TWI798315B - 以配位體／鈀之比率進行二異丁烯之鈀催化羥基羰基化的方法 - Google Patents

以配位體／鈀之比率進行二異丁烯之鈀催化羥基羰基化的方法 Download PDF

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TWI798315B
TWI798315B TW107145726A TW107145726A TWI798315B TW I798315 B TWI798315 B TW I798315B TW 107145726 A TW107145726 A TW 107145726A TW 107145726 A TW107145726 A TW 107145726A TW I798315 B TWI798315 B TW I798315B
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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

以配位體/鈀之比率進行二異丁烯之鈀催化羥基羰基化的方法。

Description

以配位體／鈀之比率進行二異丁烯之鈀催化羥基羰基化的方法
本發明係關於以配位體/鈀之比率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、醇或醛的氧化，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H2 O而發生的羥基羧化提供合成羧酸的直接且方便的方法。
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 02_image001
其中該配位體L1係以每mole鈀加入1.0 mol 至2.0 mol之範圍的配位體L1的量， d) 加入乙酸， e) 在CO中進料， 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)係Pd(acac)2 。 在該方法的一個變化形中，該配位體L1係以每mole鈀加入1.25 mol至1.75 mol之範圍的配位體L1的量。 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°C至160°C的範圍之溫度，較佳係在100°C至140°C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，該方法包含其他的方法步驟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 02_image005
在4 mL小燒瓶中加入[Pd(acac)2 ](1.75 mg, 0.25 mol%)、L1(4.44 mg, 0.375 mol%)、H2 SO4 (3.1 mg, 1.4 mol%)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(0.29 ml)、乙酸(0.85 ml)以及二異丁烯(DIBN)(2.3 mmol)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(100 µl)作為內部標準。經由GC分析測量轉化率。 以改變L1/Pd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
*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. 一種用於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 107145726-A0305-02-0007-2
     其中該配位體L1係以每莫耳鈀加入1.0mol至2.0mol之範圍的配位體的量，d)加入乙酸，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 107145726-A0305-02-0007-3
  2. 如申請專利範圍第1項所述之方法，其中在方法步驟b)中之該化合物係選自於：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，其中該配位體L1係以每莫耳鈀加入1.25mol至1.75mol之範圍的配位體的量。
  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，其中該方法包含額外的方法步驟g)：g)加入硫酸。
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JPS53111008A (en) * 1977-03-04 1978-09-28 Basf Ag Process for preparing higer alkyl carboxylate
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