KR20230092783A - Pt-DPEphos-아이오딘 착물 및 Pt-DPEphos-브로민 착물 - Google Patents

Pt-DPEphos-아이오딘 착물 및 Pt-DPEphos-브로민 착물 Download PDF

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KR20230092783A
KR20230092783A KR1020220174595A KR20220174595A KR20230092783A KR 20230092783 A KR20230092783 A KR 20230092783A KR 1020220174595 A KR1020220174595 A KR 1020220174595A KR 20220174595 A KR20220174595 A KR 20220174595A KR 20230092783 A KR20230092783 A KR 20230092783A
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complex
dpephos
bromine
iodine
ligand
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카롤린 슈나이더
랄프 약스텔
마티아스 벨러
로베르트 프랑케
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에보니크 오퍼레이션즈 게엠베하
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Abstract

Pt-DPEphos-아이오딘 착물 및 Pt-DPEphos-브로민 착물, 및 히드로포르밀화 반응의 촉매작용을 위한 그의 용도.

Description

Pt-DPEphos-아이오딘 착물 및 Pt-DPEphos-브로민 착물 {Pt-DPEphos-iodine complex and Pt-DPEphos-bromine complex}
본 발명은 Pt-DPEphos-아이오딘 착물 및 Pt-DPEphos-브로민 착물, 및 히드로포르밀화 반응의 촉매작용을 위한 그의 용도에 관한 것이다.
문헌 [P. Meessen et al., Journal of Organometallic Chemistry, 551, (1998), 165-170]에는 메틸 3-펜테노에이트의 히드로포르밀화를 위한 DPEphosPtCl2의 사용이 기재되어 있다.
Figure pat00001
본 발명의 목적은 신규 착물을 제공하는 것이다. 여기서 착물은 히드로포르밀화 반응의 촉매작용에 있어서 선행 기술에 기재된 착물과 비교하여 향상된 수율을 제공하여야 한다.
상기 목적이 청구항 제1항에 따른 착물에 의해 달성된다.
하기를 포함하는 착물:
a) Pt;
b) 화학식 (I)에 따른 리간드:
Figure pat00002
여기서 R1, R2, R3, R4, R5, R6, R7, R8은 -H, -(C1-C12)-알킬, -(C6-C20)-아릴로부터 선택되고, R5, R6, R7, R8 라디칼 중 적어도 2개는 -(C6-C20)-아릴임;
c) 아이오딘 리간드 또는 브로민 리간드.
(C1-C12)-알킬이라는 표현은 1 내지 12개의 탄소 원자를 갖는 직쇄 및 분지형 알킬 기를 포괄한다. 이들은 바람직하게는 (C1-C8)-알킬 기, 보다 바람직하게는 (C1-C6)-알킬, 가장 바람직하게는 (C1-C4)-알킬이다.
적합한 (C1-C12)-알킬 기는 특히 메틸, 에틸, 프로필, 이소프로필, n-부틸, 이소부틸, sec-부틸, tert-부틸, n-펜틸, 2-펜틸, 2-메틸부틸, 3-메틸부틸, 1,2-디메틸프로필, 1,1-디메틸프로필, 2,2-디메틸프로필, 1-에틸프로필, n-헥실, 2-헥실, 2-메틸펜틸, 3-메틸펜틸, 4-메틸펜틸, 1,1-디메틸부틸, 1,2-디메틸부틸, 2,2-디메틸부틸, 1,3-디메틸부틸, 2,3-디메틸부틸, 3,3-디메틸부틸, 1,1,2-트리메틸프로필, 1,2,2-트리메틸프로필, 1-에틸부틸, 1-에틸-2-메틸프로필, n-헵틸, 2-헵틸, 3-헵틸, 2-에틸펜틸, 1-프로필부틸, n-옥틸, 2-에틸헥실, 2-프로필헵틸, 노닐, 데실이다.
(C6-C20)-아릴이라는 표현은 6 내지 20개의 탄소 원자를 갖는 모노- 또는 폴리시클릭 방향족 히드로카르빌 라디칼을 포괄한다. 이들은 바람직하게는 (C6-C14)-아릴, 보다 바람직하게는 (C6-C10)-아릴이다.
적합한 (C6-C20)-아릴 기는 특히 페닐, 나프틸, 인데닐, 플루오레닐, 안트라세닐, 페난트레닐, 나프타세닐, 크리세닐, 피레닐, 코로네닐이다. 바람직한 (C6-C20)-아릴 기는 페닐, 나프틸 및 안트라세닐이다.
한 실시양태에서, R5, R6, R7, R8은 -(C6-C20)-아릴이다.
한 실시양태에서, R5, R6, R7, R8은 -Ph이다.
한 실시양태에서, R1 및 R4는 각각 -H이다.
한 실시양태에서, R2 및 R3은 각각 -H이다.
한 실시양태에서, 화학식 (I)의 화합물은 구조 (1)을 갖는다:
Figure pat00003
한 실시양태에서, 착물은 정확히 1개의 화학식 (I)에 상응하는 리간드를 갖는다.
한 실시양태에서, 착물은 적어도 2개의 아이오딘 리간드를 갖는다.
한 실시양태에서, 착물은 정확히 2개의 아이오딘 리간드를 갖는다.
한 실시양태에서, 착물은 적어도 2개의 브로민 리간드를 갖는다.
한 실시양태에서, 착물은 정확히 2개의 브로민 리간드를 갖는다.
착물 그 자체와 함께, 히드로포르밀화 반응의 촉매작용을 위한 그의 용도가 또한 청구된다.
히드로포르밀화 반응의 촉매작용을 위한 상기 기재된 바와 같은 착물의 용도.
본 발명이 하기에서 작업 실시예를 참조로 하여 보다 상세히 설명될 것이다.
실험 설명
바이알에 PtX2 (X = 할로겐), 리간드, 및 오븐-건조된 교반 막대를 충전하였다. 이어서, 바이알을 격막 (PTFE-코팅된 스티렌-부타디엔 고무) 및 페놀계 캡으로 밀봉하였다. 바이알을 3회 배기시키고 아르곤을 재충전하였다. 톨루엔 및 1-옥텐을 시린지를 사용하여 바이알에 첨가하였다. 바이알을 합금 플레이트에 위치시켜, 이를 아르곤 분위기 하의 파르 인스트루먼츠(Parr Instruments)로부터의 4560 시리즈 오토클레이브로 옮겼다. 오토클레이브를 CO/H2로 3회 퍼징한 후에, 합성 가스 압력을 실온에서 40 bar로 증가시켰다. 반응을 120℃에서 20 h 동안 수행하였다. 반응이 종료되면, 오토클레이브를 실온으로 냉각시키고, 조심스럽게 감압시켰다. 수율 및 선택성을 GC 분석에 의해 결정하였다.
1-옥텐의 히드로포르밀화
Figure pat00004
반응 조건:
10.0 mmol의 1-옥텐, 0.1 mol%의 PtX2, 2.2 당량의 리간드, 용매: 톨루엔, p(CO/H2): 40 bar, T: 120℃, t: 20 h.
수율:
Figure pat00005
실험 결과가 제시하는 바와 같이, 상기 목적이 본 발명에 따른 착물에 의해 달성된다.

Claims (12)

  1. 하기를 포함하는 착물:
    a) Pt;
    b) 화학식 (I)에 따른 리간드:
    Figure pat00006

    여기서 R1, R2, R3, R4, R5, R6, R7, R8은 -H, -(C1-C12)-알킬, -(C6-C20)-아릴로부터 선택되고, R5, R6, R7, R8 라디칼 중 적어도 2개는 -(C6-C20)-아릴임;
    c) 아이오딘 리간드 또는 브로민 리간드.
  2. 제1항에 있어서, R5, R6, R7, R8이 -(C6-C20)-아릴인 착물.
  3. 제1항 또는 제2항에 있어서, R5, R6, R7, R8이 -Ph인 착물.
  4. 제1항 내지 제3항 중 어느 한 항에 있어서, R1 및 R4가 각각 -H인 착물.
  5. 제1항 내지 제4항 중 어느 한 항에 있어서, R2 및 R3이 각각 -H인 착물.
  6. 제1항 내지 제5항 중 어느 한 항에 있어서, 화학식 (I)의 화합물이 구조 (1)을 갖는 것인 착물:
    Figure pat00007
  7. 제1항 내지 제6항 중 어느 한 항에 있어서, 착물이 정확히 1개의 화학식 (I)에 따른 리간드를 갖는 것인 착물.
  8. 제1항 내지 제7항 중 어느 한 항에 있어서, 착물이 적어도 2개의 아이오딘 리간드를 갖는 것인 착물.
  9. 제8항에 있어서, 착물이 정확히 2개의 아이오딘 리간드를 갖는 것인 착물.
  10. 제1항 내지 제7항 중 어느 한 항에 있어서, 착물이 적어도 2개의 브로민 리간드를 갖는 것인 착물.
  11. 제10항에 있어서, 착물이 정확히 2개의 브로민 리간드를 갖는 것인 착물.
  12. 히드로포르밀화 반응의 촉매작용을 위한 제1항 내지 제11항 중 어느 한 항에 따른 착물의 용도.
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