CN111233802B - Preparation method of furoate - Google Patents

Preparation method of furoate Download PDF

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CN111233802B
CN111233802B CN202010207334.1A CN202010207334A CN111233802B CN 111233802 B CN111233802 B CN 111233802B CN 202010207334 A CN202010207334 A CN 202010207334A CN 111233802 B CN111233802 B CN 111233802B
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furoate
production method
furfural
catalyst
nitrate
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CN111233802A (en
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傅尧
李兴龙
徐冬冬
解光霞
孔庆山
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University of Science and Technology of China USTC
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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
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen

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Abstract

The invention discloses a preparation method of furoate, which comprises the following steps: mixing furfural, an oxidation esterification catalyst, a cocatalyst and a solvent uniformly, and reacting for a period of time at a certain temperature and pressure in the presence of an oxygen source to obtain the furoate. The method has the advantages of high selectivity, few byproducts, mild reaction conditions and certain industrial application prospect.

Description

Preparation method of furoate
Technical Field
The invention relates to the technical field of chemical substance preparation, in particular to a preparation method of furoate.
Background
The furoate is one of important fine chemical products converted from biomass, is an extremely important novel synthetic spice and is widely applied to industries such as food essence, tobacco essence, cosmetic essence and the like. Meanwhile, the gasoline is an important chemical raw material and an intermediate, can be used as a gasoline antiknock agent to improve the quality of gasoline, and also has the performance of antitumor activity. Therefore, the development of a simple, efficient and low-cost synthesis method of furoate has important application value and sustainable development significance.
At present, relatively few reports are reported for preparing furoate through furfural oxidation esterification, and alkaline additives are adopted in the catalytic systems to promote the reaction, so that the conversion rate of furfural is improved. For example, a noble metal catalyst Au/TiO2 catalyzes furfural oxidative esterification with the aid of CH3ONa, and the furfural is reacted for 10 to 12 hours at the temperature of 22 ℃ and the pressure of 0.4MPa O2 to realize complete conversion, and the selectivity of the methyl furoate is 100 percent (C.H. Christensen et al. Chemsuschem,2008,1, 75). Although CH3ONa homogeneous base efficiently converts furfural to methyl furoate, the added homogeneous base is difficult to separate out and cannot be recycled, the subsequent process is complicated and requires the introduction of acid to neutralize the system, unnecessary environmental pollution is generated, and the cost is increased. Therefore, a novel catalytic system needs to be developed, and the method has important significance for efficiently and selectively catalyzing furfural to be oxidized and esterified to prepare furoate under the condition of no alkali additive.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a preparation method of furoate. The method has the advantages of high selectivity, few byproducts and mild reaction conditions.
The invention provides a preparation method of furoate, which comprises the following steps: mixing furfural, oxidation catalyst, cocatalyst and solvent, and reacting at certain temperature and pressure for a period of time in the presence of oxygen source to obtain furoate.
Preferably, the oxidation catalyst is at least one of the following dicarboximide compounds.
Figure BDA0002421584780000021
Preferably, the solvent is an alcoholic solvent; preferably, the solvent is at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, ethylene glycol and propylene glycol.
Preferably, the promoter is a metal nitrate; preferably, the promoter is at least one of copper nitrate, iron nitrate, nickel nitrate, cobalt nitrate and zinc nitrate.
Preferably, the oxygen source is at least one of oxygen gas and air.
Preferably, the reaction temperature is 10-100 ℃; preferably, the reaction temperature is 10-50 ℃.
Preferably, the reaction time is 0.5-72 h; preferably, the reaction time is 10-24 h.
Preferably, the reaction pressure is 0.1 to 10 MPa; preferably, the reaction pressure is from 0.1 to 2 MPa.
Preferably, the molar ratio of oxidation catalyst to furfural is 0.05:1 to 10: 1; preferably, the molar ratio of oxidation catalyst to furfural is from 0.05:1 to 0.3: 1.
Preferably, the molar ratio of the cocatalyst to the furfural is 0.1:1 to 10: 1; preferably, the molar ratio of co-catalyst to furfural is 0.1:1 to 0.5: 1.
The invention increases the selectivity of the reaction and improves the yield of the furoate by selecting proper oxidation catalyst, cocatalyst and oxygen source, and the reaction condition is mild, thus being suitable for industrial production.
Drawings
FIG. 1 shows the nuclear magnetic hydrogen spectrum of the product methyl furoate of example 1.
FIG. 2 shows the nuclear magnetic hydrogen spectrum of the product n-propyl furoate of example 17.
FIG. 3 shows the nuclear magnetic hydrogen spectrum of the product ethyl furoate of example 18.
FIG. 4 shows the nuclear magnetic hydrogen spectrum of the product sec-butyl furoate of example 19.
Detailed Description
In order to better explain the present invention and to facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. However, the following examples are only illustrative of the present invention and do not represent or limit the scope of the present invention.
The solvents and promoters used in the examples were purchased from Chinese medicines and the oxidation catalyst was purchased from Aladdin.
Example 1
A method for preparing furoate comprises the following steps:
adding 1mmol of furfural, 10mL of methanol, 10 mol% of catalyst 1 (in terms of the molar number of furfural) and 10 mol% of copper nitrate (in terms of the molar number of furfural) into a 25mL high-pressure reaction kettle, tightening a screw, introducing oxygen, replacing for three times, then oxygenating to 2MPa, heating to 30 ℃ under magnetic stirring for reaction for 24 hours, cooling to room temperature after the reaction is finished, adding N, N-dimethylformamide as an internal standard, adding methanol for dilution, and performing gas chromatography detection, wherein the specific detection conditions are as follows: the product content was determined by assembling a DB-FFAP (30m x 0.25. mu. m x 0.32mm) column on a GC (2104, Shimazu, FID). Setting the gasification temperature at 270 deg.C, the detection temperature at 270 deg.C, setting the column box temperature at 120 deg.C, maintaining for 1min, heating to 230 deg.C for 8min, and maintaining for 8 min. The yield of methyl furoate was 88%.
The nuclear magnetic hydrogen spectrum of methyl furoate is shown in FIG. 1. 1 H NMR(400MHz,CDCl 3 )δ7.59(dd,J＝1.7,0.9Hz,1H),7.18(dd,J＝3.5,0.9Hz,1H),6.51(dd,J＝3.5,1.8Hz,1H),3.90(s,3H)。
Example 2
The yield of methyl furoate was 80% under the same conditions as in example 1 except that copper nitrate was changed to iron nitrate and the other conditions were the same as in example 1.
Example 3
The copper nitrate was changed to cobalt nitrate under the same conditions as in example 1, and the yield of methyl furoate was 92%.
Example 4
The catalyst was changed to catalyst 3 under the same conditions as in example 1, and the yield of methyl furoate was 79%.
Example 5
The catalyst was changed to catalyst 7 under the same conditions as in example 1, and the yield of methyl furoate was 67%.
Example 6
The catalyst was changed to catalyst 12 under the same conditions as in example 1, and the yield of methyl furoate was 94%.
Example 7
The reaction temperature was changed to 60 ℃ and the other conditions were the same as in example 1, and the yield of methyl furoate was 82%.
Example 8
The reaction temperature was changed to 80 ℃ and the other conditions were the same as in example 1, and the yield of methyl furoate was 75%.
Example 9
The reaction pressure was changed to 0.1MPa, and the other conditions were the same as in example 1, whereby the yield of methyl furoate was 61%.
Example 10
The reaction pressure was changed to 4MPa, and the other conditions were the same as in example 1, whereby the yield of methyl furoate was 96%.
Example 11
The reaction time was changed to 48 hours and the other conditions were the same as in example 1, and the yield of methyl furoate was 93%.
Example 12
The reaction time was changed to 12 hours, and other conditions were the same as in example 1, and the yield of methyl furoate was 56%.
Example 13
The amount of furfural as a substrate was changed to 2mmol, and the other conditions were the same as in example 1, and the yield of methylfuroate was 63%.
Example 14
The catalyst amount was changed to 30 mol%, and the yield of methyl furoate was 89% under the same conditions as in example 1.
Example 15
The amount of the cocatalyst was changed to 50 mol%, and the yield of methyl furoate was 91% under the same conditions as in example 1.
Example 16
The oxygen was replaced with air and the other conditions were the same as in example 1, yielding 72% of methyl furoate.
Example 17
The solvent was changed to n-propanol and the other conditions were the same as in example 1, resulting in a yield of n-propyl furoate of 79%.
The nuclear magnetic hydrogen spectrum of n-propyl furoate is shown in FIG. 2. 1 H NMR(400MHz,CDCl 3 )δ7.58(d,J＝0.7Hz,1H),7.18(d,J＝3.4Hz,1H),6.51(dd,J＝3.5,1.7Hz,1H),4.27(t,J＝6.7Hz,2H),1.82–1.69(m,2H),1.01(t,J＝7.4Hz,3H)。
Example 18
The solvent was changed to ethanol and the other conditions were the same as in example 1, and the yield of ethyl furoate was 82%.
The nuclear magnetic hydrogen spectrum of the ethyl furoate is shown in fig. 3. 1 H NMR(400MHz,CDCl 3 )δ7.58(dd,J＝1.6,0.8Hz,1H),7.18(dd,J＝3.5,0.7Hz,1H),6.51(dd,J＝3.5,1.7Hz,1H),4.37(q,J＝7.1Hz,2H),1.38(t,J＝7.1Hz,3H)。
Example 19
The solvent is changed into sec-butyl alcohol, other conditions are the same as example 1, and the yield of the sec-butyl furoate is 85%.
The nuclear magnetic hydrogen spectrum of the sec-butyl furoate is shown in FIG. 4. 1 H NMR(400MHz,CDCl 3 )δ7.59(dtd,J＝3.6,1.8,0.8Hz,1H),7.24–7.10(m,1H),6.51(tdd,J＝3.9,2.3,1.5Hz,1H),5.08(dd,J＝12.2,5.9Hz,1H),1.78–1.62(m,2H),1.33(dt,J＝6.3,3.7Hz,3H),0.96(tt,J＝7.4,3.6Hz,3H)。
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (13)

1. A method for preparing furoate ester comprises the following steps: mixing furfural, oxidation catalyst, cocatalyst and solvent uniformly, reacting in the presence of oxygen source to obtain furoate,
wherein the oxidation catalyst is at least one of the following dicarboximide compounds:
Figure FDA0003692625510000011
the cocatalyst is at least one of copper nitrate, ferric nitrate, nickel nitrate, cobalt nitrate and zinc nitrate; and is provided with
The oxygen source is at least one of oxygen gas and air.
2. The method of claim 1, wherein the solvent is an alcoholic solvent.
3. The production method according to claim 1 or 2, wherein the solvent is at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, ethylene glycol, and propylene glycol.
4. The production method according to claim 1 or 2, wherein the reaction temperature is 10 to 100 ℃.
5. The production method according to claim 1 or 2, wherein the reaction temperature is 10 to 50 ℃.
6. The process according to claim 1 or 2, wherein the reaction time is 0.5 to 72 hours.
7. The process according to claim 1 or 2, wherein the reaction time is 10 to 24 hours.
8. The production method according to claim 1 or 2, wherein the reaction pressure is 0.1 to 10 MPa.
9. The production method according to claim 1 or 2, wherein the reaction pressure is 0.1 to 2 MPa.
10. The production method according to claim 1 or 2, characterized in that the molar ratio of the oxidation catalyst to the furfural is from 0.05:1 to 10: 1.
11. The production method according to claim 1 or 2, characterized in that the molar ratio of the oxidation catalyst to the furfural is 0.05:1 to 0.3: 1.
12. The production method according to claim 1 or 2, characterized in that the molar ratio of the co-catalyst to the furfural is 0.1:1 to 10: 1.
13. The production method according to claim 1 or 2, characterized in that the molar ratio of the co-catalyst to the furfural is 0.1:1 to 0.5: 1.
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Citations (4)

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Publication number Priority date Publication date Assignee Title
CN108148024A (en) * 2016-12-04 2018-06-12 中国科学院大连化学物理研究所 A kind of method of furfural oxidative esterification methylfuroate
CN109574964A (en) * 2018-12-21 2019-04-05 厦门大学 A method of preparing methylfuroate
CN109824634A (en) * 2017-11-23 2019-05-31 中国科学院大连化学物理研究所 A kind of method that furfural direct oxidation esterification prepares methylfuroate
KR20200005875A (en) * 2018-07-09 2020-01-17 한국생산기술연구원 Process for Preparing Furan-2,5-diakylcarboxylate

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CN108148024A (en) * 2016-12-04 2018-06-12 中国科学院大连化学物理研究所 A kind of method of furfural oxidative esterification methylfuroate
CN109824634A (en) * 2017-11-23 2019-05-31 中国科学院大连化学物理研究所 A kind of method that furfural direct oxidation esterification prepares methylfuroate
KR20200005875A (en) * 2018-07-09 2020-01-17 한국생산기술연구원 Process for Preparing Furan-2,5-diakylcarboxylate
CN109574964A (en) * 2018-12-21 2019-04-05 厦门大学 A method of preparing methylfuroate

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Iron-Catalyzed One-Pot Oxidative Esterification of Aldehydes;Xiao-Feng Wu等;《Eur. J. Org. Chem.》;20090128;1144-1147 *
On the process for furfural and HMF oxidative esterification over Au/ZrO2;F.Menegazzo等;《Journal of Catalysis》;20140906;第319卷;61-70 *
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