JP2022164595A - オープン外部単位とクローズド外部単位とを有するビスホスファイトの混合物、およびヒドロホルミル化における触媒混合物としてのその使用 - Google Patents
オープン外部単位とクローズド外部単位とを有するビスホスファイトの混合物、およびヒドロホルミル化における触媒混合物としてのその使用 Download PDFInfo
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Abstract
Description
化合物(1A):
ヒドロホルミル化反応の触媒作用のための上記の混合物の使用。
b)上記の混合物と、Rh、Ru、Co、Irから選択される金属からなる物質と、を加え、
c)H2とCOを投入し、
d)工程a)~工程c)からの反応混合物を加熱し、オレフィンをアルデヒドに転化する工程
を有する方法。
一般的分析
以下の調製はすべて、標準的なシュレンク技術を用いて不活性ガス下で行った。溶媒は、使用前に適切な乾燥剤を用いて乾燥させた。
生成物をNMR法で特徴づけた。化学シフト(δ)はppmで報告する。31P NMRシグナルは以下のように表す:SR31P=SR1H*(BF31P/BF1H)=SR1H*0.4048。
前駆体(3A)および前駆体(3B):
総収率:92%。異性体A:64.3質量%、異性体B:35.7質量%。
前駆体(4A)および前駆体(4B):
総収率:90%。異性体A:64.7質量%、異性体B:35.3質量%。
(1A)および(1B)の混合物:
塩素を還元するために、生成物を乾燥トルエン約20mLに溶解した。続いて、この物質を、アルゴン雰囲気下、シリカゲルを充填したフリットを用いて濾過した。まず、乾燥トルエンを用いて600mLビーカー内でシリカゲルをスラリー化し、フリットに移した。移動相として乾燥トルエンを使用した。この操作のための移動相として、乾燥トルエン約500mLを使用した。次に、得られた濾液を濃縮乾固させた。
塩素の測定:20ppm未満
総収率:35%。異性体A:54.3質量%、異性体B:45.7質量%。
(2A)および(2B)の混合物(比較混合物):
総収率:26%。異性体A:59.3質量%、異性体B:40.7質量%。
定圧装置、ガス流量計およびスパージングスターラーを備えた、HEL Group社英(英国 ハートフォードシャー)の16mLオートクレーブ内でヒドロホルミル化を行った。基質として使用するn-オクテン(Oxeno GmbH社、1-オクテンのオクテン異性体の混合物(3%)、シス+トランス-2-オクテン(49%)、シス+トランス-3-オクテン(29%)、シス+トランス-4-オクテン(16%)、構造異性体オクテン(3%))を、ナトリウムを用いて還流下で数時間加熱し、アルゴン下で蒸留した。
[Rh]:120ppm、L:Rh=1:2、圧力(p):20バール、温度(T):120℃、時間(t):4時間
ヒドロホルミル化において、n/iso選択性は、分岐鎖アルデヒド(=iso)に対する直鎖アルデヒド(=n)の比率である。n-アルデヒドの選択性は、この量の直鎖生成物が生成されたことを示す。そして、残りのパーセンテージは、分岐鎖異性体に対応する。したがって、50%の位置選択性では、n-アルデヒドとiso-アルデヒドが同じ比率で生成されている。
Claims (6)
- 前記化合物(1A)の含有量は、99.5質量%~0.5質量%の範囲であり、前記化合物(1B)の含有量は、0.5質量%~99.5質量%の範囲である、請求項1記載の混合物。
- 前記化合物(1A)の含有量は、75質量%~25質量%の範囲であり、前記化合物(1B)の含有量は、25質量%~75質量%の範囲である、請求項1または請求項2記載の混合物。
- 質量%換算の前記化合物(1A)の含有量が、前記化合物(1B)の含有量よりも多い、請求項1~請求項3のいずれか一項記載の混合物。
- ヒドロホルミル化反応の触媒作用のための請求項1~請求項4のいずれか一項記載の混合物の使用。
- a)最初にオレフィンを投入し、
b)請求項1~請求項4のいずれか一項記載の混合物と、Rh、Ru、Co、Irから選択される金属からなる物質と、を加え、
c)H2とCOを投入し、
d)前記工程a)~前記工程c)からの反応混合物を加熱し、前記オレフィンをアルデヒドに転化する工程
を有する方法。
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EP21168814.8A EP4074720B1 (de) | 2021-04-16 | 2021-04-16 | Gemisch von bisphosphiten mit einem offenen und einem geschlossenen flügelbaustein und dessen verwendung als katalysatorgemisch in der hydroformylierung |
EP21168814.8 | 2021-04-16 |
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JP7360498B2 JP7360498B2 (ja) | 2023-10-12 |
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EP (1) | EP4074720B1 (ja) |
JP (1) | JP7360498B2 (ja) |
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JPH08165266A (ja) * | 1994-12-12 | 1996-06-25 | Mitsubishi Chem Corp | アルデヒド類の製造方法 |
JP2010522187A (ja) * | 2007-03-20 | 2010-07-01 | ダウ テクノロジー インベストメンツ リミティド ライアビリティー カンパニー | 生成物異性体の制御が改善されたヒドロホルミル化方法 |
JP2016500676A (ja) * | 2012-10-12 | 2016-01-14 | エボニック デグサ ゲーエムベーハーEvonik Degussa GmbH | 構造異性ビスホスフィットの混合物 |
US20160185685A1 (en) * | 2014-12-04 | 2016-06-30 | Evonik Degussa Gmbh | Bisphosphites having a central 2,3'-biphenol unit |
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US4737588A (en) * | 1984-12-28 | 1988-04-12 | Union Carbide Corporation | Transition metal complex catalyzed reactions |
IN187044B (ja) * | 1995-01-27 | 2002-01-05 | Du Pont | |
DE102006034442A1 (de) * | 2006-07-26 | 2008-01-31 | Oxeno Olefinchemie Gmbh | Katalysatorvorstufe für einen Rh-Komplexkatalysator |
DE102006058682A1 (de) * | 2006-12-13 | 2008-06-19 | Evonik Oxeno Gmbh | Bisphosphitliganden für die übergangsmetallkatalysierte Hydroformylierung |
CN101681776B (zh) * | 2007-04-09 | 2011-10-05 | Lg化学株式会社 | 含有亚磷酸酯配体的催化剂组合物和使用该催化剂组合物的加氢甲酰化方法 |
DE102013219508A1 (de) * | 2012-10-12 | 2014-04-17 | Evonik Degussa Gmbh | Gemische konstitutionsisomerer Bisphosphite |
PL3374366T3 (pl) * | 2015-11-09 | 2020-05-18 | Evonik Operations Gmbh | Bis-fosforyny z jednostkami 2,4-dimetylofenylowymi i ich zastosowanie jako ligandów w hydroformylowaniu |
EP3293190A1 (de) * | 2016-09-07 | 2018-03-14 | Evonik Degussa GmbH | Phosphite mit einem silyloxyphenol |
EP3763723B1 (de) * | 2019-07-11 | 2022-04-13 | Evonik Operations GmbH | Bisphosphite mit einem geschlossenen und einem offenen flügelbaustein |
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PL3971195T3 (pl) | 2020-09-22 | 2023-06-19 | Evonik Operations Gmbh | Difosforyny zawierające otwarty, 2,4-metylowany blok budulcowy |
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- 2021-04-16 EP EP21168814.8A patent/EP4074720B1/de active Active
-
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- 2022-04-07 JP JP2022063710A patent/JP7360498B2/ja active Active
- 2022-04-12 US US17/718,542 patent/US11565991B2/en active Active
- 2022-04-13 TW TW111114021A patent/TW202244054A/zh unknown
- 2022-04-13 KR KR1020220045538A patent/KR20220143587A/ko not_active Application Discontinuation
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US11565991B2 (en) | 2023-01-31 |
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