CN1850819A - Method for preparing dihydro safrole - Google Patents
Method for preparing dihydro safrole Download PDFInfo
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- CN1850819A CN1850819A CN 200610035587 CN200610035587A CN1850819A CN 1850819 A CN1850819 A CN 1850819A CN 200610035587 CN200610035587 CN 200610035587 CN 200610035587 A CN200610035587 A CN 200610035587A CN 1850819 A CN1850819 A CN 1850819A
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- pyrocatechol
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Abstract
This invention relates to dihydro safrole preparation method. Catechol is used as material, goal product if got through propionyltion, reducing and methylenation three steps reaction. The technique condition is mild, generating cost is low, product whole yield is high, purity is high, so it is good preparation method that has wide industrial prospect.
Description
Technical field
The present invention relates to a kind of preparation method of dihydrosafrole.
Background technology
Dihydrosafrole is a kind of important chemical intermediate, is widely used in the building-up process of medicine, agricultural chemicals and spices, especially prepares the important source material of highly effective pesticide synergistic agent piperonyl butoxide.Its structural formula is as follows:
For a long time, dihydrosafrole mainly adopts the safrole shortening that extracts with natural sassafras wood oil to make.But in recent years, rising along with the safrole consumption, national governments are more and more tighter to the requirement of environmental regulation in addition, this is that the sassafras wood oil of raw material production is faced with global resource exhaustion with the sassafras root, cause the price of dihydrosafrole on the world market sharply soaring, seriously restricting the production based on a series of derived product of this raw material, therefore, the route of developing a feasible industrialization sassafras artificial KH is a very significant job.For this reason, the chemist of various countries has been done many explorations and research on the one hand at this, more existing bibliographical informations the method for sassafras artificial KH, comparatively typically have following several:
(1) US6342613; CN1138769; disclosing a kind of is raw material with the pyrocatechol; with methylene dichloride; Anhydrous potassium carbonate reacts in polar solvent and obtains methylenedioxybenzene, and products therefrom generates 5-propionyl benzo (1,3)-dioxole with the propionic anhydride reaction under catalyst action then; at last with products therefrom through catalytic hydrogenation reaction, obtain target product.
(2) US6252092 discloses another kind of synthetic method, and this method is a raw material with the 4-hydroxypropiophenonepreparation, obtains target product through five step principal reactions such as catalytic hydrogenation, acetic acid esterification, rearrangement, hydrolysis, methylenation.
Wherein method (1) exists the one way reaction conversion ratio low, the shortcoming that the industrialization cost is high, and method (2) reactions steps is many, it is low to reset yield, is not easy to heavy industrialization.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of new dihydrosafrole, this method can improve product yield and reduce production costs, and is easy to industrialization.
The preparation method of dihydrosafrole provided by the invention is three-step approach, comprising: (1) is raw material with the pyrocatechol, and any propionyl reagent with in propionic anhydride, propionyl chloride and the propionic acid carries out the propionyl reaction, makes 3, the 4-dihydroxyphenyl-1-propanone; (2) then with 3,4-dihydroxyphenyl-1-propanone catalytic hydrogenation generates 4-propyl group pyrocatechol;
(3) at last with 4-propyl group pyrocatechol and saturated dihalide hydrocarbon reaction, obtain dihydrosafrole.
Above-mentioned reaction process is as follows:
(1) propionyl reaction: with the pyrocatechol is raw material, with propionic anhydride, propionyl chloride or propionic acid in inert solvent under catalyst action, carry out the propionyl reaction, obtain 3, the 4-dihydroxyphenyl-1-propanone, reaction formula is:
R representative following group :-Cl in the formula (I) ,-OCOCH
2CH
3,-OH
The processing condition of reaction are: temperature of reaction is 0～70 ℃, is preferably 5～20 ℃, and the reaction times is 5～30 hours, is preferably 10～20 hours; Solvent is any in ethylene dichloride, tetrachloroethane, hexanaphthene, the dithiocarbonic anhydride; Catalyzer is AlCl
3, ZnCl
2, SnCl
2, SnCl
4, FeCl
2, FeCl
3, FeSO
4, Fe
2(SO
4)
3, H
3PO
4, HClO
4, BF
3In any; The mole proportioning of pyrocatechol and propionic anhydride, propionyl chloride or propionic acid is 1: 0.5～3; With the mole proportioning of solvent be 1: 3～10; The mole proportioning of pyrocatechol and catalyzer is 1: 0.01～1.25.After reaction finished, by extraction, washing, layering, then with the organic phase fractionation, and recrystallization obtained resultant 3,4-dihydroxyphenyl-1-propanone.
(2) reduction reaction: with 3 of gained, the 4-dihydroxyphenyl-1-propanone is hydrogenation reaction under catalyst action, generates 4-propyl group pyrocatechol, and reaction formula is:
The processing condition of reaction are: temperature of reaction is 20～100 ℃, is preferably 40～50 ℃, and the reaction times is 5～20 hours, is preferably 5～8 hours; Reaction pressure is 4～60 normal atmosphere, is preferably 10～15 normal atmosphere; Solvent for use is an alcohols, as: a kind of in methyl alcohol, ethanol, Virahol, the butanols, 3, the mole proportioning of 4-dihydroxyphenyl-1-propanone and solvent is 1: 5～15; Catalyzer is Pd, Pt, Ru or it is loaded on the inert base, as Pd/C, Pt/C, Ru/C, Pd/Al
2O
3And Pd/BaSO
4In a kind of, 3, the mole proportioning of 4-dihydroxyphenyl-1-propanone and catalyzer is 1: 0.001～0.005.After reaction finishes, the cooling suction filtration, filtrate negative pressure precipitation gets 4-propyl group pyrocatechol.
(3) methylenation reaction: will go up step gained 4-propyl group pyrocatechol and alkylene dihalide and in dipolar aprotic solvent, under the mineral alkali effect, react, and obtain the target product dihydrosafrole.Reaction formula is:
X represents halogen in the formula (II), as :-F ,-Cl ,-Br ,-I.
The processing condition of reaction are: temperature of reaction is 50～130 ℃, is preferably 110～130 ℃, in 4～10 hours reaction times, is preferably 5～6 hours; Used alkylene dihalide is a kind of in methylene fluoride, methylene dichloride, methylene bromide, the methylene iodide; Mineral alkali is NaOH, KOH, Na
2CO
3, K
2CO
3In a kind of; Solvent is N, a kind of in dinethylformamide, N,N-dimethylacetamide, the methyl-sulphoxide; The mole proportioning of 4-propyl group pyrocatechol and alkylene dihalide, mineral alkali is 1: 1～3: 2～3; The mole proportioning of 4-propyl group pyrocatechol and solvent is 1: 6～20.Reaction by extraction, washing, layering, gets target product with the organic phase fractionation after finishing then, is a kind of weak yellow liquid compound.
Operational path of the present invention is reasonable, and the processing condition gentleness is feasible, and production cost is low, the total yield of products height, and the purity height is a kind of method with wide prospects for commercial application.
The present invention is further illustrated below by following non-limiting example.
Embodiment
Embodiment 1
(1) has condensing reflux, in the reactor of agitation and dropping and heating unit, adding the 111.3g pyrocatechol, 500ml ethylene dichloride, 166g ZnCl
2, stir, be cooled to 0～5 ℃, slowly be added dropwise to the 140g propionyl chloride, dripped off in about 2 hours, and be warming up to 20 ℃ then, continue reaction 15 hours, reacted, thin up is isolated organic phase, organic phase is carried out pickling and washing, dried over sodium sulfate, precipitation successively, the residuum ethyl alcohol recrystallization gets solid 3,4-dihydroxyphenyl-1-propanone 144g, fusing point: 145～146 ℃, content is 98%, yield 85%.
(2) will go up step gained solid 3,4-dihydroxyphenyl-1-propanone 85g is dissolved in the 300ml ethanol, and adds the Pd/C catalyzer of 2g5%, then this mixture is placed autoclave, and under the pressure of 10atm in 40～45 ℃ of hydrogenations, logical hydrogen is after about 6 hours, reaction finishes, this mixture is filtered filtrate decompression precipitation, residuum ethyl alcohol recrystallization, get solid 4-propyl group pyrocatechol 75g, fusing point: 59～60 ℃, content is 98%, yield 97%.
(3) will go up step gained solid 4-propyl group pyrocatechol 31g and be dissolved in 45mlN, and in dinethylformamide and the 5ml methylene dichloride, then above-mentioned mixed solution slowly will be added dropwise to 34g K is housed in advance
2CO
3, 155mlN in the mixing solutions of dinethylformamide and 25ml methylene dichloride, keeps 110～115 ℃ of temperature of reaction, dripped off in about 2 hours, and be warming up to 120～125 ℃ then and continue reaction 3 hours, reaction finishes, be cooled to 20 ℃, filter, decompression removes solvent, residuum adds 50ml water, hexanaphthene 100ml extraction, washing, the organic phase anhydrous sodium sulfate drying, the decompression precipitation is collected 100～105 ℃/665Pa fraction, get pale yellow oily liquid body 30g, content is 98.2%, yield 90.1%.
Embodiment 2
(1) has condensing reflux, in the reactor of agitation and dropping and heating unit, adding the 111.3g pyrocatechol, the 240ml ethylene dichloride, the perchloric acid of 2ml70% stirs, be cooled to 10～15 ℃, slowly be added dropwise to the 144g propionic anhydride, dripped off in about 2 hours, be warming up to 20 ℃ then, continue reaction 15 hours, reacted thin up, isolate organic phase, organic phase is carried out pickling and washing, dried over sodium sulfate, precipitation successively, the residuum ethyl alcohol recrystallization, get solid 3,4-dihydroxyphenyl-1-propanone 136.5g, fusing point: 145～146 ℃, content is 98.1%, yield 80.5%.
(2) will go up step gained solid 3,4-dihydroxyphenyl-1-propanone 85g is dissolved in the 900ml ethanol, and adds the Pd/C catalyzer of 5g5%, then this mixture is placed autoclave, and under the pressure of 10atm in 20～25 ℃ of hydrogenations, logical hydrogen is after about 7 hours, reaction finishes, this mixture is filtered filtrate decompression precipitation, residuum ethyl alcohol recrystallization, get solid 4-propyl group pyrocatechol 69g, fusing point: 59～60 ℃, content is 98%, yield 89%.
(3) will go up step gained solid 4-propyl group pyrocatechol 31g is dissolved in 45ml methyl-sulphoxide and the 5ml methylene dichloride, then above-mentioned mixed solution slowly is added dropwise to 21g NaOH is housed in advance, in the mixing solutions of 155ml methyl-sulphoxide and 8ml methylene dichloride, keep 110～115 ℃ of temperature of reaction, dripped off in about 2 hours, be warming up to 120～125 ℃ then and continue reaction 3 hours, reaction finishes, and is cooled to 20 ℃, filters, decompression removes solvent, residuum adds 50ml water, hexanaphthene 100ml extraction, washing, the organic phase anhydrous sodium sulfate drying, the decompression precipitation is collected 100～105 ℃/665Pa fraction, gets pale yellow oily liquid body 28.9g, content is 97.5%, yield 85.8%.
Embodiment 3
(1) has condensing reflux, in the reactor of agitation and dropping and heating unit, adding the 111.3g pyrocatechol, 240ml ethylene dichloride, 170g AlCl
3, stir, be cooled to 0～5 ℃, slowly be added dropwise to the 280g propionyl chloride, dripped off in about 2 hours, be warming up to 70 ℃ then, continue reaction 15 hours, reacted, aftertreatment is with embodiment 1 step (1), get solid 3,4-dihydroxyphenyl-1-propanone 104g, content are 97%, yield 61%.
(2) will go up step gained solid 3,4-dihydroxyphenyl-1-propanone 85g is dissolved in the 600ml ethanol, and add the Pd/C catalyzer of 2g5%, then this mixture is placed autoclave, and under the pressure of 60atm in 40～45 ℃ of hydrogenations, logical hydrogen is after about 6 hours, reaction finishes, and aftertreatment gets solid 4-propyl group pyrocatechol 70g with embodiment 1 step (2), content is 98%, yield 91%.
(3) will go up step gained solid 4-propyl group pyrocatechol 31g and be dissolved in 25mlN, and in dinethylformamide and the 5ml methylene dichloride, then above-mentioned mixed solution slowly will be added dropwise to 29g KOH is housed in advance, 75mlN, in the mixing solutions of dinethylformamide and 35ml methylene dichloride, keep 50 ℃ of temperature of reaction, dripped off in about 2 hours, continue reaction 3 hours at 50 ℃, reaction finishes, and aftertreatment gets pale yellow oily liquid body 13g with embodiment 1 step (3), content is 98.1%, yield 38.8%.
Embodiment 4
(1) has condensing reflux, in the reactor of agitation and dropping and heating unit, adding the 111.3g pyrocatechol, 800ml ethylene dichloride, 329g SnCl
4, stir, be cooled to 0～5 ℃, slowly be added dropwise to the 47g propionyl chloride, dripped off in about 2 hours, be warming up to 20 ℃ then, continue reaction 3 hours, to have reacted, aftertreatment gets solid 3 with embodiment 1 step (1), and 4-dihydroxyphenyl-1-propanone 55g, content are 98%, yield 65%.
(2) will go up step gained solid 3,4-dihydroxyphenyl-1-propanone 85g is dissolved in the 300ml methyl alcohol, and add the Pd/C catalyzer of 3g5%, then this mixture is placed autoclave, and under the pressure of 4atm in 40～45 ℃ of hydrogenations, logical hydrogen is after about 20 hours, reaction finishes, and aftertreatment gets solid 4-propyl group pyrocatechol 72g with embodiment 1 step (2), content is 98%, yield 93%.
(3) will go up step gained solid 4-propyl group pyrocatechol 31g and be dissolved in 75mlN, and in dinethylformamide and the 5ml methylene bromide, then above-mentioned mixed solution slowly will be added dropwise to 27g Na is housed in advance
2CO
3225mlN, in the mixing solutions of dinethylformamide and 23ml methylene bromide, keep 110～115 ℃ of temperature of reaction, dripped off in about 2 hours, be warming up to 120～125 ℃ then and continue reaction 8 hours, reaction finishes, and aftertreatment gets pale yellow oily liquid body 29.5g with embodiment 1 step (3), content is 97.8%, yield 88.1%.
Embodiment 5
(1) has condensing reflux, in the reactor of agitation and dropping and heating unit, adding the 111.3g pyrocatechol, 500ml dithiocarbonic anhydride, the perchloric acid of 60ml70% stirs, be cooled to 10～15 ℃, slowly be added dropwise to the 197g propionic anhydride, dripped off in about 2 hours, be warming up to 20 ℃ then, continue reaction 28 hours, reacted, aftertreatment gets solid 3,4-dihydroxyphenyl-1-propanone 140g with embodiment 1 step (1), content is 98%, yield 82.7%.
(2) will go up step gained solid 3,4-dihydroxyphenyl-1-propanone 85g is dissolved in the 300ml Virahol, and add the Pd/C catalyzer of 1g5%, then this mixture is placed autoclave, and under the pressure of 10atm in 100 ℃ of hydrogenations, logical hydrogen is after about 5 hours, reaction finishes, and aftertreatment gets solid 4-propyl group pyrocatechol 68.4g with embodiment 1 step (2), content is 98%, yield 88.2%.
(3) will go up step gained solid 4-propyl group pyrocatechol 31g is dissolved in 75ml methyl-sulphoxide and the 5ml methylene iodide, then above-mentioned mixed solution slowly is added dropwise to 25g NaOH is housed in advance, in the mixing solutions of 225ml methyl-sulphoxide and 27ml methylene iodide, keep 90～95 ℃ of temperature of reaction, dripped off in about 2 hours, be warming up to 100～110 ℃ then and continue reaction 3 hours, reaction finishes, and aftertreatment gets pale yellow oily liquid body 28.3g with embodiment 1 step (3), content is 98.8%, yield 85.1%.
Embodiment 6
(1) has condensing reflux, in the reactor of agitation and dropping and heating unit, adding the 111.3g pyrocatechol, the 500ml tetrachloroethane, 166gZnCl stirs, be cooled to 10～15 ℃, slowly be added dropwise to the 112g propionic acid, dripped off in about 2 hours, be warming up to 70 ℃ then, continue reaction 28 hours, reacted, aftertreatment gets solid 3,4-dihydroxyphenyl-1-propanone 89.3g with embodiment 1 step (1), content is 98%, yield 52.7%.
(2) will go up step gained solid 3,4-dihydroxyphenyl-1-propanone 85g is dissolved in the 300ml butanols, and add the Pd/C catalyzer of 1g5%, then this mixture is placed autoclave, and under the pressure of 10atm in 100 ℃ of hydrogenations, logical hydrogen is after about 5 hours, reaction finishes, and aftertreatment gets solid 4-propyl group pyrocatechol 66.8g with embodiment 1 step (2), content is 98%, yield 86.2%.
(3) will go up step gained solid 4-propyl group pyrocatechol 31g is dissolved in 25ml methyl-sulphoxide and the 5ml methylene dichloride, then above-mentioned mixed solution slowly is added dropwise to 17g NaOH is housed in advance, in the mixing solutions of 75ml methyl-sulphoxide and 25ml methylene dichloride, keep 90～95 ℃ of temperature of reaction, dripped off in about 2 hours, be warming up to 100～110 ℃ then and continue reaction 3 hours, reaction finishes, and aftertreatment gets pale yellow oily liquid body 26.6g with embodiment 1 step (3), content is 98.8%, yield 80.1%.
Claims (7)
1, a kind of preparation method of dihydrosafrole is characterized in that with (1) be raw material with the pyrocatechol, and any propionyl reagent with in propionic anhydride, propionyl chloride and the propionic acid carries out the propionyl reaction, makes 3, the 4-dihydroxyphenyl-1-propanone; (2) then with 3,4-dihydroxyphenyl-1-propanone catalytic hydrogenation generates 4-propyl group pyrocatechol; (3) at last with 4-propyl group pyrocatechol and saturated dihalide hydrocarbon reaction, obtain dihydrosafrole.Its reaction process is as follows:
(1) synthesizes 3, the 4-dihydroxyphenyl-1-propanone
(I)
R representative following group :-Cl in the formula (I) ,-OCOCH
2CH
3,-OH
(2) synthetic 4-propyl group pyrocatechol
(3) sassafras artificial KH
(II)
X represents halogen in the formula (II), as :-F ,-Cl ,-Br ,-I.
2, the preparation method of dihydrosafrole according to claim 1 is characterized in that synthesizing 3, and in the reaction of 4-dihydroxyphenyl-1-propanone, temperature of reaction is 0～70 ℃, and the reaction times is 5～30 hours; Solvent is any in ethylene dichloride, tetrachloroethane, hexanaphthene, the dithiocarbonic anhydride; Catalyzer is AlCl
3, ZnCl
2, SnCl
2, SnCl
4, FeCl
2, FeCl
3, FeSO
4, Fe
2(SO
4)
3, H
3PO
4, HClO
4, BF
3In any; The mole proportioning of pyrocatechol and propionic anhydride, propionyl chloride or propionic acid is 1: 0.5～3; With the mole proportioning of solvent be 1: 3～10; The mole proportioning of pyrocatechol and catalyzer is 1: 0.01～1.25.
3, according to the described preparation method who gets dihydrosafrole of claim 2, it is characterized in that synthesizing 3, in the reaction of 4-dihydroxyphenyl-1-propanone, temperature of reaction is 5～20 ℃, the reaction times is 10～20 hours.
4, the preparation method of dihydrosafrole according to claim 1 is characterized in that temperature of reaction is 20～100 ℃ in the reaction of synthetic 4-propyl group pyrocatechol, and the reaction times is 5～20 hours; Reaction pressure is 4～60 normal atmosphere; Solvent for use is an alcohols, as: a kind of in methyl alcohol, ethanol, Virahol, the butanols, 3, the mole proportioning of 4-dihydroxyphenyl-1-propanone and solvent is 1: 5～15; Catalyzer is Pd, Pt, Ru or loads on the inert base, as Pd/C, Pt/C, Ru/C, Pd/Al
2O
3And Pd/BaSO
4In a kind of, 3, the mole proportioning of 4-dihydroxyphenyl-1-propanone and catalyzer is 1: 0.001～0.005.
5, the preparation method of dihydrosafrole according to claim 4 is characterized in that temperature of reaction is 40～50 ℃ in the reaction of synthetic 4-propyl group pyrocatechol, and the reaction times is 5～8 hours; Reaction pressure 10～15 normal atmosphere.
6, the preparation method of dihydrosafrole according to claim 1 is characterized in that in the reaction of sassafras artificial KH temperature of reaction is 50～130 ℃, and the reaction times is 4～10 hours; Used alkylene dihalide is a kind of in methylene fluoride, methylene dichloride, methylene bromide, the methylene iodide; Mineral alkali is NaOH, KOH, Na
2CO
3, K
2CO
3In a kind of; Solvent is N, a kind of in dinethylformamide, N,N-dimethylacetamide, the methyl-sulphoxide; The mole proportioning of 4-propyl group pyrocatechol and alkylene dihalide, mineral alkali is 1: 1～3: 2～3; The mole proportioning of 4-propyl group pyrocatechol and solvent is 1: 6～20.
7, the preparation method of dihydrosafrole according to claim 6 is characterized in that in the reaction of sassafras artificial KH temperature of reaction is 110～130 ℃, and the reaction times is 5～6 hours.
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|---|---|---|---|
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|---|---|---|---|
| CNB2006100355875A CN100473650C (en) | 2006-05-24 | 2006-05-24 | Method for preparing dihydro safrole |
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| CN100473650C CN100473650C (en) | 2009-04-01 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106632228A (en) * | 2016-08-05 | 2017-05-10 | 成都建中香料香精有限公司 | Preparation method of dihydrosafrole |
| CN108844932A (en) * | 2018-05-30 | 2018-11-20 | 中国烟草总公司郑州烟草研究院 | A kind of time-resolved fluoroimmunoassay chromatograph test strip and its preparation method and application detecting safrole |
| CN114644574A (en) * | 2020-12-21 | 2022-06-21 | 湖南大学 | Dioxime ether compound and preparation method and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018150230A1 (en) | 2017-02-14 | 2018-08-23 | Anthea Aromatics Private Limited | A process for preparation of alkenyl and alkyl derivatives of alkylenedioxybenzene |
-
2006
- 2006-05-24 CN CNB2006100355875A patent/CN100473650C/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106632228A (en) * | 2016-08-05 | 2017-05-10 | 成都建中香料香精有限公司 | Preparation method of dihydrosafrole |
| CN106632228B (en) * | 2016-08-05 | 2019-07-02 | 成都建中香料香精有限公司 | A kind of preparation method of dihydrosafrole |
| CN108844932A (en) * | 2018-05-30 | 2018-11-20 | 中国烟草总公司郑州烟草研究院 | A kind of time-resolved fluoroimmunoassay chromatograph test strip and its preparation method and application detecting safrole |
| CN108844932B (en) * | 2018-05-30 | 2020-10-30 | 中国烟草总公司郑州烟草研究院 | Time-resolved fluorescence immunochromatographic test strip for detecting safrole as well as preparation method and application thereof |
| CN114644574A (en) * | 2020-12-21 | 2022-06-21 | 湖南大学 | Dioxime ether compound and preparation method and application thereof |
| CN114644574B (en) * | 2020-12-21 | 2023-03-14 | 湖南大学 | Dioxime ether compound and preparation method and application thereof |
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