TWI695825B - 將烯烴直接轉化為羧酸之方法 - Google Patents

將烯烴直接轉化為羧酸之方法 Download PDF

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TWI695825B
TWI695825B TW107145575A TW107145575A TWI695825B TW I695825 B TWI695825 B TW I695825B TW 107145575 A TW107145575 A TW 107145575A TW 107145575 A TW107145575 A TW 107145575A TW I695825 B TWI695825 B TW I695825B
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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

一種將烯烴直接轉化為羧酸之方法。

Description

將烯烴直接轉化為羧酸之方法
本發明係關於一種將烯烴直接轉化為羧酸之方法。
烯烴係用於聚合物、藥品、溶劑及食品添加劑的製備。獲得羧酸的途徑一般包括烴類、醇類或醛類之氧化，烯烴類藉由臭氧分解進行之氧化裂解，三酸甘油酯、腈類、酯類或醯胺類之水解，格任亞(Grignard)或有機鋰試劑之羧化，以及鹵化反應中甲基酮之鹵化和後續水解。
本發明目的係提供一種烯烴可藉以直接轉化成羧酸之方法。 在此申請案內文中，”直接轉化”擬意指反應係在單一步驟中完成，即無中間產物之分離或後處理或類似步驟。 此在反應過程中不排除形成繼續直接轉化之中間物。
該目的可藉由根據請求項第1項之方法達到。 一種方法，其包括下列程序步驟： a) 添加烯烴； b) 添加錯合物，其包含結構(1)之化合物以及Pd， 或添加結構(1)之化合物及含Pd之物質
Figure 02_image001
(1) c) 饋入CO； d) 加熱該反應混合物以使該烯烴轉化成羧酸，其中該烯烴係直接轉化成該羧酸。 在該方法之變化例中，該程序步驟b)之物質係選自：PdCl2 、PdBr2 、Pd(acac)2 、Pd(dba)2 (dba=二亞苄基丙酮)、PdCl2 (CH3 CN)2 。 在該方法之變化例中，該程序步驟b)之物質係Pd(acac)2 。 在該方法之變化例中，該方法包括附加程序步驟e)： e)添加乙酸。 在該方法之變化例中，該方法包括附加程序步驟f)： f)添加水。 在該方法之變化例中，該方法包括附加程序步驟g)： g)添加對-甲苯磺酸(PTSA)。 在該方法之變化例中，該反應混合物係在程序步驟d)中加熱至範圍從80℃至160℃之溫度。 在該方法之較佳變化例中，該反應混合物係在程序步驟d)中加熱至範圍從100℃至140℃之溫度。 在該方法之變化例中，在程序步驟c)中饋入該CO以使該反應係在範圍從20巴至60巴之CO壓力下進行。 在該方法之較佳變化例中，在程序步驟c)中饋入CO以使該反應係在範圍從30巴至50巴之CO壓力下進行。 本發明藉由參考工作實例更具體地說明於下文中。 配位基之變化
Figure 02_image003
將Pd(acac)2 ](3.05毫克，0.25莫耳%)、配位基(X )(1.0莫耳%)、對-甲苯磺酸(28.5毫克，3.75莫耳%)及經烘乾之攪拌棒裝入4毫升小玻璃瓶中。然後以隔膜(塗有PTFE之苯乙烯-丁二烯橡膠)及酚樹脂瓶蓋密封小玻璃瓶。抽空該小玻璃瓶並反覆以氬氣裝滿三次。利用注射器將H2 O(0.5毫升)、乙酸(1.5毫升)及二異丁烯(DIBN)(4.0毫莫耳)加入小玻璃瓶中。將小玻璃瓶置於一合金盤中，再將其移至一處於氬氣氛圍下購自Parr Instruments之4560系列高壓釜(300毫升)中。以CO沖洗該高壓釜三次之後，在室溫下將CO的壓力增加至40巴。令反應在120℃下進行20小時。在反應結束時，將高壓釜冷卻至室溫並小心地減壓。然後加入異辛烷(100微升)作為內標準品。藉由GC分析測量轉化率。 以改變配位基(X)，X = 1至8的方式進行上述實驗。 結果係彙集於下表1中： 表1
Figure 02_image005
*本發明方法 烯烴之變化
Figure 02_image007
將Pd(acac)2 ](3.07毫克，0.25莫耳%)、配位基(1 ) (20.64毫克，1.0莫耳%)、對-甲苯磺酸(28.5毫克，3.75莫耳%)及經烘乾之攪拌棒裝入4毫升小玻璃瓶中。然後以隔膜(塗有PTFE之苯乙烯-丁二烯橡膠)及酚樹脂瓶蓋密封小玻璃瓶。然後以針令小玻璃瓶通大氣。抽空該小玻璃瓶並反覆以氬氣裝滿三次。利用注射器將H2 O(0.5毫升)、乙酸(1.5毫升)及烯烴(4.0毫莫耳)加入小玻璃瓶中。將小玻璃瓶置於一合金盤中，再將其移至一處於氬氣氛圍下購自Parr Instruments之4560系列高壓釜(300毫升)中。以CO沖洗該高壓釜三次之後，在室溫下將CO的壓力增加至40巴。令反應在120℃下進行20小時。在反應結束時，將高壓釜冷卻至室溫並小心地減壓。然後加入異辛烷(100微升)作為內標準品。藉由GC分析測量轉化率。 透過改變烯烴重覆上述實驗。 結果係匯集於下表2中： 表2：
Figure 02_image009
如實驗結果顯示，藉由根據本發明方法可達到該目的。

Claims (7)

  1. 一種將烯烴直接轉化為羧酸之方法，其包括下列程序步驟：a)添加烯烴；b)添加錯合物，其包含結構(1)之化合物以及Pd，或添加結構(1)之化合物及含Pd之物質
    Figure 107145575-A0305-02-0009-1
     c)饋入CO：d)加熱該反應混合物以使該烯烴轉化成羧酸，其中該烯烴係直接轉化成該羧酸。
  2. 根據請求項1之方法，其中該程序步驟b)之物質係選自：PdCl2、PdBr2、Pd(acac)2、Pd(dba)2(dba=二亞苄基丙酮)、PdCl2(CH3CN)2。
  3. 根據請求項1之方法，其中該方法包括附加程序步驟e)： e)添加乙酸。
  4. 根據請求項1至3中任一項之方法，其中該方法包括附加程序步驟f)：f)添加水。
  5. 根據請求項1至3中任一項之方法，其中該方法包括附加程序步驟g)：g)添加對-甲苯磺酸。
  6. 根據請求項1至3中任一項之方法，其中該反應混合物係在程序步驟d)中加熱至範圍從80℃至160℃之溫度。
  7. 根據請求項1至3中任一項之方法，其中在程序步驟c)中饋入該CO以使該反應係在範圍從20巴至60巴之CO壓力下進行。
TW107145575A 2017-12-21 2018-12-18 將烯烴直接轉化為羧酸之方法 TWI695825B (zh)

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