CN109942390A - The method for preparing Iso E Super - Google Patents
The method for preparing Iso E Super Download PDFInfo
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- CN109942390A CN109942390A CN201711382482.1A CN201711382482A CN109942390A CN 109942390 A CN109942390 A CN 109942390A CN 201711382482 A CN201711382482 A CN 201711382482A CN 109942390 A CN109942390 A CN 109942390A
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- solid
- ketone
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- cyclisation
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Abstract
The present invention provides a kind of method for preparing Iso E Super, the method includes the cyclisation ketone intermediate of formula (I) is carried out cyclization in the presence of solid acid catalyst, obtains the Iso E Super comprising isomer mixture.
Description
Technical field
The present invention relates to fragrance preparation fields.More particularly it relates to a kind of Iso E Super (Iso E super)
Improvement preparation process.Particularly, the present invention provides a kind of method with solid acid catalysis cyclisation step synthesis ambrotone.
Background technique
Ambrotone is colourless to lurid liquid.As one of maximum perfume monomer of tonnage is produced per year in the world, extensively
It is general to be applied among the formula such as perfume, perfumed soap, cosmetics and detergent.Iso E super is International Perfume & Essence Co.
(IFF) ambrotone trade name.Commercially available ambrotone is the mixture of isomeric compound, the structure of main component such as following formula institute
Show, difference is mainly the different distributions of double bond (dotted line indicates in place of double bond that may be present).
Therefore, ambrotone is the isomer mixture comprising following various compound
In disclosed report, for example, US3911018, US3929677, US616018, US737506, CN106045834,
CN103058842, CN103265419 etc., ambrotone are all to be prepared using three-step synthesis method (referring to following reaction route I): the
One step is condensed butanone under the catalysis of acid or alkali and acetaldehyde obtains 3- methyl -3- amylene -2- ketone (3M3P)；Second step, laurene
Diels-Alder reaction occurs with 3M3P and generates cyclisation ketone (Iso Precyclemone, abbreviation Iso Pre)；Third step, Iso
Cyclisation occurs under acid catalysis and generates ambrotone (Iso E) for Pre cyclisation ketone.
Reaction route I
In the report as above enumerated, the third step of ambrotone synthesis, i.e. cyclisation step typically use phosphoric acid, sulphur
The inorganic acids such as acid, hydrochloric acid, boron trifluoride or boron trifluoride etherate are as catalyst, under heating conditions in batch still
In be conducted batch-wise.Therefore, it industrially unavoidably needs to carry out the operation such as alkali neutralization and washing liquid separation, generates a large amount of waste water,
Environmental pressure is not only caused, also will increase operating cost.
Summary of the invention
The unfavorable feature of a large amount of spent acid is generated for existing ambrotone cyclisation step, the present invention is using solid acid as catalysis
Agent and fixed bed reactors produce Iso E Super by the cyclisation of Iso Pre, thus industrially to provide a kind of condition appearance
The technique that easy to control, operating cost is saved and eliminates waste water.
More specifically, the present invention provides a kind of method for preparing Iso E Super, which comprises
By the cyclisation ketone intermediate of formula (I)
Cyclization is carried out in the presence of solid acid catalyst, is obtained the isomers comprising following various compound and is mixed
The Iso E Super of object
The cyclisation ketone of formula (I) of the invention can be synthesized by any chemical/biological synthetic route or from its it is natural come
Extraction/separation in source.In a preferred embodiment of the invention, the cyclisation ketone of formula (I) is by laurene and 3- methyl -3-
Diels-Alder reaction generation occurs for amylene -2- ketone (3M3P) and/or 3- methyl -3- amylene -2- ketone (3M3P) is by butanone
It is condensed under the catalysis of acid or alkali with acetaldehyde.Occurred above by laurene and 3- methyl -3- amylene -2- ketone (3M3P)
Diels-Alder reaction generates the reaction of the cyclisation ketone of formula (I) and is condensed under the catalysis of acid or alkali by butanone and acetaldehyde and produced
The reaction of 3- methyl -3- amylene -2- ketone (3M3P) is well known to those skilled in the art, and may refer to for example
US3911018, US3929677, US616018, US737506, CN106045834, CN103058842, CN103265419 etc..
In a preferred embodiment of the invention, solid acid catalyst used in method of the invention be selected from by with
The group of lower composition: solid phosphoric acid, solid sulfoacid resin or their combination.Preferably, the solid phosphoric acid/sulfonic acid type resin
Catalyst is selected from the group being made up of:Serial (DuPont Corporation) (perfluorosulfonic acid type resin),Serial (Dow) (sulfonic resin),Serial (Dow),Series (drift
Lai Te company), D72 and NKC catalyst series (Nankai University), DZH resin (Dandong jewel), SPAC-1 solid phosphoric acid urge
Agent (SPA catalyst, Liaoning Haitai) or their any combination.
In a preferred embodiment of the invention, the solid acid catalyst is (strong-acid type [H]) solid polyphenyl second
Alkene sulfonate resin or fluoridized cation exchange resin.
The dosage of solid acid catalyst in method of the invention is not particularly limited, it is preferred that solid acid catalysis
The 100% of the mole of cyclisation ketone intermediate of the dosage of agent less than the formula (I), is preferably smaller than cyclized mole of ketone intermediate
Amount 90%, 80%, 70%, 60% or 50%, preferably smaller than it is described cyclisation ketone intermediate mole 40%, 30%,
20% or 10%, 0.1 to 20%, most preferably the 0.5 to 5% of the mole of the more preferably described cyclisation ketone intermediate.
Cyclization in method of the invention can carry out in the reaction system containing solvent or without containing solvent.Institute
State solvent preferable organic solvent, the preferably described organic solvent is selected from the group being made up of: toluene, ethylbenzene, dimethylbenzene, methanol,
Ethyl alcohol, isopropanol, atoleine or their combination.
In a preferred embodiment of the invention, the cyclization is carried out continuously in fixed bed reactors,
Filled with the solid acid catalyst and other optional fillers (such as in fixed bed reactors in the fixed bed reactors
The quartz sand at both ends).
In the cyclization of method of the invention, the temperature of the fixed bed reactors is controlled in 60 to 190 DEG C (such as
60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C and
190 DEG C), preferably within the scope of 80 to 150 DEG C.The solid acid catalyst can be preheated before reactions.
In addition to above-mentioned cyclization step, method of the invention can also include carrying out reaction product (ambrotone crude product)
The step of rectifying.
In a preferred embodiment of the invention, the conversion ratio of the cyclisation ketone of formula (I) is big in the method for the invention
In 90%, preferably greater than 95%.
Conversion ratio=(molar equivalent/total raw material molar equivalent for having converted raw material) x 100%.
In one embodiment of the invention, solid phosphoric acid or solid sulfoacid resin are filled into fixed bed reaction
Iso Pre cyclisation ketone is continuously passed through the solid acid filled layer of preheating with pump, then collects cooling reaction mixture by device,
It is rectifying to obtain fragrance and coloration compliance product (referring to Fig. 1).
As shown in Figure 1, filled solid acid catalyst and quartz sand in fixed-bed tube reactor, are heated to certain temperature
Iso Pre cyclisation ketone is pumped into according to certain flow velocity, after tubular reactor and catalyst contact, it is thick to obtain reaction by degree
Product obtain the ambrotone product of fragrance and coloration compliance after rectifying.
Fixed bed is a kind of tubular reactor of filled solid catalyst, and it is (gas-solid or liquid-solid that it is suitable for two-phase systems
System) and three-phase system (gas-liquid-solid).In order to reach reaction rate, yield and the heat transfer efficiency of optimization, the tubular type of fixed bed
Reactor has generally required suitable length, diameter, catalyst bed layer height and catalyst particle size.
Generally, fixed-bed tube reactor caliber range is between 10-3000 millimeters, and length range is in 90-20000 milli
Between rice, volume range is in 8x10-6- 100 cubic metres of (S.T.Sie and R.Krishna, Reviews in Chemical
Engineering,1998,14(3):203-252)。
Generally, the residence time (retention time) of liquid material was at 1-250 minutes, it is preferable that 10-150 minutes.
Retention time=fixed-bed catalysts stacking volume/material flow
Generally, 0.1-1.5 millimeters of the average grain diameter of solid sulfoacid catalyst, it is preferable that 0.2-1.2 millimeters.
Generally, the size of solid phosphoric acid strip preformed catalyst is 6 millimeters of x (1-15) millimeters.
The present invention has the advantage that instead of inorganic acid, due to taking solid acid catalysis successive reaction such as sulfuric acid, phosphorus
Acid etc. eliminates the generation of waste water；Meanwhile the fixed bed reactors of solid acid filling ensure that the stability, easy to operate of technique
Property and operating efficiency；The color of crude reaction is shallower, and colourless liquid is obtained after rectifying, than liquid acid catalytic reaction products color matter
It measures more excellent.
Detailed description of the invention
Fig. 1 is the schematic diagram for the fixed bed reactors that the present invention uses；With
Fig. 2 is the GC chromatogram of product in embodiment 1.
Specific embodiment
Hereinafter with reference to embodiment the present invention is described in detail, the embodiment is only intended to illustrate the present invention, without
It is intended to limit the scope of the invention.The scope of the present invention is specifically limited by appended claims.
Embodiment 1
As shown in Figure 1, tubular reactor (Tianjin Peng Xiang development in science and technology Co., Ltd, the micro-/product catalytic reaction of fixed bed
Agent evaluating apparatus) it is 56 centimetres long, 1.5 centimetres of internal diameter, it is sequentially filled 25 grams of quartz sands, 15 grams of Dow from bottom to top
Amberlyst35 sulfonate resin and 60 grams of quartz sand mix mixture, 17 grams of quartz sands thoroughly.Catalyst filled layer is warming up to
After 110 DEG C, by Iso Pre (i.e. the cyclisation ketone intermediate of formula (I)) (being commercially available from International Perfume & Essence Co. (IFF)) with
The speed of 1.5mL/min is pumped into, and the light yellow liquid of outflow is collected after being cooled to room temperature, and feed stock conversion is greater than 97%.Into one
Colourless liquid is obtained after step rectifying (115-120 DEG C/1.0mmHg), meets fragrance and quality of colour requirement.The GC chromatography of product is such as
(Agilent 7890A, HP-5 column) shown in Fig. 2, the gaseous mass spectrum result of product meet expected (M+=234,144 (100)；GC-
MS, Agilent 7890A, 5975C detector, HP-5 column), it was demonstrated that it is fragrant to have obtained the ambrotone comprising three kinds of isomer mixtures
Material.
Embodiment 2
It is filled with embodiment 1 using identical tubular reactor and identical catalyst, catalyst filled layer is warming up to
After 90 DEG C, Iso Pre is pumped into simultaneously with the speed of 0.5mL/min and toluene 0.1mL/min, the light yellow liquid of outflow is cold
But to collecting after room temperature, feed stock conversion is greater than 97%.Colourless liquid is obtained after further rectifying, meets fragrance and quality of colour
It is required that.
Embodiment 3
Identical tubular reactor is used with embodiment 1, is sequentially filled 25 grams of quartz sands, 15 grams of Dandongs from bottom to top
DZH sulfonate resin and 60 grams of quartz sand mix mixture, 17 grams of quartz sands thoroughly.It will after catalyst filled layer is warming up to 110 DEG C
Iso Pre is pumped into the speed of 0.5ml/min, and the light yellow liquid of outflow is collected after being cooled to room temperature, and feed stock conversion is greater than
97%.Colourless liquid is obtained after further rectifying, meets fragrance and quality of colour requirement.
Embodiment 4
Identical tubular reactor is used with embodiment 1, is sequentially filled 40 grams of quartz sands, 15 grams of Dow from bottom to top
Amberlyst36 sulfonate resin and 30 grams of quartz sand mix mixture, 32 grams of quartz sands thoroughly.Catalyst filled layer is added for heating
Iso Pre is pumped into the speed of 0.5ml/min after to 100 DEG C, the light yellow liquid of outflow is collected after being cooled to room temperature, raw material
Conversion ratio is greater than 97%.Colourless liquid is obtained after further rectifying, meets fragrance and quality of colour requirement.
Embodiment 5
Identical tubular reactor is used with embodiment 1, is sequentially filled 25 grams of quartz sands, 15 gram of 20 mesh -40 from bottom to top
Mesh solid phosphoric acid SPAC-1 (Liaoning Haitai) and 60 grams of quartz sand mix mixture, 17 grams of quartz sands thoroughly.Catalyst is filled out in heating
It fills layer to be added to being pumped into Iso Pre with the speed of 0.5ml/min after 100 DEG C, after the light yellow liquid of outflow is cooled to room temperature
It collects, feed stock conversion is greater than 97%.Colourless liquid is obtained after further rectifying, meets fragrance and quality of colour requirement.
The above description is only a preferred embodiment of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of method for preparing Iso E Super, which comprises
By the cyclisation ketone intermediate of formula (I)
Cyclization is carried out in the presence of solid acid catalyst, obtains the isomer mixture comprising following various compound
Iso E Super
2. according to the method described in claim 1, wherein the cyclisation ketone of the formula (I) is by laurene and 3- methyl -3- amylene -
2- ketone (3M3P) occurs Diels-Alder reaction and generates.
3. according to the method described in claim 2, wherein the 3- methyl -3- amylene -2- ketone (3M3P) is by butanone and acetaldehyde
It is condensed under the catalysis of acid or alkali.
4. according to the method described in claim 1, wherein the solid acid catalyst is selected from the group being made up of: solid phosphorus
Acid, solid sulfoacid resin or their combination.
5. according to the method described in claim 4, wherein the solid acid catalyst is (strong-acid type) solid polystyrene sulfonic acid
Resin or fluoridized cation exchange resin.
6. the method according to any one of claims 1 to 5, wherein the cyclization is without using solvent or organic molten
It is carried out in agent, the preferably described organic solvent is selected from the group being made up of: toluene, ethylbenzene, dimethylbenzene, methanol, ethyl alcohol, isopropyl
Alcohol, atoleine or their combination.
7. the method according to any one of claims 1 to 5, wherein the cyclization is connected in fixed bed reactors
It is continuous to carry out, the solid acid catalyst is filled in the fixed bed reactors.
8. excellent according to the method described in claim 7, wherein the temperature of the fixed bed reactors is controlled in 60 to 190 DEG C
It selects within the scope of 80 to 150 DEG C.
9. the method according to any one of claims 1 to 5, the method also includes reaction product is carried out to the step of rectifying
Suddenly.
10. the method according to any one of claims 1 to 5, wherein the conversion ratio of the cyclisation ketone of formula (I) is greater than 90%,
Preferably greater than 95%.
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| CN201711382482.1A CN109942390A (en) | 2017-12-20 | 2017-12-20 | The method for preparing Iso E Super |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711382482.1A CN109942390A (en) | 2017-12-20 | 2017-12-20 | The method for preparing Iso E Super |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0640992A (en) * | 1992-07-23 | 1994-02-15 | Takasago Internatl Corp | Production of ionone compound |
| US5707961A (en) * | 1995-05-16 | 1998-01-13 | Givaudan-Roure (International) Sa | Odorant compounds and compositions |
| US20080114189A1 (en) * | 2005-02-21 | 2008-05-15 | Givaudan Sa | Cyclisation Process |
| CN103265419A (en) * | 2013-05-22 | 2013-08-28 | 安徽省三环纸业集团香料科技发展有限公司 | Preparation method of ambrotone |
| CN106045834A (en) * | 2016-07-04 | 2016-10-26 | 福建青松股份有限公司 | Method for preparing ambrotone |
-
2017
- 2017-12-20 CN CN201711382482.1A patent/CN109942390A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0640992A (en) * | 1992-07-23 | 1994-02-15 | Takasago Internatl Corp | Production of ionone compound |
| US5707961A (en) * | 1995-05-16 | 1998-01-13 | Givaudan-Roure (International) Sa | Odorant compounds and compositions |
| US20080114189A1 (en) * | 2005-02-21 | 2008-05-15 | Givaudan Sa | Cyclisation Process |
| CN103265419A (en) * | 2013-05-22 | 2013-08-28 | 安徽省三环纸业集团香料科技发展有限公司 | Preparation method of ambrotone |
| CN106045834A (en) * | 2016-07-04 | 2016-10-26 | 福建青松股份有限公司 | Method for preparing ambrotone |
Non-Patent Citations (1)
| Title |
|---|
| 唐健: "龙涎酮的合成", 《河北化工》 * |
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