CN112898244B - Method for synthesizing gamma-valerolactone - Google Patents
Method for synthesizing gamma-valerolactone Download PDFInfo
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- CN112898244B CN112898244B CN201911217788.0A CN201911217788A CN112898244B CN 112898244 B CN112898244 B CN 112898244B CN 201911217788 A CN201911217788 A CN 201911217788A CN 112898244 B CN112898244 B CN 112898244B
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- reaction
- valerolactone
- complex catalyst
- iridium complex
- methyl levulinate
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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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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Abstract
The invention discloses a method for synthesizing gamma-valerolactone. The method comprises the following steps: adding methyl levulinate and CH into a reaction vessel 3 And heating the OH and iridium complex catalyst for reaction for several hours, cooling to room temperature, spin-drying the solvent, and separating by a column to obtain the target compound. According to the invention, methyl levulinate and methanol are reacted under the catalytic action of the iridium metal catalyst to synthesize a target product in one step, the raw material used for the reaction is a commercialized reagent, the water generated by the reaction is a byproduct, and no environmental pollution is caused.
Description
Technical Field
The invention belongs to the technical field of organic chemistry, and particularly relates to a method for synthesizing gamma-valerolactone.
Background
Chemical name of gamma-Valerolactone (gamma-Valerolactone): 4-methylbutyrolactone, an intermediate useful as a resin solvent and various related compounds. Gamma valerolactone has vanillin and coconut aroma; the method is mainly used for preparing essences of peach type, coconut type, vanilla type and the like. It is also commonly used as a lubricant, plasticizer, gelling agent for nonionic surfactants, lactone-type additive for leaded gasoline, for dyeing of cellulose esters and synthetic fibers. Although the synthesis method of gamma-valerolactone has been developed, in the original report, the synthesis method uses toxic chemical reagents, multiple organic reactions and organic solvents, has low atom economy and pollutes the environment.
Disclosure of Invention
The invention aims to provide a method for synthesizing gamma-Valerolactone.
The invention is realized by the following technical scheme: a process for the synthesis of gamma valerolactone) (formula I) comprising
By methyl levulinate (formula II)
With CH under the action of iridium complex catalyst 3 A step of generating a target product by the reaction of OH (formula III),
CH 3 OH
III
the reaction formula is
The method is realized by the following steps:
in a reaction vessel, methyl levulinate (formula II), CH are added 3 And heating OH (formula III) and an iridium complex catalyst for reaction for several hours, cooling to room temperature, spin-drying the solvent, and separating by a column to obtain the target compound.
Further, the iridium complex catalyst used in the present invention is water-soluble metal-ligand bifunctional iridium, preferably [ Cp Ir (2,2' -bpyO) (H) 2 O)][Na + ]The structure is as follows:
further, the iridium complex catalyst was used in an amount of 1mol% relative to methyl levulinate.
Further, methyl levulinate is reacted with CH 3 The OH ratio was 0.13:2 (g/mL).
Further, the reaction temperature is 130 +/-10 ℃, and the reaction time is not less than 10h.
Further, the reaction was carried out under nitrogen protection.
Compared with the prior art, the method has the advantages that the gamma-valerolactone is directly synthesized by the reaction of methyl levulinate (formula II) and methanol (formula III) under the catalytic action of the iridium catalyst. The reaction exhibits three significant advantages over existing methods: 1) Methanol is used as a raw material and a solvent simultaneously in the reaction of the invention, and compared with the prior synthesis method which adopts organic matters as the solvent, the method is more environment-friendly; 2) The raw materials used in the reaction are commercial reagents, and the alcohol is an environment-friendly and low-toxicity chemical reagent; 3) The water produced by the reaction is a byproduct, and the environment is not polluted. Therefore, the reaction meets the requirement of green chemistry and has wide development prospect.
Detailed Description
The following examples are shown to illustrate certain embodiments of the present invention and should not be construed as limiting the scope of the invention. Many modifications, variations and changes in materials, methods and reaction conditions may be made simultaneously with respect to the disclosure herein. All such modifications, variations and changes are intended to fall within the spirit and scope of the present invention.
Example 1:
methyl levulinate (130mg, 1mmol), [ Cp. Multidot.Ir (2,2' -bpyO) (H 2 O)][Na + ](5.7mg,0.01mmol，1mol％)、CH 3 OH (2 mL) was added to a dry 25mL Kjeldahl tube in sequence, and the reaction mixture was allowed to react at 130 ℃ for 12 hours under nitrogen, after which it was cooled to room temperature. The solvent was removed by rotary evaporation and then purified by column chromatography (developer: n-hexane/ethyl acetate) to give the pure title compound in the following yields: 70 percent.
1 H NMR(500MHz,CDCl3)δ4.65(sxt,J＝6.6Hz,1H),2.57-2.53(m,2H),2.37(sxt,J＝6.6Hz,1H),1.87-1.78(m,1H),1.42(d,J＝6.3Hz,3H)； 13 C NMR(125MHz,CDCl3)δ176.9,76.9,29.3,28.7,20.6.。
Claims (6)
1. A method for synthesizing gamma-valerolactone I is characterized by comprising
Reacting methyl peroxylevulinate II
With CH under the action of iridium complex catalyst 3 A step of generating a target product by OHI reaction,
CH 3 OH
III；
wherein the iridium complex catalyst is [ Cp-Ir (2,2' -bpyO) (H) 2 O)][Na + ]The structure is as follows:
2. the method of claim 1, comprising the steps of:
adding methyl levulinate and CH into a reaction vessel 3 Heating OH and an iridium complex catalyst for a period of time, cooling to room temperature, spin-drying the solvent, and then separating by a column to obtain the target compound.
3. The method according to claim 1 or 2, wherein the iridium complex catalyst is used in an amount of 1mol% relative to the methyl levulinate.
4. The method of claim 1 or 2, wherein the methyl levulinate is reacted with CH 3 The OH ratio was 0.13 g: 2mL.
5. The process of claim 1 or 2, wherein the reaction temperature is 130 ± 10 ℃ and the reaction time is not less than 10 hours.
6. The process of claim 1 or 2, wherein the reaction is carried out under nitrogen.
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| CN201911217788.0A CN112898244B (en) | 2019-12-03 | 2019-12-03 | Method for synthesizing gamma-valerolactone |
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| CN201911217788.0A CN112898244B (en) | 2019-12-03 | 2019-12-03 | Method for synthesizing gamma-valerolactone |
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| CN112898244B true CN112898244B (en) | 2022-12-13 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805316A (en) * | 2010-04-22 | 2010-08-18 | 复旦大学 | Method for preparing Gamma-valerolactone by using supported iridium catalyst |
| CN102558108A (en) * | 2011-12-22 | 2012-07-11 | 南开大学 | Process for preparing gamma-valerolactone by utilizing iridium-pincer ligand complex catalyst |
| CN104829559A (en) * | 2015-05-29 | 2015-08-12 | 厦门大学 | Method of preparing Nu-valerolactone from methyl levulinate |
| CN104203892B (en) * | 2012-02-23 | 2017-03-22 | 关东化学株式会社 | Dehydrogenation catalyst, and carbonyl compound and hydrogen production method using said catalyst |
| CN107253937A (en) * | 2017-08-03 | 2017-10-17 | 厦门大学 | A kind of synthetic method of γ valerolactones |
-
2019
- 2019-12-03 CN CN201911217788.0A patent/CN112898244B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805316A (en) * | 2010-04-22 | 2010-08-18 | 复旦大学 | Method for preparing Gamma-valerolactone by using supported iridium catalyst |
| CN102558108A (en) * | 2011-12-22 | 2012-07-11 | 南开大学 | Process for preparing gamma-valerolactone by utilizing iridium-pincer ligand complex catalyst |
| CN104203892B (en) * | 2012-02-23 | 2017-03-22 | 关东化学株式会社 | Dehydrogenation catalyst, and carbonyl compound and hydrogen production method using said catalyst |
| CN104829559A (en) * | 2015-05-29 | 2015-08-12 | 厦门大学 | Method of preparing Nu-valerolactone from methyl levulinate |
| CN107253937A (en) * | 2017-08-03 | 2017-10-17 | 厦门大学 | A kind of synthetic method of γ valerolactones |
Non-Patent Citations (5)
| Title |
|---|
| Efficient Catalytic Hydrogenation of Alkyl Levulinates to γ-Valerolactone;Rosa Padilla等;《Green Chemistry》;20190828;第21卷(第19期);第1-7页 * |
| Hydrogen Production from a Methanol–Water Solution Catalyzed by an Anionic Iridium Complex Bearing a Functional Bipyridonate Ligand under Weakly Basic Conditions;Ken-ichi Fujita 等;《Angew.Chen.Int.Ed.》;20151231(第54期);第9057-9060页 * |
| Rosa Padilla等.Efficient Catalytic Hydrogenation of Alkyl Levulinates to γ-Valerolactone.《Green Chemistry》.2019,第21卷(第19期),第1-7页. * |
| Transfer Hydrogenation of Ketones and Imines with Methanol under Base-Free Conditions Catalyzed by an Anionic Metal−Ligand Bifunctional Iridium Catalyst;Rongzhou Wang 等;《J. Org. Chem.》;20200108(第85期);第2242-2249页 * |
| 多相催化乙酰丙酸甲酯合成γ-戊内酯的研究;蒋龙飞等;《食品工业科技》;20121231;第33卷(第4期);第365-367、392页 * |
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