CN115490576B - 一种反式-2-烯烃的合成方法 - Google Patents
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- 239000003054 catalyst Substances 0.000 claims abstract description 59
- 239000010948 rhodium Substances 0.000 claims abstract description 28
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 8
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 8
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- 230000003197 catalytic effect Effects 0.000 description 2
- 229960002217 eugenol Drugs 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- DQQJYBYIABSMFM-UHFFFAOYSA-N methyl 2-benzylprop-2-enoate Chemical compound COC(=O)C(=C)CC1=CC=CC=C1 DQQJYBYIABSMFM-UHFFFAOYSA-N 0.000 description 2
- 229940116837 methyleugenol Drugs 0.000 description 2
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- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 229930015698 phenylpropene Natural products 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 description 1
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- 150000002576 ketones Chemical class 0.000 description 1
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- 239000002184 metal Substances 0.000 description 1
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- 238000005580 one pot reaction Methods 0.000 description 1
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- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
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- 238000001291 vacuum drying Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/001—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by modification in a side chain
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- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/23—Rearrangement of carbon-to-carbon unsaturated bonds
- C07C5/25—Migration of carbon-to-carbon double bonds
- C07C5/2506—Catalytic processes
- C07C5/2562—Catalytic processes with hydrides or organic compounds
- C07C5/2593—Catalytic processes with hydrides or organic compounds containing phosphines, arsines, stibines or bismuthines
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- C07C67/293—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
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Abstract
本发明公开了一种反式‑2‑烯烃的合成方法。1‑烯烃在聚合物负载铑催化剂的作用下,经加热发生烯烃的异构化反应得到反式‑2‑烯烃。所述聚合物负载铑催化剂是具有如下结构:本发明提供的催化剂Rh/POP‑PPh3‑SO3Na催化的1‑烯烃的异构化反应,具有高催化速率(TON高达4800)和底物适用性,具有好的稳定性,催化剂容易回收且能循环使用五次。
Description
技术领域
本发明涉及一种反式-2-烯烃的合成方法。具体说,是涉及多孔有机聚合物负载铑催化剂在烯烃异构化反应中的应用,属于有机化学技术领域。
技术背景
烯烃是一类重要的化工原料,通过已开发的合成方法,C=C双键可以进一步转化为各种化学品。烯烃异构化不仅为通过双键迁移获得所需烯烃提供了一条绿色途径,而且还能够通过串联、顺序和多米诺工艺合成高附加值化学品的多步“一锅”催化反应。除了经典的酸碱催化剂外,过渡金属催化的烯烃异构化已被广泛研究。在Rh催化烯烃转化的情况下,尽管所开发的方法是有效和选择性的,但反应底物仅限于N-allylamines和具有官能团取向的β,γ-不饱和酮。此外,均相催化剂受到催化剂与混合物分离和可回收性的困扰。
多孔有机聚合物(POPs)作为多相催化应用的高效材料,由于其高表面积、稳定的支架和可控的功能而受到广泛的研究关注。特别是对于由膦配体组成的POPs,聚合物骨架中高浓度的膦配体不仅减少了金属的损失,提高了反应的选择性,而且还可以有效分散金属颗粒,形成均相催化剂一样的单一活性位点。在此,我们报道了一种多孔有机聚合物负载铑催化剂(Rh/POPPPh3-SO3Na)催化的烯烃异构化反应。
发明内容
1.一种反式-2-烯烃的合成方法,其特征在于所述的方法为:如通式1所示的1-烯烃(式I),在聚合物负载铑催化剂的作用下,在有机溶剂中加热反应;反应完全后,离心分离催化剂,滤液分离处理得到如式II的反式-2-烯烃;
R分别独立选自氢、C1~C10的烷烃基、C1~C10的烷氧基、
其中Rx和Rx'分别独立选自氢、羟基、磺酸基、卤素、腈基、C1~C10的烷烃基、C1~C10的烷氧基、C1~C10的烷酰基、C1~C10的酯基;
2.步骤(1)中聚合物负载铑催化剂(Rh/POP-PPh3-SO3Na),具有如下结构;
催化剂Rh/POP-PPh3-SO3Na通过以下反应过程制备:
3.步骤(1)中所述有机溶剂选自苯、甲苯、二甲苯、三甲苯、乙腈、乙醚、四氢呋喃、甲基叔丁基醚、乙二醇二甲醚、氯仿、二氯甲烷、甲醇、乙醇、异丙醇、N,N–二甲基甲酰胺、二甲基亚砜或N-甲基吡咯烷酮。
4.步骤(1)中反应温度为60~150℃。
与现有技术相比,本发明具有如下显著效果:
1.本发明提供的催化剂Rh/POP-PPh3-SO3Na用于1-烯烃的异构化反应,均具有高催化速率(TON高达4800)和底物适用性。
2.本发明提供的催化剂Rh/POP-PPh3-SO3Na,在烯烃异构化反应的应用中,具有好的稳定性,催化剂容易回收且能循环使用五次。
具体实施方式
下面结合实施例对本发明作进一步详细、完整地说明。
实施例1
下述实施例中所用的催化剂Rh/POP-PPh3-SO3Na通过以下反应过程制备:
在手套箱中,将3vPPh3(100.0mg),对苯乙烯磺酸钠(20.2mg),AIBN(4.0mg)和四氢呋喃(2mL)加入Schlenk烧瓶中。混合物加热到100℃反应24h,离心分离得到产物,产物用甲苯(4×2mL)洗涤,真空干燥,得到催化剂POP-PPh3-SO3Na(106.5mg)。
在手套箱中,将POP-PPh3-SO3Na(100.0mg),Rh(acac)(CO)2(3.65mg)和甲苯(5mL)加入Schlenk烧瓶中。在N2气氛下,室温搅拌24h后,用离心机分离,再用甲苯洗涤。减压去除残留溶剂后,得到Rh/POP-PPh3-SO3Na(98.2mg)。
实施例2
Rh/POP-PPh3-SO3Na催化剂催化4-烯丙基苯甲醚(底物:催化剂=1×103)的异构化反应
在手套箱里,向Schlenk烧瓶中加入催化剂(5.6mg),4-烯丙基苯甲醚(0.19mL,1.26mmol),无水乙醇(2mL)和水(10μL)然后油浴120℃下搅拌反应24h。反应完成后,等降至室温,离心分离后加入癸烷(3μL)作为内标物,搅拌均匀后测气相。产率为94%,E/Z比为14,TON值为940。
实施例3
Rh/POP-PPh3-SO3Na催化剂催化甲基丁香酚(底物:催化剂=1×103)的异构化反应在手套箱里,向Schlenk烧瓶中加入催化剂(5.6mg),甲基丁香酚(0.22mL,1.26mmol),无水乙醇(2mL)和水(10μL)然后油浴130℃下搅拌反应24h。反应完成后,等降至室温,离心分离后加入癸烷(3μL)作为内标物,搅拌均匀后测气相。产率为93%,E/Z比为13,TON值为930。
实施例4
Rh/POP-PPh3-SO3Na催化剂催化乙酸丁香酚酯(底物:催化剂=1×103)的异构化反应在手套箱里,向Schlenk烧瓶中加入催化剂(5.6mg),乙酸丁香酚酯(0.24mL,1.26mmol),无水乙醇(2mL)和水(10μL)然后油浴100℃下搅拌反应24h。反应完成后,等降至室温,离心分离后加入癸烷(3μL)作为内标物,搅拌均匀后测气相。产率为96%,E/Z比为9,TON值为960。
实施例5
Rh/POP-PPh3-SO3Na催化剂催化丁香酚(底物:催化剂=1×103)的异构化反应
在手套箱里,向Schlenk烧瓶中加入催化剂(5.6mg),丁香酚(0.19mL,1.26mmol),无水乙醇(2mL)和水(10μL)然后油浴110℃下搅拌反应24h。反应完成后,等降至室温,离心分离后加入癸烷(3μL)作为内标物,搅拌均匀后测气相。产率为93%,E/Z比为18,TON值为930。
实施例6
Rh/POP-PPh3-SO3Na催化剂催化烯丙苯(底物:催化剂=5×102)的异构化反应
在手套箱里,向Schlenk烧瓶中加入催化剂(5.6mg),烯丙苯(83μL,0.63mmol),无水乙醇(2mL)和水(10μL)然后油浴120℃下搅拌反应24h。反应完成后,等降至室温,离心分离后加入癸烷(3μL)作为内标物,搅拌均匀后测气相。产率为95%,E/Z比为12,TON值为475。
实施例7
Rh/POP-PPh3-SO3Na催化剂催化1-烯丙基-2-甲苯(底物:催化剂=5×102)的异构化反应在手套箱里,向Schlenk烧瓶中加入催化剂(5.6mg),1-烯丙基-2-甲苯(93μL,0.63mmol),无水乙醇(2mL)和水(10μL)然后油浴120℃下搅拌反应24h。反应完成后,等降至室温,离心分离后加入癸烷(3μL)作为内标物,搅拌均匀后测气相。产率为90%,E/Z比为26,TON值为450。
实施例8
Rh/POP-PPh3-SO3Na催化剂催化2-烯丙基酚(底物:催化剂=5×102)的异构化反应
在手套箱里,向Schlenk烧瓶中加入催化剂(5.6mg),2-烯丙基酚(82μL,0.63mmol),无水乙醇(2mL)和水(10μL)然后油浴120℃下搅拌反应24h。反应完成后,等降至室温,离心分离后加入癸烷(3μL)作为内标物,搅拌均匀后测气相。产率为52%,E/Z比为14,TON值为260。
实施例9
Rh/POP-PPh3-SO3Na催化剂催化1-烯丙基萘(底物:催化剂=5×102)的异构化反应
在手套箱里,向Schlenk烧瓶中加入催化剂(5.6mg),1-烯丙基萘(0.11mL,0.63mmol),无水乙醇(2mL)和水(10μL)然后油浴120℃下搅拌反应24h。反应完成后,等降至室温,离心分离后加入癸烷(3μL)作为内标物,搅拌均匀后测气相。产率为89%,E/Z比为5,TON值为445。
实施例10
Rh/POP-PPh3-SO3Na催化剂催化2-苄基丙烯酸甲酯(底物:催化剂=5×102)的异构化反应
在手套箱里,向Schlenk烧瓶中加入催化剂(5.6mg),2-苄基丙烯酸甲酯(111mg,0.63mmol),无水乙醇(2mL)和水(10μL)然后油浴120℃下搅拌反应24h。反应完成后,等降至室温,离心分离后加入癸烷(3μL)作为内标物,搅拌均匀后测气相。产率为70%,TON值为350。
实施例11
Rh/POP-PPh3-SO3Na催化剂催化1-己烯(底物:催化剂=5×103)的异构化反应
在手套箱里,向Schlenk烧瓶中加入催化剂(5.6mg),1-己烯(0.78mL,6.3mmol),无水乙醇(2mL)和水(10μL)然后油浴120℃下搅拌反应24h。反应完成后,等降至室温,离心分离后加入癸烷(3μL)作为内标物,搅拌均匀后测气相。产率为96%,E/Z比为2,TON值为4800。
实施例12
Rh/POP-PPh3-SO3Na催化剂催化1-辛烯(底物:催化剂=5×103)的异构化反应
在手套箱里,向Schlenk烧瓶中加入催化剂(5.6mg),1-辛烯(0.99mL,6.3mmol),无水乙醇(2mL)和水(10μL)然后油浴120℃下搅拌反应24h。反应完成后,等降至室温,离心分离后加入癸烷(3μL)作为内标物,搅拌均匀后测气相。产率为81%,E/Z比为2,TON值为4050。
实施例13
Rh/POP-PPh3-SO3Na催化剂催化1-癸烯(底物:催化剂=5×103)的异构化反应
在手套箱里,向Schlenk烧瓶中加入催化剂(5.6mg),1-癸烯(1.2mL,6.3mmol),无水乙醇(2mL)和水(10μL)然后油浴130℃下搅拌反应24h。反应完成后,等降至室温,离心分离后加入癸烷(3μL)作为内标物,搅拌均匀后测气相。产率为76%,E/Z比为2,TON值为3800。
实施例14
在手套箱里,向Schlenk烧瓶中加入催化剂(5.6mg),4-烯丙基苯甲醚(0.19mL,1.26mmol),无水乙醇(2mL)和水(10μL)然后油浴130℃下搅拌反应5h。反应完成后,等降至室温,将反应体系离心分离出上层产物和下层催化剂。分离出的催化剂在手套箱里向Schlenk烧瓶中重新加入4-烯丙基苯甲醚(0.19mL,1.26mmol),无水乙醇(2mL)和水(10μL)油浴120℃下搅拌反应5h。上层产物加入癸烷(3μL)作为内标物,搅拌均匀后测气相。如此循环5次。具体测试数据如下:
以上实施例仅用以说明本发明的技术方案,而非对其进行限制;尽管参照前述实施例对本发明进行了详细的说明,对于本领域的普通技术人员来说,依然可以对前述实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换;而这些修改或替换,并不使相应技术方案的本质脱离本发明所要求保护的技术方案的精神和范围。
Claims (3)
1.一种反式-2-烯烃的合成方法,其特征在于所述的方法为:如通式1所示的1-烯烃I,在聚合物负载铑催化剂的作用下,在有机溶剂中加热反应;反应完全后,离心分离催化剂,滤液分离处理得到如式II的反式-2-烯烃;
R分别独立选自氢、C1~C10的烷烃基、C1~C10的烷氧基、
其中Rx和Rx'分别独立选自氢、羟基、磺酸基、卤素、腈基、C1~C10的烷烃基、C1~C10的烷氧基、C1~C10的烷酰基、C1~C10的酯基;
聚合物负载铑催化剂,具有如下结构:
2.根据权利要求1所述,其特征在于,所述有机溶剂选自苯、甲苯、二甲苯、三甲苯、乙腈、乙醚、四氢呋喃、甲基叔丁基醚、乙二醇二甲醚、氯仿、二氯甲烷、甲醇、乙醇、异丙醇、N,N–二甲基甲酰胺、二甲基亚砜或N-甲基吡咯烷酮。
3.根据权利要求1所述,其特征在于,反应温度为60~150℃。
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