WO2021138908A1 - γ-戊内酯的制备方法 - Google Patents

γ-戊内酯的制备方法 Download PDF

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WO2021138908A1
WO2021138908A1 PCT/CN2020/071485 CN2020071485W WO2021138908A1 WO 2021138908 A1 WO2021138908 A1 WO 2021138908A1 CN 2020071485 W CN2020071485 W CN 2020071485W WO 2021138908 A1 WO2021138908 A1 WO 2021138908A1
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nickel
valerolactone
reaction
levulinic acid
compound
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PCT/CN2020/071485
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French (fr)
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傅尧
邓晋
扎达巴哈特
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中国科学技术大学
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/32—Oxygen atoms
    • C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form

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  • the invention relates to a preparation method of chemicals, in particular to a preparation method of ⁇ -valerolactone.
  • Gamma-valerolactone is a biomass platform molecule with high potential application value. It can be used as a new fuel and as a source of organic carbon for the synthesis of high value-added chemicals.
  • the preparation of ⁇ -valerolactone mainly takes the biomass platform molecule levulinic acid as the raw material, and is obtained through the hydrogenation reduction and lactonization of a heterogeneous catalyst or a homogeneous catalyst.
  • homogeneous catalysts compared to heterogeneous catalysts, homogeneous catalysts have high catalytic efficiency and are easy to scale up industrially because they are not restricted by mass transfer.
  • the preparation of ⁇ -valerolactone by the existing process has high catalyst cost, additional equivalent additives, harsh reaction conditions, high production cost, difficulty in large-scale production, and environmental pollution and other problems.
  • the purpose of the present invention is to provide a new method for preparing ⁇ -valerolactone, which can overcome some or all of the defects of the prior art.
  • the present invention relates to a method for preparing ⁇ -valerolactone, which is characterized in that it comprises the following steps: after mixing levulinic acid, a nickel-containing compound and an organic phosphine compound, a reduction reaction is performed in the presence of a reducing agent to obtain ⁇ -valerolactone .
  • nickel-containing compounds include +2 nickel salts and hydrates thereof, such as nickel sulfate, nickel acetate, nickel formate, nickel levulinate, nickel carbonate, nickel halides (such as nickel chloride, nickel bromide, and nickel).
  • Nickel iodide nickel trifluoromethanesulfonate, nickel perchlorate, nickel acetylacetonate, nickel tetrafluoroborate and its hydrate
  • nickel oxide and hydroxide that can form nickel levulinate in situ with the raw material levulinic acid Nickel, metallic nickel.
  • the organophosphine compound refers to an organophosphine compound having the following general formula:
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently selected from an alkyl group, a cycloalkyl group, and an aryl group.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each optionally substituted with alkyl or alkoxy.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are selected from alkyl, R 1 and R 2 , R 3 and R 4 and/or R 5 and R 6 , Together with the P atom to which they are attached, a 5- or 6-membered ring is formed; optionally, the 5- or 6-membered ring is substituted by an alkyl or alkoxy group.
  • the aryl group is phenyl
  • alkyl groups include, but are not limited to, C 1-6 alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-pentyl, n-hexyl, and the like.
  • cycloalkyl includes, but is not limited to, C 3-6 cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl.
  • alkoxy includes, but is not limited to, C 1-6 alkoxy, such as methoxy, ethoxy, isopropoxy and the like.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently selected from cyclohexyl, phenyl, or R 1 and R 2 , R 3 and R 4 and/or R 5 Together with R 6 together with the P atom to which they are attached, a 5- or 6-membered ring is formed; the cyclohexyl, phenyl or 5- or 6-membered ring is optionally substituted with alkyl or alkoxy.
  • the organophosphine compound is selected from:
  • the reducing agent is hydrogen or formic acid.
  • the hydrogen pressure during the reduction reaction is 1-100 atmospheres, preferably 1-50 atmospheres.
  • the molar ratio of formic acid to levulinic acid is 1:1-10:1, preferably 2:1-5:1.
  • the reaction temperature is 90-200°C, preferably 130-170°C.
  • the molar ratio of levulinic acid and the nickel-containing compound is 10:1 to 100000:1, preferably 20:1 to 50000:1, preferably 50:1 to 20000:1, preferably 100:1 to 10000: 1.
  • the molar ratio of levulinic acid and organophosphine compound is 10:1 to 100000:1, preferably 20:1 to 50000:1, preferably 50:1 to 20000:1, preferably 100:1 to 10000: 1.
  • the method of the present invention further includes the step of subjecting the hydrolysate after acid hydrolysis of biomass-based carbohydrates to vacuum distillation to obtain levulinic acid.
  • biomass-based carbohydrates include glucose, fructose, sucrose, starch, and cellulose.
  • the method of the present invention further includes the following steps: after the reaction is completed, the reaction solution is subjected to vacuum distillation, and the by-product water is separated to obtain the target compound ⁇ -valerolactone; and the distillation residue (with The unreacted levulinic acid (mainly) is fed with hydrogen again or formic acid is added to carry out the reaction, and it is converted into ⁇ -valerolactone.
  • the method of the present invention is characterized in that the reduction reaction is performed in the absence of a solvent.
  • the method of the present invention is characterized in that the reduction reaction is performed in the presence of a solvent.
  • the solvent includes but is not limited to: water, lower alcohols (C 1-6 alcohols, such as methanol, ethanol, isopropanol), cyclic ethers (such as tetrahydrofuran, dioxane).
  • the invention has the following advantages: low catalyst cost, no reaction solvent, high unit productivity, high product yield, high catalytic efficiency of the catalyst and easy separation from the product by distillation, simple process, mild reaction conditions, environmental friendliness, and easy industrial scale-up. It has strong industrial application significance.
  • Figure 1 is a gas chromatographic analysis spectrum in Example 1.
  • Figure 2 The hydrogen NMR spectrum of the main fraction ⁇ -valerolactone.
  • Chromatographic column DB-FFAP capillary chromatographic column, column temperature: 120°C for 1 min, 15°C/min to 225°C and hold for 3 minutes, gasification chamber temperature 250°C, FID detector temperature: 280°C.
  • Example 25 The operation process is similar to Example 25, showing the reaction effects of different nickel salts, different phosphine ligands, different reaction times, different reaction temperatures, and different reaction hydrogen pressures, as shown in Table 4:
  • This example shows an example of the use of solvents in the present invention.
  • This example shows an example of using formic acid as a reducing agent in the present invention.
  • the weighed levulinic acid (5.8kg, 50mol), 1,3-bis(diphenylphosphino)propane ( 20 g, 0.05 mol) and nickel acetate tetrahydrate (12.5 g, 0.05 mol) were sequentially placed in a 10L stainless steel autoclave. Seal the autoclave, turn on the mechanical stirring, and control the speed to 550 rpm. After replacing the air in the autoclave with nitrogen 5 times, it was charged with 15 atm of hydrogen. Turn on the heating, increase the temperature from room temperature to 150°C within 1h, and keep the temperature at 150°C for about 18h. During the reaction process, the pressure of the reaction system is adjusted to maintain the range of 13-16 atm through the inlet valve.
  • the present invention realizes a method for preparing ⁇ -valerolactone.
  • the invention has the following advantages: low catalyst cost, no reaction solvent, high unit productivity, high product yield, high catalytic efficiency of the catalyst and easy separation from the product by distillation, simple process, mild reaction conditions, environmental friendliness, and easy industrial scale-up. It has strong industrial application significance.

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  • Organic Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

本发明涉及一种γ-戊内酯的制备方法，所述方法包括将乙酰丙酸、含镍化合物和有机膦化合物混合后进行还原反应得到γ-戊内酯。本发明的方法催化剂成本低廉，无需反应溶剂，单位产能高，产物收率高，催化剂催化效率高且易通过蒸馏与产物进行分离，工艺简单，反应条件温和，环境友好，易于工业放大，具有很强的工业应用意义。

Description

γ-戊内酯的制备方法 技术领域
本发明涉及化学品的制备方法，尤其涉及一种γ-戊内酯的制备方法。
背景技术
γ-戊内酯是一种潜在应用价值很高的生物质平台分子，既可以作为新型燃料使用，又可以作为有机碳的来源用于合成高附加值的化学品。目前，γ-戊内酯的制备主要以生物质平台分子乙酰丙酸为原料，通过非均相催化剂或均相催化剂加氢还原和内酯化获得。一般而言，相对于非均相催化剂，均相催化剂催化效率高，且由于不受传质限制而易于工业放大。因此，已发展了很多均相催化乙酰丙酸或乙酰丙酸酯还原为γ-戊内酯的方法(ChemSusChem 2016,9,2037–2047)。但这些催化剂基本是以贵金属Ru、Ir、Pd为主，高昂的价格限制了其使用。
文献(Synlett 2014,25,2748–2752)报道了使用有机膦络合铁盐催化制备γ-戊内酯，但原料必须使用乙酰丙酸酯，且需要使用甲酸作为还原剂。
文献(Chin.J.Chem.2015,33,405–408)报道了使用铁络合物催化制备γ-戊内酯，但原料也同样必须使用乙酰丙酸酯，且需要使用异丙醇作为还原剂，并且催化剂制备困难。
文献(Chem.Commun.,2015,51,14199–14202)报道了使用羰基铁络合物催化乙酰丙酸还原制备γ-戊内酯，但需要使用甲酸作为还原剂，且需要加入当量的咪唑碱活化催化剂。
文献(ChemSusChem 2018,11,1474–1478)报道了使用有机铁络合物催化乙酰丙酸还原制备γ-戊内酯，但同样需要加入当量的叔丁醇钾活化催化剂，并且催化剂制备困难。
因此，总体来说，以现有工艺制备γ-戊内酯存在着催化剂成本高，需要额外添加当量助剂，反应条件苛刻，生产成本高，难以规模化生产，同时还存在环境污染等问题。
发明内容
鉴于此，本发明的目的在于提供一种新的制备γ-戊内酯的方法，其可以克 服现有技术的部分或全部缺陷。
本发明涉及一种γ-戊内酯的制备方法，其特征在于，包括以下步骤：将乙酰丙酸、含镍化合物和有机膦化合物混合后在还原剂存在下进行还原反应得到γ-戊内酯。
在一些实施方案中，含镍化合物包括+2价镍盐及其水合物，例如硫酸镍、乙酸镍、甲酸镍、乙酰丙酸镍、碳酸镍、卤化镍(例如氯化镍、溴化镍和碘化镍)、三氟甲磺酸镍、高氯酸镍、乙酰丙酮镍、四氟硼酸镍及其水合物；以及能够与原料乙酰丙酸原位生成乙酰丙酸镍的氧化镍、氢氧化镍、金属镍。
在一些实施方案中，有机膦化合物是指具有如下通式的有机膦化合物：
Figure PCTCN2020071485-appb-000001
其中n＝1-6，例如n＝1、2、3、4、5或6，优选n＝2或3，
并且R 1、R 2、R 3、R 4、R 5和R 6各自独立地选自烷基、环烷基和芳基。
在一些实施方案中，R 1、R 2、R 3、R 4、R 5和R 6各自任选地被烷基或烷氧基取代。
在一些实施方案中，当R 1、R 2、R 3、R 4、R 5和R 6选自烷基时，R 1与R 2、R 3与R 4和/或R 5与R 6，连同它们所连接的P原子一起，形成5或6元环；任选地，该5或6元环被烷基或烷氧基取代。
在一些实施方案中，所述芳基是苯基。
如本文中使用的，烷基包括但不限于C 1-6烷基，如甲基、乙基、正丙基、异丙基、叔丁基、正戊基、正己基等。
如本文中使用的，环烷基包括但不限于C 3-6环烷基，如环丙基、环丁基、环戊基、环己基。
如本文中使用的，烷氧基包括但不限于C 1-6烷氧基、如甲氧基、乙氧基、异丙氧基等。
在一些实施方案中，R 1、R 2、R 3、R 4、R 5和R 6各自独立地选自环己基、苯基或者R 1与R 2、R 3与R 4和/或R 5与R 6连同它们所连接的P原子一起形成5或6元环；所述环己基、苯基或者5或6元环任选地被烷基或烷氧基取代。
在一些实施方案中，所述有机膦化合物选自：
Figure PCTCN2020071485-appb-000002
在一些实施方案中，还原剂是氢气或甲酸。
在一些实施方案中，还原反应时氢气压力为1-100个大气压，优选1-50个大气压。
在一些实施方案中，甲酸与乙酰丙酸的摩尔比为1:1-10:1，优选2:1-5:1。
在一些实施方案中，反应温度为90-200℃，优选130-170℃。
在一些实施方案中，乙酰丙酸和含镍化合物的摩尔比为10:1-100000:1，优选20:1-50000:1，优选50:1-20000:1，优选100:1-10000:1。
在一些实施方案中，乙酰丙酸和有机膦化合物的摩尔比为10:1-100000:1，优选20:1-50000:1，优选50:1-20000:1，优选100:1-10000:1。
在一些实施方案中，本发明的方法还包括以下步骤：将生物质基碳水化合物进行酸水解后的水解产物通过减压蒸馏以获得乙酰丙酸。在一些实施方案中，所述生物质基碳水化合物包括葡萄糖、果糖、蔗糖、淀粉和纤维素。
在一些实施方案中，本发明的方法还包括以下步骤：反应完毕后，将反应液进行减压蒸馏，分离出副产物水后，得到目标化合物γ-戊内酯；以及将蒸馏残余物(以未反应完毕的乙酰丙酸为主)再次通入氢气或加入甲酸进行所述反应，转变为γ-戊内酯。
在一些实施方案中，本发明的方法的特征在于：在无溶剂的情况下进行还原反应。
在一些实施方案中，本发明的方法的特征在于：在溶剂的存在下进行还原反应。所述溶剂包括但不限于：水、低级醇类(C 1-6醇，如甲醇、乙醇、异丙醇)、环醚(如四氢呋喃、二氧六环)。
本发明具有以下优点：催化剂成本低廉，无需反应溶剂，单位产能高，产物收率高，催化剂催化效率高且易通过蒸馏与产物进行分离，工艺简单，反应条 件温和，环境友好，易于工业放大，具有很强的工业应用意义。
附图说明
图1为实施例1中气相色谱分析谱图。
图2为主馏分γ-戊内酯的核磁氢谱图。
具体实施方式
为了便于理解本发明，本发明列举实施例如下。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。
实施例1：
10ml Schlenk反应管中加入乙酰丙酸(580mg，5mmol)，四水合乙酸镍(12.4mg，0.05mmol)和triphos
Figure PCTCN2020071485-appb-000003
(31.2mg，0.05mmol)。Schlenk反应管上接氢气球，在常压(1atm)氢气氛围中于150℃搅拌反应20h。反应完毕后冷却，反应液中加入内标N-甲基吡咯烷酮，用N,N-二甲基乙酰胺稀释后，进行气相色谱分析，γ-戊内酯收率为98％。
气相色谱检测条件：
色谱柱：DB-FFAP毛细管色谱柱，柱温：120℃保持1min，15℃/min升温至225℃并保持3min，气化室温度250℃，FID检测器温度：280℃。
气相分析谱图如图1所示。
实施例2-11：
操作过程与实施例1类似，不同之处在于将四水合乙酸镍替换成不同的镍盐，反应效果如下表1所示：
表1
Figure PCTCN2020071485-appb-000004
Figure PCTCN2020071485-appb-000005
实施例12-19：
操作过程与实施例1类似，不同之处在于将triphos
Figure PCTCN2020071485-appb-000006
替换成不同的有机膦配体，反应效果如下表2所示：
表2
Figure PCTCN2020071485-appb-000007
实施例20-24：
100ml高压釜内加入9.0g生物质基碳水化合物，50ml稀盐酸(0.8mol/L)，在 氮气氛围中于200℃搅拌反应1h。反应完毕后冷却，水解液用NaOH调节pH值至2左右，过滤。滤液浓缩后减压蒸馏蒸出乙酰丙酸。在获得的乙酰丙酸中加入1mol％四水合乙酸镍和1mol％triphos
Figure PCTCN2020071485-appb-000008
在常压(1atm)氢气氛围中于150℃搅拌反应20h。反应完毕后冷却，反应液中加入内标N-甲基吡咯烷酮，用N,N-二甲基乙酰胺稀释后，进行气相色谱分析，反应效果如下表3所示：
表3
Figure PCTCN2020071485-appb-000009
实施例25：
50ml不锈钢高压釜中加入乙酰丙酸(5.80g，50mmol)，四水合乙酸镍(12.4mg，0.05mmol)和triphos
Figure PCTCN2020071485-appb-000010
(31.2mg，0.05mmol)。置换空气后，充入氢气至10atm后，于150℃搅拌反应20h。反应完毕后冷却，释放剩余氢气，反应液中加入内标N-甲基吡咯烷酮，用N,N-二甲基乙酰胺稀释后，进行气相色谱分析，γ-戊内酯收率为97％。
实施例26-30：
操作过程与实施例25类似，展示不同镍盐、不同膦配体、不同反应时间、不同反应温度以及不同反应氢压的反应效果，如表4所示：
Figure PCTCN2020071485-appb-000011
Figure PCTCN2020071485-appb-000012
实施例31：
本实施例展现了本发明使用溶剂的实例。
50ml不锈钢高压釜中加入乙酰丙酸(0.58g，5mmol)，四水合乙酸镍(1.24mg，0.005mmol)，triphos
Figure PCTCN2020071485-appb-000013
(3.12mg，0.005mmol)和5ml水作为溶剂。置换空气后，充入氢气至10atm后，于150℃搅拌反应20h。反应完毕后冷却，释放剩余氢气，反应液中加入内标N-甲基吡咯烷酮，用N,N-二甲基乙酰胺稀释后，进行气相色谱分析，γ-戊内酯收率为98％。
实施例32：
本实施例展现了本发明使用甲酸作为还原剂的实例。
10ml Schlenk反应管中加入乙酰丙酸(580mg，5mmol)，四水合乙酸镍(12.4mg，0.05mmol)，triphos(31.2mg，0.05mmol)和甲酸(460mg，10mmol)。于150℃搅拌反应20h。反应完毕后冷却，反应液中加入内标N-甲基吡咯烷酮，用N,N-二甲基乙酰胺稀释后，进行气相色谱分析，γ-戊内酯收率为94％。
实施例33：
将已称量的乙酰丙酸(5.8kg，50mol)，1,3-双(二苯基膦基)丙烷(
Figure PCTCN2020071485-appb-000014
20g，0.05mol)和四水合乙酸镍(12.5g，0.05mol)依次放入10L不锈钢高压釜中。密封高压釜，打开机械搅拌，并将速度控制到550rpm。用氮置换高压釜中的空 气5次后，充入15atm的氢。开启加热，于1h内由室温升温至150℃，并保持150℃约18h。在反应过程中，通过进气阀调节反应系统的压力维持在13-16atm的范围内。反应进行约18小时后，氢的消耗速率显着降低。通过取样阀取出少量反应溶液用N,N-二甲基乙酰胺稀释后，进行GC分析。气相色谱分析表明，原料的转化率为约95％。停止加热，通入内冷却水以冷却反应系统。当反应体系达到室温时，小心释放釜中的残留氢。通过高压釜的底阀取出5935g反应溶液。反应溶液用水泵进行减压蒸馏，并将真空度控制在15±5mmHg的范围内。在不同温度下收集馏分，馏分组成如下表5所示：
表5
Figure PCTCN2020071485-appb-000015
蒸馏损失：5847.5g-5935g＝87.5g
乙酰丙酸转化率：(1-272.5g/5800g)×100％＝95.3％
γ-戊内酯收率：4714g/5000g＝94.3％
分离γ-戊内酯收率：4058g/5000g＝81.2％(纯度>98％)
主馏分的核磁氢谱图如图2所示。
取50g蒸馏残余物，投入500ml不锈钢高压釜中，置换空气后，充入氢气至10atm后，于150℃搅拌反应20h。反应完毕后冷却，释放剩余氢气，进行气相色谱分析，剩余的乙酰丙酸基本完全转化，γ-戊内酯收率98％。
通过以上实施例可以看出，本发明实现了一种γ-戊内酯的制备方法。本发明具有以下优点：催化剂成本低廉，无需反应溶剂，单位产能高，产物收率高，催化剂催化效率高且易通过蒸馏与产物进行分离，工艺简单，反应条件温和，环境友好，易于工业放大，具有很强的工业应用意义。
以上显示和描述了本发明的基本原理、主要特征和优点。本行业的技术人员应该了解，上述实施例不以任何形式限制发明，凡采用等同替换或等效变换的方式所获得的技术方案，均落在本发明的保护范围内。

Claims (10)

  1. 一种γ-戊内酯的制备方法，其特征在于，包括以下步骤：将乙酰丙酸、含镍化合物和有机膦化合物混合后，在还原剂存在下进行还原反应得到γ-戊内酯。
  2. 根据权利要求1所述的方法，其中所述含镍化合物选自+2价镍盐及其水合物，例如硫酸镍、乙酸镍、甲酸镍、乙酰丙酸镍、碳酸镍、卤化镍、三氟甲磺酸镍、高氯酸镍、乙酰丙酮镍、四氟硼酸镍及其水合物；以及与原料乙酰丙酸原位生成乙酰丙酸镍的氧化镍、氢氧化镍、金属镍。
  3. 根据权利要求1所述的方法，其中所述有机膦化合物是具有如下通式的有机膦化合物：
    Figure PCTCN2020071485-appb-100001
    其中n＝1、2、3、4、5或6，
    并且R 1、R 2、R 3、R 4、R 5和R 6各自独立地选自烷基、环烷基和芳基；优选地，R 1、R 2、R 3、R 4、R 5和R 6各自任选地被烷基或烷氧基取代。
  4. 根据权利要求3所述的方法，其中当R 1、R 2、R 3、R 4、R 5和R 6选自烷基时，R 1与R 2、R 3与R 4和/或R 5与R 6，连同它们所连接的P原子一起，形成5或6元环；任选地，该5或6元环被烷基或烷氧基取代。
  5. 根据权利要求3所述的方法，其中所述芳基是苯基。
  6. 根据权利要求3所述的方法，其中R 1、R 2、R 3、R 4、R 5和R 6各自独立地选自环己基、苯基或者R 1与R 2、R 3与R 4和/或R 5与R 6连同它们所连接的P原子一起形成5或6元环；所述环己基、苯基或者5或6元环任选地被烷基或烷氧基取代；
    优选地，所述有机膦化合物选自：
    Figure PCTCN2020071485-appb-100002
    Figure PCTCN2020071485-appb-100003
  7. 根据权利要求1所述的方法，所述还原剂为氢气或甲酸；
    优选地，所述还原反应时氢气压力为1-100个大气压，优选1-50个大气压；
    优选地，甲酸与乙酰丙酸的摩尔比为1:1-10:1；
    优选地，反应温度为90-200℃，优选为130-170℃。
  8. 根据权利要求1所述的方法，所述乙酰丙酸和所述含镍化合物的摩尔比为10:1-100000:1；和/或所述乙酰丙酸和所述有机膦化合物的摩尔比为10:1-100000:1。
  9. 根据权利要求1所述的方法，所述方法还包括以下步骤：
    将生物质基碳水化合物进行酸水解后的水解产物通过减压蒸馏以获得所述乙酰丙酸；
    优选地，所述生物质基碳水化合物包括葡萄糖、果糖、蔗糖、淀粉和纤维素；
    优选地，所述方法还包括以下步骤：
    反应完毕后，将反应液进行减压蒸馏，分离出副产物水后，得到目标化合物γ-戊内酯；以及
    将蒸馏残余物再次通入氢气或加入甲酸进行所述还原反应，使未反应完毕的乙酰丙酸转变为γ-戊内酯。
  10. 根据权利要求1所述的方法，所述方法的特征在于：在无溶剂的情况下进行所述还原反应；或者
    所述方法的特征在于：在溶剂的存在下进行所述还原反应；优选地，所述溶剂选自：水、低级醇类(甲醇、乙醇、异丙醇)、环醚(四氢呋喃、二氧六环)。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114057673A (zh) * 2021-12-13 2022-02-18 中国科学技术大学 一种γ-或δ-取代的烷基手性内酯的合成方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2368366A (en) * 1942-08-21 1945-01-30 Monsanto Chemicals Process for the production of lactones
US20030105341A1 (en) * 2001-07-19 2003-06-05 Tsukasa Sotoguchi Process for producing optically active gamma-butyrolactone
CN101376650A (zh) * 2008-09-08 2009-03-04 中国科学技术大学 一种以乙酰丙酸和甲酸直接制备γ-戊内酯的方法
CN111087369A (zh) * 2020-01-10 2020-05-01 中国科学技术大学 γ-戊内酯的制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2368366A (en) * 1942-08-21 1945-01-30 Monsanto Chemicals Process for the production of lactones
US20030105341A1 (en) * 2001-07-19 2003-06-05 Tsukasa Sotoguchi Process for producing optically active gamma-butyrolactone
CN101376650A (zh) * 2008-09-08 2009-03-04 中国科学技术大学 一种以乙酰丙酸和甲酸直接制备γ-戊内酯的方法
CN111087369A (zh) * 2020-01-10 2020-05-01 中国科学技术大学 γ-戊内酯的制备方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HENGST KONSTANTIN, SCHUBERT MARTIN, CARVALHO HUDSON W.P., LU CHANGBO, KLEIST WOLFGANG, GRUNWALDT JAN-DIERK: "Synthesis of γ-valerolactone by Hydrogenation of Levulinic Acid over Supported Nickel Catalysts.", APPLIED CATALYSIS A: GENERAL, vol. 502, 1 August 2015 (2015-08-01), pages 18 - 26, XP055827875, ISSN: 0926-860X, DOI: 10.1016/j.apcata.2015.05.007 *
ROBERT V. CHRISTIAN JR., HORACE D. BROWN, R. M. HIXON: "Derivatives of γ-Valerolactone 1, 4-Pentanediol and 1, 4-Bis(2-cyanoethoxy)pentane", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 69, no. 8, 1 August 1947 (1947-08-01), pages 1961 - 1963, XP055827878, ISSN: 0002-7863, DOI: 10.1021/ja01200a036 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114057673A (zh) * 2021-12-13 2022-02-18 中国科学技术大学 一种γ-或δ-取代的烷基手性内酯的合成方法

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