CN118146071A - Synthesis process of 4- (2-methylallyl) -1, 2-benzenediol - Google Patents
Synthesis process of 4- (2-methylallyl) -1, 2-benzenediol Download PDFInfo
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- CN118146071A CN118146071A CN202410259717.1A CN202410259717A CN118146071A CN 118146071 A CN118146071 A CN 118146071A CN 202410259717 A CN202410259717 A CN 202410259717A CN 118146071 A CN118146071 A CN 118146071A
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- benzenediol
- methylallyl
- phenol
- methylallyloxy
- catalyst
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- 125000005394 methallyl group Chemical group 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 24
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 23
- 230000008569 process Effects 0.000 title claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- AAXBKJXGVXNSHI-UHFFFAOYSA-N 2-(2-methylprop-2-enoxy)phenol Chemical compound CC(=C)COC1=CC=CC=C1O AAXBKJXGVXNSHI-UHFFFAOYSA-N 0.000 claims abstract description 16
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- -1 aluminum triacetylacetone Chemical compound 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 10
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000007599 discharging Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- 239000008096 xylene Substances 0.000 claims description 2
- 238000005821 Claisen rearrangement reaction Methods 0.000 abstract description 9
- 238000005952 Cope rearrangement reaction Methods 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- ZOXWHYCFEIIAIL-UHFFFAOYSA-N furan phenol Chemical compound C1(=CC=CC=C1)O.O1C=CC=C1.C1(=CC=CC=C1)O ZOXWHYCFEIIAIL-UHFFFAOYSA-N 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000007363 ring formation reaction Methods 0.000 description 4
- XIYKRJLTYKUWAM-UHFFFAOYSA-N 3,4-methylenedioxyphenylpropan-2-one Chemical compound CC(=O)CC1=CC=C2OCOC2=C1 XIYKRJLTYKUWAM-UHFFFAOYSA-N 0.000 description 3
- ZWRLWJAFBLTMSQ-UHFFFAOYSA-N Docosa-7,10,14-triensaeure Natural products C1C(C)=C2CC(C)(C)CC2C(O)C2=COC=C21 ZWRLWJAFBLTMSQ-UHFFFAOYSA-N 0.000 description 3
- YKASHPSKFYVZRC-UHFFFAOYSA-M furan-2-ylmethyl(trimethyl)azanium;iodide Chemical compound [I-].C[N+](C)(C)CC1=CC=CO1 YKASHPSKFYVZRC-UHFFFAOYSA-M 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006462 rearrangement reaction Methods 0.000 description 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 102000052567 Anaphase-Promoting Complex-Cyclosome Apc1 Subunit Human genes 0.000 description 1
- 206010020772 Hypertension Diseases 0.000 description 1
- 108091006463 SLC25A24 Proteins 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- CJCSPKMFHVPWAR-JTQLQIEISA-N alpha-methyl-L-dopa Chemical compound OC(=O)[C@](N)(C)CC1=CC=C(O)C(O)=C1 CJCSPKMFHVPWAR-JTQLQIEISA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000002260 anti-inflammatory agent Substances 0.000 description 1
- 229940124599 anti-inflammatory drug Drugs 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YBHILYKTIRIUTE-UHFFFAOYSA-N berberine Chemical compound C1=C2CC[N+]3=CC4=C(OC)C(OC)=CC=C4C=C3C2=CC2=C1OCO2 YBHILYKTIRIUTE-UHFFFAOYSA-N 0.000 description 1
- 229940093265 berberine Drugs 0.000 description 1
- QISXPYZVZJBNDM-UHFFFAOYSA-N berberine Natural products COc1ccc2C=C3N(Cc2c1OC)C=Cc4cc5OCOc5cc34 QISXPYZVZJBNDM-UHFFFAOYSA-N 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- WCOATMADISNSBV-UHFFFAOYSA-K diacetyloxyalumanyl acetate Chemical compound [Al+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WCOATMADISNSBV-UHFFFAOYSA-K 0.000 description 1
- 206010015037 epilepsy Diseases 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000004770 neurodegeneration Effects 0.000 description 1
- 239000002547 new drug Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229940126585 therapeutic drug Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/001—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by modification in a side chain
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/18—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with unsaturation outside the aromatic ring
- C07C39/19—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with unsaturation outside the aromatic ring containing carbon-to-carbon double bonds but no carbon-to-carbon triple bonds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis process of 4- (2-methylallyl) -1, 2-benzenediol, which belongs to the technical field of organic synthesis and comprises the following steps: adding ethylene glycol monomethyl ether into 2- (2-methylallyloxy) phenol under stirring, mixing for 20-30min, adding dimethylbenzene and catalyst aluminum triacetylacetone, stirring at a constant temperature of 170-185 ℃ for reacting for 150-180min, cooling, and discharging to obtain colorless liquid, namely 4- (2-methylallyl) -1, 2-benzenediol. The invention uses catalyst aluminum triacetylacetonate to catalyze 2- (2-methylallyloxy) phenol to generate Claisen rearrangement and Cope rearrangement to prepare 4- (2-methylallyl) -1, 2-benzenediol, and finally achieves the aim of improving the yield and purity of the 4- (2-methylallyl) -1, 2-benzenediol by controlling reaction conditions and selecting the catalyst and the dosage thereof.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a synthesis process of 4- (2-methallyl) -1, 2-benzenediol.
Background
4- (2-Methylallyl) -1, 2-benzenediol is a cyclization reaction byproduct in the synthesis process of the pesticide intermediate furan phenol.
Chinese patent CN103319452B discloses a method for preparing 3, 4-methylenedioxyphenyl-2-propanone from furan phenol by-product, 3, 4-methylenedioxyphenyl-2-propanone is an important raw material for synthesizing a drug LY300164 for treating epilepsy and neurodegeneration, is an important intermediate for synthesizing a hypertension therapeutic drug α -methyldopa, and is also an important intermediate for synthesizing an antibacterial anti-inflammatory drug berberine, an anti-tumor new drug and the like. The method for successfully synthesizing the 3, 4-methylenedioxyphenyl-2-propanone by using the furan phenol byproduct (2-methallyl) -1, 2-benzenediol as a raw material widens the development direction of the 4- (2-methallyl) -1, 2-benzenediol, and simultaneously reflects the important role of the 4- (2-methallyl) -1, 2-benzenediol in the field of drug synthesis.
However, since the current 4- (2-methallyl) -1, 2-benzenediol is mainly extracted from byproducts generated during the synthesis of the pesticide intermediate furan phenol, along with the reduction of the market demand of the pesticide intermediate furan phenol, it is necessary to develop a high-yield synthesis process of 4- (2-methallyl) -1, 2-benzenediol.
Chinese patent CN106673967B discloses a process for preparing 4- (2-methylallyl) -1, 2-benzenediol by screening a large number of catalysts, and finally selecting to catalyze 2- (2-methylallyloxy) phenol to undergo rearrangement reaction (including Claisen rearrangement and Cope rearrangement reaction which continuously occur) by using gamma-alumina to prepare 4- (2-methylallyl) -1, 2-benzenediol. The invention aims to further improve the process conditions and the selection of the catalyst and improve the yield of the 4- (2-methylallyl) -1, 2-benzenediol.
Disclosure of Invention
The invention aims to break away from the limit of purification and preparation of 4- (2-methylallyl) -1, 2-benzenediol from furan phenol synthesis byproducts, provides a synthesis process of 4- (2-methylallyl) -1, 2-benzenediol, and improves the yield of 4- (2-methylallyl) -1, 2-benzenediol by improving the synthesis process.
The aim of the invention can be achieved by the following technical scheme:
a synthesis process of 4- (2-methylallyl) -1, 2-benzenediol comprises the following steps:
Adding ethylene glycol monomethyl ether into 2- (2-methylallyloxy) phenol under stirring, mixing for 20-30min, adding dimethylbenzene and catalyst aluminum triacetylacetone, stirring at a constant temperature of 170-185 ℃ for reacting for 150-180min, cooling, and discharging to obtain colorless liquid, namely 4- (2-methylallyl) -1, 2-benzenediol.
Further, the mass fraction of the 2- (2-methylallyloxy) phenol is 98%.
Further, the dosage ratio of the 2- (2-methylallyloxy) phenol, the ethylene glycol monomethyl ether, the xylene and the catalyst aluminum triacetylacetonate is 169.5g to 100g to 80-100g to 3.7-4.2g.
Further, the purity of the 4- (2-methylallyl) -1, 2-benzenediol is 99.0% -99.2%.
The principle of the invention is as follows:
The invention improves on the basis of synthesizing furan phenol (formula 3 below), researches the formation mechanism of a byproduct 4- (2-methylallyl) -1, 2-benzenediol (formula 4 below), and realizes the aim of improving the conversion of the byproduct 4- (2-methylallyl) -1, 2-benzenediol into a main product by improving the synthesis process. First, as shown in the following formula, a main synthesis process of furan phenol is that 2- (2-methylallyloxy) phenol (formula 1 below) is heated under the action of a catalyst to perform Claisen rearrangement to generate 3- (2-methylallyl) -1, 2-benzenediol (formula 2 below), 3- (2-methylallyl) -1, 2-benzenediol is unstable, cyclization is continued to generate furan phenol, meanwhile, 3- (2-methylallyl) -1, 2-benzenediol is parallel to perform Cope rearrangement, methallyl rearranges to the para position to generate a byproduct 4- (2-methylallyl) -1, 2-benzenediol, so that under the heating condition, as long as 2- (2-methylallyloxy) phenol performs Claisen rearrangement, the cyclization reaction generates furan phenol, meanwhile, the Cope rearrangement reaction occurs, because: both the Claisen rearrangement and the Cope rearrangement are thermal rearrangement reactions, and chain reactions are very easy to occur under heating conditions to generate the unavoidable byproduct 4- (2-methylallyl) -1, 2-benzenediol.
It has been found that 3- (2-methylallyl) -1, 2-benzenediol has a relatively low rate of cyclization reaction in the absence of a catalyst, and aluminum alkoxide catalysts (aluminum isoamyl alcohol, etc.) are generally selected as the furanol synthesis catalysts in the prior art, and aluminum isoamyl alcohol is cyclized with oxygen ions in phenolic hydroxyl groups in 3- (2-methylallyl) -1, 2-benzenediol by providing hydrogen ions and complexation to prepare furanol.
The innovation point of the invention is that: through theoretical calculation, the activation energy required for Claisen rearrangement is lower than that for Cope rearrangement, and by studying the structures of 4- (2-methallyl) -1, 2-benzenediol and furanol, it was found that there is a difference in the spatial structure of the transition states in Claisen rearrangement and Cope rearrangement, the cyclic transition state formed by allyl ether in Claisen rearrangement and the aromatic ring are almost coplanar, and the cyclic transition state formed in Cope rearrangement and the aromatic ring are in approximately vertical planes. The present invention is therefore directed to improving the yield of 4- (2-methallyl) -1, 2-benzenediol by controlling the reaction conditions (reaction temperature and reaction time) and the choice of catalyst.
The invention has the beneficial effects that:
The invention provides a synthesis process of 4- (2-methylallyl) -1, 2-benzenediol, which utilizes a catalyst aluminum triacetate to catalyze 2- (2-methylallyloxy) phenol to generate Claisen rearrangement and Cope rearrangement to prepare 4- (2-methylallyl) -1, 2-benzenediol, and finally achieves the aim of improving the yield and purity of the 4- (2-methylallyl) -1, 2-benzenediol by controlling reaction conditions and selecting the catalyst and the dosage thereof.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention discloses a synthesis process of 4- (2-methylallyl) -1, 2-benzenediol, which comprises the following steps: 100g of ethylene glycol monomethyl ether is added into 169.5g of 2- (2-methylallyloxy) phenol (the mass fraction is 98%), the mixture is mixed for 20 to 30min, 80 to 100g of dimethylbenzene and 3.7 to 4.2g of aluminum triacetylacetone serving as a catalyst are added into the mixture, the mixture is stirred and reacted for 150 to 180min at a constant temperature of 170 to 185 ℃, the mixture is cooled and discharged, colorless liquid is obtained, the main component of the colorless liquid is 4- (2-methylallyl) -1, 2-benzenediol, and the colorless liquid is analyzed by a liquid chromatography-mass spectrometer, and the result is ：LC-MS(APC1,Pos)m/Z:164;'HNMR(CDCl3)δ:1.66(s,3H,CH3),3.20(s,2H,ArCH2),4.71-4.78(m,2H,C＝CH2),5.14(s,2H,OH,6.63(dd,J＝7.8Hz,J＝2.1Hz,1H, -H of benzene ring, 6.71 (d, J=2.1 Hz,1H and 3-H of benzene ring) and 6.77 to 6.80 (d, J=7.8 Hz,1H and 6-H of benzene ring) of benzene ring. As a result, the resulting off-white solid was 4- (2-methallyl) -1, 2-benzenediol.
Example 1
A synthesis process of 4- (2-methylallyl) -1, 2-benzenediol comprises the following steps:
Adding 100g of ethylene glycol monomethyl ether into 169.5g of 2- (2-methylallyloxy) phenol (the mass fraction is 98%), mixing for 20min, adding 80g of dimethylbenzene and 3.7g of aluminum triacetylacetone serving as a catalyst, stirring at constant temperature for reacting for 150min at 170 ℃, cooling and discharging to obtain colorless liquid, namely 4- (2-methylallyl) -1, 2-benzenediol, and standing for a period of time to obtain white-like solid, wherein the white-like solid is detected to have the main component of 4- (2-methylallyl) -1, 2-benzenediol, the purity of which is 99.0%, and the calculated yield is 94.5%.
Example 2
A synthesis process of 4- (2-methylallyl) -1, 2-benzenediol comprises the following steps:
Adding 100g of ethylene glycol monomethyl ether into 169.5g of 2- (2-methylallyloxy) phenol (mass fraction 98%), mixing for 30min, adding 90g of dimethylbenzene and 4.0g of aluminum triacetylacetone serving as a catalyst, stirring at a constant temperature for 180min, cooling and discharging to obtain colorless liquid, namely 4- (2-methylallyl) -1, 2-benzenediol, and standing for a period of time to obtain white-like solid, wherein the white-like solid is detected to have the main component of 4- (2-methylallyl) -1, 2-benzenediol, the purity of which is 99.2%, and the calculated yield is 95.1%.
Example 3
A synthesis process of 4- (2-methylallyl) -1, 2-benzenediol comprises the following steps:
Adding 100g of ethylene glycol monomethyl ether into 169.5g of 2- (2-methylallyloxy) phenol (mass fraction 98%), mixing for 30min, adding 100g of dimethylbenzene and 4.2g of aluminum triacetylacetone serving as a catalyst, stirring at constant temperature at 185 ℃ for reacting for 180min, cooling, discharging to obtain colorless liquid, namely 4- (2-methylallyl) -1, 2-benzenediol, and standing for a period of time to obtain an off-white solid, wherein the off-white solid is detected to have the main component of 4- (2-methylallyl) -1, 2-benzenediol, the purity of which is 99.1%, and the calculated yield is 95.0%.
It should be noted that in this document, terms such as "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents.
Claims (4)
1. The synthesis process of 4- (2-methylallyl) -1, 2-benzenediol is characterized by comprising the following steps:
Adding ethylene glycol monomethyl ether into 2- (2-methylallyloxy) phenol under stirring, mixing for 20-30min, adding dimethylbenzene and catalyst aluminum triacetylacetone, stirring at a constant temperature of 170-185 ℃ for reacting for 150-180min, cooling, and discharging to obtain colorless liquid, namely 4- (2-methylallyl) -1, 2-benzenediol.
2. The process for synthesizing 4- (2-methylallyl) -1, 2-benzenediol according to claim 1, wherein the mass fraction of the 2- (2-methylallyloxy) phenol is 98%.
3. The process for synthesizing 4- (2-methylallyl) -1, 2-benzenediol according to claim 1, wherein the dosage ratio of 2- (2-methylallyloxy) phenol, ethylene glycol monomethyl ether, xylene and aluminum triacetylacetonate catalyst is 169.5 g/100 g/80-100 g/3.7-4.2 g.
4. The process for the synthesis of 4- (2-methylallyl) -1, 2-benzenediol according to claim 1, wherein the purity of 4- (2-methylallyl) -1, 2-benzenediol is between 99.0% and 99.2%.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4324731A (en) * | 1979-12-07 | 1982-04-13 | Rhone-Poulenc Agrochimie | Process for the preparation of 2,3-dihydro-2,2-dimethyl-7-hydroxybenzofuran |
| CN103562169A (en) * | 2011-06-13 | 2014-02-05 | Fmc有限公司 | Purification process for para-methallylpyrocatechol |
| CN106673967A (en) * | 2016-11-14 | 2017-05-17 | 湖南海利株洲精细化工有限公司 | Preparation method of 4-(2-methylallyl)-1,2-benzenediol |
| CN111393275A (en) * | 2020-04-28 | 2020-07-10 | 上海现代哈森（商丘）药业有限公司 | Method for synthesizing intermediate farnesyl acetone and method for synthesizing phytol, isophytol and geranylgeraniol by using intermediate farnesyl acetone |
| CN117486695A (en) * | 2023-11-27 | 2024-02-02 | 山东泓瑞医药科技股份公司 | Veratone synthesis method based on claisen rearrangement and etherification reaction |
-
2024
- 2024-03-07 CN CN202410259717.1A patent/CN118146071B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4324731A (en) * | 1979-12-07 | 1982-04-13 | Rhone-Poulenc Agrochimie | Process for the preparation of 2,3-dihydro-2,2-dimethyl-7-hydroxybenzofuran |
| CN103562169A (en) * | 2011-06-13 | 2014-02-05 | Fmc有限公司 | Purification process for para-methallylpyrocatechol |
| CN106673967A (en) * | 2016-11-14 | 2017-05-17 | 湖南海利株洲精细化工有限公司 | Preparation method of 4-(2-methylallyl)-1,2-benzenediol |
| CN111393275A (en) * | 2020-04-28 | 2020-07-10 | 上海现代哈森（商丘）药业有限公司 | Method for synthesizing intermediate farnesyl acetone and method for synthesizing phytol, isophytol and geranylgeraniol by using intermediate farnesyl acetone |
| CN117486695A (en) * | 2023-11-27 | 2024-02-02 | 山东泓瑞医药科技股份公司 | Veratone synthesis method based on claisen rearrangement and etherification reaction |
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