TW202214666A - ６，６’－（〔１，１’－聯苯基〕－２，３’－二基雙（氧基））雙二苯并〔ｄ，ｆ〕〔１，３，２〕二磷呯 - Google Patents

６，６’－（〔１，１’－聯苯基〕－２，３’－二基雙（氧基））雙二苯并〔ｄ，ｆ〕〔１，３，２〕二磷呯 Download PDF

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TW202214666A
TW202214666A TW110129943A TW110129943A TW202214666A TW 202214666 A TW202214666 A TW 202214666A TW 110129943 A TW110129943 A TW 110129943A TW 110129943 A TW110129943 A TW 110129943A TW 202214666 A TW202214666 A TW 202214666A
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biphenyl
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diylbis
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羅柏特 法蘭克
亞敏 柏納
斯文尼亞 克勞斯
戴特雷夫 瑟倫特
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德商贏創運營有限公司
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Abstract

6,6'-([1,1'-聯苯基]-2,3'-二基雙(氧基))雙二苯並[d,f][1,3,2]二㗁磷呯及其在氫甲醯化中之用途。

Description

６，６’－（〔１，１’－聯苯基〕－２，３’－二基雙（氧基））雙二苯并〔ｄ，ｆ〕〔１，３，２〕二磷呯
本發明係關於6,6'-([1,1'-聯苯基]-2,3'-二基雙(氧基))雙二苯並[d,f][1,3,2]二㗁磷呯及其在氫甲醯化中之用途。
含磷化合物作為配位基在多種反應中例如在氫化、氫氰化以及亦在氫甲醯化中扮演至關重要的角色。
在催化劑存在下，烯烴化合物、一氧化碳及氫氣之間反應產生具有多一個碳原子的醛之反應稱為氫甲醯化或羰氧化法(oxo process)。在這些反應中所使用的催化劑通常是元素週期表第VIII族過渡金屬之化合物。已知的配位基係例如來自膦、亞磷酸酯(phosphite)及亞膦酸酯(phosphonite)類的化合物，其各者含有三價磷P III。關於烯烴之氫甲醯化情況的良好概述可見於R. Franke, D. Selent, A. Börner, “Applied Hydroformylation”, Chem. Rev., 2012, DOI:10.1021/cr3001803。
在EP 0 577 042 A1第6頁中描述以下配位基：
Figure 02_image001
。
本發明之技術目的是提供與先前技術已知的配位基相比在烯烴的氫甲醯化中展現出增加的正/異選擇性之新配位基。
該目的係藉由如請求項1之化合物來實現。
一種結構(I)之化合物：
Figure 02_image003
其中R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8係選自：-H、-(C 1-C 12)烷基、-O-(C 1-C 12)烷基。
在一個實施例中，R 1、R 4、R 5、R 8係選自：-H、-(C 1-C 12)烷基。
在一個實施例中，基團R 1、R 4、R 5、R 8中之至少一者係-H。
在一個實施例中，R 1、R 4、R 5、R 8係-H。
在一個實施例中，R 2、R 3、R 6、R 7係選自：-H-、-O-(C 1-C 12)烷基。
在一個實施例中，基團R 2、R 3、R 6、R 7中之至少一者係-H。
在一個實施例中，R 2、R 3、R 6、R 7係-H。
在一個實施例中，化合物具有結構(1)：
Figure 02_image005
。
除了化合物本身，其用於催化氫甲醯化反應之用途亦為所請。 上述化合物用在配位基-金屬錯合物中以催化氫甲醯化反應。
額外所請的是一種方法，在該方法中使用上述化合物作為配位基。
一種方法，其包含下列方法步驟： a)初始地裝入烯烴， b)添加上述化合物及含有選自下列之金屬的物質：Rh、Ru、Co、Ir， c)饋入H 2及CO， d)加熱來自步驟a)至c)的反應混合物，而將烯烴轉化為醛。
在一較佳實施例中，金屬係Rh。
在此亦可過量使用配位基，並且各配位基以結合形式作為配位基-金屬錯合物存在的情況並非自動地；反而是可作為游離配位基存在於反應混合物中。
反應在慣用的條件下進行。
較佳者係80℃至160℃的溫度及10至60巴的壓力。 特佳者係100℃至140℃的溫度及20至50巴的壓力。
在本發明之方法中用於加氫甲醯化之反應物係烯烴或烯烴的混合物，尤其是具有2至24個、較佳係3至16個且更佳係3至12個碳原子並具有末端或內部C-C雙鍵之單烯烴，例如1-丙烯；1-丁烯；2-丁烯；1-或2-戊烯；2-甲基-1-丁烯；2-甲基-2-丁烯；3-甲基-1-丁烯；1-、2-或3-己烯；在丙烯之二聚合中所得之C 6烯烴混合物(二丙烯)；庚烯；2-或3-甲基-1-己烯；辛烯；2-甲基庚烯；3-甲基庚烯；5-甲基-2-庚烯；6-甲基-2-庚烯；2-乙基-1-己烯；在丁烯之二聚合中所得之C 8烯烴混合物(二正丁烯、二異丁烯)；壬烯；2-或3-甲基辛烯；在丙烯之三聚合中所得之C 9烯烴混合物(三丙烯)；癸烯；2-乙基-1-辛烯；十二烯；在丙烯之四聚合或丁烯之三聚合中所得之C 12烯烴混合物(四丙烯或三丁烯)；十四烯；十六烯；在丁烯之四聚合中所得之C 16烯烴混合物(四丁烯)；及藉由烯烴之共寡聚合所產生之具有不同碳原子數(較佳係2至4個)的烯烴混合物。
使用本發明之配位基的本發明之方法可用於α-烯烴、末端支鏈烯烴、內部烯烴及內部支鏈烯烴的氫甲醯化。
下文將參考例示性實施例詳細說明本發明。
工作程序 一般分析
以下所有製備都是在惰性氣體下使用標準Schlenk技術進行。溶劑在使用前用合適的乾燥劑乾燥。 產物藉由NMR光譜示性。化學位移(δ)係以ppm記述。 31P NMR信號參考如下：SR 31P=SR 1H * (BF 31P/BF 1H) =SR 1H * 0.4048。
6,6'-([1,1'-聯苯基]-2,3'-二基雙(氧基))雙二苯並[d,f][1,3,2]二㗁磷呯(1)之合成
Figure 02_image007
將0.10 g的2,3'-聯苯酚(0.56 mmol)及0.3 ml的三乙胺(2.24 mmol)於4 ml的THF中之溶液在-20℃下逐滴添加至0.39 g於4 ml的THF中之6-氯二苯並[ d,f][1,3,2]-二㗁磷呯(1.56 mmol)中。將溶液進一步攪拌並溫熱至室溫過夜。然後在減壓下除去溶劑，將殘餘物置於10 ml的甲苯中並通過G4玻璃料過濾。然後在減壓下移除濾液的溶劑。將留下的黃色油狀物藉由管柱層析法(洗提液混合物為二氯甲烷/正庚烷=3：7)進行後處理(worked up)。得到0.10 g的白色固體(產率：30%)。 1H NMR (300 MHz, CD 2Cl 2): δ (ppm)=7.39-7.53 (m; 6H); 7.18-7.39 (m; 16H); 7.00-7.05 (m; 2H)。 13C NMR (75 MHz, CD 2Cl 2): δ (ppm)=151.8 (d; J CP=7.9 Hz); 149.2 (d; J CP=5.0 Hz); 149.2 (d; J CP=5.0 Hz); 149.0 (d; J CP=7.6 Hz; C ArOP); 139.9; (d; J CP=3.2 Hz); 133.3; 131.5; 131.4 (d; J CP=3.3 Hz); 131.3 (d; J CP=3.3 Hz); 130.3; 130.2; 129.9; 129.6; 129.4; 126.3; 125.8; 125.8; 125.1; 122.4; 122.3; 121.4; 121.2; 119.8; 119.6。 31P NMR (121 MHz, CD 2Cl 2): δ (ppm)=144.3 (s); 144.0 (s)。 HRMS (ESI):C 36H 24O 6P 2(M+H +)之計算值615.11209，實測值615.11174。C 36H 24O 6P 2(M+Na +)之計算值637.09403，實測值637.09386。
2,2'-雙(二苯並[d,f][1,3,2]二㗁磷呯-6-基氧基)-1,1'-聯苯(2)之合成(比較性配位基)
Figure 02_image009
將0.99 g的2,2'-聯苯酚(5.29 mmol)及3 ml的三乙胺(21.2 mmol)於7 ml的THF中之溶液在-20℃下逐滴添加至2.65 g於7 ml的THF中之6-氯二苯並[ d,f][1,3,2]-二㗁磷呯(10.59 mmol)中。將溶液在室溫下進一步攪拌過夜。然後在減壓下移除溶劑並將殘餘物置於15ml的甲苯中。通過G4玻璃料過濾混濁溶液，然後在減壓下移除濾液中的殘餘溶劑。將油狀殘餘物溶解在少量的二氯甲烷(大約3 ml)中。然後在攪拌下添加正庚烷直至溶液變混濁。將溶液在冰箱中放置過夜，第二天傾析出澄清的上清液，並在減壓下乾燥固體。得到1.09 g的黃白色固體(產率：34%)。 1H NMR (300 MHz, CD 2Cl 2): δ (ppm)=7.30-7.49 (m; 11H); 7.23-7.29 (m; 9H); 6.85-6.94 (m; 4H)。 13C NMR (75 MHz, CD 2Cl 2): δ (ppm)=149.9 (m; C ArOP); 149.2 (m; C ArOP); 132.5; 131.3; 130.6; 130.0; 129.5; 129.4; 125.6; 124.6; 122.3; 120.8 (m)。 31P NMR (121 MHz, CD 2Cl 2): δ (ppm)=144.7 (s)。 HRMS (ESI): C 36H 24O 6P 2(M+H) +之計算值615.11209，實測值615.11203。C 36H 24O 6P 2(M+Na) +之計算值637.09403，實測值637.09394。 催化實驗
在16 ml高壓釜中進行氫甲醯化，該高壓釜係來自HEL Group，Hertfordshire，United Kingdom，配備有保壓閥、氣體流量計及鼓泡攪拌器。將用作基質(Oxeno GmbH，由下列所組成之辛烯異構物的混合物：1-辛烯：3%；順+反-2-辛烯：49%；順+反-3-辛烯：29%；順+反-4-辛烯：16%；結構異構辛烯：3%)的正辛烯以鈉在回流下加熱數小時並在氬氣下蒸餾。
用於實驗的反應溶液係在氬氣氣氛下預先製備。為此，稱出0.0021 g的Rh(acac)(CO) 2及對應量的亞磷酸酯化合物並用8.0 ml的甲苯稀釋。判定在各情況下引入的甲苯質量以供GC分析。接著添加1.80 g的正辛烯(16 mmol)。接著將所製備之溶液引入高壓釜中，用氬氣沖洗三次並用合成氣(Linde；H 2(99.999%)：CO(99.997%)=1：1)沖洗三次。接著在10巴的總壓力及攪拌(900 rpm)下將高壓釜加熱至所欲溫度。在達到反應溫度時，將合成氣壓力增加至20巴，並將反應在恆壓下進行4小時。在反應時間結束時，將高壓釜冷卻至室溫，在攪拌的同時減壓並用氬氣沖洗。在反應結束時移出0.5 ml的各反應混合物，用4 ml的戊烷稀釋並藉由氣相層析法分析：HP 5890系列II plus，PONA，50 m x 0.2 mm x 0.5 µm。將殘餘烯烴及醛以溶劑甲苯為內標準品進行定量判定。 催化實驗之結果
反應條件1： [Rh]：1.0*10 -3mol/l，L：Rh=1：2，p：20巴，T：120℃；t：4小時
Figure 02_image011
反應條件2： [Rh]：1.0*10 -3mol/l，L：Rh=1：4，p：20巴，T：120℃；t：4小時
Figure 02_image013
選擇性之定義： 在氫甲醯化中存在正/異選擇性，其係直鏈醛(=n)與支鏈醛(=iso)之比。在此關於正醛的選擇性表示形成了該量的直鏈產物。其餘的百分比則對應於支鏈異構物。因此，在50%的位置選擇性下，正醛及異醛係以等比例形成。
與比較性配位基(2)相比，本發明之化合物(1)實現了選擇性的增加。
所進行的實驗證實了所述目的係藉由本發明之化合物來實現。
Figure 110129943-A0101-11-0002-1

Claims (10)

  1. 一種結構(I)之化合物，
    Figure 03_image001
    其中R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8係選自：-H、-(C 1-C 12)烷基、-O-(C 1-C 12)烷基。
  2. 如請求項1之化合物， 其中R 1、R 4、R 5、R 8係選自：-H、-(C 1-C 12)烷基。
  3. 如請求項1或2之化合物， 其中基團R 1、R 4、R 5、R 8中之至少一者係-H。
  4. 如請求項1至3中任一項之化合物， 其中R 1、R 4、R 5、R 8係-H。
  5. 如請求項1至4中任一項之化合物， 其中R 2、R 3、R 6、R 7係選自：-H-、-O-(C 1-C 12)烷基。
  6. 如請求項1至5中任一項之化合物， 其中基團R 2、R 3、R 6、R 7中之至少一者係-H。
  7. 如請求項1至6中任一項之化合物， 其中R 2、R 3、R 6、R 7係-H。
  8. 如請求項1至7中任一項之化合物， 其中該化合物具有結構(1)：
    Figure 03_image003
    。
  9. 一種如請求項1至8中任一項之化合物之用途， 其係用在配位基-金屬錯合物中以催化氫甲醯化反應。
  10. 一種方法，其包含下列方法步驟： a)初始地裝入烯烴， b)添加如請求項1至8中任一項之化合物及含有選自下列之金屬的物質：Rh、Ru、Co、Ir， c)饋入H 2及CO， d)加熱來自步驟a)至c)的反應混合物，而將烯烴轉化為醛。
TW110129943A 2020-08-18 2021-08-13 ６，６’－（〔１，１’－聯苯基〕－２，３’－二基雙（氧基））雙二苯并〔ｄ，ｆ〕〔１，３，２〕二磷呯 TW202214666A (zh)

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