CN110256386A - A kind of synthetic method of fragrance rose ethereal essence - Google Patents
A kind of synthetic method of fragrance rose ethereal essence Download PDFInfo
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- CN110256386A CN110256386A CN201810200353.4A CN201810200353A CN110256386A CN 110256386 A CN110256386 A CN 110256386A CN 201810200353 A CN201810200353 A CN 201810200353A CN 110256386 A CN110256386 A CN 110256386A
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- chloride
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- prenol
- benzaldehyde
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D309/18—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member containing only hydrogen and carbon atoms in addition to the ring hetero atom
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Abstract
The invention discloses a kind of synthetic methods of fragrant rose ethereal essence, the method are as follows: using benzaldehyde and prenol as raw material, using non-strong protonic acid or lewis acid as catalyst, in inert non-protonic solvent, fully reacting at a reflux temperature, gained reaction mixture is post-treated to obtain 4- methyl -2- phenyl-pyrane.Method of the present invention uses mild catalyst, its benzaldehyde or prenol using equivalent less than 1 equivalent, the water that reaction generates is removed using azeotrope with water solvent, improve the selectivity of reaction, reaction molar yield can be up to 90% or so, with economic, green, easy and high yield feature, it is suitble to large-scale industrial production.
Description
Technical field
This application involves a kind of synthetic methods of chemical Perfume Fragrance rose ethereal essence.
Background technique
Fragrant rose oxide be 4- methyl -2- phenyl-dihydropyran double bond isomeric mixture (structural formula as I, II and
III), there is a kind of strongly penetrating rose feature, and with green fragrant, spiceleaf and metal gas.Especially suitable for that
Based on rose, spiceleaf type in the air freshener of odor type.In addition, fragrant rose oxide can also synthesize it by chemical conversion
Its important fragrance, as road stand ether (referring to United States Patent (USP) 5219836 and Tetrahedron Letters, 1970,51,4507-
And 3- methyl -5- phenyl amylalcohol 4508) (referring to Swiss Patent CH655932 and United States Patent (USP) US 6600079).
Fragrant rose oxide is the mixture (I, II and III) of 4- methyl -2- phenyl-dihydropyran double bond isomer,
Structure is as follows:
Industrial fragrance rose oxide is synthesized as starting material according to one pot reaction by benzaldehyde and prenol
(referring to formula 2).For example, Swiss Patent CH655932 report uses Bronsted acid such as hydrochloric acid, sulfuric acid or p-methyl benzenesulfonic acid are urged the most
The synthetic method of agent.But these strong acid catalysts are because will cause the corrosion of equipment, are unfavorable in industrial production.
In addition, raw material prenol and product are all sensitive to strong acid, so often reaction yield is lower.More disadvantageously, highly acid is urged
Agent will lead to while generating more hydration pyrans by-product (referring to formula 2), difficulty be brought for subsequent isolate and purify, into one
Step influences the yield of entire technique.
Therefore, industrial to need to find more efficient and mild catalyst to improve the economy of the process route and set
Standby compatibility.
Summary of the invention
In order to solve the problems existing in the prior art, the present invention is directed to establish a kind of economic, easy and efficient fragrant rose
Ether synthesis technology.
The method of fragrance rose ethereal essence shown in a kind of synthesis formula (I), it is characterised in that: the method is according to as follows
It is prepared by step:
Using benzaldehyde and prenol as raw material, using non-strong protonic acid or lewis acid as catalyst, in inert non-matter
In sub- property solvent, fully reacting at a reflux temperature, gained reaction mixture is post-treated to obtain 4- methyl -2- phenyl-pyrane；
The ratio between described amount of substance of benzaldehyde and prenol, catalyst is 25-200:100:0.001-15 (preferably 50-
200:100:0.01-5)；
The R is
Further, the non-strong protonic acid is para-methylbenzenepyridinsulfonate sulfonate.
Further, the lewis acid is iodine (I2), inidum chloride (InCl3), indium bromide (InBr3), trifluoromethanesulfonic acid indium
(In(OTf)3), indium sulfate (In2(SO4)3), trifluoromethanesulfonic acid scandium (Sc (OTf)3), Trimethylsilyl trifluoromethanesulfonate
(TMSOTf), boron trifluoride (BF3), zinc chloride (ZnCl2), the new (ZnBr of bromination2), ferric sulfate (Fe2(SO4)3), ferrous sulfate
(FeSO4) iron chloride (FeCl3), aluminum sulfate (Al2(SO4)3), stannic chloride (SnCl4), stannous chloride (SnCl2), magnesium chloride
(MgCl2), magnesium bromide (MgBr2), nickel chloride (NiCl2), nickelous bromide (NiBr2), titanium tetrachloride (TiCl4), lithium chloride (LiCl),
Lithium bromide (LiBr) or group of the lanthanides chloride (LaCl3), the Prins reaction of benzaldehyde and prenol can be catalyzed.
Further, the lewis acid is preferably iodine (I2), trifluoromethanesulfonic acid indium (In (OTf)3), trifluoromethanesulfonic acid
Trimethylsilyl group (TMSOTf) or ferric sulfate (Fe2(SO4)3)。
No matter use PPTS or Louis acid catalysis, the reaction of synthesizing dihydro pyrans in inert non-protonic solvent into
Row, such as alkane, aromatic hydrocarbon, halogenated alkane, halogenated aromatic or any several mixed solvent；Specifically, solvent is preferably
Benzene, toluene, ethylbenzene, cyclohexene, heptane, dimethylbenzene or any several mixed solvent.
Further, the additional amount of the non-protonic solvent is calculated as 0.5-20g/ with the quality of the prenol
G, preferably 0.5-5g/g.
The post-processing approach of reaction mixture of the present invention are as follows: after reaction, add into gained reaction mixture
The acetic acid aqueous solution and water for entering 5% successively wash, and merge organic phase, and evaporating solvent under reduced pressure obtains gained crude product rectification under vacuum
Target product.
Generally, the temperature of reaction is the reflux temperature of the non-protonic solvent, reacts the water of generation using solvent
The mode of azeotropic distillation removes, and the direction for promoting reaction to generate to dihydropyran is completed.
Compared with prior art, the beneficial effects of the present invention are:
Method of the present invention uses mild catalyst, the benzaldehyde or iso-amylene using equivalent less than 1 equivalent
Alcohol removes the water that reaction generates using azeotrope with water solvent, improves the selectivity of reaction, and reaction molar yield can be up to 90%
Left and right has economic, green, easy and high yield feature, is suitble to large-scale industrial production.
Specific embodiment
As it appears from the above, the present invention reports: in the presence of catalysts and solvents, benzaldehyde and prenol occur
Prins reaction generates dihydropyrane compound, and rectifying obtains rose fragrance ethereal essence after purification.
The following examples, which are described in detail, prepares fragrant rose oxide using method disclosed herein.Those skilled in the art
It is clear that can be carried out many improvement to material and method without departing substantially from disclosure range.
Unless otherwise noted, all reaction reagents are to analyze pure, herein percentage to indicate weight percent (w/w).
Embodiment 1
387 are added in one liter of jacket reactor equipped with mechanical stirring, Dean-Stark water segregator and dropping funel
Gram (3.65mol) benzaldehyde, 400 milliliters of toluene and 0.73 gram of PPTS.(3.0mmol) is heated to latter hour of flowing back, through 10
300 grams of (3.49mol) prenols are added dropwise in hour, are added dropwise subsequent continuous maintained until water segregator stopping is collected into reaction generation
Water, be cooled to room temperature.200 milliliters grams 5% of acetic acid aqueous solution is added and 200 milliliters of water successively washs.It returns under reduced pressure
After receiving solvent, crude product purifies to obtain 480 grams of dihydropyran products (83-84 DEG C/1mmHg, molar yield 79%) through rectifying.
Embodiment 2
500 are added in one liter of jacket reactor equipped with mechanical stirring, Dean-Stark water segregator and dropping funel
Gram (4.72mol) benzaldehyde, 500 milliliters of dimethylbenzene and 0.85 gram of PPTS (3.4mmol).It is heated to latter hour of flowing back, through 12
300 grams of (3.49mol) prenols of dropwise addition in a hour, be added dropwise it is subsequent it is continuous maintain the reflux for until water segregator stopping be collected into it is anti-
The water that should be generated, is cooled to room temperature.200 milliliters grams 5% of acetic acid aqueous solution is added and 200 milliliters of water successively washs.Subtracting
After depressing recycling design, crude product through rectifying purify to obtain 460 grams of dihydropyran products (83-84 DEG C/1mmHg, molar yield
75%).
Embodiment 3
387 are added in one liter of jacket reactor equipped with mechanical stirring, Dean-Stark water segregator and dropping funel
Gram (3.65mol) benzaldehyde, 180 milliliters of toluene and 0.35 gram of ferric sulfate (0.87mmol).It is heated to latter hour of flowing back, through 8
300 grams of (3.49mol) prenols of dropwise addition in a hour, be added dropwise it is subsequent it is continuous maintain the reflux for a hour, then stop heating
It is cooled to room temperature.200 milliliters grams 5% of acetic acid aqueous solution is added and 200 milliliters of water successively washs.Solvent is recovered under reduced pressure, it will
Crude product through rectification under vacuum obtain 540 grams of dihydropyran products (83-84 DEG C/1mmHg, molar yield 89%.)
Embodiment 4
400 are added in one liter of jacket reactor equipped with mechanical stirring, Dean-Stark water segregator and dropping funel
Gram (3.77mol) benzaldehyde, 250 milliliters of toluene and 0.049 gram of trifluoromethanesulfonic acid indium (0.087mmol).It is heated to flowing back latter
Hour, 300 grams of (3.49mol) prenols are added dropwise through 6 hours, be added dropwise it is subsequent it is continuous maintain the reflux for a hour, then
Stop heating being cooled to room temperature.200 milliliters grams 5% of acetic acid aqueous solution is added and 200 milliliters of water successively washs.It is recovered under reduced pressure
Solvent, by crude product through rectification under vacuum obtain 414 grams of dihydropyran products (83-84 DEG C/1mmHg, molar yield 68%.)
Embodiment 5
400 are added in one liter of jacket reactor equipped with mechanical stirring, Dean-Stark water segregator and dropping funel
Gram (3.77mol) benzaldehyde, 250 milliliters of toluene and 10.9 grams of iodine (43mmol).It is heated to latter hour of flowing back, through 14 hours
300 grams of (3.49mol) prenols are added dropwise, be added dropwise it is subsequent it is continuous maintain the reflux for a hour, be cooled to room temperature.It is added 200
Milliliter gram 5% acetic acid aqueous solution and 200 milliliters of water successively wash.Solvent is recovered under reduced pressure, crude product is obtained through rectification under vacuum
365 grams of dihydropyran products (83-84 DEG C/1mmHg, molar yield 60%.)
Embodiment 6
400 are added in one liter of jacket reactor equipped with mechanical stirring, Dean-Stark water segregator and dropping funel
Gram (3.77mol) benzaldehyde, 250 milliliters of toluene and 0.52 gram of Trimethylsilyl trifluoromethanesulfonate (2.3mmol).It is heated to flowing back
300 grams of (3.49mol) prenols are added dropwise through 14 hours in latter hour, be added dropwise it is subsequent it is continuous maintain the reflux for a hour,
It is cooled to room temperature.200 milliliters grams 5% of acetic acid aqueous solution is added and 200 milliliters of water successively washs.Solvent is recovered under reduced pressure, it will
Crude product through rectification under vacuum obtain 353 grams of dihydropyran products (83-84 DEG C/1mmHg, molar yield 58%.)
Claims (10)
1. a kind of method of fragrance rose ethereal essence shown in synthesis formula (I), it is characterised in that: the method is according to following step
Suddenly it is prepared:
Using benzaldehyde and prenol as raw material, using non-strong protonic acid or lewis acid as catalyst, in inert aprotic
In solvent, fully reacting at a reflux temperature, gained reaction mixture is post-treated to obtain the perfume of fragrance rose oxide shown in formula (I)
Material；The ratio between described amount of substance of benzaldehyde and prenol, catalyst is 25-200:100:0.001-15；
The R is
2. synthetic method according to claim 1, it is characterised in that: the non-strong protonic acid is p-methyl benzenesulfonic acid pyridine
Salt.
3. synthetic method according to claim 1, it is characterised in that: the lewis acid is iodine, inidum chloride, bromination
Indium, trifluoromethanesulfonic acid indium, indium sulfate, trifluoromethanesulfonic acid scandium, Trimethylsilyl trifluoromethanesulfonate, boron trifluoride, zinc chloride, bromination
Zinc, ferrous sulfate, ferric sulfate, iron chloride, aluminum sulfate, stannic chloride, stannous chloride, magnesium chloride, magnesium bromide, nickel chloride, nickelous bromide,
Titanium tetrachloride, lithium chloride, lithium bromide or group of the lanthanides chloride.
4. according to synthetic method described in right 3, it is characterised in that: the lewis acid is iodine, trifluoromethanesulfonic acid indium, trifluoro
Methanesulfonic acid trimethylsilyl group or ferric sulfate.
5. synthetic method according to claim 1, it is characterised in that: the non-protonic solvent be alkane, aromatic hydrocarbon,
Halogenated alkane, halogenated aromatic or any several mixed solvent.
6. according to the method described in claim 5, it is characterized by: the non-protonic solvent be benzene, toluene, cyclohexene,
Heptane, dimethylbenzene or ethylbenzene or in which any several mixed solvent.
7. method according to claim 5 or 6, it is characterised in that: the additional amount of the non-protonic solvent is with described
The quality of prenol be calculated as 0.5-5g/g.
8. according to the method described in claim 7, it is characterized by: the additional amount of the non-protonic solvent is with described different
The quality of pentenol is calculated as 0.5-2g/g.
9. according to the method described in claim 1, it is characterized by: the substance of the benzaldehyde and prenol, catalyst
The ratio between amount be 25-200:100:0.01-5.
10. according to the method described in claim 1, it is characterized by: the post-processing approach of the reaction mixture are as follows: reaction
After, 5% acetic acid aqueous solution is added into gained reaction mixture and water successively washs, merges organic phase, removes under reduced pressure
Gained crude product rectification under vacuum is obtained target product by solvent.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111377897A (en) * | 2018-12-28 | 2020-07-07 | 国际香料和香精公司 | Synthetic method of aromatic rose oxide perfume |
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2018
- 2018-03-12 CN CN201810200353.4A patent/CN110256386A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111377897A (en) * | 2018-12-28 | 2020-07-07 | 国际香料和香精公司 | Synthetic method of aromatic rose oxide perfume |
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Application publication date: 20190920 |