CN115466234A - Novel preparation method of gamma-heptalactone - Google Patents
Novel preparation method of gamma-heptalactone Download PDFInfo
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- CN115466234A CN115466234A CN202211312347.0A CN202211312347A CN115466234A CN 115466234 A CN115466234 A CN 115466234A CN 202211312347 A CN202211312347 A CN 202211312347A CN 115466234 A CN115466234 A CN 115466234A
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- VLSVVMPLPMNWBH-UHFFFAOYSA-N Dihydro-5-propyl-2(3H)-furanone Chemical compound CCCC1CCC(=O)O1 VLSVVMPLPMNWBH-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 14
- 230000000694 effects Effects 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 12
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 11
- GGUBFICZYGKNTD-UHFFFAOYSA-N triethyl phosphonoacetate Chemical compound CCOC(=O)CP(=O)(OCC)OCC GGUBFICZYGKNTD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000009471 action Effects 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- 238000005984 hydrogenation reaction Methods 0.000 claims description 11
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- MWZBTMXISMOMAE-AATRIKPKSA-N (E)-ethyl 3-(2-furyl)acrylate Chemical compound CCOC(=O)\C=C\C1=CC=CO1 MWZBTMXISMOMAE-AATRIKPKSA-N 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- XXDAXUSYDPWTPK-UHFFFAOYSA-N 2-(oxo-lambda5-phosphanylidyne)acetic acid Chemical compound P(=O)#CC(=O)O XXDAXUSYDPWTPK-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- 239000012044 organic layer Substances 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 3
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000007363 ring formation reaction Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000007868 Raney catalyst Substances 0.000 claims 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 3
- NHXSTXWKZVAVOQ-UHFFFAOYSA-N Ethyl furoate Chemical compound CCOC(=O)C1=CC=CO1 NHXSTXWKZVAVOQ-UHFFFAOYSA-N 0.000 abstract description 2
- 235000013599 spices Nutrition 0.000 abstract description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 125000000457 gamma-lactone group Chemical group 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 238000003747 Grignard reaction Methods 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 2
- 229910001623 magnesium bromide Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011953 free-radical catalyst Substances 0.000 description 1
- 150000004721 gamma keto acids Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000007273 lactonization reaction Methods 0.000 description 1
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- HVCNEOVTZJYUAI-UHFFFAOYSA-N non-4-enoic acid Chemical compound CCCCC=CCCC(O)=O HVCNEOVTZJYUAI-UHFFFAOYSA-N 0.000 description 1
- 235000014571 nuts Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- -1 triethyl phosphoryl acetate Chemical compound 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a novel preparation method of gamma-heptalactone, belonging to the technical field of spice preparation, comprising the following steps: reacting triethyl phosphonoacetate and furfural serving as raw materials under the action of an alkaline catalyst A to obtain a 2-ethyl furanoate intermediate; the intermediate of 2-furan ethyl acrylate is subjected to hydrocyclization under the action of a high-activity metal catalyst B under the control of pressure and temperature to obtain gamma-heptalactone; taking triethyl phosphonoacetate as a raw material, carrying out a Horner-Woltz Watts-Eimers reaction on the triethyl phosphonoacetate and furfural which is easily obtained from the raw material under an alkaline condition to synthesize an intermediate of 2-furan ethyl acrylate, and then hydrogenating the intermediate by taking high-activity metal as a catalyst to obtain gamma-heptalactone; the invention has the advantages of low price of synthesized raw materials, high yield of products, no isomer in the products, high purity, simple reaction condition, simple process route and high industrial application value.
Description
Technical Field
The invention belongs to the technical field of spice preparation, and particularly relates to a novel preparation method of gamma-heptalactone.
Background
Gamma-heptalactone is also called as propyl-heptalactone, is mainly used in edible essence, can also be added into some cosmetic essence and perfume in a small amount, can play a role of drawing dragon eye, and is the edible essence which is allowed to be used and specified in GB 2760-96. The method is mainly used for preparing essence of nuts, coconuts, fruits and the like, and is used for preparing essence of daily cosmetics and tobacco, so that the efficient, simple and convenient synthesis of the gamma-heptalactone is always widely regarded.
The main synthesis method at present is as follows: peroxide is taken as a free radical catalyst, acrylic acid and butanol are taken as raw materials, and the gamma-heptalactone is obtained by the free radical addition reaction under the condition of the catalyst.
In 1995, sunQingling proposed a method for synthesizing gamma-lactone from aldehyde in journal society of the chemical world: taking aldehyde as a starting material, carrying out heating condensation and decarbonization on the aldehyde and malonic acid in the presence of a pyridine (or triethylamine) catalyst to prepare an intermediate product of olefine acid, and then carrying out intramolecular cyclization in the presence of an HY type molecular sieve to finally generate corresponding gamma-lactone, wherein the product yield is 58.8 percent at most; but the process is complicated to operate.
The prior art discloses that fatty alcohol is used as a raw material, the fatty alcohol is subjected to bromination and Grignard reaction to obtain fatty group magnesium bromide, the fatty group magnesium bromide and furfural are subjected to Grignard reaction, gamma-keto acid is obtained through ring opening rearrangement, and gamma-lactone is obtained through hydrogenation lactonization; the furfural has low price and is easy to obtain, and the method has certain market prospect; but the process steps are more, which is not beneficial to industrial scale-up.
Patent Akira Y.preparation of gamma-alkyl 1-gamma-lactone.Jpn Pat 55133371,1980 reports a process for preparing gamma-lactone from 4 nonenoic acid by cyclization reaction in the presence of polyphosphoric acid, acidic ion exchange resin, solid phosphoric acid and other acidic catalysts, with a yield of 52.3%; the method has short synthetic route and simple reaction condition, but has more byproducts, low product yield and quality and no environmental economy due to the strong oxidizing property of concentrated sulfuric acid.
Therefore, it is necessary to provide a method for preparing γ -heptalactone with high efficiency and simplicity.
Disclosure of Invention
In order to solve the technical problems mentioned in the background art, the invention provides a novel preparation method of gamma-heptalactone.
The purpose of the invention can be realized by the following technical scheme:
a novel preparation method of gamma-heptalactone comprises the following steps:
step a: reacting triethyl phosphonoacetate and furfural serving as raw materials under the action of an alkaline catalyst A to obtain a 2-ethyl furanoate intermediate;
step b: the intermediate of 2-furan ethyl acrylate is subjected to hydrocyclization under the action of a high-activity metal catalyst B under the control of pressure and temperature to obtain gamma-heptalactone;
the reaction process is specifically as follows:
the specific operation method of the step a is as follows:
adding deionized water into a three-neck flask, slowly adding an alkaline catalyst A under stirring, adding triethyl phosphorylacetate after stirring and dissolving, controlling the temperature to be 35-40 ℃, dropwise adding furfural, controlling the dropwise adding temperature to be 35-40 ℃, after dropwise adding is finished, carrying out heat preservation reaction for 12 hours, standing for 1 hour, separating an organic layer, and carrying out post-treatment to obtain the ethyl 2-furan acrylate.
Further, the basic catalyst a is one of potassium carbonate, sodium hydroxide, sodium carbonate and sodium methoxide, preferably potassium carbonate.
Further, the molar ratio of the triethyl phosphorylacetate to the basic catalyst a was 1:1-2, preferably 1:2.
further, the molar ratio of the furfural to the triethyl phosphonoacetate is 1-2:1, preferably 1.6:1.
the specific operation method of the step b is as follows:
adding 2-furan ethyl acrylate and a high-activity metal catalyst B into a hydrogenation kettle, replacing air with nitrogen, replacing nitrogen with hydrogen, controlling pressure and temperature, stirring for reaction for 5-15h, and filtering to remove the high-activity metal catalyst B to obtain the gamma-heptalactone.
Further, the high-activity metal catalyst B is one of ruthenium carbon, palladium carbon and raney nickel catalyst, preferably palladium carbon.
Further, the amount of the high-activity metal catalyst B is 1-10% by taking the mass of the 2-furan ethyl acrylate intermediate as 100%; preferably 10%.
Further, the specific conditions of pressure and temperature are controlled as follows: the hydrogenation pressure is 0.5-1MPa, the reaction temperature is 100-150 ℃, and the reaction time is 5-15h. The preferential conditions are that the hydrogenation pressure is 1MPa, the reaction temperature is 100 ℃ and the reaction time is 15h.
The invention has the beneficial effects that:
aiming at the defects of the prior art, the invention provides a novel preparation method of gamma-heptalactone, which comprises the steps of taking triethyl phosphorylacetate as a raw material, carrying out a Horner-Wozowski-Eimens reaction on the triethyl phosphorylacetate and furfural which is easily obtained as the raw material under an alkaline condition to synthesize a 2-furan ethyl acrylate intermediate, and then taking high-activity metal as a catalyst to carry out hydrogenation to obtain the gamma-heptalactone; the invention has the advantages of low price of synthesized raw materials, high yield of products, no isomer in the products, high purity, simple reaction condition, simple process route and high industrial application value.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparation of ethyl 2-furanacrylate:
adding 240g of water into a 1000ml three-neck flask with a stirring device, a thermometer and a dropping funnel, starting stirring, slowly adding 35g (0.875 mol) of sodium hydroxide, stirring until the sodium hydroxide is dissolved, adding 100g (0.446 mol) of triethyl phosphonoacetate after stirring and dissolving, controlling the temperature to be 35 ℃, starting dropping 69g (0.718 mol) of furfural after the kettle temperature is stable, wherein the dropping time is 3 hours, and the dropping temperature is controlled to be 35 ℃. After dropwise adding, preserving heat for 12h, standing for 1h, separating an organic layer, extracting a water phase twice by using 60g of methyl tert-butyl ether, combining organic phases, washing for 2 times by using saturated brine, distilling out the methyl tert-butyl ether at normal pressure, collecting a furfural component at 70-90 ℃ under high vacuum and reduced pressure, and collecting a component fraction at 90-110 ℃ by using a fractionating column under reduced pressure to obtain 64.59g (0.36 mol) of 2-furan ethyl acrylate, wherein the yield is 80.17%, and the purity is 92% (GC).
Example 2
Preparation of ethyl 2-furanacrylate:
adding 240g of water into a 1000ml three-neck flask with a stirring device, a thermometer and a dropping funnel, starting stirring, slowly adding 123g (0.891 mol) of potassium carbonate, stirring until the potassium carbonate is dissolved, adding 100g (0.446 mol) of triethyl phosphoryl acetate after stirring and dissolving, controlling the temperature at 40 ℃, starting dropping 69g (0.718 mol) of furfural after the kettle temperature is stable, wherein the dropping time is 4 hours, and the dropping temperature is controlled at 40 ℃. Dropwise adding the mixture, keeping the temperature for 12h, standing for 1h, separating an organic layer, extracting a water phase twice by using 60g of methyl tert-butyl ether, combining organic phases, washing 2 times by using saturated saline, evaporating the methyl tert-butyl ether at normal pressure, collecting a furfural component at 70-90 ℃ under high vacuum and reduced pressure, and collecting a component fraction at 90-110 ℃ under reduced pressure by using a fractionating column to obtain 70.25g (0.402 mol) of 2-furan ethyl acrylate, wherein the yield is 90.03%, and the purity is 95% (GC) and is reserved for the next step.
Example 3
Preparation of ethyl 2-furanacrylate:
compared with example 2, the input amount of the reactant furfural was changed to 45g (0.468 mol), and the remaining preparation and post-treatment steps were the same as in example 2, to obtain 42g (0.230 mol) of ethyl 2-furanacrylate, a yield of 51.56%, and a purity of 91% (GC).
Example 4
Preparation of gamma-heptalactone:
60g (95% 0.361mol) of the crude ethyl-2-furanacrylate of example 2, 6g of Raney nickel catalyst, air-substituted with nitrogen, nitrogen-substituted with hydrogen, charged with hydrogen to 0.5MPa, and heated to 100 ℃ with stirring, were charged into a 500ml high-pressure hydrogenation vessel. The reaction was stirred continuously until the pressure did not drop, which took 15 hours. After cooling to room temperature, the catalyst was filtered off to give 30.45g (0.221 mol) of a γ -heptalactone fraction having a purity of 93% (GC) and a yield of 64.41%. The crude product is rectified under reduced pressure to obtain 21.51g (0.167 mol) of finished gamma-heptalactone product with the content of 99.25 percent and the total reaction yield of 43.71 percent.
Example 5
Preparation of gamma-heptalactone:
60g (GC: 95% 0.361mol) of the crude ethyl 2-furanacrylate obtained in example 2, 6g of a palladium-on-carbon catalyst, air-replaced with nitrogen, nitrogen-replaced with hydrogen, charged with hydrogen to 0.5MPa, and heated to 100 ℃ with stirring in a 500ml high-pressure hydrogenation vessel. The reaction was stirred until the pressure did not drop, which took 15 hours. Cooled to room temperature and the catalyst was filtered off. The filtrate was subjected to distillation under reduced pressure to collect 35.12g (0.263 mol) of a γ -heptalactone fraction having a purity of 96% (GC) and a yield of 76.69%. The crude product is rectified under reduced pressure to obtain 28.35g (0.219 mol) of finished gamma-heptalactone product with the content of 99.2 percent and the total reaction yield of 57.59 percent.
Example 6
Preparation of gamma-heptalactone:
60g (95% by weight: 0.361mol) of the crude ethyl 2-furanacrylate obtained in example 2, 6g of a palladium-carbon catalyst, air-substituted with nitrogen, nitrogen-substituted with hydrogen, charged with hydrogen to 1MPa, and heated to 100 ℃ with stirring, were charged in a 500ml high-pressure hydrogenation vessel. The reaction was stirred until the pressure did not drop, which took about 15 hours. Cooled to room temperature and the catalyst was filtered off. The filtrate was subjected to distillation under the reduced pressure to collect 40.26g (0.30 mol) of a γ -heptalactone fraction having a purity of 95.56% (GC) and a yield of 87.51%. The crude product is rectified under reduced pressure to obtain 35.12g (0.272 mol) of finished gamma-heptalactone product, the content is 99.4 percent, and the total reaction yield is 71.48 percent.
In the description of the specification, reference to the description of "one embodiment," "an example," "a specific example" or the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (9)
1. A novel preparation method of gamma-heptalactone is characterized by comprising the following steps:
step a: reacting triethyl phosphorylacetate and furfural serving as raw materials under the action of an alkaline catalyst A to obtain a 2-furan ethyl acrylate intermediate;
step b: the intermediate of 2-furan ethyl acrylate is subjected to hydrogenation cyclization under the action of a high-activity metal catalyst B under the control of pressure and temperature to obtain gamma-heptalactone.
2. The novel process for preparing γ -heptalactone according to claim 1, wherein the basic catalyst A is one of potassium carbonate, sodium hydroxide, sodium carbonate and sodium methoxide.
3. The novel process for preparing γ -heptalactone according to claim 1, wherein the molar ratio of triethyl phosphonoacetate to basic catalyst a is 1:1-2.
4. The novel process for preparing γ -heptalactone according to claim 1, wherein the molar ratio of furfural to triethyl phosphonoacetate is 1-2:1.
5. the novel process for preparing γ -heptalactone according to claim 1, wherein the high-activity metal catalyst B is one of ruthenium on carbon, palladium on carbon and raney nickel.
6. The novel process for preparing gamma-heptalactone according to claim 1, wherein the amount of the high activity metal catalyst B is 1-10% by mass of the intermediate of 2-furanacrylic acid ethyl ester.
7. The novel method for preparing γ -heptalactone according to claim 1, wherein the controlling of the pressure and temperature in the step b is specifically: the hydrogenation pressure is 0.5-1MPa, and the reaction temperature is 100-150 ℃.
8. The novel method for preparing gamma-heptalactone according to claim 1, wherein the step a is specifically performed as follows:
adding deionized water into a three-neck flask, adding an alkaline catalyst A under stirring, adding triethyl phosphorylacetate after stirring and dissolving, controlling the temperature to be 35-40 ℃, dropwise adding furfural, after dropwise adding, carrying out heat preservation reaction for 12 hours, standing for 1 hour, separating an organic layer, and carrying out post-treatment to obtain the 2-furan ethyl acrylate.
9. The novel method for preparing γ -heptalactone according to claim 1, wherein the step b is specifically performed as follows:
adding 2-furan ethyl acrylate and a high-activity metal catalyst B into a hydrogenation kettle, replacing air with nitrogen, replacing nitrogen with hydrogen, controlling pressure and temperature, stirring for reaction for 5-15h, and filtering to remove the high-activity metal catalyst B to obtain the gamma-heptalactone.
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| PCT/CN2023/099795 WO2024087650A1 (en) | 2022-10-25 | 2023-06-13 | PREPARATION METHOD FOR γ-HEPTALACTONE |
| ZA2023/08006A ZA202308006B (en) | 2022-10-25 | 2023-08-17 | Novel method for preparing γ-heptalactone |
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