TWI789468B - Ｏ之比率來進行二異丁烯之鈀催化羥基羰基化的方法 - Google Patents

Ｏ之比率來進行二異丁烯之鈀催化羥基羰基化的方法 Download PDF

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TWI789468B
TWI789468B TW107145724A TW107145724A TWI789468B TW I789468 B TWI789468 B TW I789468B TW 107145724 A TW107145724 A TW 107145724A TW 107145724 A TW107145724 A TW 107145724A TW I789468 B TWI789468 B TW I789468B
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桑睿
彼得 庫米伊克
董開武
雷夫 傑克斯泰爾
馬席爾斯 貝勒
羅柏特 法蘭克
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Abstract

依3,5,5-三甲基己酸/H2 O之比率來進行二異丁烯之鈀催化羥基羰基化的方法。

Description

依３，５，５－三甲基己酸／Ｈ２Ｏ之比率來進行二異丁烯之鈀催化羥基羰基化的方法
本發明係關於依3,5,5-三甲基己酸/H2 O之比率來進行二異丁烯之鈀催化羥基羰基化的方法。
包括丙酸、己二酸以及脂肪酸的羧酸用於製備聚合物、藥物、溶劑和食品添加劑。產生羧酸的途徑通常包括烴類、醇類或醛類的氧化，經由臭氧分解的烯烴的氧化裂解，甘油三酯、腈、酯或醯胺的水解，格氏試劑(Grignard)或有機鋰試劑的羧化，以及鹵化和隨後鹵代反應中的甲基酮的水解。 烯烴的羥基羧化是用於獲得羧酸的非常有前途以及環境友好的方法。經由甲醇的羰基化產生乙酸，其與碘化物進行。在Koch反應中，向烯烴中加入水和一氧化碳是經由強鹼催化的。該方法對於形成二級和三級碳陽離子的烯烴是有效的，例如，異丁烯至新戊酸。通過同時向烯烴/炔烴中加入CO和H2 O而發生的羥基羧化提供合成羧酸直接且方便的方法。
本發明之目的係提供在二異丁烯(DIBN)之鈀催化羥基羰基化中的良好轉換方法。 經由如申請專利範圍第1項所述之方法完成該目的。 方法，包含以下步驟： a) 加入二異丁烯， b) 加入含有鈀的化合物，其中該鈀係具有能形成錯合物之能力， c) 加入配位體L1 ：
Figure 02_image001
d) 加入3,5,5-三甲基己酸及水，其中基於所使用的體積範圍為0.75/1.25至1.8/0.2之比率， e) CO進料， f) 加熱該反應混合物以使該二異丁烯轉變為該化合物P1 ：
Figure 02_image003
。 在該方法的一個變化形中，該化合物在方法步驟b)係選自於：PdCl2 、PdBr2 、Pd(acac)2 、Pd(dba)2 (dba =二苯乙烯基丙酮)、PdCl2 (CH3 CN)2 。 在該方法的一個變化形中，該方法步驟b)中之該化合物係Pd(acac)2 。 在該方法的一個變化形中，該方法包含該其他的反應步驟g)： g) 加入CF3 SO3 H。 在該方法的一個變化形中，在方法步驟f)中該反應混合物係加熱至80℃至160℃的範圍之溫度， 較佳係在100℃至140℃的範圍之溫度。 在該方法的一個變化形中，在方法步驟e)中進料該CO以使該反應在20巴至60巴之範圍的CO壓力下進行，較佳係30巴至50巴之範圍。 在該方法的一個變化形中，該3,5,5-三甲基己酸及水的比率係基於所使用的體積在1.0/1.0至1.8/0.2之範圍。 在該方法的一個變化形中，每1 mmol的二異丁烯加入3,5,5-三甲基己酸量係在0.3 ml至0.4 ml之範圍。
經由以下的工作實施例更詳細地闡述本發明。
Figure 02_image005
在4 mL小燒瓶中加入[Pd(acac)2 ](3.05mg，0.25mol％)、L1(20.64mg，1.0mol％)和已烘箱乾燥的攪拌棒。然後用隔膜(PTFE塗覆的苯乙烯-丁二烯橡膠)和酚醛樹脂蓋密封小燒瓶。將小燒瓶抽真空並用氬氣再填充三次。H2 O (0.5 ml)、3,5,5-三甲基己酸(1.5 ml)、二異丁烯(DIBN)(4.0 mmol)和CF3 SO3 (7.5 mol%)經由針筒加入至小燒瓶。將小燒瓶至於合金板上，在氬氣氛下將其轉移至Parr Instruments的4560系列高壓滅菌器(300 ml)中。用CO沖洗高壓滅菌器三次後，在室溫下CO的壓力增加到40巴。反應在120℃下進行20小時。在反應結束時，將高壓滅菌器冷卻至室溫並小心地解壓。然後加入異辛烷(100 µl)作為內部標準品。經由GC分析測量轉化率。 以改變3,5,5-三甲基己酸/水的比率重複上述實驗。維持所有其他的參數。 該結果整理如下表中。
Figure 02_image007

Claims (7)

  1. 一種依3,5,5-三甲基己酸/H2O之比率來進行二異丁烯之鈀催化羥基羰基化的方法，其包含以下步驟：a)加入二異丁烯，b)加入含有鈀的化合物，其中該鈀係具有能形成錯合物之能力，c)加入配位體L1：
    Figure 107145724-A0305-02-0007-1
     d)加入3,5,5-三甲基己酸及水，其中基於所使用的體積範圍為0.75/1.25至1.8/0.2之比率，e)CO進料，f)加熱反應混合物以使該二異丁烯轉變為化合物P1：
    Figure 107145724-A0305-02-0007-2
  2. 如申請專利範圍第1項所述之方法，其中該化合物在方法步驟b)係選自於：PdCl2、PdBr2、Pd(acac)2、Pd(dba)2(dba=二苯乙烯基丙酮)、PdCl2(CH3CN)2。
  3. 如申請專利範圍第1項及第2項任一項所述之方法，其中該方法包含該其他的反應步驟g)：g)加入CF3SO3H。
  4. 如申請專利範圍第1項及第2項任一項所述之方法，其中在方法步驟f)中該反應混合物係加熱至80℃至160℃的範圍之溫度。
  5. 如申請專利範圍第1項及第2項任一項所述之方法，其中在方法步驟e)中進料該CO以使該反應在20巴至60巴之範圍的CO壓力下進行。
  6. 如申請專利範圍第1項及第2項任一項所述之方法，其中該3,5,5-三甲基己酸及水的比率係基於所使用的體積在1.0/1.0至1.8/0.2之範圍。
  7. 如申請專利範圍第1項及第2項任一項所述之方法，其中每1mmol的二異丁烯加入3,5,5-三甲基己酸量係在0.3ml至0.4ml之範圍。
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