CN113831223A - Method for simultaneously preparing 2-methyl resorcinol and 4-methyl resorcinol - Google Patents
Method for simultaneously preparing 2-methyl resorcinol and 4-methyl resorcinol Download PDFInfo
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- CN113831223A CN113831223A CN202111203547.8A CN202111203547A CN113831223A CN 113831223 A CN113831223 A CN 113831223A CN 202111203547 A CN202111203547 A CN 202111203547A CN 113831223 A CN113831223 A CN 113831223A
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- resorcinol
- methyl resorcinol
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- FNYDIAAMUCQQDE-UHFFFAOYSA-N 4-methylbenzene-1,3-diol Chemical compound CC1=CC=C(O)C=C1O FNYDIAAMUCQQDE-UHFFFAOYSA-N 0.000 title claims abstract description 85
- ZTMADXFOCUXMJE-UHFFFAOYSA-N 2-methylbenzene-1,3-diol Chemical compound CC1=C(O)C=CC=C1O ZTMADXFOCUXMJE-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 24
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 80
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 23
- 230000005526 G1 to G0 transition Effects 0.000 claims abstract description 13
- 229910001463 metal phosphate Inorganic materials 0.000 claims abstract description 13
- LQFNMFDUAPEJRY-UHFFFAOYSA-K lanthanum(3+);phosphate Chemical compound [La+3].[O-]P([O-])([O-])=O LQFNMFDUAPEJRY-UHFFFAOYSA-K 0.000 claims description 7
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 claims description 7
- 239000004137 magnesium phosphate Substances 0.000 claims description 7
- 229910000157 magnesium phosphate Inorganic materials 0.000 claims description 7
- 229960002261 magnesium phosphate Drugs 0.000 claims description 7
- 235000010994 magnesium phosphates Nutrition 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 4
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 3
- 239000001506 calcium phosphate Substances 0.000 claims description 3
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 3
- 235000011010 calcium phosphates Nutrition 0.000 claims description 3
- TYAVIWGEVOBWDZ-UHFFFAOYSA-K cerium(3+);phosphate Chemical compound [Ce+3].[O-]P([O-])([O-])=O TYAVIWGEVOBWDZ-UHFFFAOYSA-K 0.000 claims description 3
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 claims description 3
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 claims description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 3
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 3
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 3
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 3
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 29
- DONPBOYMUMBGCQ-UHFFFAOYSA-N 7-oxabicyclo[3.3.1]nona-1(9),2,4-triene Chemical compound C1=CC(COC2)=CC2=C1 DONPBOYMUMBGCQ-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000543 intermediate Substances 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 239000003814 drug Substances 0.000 abstract description 5
- 239000012847 fine chemical Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003889 chemical engineering Methods 0.000 abstract description 4
- 229940079593 drug Drugs 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000011987 methylation Effects 0.000 abstract description 2
- 238000007069 methylation reaction Methods 0.000 abstract description 2
- 239000006227 byproduct Substances 0.000 description 19
- ASHGTJPOSUFTGB-UHFFFAOYSA-N 3-methoxyphenol Chemical compound COC1=CC=CC(O)=C1 ASHGTJPOSUFTGB-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 239000000376 reactant Substances 0.000 description 9
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 3
- DPZNOMCNRMUKPS-UHFFFAOYSA-N 1,3-Dimethoxybenzene Chemical compound COC1=CC=CC(OC)=C1 DPZNOMCNRMUKPS-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- FECNOIODIVNEKI-UHFFFAOYSA-N 2-[(2-aminobenzoyl)amino]benzoic acid Chemical class NC1=CC=CC=C1C(=O)NC1=CC=CC=C1C(O)=O FECNOIODIVNEKI-UHFFFAOYSA-N 0.000 description 1
- -1 acyl resorcinol Chemical compound 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- HJSLFCCWAKVHIW-UHFFFAOYSA-N cyclohexane-1,3-dione Chemical compound O=C1CCCC(=O)C1 HJSLFCCWAKVHIW-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N methyl monoether Natural products COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000013558 reference substance Substances 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
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by condensation involving hydroxy groups of phenols or alcohols or the ether or mineral ester group derived therefrom
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a method for simultaneously preparing 2-methyl resorcinol and 4-methyl resorcinol, belonging to the technical field of organic synthesis. The invention comprises the following steps: the resorcinol and the methanol are subjected to alkylation reaction by a metal phosphate stationary phase catalyst to obtain 2-methyl resorcinol and 4-methyl resorcinol. According to the invention, the metal phosphate is used as the catalyst, 2-methyl resorcinol and 4-methyl resorcinol can be obtained simultaneously by controlling the type of the catalyst, the conversion rate of resorcinol is high, the combined selectivity of 2-methyl resorcinol and 4-methyl resorcinol can reach 60% at most, the selectivity of hydroxyanisole among other products is about 30%, the selectivity of m-xylylene ether is about 5%, the obtained products are important intermediates for fine chemical engineering, organic chemistry and drug synthesis, and the economic benefit is high. Meanwhile, the invention takes the methanol as the methylation reagent, is environment-friendly and low in price, and reduces the production cost.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a method for simultaneously preparing 2-methyl resorcinol and 4-methyl resorcinol.
Background
2-MethylResorcinol, also known as 2, 6-Dihydroxytoluene, CAS:608-25-3, molecular formula C7H8O2Molecular weight 124.137, melting point 118 ℃ and relative density 1.21g/cm3. The 2-methyl resorcinol is a nearly white powder, is mainly used for medical intermediates, pesticide intermediates, dye intermediates and the like, and is commonly used as a hair dyeing auxiliary agent.
4-methylresorcinol, also known as methyl-1, 3-benzenediol and 2, 4-dihydroxytoluene, CAS number 496-73-1, formula C7H8O2The molecular weight is 124.137, the melting point is 104-108 ℃, and the relative density is 1.210g/cm3. 4-methyl resorcinol is an important organic synthesis intermediate and is widely used in fine chemical industries such as dye, medicine, pesticide, cosmetics and the like.
The synthesis method of 2-methyl resorcinol is more, and is mainly divided into a 2, 6-diaminotoluene method, a p-methylbenzoic acid method, a glutaric acid method, a 1, 3-cyclohexanedione method and a resorcinol method according to different reaction raw materials, wherein the resorcinol method has a certain industrial application prospect. However, the method has low selectivity and high cost of 2-methyl resorcinol, and causes expensive products.
The synthesis method of 4-methyl resorcinol is less reported and is generally prepared by reducing acyl resorcinol in a liquid phase system. In the preparation of 4-alkyl resorcinol in the prior art, the defects of low conversion rate of raw materials, low product selectivity and more byproducts are generally existed.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for simultaneously preparing 2-methylresorcinol and 4-methylresorcinol. The synthesis method of the invention has high selectivity for 2-methyl resorcinol and 4-methyl resorcinol.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for simultaneously preparing 2-methyl resorcinol and 4-methyl resorcinol, which comprises the following steps:
the resorcinol and the methanol are subjected to alkylation reaction by a metal phosphate stationary phase catalyst to obtain 2-methyl resorcinol and 4-methyl resorcinol.
Preferably, the metal phosphate is one or more of aluminum phosphate, lanthanum phosphate, zirconium phosphate, cerium phosphate, zinc phosphate, calcium phosphate, magnesium phosphate and chromium phosphate.
Preferably, the mass ratio of the resorcinol to the methanol is (0.2-2.0): 1.
preferably, the mass ratio of the resorcinol to the methanol is (0.25-1.5): 1.
preferably, the total velocity of the resorcinol and the methanol passing through the stationary phase catalyst is 0.1-2.0 mL/(g.h).
Preferably, the temperature of the alkylation reaction is 200-400 ℃.
Preferably, the alkylation reaction is carried out under an inert atmosphere.
Preferably, the alkylation reaction is followed by the separation of the obtained 2-methylresorcinol and 4-methylresorcinol, the separation comprising:
and distilling, rectifying and fractionating the alkylation reaction solution to respectively obtain 2-methyl resorcinol and 4-methyl resorcinol.
The invention provides a method for simultaneously preparing 2-methyl resorcinol and 4-methyl resorcinol, which comprises the following steps: the resorcinol and the methanol are subjected to alkylation reaction by a metal phosphate stationary phase catalyst to obtain 2-methyl resorcinol and 4-methyl resorcinol. According to the invention, the metal phosphate is used as the catalyst, 2-methyl resorcinol and 4-methyl resorcinol can be obtained simultaneously by controlling the type of the catalyst, the conversion rate of resorcinol is high, the combined selectivity of 2-methyl resorcinol and 4-methyl resorcinol can reach 60% at most, the selectivity of hydroxyanisole among other products is about 30%, and the selectivity of m-xylylene ether is about 5%. The products obtained by the reaction are important intermediates for fine chemical engineering, organic chemistry and drug synthesis, and have higher economic benefit. Meanwhile, the invention takes the methanol as the methylation reagent, is environment-friendly and low in price, and reduces the production cost.
Detailed Description
The invention provides a method for simultaneously preparing 2-methyl resorcinol and 4-methyl resorcinol, which comprises the following steps:
the resorcinol and the methanol are subjected to alkylation reaction by a metal phosphate stationary phase catalyst to obtain 2-methyl resorcinol and 4-methyl resorcinol.
In the present invention, the metal phosphate is preferably one or more of aluminum phosphate, lanthanum phosphate, zirconium phosphate, cerium phosphate, zinc phosphate, calcium phosphate, magnesium phosphate, and chromium phosphate.
In the invention, the mass ratio of the resorcinol to the methanol is (0.2-2.0): 1, more preferably (0.25 to 1.5): 1, and more preferably (0.5 to 1.5): 1.
in the present invention, the resorcinol and methanol are preferably passed through a metal phosphate stationary phase catalyst in the form of a mixture of resorcinol and methanol. In the invention, the total velocity of the resorcinol and the methanol passing through the stationary phase catalyst is preferably 0.1-2.0 mL/(g.h), and more preferably 0.2-1.5 mL/(g.h). In the present invention, the 0.1-2.0 mL/(g.h) means that the volume of the liquid phase mixture of resorcinol and methanol passing per gram of the catalyst per hour is 0.1-2.0 mL.
In the invention, the temperature of the alkylation reaction is preferably 200-400 ℃, and more preferably 230-300 ℃.
In the present invention, the alkylation reaction is preferably carried out under an inert atmosphere, preferably nitrogen and/or argon.
In the present invention, the alkylation reaction is preferably carried out in a fixed bed reactor, and the metal phosphate stationary phase catalyst is loaded in a fixed bed of the fixed bed reactor. In the present invention, the alkylation reaction specifically comprises:
mixing resorcinol and methanol to obtain a reaction solution;
and (3) under an inert atmosphere, heating the fixed bed to the alkylation reaction temperature, injecting a reaction solution, and carrying out alkylation reaction.
In the invention, the temperature of the fixed bed is preferably 200-400 ℃, and when the reaction liquid is close to the fixed bed, the reaction liquid is converted into a gaseous state and passes through the fixed bed loaded with the metal phosphate stationary phase catalyst in the form of the gaseous state. The invention preferably uses a constant flow pump to send the reaction liquid into a fixed bed reactor for reaction. In the present invention, the reaction liquid is preferably fed through a liquid feeding device, and the liquid mixed with the product and the reactant is collected at the end of the fixed bed.
In the present invention, the alkylation reaction is followed by a separation of the obtained 2-methylresorcinol and 4-methylresorcinol, the separation comprising:
and distilling, rectifying and fractionating the alkylation reaction solution to respectively obtain 2-methyl resorcinol and 4-methyl resorcinol.
In the present invention, since resorcinol and methanol pass through the stationary phase catalyst in a gaseous form, the resultant reactant does not need to be separated from the stationary phase catalyst.
The method for simultaneously preparing 2-methylresorcinol and 4-methylresorcinol according to the present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
In the embodiment, resorcinol and methanol are mixed according to a mass ratio of 1.5:1 to prepare a reaction solution, a lanthanum phosphate catalyst is placed in a fixed bed reactor, then the fixed bed reactor is heated to 260 ℃ under a nitrogen atmosphere, the reaction solution is fed into the fixed bed reactor by an advection pump according to a flow rate of 1.5mL of the reaction solution passing through each gram of the lanthanum phosphate catalyst per hour, so that the resorcinol and the methanol are subjected to alkylation reaction under the action of the lanthanum phosphate catalyst, and products of 2-methylresorcinol, 4-methylresorcinol and a byproduct of m-hydroxyanisole are collected after the reaction is finished. In this example, the conversion of the reactant resorcinol was 50%, the selectivity to 2-methylresorcinol was 35%, the selectivity to 4-methylresorcinol was 25%, the combined selectivity was 60%, the selectivity to the by-product m-hydroxyanisole was 28%, the selectivity to the m-xylylene ether was 5%, and the other by-products were about 7%. The 2-methyl resorcinol, the 4-methyl resorcinol, the m-hydroxy anisole, the m-phenyl dimethyl ether and the like obtained by the reaction are important intermediates for fine chemical engineering, organic chemistry and drug synthesis, and have higher economic benefit.
Wherein: the calculation method of the resorcinol conversion rate and the product selectivity comprises the following steps:
the resorcinol is taken as a reference substance, and is calculated by a normalization method, which comprises the following steps:
C＝(f1A1+f2A2+f3A3+f4A4++f5A5)/(f1A1+f2A2+f3A3+f4A4++f5A5+A)
Sn＝fnAn/(f1A1+f2A2+f3A3+f4A4++f5A5)
Yn＝C×Sn；
wherein, C: conversion of Resorcinol
Sn: product n selectivity
Yn: yield of product n
f1: correction factor for m-hydroxyanisole
f2: correction factor for m-dimethoxy benzene
f3: 2-methylresorcinol correction factor
f4: 4-methylresorcinol correction factor
f5: other by-product correction factors
A1: peak area of m-hydroxyanisole
A2: area of m-dimethoxy benzene peak
A3: 2-MethylResorcinol Peak area
A4: 4-MethylResorcinol Peak area
A5: total area of other by-product peaks
A: resorcinol peak area.
Example 2
In the embodiment, resorcinol and methanol are mixed according to the mass ratio of 1:1 to prepare a reaction solution, a magnesium phosphate catalyst is placed in a fixed bed reactor, then the fixed bed reactor is heated to 230 ℃ under the argon atmosphere, the reaction solution is fed into the fixed bed reactor by an advection pump according to the flow rate of 1mL of the reaction solution passing through each gram of the magnesium phosphate catalyst per hour, so that the resorcinol and the methanol are subjected to alkylation reaction under the action of the magnesium phosphate catalyst, and the product is collected after the reaction is finished. In this example, the conversion of the reactant resorcinol was 58%, the selectivity to 2-methylresorcinol was 33%, the selectivity to 4-methylresorcinol was 23%, the combined selectivity was 56%, the selectivity to the by-product m-hydroxyanisole was 32%, the selectivity to the m-xylylene ether was 4%, and the other by-products were about 8%. The 2-methyl resorcinol, the 4-methyl resorcinol and the byproduct m-hydroxyanisole obtained by the reaction are important intermediates for fine chemical engineering, organic chemistry and drug synthesis, and have higher economic benefit.
Example 3
The difference from example 2 is that the reaction temperature is 350 ℃. The test shows that the conversion rate of the reactant resorcinol is 86%, the selectivity of 2-methyl resorcinol is 24%, the selectivity of 4-methyl resorcinol is 18%, the combined selectivity of the two is 42%, the selectivity of the byproduct m-hydroxyanisole is 40%, the selectivity of the m-anisole is 8%, and the selectivity of other byproducts is about 10%.
Example 4
The difference from example 2 is that the catalyst is a lanthanum phosphate catalyst. The conversion of the reactant resorcinol was tested to be 68%, the selectivity to 2-methylresorcinol was 34%, the selectivity to 4-methylresorcinol was 39%, the combined selectivity was 73%, the selectivity to the by-product m-hydroxyanisole was 20%, the selectivity to m-xylylene ether was 2%, and the other by-products were about 5%.
Example 5
The difference from example 2 is that 0.1mL of the reaction solution was passed per gram of the magnesium phosphate catalyst per hour. The conversion of the reactant resorcinol was found to be 87%, the selectivity to 2-methylresorcinol was found to be 21%, the selectivity to 4-methylresorcinol was found to be 23%, the combined selectivity was found to be 44%, the selectivity to the by-product m-hydroxyanisole was found to be 37%, the selectivity to m-xylylene ether was found to be 9%, and the other by-products were found to be about 10%.
Example 6
The difference from example 2 is that the mass ratio of resorcinol to methanol is 0.2: 1. the conversion of the reactant resorcinol was 69%, the selectivity to 2-methylresorcinol was 28%, the selectivity to 4-methylresorcinol was 21%, the combined selectivity was 49%, the selectivity to the by-product m-hydroxyanisole was 40%, the selectivity to m-xylylene ether was 5%, and the other by-products were about 6%.
Example 7
The difference from the example 2 is that the mass ratio of the resorcinol to the methanol is 2: 1. the test shows that the conversion rate of the reactant resorcinol is 46%, the selectivity of 2-methyl resorcinol is 38%, the selectivity of 4-methyl resorcinol is 40%, the combined selectivity of the two is 78%, the selectivity of the byproduct m-hydroxyanisole is 13%, the selectivity of m-anisole is 5%, and the selectivity of other byproducts is about 4%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A method for simultaneously preparing 2-methylresorcinol and 4-methylresorcinol, comprising the steps of:
the resorcinol and the methanol are subjected to alkylation reaction by a metal phosphate stationary phase catalyst to obtain 2-methyl resorcinol and 4-methyl resorcinol.
2. The method of claim 1, wherein the metal phosphate is one or more of aluminum phosphate, lanthanum phosphate, zirconium phosphate, cerium phosphate, zinc phosphate, calcium phosphate, magnesium phosphate, and chromium phosphate.
3. The method according to claim 1, wherein the mass ratio of the resorcinol to the methanol is (0.2-2.0): 1.
4. the method according to claim 1, wherein the mass ratio of the resorcinol to the methanol is (0.25-1.5): 1.
5. the method according to claim 1, wherein the total velocity of the resorcinol and the methanol passing through the stationary phase catalyst is 0.1-2.0 mL/(g-h).
6. The method according to claim 1 or 5, wherein the temperature of the alkylation reaction is 200 to 400 ℃.
7. The process of claim 1, wherein the alkylation reaction is carried out under an inert atmosphere.
8. The method of claim 1, wherein after the alkylation reaction, further comprising separating the resulting 2-methylresorcinol and 4-methylresorcinol, wherein the separating comprises:
and distilling, rectifying and fractionating the alkylation reaction solution to respectively obtain 2-methyl resorcinol and 4-methyl resorcinol.
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