方法，其中取代基、符號及指數具下列之定義：Y 係NR1R2或OR3，R1 係氫或COR4，R2 係COR4，R3 係Si(R5)3或2,2-二甲基丙醯基，R4 係第三丁基，R5 係異丙基，Hal 係溴或碘，R 係氟、甲基或甲氧基，X1 係氫或甲基，X2 係氫或甲基，X3 係氫或甲基，X4 係氫或甲基，或X1及X2，或X3及X4，或X1與X3 一起與其鍵結之碳原子形成一3-至7-員之飽和環，或Y與X1 一起與其鍵結之碳原子形成一5-至7-員之飽和環，m 係0、1、2或3。
  3. 如請求項1或2之方法，其中所述使用之鈀催化劑是選自包括Pd(OAc)2、三(二亞芐丙酮)二鈀(0)、PdCl2及PdBr2族群之化合物。
  4. 如請求項3之方法，其中所使用的是Pd(OAc)2。
  5. 如請求項1或2之方法，其中是使用三苯基膦作為配位子。
  6. 如請求項1或2之方法，其中是使用四(三苯基膦基)鈀作為組合之鈀催化劑及配位子。
  7. 如請求項1或2之方法，其中鈀催化劑及配位子，或其組合之使用量是0.1至10莫耳%，以化合物(II)計。
  8. 如請求項7之方法，其中鈀催化劑及配位子，或其組合之使用量是1至5莫耳%，以化合物(II)計。
  9. 如請求項1或2之方法，其中所述使用之鹼係鹼金屬碳酸鹽與鹼金屬三甲基乙酸鹽之混合物。
  10. 如請求項1或2之方法，其中所使用之鹼係1-至5-莫耳比，以化合物(II)計。
  11. 如請求項1或2之方法，其中所述使用之溶劑係選自芳香族類。
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