TWI790332B - 在乙酸／二異丁烯比率下進行二異丁烯之鈀催化羥基羰基化的方法 - Google Patents

在乙酸／二異丁烯比率下進行二異丁烯之鈀催化羥基羰基化的方法 Download PDF

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TWI790332B
TWI790332B TW107145636A TW107145636A TWI790332B TW I790332 B TWI790332 B TW I790332B TW 107145636 A TW107145636 A TW 107145636A TW 107145636 A TW107145636 A TW 107145636A TW I790332 B TWI790332 B TW I790332B
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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

在乙酸/二異丁烯比率下進行二異丁烯之鈀催化羥基羰基化的方法。

Description

在乙酸／二異丁烯比率下進行二異丁烯之鈀催化羥基羰基化的方法
本發明係關於在乙酸/二異丁烯比率下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，其用碘化物進行。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H2O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。該反應必須在一個步驟中進行。
經由如申請專利範圍第1項所述之方法完成該目的。
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 107145636-A0305-02-0004-1
d)加入乙酸，其中以每mole二異丁烯計，該乙酸的添加量在5mol至8mol之範圍，e)進料CO，f)加熱反應混合物以使該二異丁烯轉變為化合物P1：
Figure 107145636-A0305-02-0005-2
在該方法的一個變化形中，在方法步驟b)中的該化合物係選自於：PdCl2、PdBr2、Pd(acac)2、Pd(dba)2(dba=二苯乙烯基丙酮)、PdCl2(CH3CN)2。
在該方法的一個變化形中，在方法步驟b)中的該化合物係Pd(acac)2。
在該方法的一個變化形中，以每mole二異丁烯計，該乙酸的添加量在6mol至7mol之範圍。
在該方法的一個變化形中，在方法步驟f)中的該反應混合物係加熱至範圍在80℃至160℃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10巴至40巴之範圍的CO壓力下進行，較佳係10巴至30巴之範圍。
在該方法的一個變化形中，該方法包含該額外的方法步驟g)：g)加入硫酸。
經由以下的工作實施例更詳細地闡述本發明。
Figure 107145636-A0305-02-0006-3
在4mL小燒瓶中加入[Pd(acac)2](1.94mg,0.25mol%)、L1(4.92mg,0.375mol%)、H2SO4(1.3mg,0.52mol%)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。H2O(0.23ml)、乙酸(0.87ml)以及二異丁烯(DIBN)(2.5mmol)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(300ml)中。用CO沖洗高壓滅菌器三次後，在室溫下CO的壓力增加到15巴，且接著以N2將壓力增加到25巴。反應在120℃下進行3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(100μl)作為內部標準品。經由GC分析測量轉化率。
以改變CH3COOH/DIBN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 107145636-A0305-02-0007-5
*本發明方法
如實驗結果所示，該目的通過本發明的方法實現。

Claims (6)

  1. 一種進行二異丁烯之鈀催化羥基羰基化的方法，其包含以下方法步驟：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 107145636-A0305-02-0008-6
     d)加入乙酸，其中以每mole二異丁烯計，該乙酸的添加量在5mol至8mol之範圍，e)進料CO，f)加熱反應混合物以使該二異丁烯轉變為化合物P1：
    Figure 107145636-A0305-02-0008-7
  2. 如申請專利範圍第1項所述之方法，其中在方法步驟b)中的該化合物係選自於： 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項至第2項中任一項所述之方法，其中以每mole二異丁烯計，該乙酸的添加量在6mol至7mol之範圍。
  4. 如申請專利範圍第1項至第2項中任一項所述之方法，其中在方法步驟f)中的該反應混合物係加熱至範圍在80℃至160℃之溫度。
  5. 如申請專利範圍第1項至第2項中任一項所述之方法，其中在方法步驟e)中進料該CO以使該反應在10巴至40巴之範圍的CO壓力下進行。
  6. 如申請專利範圍第1項至第2項中任一項所述之方法，其中該方法包含該額外的方法步驟g)：g)加入硫酸。
TW107145636A 2017-12-21 2018-12-18 在乙酸／二異丁烯比率下進行二異丁烯之鈀催化羥基羰基化的方法 TWI790332B (zh)

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EP1657230A1 (de) * 2004-11-16 2006-05-17 Celanese Chemicals Europe GmbH Verfahren zur Herstellung von aliphatischen geradkettigen und ß-alkylverzweigten Carbonsäuren
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