CN112479878A - Method for preparing 6, 8-dichloro ethyl caprylate - Google Patents
Method for preparing 6, 8-dichloro ethyl caprylate Download PDFInfo
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/307—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/317—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
- C07C67/327—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups by elimination of functional groups containing oxygen only in singly bound form
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Abstract
The invention provides a method for preparing 6, 8-dichloro ethyl caprylate. As shown in the following reaction formula, the method comprises the following reactions: oxidizing and esterifying the compound 1 to obtain a compound 2, dehydrating to generate a compound 3, and performing Prins condensation reaction to obtain a compound4, then hydrolyzing and hydrogenating to obtain a compound 5, and finally chlorinating to obtain the 6, 8-dichloro ethyl caprylate. The method has the characteristics of easily obtained raw materials, simple process, high efficiency and environmental protection.
Description
Technical Field
The invention relates to the field of chemical synthesis, and particularly relates to a method for synthesizing 6, 8-dichloro ethyl caprylate.
Background
The lipoic acid belongs to a class of compounds in B vitamins, plays a role of coenzyme in a multienzyme system, is an antioxidant, has better antioxidant effect than vitamins, and can eliminate free radicals for accelerating aging and causing diseases; can improve insulin function and heart rate variability of diabetic; treating hepatitis C; protecting kidney and pancreas; preventing cataract; inhibiting HIV proliferation. Ethyl 6, 8-dichlorooctanoate is an important organic intermediate for synthesizing lipoic acid. At present, methods for synthesizing 6, 8-dichloro ethyl octanoate mainly comprise an adipic acid route, a cyclohexanone route and the like. Xi Lu Ming et al introduced the synthesis of 6, 8-dichloro methyl octanoate by methyl esterification, chlorination, ethylene addition, reduction chlorination of adipic acid (as shown in the following reaction scheme), which resulted in a large amount of solid waste and liquid waste, and the formation of polymer and difficult separation.
In another route, cyclohexanone and vinyl ethyl ether are used as raw materials, and CN 107673972 discloses a method for synthesizing ethyl 6, 8-dichlorooctanoate by using cyclohexanone and vinyl ethyl ether as raw materials (as shown in the following reaction formula). The starting material of the route is easy to obtain, and the route is a synthesis route with industrial potential, but the number of byproducts is relatively large.
In conclusion, the existing method for preparing the ethyl 6, 8-dichlorooctoate has the disadvantages of harsh reaction conditions, long steps, low yield and environmental pollution caused by a large amount of waste water generated in the reaction process.
Disclosure of Invention
The invention aims to provide a method for preparing 6, 8-dichloro ethyl caprylate, which has the characteristics of easily obtained raw materials, simple process, high efficiency and environmental protection.
According to one aspect of the present invention, there is provided a process for the preparation of ethyl 6, 8-dichlorooctanoate, said process comprising the steps of:
as shown in the reaction formula, a compound 1 is subjected to oxidation esterification to obtain a compound 2, then the compound 2 is dehydrated to generate a compound 3, then the compound 4 is subjected to Prins condensation reaction to obtain a compound 5, and finally the compound 5 is subjected to hydrolysis hydrogenation to obtain 6, 8-dichloro ethyl caprylate.
In a specific embodiment, the method comprises the steps of:
1) adding the compound 1, a catalyst 1, an oxidant, ethanol and a water-carrying agent into a reaction kettle for reaction, continuously evaporating the water-carrying agent and water, finishing the reaction when no water is generated, and distilling the product to obtain a compound 2;
2) introducing the compound 2 into a fixed bed reactor filled with the catalyst 2, heating to the reaction temperature in a nitrogen atmosphere, introducing reactants into the reactor by using a plunger pump for reaction, and distilling and purifying the product to obtain a compound 3;
3) adding a compound 3, a solvent, a formaldehyde source and a catalyst 3 into a reaction kettle for reaction, and distilling and refining a product to obtain a compound 4;
4) adding a compound 4, water and a catalyst 4 into a reaction kettle, reacting in a hydrogen atmosphere, and distilling a product to obtain a compound 5;
5) adding the compound 5 into a flask, purging a reaction system with nitrogen, adding a chlorinating agent into the flask, heating for reflux reaction, and distilling to obtain the 6, 8-dichloro ethyl caprylate.
In a specific embodiment, in step 1), the catalyst 1 is a supported metal catalyst, the supported metal catalyst comprises a metal active component and a carrier, the metal active component comprises one or more of Pd, Pt, Ru, Rh, Ir, Ni and Cu, and the carrier comprises one or more of activated carbon, alumina, silica, titania, niobium pentoxide, sulfated zirconia, zirconia and a molecular sieve; alternatively, the catalyst may be one or more of activated carbon, alumina, silica, titania, niobium pentoxide, sulfated zirconia, molecular sieves, sulfonated macroporous resins, Amberlyst-15 or Amberlyst-35.
In a specific embodiment, in step 1), the mass ratio of the catalyst 1 to the compound 1 is 1:20 to 20000, preferably 1: 500-1000.
In a specific embodiment, in step 1), the water-carrying agent is selected from any one or a combination of two or more of benzene, toluene, xylene, chloroform and dichloroethane.
In a specific embodiment, in step 1), the oxidant is selected from any one or a combination of two or more of air, oxygen, hydrogen peroxide, peroxyorganic acid, m-chloroperoxybenzoic acid, dichloroisocyanuric acid and sodium hypochlorite.
In a particular embodiment, in step 1), the molar ratio between compound 1 and ethanol is from 1:1 to 1: 10.
In a particular embodiment, in step 1), the reaction temperature is between 50 and 250 ℃, preferably between 90 and 100 ℃.
In a particular embodiment, in step 2), the catalyst 2 comprises one or more of gamma-alumina, silica, niobium pentoxide, sulfonated activated carbon, molecular sieves, zirconia.
In a specific embodiment, in step 2), the reaction temperature is 250-600 ℃.
In a specific embodiment, in step 2), the space velocity of the reactant feeding is 0.01-6h-1Preferably 0.02-4h-1。
In a specific embodiment, in step 3), the catalyst 3 comprises ion exchange resin, sulfonated macroporous resin, Nafion, activated carbon, carbon nanotubes, γ -Al2O3、SiO2、ZrO2、WO3、Nb2O5Zeolites, etcOne or more of the sub-sieves, the ion exchange resin may be Amberlyst-15, Amberlyst-35.
In a specific embodiment, in step 3), the mass ratio of the catalyst 3 and the compound 3 is 1:30-200
In a specific embodiment, in step 3), the solvent comprises any one of water, methanol, ethanol, tetrahydrofuran, 1, 4-dioxane, and acetonitrile.
In a particular embodiment, in step 3), the formaldehyde source comprises aqueous formaldehyde or paraformaldehyde.
In a specific embodiment, in step 3), the reaction temperature is 60-200 ℃, preferably 100-150 ℃.
In a particular embodiment, in step 3), the reaction time is between 30 minutes and 60 hours, preferably between 10 and 20 hours.
In a specific embodiment, in step 4), the catalyst 4 is a supported metal catalyst, the supported metal catalyst comprises a metal active component and a carrier, and the metal active component comprises one or more of Pd, Pt, Ru, Rh, Ir, Ni and Cu; the carrier comprises one or more of activated carbon, alumina, silica, titanium oxide and molecular sieve.
In a specific embodiment, in step 4), the mass ratio of catalyst 4 and compound 4 is 1:20 to 200.
In a particular embodiment, in step 4), the mass ratio of compound 4 to water is from 1:0.1 to 1: 1.
In a specific embodiment, in step 4), the reaction temperature is 60-200 ℃, preferably 100-150 ℃.
In a particular embodiment, in step 4), the reaction pressure is between 0.3 and 6 MPa.
In a particular embodiment, in step 5), the chlorinating agent comprises HCl, aqueous HCl, PCl3、PCl5、SOCl2、CHCl3、ZnCl2Or CCl4One or more of (a).
In a particular embodiment, in step 5), the reaction temperature is between 50 and 250 ℃.
In a particular embodiment, in step 5), the reaction time is between 30 minutes and 60 hours, preferably between 2 and 3 hours.
The invention has the advantages of
The invention takes 7-hydroxyheptanal as raw material, and adopts a simple, easy and efficient method to synthesize 6, 8-dichloro ethyl caprylate. The method obtains the 6, 8-dichloro ethyl caprylate through the steps of oxidation, esterification, dehydration, Prins condensation, hydrolysis and chlorination, in the process, a catalytic reaction method is mostly adopted, the atom utilization rate is high, and less organic chemical reagents are adopted, so that the wastewater pollution is greatly reduced, the process route is clean (only a small amount of wastewater is discharged in the last chlorination step), and compared with the traditional method reported at present, the initial raw materials are cheap and easy to obtain, the final product quality yield exceeds 55% (the prior art reports that the yield is less than 30%), the cost advantage is achieved, and the industrial amplification is easy.
Detailed Description
The present invention is described in detail below by way of specific examples, which, however, are not intended to limit the scope of the present application.
In this application, the use of the terms "catalyst 1", "catalyst 2", "catalyst 3" … …, etc. are used only to distinguish one catalyst from another, and have no other meaning.
In the following examples 1-3, the product ethyl 6, 8-dichlorooctanoate was prepared by the following reaction scheme:
example 1
Step 1: adding 104g of the compound 1 into a reaction kettle, adding 100g of absolute ethyl alcohol, 0.1g of Pd/HZSM-5 catalyst and 100ml of toluene, continuously introducing air into the system, heating to 90 ℃, continuously evaporating the toluene and water, continuously adding the toluene into the system again until no water is evaporated, cooling, distilling the product under reduced pressure to obtain 118g of a compound 2(2.5mmHg, 101-104 ℃), wherein the molar yield of the compound 2 is 85%.
Step 2: adding 5g of gamma-alumina into the fixed bed, taking nitrogen as carrier gas, heating to 350 ℃, and reacting the compound 2 for 0.02h-1Pumping the product into a fixed bed layer, and collecting the product after condensation and gas-liquid separation. The product was distilled under reduced pressure to give 79g of Compound 3(30mmHg, 69-71 ℃ C.), in a molar yield of 75% of Compound 3.
And step 3: 79g of Compound 3, 35g of paraformaldehyde, 100ml of methanol and 1.0g of Amberlyst-15 resin were charged into a reaction vessel and reacted at 100 ℃ for 10 hours. After completion of the reaction, filtration was carried out, and distillation under reduced pressure was continued after evaporation of methanol to obtain 91g of Compound 4(0.5mmHg, 121 ℃ C.), the molar yield of Compound 4 being 83%.
And 4, step 4: 91g of compound 4, 20g of water and 1g of Pt/gamma-Al are added to the reaction kettle2O3Catalyst, sealing the reactor and then using N2And (3) maintaining the pressure for 3MPa after 5 times of replacement to ensure that the pressure of the reaction kettle is released after no gas leakage, filling 5MPa hydrogen, heating to 100 ℃ for reaction, supplementing the hydrogen in the reaction process until the pressure is unchanged, cooling, distilling after pressure release to obtain 69g of compound 5(2mmHg, 149-154 ℃), wherein the molar yield of the compound 5 is 81%.
And 5: 85ml of thionyl chloride was added to the flask, stirred, and 69g of Compound 5 was slowly dropped thereinto over about 2 hours, and the gas generated during the dropping was absorbed with an alkali. After the dropwise addition, the mixture was heated to 80 ℃ for reflux for 2 hours, and 70g of ethyl 6, 8-dichlorooctanoate (2mmHg, 124-.
Example 2
Step 1: 106g of Compound 1, 100g of ethanol, 0.1g of Pt/Nb2O5Catalyst and 100ml toluene, continuously introducing air into the system, heating to 100 ℃, at the moment, evaporating toluene and water, continuously adding toluene into the system again until no water is evaporated, cooling, distilling the product to obtain 114g of compound 2(2.5mmHg, 101-.
Step 2: adding 5g H-ZSM-5 into the fixed bed, taking nitrogen as carrier gas, heating to 400 ℃, and reacting the compound 2 for 0.02h-1Is empty ofPumping into fixed bed layer, condensing and gas-liquid separating to obtain product, and collecting. The product was distilled to give 73g of Compound 3(30mmHg, 69-71 deg.C), the compound 3 in 71% molar yield.
And step 3: 73g of compound 3, 40g of paraformaldehyde, 100ml of methanol and 1.0g H-ZSM-5 are added into a reaction kettle and reacted for 10 hours at 100 ℃. After completion of the reaction, the reaction mixture was filtered, methanol was distilled off, and the reaction mixture was distilled under reduced pressure to obtain 83g of Compound 4(0.5mmHg, 121 ℃ C.), in which the molar yield of Compound 4 was 82%.
And 4, step 4: 83g of compound 4, 20g of water and 1g of Ni/gamma-Al are added into a reaction kettle2O3Catalyst, sealing the reactor and then using N2And (3) maintaining the pressure for 3MPa after 5 times of replacement to ensure that the pressure of the reaction kettle is released after no gas leakage, filling 5MPa hydrogen, heating to 100 ℃ for reaction, supplementing the hydrogen in the reaction process until the pressure is unchanged, cooling, distilling after pressure release to obtain 65g of a compound 5(2mmHg, 149-154 ℃), wherein the molar yield of the compound 5 is 83%.
And 5: a flask was charged with 65g of Compound 5, 25g of Zinc chloride and 160ml of concentrated hydrochloric acid, heated to 100 ℃ and refluxed for 3 hours, cooled, and the organic layer was separated. The organic phase was washed with saturated brine, dried over anhydrous calcium chloride and distilled to give 61g of ethyl 6, 8-dichlorooctanoate (2mmHg, 124-.
Example 3
Step 1: 100g of the compound 1, 100g of ethanol and 0.1g of Pt/gamma-A are added into a reaction kettle2O3Catalyst and 100ml toluene, continuously introducing air into the system, heating to 100 ℃, at the moment, distilling out toluene and water, continuously adding toluene into the system again until no water is distilled out, cooling, distilling the product to obtain 115g of compound 2(2.5mmHg, 101-.
Step 2: 5g of gamma-Al are added to the fixed bed2O3Heating to 400 deg.C with nitrogen as carrier gas, and reacting for 0.02h-1Pumping the product into a fixed bed layer, and collecting the product after condensation and gas-liquid separation. The product was distilled to give 75g of Compound 3(30mmHg, 69-71 ℃ C.), in 73% molar yield of Compound 3.
And step 3: 75g of Compound 3, 40g of paraformaldehyde, 100ml of methanol and 1.0g of Amberlyst-15 were charged into a reaction vessel and reacted at 100 ℃ for 10 hours. After completion of the reaction, the reaction mixture was filtered, methanol was distilled off, and the distillation under reduced pressure was carried out to obtain 90g of Compound 4(0.5mmHg, 121 ℃ C.), whereby the molar yield of Compound 4 was 87%.
And 4, step 4: 90g of compound 4, 20g of water and 1g of Pd/gamma-Al are added into a reaction kettle2O3Sealing the kettle and then using N2And (3) maintaining the pressure for 3MPa after 5 times of replacement to ensure that the pressure of the reaction kettle is released after no gas leakage, filling 5MPa hydrogen, heating to 100 ℃ for reaction, supplementing the hydrogen in the reaction process until the pressure is unchanged, cooling, distilling after pressure release to obtain 77g of a compound 5(2mmHg, 149-154 ℃), wherein the molar yield of the compound 5 is 89%.
And 5: 85ml of thionyl chloride was added to the flask, stirred, and 77g of Compound 5 was slowly dropped thereinto over about 2 hours, and the gas generated during the dropping was absorbed with an alkali. After the end of the dropwise addition, the mixture was heated to 80 ℃ and refluxed for 2 hours, and 78g of ethyl 6, 8-dichlorooctanoate (2mmHg, 124-.
Claims (10)
1. A process for preparing ethyl 6, 8-dichlorooctanoate comprising:
according to the reaction formula, the compound 1 is oxidized and esterified to obtain a compound 2, then dehydrated to generate a compound 3, then subjected to Prins condensation reaction to obtain a compound 4, then subjected to hydrolysis and hydrogenation to obtain a compound 5, and finally chlorinated to obtain the 6, 8-dichloro ethyl caprylate.
2. The method according to claim 1, comprising the steps of:
1) adding the compound 1, a catalyst 1, an oxidant, ethanol and a water-carrying agent into a reaction kettle for reaction, evaporating the water-carrying agent and water, finishing the reaction when no water is generated, and distilling the product to obtain a compound 2;
2) introducing the compound 2 into a fixed bed reactor filled with the catalyst 2, heating to the reaction temperature in a nitrogen atmosphere, introducing reactants into the reactor by using a plunger pump for reaction, and distilling and purifying the product to obtain a compound 3;
3) adding a compound 3, a solvent, a formaldehyde source and a catalyst 3 into a reaction kettle for reaction, and distilling and refining a product to obtain a compound 4;
4) adding a compound 4, water and a catalyst 4 into a reaction kettle, reacting in a hydrogen atmosphere, and distilling a product to obtain a compound 5; and
5) adding a compound 5 into a flask, purging a reaction system by nitrogen, adding a chlorinating agent into the flask, heating for reflux reaction, distilling to obtain 6, 8-dichloro ethyl caprylate,
the catalyst 1 is a supported metal catalyst, the supported metal catalyst comprises a metal active component and a carrier, the metal active component comprises one or more of Pd, Pt, Ru, Rh, Ir, Ni and Cu, and the carrier comprises one or more of active carbon, alumina, silica, titanium oxide, niobium pentoxide, sulfated zirconia, zirconia and a molecular sieve; or the catalyst is one or more of activated carbon, alumina, silicon oxide, titanium oxide, niobium pentoxide, sulfated zirconia, a molecular sieve, sulfonated macroporous resin, Amberlyst-15 or Amberlyst-35;
the catalyst 2 comprises one or more of gamma-alumina, silicon dioxide, niobium pentoxide, sulfonated activated carbon, molecular sieve and zirconia;
the catalyst 3 comprises one or more of ion exchange resin, sulfonated macroporous resin, Nafion, activated carbon, carbon nano tubes, gamma-Al 2O3, SiO2, ZrO2, WO3, Nb2O5 and zeolite molecular sieves; and
the catalyst 4 is a supported metal catalyst, the supported metal catalyst comprises a metal active component and a carrier, and the metal active component comprises one or more of Pd, Pt, Ru, Rh, Ir, Ni and Cu; the carrier comprises one or more of activated carbon, alumina, silica, titanium oxide and molecular sieve.
3. The method of claim 2, wherein the first and second light sources are selected from the group consisting of,
wherein, in the step 1),
the mass ratio of the catalyst 1 to the compound 1 is 1: 20-20000;
the water-carrying agent is selected from any one or the combination of more than two of benzene, toluene, xylene, chloroform and dichloroethane;
the oxidant is selected from one or the combination of more than two of air, oxygen, hydrogen peroxide, peroxy organic acid, m-chloroperoxybenzoic acid, dichloroisocyanuric acid and sodium hypochlorite;
the molar ratio of the compound 1 to the ethanol is 1:1-1: 10.
4. The method of claim 2, wherein the first and second light sources are selected from the group consisting of,
wherein, in the step 3),
the mass ratio of the catalyst 3 to the compound 3 is 1: 30-200;
the solvent comprises any one of water, methanol, ethanol, tetrahydrofuran, 1, 4-dioxane and acetonitrile;
the formaldehyde source comprises aqueous formaldehyde or paraformaldehyde.
5. The method of claim 2, wherein the first and second light sources are selected from the group consisting of,
wherein, in the step 4),
the mass ratio of the catalyst 4 to the compound 4 is 1: 20-200; the mass ratio of the compound 4 to water is 1:0.1-1: 1.
6. The method of claim 2, wherein the first and second light sources are selected from the group consisting of,
wherein, in the step 5), the chlorinating agent comprises HCl, HCl aqueous solution and PCl3、PCl5、SOCl2、CHCl3、ZnCl2Or CCl4One or more of (a).
7. The method of claim 2, wherein the first and second light sources are selected from the group consisting of,
wherein the reaction temperature of the step 1) is 50-250 ℃;
the reaction temperature of the step 2) is 250-600 ℃, and the space velocity of the reactant feeding is 0.01-6h-1；
The reaction temperature of the step 3) is 60-200 ℃, and the reaction time is 30 minutes-60 hours;
the reaction temperature of the step 4) is 60-200 ℃, and the reaction pressure is 0.3-6 MPa;
the reaction temperature of the step 5) is 50-250 ℃, and the reaction time is 30 minutes-60 hours.
8. The method of claim 2, wherein the first and second light sources are selected from the group consisting of,
wherein the reaction temperature of the step 1) is 90-100 ℃; the reaction temperature of the step 3) is 100-150 ℃; the reaction temperature in the step 4) is 100-150 ℃.
9. The method of claim 2, wherein the first and second light sources are selected from the group consisting of,
wherein the reaction time of the step 3) is 10-20 hours; the reaction time of step 5) is 2-3 hours.
10. The method of claim 2, wherein the first and second light sources are selected from the group consisting of,
wherein, in the step 1), the mass ratio of the catalyst 1 to the compound 1 is 1: 500-1000;
in the step 2), the space velocity of the reactant feeding is 0.02-4h-1。
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| CN113185494A (en) * | 2021-05-17 | 2021-07-30 | 苏州富士莱医药股份有限公司 | Preparation method of R-lipoic acid |
| CN113429386A (en) * | 2021-07-09 | 2021-09-24 | 苏州富士莱医药股份有限公司 | Synthetic method of R-lipoic acid |
| CN113773182A (en) * | 2021-09-10 | 2021-12-10 | 风火轮(上海)生物科技有限公司 | Method for synthesizing 6, 8-dichloro caprylic acid ester |
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