CN110483265B - 一种二烯醛或二烯酮类化合物的合成方法 - Google Patents

一种二烯醛或二烯酮类化合物的合成方法 Download PDF

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CN110483265B
CN110483265B CN201910713552.XA CN201910713552A CN110483265B CN 110483265 B CN110483265 B CN 110483265B CN 201910713552 A CN201910713552 A CN 201910713552A CN 110483265 B CN110483265 B CN 110483265B
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王永强
潘高飞
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Abstract

本发明公开了一种二烯醛或二烯酮化合物的合成方法,其以烯醛或烯酮为起始原料,钯化合物为催化剂,氧气为氧化剂,三氟乙酸为添加剂,在极性有机溶剂中经一步脱氢反应合成得到(EE)‑二烯醛和(EE)‑二烯酮类化合物。本发明方法实现了过渡金属催化氧化脱氢合成单一立体构型的(EE)‑二烯醛和(EE)‑二烯酮类化合物,其与传统方法相比原料便宜易得,操作简单,底物适应范围更广,反应效率更高,环境友好,产率高,原子利用率高。

Description

一种二烯醛或二烯酮类化合物的合成方法
技术领域
本发明涉及一种一种二烯醛或二烯酮类化合物的合成方法,具体涉及一种(EE)-二烯醛或(EE)-二烯酮化合物合成方法,属于有机合成技术领域。
背景技术
共轭的(E, E)-二烯羰基结构单元在天然产物中普遍存在,例如从真菌中提取出来的荧光染料Epicocconone,具有抗癌活性的Asukamycin、Mezerein,重要的抗生素Pecilocin,广谱抗惊厥药物Piperine等,都含有(E, E)-二烯结构单元。
Figure DEST_PATH_IMAGE001
此外,共轭的(E, E)-二烯醛和二烯酮在有机化学转化中具有广泛的用途,由于其结构的特殊性,既包含羰基又包含(E, E)-二烯结构单元,因此被广泛的应用于1,2加成、1,4加成、1,6加成、环加成以及D-A反应中。
传统的关于二烯醛和二烯酮合成方法主要包括Wittig-反应、Knoevenagel反应以及一些加成-消除反应,虽然这些方法在合成一些特定的化合物中得到很好的应用,但是这些反应都或多或少的存在一些缺点,比如Wittig-反应需要事先制备合适的叶立德前体;Knoevenagel反应常常反应位点是非常活泼的亚甲基,对反应底物的要求较高。因此这些传统的方法从原子经济性、步骤经济性、可操作性和环境保护方面具有很大提升空间。
近年来,利用过渡金属氧化脱氢策略构建碳碳双键的反应取得了很大发展,这类方法是直接通过切断连续的 C-H 键而构建碳碳双键。然而,利用便宜易得的烯醛通过γ,δ-氧化脱氢的方法构建联烯还没有被人们报道。本发明报道了一种利用烯醛或烯酮通过γ,δ-氧化脱氢的构建(EE)-二烯醛和(EE)-二烯酮的方法。这种方法用于制备不饱和二烯醛、酮不仅合成步骤非常简洁,而且节能环保,具有很好的经济效益和应用价值。
发明内容
本发明的目的在于提供一种操作简单、底物普适性广、官能团的兼容性强,反应效率高、环境友好、符合绿色化学要求的(E, E)-二烯醛和二烯酮的合成方法。
本发明实现过程如下:
一种二烯醛或二烯酮类化合物的合成方法:以结构通式(I)所示的烯醛或烯酮为起始原料,钯催化剂存在下,氧气为氧化剂,三氟乙酸为添加剂,在极性有机溶剂中经一步合成得到结构通式(II)所示的二烯醛或二烯酮类化合物,
Figure 288002DEST_PATH_IMAGE002
其中,R1选自H、C1~C10烷基,卤素基、羟基、甲氧基、H取代的芳香基;R2~R5独立地选自H、C1~C10烷基;R6选自H、C1~C10烷基,卤素基、羟基、甲氧基、H取代的芳香环。
上述钯催化剂选自Pd(OAc)2,Pd(TFA)2,Pd(PPh3)4,Pd2(dba)3,PdCl2,优选自Pd(OAc)2
上述极性有机溶剂选自DMF、DMSO、CH3CN、THF,优选自二甲亚砜、乙腈。
所述H取代的芳香环如苯基、萘基,芳香杂环基如呋喃基、噻吩基、吡咯基、噻唑基、吡唑基、咪唑基、噁唑基、异噁唑基、吡啶基、哒嗪基、嘧啶基、吡嗪基、喹啉基、异喹啉基、吲哚基、嘌呤基,以及上述苯并芳香杂环基。
本发明在重要添加剂为三氟乙酸,使用三氟乙酸可获得高的产率,其他的酸包括有机酸和无机酸表现较差。
本发明的优点:(1)本发明实现了γ,δ-氧化脱氢反应,此方法与传统方法相比原料易得,操作简便,底物适应范围更广,反应效率更高,环境友好,产率高,原子利用率高。(2)羰基的αβγδ位有取代基的底物都能取得较好的结果。
具体实施方式
实施例1
Figure DEST_PATH_IMAGE003
在一个100 mL的圆底烧瓶中,加入原料Ia,醋酸钯(10 mol%)将圆底烧瓶密封并抽成真空状态,用氧气求将圆底烧瓶填充。接下来,依次加入处理好的DMSO,三氟乙酸,所有物质添加完毕后,在氧气氛围中充分搅拌。反应混合液在80 ℃搅拌至TLC(薄层色谱)监测反应不再进行。反应完毕后,冷却至室温,混合液用100 mL乙酸乙酯分散,用5 mL水萃取有机相3次,再用5 mL饱和食盐水萃取有机相3次,接下来,有机相用无水硫酸钠干燥大于30min。过滤,浓缩,柱色谱分离得到目标化合物IIa。
(3E,5E)-octa-3,5-dien-2-one (IIa) 产物为淡黄色油装液体,产率为73%。Rf =0.56 (EtOAc / hexanes 1 : 30). 1H NMR (400 MHz, CDCl3): δ = 7.11 (dd, J =15.6, 9.6 Hz, 1H), 6.31 – 6.13 (m, 2H), 6.06 (d, J = 15.7 Hz, 1H), 2.26 (s,3H), 2.22 – 2.10 (m, 2H), 1.06 (t, J = 7.4 Hz, 3H). 13C NMR (100 MHz, CDCl3):δ = 198.6, 147.0, 144.0, 128.8, 127.9, 27.1, 26.1, 12.8. HRMS (ESI) forC8H13O [M+H+]: Calcd: 147.0780; Found: 147.0788. IR (KBr): 2925, 2854, 1722,1670, 1459, 1257, 1054, 1012, 800, 617 cm-1
实施例2
Figure 536580DEST_PATH_IMAGE004
在一个100 mL的圆底烧瓶中,加入原料Ib,醋酸钯(10 mol%)将圆底烧瓶密封并抽成真空状态,用氧气求将圆底烧瓶填充。接下来,依次加入处理好的DMSO,三氟乙酸,所有物质添加完毕后,在氧气氛围中充分搅拌。反应混合液在80 ℃搅拌至TLC(薄层色谱)监测反应不再进行。反应完毕后,冷却至室温,混合液用100 mL乙酸乙酯分散,用5 mL水萃取有机相3次,再用5 mL饱和食盐水萃取有机相3次,接下来,有机相用无水硫酸钠干燥大于30min。过滤,浓缩,柱色谱分离得到目标化合物IIb。
(2E,4E)-1-phenylhepta-2,4-dien-1-one (IIb) 产物为黄色油状液体,产率65%。Rf = 0.39 (EtOAc / hexanes 1 : 30); 1H NMR (400 MHz, CDCl3): δ = 7.99 –7.90 (m, 2H), 7.58 – 7.53 (m, 1H), 7.47 (t, J = 7.5 Hz, 2H), 7.44 – 7.38 (m,1H), 6.89 (d, J = 15.0 Hz, 1H), 6.31 (dd, J = 6.2, 2.8 Hz, 2H), 2.29 – 2.20(m, 2H), 1.08 (t, J = 7.4 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ = 191.1, 148.0,145.7, 138.4, 132.7, 128.7, 128.5, 128.3, 123.7, 26.4, 13.0. HRMS (ESI) forC13H15O [M+H+]: Calcd: 187.1117; Found: 187.1115. IR (KBr): 3062, 2960, 2867,1673, 1619, 1452, 1284, 1103, 1010, 798, 696 cm-1
实施例3
Figure DEST_PATH_IMAGE005
在一个100 mL的圆底烧瓶中,加入原料Ic,醋酸钯(10 mol%)将圆底烧瓶密封并抽成真空状态,用氧气求将圆底烧瓶填充。接下来,依次加入处理好的DMSO,三氟乙酸,所有物质添加完毕后,在氧气氛围中充分搅拌。反应混合液在80 ℃搅拌至TLC(薄层色谱)监测反应不再进行。反应完毕后,冷却至室温,混合液用100 mL乙酸乙酯分散,用5 mL水萃取有机相3次,再用5 mL饱和食盐水萃取有机相3次,接下来,有机相用无水硫酸钠干燥大于30min。过滤,浓缩,柱色谱分离得到目标化合物IIc。
(2E,4E)-1,5-diphenylpenta-2,4-dien-1-one (IIc) 产物为黄色固体,产率73%。熔点91 – 94%。Rf = 0.46 (EtOAc / hexanes 1 : 20); 1H NMR (400 MHz, CDCl3):δ = 7.97 (d, J = 7.1 Hz, 2H), 7.65 – 7.51 (m, 2H), 7.46 (dd, J = 10.4, 4.7Hz, 4H), 7.39 – 7.26 (m, 3H), 7.07 (d, J = 14.9 Hz, 1H), 6.99 (d, J = 8.7 Hz,2H). 13C NMR (100 MHz, CDCl3): δ = 190.5, 144.9, 142.0, 138.3, 136.1, 132.7,129.3, 128.9, 128.6, 128.4, 127.4, 127.0, 125.5. HRMS (ESI) for C17H14NaO [M+Na+]: Calcd: 257.0937; Found: 257.0925. IR (KBr): 3060, 3029, 2958, 2928,2597, 1963, 1903, 1717, 1682, 1657, 1578, 1284, 1253, 1010, 695 cm-1
实施例4
Figure 652828DEST_PATH_IMAGE006
在一个100 mL的圆底烧瓶中,加入原料Id,醋酸钯(10 mol%)将圆底烧瓶密封并抽成真空状态,用氧气求将圆底烧瓶填充。接下来,依次加入处理好的DMSO,三氟乙酸,所有物质添加完毕后,在氧气氛围中充分搅拌。反应混合液在80 ℃搅拌至TLC(薄层色谱)监测反应不再进行。反应完毕后,冷却至室温,混合液用100 mL乙酸乙酯分散,用5 mL水萃取有机相3次,再用5 mL饱和食盐水萃取有机相3次,接下来,有机相用无水硫酸钠干燥大于30min。过滤,浓缩,柱色谱分离得到目标化合物IId。
(2E,4E)-octa-2,4-dienal (IId) 产物为白色液体,产率81%。R f= 0.49 (EtOAc/ hexanes 1 : 30); 1H NMR (400 MHz, CDCl3): δ = 9.54 (d, J = 8.0 Hz, 1H), 7.17– 7.01 (m, 1H), 6.39 – 6.21 (m, 2H), 6.08 (dd, J = 15.4, 8.0 Hz, 1H), 2.21(dd, J = 13.4, 7.1 Hz, 2H), 1.49 (dt, J = 14.7, 7.3 Hz, 2H), 0.94 (t, J = 7.4Hz, 3H). 13C NMR (100 MHz, CDCl3): δ = 194.2, 153.1, 147.3, 130.2, 128.9,35.3, 21.9, 13.8. HRMS (ESI) for C8H12NaO [M+Na+]: Calcd: 147.0780; Found:147.0789. IR (KBr): 2923, 2854, 1681, 1459, 1374, 1116, 792 cm-1
实施例5
Figure DEST_PATH_IMAGE007
在一个100 mL的圆底烧瓶中,加入原料Ie,醋酸钯(10 mol%)将圆底烧瓶密封并抽成真空状态,用氧气求将圆底烧瓶填充。接下来,依次加入处理好的DMSO,三氟乙酸,所有物质添加完毕后,在氧气氛围中充分搅拌。反应混合液在80 ℃搅拌至TLC(薄层色谱)监测反应不再进行。反应完毕后,冷却至室温,混合液用100 mL乙酸乙酯分散,用5 mL水萃取有机相3次,再用5 mL饱和食盐水萃取有机相3次,接下来,有机相用无水硫酸钠干燥大于30min。过滤,浓缩,柱色谱分离得到目标化合物IIe。
(2E,4E)-5-(benzo[d][1,3]dioxol-5-yl)penta-2,4-dienal (IIe)产物为黄色固体。熔点77 – 78 oC。 Rf = 0.45 (EtOAc / hexanes 1 : 10).1H NMR (400 MHz,CDCl3): δ= 9.59 (d, J = 8.0 Hz, 1H), 7.24 (dd, J = 14.9, 10.4 Hz, 1H), 7.08 –6.75 (m, 5H), 6.23 (dd, J = 15.1, 8.0 Hz, 1H), 6.01 (s, 2H). 13C NMR (100MHz, CDCl3) : δ= 193.7, 152.5, 149.3, 148.5, 142.4, 131.0, 130.2, 124.6,123.8, 108.8, 106.2, 101.7.HRMS (ESI) for C12H10O3Na [M+Na+]: Calcd:225.0522; Found: 225.0506.IR (KBr): 2914, 1675,1599, 1495, 1444, 1359, 1296,1253, 1195,1154, 1035, 983, 797 cm-1

Claims (3)

1.一种二烯醛或二烯酮类化合物的合成方法,其特征在于:以结构通式(I)所示的烯醛或烯酮为起始原料,醋酸钯催化剂存在下,氧气为氧化剂,三氟乙酸为添加剂,在极性有机溶剂中经一步合成得到结构通式(II)所示的二烯醛或二烯酮类化合物,
Figure 523022DEST_PATH_IMAGE001
其中,R1选自H、C1的烷基,卤素基、羟基、甲氧基;R2~R5为H;R6选自H、C1~C10烷基,卤素基、羟基、甲氧基。
2.根据权利要求1所述的合成方法,其特征在于:所述的极性有机溶剂选自DMF、DMSO、CH3CN、THF。
3.根据权利要求2所述的合成方法,其特征在于:所述的极性有机溶剂选自DMSO、CH3CN。
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