Study on octenes alkoxycarbonylation to methyl <italic style="font-style: italic">n</italic>-nonanoates catalyzed by palladium

WANG Xingyong; LI Hongchen; LEI Shuai; XU Bingfeng; CHEN He; FU Songbao

doi:10.12434/j.issn.2097-2547.20240162

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Study on octenes alkoxycarbonylation to methyl n-nonanoates catalyzed by palladium

- Study on octenes alkoxycarbonylation to methyl n-nonanoates catalyzed by palladium
- Vol. 49, Issue 12, Pages: 33-38(2024)
- 作者机构：
  
  中海油化工与新材料科学研究院（北京）有限公司，北京 102209
- 作者简介：
- 基金信息：
- DOI：10.12434/j.issn.2097-2547.20240162
  CLC： TQ225.2
- Published：25 December 2024，
  
  Received：17 April 2024，
  
  Revised：14 June 2024，
- 稿件说明：
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王兴永,李鸿辰,雷帅等.钯催化辛烯烷氧基羰基化制备正壬酸甲酯研究[J].低碳化学与化工,2024,49(12):33-38.

WANG Xingyong,LI Hongchen,LEI Shuai,et al.Study on octenes alkoxycarbonylation to methyl n-nonanoates catalyzed by palladium[J].Low-carbon Chemistry and Chemical Engineering,2024,49(12):33-38.
王兴永,李鸿辰,雷帅等.钯催化辛烯烷氧基羰基化制备正壬酸甲酯研究[J].低碳化学与化工,2024,49(12):33-38. DOI： 10.12434/j.issn.2097-2547.20240162.

WANG Xingyong,LI Hongchen,LEI Shuai,et al.Study on octenes alkoxycarbonylation to methyl n-nonanoates catalyzed by palladium[J].Low-carbon Chemistry and Chemical Engineering,2024,49(12):33-38. DOI： 10.12434/j.issn.2097-2547.20240162.

摘要

烷氧基羰基化反应是一步合成高价值酯类产品的重要方法，在精细化工领域有着重要的应用。但中长链烯烃反应速率较慢，工业生产应用时往往面临成本高、产物选择性差和催化剂易分解等难题。讨论了利用新型催化体系将内端或末端辛烯经烷氧基羰基化反应转化为正壬酸甲酯类化合物，分别探究了膦配体、催化剂、温度、压力、醇类和不同烯烃对辛烯烷氧基羰基化反应的影响，并结合分析结果阐释了辛烯烷氧基羰基化的反应机理。结果表明，在反应体系中引入含有二茂铁骨架的不对称双膦配体（L8）具有较好的催化活性和产物选择性，在最优反应条件（130 ℃、4 MPa、0.1 mol 1-辛烯、5.0 mmol对甲苯磺酸、0.1 mmol Pd(acac)

和0.3 mmol膦配体L8反应15 h）下表现出最优活性，此时1-辛烯转化率、壬酸甲酯产率和正壬酸甲酯与异壬酸甲酯物质的量比分别为99%、99%和17.2。与其他膦配体相比，膦配体L8中的二茂铁基团具有独特的电子性质，可以通过调节电子云密度影响膦配体的电子效应，从而优化金属中心的电子状态，提高催化剂的活性和产物选择性。此外，二茂铁骨架的刚性有助于配体在配位过程中保持特定的空间位阻，从而提高中长链烯烃烷氧基羰基化的产物选择性。

Abstract

Alkoxycarbonylation reaction is an important method for the one-step synthesis of high-value ester products

which has important applications in the field of fi

ne chemicals. However

the reaction rate of medium- and long-chain olefins is low

and the industrial production applications often face difficulties such as high cost

poor product selectivity and easy decomposition of catalysts. Novel catalytic systems were used to convert endo- or terminal-octenes to methyl

-nonanoates by alkoxycarbonylation. The influence of phosphine ligands

catalysts

temperatures

pressures

alcohols and different olefins on the alkoxycarbonylation of octenes were investigated

respectively. Combined with the analysis results

the reaction mechanism of octene alkoxycarbonylation was explained. The results show that the introduction of asymmetric bisphosphine ligands (L8) containing ferrocene skeleton into the reaction system has good catalytic activity and product selectivity. And under the optimal reaction conditions (130 °C

4 MPa

0.1 mol 1-octene

5.0 mmol

-toluenesulfonic acid

0.1 mmol Pd(acac)

0.3 mmol phosphine ligand L8 and reaction for 15 h)

the reaction shows the best activity. At the moment

conversion rate of 1-octene

yield of methyl nonanoates and molar ratio of stereomers and isomers methyl nonanoates are 99%

99% and 17.2

respectively. Compared with other ligands

the ferrocene moiety in the phosphine ligand L8 has unique electronic properties

which can influence the electronic effect of the phosphine ligand by adjusting the electron cloud density

thus optimizing the electronic state of the metal center and improving the activity and product selectivity of the catalysts. In addition

the rigidity of the ferrocene backbone helps the ligands to maintain a specific spatial site resistance during the coordination process

contributing to the improved product selectivity of alkoxycarbonylation of medium- and long-chain olefins.

关键词

烷氧基羰基化辛烯钯催化剂膦配体正壬酸甲酯

Keywords

alkoxycarbonylationoctenespalladium catalystsphosphine ligandsmethyl n-nonanoates

references

TADDEO F, VITIELLO R, TESSER R, et al. Nonanoic acid esterification with 2-ethylhexanol: From batch to continuous operation [J]. Chemical Engineering Journal, 2022, 444: 136572-136583.

余勃, 袁校文, 张耀宗, 等. 有机中间体对壬酰氧基苯磺酸钠的合成[J]. 南昌大学学报, 2019, 43(4): 39-42.

YU B, YUAN X W, ZHANG Y Z, et al. Synthesis of sodium p-nonanoyl benzenesulfonate from organic intermediates [J]. Journal of Nanchang University, 2019, 43(4): 39-42.

SONG T, REN L, LI W B, et al. An eco-friendly sustainable plasticizer from isosorbide and nonanoic acid: Synthesis and application [J]. Journal of Polymer Research, 2024, 31(1): 1.

李文博, 任亮, 陶子俊, 等. 异山梨醇基增塑剂的制备及其增塑PVC的性能[J]. 工程塑料应用, 2021, 49(4): 123-126.

LI W B, REN L, TAO Z J, et al. Preparation of isosorbide based plasticizer and its properties for plasticizing PVC [J]. Engineering Plastics Application, 2021, 49(4): 123-126.

ALVAREZ F, ARENA M, AUTERI D, et al. Peer review of the pesticide risk assessment of the active substance pelargonic acid (nonanoic acid) [J]. European Food Safety Authority, 2021, 19(8): 6813-6840.

RESTU W K, SEPTIYANTI M, TRIWULANDARI E, et al. The preparation of nanoemulsion formulation from pelargonic acid in lignin carrier and its application to weeds [J]. Journal of The Institution of Engineers (India): Series E, 2023, 104(2): 297-303.

随山红, 李爽. 双配体铑-膦体系用于1-辛烯氢甲酰化制备壬醛的研究[J]. 现代化工, 2022, 42(S2): 307-310.

SUI S H, LI S. Study on hydroformylation of 1-octene over rhodium-phosphine catalytic system with dual-ligands [J]. Modern Chemical Industry, 2022, 42(S2): 307-310.

何珍红, 侯震山, 王永垒, 等. 水溶性钯膦络合物催化1-辛烯的氢羧基化反应[J]. 分子催化, 2011, 25(5): 406-414.

HE Z H, HOU Z S, WANG Y L, et al. Hydrocarboxylation of 1-octene catalyzed by water-soluble palladium-phosphine complexes [J]. Journal of Molecular Catalysis, 2011, 25(5): 406-414.

YANG X, DU Y R, GUAN P X, et al. The one-pot encapsulation of palladium complexes into covalent organic frameworks enables the alkoxycarbonylation of olefins [J]. ChemCatChem, 2022, 14(4): 1-11.

AMÉZQUITA-VALENCIA M, ACHONDUH G, ALPER H, et al. Pd-catalyzed regioselective alkoxycarbonylation of 1‑alkenes using a Lewis acid [SnCl2 or Ti(OiPr)4] and a phosphine [J]. The Journal of Organic Chemistry, 2015, 80(12): 6419-6424.

LI H Q, DONG K W, JIAO H J, et al. The scope and mechanism of palladium-catalysed Markovnikov alkoxycarbonylation of alkenes [J]. Nature Chemistry, 2016, 8: 1159-1166.

TAY D W P, NOBBS J D, AITIPAMULA S, et al. Directing selectivity to aldehydes, alcohols, or esters with diphobane ligands in Pd-catalyzed alkene carbonylations [J]. Organometallics, 2021, 40(12): 1914-1925.

AKIRI S O, OJWACH S O, Methoxycarbonylation of olefins catalysed by homogeneous palladium(II) complexes of (phenoxy)imine ligands bearing alkoxy silane groups [J]. Inorganica Chimica Acta, 2019, 489: 236-243.

ZULUA Z, NYAMATO G S, TSHABALALA T A, et al. Palladium(II) complexes of (pyridyl)imine ligands as catalysts for the methoxycarbonylation of olefins [J]. Inorganica Chimica Acta, 2020, 501: 119270.

RODRIGUEZ C G, FOSTER D F, EASTHAMC G R, et al. Highly selective formation of linear esters from terminal and internal alkenes catalysed by palladium complexes of bis-(di-tert-butylphosphinomethyl)benzene [J]. Chemical Communications, 2004, 15: 1720-1721.

NOBBS J D, LOW C H, STUBBS L P, et al. Isomerizing methoxycarbonylation of alkenes to esters using a bis(phosphorinone)xylene palladium catalyst [J]. Organometallics, 2017, 36(2): 391-398.

HOLZAPFEL C, BREDENKAMP T. An empirical study of phosphine ligands for the methoxycarbonylation of medium-chain alkenes [J]. ChemCatChem 2015, 7: 2598-2606.

BREDENKAMP T, HOLZAPFEL C. Toward the development of efficient and stable Pd‑catalysts for the methoxycarbonylation of medium chain alkenes [J]. Journal of the Iranian Chemical Society, 2016, 13: 421-427.

DONG K W, SANG R, FANG X J, et al. Efficient Palladium-catalyzed alkoxycarbonylation of bulk industrial olefins using ferrocenyl phosphine ligands [J]. Angewandte Chemie International Edition, 2017, 129(19): 5351-5355.

CAO Z S, WANG Q, NEUMANN H, et al. Regiodivergent carbonylation of alkenes: Selective palladium-catalyzed synthesis of linear and branched selenoesters [J]. Angewandte Chemie International Edition, 2024, 136(2): e202313714.

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Study on octenes alkoxycarbonylation to methyl n-nonanoates catalyzed by palladium

DOI：10.12434/j.issn.2097-2547.20240162

摘要

Abstract

关键词

Keywords

references