TW202340223A - 鉑（Ｐｔ）－聯苯－碘錯合物及鉑（Ｐｔ）－聯苯－溴錯合物 - Google Patents

鉑（Ｐｔ）－聯苯－碘錯合物及鉑（Ｐｔ）－聯苯－溴錯合物 Download PDF

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TW202340223A
TW202340223A TW111147949A TW111147949A TW202340223A TW 202340223 A TW202340223 A TW 202340223A TW 111147949 A TW111147949 A TW 111147949A TW 111147949 A TW111147949 A TW 111147949A TW 202340223 A TW202340223 A TW 202340223A
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complex
biphenyl
alkyl
bromine
iodine
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卡羅琳 史耐德
雷夫 傑克斯泰爾
馬席爾斯 貝勒
羅柏特 法蘭克
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德商贏創運營有限公司
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    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
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Abstract

一種Pt-聯苯-碘錯合物及Pt-聯苯-溴錯合物，以及彼等於催化氫甲醯化反應之用途。

Description

鉑（Ｐｔ）－聯苯－碘錯合物及鉑（Ｐｔ）－聯苯－溴錯合物
本發明係關於一種Pt-聯苯-碘錯合物及Pt-聯苯-溴錯合物，以及彼等於催化氫甲醯化反應之用途。
EP 2663573 B1記載一種用於製備( 1)的方法。
本發明的目標之一在於提供一種新穎的錯合物。在催化氫甲醯化反應中，該錯合物應使得產率增加。 藉由請求項1之錯合物達成此目標。
一種錯合物，其包含： a) Pt； b) 對應於式(I)之配位基： 其中R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10、R 11、R 12係選自：-H、-(C 1-C 12)-烷基、-O-(C 1-C 12)-烷基、-(C 6-C 20)-芳基； c) 碘配位基或溴配位基。 (C 1-C 12)-烷基之表述涵蓋具有1至12個碳原子之直鏈及支鏈烷基。這些較佳地為(C 1-C 8)-烷基基團，更佳地為(C 1-C 6)-烷基，最佳地為(C 1-C 4)-烷基。 合適的(C 1-C 12)-烷基基團尤其為甲基、乙基、丙基、異丙基、正丁基、異丁基、二級丁基、三級丁基、正戊基、2-戊基、2-甲基丁基、3-甲基丁基、1,2-二甲基丙基、1,1-二甲基丙基、2,2-二甲基丙基、1-乙基丙基、正己基、2-己基、2-甲基戊基、3-甲基戊基、4-甲基戊基、1,1-二甲基丁基、1,2-二甲基丁基、2,2-二甲基丁基、1,3-二甲基丁基、2,3-二甲基丁基、3,3-二甲基丁基、1,1,2-三甲基丙基、1,2,2-三甲基丙基、1-乙基丁基、1-乙基-2-甲基丙基、正庚基、2-庚基、3-庚基、2-乙基戊基、1-丙基丁基、正辛基、2-乙基己基、2-丙基庚基、壬基、癸基。 (C 1-C 12)-烷基的定義亦類似地適用於-O-(C 1-C 12)-烷基中的(C 1-C 12)-烷基。 (C 6-C 20)-芳基之表述涵蓋具有6至20個碳原子的單環或多環芳香烴基團。這些較佳地為(C 6-C 14)-芳基，更佳地為(C 6-C 10)-芳基。 合適的(C 6-C 20)-芳基基團尤其為苯基、萘基、茚基、茀基、蒽基、菲基、稠四苯基、基、芘基、蔲基。較佳的(C 6-C 20)-芳基基團為苯基、萘基及蒽基。 在一個實施方式中，R 1、R 2、R 3、R 4係選自：-(C 1-C 12)-烷基、-O-(C 1-C 12)-烷基。 在一個實施方式中，R 1及R 4為-(C 1-C 12)-烷基。 在一個實施方式中，R 1及R 4為-三級丁基(- tBu)。 在一個實施方式中，R 2及R 3為-O-(C 1-C 12)-烷基。 在一個實施方式中，R 2及R 3為-OMe。 在一個實施方式中，R 5、R 6、R 7、R 8、R 9、R 10、R 11、R 12為-H。 在一個實施方式中，該式(I)化合物具有結構(1)： 在一個實施方式中，該錯合物具有恰好一個對應於式(I)之配位基。 在一個實施方式中，該錯合物具有至少兩個碘配位基。 在一個實施方式中，該錯合物具有恰好兩個碘配位基。 在一個實施方式中，該錯合物具有至少兩個溴配位基。 在一個實施方式中，該錯合物具有恰好兩個溴配位基。 連同該錯合物本身，本案亦請求保護其用於催化氫甲醯化反應之用途。 一種上述錯合物用於催化氫甲醯化反應之用途。 以下參照工作例更詳細地闡述本發明。 實驗說明 將PtX 2(X=鹵素)、配位基、及經烘箱乾燥之攪拌棒裝填至小瓶。接著以隔板(PTFE塗覆之苯乙烯-丁二烯橡膠)與酚樹脂蓋子密封小瓶。抽空小瓶並重新充入氬氣，進行三次。使用注射器將甲苯及1-辛烯加入小瓶。將小瓶放置於合金板中，接著於氬氣環境下送入至Parr儀器(Parr Instruments)之4560系列的高壓釜。以CO/H 2沖洗高壓釜三次之後，於室溫將合成氣壓力增加至40巴。反應於120℃進行20小時。於反應終止時，冷卻高壓釜至室溫並小心地洩壓。藉由氣相層析分析(GC analysis)鑑定產率及選擇性。 鹵素的變化 反應條件： 1.0 mmol的1-辛烯、1.0 mol%的PtX 2、2.2當量的配位基( 1)、溶劑：甲苯、p(CO/H 2)：40巴(bar)、T：120℃、t：20小時。 產率： 如上實驗結果所示，藉由本發明的錯合物達成目標。

Claims (12)

  1. 一種錯合物，其包含： a) Pt； b) 對應於式(I)之配位基： 其中R 1、R 2、R 3、R 4、R 5、R 6、R 7、R 8、R 9、R 10、R 11、R 12係選自：-H、-(C 1-C 12)-烷基、-O-(C 1-C 12)-烷基、-(C 6-C 20)-芳基； c) 碘配位基或溴配位基。
  2. 如請求項1之錯合物， 其中R 1、R 2、R 3、R 4係選自：-(C 1-C 12)-烷基、-O-(C 1-C 12)-烷基。
  3. 如請求項1及2中任一項之錯合物， 其中R 1及R 4為-(C 1-C 12)-烷基。
  4. 如請求項1至3中任一項之錯合物， 其中R 2及R 3為-O-(C 1-C 12)-烷基。
  5. 如請求項1至4中任一項之錯合物， 其中R 5、R 6、R 7、R 8、R 9、R 10、R 11、R 12為-H。
  6. 如請求項1至5中任一項之錯合物， 其中該式(I)化合物具有結構(1)： 。
  7. 如請求項1至6中任一項之錯合物， 其中該錯合物具有恰好一個對應於式(I)之配位基。
  8. 如請求項1至7中任一項之錯合物， 其中該錯合物具有兩個碘配位基。
  9. 如請求項8之錯合物， 其中該錯合物具有恰好兩個碘配位基。
  10. 如請求項1至7中任一項之錯合物， 其中該錯合物具有至少兩個溴配位基。
  11. 如請求項10之錯合物， 其中該錯合物具有恰好兩個溴配位基。
  12. 一種如請求項1至11中任一項之錯合物於催化氫甲醯化反應之用途。
TW111147949A 2021-12-17 2022-12-14 鉑（Ｐｔ）－聯苯－碘錯合物及鉑（Ｐｔ）－聯苯－溴錯合物 TWI846205B (zh)

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EP21215366.2A EP4198001B1 (de) 2021-12-17 2021-12-17 Pt-biphenyl-iod-komplex und pt-biphenyl-brom-komplex
EP21215366.2 2021-12-17

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TW202340223A true TW202340223A (zh) 2023-10-16
TWI846205B TWI846205B (zh) 2024-06-21

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JP2023090660A (ja) 2023-06-29
EP4198001A1 (de) 2023-06-21
EP4198001B1 (de) 2024-05-22
US20230192743A1 (en) 2023-06-22
CN116265481A (zh) 2023-06-20

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