TWI679193B - 使用甲酸作為ｃｏ源之甲氧羰基化反應 - Google Patents

使用甲酸作為ｃｏ源之甲氧羰基化反應 Download PDF

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TWI679193B
TWI679193B TW107127034A TW107127034A TWI679193B TW I679193 B TWI679193 B TW I679193B TW 107127034 A TW107127034 A TW 107127034A TW 107127034 A TW107127034 A TW 107127034A TW I679193 B TWI679193 B TW I679193B
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桑睿
Rui SANG
劉劼
Jie Liu
董開武
Kaiwu DONG
雷夫 傑克斯泰爾
Ralf Jackstell
馬席爾斯 貝勒
Matthias Beller
羅柏特 法蘭克
Robert Franke
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德商贏創德固賽有限責任公司
Evonik Degussa Gmbh
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Abstract

一種使用甲酸做為CO源之甲氧羰基化反應的方法。

Description

使用甲酸作為ＣＯ源之甲氧羰基化反應
本發明係關於一種使用甲酸做為CO源之甲氧羰基化反應的方法。
烯類之甲氧羰基化反應是一種重要性逐漸提高之方法。在典型的甲氧羰基化反應中，烯烴係在包含配位基和金屬之觸媒的存在下與CO和MeOH反應：在此，CO以氣體形態導入反應槽中。
本發明之目的是要提供一種利用CO氣體以外之CO源之方法，該CO源被導入該反應槽中。該方法將獲得高產率的甲酯。 　　本發明之目的係藉由根據申請專利範圍第1項的方法達成。 　　該方法為一種包含下列方法步驟的方法： 　　a) 添加烯烴； 　　b) 添加包含Pd之化合物，其中該Pd能形成錯合物； 　　c) 添加通式(I )之化合物：其中R1 、R2 、R3 、R4 各自獨立選自：-H、-(C1 -C12 )-烷基、-O-(C1 -C12 )-烷基、-(C4 -C14 )-芳基、-O-(C4 -C14 )-芳基、環烷基、-(C1 -C12 )-雜烷基、-O-(C1 -C12 )-雜烷基、 -(C3 -C14 )-雜芳基、-O-(C3 -C14 )-雜芳基、-COO-烷基、 -COO-芳基、-C-O-烷基、-C-O-芳基、NH2 、鹵素，且該等殘基也能形成較大縮合環； 　　其中該經列舉之烷基基團、芳基基團、環烷基、雜烷基基團、雜芳基基團可經下列取代： 　　-(C1 -C12 )-烷基、-O-(C1 -C12 )-烷基、鹵素； 　　且該等基團R1 、R2 、R3 、R4 中之至少一者不表示苯基； 　　d) 添加MeOH和HCOOH， 　　其中基於所用之體積，該MeOH/HCOOH比率是在1.55:0.45至1.1:0.9之範圍中； 　　e) 加熱該反應混合物以轉變該烯烴成甲酯。 　　在該方法之一變化型中，不供應CO氣體至該反應混合物。 　　在該方法之一變化型中，HCOOH用作為該反應之唯一CO源。 　　在該方法之一變化型中，在方法步驟b)中之化合物係選自：Pd(acac)2 、PdCl2 、Pd(dba)3 *CH3 Cl(dba=二亞苄基丙酮)、Pd(OAc)2 、Pd(TFA)2 、Pd(CH3 CN)Cl2 。 　　在該方法之一變化型中，在方法步驟b)中之化合物係Pd(OAc)2 。 　　在該方法之一變化型中，該方法包含額外方法步驟f)： 　　f)添加酸。 　　在該方法之一變化型中，該酸係選自：H2 SO4 、CH3 SO3 H、CF3 SO3 H、PTSA (對-甲苯磺酸)。 　　在該方法之一變化型中，該酸是PTSA(對-甲苯磺酸)。 　　在該方法之一變化型中，基於所用之體積，該MeOH/HCOOH比率是在1.5:0.5至1.2:0.8之範圍中。 　　在該方法之一變化型中，R1 、R2 、R3 、R4 各自獨立選自：-(C1 -C12 )-烷基、-O-(C1 -C12 )-烷基、-(C4 -C14 )-芳基、 -O-(C4 -C14 )-芳基、環烷基、-(C1 -C12 )-雜烷基、-O-(C1 -C12 )-雜烷基、-(C3 -C14 )-雜芳基、-O-(C3 -C14 )-雜芳基、 -COO-烷基、-COO-芳基、-C-O-烷基、-C-O-芳基、NH2 、鹵素，且該等殘基也能形成較大縮合環； 　　其中該經列舉之烷基基團、芳基基團、環烷基、雜烷基基團、雜芳基基團可經下列取代： 　　-(C1 -C12 )-烷基、-O-(C1 -C12 )-烷基、鹵素； 　　且該等基團R1 、R2 、R3 、R4 中之至少一者不表示苯基。 　　在該方法之一變化型中，R1 、R2 、R3 、R4 各自獨立選自：-(C1 -C12 )-烷基、-(C4 -C14 )-芳基、環烷基、-(C1 -C12 )-雜烷基、-(C3 -C14 )-雜芳基、鹵素，且該等殘基也能形成較大縮合環； 　　其中該經列舉之烷基基團、芳基基團、環烷基、雜烷基基團、雜芳基基團可經下列取代： 　　-(C1 -C12 )-烷基、-O-(C1 -C12 )-烷基、鹵素； 　　且該等基團R1 、R2 、R3 、R4 之至少一者不表示苯基。 　　在該方法之一變化型中，R1 、R2 、R3 、R4 各自獨立選自：-(C1 -C12 )-烷基、環烷基、-(C3 -C14 )-雜芳基，且該等殘基也能形成較大縮合環； 　　其中該經列舉之烷基基團、環烷基、雜芳基基團可經下列取代： 　　-(C1 -C12 )-烷基、-O-(C1 -C12 )-烷基、鹵素； 　　且該等基團R1 、R2 、R3 、R4 中之至少一者不表示苯基。 　　在該方法之一變化型中，R1 、R4 各自獨立選自：-(C1 -C12 )-烷基、環烷基，且該等殘基也能形成較大縮合環； 　　其中該經列舉之烷基基團、環烷基可經下列取代： 　　-(C1 -C12 )-烷基、-O-(C1 -C12 )-烷基、鹵素。 　　在該方法之一變化型中，R2 、R3 各自獨立表示：-(C3 -C14 )-雜芳基， 　　其中該經列舉之雜芳基基團可經如下者取代： 　　-(C1 -C12 )-烷基、-O-(C1 -C12 )-烷基、鹵素。 　　在該方法之一變化型中，通式(I )之化合物具有結構(2 )：。 　　在該方法之一變化型中，通式(I )之化合物具有結構(3 )：。 　　除了所述之方法之外，本發明也主張化合物本身的權利。 　　該化合物為具有結構(3 )之化合物：。
本發明將藉由以下的實施例而更詳細說明。 A) 利用HCOOH之經Pd催化之四甲基乙烯1a 的甲氧羰基化反應：MeOH與HCOOH之比率的影響添加[Pd(OAc)2 ] (1.12 mg, 0.25 mol%)、(2 )(8.72 mg, 1.0 mol%)、對-甲苯磺酸(PTSA·H2 O)(15.2 mg, 4 mol%)和經烘乾之攪拌棒至經密封之35 ml管內。將管與蓋子一同置於具有大開口之長的Schlenk管。Schlenk管經抽空且再填充氬重複三次。在氬氣環境下，使用注射器將1a (2 mmol)、MeOH (X ml)和HCOOH(Y ml) (X ml + Y ml = 2 ml)注入至35 ml管中。然後用蓋子將35 ml管密封。反應在100℃下進行超過13小時。在反應結束後，在無額外冷卻且小心洩壓下，令反應管到達室溫。然後，注射異辛烷(100 μl)作為內部標準。轉化率藉由GC分析測量。 　　結果摘述於如下表1：B) 利用HCOOH之經Pd催化之四甲基乙烯1a 的甲氧羰基化反應：配位基之影響在氬氣環境下，添加[Pd(OAc)2 ](1.12 mg, 0.25 mol%)、配位基(1 mol%)、對-甲苯磺酸(PTSA·H2 O)(15.2 mg, 4 mol%)和經烘乾之攪拌棒至經密封之35 ml管。將管與蓋子一同置於具有大開口之長的Schlenk管。Schlenk管經抽空且再填充氬重複三次。使用注射器將1a (2 mmol)、HCOOH (0.5 ml)和MeOH (1.5 ml)注入至35 ml管中。然後用蓋子密封35 ml管。反應在100℃下進行超過13小時。在反應結束後，在無額外冷卻(若使用極冷之水，則管可能爆裂)且小心洩壓下，令反應管到達室溫。然後，注射異辛烷(100 μl)作為內部標準。轉化率藉由GC分析測量。 　　結果摘述於如下表2：如上述實驗所顯示，本發明之目的係藉由根據本發明之方法達成。

Claims (15)

  1. 一種使用甲酸作為CO源之甲氧羰基化反應的方法，其包含下列方法步驟：a)添加烯烴；b)添加包含Pd之化合物，其中該Pd能形成錯合物；c)添加通式(I)之化合物：其中R1、R2、R3、R4各自獨立選自：-H、-(C1-C12)-烷基、-O-(C1-C12)-烷基、-(C4-C14)-芳基、-O-(C4-C14)-芳基、環烷基、-(C1-C12)-雜烷基、-O-(C1-C12)-雜烷基、-(C3-C14)-雜芳基、-O-(C3-C14)-雜芳基、-COO-烷基、-COO-芳基、-C-O-烷基、-C-O-芳基、NH2、鹵素，且該等殘基也能形成較大縮合環；其中該經列舉之烷基基團、芳基基團、環烷基、雜烷基基團、雜芳基基團可經下列取代：-(C1-C12)-烷基、-O-(C1-C12)-烷基、鹵素；且該等基團R1、R2、R3、R4中之至少一者不表示苯基；d)添加MeOH和HCOOH，其中基於所用之體積，該MeOH/HCOOH比率是在1.55：0.45至1.1：0.9之範圍中；e)加熱該反應混合物以轉變該烯烴成甲酯。
  2. 如申請專利範圍第1項之方法，其中不供應CO氣體至該反應混合物。
  3. 如申請專利範圍第1或2項之方法，其中HCOOH用作為該反應之唯一CO源。
  4. 如申請專利範圍第1項之方法，其中在方法步驟b)中之化合物係選自：Pd(acac)2、PdCl2、Pd(dba)3*CH3Cl(dba=二亞苄基丙酮)、Pd(OAc)2、Pd(TFA)2、Pd(CH3CN)Cl2。
  5. 如申請專利範圍第1項之方法，其中該方法包含額外方法步驟f)：f)添加酸。
  6. 如申請專利範圍第5項之方法，其中該酸係選自：H2SO4、CH3SO3H、CF3SO3H、PTSA。
  7. 如申請專利範圍第1項之方法，其中基於所用之體積，該MeOH/HCOOH比率是在1.5：0.5至1.2：0.8之範圍中。
  8. 如申請專利範圍第1項之方法，其中R1、R2、R3、R4各自獨立選自：-(C1-C12)-烷基、-O-(C1-C12)-烷基、-(C4-C14)-芳基、-O-(C4-C14)-芳基、環烷基、-(C1-C12)-雜烷基、-O-(C1-C12)-雜烷基、-(C3-C14)-雜芳基、-O-(C3-C14)-雜芳基、-COO-烷基、-COO-芳基、-C-O-烷基、-C-O-芳基、NH2、鹵素，且該等殘基也能形成較大縮合環；其中該經列舉之烷基基團、芳基基團、環烷基、雜烷基基團、雜芳基基團可經下列取代：-(C1-C12)-烷基、-O-(C1-C12)-烷基、鹵素；且該等基團R1、R2、R3、R4中之至少一者不表示苯基。
  9. 如申請專利範圍第1項之方法，其中R1、R2、R3、R4各自獨立選自：-(C1-C12)-烷基、-(C4-C14)-芳基、環烷基、-(C1-C12)-雜烷基、-(C3-C14)-雜芳基、鹵素，且該等殘基也能形成較大縮合環；其中該經列舉之烷基基團、芳基基團、環烷基、雜烷基基團、雜芳基基團可經下列取代：-(C1-C12)-烷基、-O-(C1-C12)-烷基、鹵素；且該等基團R1、R2、R3、R4中之至少一者不表示苯基。
  10. 如申請專利範圍第1項之方法，其中R1、R2、R3、R4各自獨立選自：-(C1-C12)-烷基、環烷基、-(C3-C14)-雜芳基，且該等殘基也能形成較大縮合環；其中該經列舉之烷基基團、環烷基、雜芳基基團可經下列取代：-(C1-C12)-烷基、-O-(C1-C12)-烷基、鹵素；且該等基團R1、R2、R3、R4中之至少一者不表示苯基。
  11. 如申請專利範圍第1項之方法，其中R1、R4各自獨立選自：-(C1-C12)-烷基、環烷基，且該等殘基也能形成較大縮合環；其中該經列舉之烷基基團、環烷基可經下列取代：-(C1-C12)-烷基、-O-(C1-C12)-烷基、鹵素。
  12. 如申請專利範圍第1項之方法，其中R2、R3各自獨立表示：-(C3-C14)-雜芳基，其中該經列舉之雜芳基基團可經下列取代：-(C1-C12)-烷基、-O-(C1-C12)-烷基、鹵素。
  13. 如申請專利範圍第1項之方法，其中通式(I)之化合物具有結構(2)：
  14. 如申請專利範圍第1項之方法，其中通式(I)之化合物具有結構(3)：
  15. 一種具有結構(3)之化合物，
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