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CN104418771B - Preparation and application of DMAP hydrochloride as catalyst of recoverable acylation reaction - Google Patents

Preparation and application of DMAP hydrochloride as catalyst of recoverable acylation reaction Download PDF

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CN104418771B
CN104418771B CN201310375967.3A CN201310375967A CN104418771B CN 104418771 B CN104418771 B CN 104418771B CN 201310375967 A CN201310375967 A CN 201310375967A CN 104418771 B CN104418771 B CN 104418771B
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carbon
dmap
hydrochloride
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solvent
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CN104418771A (en
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汪清民
刘智慧
马巧巧
姜育田
季玉祥
赵卫东
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Nankai University
Adama Anpon Jiangsu Ltd
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Jiangsu Anpon Electrochemical Co Ltd
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Abstract

本发明涉及对二甲氨基吡啶(DMAP)盐酸盐催化的酰基化反应(反应式如下)。DMAP溶于非极性溶剂中，通入干燥的氯化氢气体，过滤得到DMAP盐酸盐。惰性醇、酚及胺在无溶剂或有机溶剂条件下，加入催化量的DMAP盐酸盐，在0‑130℃下与酰基化试剂反应完全，加入非极性溶剂，过滤可回收催化剂DMAP盐酸盐。滤液水洗、碱洗、分液、有机相干燥，蒸除溶剂可得到酰基化产物。回收的DMAP盐酸盐可以进入下一个催化循环。 The present invention relates to the acylation reaction catalyzed by p-dimethylaminopyridine (DMAP) hydrochloride (the reaction formula is as follows). DMAP was dissolved in a non-polar solvent, passed through dry hydrogen chloride gas, and filtered to obtain DMAP hydrochloride. Add a catalytic amount of DMAP hydrochloride to inert alcohols, phenols and amines under the condition of no solvent or organic solvent, react completely with the acylating reagent at 0-130°C, add non-polar solvent, filter and recover the catalyst DMAP hydrochloride Salt. Wash the filtrate with water, wash with alkali, separate liquid, dry the organic phase, and evaporate the solvent to obtain the acylated product. The recovered DMAP hydrochloride can enter the next catalytic cycle.

Description

DMAP盐酸盐作为可回收酰基化反应催化剂的制备和应用Preparation and Application of DMAP Hydrochloride as Recyclable Acylation Catalyst

技术领域technical field

本发明涉及DMAP盐酸盐作为可回收酰基化反应催化剂的制备和应用。The present invention relates to the preparation and application of DMAP hydrochloride as a recyclable acylation catalyst.

背景技术Background technique

DMAP是常用的酰基化反应的催化剂，它的负载和回收有大量的工作报道。其主要方法有：DMAP负载在高分子材料中，得到可溶性的DMAP衍生物，但是却难以实现催化剂的回收(见文献：1.Price，K.E.；Mason，B.P.；Bogdan，A.R.；et al.J.Am.Chem.Soc.2006，128，10376-10377.2.Liang，C.O.；Helms，B.;Hawker,C.J.；et al.Chem.Commun2003，2524-2525.)；硅胶及高分子负载的非均相DMAP催化剂，但是其催化活性往往大大降低(见文献：1.Chen，H.-T.；Huh，S.；Wiench，J.W.；et al.J.Am.Chem.Soe.2005，127，13305-13311.2.Yuang，J.-H.；Shi，M.Adv.Synth.Catal.2003，345，953-955.3.Corma，A.；Garcia，H.；Leyva,A.Chem.Commun2003，2806-2807.)。近年来新型的高分子负载的高活性、易回收的DMAP衍生物也受到广泛的关注(见文献：1.Zhang，Y.；Zhang，Y.；Sun，Y.L.；etal.Chem.Eur.J.2012,18,6328-6334.2.D'Elia,V.；Liu，Y.H.；Zipse，H.Eur.J.Org.Chem.2011，1527-1533.3.Zhao，B.;Jiang，X.M.；Li，D.J.；etal.J.Polym.Sci.，Part A：Polym.Chem.2008，46，3438-3446.)。但是，所有的这些催化剂都有极大的分子量，同时其载体都需要多步的合成，限制了它的应用。结构简单的DMAP的多氟羧酸盐、DMAP糖精络合物也可作为可回收的酰基化反应催化剂(见文献：1.Vuluga，D.；Legros，J.；Crousse，B.；et al.Chem.Eur.J.2010，16，1776-1779.2.Lu，N.；Chang，W.-H.；Tu，W.-H.;et al.Chem.Commun2011，47，7227-7229.)。但是它们不适用于酰氯等强酸性的酰基化试剂，由于反应会放出氯化氢等强酸，催化剂可能与强酸形成新的盐而破坏原来的结构。DMAP is a commonly used catalyst for acylation reactions, and its loading and recovery have been extensively reported. Its main method has: DMAP loads in polymer material, obtains soluble DMAP derivative, but is difficult to realize the recovery of catalyst (see literature: 1.Price, K.E.; Mason, B.P.; Bogdan, A.R.; et al.J. Am.Chem.Soc.2006, 128, 10376-10377.2.Liang, C.O.; Helms, B.; Hawker, C.J.; et al.Chem.Commun2003, 2524-2525.); Silica gel and polymer loaded heterogeneous DMAP catalyst, but its catalytic activity is often greatly reduced (see literature: 1.Chen, H.-T.; Huh, S.; Wiench, J.W.; et al.J.Am.Chem.Soe.2005, 127, 13305-13311.2 . Yuang, J.-H.; Shi, M. Adv. Synth. Catal. 2003, 345, 953-955. 3. Corma, A.; Garcia, H.; Leyva, A. Chem. Commun 2003, 2806-2807.) . In recent years, the highly active and easily recyclable DMAP derivatives loaded with new polymers have also received extensive attention (see literature: 1. Zhang, Y.; Zhang, Y.; Sun, Y.L.; etal.Chem.Eur.J. 2012,18,6328-6334.2.D'Elia,V.; Liu, Y.H.; Zipse, H.Eur.J.Org.Chem.2011,1527-1533.3.Zhao, B.;Jiang,X.M.;Li,D.J.; et al. J. Polym. Sci., Part A: Polym. Chem. 2008, 46, 3438-3446.). However, all of these catalysts have extremely high molecular weight, and their supports require multi-step synthesis, which limits their applications. The polyfluorocarboxylates of DMAP and DMAP saccharin complexes with simple structure can also be used as recyclable acylation catalysts (see literature: 1.Vuluga, D.; Legros, J.; Crousse, B.; et al. Chem. Eur. J. 2010, 16, 1776-1779.2. Lu, N.; Chang, W.-H.; Tu, W.-H.; et al. Chem. Commun2011, 47, 7227-7229.). However, they are not suitable for strongly acidic acylating reagents such as acid chlorides. Since the reaction will release strong acids such as hydrogen chloride, the catalyst may form new salts with strong acids and destroy the original structure.

发明内容Contents of the invention

本发明的目的是提供一种高效、易制备、适用性广、可回收的酰基化反应催化剂的制备及应用方法。The purpose of the present invention is to provide a preparation and application method of an acylation reaction catalyst with high efficiency, easy preparation, wide applicability and recyclability.

本发明的DMAP盐酸盐催化的酰基化反应合成如下(方程式1)The DMAP hydrochloride catalyzed acylation reaction of the present invention is synthesized as follows (Equation 1)

方程式1：Equation 1:

其中R-X代表2-6碳烷基酰氯、2-6碳烷基酸酐、1-6碳烷氨基甲酰氯、1-6碳烷氧基甲酰氯、4-12个碳的碳酸酐、取代或非取代的苯甲酰氯、取代或非取代的苯甲酸酐、1-6碳的磺酰氯、1-6碳的磺酸酐、取代或非取代的苯磺酰氯、取代或非取代的苯磺酸酐、3-18碳的磷酰氯。其中芳环上的取代基为一个或一个以上下述基团卤素、1-4碳烷基、1-4碳烷氧基、1-4碳卤代烷基、1-4碳卤代烷氧基、1-4碳烷氧烷基、1-4碳烷硫基、硝基、氰基、1-4碳烷基羰基。Where R-X represents 2-6 carbon alkyl acid chloride, 2-6 carbon alkyl acid anhydride, 1-6 carbon alkane carbamoyl chloride, 1-6 carbon alkoxy formyl chloride, 4-12 carbonic anhydride, substituted or non Substituted benzoyl chloride, substituted or unsubstituted benzoic anhydride, 1-6 carbon sulfonyl chloride, 1-6 carbon sulfonic anhydride, substituted or unsubstituted benzenesulfonyl chloride, substituted or unsubstituted benzenesulfonic anhydride, 3 Phosphorus oxychloride at carbon -18. Wherein the substituent on the aromatic ring is one or more of the following groups halogen, 1-4 carbon alkyl, 1-4 carbon alkoxy, 1-4 carbon haloalkyl, 1-4 carbon haloalkoxy, 1- 4-carbon alkoxyalkyl, 1-4-carbon alkylthio, nitro, cyano, 1-4-carbon alkylcarbonyl.

R1、R2代表1-6碳烷基、1-6碳的卤代烷基、5-12碳的环烷基、烯丙基、炔丙基，烯基、苯基、吡啶基、萘基，各基团是未取代的，或是被一个或一个以上下述基团取代：卤素、1-4碳烷基、1-4碳烷氧基、1-4碳卤代烷基、1-4碳卤代烷氧基、1-4碳烷氧烷基、1-4碳烷硫基、硝基、氰基、1-4碳烷基羰基。R 1 and R 2 represent 1-6 carbon alkyl, 1-6 carbon haloalkyl, 5-12 carbon cycloalkyl, allyl, propargyl, alkenyl, phenyl, pyridyl, naphthyl, Each group is unsubstituted or substituted by one or more of the following groups: halogen, 1-4 carbon alkyl, 1-4 carbon alkoxy, 1-4 carbon haloalkyl, 1-4 carbon haloalkane Oxygen, 1-4 carbon alkoxyalkyl, 1-4 carbon alkylthio, nitro, cyano, 1-4 carbon alkylcarbonyl.

R3代表1-6碳烷酰基、苯甲酰基、或与R2及它们相连的氮共同代表吡唑环、吡咯环、噻唑环、恶唑环。各基团是未取代的或是被一个或一个以上下述基团取代：卤素、1-4碳烷基、1-4碳烷氧基、1-4碳卤代烷基、1-4碳卤代烷氧基、1-4碳烷氧烷基、1-4碳烷硫基、硝基、氰基、1-4碳烷基羰基。R 3 represents 1-6 carbon alkanoyl, benzoyl, or together with R 2 and the nitrogen connected to them represent pyrazole ring, pyrrole ring, thiazole ring, oxazole ring. Each group is unsubstituted or substituted by one or more of the following groups: halogen, 1-4 carbon alkyl, 1-4 carbon alkoxy, 1-4 carbon haloalkyl, 1-4 carbon haloalkoxy Group, 1-4 carbon alkoxyalkyl, 1-4 carbon alkylthio, nitro, cyano, 1-4 carbon alkylcarbonyl.

本发明的方法是：DMAP溶于非极性溶剂中，通入干燥的氯化氢气体，过滤得到DMAP盐酸盐。惰性醇、酚及胺在无溶剂或有机溶剂条件下，加入催化量的DMAP盐酸盐，在0-130℃下与酰基化试剂反应完全，加入非极性溶剂，过滤可回收催化剂DMAP盐酸盐。滤液水洗、碱洗、分液、有机相干燥，蒸除溶剂可得到酰基化产物。回收的DMAP盐酸盐可以进入下一个催化循环。The method of the invention is as follows: DMAP is dissolved in a non-polar solvent, and dry hydrogen chloride gas is passed through, and the DMAP hydrochloride is obtained by filtering. Add a catalytic amount of DMAP hydrochloride to inert alcohols, phenols and amines under the condition of no solvent or organic solvent, react completely with the acylating reagent at 0-130°C, add a non-polar solvent, filter and recover the catalyst DMAP hydrochloride Salt. Wash the filtrate with water, wash with alkali, separate liquid, dry the organic phase, and evaporate the solvent to obtain the acylated product. The recovered DMAP hydrochloride can enter the next catalytic cycle.

本反应中所用的惰性醇、酚及胺与酰基化试剂和DMAP盐酸盐的摩尔比为1：1.1：0.05。反应可在0-130℃范围内进行，最佳反应温度为60-110℃。The molar ratio of the inert alcohol, phenol and amine used in this reaction to the acylating agent and DMAP hydrochloride is 1:1.1:0.05. The reaction can be carried out in the range of 0-130°C, and the optimum reaction temperature is 60-110°C.

本发明中反应可不用溶剂或使用下列有机溶剂：芳烃，如甲苯、二甲苯等；烷烃，如正己烷、环己烷、正戊烷、正庚烷、石油醚等；醚，如四氢呋喃、1，4-二氧六环等；卤代烃，如二氯甲烷、1,2-二氯乙烷、氯仿等。最佳溶剂为甲苯。Reaction can be without solvent or use following organic solvent among the present invention: aromatic hydrocarbon, as toluene, xylene etc.; , 4-dioxane, etc.; halogenated hydrocarbons, such as dichloromethane, 1,2-dichloroethane, chloroform, etc. The best solvent is toluene.

本反应时间为0.1-24小时，最佳反应时间为2-6小时。The reaction time is 0.1-24 hours, and the optimum reaction time is 2-6 hours.

本发明的DMAP盐酸盐可由下述方法制备：将DMAP溶于甲苯中，室温搅拌通入干燥的氯化氢气体，反应体系析出白色固体。过滤、真空干燥得DMAP盐酸盐。The DMAP hydrochloride of the present invention can be prepared by the following method: DMAP is dissolved in toluene, and dry hydrogen chloride gas is introduced into the reaction system with stirring at room temperature, and a white solid is precipitated in the reaction system. Filter and vacuum dry to obtain DMAP hydrochloride.

本发明的DMAP盐酸盐催化的酰基化反应可由下述方法进行。操作a：反应物为液体时，反应在无溶剂条件下进行。在底物加入催化量DMAP盐酸盐，室温搅拌使之溶解，加入酰基化试剂，控制反应温度至所需温度，GC或TLC检测反应完成后，冷却反应体系至室温。向反应体系中加入正己烷，过滤回收催化剂，真空干燥后投入下一次循环。滤液分别用水、饱和碳酸氢钠、饱和食盐水洗涤，MgSO4干燥，减压脱溶后得产物。操作b：反应物为固体时，反应在甲苯体系中进行。将底物溶于甲苯中，加入催化量DMAP盐酸盐，室温搅拌使之溶解，加入酰基化试剂。控制反应温度至所需温度，GC或TLC检测反应完成后，冷却反应体系至室温。向反应体系中加入正己烷，抽滤回收催化剂，真空干燥，投入下一次循环。滤液分别用水、饱和碳酸氢钠、饱和食盐水洗涤，MgSO4干燥，减压脱溶得产物。本反应中底物与酰基化试剂和DMAP盐酸盐的摩尔比是1：1.1：0.05。The DMAP hydrochloride catalyzed acylation reaction of the present invention can be carried out by the following method. Operation a: When the reactant is liquid, the reaction is carried out without solvent. Add a catalytic amount of DMAP hydrochloride to the substrate, stir at room temperature to dissolve it, add an acylating reagent, control the reaction temperature to the desired temperature, and cool the reaction system to room temperature after GC or TLC detects that the reaction is complete. Add n-hexane into the reaction system, filter and recover the catalyst, and put it into the next cycle after vacuum drying. The filtrate was washed with water, saturated sodium bicarbonate, and saturated brine, dried over MgSO 4 , and the product was obtained after precipitation under reduced pressure. Operation b: when the reactant is solid, the reaction is carried out in a toluene system. Dissolve the substrate in toluene, add a catalytic amount of DMAP hydrochloride, stir at room temperature to dissolve it, and add an acylating reagent. Control the reaction temperature to the desired temperature, and after the completion of the reaction detected by GC or TLC, cool the reaction system to room temperature. Add n-hexane to the reaction system, recover the catalyst by suction filtration, dry it in vacuum, and put it into the next cycle. The filtrate was washed with water, saturated sodium bicarbonate, and saturated brine, dried over MgSO 4 , and precipitated under reduced pressure to obtain the product. The molar ratio of substrate to acylating reagent and DMAP hydrochloride in this reaction is 1:1.1:0.05.

具体实施方法Specific implementation method

下述的实例中，熔点未经校正。In the following examples, melting points are uncorrected.

实施例1：DMAP盐酸盐的合成：Embodiment 1: the synthesis of DMAP hydrochloride:

在100mL圆底烧瓶中加入30mL甲苯、5.0g(40.9mmol)DMAP，电磁搅拌使之溶解。向体系中通入2.92g(80mmol)干燥的HCI气体，体系中立即析出白色固体。室温反应1h，抽滤、真空干燥得白色固体6.28g，收率96.9％，熔点：220-221℃。1H NMR(400MHz，CDCl3)δ15.45(br,1H)，8.14(t，J=6.8Hz，2H)，6.78(d，J=6.8Hz，2H)，3.27(s，6H).13C NMR(100MHz，CDCl3)δ138.6，106.8，40.3.Add 30 mL of toluene and 5.0 g (40.9 mmol) of DMAP into a 100 mL round-bottomed flask, and stir it electromagnetically to dissolve it. 2.92g (80mmol) of dry HCI gas was introduced into the system, and a white solid was precipitated in the system immediately. React at room temperature for 1 h, filter with suction, and dry in vacuo to obtain 6.28 g of white solid, yield 96.9%, melting point: 220-221°C. 1 H NMR (400MHz, CDCl3) δ15.45(br, 1H), 8.14(t, J=6.8Hz, 2H), 6.78(d, J=6.8Hz, 2H), 3.27(s, 6H). 13 C NMR (100MHz, CDCl 3 ) δ138.6, 106.8, 40.3.

实施例2：1-氰基环己醇的特戊酰化反应：Embodiment 2: the pivaloylation reaction of 1-cyano cyclohexanol:

在10mL单口瓶中加入2.50g(20mmol)1-氰基环己醇、0.16g(1mmol)DMAP盐酸盐和2.64g(22mmol)的特戊酰氯。控制反应温度至110℃，反应4小时，冷却反应体系至室温。向反应体系中加入20mL正己烷，过滤回收催化剂，真空干燥后投入下一次循环。滤液用分别有20mL水、20mL饱和碳酸氢钠、15mL饱和食盐水洗涤，MgSO4干燥，减压脱溶、快速柱层析得产物无色油状物3.97g，收率95.0％。1H NMR(400MHz，CDCl3)δ2.29-2.17(m，2H)，2.04-1.89(m，2H)，1.79-1.66(m，4H)，1.64-1.53(m，1H)，1.49-1.37(m，1H)，1.26(s，9H).Add 2.50 g (20 mmol) of 1-cyanocyclohexanol, 0.16 g (1 mmol) of DMAP hydrochloride and 2.64 g (22 mmol) of pivaloyl chloride into a 10 mL single-necked bottle. Control the reaction temperature to 110° C., react for 4 hours, and cool the reaction system to room temperature. Add 20 mL of n-hexane to the reaction system, filter and recover the catalyst, dry it in vacuum and put it into the next cycle. The filtrate was washed with 20 mL of water, 20 mL of saturated sodium bicarbonate, and 15 mL of saturated brine, dried over MgSO 4 , precipitated under reduced pressure, and flash column chromatography to obtain 3.97 g of a colorless oil with a yield of 95.0%. 1 H NMR (400MHz, CDCl 3 ) δ2.29-2.17 (m, 2H), 2.04-1.89 (m, 2H), 1.79-1.66 (m, 4H), 1.64-1.53 (m, 1H), 1.49-1.37 (m, 1H), 1.26(s, 9H).

实施例3：邻硝基苯酚的苯甲酰化反应：Embodiment 3: the benzoylation reaction of o-nitrophenol:

在50mL单口瓶中加入2.78g(20mmol)邻硝基苯酚、20mL甲苯、0.16g(1mmol)DMAP盐酸盐和4.52g(22mmol)的苯甲酸酐。控制反应温度至60℃，反应4小时，冷却反应体系至室温。向反应体系中加入20mL正己烷，过滤回收催化剂，真空干燥后投入下一次循环。滤液用分别有20mL水、20mL饱和碳酸氢钠、15mL饱和食盐水洗涤，MgS04干燥，减压脱溶、快速柱层析得产物淡黄色油状物4.67g，收率96.1％。1H NMR(400MHz，CDCl3)δ8.25-8.18(m，2H)，8.16(dd，J=8.0，1.6Hz，1H)，7.75-7.66(m，2H)，7.54(t，J=7.6Hz，2H)，7.48-7.43(m，1H)，7.43-7.37(m，1H).Add 2.78g (20mmol) of o-nitrophenol, 20mL of toluene, 0.16g (1mmol) of DMAP hydrochloride and 4.52g (22mmol) of benzoic anhydride into a 50mL single-necked bottle. Control the reaction temperature to 60° C., react for 4 hours, and cool the reaction system to room temperature. Add 20 mL of n-hexane to the reaction system, filter and recover the catalyst, dry it in vacuum and put it into the next cycle. The filtrate was washed with 20 mL of water, 20 mL of saturated sodium bicarbonate, and 15 mL of saturated brine, dried over MgSO 4 , precipitated under reduced pressure, and flash column chromatography to obtain 4.67 g of a pale yellow oil with a yield of 96.1%. 1 H NMR (400MHz, CDCl 3 ) δ8.25-8.18(m, 2H), 8.16(dd, J=8.0, 1.6Hz, 1H), 7.75-7.66(m, 2H), 7.54(t, J=7.6 Hz, 2H), 7.48-7.43(m, 1H), 7.43-7.37(m, 1H).

同样方法可合成下列酰基化产物，见表1和表2，但并不限定本发明。The following acylation products can be synthesized by the same method, see Table 1 and Table 2, but the present invention is not limited.

表1 DMAP盐酸盐催化的酸酐的酰基化反应Table 1 Acylation reaction of acid anhydride catalyzed by DMAP hydrochloride

[a]20mmol底物、溶解于20mL甲苯中，向此溶液中加入1mmol催化剂、22mmol酸酐，加热至所需温度直至反应完成(见实施例3)。[b]对于液体底物，反应可在无溶剂条件下进行(见实施例2)。[c]分离收率。[a] 20mmol of substrate was dissolved in 20mL of toluene, 1mmol of catalyst and 22mmol of acid anhydride were added to the solution, and heated to the desired temperature until the reaction was completed (see Example 3). [b] For liquid substrates, the reaction can be performed under solvent-free conditions (see Example 2). [c] Isolated yield.

表2 DMAP盐酸盐催化的酰氯的酰基化反应Table 2 Acylation reactions of acid chlorides catalyzed by DMAP hydrochloride

[a]20mmol底物、溶解于20mL甲苯中，向此溶液中加入1mmol催化剂、22mmol酰氯，加热至所需温度直至反应完成(见实施例3)。[b]对于液体底物，反应可在无溶剂条件下进行(见实施例2)。[c]Y代表5％的DMAP盐酸盐作催化剂，N代表无催化剂。[d]转化率基于回收的原料计算。[e]分离收率。[a] 20mmol of substrate was dissolved in 20mL of toluene, 1mmol of catalyst and 22mmol of acid chloride were added to the solution, and heated to the required temperature until the reaction was completed (see Example 3). [b] For liquid substrates, the reaction can be performed under solvent-free conditions (see Example 2). [c] Y represents 5% DMAP hydrochloride as a catalyst, N represents no catalyst. [d] Conversion calculated based on recovered feedstock. [e] Isolated yield.

乙酸三氯苯酚酯，白色晶体，熔点49-50℃。1H NMR(400MHz，CDCl3)δ7.37(s.2H)，2.39(s，3H).Trichlorophenol acetate, white crystal, melting point 49-50°C. 1 H NMR (400MHz, CDCl 3 ) δ7.37(s.2H), 2.39(s, 3H).

苯甲酸三氯苯酚酯，白色晶体，熔点70-71℃。1H NMR(400MHz，CDCl3)δ8.24(d，J=7.2Hz，2H)，7.69(t，J=7.2Hz，1H)，7.55(t，J=7.6Hz，2H)，7.43(s，2H).Trichlorophenol benzoate, white crystal, melting point 70-71°C. 1 H NMR (400MHz, CDCl 3 ) δ8.24(d, J=7.2Hz, 2H), 7.69(t, J=7.2Hz, 1H), 7.55(t, J=7.6Hz, 2H), 7.43(s , 2H).

乙酸环己醇酯，无色液体。1H NMR(400MHz，CDCl3)δ4.83-4.63(m，1H)，2.04(s，3H)，1.90-1.83(m，2H)，1.77-1.67(m，2H)，1.58-1.50(m，1H)，1.46-1.29(m，4H)，1.28-1.19(m，1H).Cyclohexanol acetate, a colorless liquid. 1 H NMR (400MHz, CDCl3) δ4.83-4.63 (m, 1H), 2.04 (s, 3H), 1.90-1.83 (m, 2H), 1.77-1.67 (m, 2H), 1.58-1.50 (m, 1H), 1.46-1.29(m, 4H), 1.28-1.19(m, 1H).

苯甲酸环己醇酯，无色液体。1H NMR(400MHz，CDCl3)δ8.08(d，J=7.2Hz，2H)，7.58(t，J=7.2Hz，1H)，7.47(t，J=7.6Hz，2H)，5.07(ddd，J=12.4，8.4，3.6Hz，1H)，2.02-1.94(m，2H)，1.86-1.78(m，2H)，1.66-1.56(m，3H)，1.53-1.34(m，3H).Cyclohexanol Benzoate, a colorless liquid. 1 H NMR (400MHz, CDCl 3 ) δ8.08(d, J=7.2Hz, 2H), 7.58(t, J=7.2Hz, 1H), 7.47(t, J=7.6Hz, 2H), 5.07(ddd , J=12.4, 8.4, 3.6Hz, 1H), 2.02-1.94(m, 2H), 1.86-1.78(m, 2H), 1.66-1.56(m, 3H), 1.53-1.34(m, 3H).

乙酸-1-苯乙醇酯，无色液体。1H NMR(400MHz，CDCl3)δ7.35(d，J=4.0Hz，4H)，7.30(dd，J=8.4，4.0Hz，1H)，5.88(q，J=6.4Hz，1H)，2.08(s，3H)，1.54(d，J=6.4Hz，3H).1-Phenylethyl acetate, a colorless liquid. 1 H NMR (400MHz, CDCl 3 ) δ7.35(d, J=4.0Hz, 4H), 7.30(dd, J=8.4, 4.0Hz, 1H), 5.88(q, J=6.4Hz, 1H), 2.08 (s, 3H), 1.54 (d, J=6.4Hz, 3H).

苯甲酸-1-苯乙醇酯，无色液体。1H NMR(400MHz，CDCl3)δ8.08(d，J=7.2Hz，2H)，7.56(t，J=7.2Hz，1H)，7.44(t，J=7.6Hz，4H)，7.37(t，J=7.6Hz，2H)，7.30(t，J=7.2Hz，1H)，6.14(q，J=6.8Hz，1H)，1.68(d，J=6.8Hz，3H).1-Phenylethyl Benzoate, a colorless liquid. 1 H NMR (400MHz, CDCl 3 ) δ8.08(d, J=7.2Hz, 2H), 7.56(t, J=7.2Hz, 1H), 7.44(t, J=7.6Hz, 4H), 7.37(t , J=7.6Hz, 2H), 7.30(t, J=7.2Hz, 1H), 6.14(q, J=6.8Hz, 1H), 1.68(d, J=6.8Hz, 3H).

乙酸薄荷醇酯。1H NMR(400MHz，CDCl3)δ4.67(td，J=10.8，4.4Hz，1H)，2.04(s，3H)，2.02-1.95(M，1H)，1.92-1.81(m，1H)，1.73-1.62(m，2H)，1.54-1.42(m，1H)，1.40-1.32(m，1H)，1.12-1.03(m，1H)，1.01-0.94(m，1H)，0.92-0.87(m，6H)，0.76(d，J=7.2Hz，3H).Menthyl Acetate. 1 H NMR (400MHz, CDCl 3 ) δ4.67(td, J=10.8, 4.4Hz, 1H), 2.04(s, 3H), 2.02-1.95(M, 1H), 1.92-1.81(m, 1H), 1.73-1.62(m, 2H), 1.54-1.42(m, 1H), 1.40-1.32(m, 1H), 1.12-1.03(m, 1H), 1.01-0.94(m, 1H), 0.92-0.87(m , 6H), 0.76(d, J=7.2Hz, 3H).

苯甲酸薄荷醇酯，白色晶体，熔点49-50℃。1H NMR(400MHz，CDCl3)δ8.10-8.00(m，2H)，7.55(t，J=7.2Hz，1H)，7.44(t，J=7.6Hz，2H)，4.93(td，J=10.8，4.4Hz，1H)，2.17-2.10(m，1H)，2.02-1.92(m，1H)，1.77-1.69(m，2H)，1.62-1.52(m，2H)，1.19-1.05(m，2H)，0.96-0.90(m，6H)，0.79(d，J=6.8Hz，3H).Menthyl Benzoate, white crystal, melting point 49-50°C. 1 H NMR (400MHz, CDCl 3 ) δ8.10-8.00(m, 2H), 7.55(t, J=7.2Hz, 1H), 7.44(t, J=7.6Hz, 2H), 4.93(td, J= 10.8, 4.4Hz, 1H), 2.17-2.10(m, 1H), 2.02-1.92(m, 1H), 1.77-1.69(m, 2H), 1.62-1.52(m, 2H), 1.19-1.05(m, 2H), 0.96-0.90(m, 6H), 0.79(d, J=6.8Hz, 3H).

乙酸-1-氰基环己醇酯，无色液体。1H NMR(400MHz，CDCl3)δ2.33-2.25(m，2H)，2.11(s，3H)，1.88-1.79(m，2H)，1.77-1.71(m，2H)，1.69-1.61(m，3H)，1.41-1.29(m，1H).1-cyanocyclohexanol acetate, a colorless liquid. 1 H NMR (400MHz, CDCl 3 ) δ2.33-2.25(m, 2H), 2.11(s, 3H), 1.88-1.79(m, 2H), 1.77-1.71(m, 2H), 1.69-1.61(m , 3H), 1.41-1.29(m, 1H).

苯甲酸-1-氰基环己醇酯，白色晶体，熔点75-76℃。1H NMR(400MHz，CDCl3)δ8.06(d，J=7.6Hz，2H)，7.63(t，J=7.6Hz，1H)，7.49(t，J=7.6Hz，2H)，2.48-2.34(m，2H)，2.13-2.01(m，2H)，1.88-1.72(m，4H)，1.69-1.63(m，1H)，1.52-1.40(m，1H).Benzoic acid-1-cyanocyclohexanol ester, white crystal, melting point 75-76°C. 1 H NMR (400MHz, CDCl 3 ) δ8.06(d, J=7.6Hz, 2H), 7.63(t, J=7.6Hz, 1H), 7.49(t, J=7.6Hz, 2H), 2.48-2.34 (m, 2H), 2.13-2.01(m, 2H), 1.88-1.72(m, 4H), 1.69-1.63(m, 1H), 1.52-1.40(m, 1H).

乙酸-1-乙氧酰基环己醇酯，无色液体。1H NMR(400MHz，CDCl3)δ4.17(q，J=7.2Hz，2H)，2.13(d，J=12.8Hz，2H)，2.10(s，3H)，1.83-1.73(m，2H)，1.70-1.59(m，4H)，1.58-1.48(m，2H)，1.25(t，J=7.2Hz，3H).1-Ethoxyacyl cyclohexanol acetate, a colorless liquid. 1 H NMR (400MHz, CDCl 3 ) δ4.17(q, J=7.2Hz, 2H), 2.13(d, J=12.8Hz, 2H), 2.10(s, 3H), 1.83-1.73(m, 2H) , 1.70-1.59(m, 4H), 1.58-1.48(m, 2H), 1.25(t, J=7.2Hz, 3H).

苯甲酸-1-乙氧酰基环己醇酯，无色液体。1H NMR(400MHz，CDCl3)δ8.09(d，J=7.2Hz，2H)，7.60(t，J=7.2Hz，1H)，7.48(t，J=7.6Hz，2H)，4.23(q，J=7.2Hz，2H)，2.34(d，J=14.4Hz，2H)，1.95-1.86(m，2H)，1.77-1.60(m，5H)，1.43-1.32(m，1H)，1.25(t，J=7.2Hz，3H).13CNMR(100MHz，CDCl3)δ172.7，165.1，133.1，130.311，129.7，128.4，80.3，61.1，32.22，25.1，21.4，14.1.HRMS(ESI)rn／z Calcd.for C16H21O4(M+H)：277.1434.Found：277.1435.1-Ethoxyyl cyclohexanol benzoate, a colorless liquid. 1 H NMR (400MHz, CDCl 3 ) δ8.09(d, J=7.2Hz, 2H), 7.60(t, J=7.2Hz, 1H), 7.48(t, J=7.6Hz, 2H), 4.23(q , J=7.2Hz, 2H), 2.34(d, J=14.4Hz, 2H), 1.95-1.86(m, 2H), 1.77-1.60(m, 5H), 1.43-1.32(m, 1H), 1.25( t, J=7.2Hz, 3H). 13 CNMR (100MHz, CDCl 3 ) δ172.7, 165.1, 133.1, 130.311, 129.7, 128.4, 80.3, 61.1, 32.22, 25.1, 21.4, 14.1.HRMS(ESI)rn／ z Calcd. for C 16 H 21 O 4 (M+H): 277.1434. Found: 277.1435.

乙酸苯酚酯，无色液体。1H NMR(400MHz，CDCl3)δ7.38(t，J=8.0Hz，2H)，7.23(t，J=7.2Hz，1H)，7.08(d，J=7.6Hz，2H)，2.30(s，3H).Phenyl acetate, a colorless liquid. 1 H NMR (400MHz, CDCl 3 ) δ7.38(t, J=8.0Hz, 2H), 7.23(t, J=7.2Hz, 1H), 7.08(d, J=7.6Hz, 2H), 2.30(s , 3H).

苯甲酸苯酚酯，白色固体，熔点71-72℃.1H NMR(400MHz，CDCl3)δ8.21(dd，J=8.4，7.6Hz，2H)，7.63(dd，J=11.6，4.4Hz，1H)，7.51(t，J=7.6Hz，2H)，7.43(dd，J=8.0，7.6Hz，2H)，7.31-7.25(m，1H)，7.22(dd，J=8.4，1.0Hz，2H).Phenyl benzoate, white solid, melting point 71-72°C. 1 H NMR (400MHz, CDCl 3 ) δ8.21 (dd, J=8.4, 7.6Hz, 2H), 7.63 (dd, J=11.6, 4.4Hz, 1H), 7.51(t, J=7.6Hz, 2H), 7.43(dd, J=8.0, 7.6Hz, 2H), 7.31-7.25(m, 1H), 7.22(dd, J=8.4, 1.0Hz, 2H ).

乙酸2，4-二氯苯酚酯，无色液体。1H NMR(400MHz，CDCl3)δ7.03(s，1H)，7.02-6.97(m，1H)，6.87(d，J=8.0Hz，1H)，2.30(s，6H)，2.14(s，3H).2,4-dichlorophenol acetate, a colorless liquid. 1 H NMR (400MHz, CDCl 3 ) δ7.03(s, 1H), 7.02-6.97(m, 1H), 6.87(d, J=8.0Hz, 1H), 2.30(s, 6H), 2.14(s, 3H).

苯甲酸-2，4-二氯苯酚酯，无色液体。1H NMR(400MHz，CDCl3)δ8.22(d，J=8.0Hz，2H)，7.64(t，J=7.6Hz，1H)，7.52(t，J=7.6Hz，2H)，7.09(s，1H)，7.05(T，J=8.4Hz，1H)，7.01(d，J=8.0Hz，1H)，2.34(s，3H)，2.19(s，3H).2,4-dichlorophenol benzoate, a colorless liquid. 1 H NMR (400MHz, CDCl 3 ) δ8.22(d, J=8.0Hz, 2H), 7.64(t, J=7.6Hz, 1H), 7.52(t, J=7.6Hz, 2H), 7.09(s , 1H), 7.05(T, J=8.4Hz, 1H), 7.01(d, J=8.0Hz, 1H), 2.34(s, 3H), 2.19(s, 3H).

乙酸邻硝基酚酯，淡黄色液体。1H NMR(400MHz，CDCl3)δ8.10(dd，J=8.0，1.6Hz，1H)，7.66(td，J=8.0，1.6Hz，1H)，7.28(td，J=8.0，1.2Hz，1H)，7.25(dd，J=8.0，1.2Hz，1H)，2.38(s，3H).O-nitrophenol acetate, pale yellow liquid. 1 H NMR (400MHz, CDCl 3 ) δ8.10(dd, J=8.0, 1.6Hz, 1H), 7.66(td, J=8.0, 1.6Hz, 1H), 7.28(td, J=8.0, 1.2Hz, 1H), 7.25(dd, J=8.0, 1.2Hz, 1H), 2.38(s, 3H).

苯甲酸邻硝基酚酯，淡黄色液体。1H NMR(400MHz，CDCl3)δ8.25-8.18(m，2H)，8.16(dd，J=8.0，1.6Hz，1H)，7.75-7.66(m，2H)，7.54(t，J=7.6Hz，2H)，7.48-7.43(m，1H)，7.43-7.37(m，1H).o-nitrophenol benzoate, light yellow liquid. 1 H NMR (400MHz, CDCl 3 ) δ8.25-8.18(m, 2H), 8.16(dd, J=8.0, 1.6Hz, 1H), 7.75-7.66(m, 2H), 7.54(t, J=7.6 Hz, 2H), 7.48-7.43(m, 1H), 7.43-7.37(m, 1H).

2-氧杂-2H-色满-4-基乙酸酯，白色固体，熔点108-110℃。1H NMR(400MHz，CDCl3)δ7.66(dd，J=8.0，1.2Hz，1H)，7.61(td，J=8.0，1.6Hz，1H)，7.39(d，J=8.4Hz，1H)，7.34(td，J=7.6，0.8Hz，1H)，6.55(s，1H)，2.48(s，3H).HRMS(ESI)m／z Calcd.for C11H8NaO4(M+Na)：227.0315.Found：227.0317.2-Oxa-2H-chroman-4-yl acetate, white solid, melting point 108-110°C. 1 H NMR (400MHz, CDCl 3 ) δ7.66(dd, J=8.0, 1.2Hz, 1H), 7.61(td, J=8.0, 1.6Hz, 1H), 7.39(d, J=8.4Hz, 1H) , 7.34(td, J=7.6, 0.8Hz, 1H), 6.55(s, 1H), 2.48(s, 3H).HRMS(ESI)m/z Calcd.for C 11 H 8 NaO 4 (M+Na) :227.0315.Found: 227.0317.

2-氧杂-2H-色满-4-基苯甲酸酯，白色固体，熔点128-130℃.1H NMR(400MHz，CDCl3)δ8.30-8.25(m，2H)，7.80-7.72(m，2H)，7.67-7.58(m，3H)，7.46-7.41(m，1H)，7.37-7.32(m，1H)，6.66(s，1H).2-Oxa-2H-chroman-4-ylbenzoate, white solid, melting point 128-130°C. 1 H NMR (400MHz, CDCl 3 ) δ8.30-8.25 (m, 2H), 7.80-7.72 (m, 2H), 7.67-7.58(m, 3H), 7.46-7.41(m, 1H), 7.37-7.32(m, 1H), 6.66(s, 1H).

2-氧杂-1，2-二氢喹啉-4-基乙酸酯，白色固体，熔点>260℃。1H NMR(400MHz，DMSO)δ11.93(s，1H)，7.67(d，J=8.0Hz，1H)，7.59(t，J=7.6Hz，1H)，7.39(d，J=8.4Hz，1H)，7.23(t，J=7.6Hz，1H)，6.41(s，1H)，2.44(s，3H).HRMS(ESI)m／z Calcd.for C11H9NO3Na(M+Na)：226.0475，Found：226.0475.2-Oxa-1,2-dihydroquinolin-4-yl acetate, white solid, melting point >260°C. 1 H NMR (400MHz, DMSO) δ11.93(s, 1H), 7.67(d, J=8.0Hz, 1H), 7.59(t, J=7.6Hz, 1H), 7.39(d, J=8.4Hz, 1H), 7.23(t, J=7.6Hz, 1H), 6.41(s, 1H), 2.44(s, 3H). HRMS(ESI) m/z Calcd. for C11H 9 NO 3 Na(M+Na): 226.0475, Found: 226.0475.

2-氧杂-1，2-二氢喹啉-4-基苯甲酸酯，白色固体，熔点234-236℃。1H NMR(400MHz，DMSO)δ11.99(s，1H)，8.24(d，J=7.2Hz，2H)，7.83(t，J=7.6Hz，1H)，7.71-7.57(m，4H)，7.42(d，J=8.0Hz，1H)，7.23(t，J=7.2Hz，1H)，6.63(s，1H).2-Oxa-1,2-dihydroquinolin-4-ylbenzoate, white solid, melting point 234-236°C. 1 H NMR (400MHz, DMSO) δ11.99(s, 1H), 8.24(d, J=7.2Hz, 2H), 7.83(t, J=7.6Hz, 1H), 7.71-7.57(m, 4H), 7.42(d, J=8.0Hz, 1H), 7.23(t, J=7.2Hz, 1H), 6.63(s, 1H).

乙酰柠檬酸三乙酯，无色液体。1H NMR(400MHz，CDCl3)δ4.25(q，J=7.2Hz，2H)，4.17(q，J=7.2Hz，4H)，2.10(s，3H)，1.33-1.25(m，9H).13C NMR(100MHz，CDCl3)δ170.0，169.9.169.4，78.7，62.6，61.3，39.3，21.45，14.69.Acetyl triethyl citrate, a colorless liquid. 1 H NMR (400MHz, CDCl 3 ) δ4.25(q, J=7.2Hz, 2H), 4.17(q, J=7.2Hz, 4H), 2.10(s, 3H), 1.33-1.25(m, 9H) . 13 C NMR (100MHz, CDCl 3 ) δ170.0, 169.9.169.4, 78.7, 62.6, 61.3, 39.3, 21.45, 14.69.

苯甲酰柠檬酸三乙酯，无色液体。1H NMR(400MHz，CDCl3)δ8.07-7.99(m，2H)，7.61(t，J=7.6Hz，1H)，7.47(t，J=7.6Hz，2H)，4.30(q，J=7.2Hz，2H)，4.19-4.05(m，4H)，1.31(t，J=7.2Hz，3H)，1.21(t，J=7.2Hz，6H).13C NMR(100MHz，CDCl3)δ169.4，168.9，164.9，133.5，130.2，129.9，129.4，128.5，128.4，78.6，62.2，60.9，14.0，13.9.Benzoyl triethyl citrate, a colorless liquid. 1 H NMR (400MHz, CDCl 3 ) δ8.07-7.99(m, 2H), 7.61(t, J=7.6Hz, 1H), 7.47(t, J=7.6Hz, 2H), 4.30(q, J= 7.2Hz, 2H), 4.19-4.05(m, 4H), 1.31(t, J=7.2Hz, 3H), 1.21(t, J=7.2Hz, 6H). 13 C NMR (100MHz, CDCl 3 ) δ169. 4, 168.9, 164.9, 133.5, 130.2, 129.9, 129.4, 128.5, 128.4, 78.6, 62.2, 60.9, 14.0, 13.9.

乙酸金刚烷醇酯，无色液体。1H NMR(400MHz，CDCl3)δ2.16(s，3H)，2.11(s，3H)，2.10(s，3H)，1.97(s，3H)，1.66(s，6H).13C NMR(100MHz，CDCl3)δ169.1，79.2，40.3，35.2，29.8，21.6.Adamantyl acetate, a colorless liquid. 1 H NMR (400MHz, CDCl 3 ) δ2.16(s, 3H), 2.11(s, 3H), 2.10(s, 3H), 1.97(s, 3H), 1.66(s, 6H). 13 C NMR( 100MHz, CDCl 3 ) δ169.1, 79.2, 40.3, 35.2, 29.8, 21.6.

苯甲酸金刚烷醇酯，无色液体。1H NMR(400MHz，CDCl3)δ8.02-7.96(m，2H)，7.52(t，J=7.6Hz，1H)，7.41(t，J=7.6Hz，2H)，2.26(s，6H)，2.22(s，3H)，1.79-1.67(m，6H).Adamantyl Benzoate, Colorless Liquid. 1 H NMR (400MHz, CDCl 3 ) δ8.02-7.96(m, 2H), 7.52(t, J=7.6Hz, 1H), 7.41(t, J=7.6Hz, 2H), 2.26(s, 6H) , 2.22(s, 3H), 1.79-1.67(m, 6H).

特戊酸三氯苯酚酯，白色固体，熔点60-61℃。1H NMR(400MHz，CDCl3)δ7.36(s，2H)，1.41(s，9H).Trichlorophenol pivalate, white solid, melting point 60-61°C. 1 H NMR (400MHz, CDCl 3 ) δ7.36(s, 2H), 1.41(s, 9H).

特戊酸邻硝基酚酯，淡黄色液体。1H NMR(400MHz，CDCl3)δ8.08(dd，J=8.0，1.6Hz,1H)，7.64(td，J=8.0，1.6Hz，1H)，7.38(td，J=8.0，0.8Hz1H)，7.19(dd，J=8.1，0.8Hz，1H)，1.39(s，9H).o-nitrophenol pivalate, light yellow liquid. 1 H NMR (400MHz, CDCl 3 ) δ8.08 (dd, J=8.0, 1.6Hz, 1H), 7.64 (td, J=8.0, 1.6Hz, 1H), 7.38 (td, J=8.0, 0.8Hz1H) , 7.19(dd, J=8.1, 0.8Hz, 1H), 1.39(s, 9H).

特戊酸对硝基酚酯，白色晶体，熔点95-96℃。1H NMR(400MHz，CDCl3)δ8.27(d，J=9.2Hz，2H)，7.25(d，J=9.2Hz，2H)，1.38(s，9H).p-nitrophenol pivalate, white crystal, melting point 95-96°C. 1 H NMR (400MHz, CDCl 3 ) δ8.27(d, J=9.2Hz, 2H), 7.25(d, J=9.2Hz, 2H), 1.38(s, 9H).

2，6-二氟-N-特戊酰基苯甲酸酯，白色针状晶体，熔点159-160℃。1H NMR(400MHz，CDCl3)δ8.55(s，1H)，7.45-7.37(m，1H)，6.95(t，J=8.0Hz，2H)，1.27(s，9H).13C NMR(100MHz，CDCl3)δ176.3，162.3，160.7，158.2，132.0，111.8，40.1，26.8.HRMS(ESI)m／zCalcd.for C12H14F2NO2(M+H)：242.0987.Found：242.0987.2,6-Difluoro-N-pivaloyl benzoate, white needle crystal, melting point 159-160°C. 1 H NMR (400MHz, CDCl 3 ) δ8.55(s, 1H), 7.45-7.37(m, 1H), 6.95(t, J=8.0Hz, 2H), 1.27(s, 9H). 13 C NMR( 100MHz, CDCl 3 ) δ176.3, 162.3, 160.7, 158.2, 132.0, 111.8, 40.1, 26.8. HRMS (ESI) m/z Calcd. for C 12 H 14 F 2 NO 2 (M+H): 242.0987. Found: 242.0987.

2，6-二氟-M苯甲酰基苯甲酸酯，白色针状晶体，熔点137-139℃。1H NMR(400MHz，CDCl3)δ9.04(s，1H)，7.90-7.85(m，2H)，7.66-7.61(m，1H)，7.55-7.49(m，2H)，7.48-7.41(m，1H)，6.99(t，J=8.4Hz，2H).2,6-Difluoro-M benzoyl benzoate, white needle crystal, melting point 137-139°C. 1 H NMR (400MHz, CDCl 3 ) δ9.04(s, 1H), 7.90-7.85(m, 2H), 7.66-7.61(m, 1H), 7.55-7.49(m, 2H), 7.48-7.41(m , 1H), 6.99(t, J=8.4Hz, 2H).

特戊酸-1-氰基环己醇酯，无色液体。1HNMR(400MHz，CDCl3)δ2.29-2.17(m，2H)，2.04-1.89(m，2H)，1.79-1.66(m，4H)，1.64-1.53(m，1H)，1.49-1.37(m，1H)，1.26(s，9H).1-cyanocyclohexanol pivalate, a colorless liquid. 1 HNMR (400MHz, CDCl 3 ) δ2.29-2.17 (m, 2H), 2.04-1.89 (m, 2H), 1.79-1.66 (m, 4H), 1.64-1.53 (m, 1H), 1.49-1.37 ( m, 1H), 1.26(s, 9H).

特戊酸-1-乙氧酰基环己醇酯，无色液体。1H NMR(400MHz，CDCl3)δ4.15(q，J=7.2Hz，2H)，2.16(d，J=12.8Hz，2H)，1.80-1.70(m，2H)，1.70-1.61(m，3H)，1.57-1.44(m，2H)，1.34-1.25(m，1H)，1.24(s，9H)，1.23(t，J=7.2Hz，3H).13C NMR(100MHz，CDCl3)δ176.1，171.9，78.4，60.0，38.0，31.2，26.3，24.3，20.2，13.2.1-Ethoxyacylcyclohexyl pivalate, a colorless liquid. 1 H NMR (400MHz, CDCl 3 ) δ4.15(q, J=7.2Hz, 2H), 2.16(d, J=12.8Hz, 2H), 1.80-1.70(m, 2H), 1.70-1.61(m, 3H), 1.57-1.44(m, 2H), 1.34-1.25(m, 1H), 1.24(s, 9H), 1.23(t, J=7.2Hz, 3H). 13 C NMR(100MHz, CDCl 3 )δ176 .1, 171.9, 78.4, 60.0, 38.0, 31.2, 26.3, 24.3, 20.2, 13.2.

特戊酸金刚烷醇酯。1H NMR(400MHz，CDCl3)δ2.15(s，3H)，2.09(s，3H)，2.08(s，3H)，1.66(s，6H)，1.14(s，9H).13C NMR(100MHz，CDCl3)δ176.6，78.4，40.2，38.2，35.3，29.8，26.2，25.5.Adamantyl pivalate. 1 H NMR (400MHz, CDCl 3 ) δ2.15(s, 3H), 2.09(s, 3H), 2.08(s, 3H), 1.66(s, 6H), 1.14(s, 9H). 13 C NMR( 100MHz, CDCl 3 ) δ176.6, 78.4, 40.2, 38.2, 35.3, 29.8, 26.2, 25.5.

2-氧杂-2H-色满-4-基特戊酸酯，白色固体，115-116℃。1H NMR(400MHz，CDCl3)δ7.63-7.56(m，2H)，7.38(d，J=8.4Hz，1H)，7.35-7.28(m，1H)，6.48(s，1H)，1.45(s，9H).2-Oxa-2H-chroman-4-yl pivalate, white solid, 115-116°C. 1 H NMR (400MHz, CDCl 3 ) δ7.63-7.56(m, 2H), 7.38(d, J=8.4Hz, 1H), 7.35-7.28(m, 1H), 6.48(s, 1H), 1.45( s, 9H).

2-氧杂-1，2-二氢喹啉-4-基特戊酸酯，白色固体，熔点219-221℃。1H NMR(400MHz，CDCl3)δ12.65(s，1H)，7.55(d，J=8.0Hz，1H)，7.51-7.46(m，1H)，7.42(d，J=8.0Hz，1H)，7.19-7.14(m，1H)，6.55(s，1H)，1.39(s，9H).13C NMR(100MHz，CDCl3)δ175.0，165.4，157.4，138.8，131.5，122.8，122.1，116.7，115.9，111.1，39.8，27.2.HRMS(ESI)m／zCalcd.for C14H16NO3：246.1125.Found：246.1128.2-Oxa-1,2-dihydroquinolin-4-yl pivalate, white solid, melting point 219-221°C. 1 H NMR (400MHz, CDCl 3 ) δ12.65(s, 1H), 7.55(d, J=8.0Hz, 1H), 7.51-7.46(m, 1H), 7.42(d, J=8.0Hz, 1H) , 7.19-7.14 (m, 1H), 6.55 (s, 1H), 1.39 (s, 9H). 13 C NMR (100MHz, CDCl 3 ) δ175.0, 165.4, 157.4, 138.8, 131.5, 122.8, 122.1, 116.7 , 115.9, 111.1, 39.8, 27.2. HRMS (ESI) m/z Calcd. for C 14 H 16 NO 3 : 246.1125. Found: 246.1128.

特戊酸-2-羟基吡啶醇酯。1H NMR(400MHz，CDCl3)δ8.42(dd，J=4.8，1.6Hz，1H)，7.79(td，J=8.0，2.0Hz，1H)，7.22(dd，J=7.2，4.8Hz，1H)，7.04(d，J=8.0Hz，1H)，139(s，9H).2-Hydroxypyridinyl pivalate. 1 H NMR (400MHz, CDCl 3 ) δ8.42(dd, J=4.8, 1.6Hz, 1H), 7.79(td, J=8.0, 2.0Hz, 1H), 7.22(dd, J=7.2, 4.8Hz, 1H), 7.04(d, J=8.0Hz, 1H), 139(s, 9H).

苯甲酸-2-羟基吡啶醇酯。1H NMR(400MHz，CDCl3)δ8.48(dd，J=4.8，1.6Hz，1H)，8.26-8.21(m，2H)，7.86(td，J=7.8，2.0Hz，lH)，7.65(t，J=7.5Hz，1H)，7.51(d，J=7.6Hz，2H)，7.28(td，J=7.2，4.8Hz，1H)，7.23(d，J=8.1Hz，1H).2-Hydroxypyridinol Benzoate. 1 H NMR (400MHz, CDCl 3 ) δ8.48(dd, J=4.8, 1.6Hz, 1H), 8.26-8.21(m, 2H), 7.86(td, J=7.8, 2.0Hz, 1H), 7.65( t, J=7.5Hz, 1H), 7.51(d, J=7.6Hz, 2H), 7.28(td, J=7.2, 4.8Hz, 1H), 7.23(d, J=8.1Hz, 1H).

1-苯甲酰基-4，5-二氰基咪唑，白色固体，熔点89-91℃。1H NMR(400MHz，CDCl3)δ8.10(s，1H)，7.89-7.82(m，3H)，7.71-7.65(m，2H).13C NMR(100MHz，CDCl3)δ141.6，136.1，134.69，130.6，129.8，126.1，111.611，110.6，107.1.1-Benzoyl-4,5-dicyanoimidazole, white solid, melting point 89-91°C. 1 H NMR (400MHz, CDCl 3 ) δ8.10(s, 1H), 7.89-7.82 (m, 3H), 7.71-7.65 (m, 2H). 13 C NMR (100MHz, CDCl 3 ) δ141.6, 136.1 , 134.69, 130.6, 129.8, 126.1, 111.611, 110.6, 107.1.

异丁酸邻硝基酚酯，淡黄色液体。1H NMR(400MHz，CDCl3)δ8.09(d，J=8.0Hz，1H)，7.65(t，J=8.0Hz，1H)，7.40(t，J=8.0Hz，1H)，7.23(d，J=8.0Hz，1H)，2.96-2.83(m，1H)，1.36(d，J=7.2Hz，6H).O-nitrophenol isobutyrate, light yellow liquid. 1 H NMR (400MHz, CDCl 3 ) δ8.09(d, J=8.0Hz, 1H), 7.65(t, J=8.0Hz, 1H), 7.40(t, J=8.0Hz, 1H), 7.23(d , J=8.0Hz, 1H), 2.96-2.83(m, 1H), 1.36(d, J=7.2Hz, 6H).

2-硝基苯基二甲氨基甲酸酯。1H NMR(400MHz，CDCl3)δ8.06(dd，J=8.0，1.6Hz，1H)，7.63(td，J=8.0，1.6Hz，1H)，7.35(td，J=8.0，1.2Hz，1H)，7.31(dd，J=8.0，1.2Hz，1H)，3.15(s，3H)，3.04(s，3H).13C NMR(100MHz，CDCl3)δ152.4，144.0，141.1，133.5，124.9，124.5，35.9，35.6.HRMS(ESI)m／z Calcd.for C9H10N2O4Na(M+Na)：233.0533.Found：233.0529.2-Nitrophenyldimethylcarbamate. 1 H NMR (400MHz, CDCl 3 ) δ8.06(dd, J=8.0, 1.6Hz, 1H), 7.63(td, J=8.0, 1.6Hz, 1H), 7.35(td, J=8.0, 1.2Hz, 1H), 7.31(dd, J=8.0, 1.2Hz, 1H), 3.15(s, 3H), 3.04(s, 3H). 13 C NMR (100MHz, CDCl3) δ152.4, 144.0, 141.1, 133.5, 124.9 , 124.5, 35.9, 35.6. HRMS (ESI) m/z Calcd. for C 9 H 10 N 2 O 4 Na (M+Na): 233.0533. Found: 233.0529.

实施例4：催化剂的回收利用：Embodiment 4: the recycling of catalyst:

在25mL单口瓶中加入1.89g(10mmol)邻硝基苯酚、10mL甲苯、78.5mg(0.5mmol)DMAP盐酸盐和2.26g(11mmol)的苯甲酸酐。控制反应温度至60℃，TLC检测反应完成后，冷却反应体系至室温。向反应体系中加入10mL正己烷、静置5分钟、过滤，用10mL正己烷洗涤反应瓶，过滤。所回收的催化剂为白色固体，直接投入到原反应瓶进行下一次催化循环。合并的滤液用分别有10mL水、10mL饱和碳酸氢钠、15mL饱和食盐水洗涤，MgSO4干燥，减压脱溶、快速柱层析得产物，计算收率。经过9次循环后，将剩余的催化剂全部过滤回收、真空干燥、称重62.6mg，经计算单次回收率大于98％。Add 1.89g (10mmol) of o-nitrophenol, 10mL of toluene, 78.5mg (0.5mmol) of DMAP hydrochloride and 2.26g (11mmol) of benzoic anhydride into a 25mL single-necked bottle. The reaction temperature was controlled to 60° C., and after the completion of the reaction detected by TLC, the reaction system was cooled to room temperature. Add 10 mL of n-hexane to the reaction system, let it stand for 5 minutes, filter, wash the reaction flask with 10 mL of n-hexane, and filter. The recovered catalyst is a white solid, which is directly put into the original reaction bottle for the next catalytic cycle. The combined filtrates were washed with 10 mL of water, 10 mL of saturated sodium bicarbonate, and 15 mL of saturated brine, dried over MgSO 4 , precipitated under reduced pressure, and subjected to flash column chromatography to obtain the product, and the yield was calculated. After 9 cycles, all the remaining catalysts were recovered by filtration, vacuum-dried, and weighed 62.6 mg, and the single recovery rate was calculated to be greater than 98%.

催化剂的回收利用同样可适用于下列反应，见表3，但并不限定本发明。Catalyst recycling is also applicable to the following reactions, see Table 3, but does not limit the present invention.

表3 DMAP盐酸盐的回收Table 3 Recovery of DMAP hydrochloride

[a]反应操作同实施例4。[b]对于液体底物，反应可在无溶剂条件下进行(见实施例2)，催化剂的回收按实施例4操作。[c]分离收率。[d]经过所测试的循环次数后，回收的催化剂的质量。[a] The reaction operation is the same as in Example 4. [b] For the liquid substrate, the reaction can be carried out under solvent-free conditions (see Example 2), and the recovery of the catalyst is operated according to Example 4. [c] Isolated yield. [d] The mass of catalyst recovered after the number of cycles tested.

Claims (5)

1.对二甲氨基吡啶(DMAP)盐酸盐作为酰基化反应催化剂的应用：如下反应式中所限定的惰性醇、酚及胺在无溶剂或有机溶剂条件下，加入催化量的DMAP盐酸盐，在0-130℃下与酰基化试剂反应完全，加入非极性溶剂，过滤回收催化剂DMAP盐酸盐，滤液水洗、碱洗、分液、有机相干燥，蒸除溶剂得到酰基化产物，回收的DMAP盐酸盐进入下一个催化循环：1. The application of p-dimethylaminopyridine (DMAP) hydrochloride as an acylation catalyst: the inert alcohol, phenol and amine defined in the following reaction formula are added catalytic amount of DMAP hydrochloric acid under solvent-free or organic solvent conditions salt, react completely with the acylating reagent at 0-130°C, add a non-polar solvent, filter and recover the catalyst DMAP hydrochloride, wash the filtrate with water, wash with alkali, separate liquid, dry the organic phase, and evaporate the solvent to obtain the acylated product. The recovered DMAP hydrochloride enters the next catalytic cycle: 其中R-X代表2-6碳烷基酰氯、2-6碳烷基酸酐、1-6碳烷氨基甲酰氯、1-6碳烷氧基甲酰氯、取代或非取代的苯甲酰氯、取代或非取代的苯甲酸酐、1-6碳的磺酰氯、1-6碳的磺酸酐、取代或非取代的苯磺酰氯、取代或非取代的苯磺酸酐、3-18碳的磷酰氯，其中芳环上的取代基为一个或一个以上下述基团卤素、1-4碳烷基、1-4碳烷氧基、1-4碳卤代烷基、1-4碳卤代烷氧基、1-4碳烷氧烷基、1-4碳烷硫基、硝基、氰基、1-4碳烷基羰基；Where R-X represents 2-6 carbon alkyl acid chloride, 2-6 carbon alkyl acid anhydride, 1-6 carbon alkane carbamoyl chloride, 1-6 carbon alkoxy formyl chloride, substituted or unsubstituted benzoyl chloride, substituted or non Substituted benzoic anhydride, 1-6 carbon sulfonyl chloride, 1-6 carbon sulfonic anhydride, substituted or unsubstituted benzenesulfonyl chloride, substituted or unsubstituted benzenesulfonic anhydride, 3-18 carbon phosphorus oxychloride, wherein The substituents on the ring are one or more of the following groups halogen, 1-4 carbon alkyl, 1-4 carbon alkoxy, 1-4 carbon haloalkyl, 1-4 carbon haloalkoxy, 1-4 carbon Alkoxyalkyl, 1-4 carbon alkylthio, nitro, cyano, 1-4 carbon alkylcarbonyl; R代表2-6碳烷基酰基、1-6碳烷氨基甲酰基、1-6碳烷氧基甲酰基、取代或非取代的苯甲酰基、1-6碳的磺酰基、取代或非取代的苯磺酰基、3-18碳的磷酰基；R represents 2-6 carbon alkyl acyl, 1-6 carbon alkyl carbamoyl, 1-6 carbon alkoxy formyl, substituted or unsubstituted benzoyl, 1-6 carbon sulfonyl, substituted or unsubstituted benzenesulfonyl, 3-18 carbon phosphoryl; R1、R2代表1-6碳烷基、5-12碳的环烷基、烯丙基、炔丙基，烯基、苯基、吡啶基、萘基；R 1 and R 2 represent 1-6 carbon alkyl, 5-12 carbon cycloalkyl, allyl, propargyl, alkenyl, phenyl, pyridyl, naphthyl; R3代表1-6碳烷酰基、苯甲酰基。R 3 represents 1-6 carbon alkanoyl, benzoyl. 2.根据权利要求1所述的应用，其特征在于所用的惰性醇、酚及胺与酰基化试剂和DMAP盐酸盐的摩尔比为1∶1.1∶0.05。2. The application according to claim 1, characterized in that the molar ratio of the used inert alcohol, phenol and amine to the acylating agent and DMAP hydrochloride is 1: 1.1: 0.05. 3.根据权利要求1所述的应用，其特征在于反应在无溶剂条件下进行。3. The application according to claim 1, characterized in that the reaction is carried out under solvent-free conditions. 4.根据权利要求1所述的应用，其特征在于反应在有机溶剂甲苯、二甲苯、正己烷、环己烷、正戊烷、正庚烷、石油醚、四氢呋喃、1，4-二氧六环、二氯甲烷、1，2-二氯乙烷或氯仿中进行。4. application according to claim 1, is characterized in that reacting in organic solvent toluene, xylene, normal hexane, cyclohexane, normal pentane, normal heptane, sherwood oil, THF, 1,4-dioxane ring, dichloromethane, 1,2-dichloroethane or chloroform. 5.根据权利要求1所述的应用，其特征在于反应时间为0.1-24小时。5. The application according to claim 1, characterized in that the reaction time is 0.1-24 hours.
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