CN104803958A - Preparation technique for florosa - Google Patents
Preparation technique for florosa Download PDFInfo
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- CN104803958A CN104803958A CN201510159723.0A CN201510159723A CN104803958A CN 104803958 A CN104803958 A CN 104803958A CN 201510159723 A CN201510159723 A CN 201510159723A CN 104803958 A CN104803958 A CN 104803958A
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- lily
- prenol
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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
- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D309/10—Oxygen atoms
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- Pyrane Compounds (AREA)
Abstract
The invention belongs to the technical field of fine chemical engineering, relates to florosa, and particularly relates to a preparation technique of florosa. The technical scheme provided by the invention is as follows: continuously putting isovaleraldehyde, 3-methyl-2-buten-1-ol and an acid catalyst into a jet mixing reactor for reaction according to a certain molar ratio under a certain temperature condition; meanwhile, continuously outputting reaction mixtures according to the feeding proportion so as to prepare florosa. The jet mixing reactor is used to carry out the continuous synthesis of florosa, and has better heat and mass transfer performance as compared with the conventional kettle-type batch reactor and the fixed reactor, and the reaction efficiency can be effectively improved; by adopting an acid compound as the catalyst, the conversion rate is greatly improved, the yield is up to 75-85%, and the conversion rate is up to 90% or above; meanwhile, during industrial application, by adopting the efficient jet mixing reactor, the hardware equipment investment in reaction units can be effectively reduced.
Description
Technical field
The invention belongs to technical field of fine, relate to lily of the valley pyrans, particularly relate to a kind of preparation technology of lily of the valley pyrans.
Background technology
Lily of the valley pyrans, is also named and strokes soft spreading, chemistry 2-(2-methyl-propyl)-4-methyl-4 hydrogen pyrans-4-alcohol by name, or 4-methyl-2-(2-methyl-propyl)-2H-tetrahydropyrans-4-alcohol, and its molecular structural formula is:
there is pure and fresh, soft, natural fragrance of a flower fragrance, flores convallariae aromatic.This compound almost can be applied in all types of perfume, can produce the flowery odour of gracefulness, disperse, and does not change the original odour characteristics of essence, and lasting is lasting, and in the cosmeticses of everyday use such as perfume, face cream, toilet powder shui, energy stable existence, is good perfume material.
The domestic report that there is no large-scale industrial production synthesis lily of the valley pyrans at present, Fen Meiyi (Firmenich) company of Switzerland and BASF (BadischeAnilin-und-Soda-Fabrik) company of Germany have the ability to carry out suitability for industrialized production in the world.
A Chinese patent applied for by BASF European Co., Ltd has set forth the preparation method of the tetrahydropyrans alcohol that 2-replaces, and its document number is CN102428077.In the method, particularly accordingly the method preparing 2-isobutyl--4-hydroxy-4-methyl tetrahydropyrans is reacted by prenol and isovaleric aldehyde.
Patent JP2007-154069 describes the method preparing pyrans alcohol, prenol and corresponding aldehyde react in the aqueous solution of an acidic catalyst, temperature of reaction controls at 0 ~ 100 DEG C, catalyzer carries out under the aqueous catalyst solution concentration of 1 ~ 10 % by weight, or at 0 ~ 30 DEG C, catalyzer carries out under 10 % by weight or greater concn aqueous catalyst solution concentration, the first-selected ion exchange resin of catalyzer.
Summary of the invention
In order to carry out industrialization continuous seepage better, improving lily of the valley pyrans productive rate and yield, the invention discloses a kind of preparation technology of lily of the valley pyrans.
Technical scheme of the present invention is, isovaleric aldehyde and prenol and an acidic catalyst are inputted jet-type mixing reactor by certain molar ratio continuously under certain temperature condition react, carry out the preparation of lily of the valley pyrans simultaneously by the mode of the continuous output-response mixture of charge proportion.
A preparation technology for lily of the valley pyrans, comprises the steps:
A, prenol and catalyzer to be added in injection reactor, then add isovaleric aldehyde, temperature of reaction 10 ~ 60 DEG C, preferably 20 ~ 40 DEG C; Circulating reaction 4 ~ 8h, 10 ~ 30min recycle to extinction controlled circulation amount; Wherein, the mol ratio of described prenol and isovaleric aldehyde is 0.5 ~ 1:1, preferably 0.7 ~ 0.9:1; The weight ratio of catalyzer and prenol is 1 ~ 10:100, preferably 5 ~ 9:100; Reactor pressure 0.1 ~ 1Mpa, preferably 0.3 ~ 0.5MPa;
B, add the mixture of prenol that weight ratio is 1:0.01 ~ 0.1 and catalyzer continuously to injection reactor with 1 ~ 5ml/h speed, add isovaleric aldehyde continuously with 2 ~ 6ml/h speed, control mixture discharging with the speed of 3 ~ 11ml/h;
C, by mixture through solvent extraction, washing, obtain lily of the valley pyrans after rectifying, described solvent is aromatic hydrocarbon or naphthenic hydrocarbon, or by it with the mixed solvent of arbitrary proportion, as toluene, hexanaphthene.
Catalyzer of the present invention is acidic cpd, as methylsulfonic acid, sal enixum, tosic acid, ferric sulfate, magnesium sulfate, aluminum oxide, and preferred tosic acid, the more preferably 20% tosic acid aqueous solution.
Reactional equation of the present invention is as follows:
The present invention adopts acidic cpd as catalyzer, and utilize efficient injection reactor as reaction unit, prepare product yield up to 75 ~ 85%, transformation efficiency is more than 90%.
The present invention's reactant feed used and injection reactor, be commercially available.
Beneficial effect
The present invention uses injection reactor to carry out the preparation synthesis of lily of the valley pyrans continuous reaction, compare traditional autoclave rhythmic reaction and fix biography reactor and there is better heat transfer and mass transfer performances, effectively can improve reaction efficiency, acidic cpd is adopted greatly to improve transformation efficiency as catalyzer, yield is high by 75 ~ 85%, and transformation efficiency reaches more than 90%; Simultaneously in industrial applications process because utilizing efficient injection reactor, the hardware device investment of reaction member can be effectively reduced.
Embodiment
Below in conjunction with example, the present invention is described in detail, and to make those skilled in the art understand the present invention better, but the present invention is not limited to following instance.
Embodiment 1
344.52g prenol and 20% tosic acid solution 17g (prenol and tosic acid weight ratio 1:0.05) is dropped in 1L injection reactor, drop into isovaleric aldehyde 378.97g (prenol and isovaleric aldehyde mol ratio 1:1.1) again, circulating reaction 2h at control temperature of reaction 25 DEG C, internal circulating load control 9L/h, control after 2h to add with 35.6ml/h the prenol and 20% tosic acid mixture that mol ratio is 1:0.005 to injection reactor continuously, isovaleric aldehyde is added continuously with 41.4ml/h, control with the outside continuous discharge of 77ml/h, sampling vapor-phase chromatography detects that in compound, lily of the valley pyrans yield is 85%, show that its transformation efficiency is 91%.
Embodiment 2
301.45g prenol and 20% tosic acid solution 15g (prenol and tosic acid weight ratio 1:0.05) is dropped in 1L injection reactor, drop into isovaleric aldehyde 452.18g (prenol and isovaleric aldehyde mol ratio 1:1.5) again, circulating reaction 2h at control temperature of reaction 40 DEG C, internal circulating load control 9L/h, control after 2h to add with 30.5ml/h the prenol and 20% tosic acid mixture that mol ratio is 1:0.005 to injection reactor continuously, isovaleric aldehyde is added continuously with 48.5ml/h, control with the outside continuous discharge of 79ml/h, sampling vapor-phase chromatography detects that in compound, lily of the valley pyrans total recovery is 80%, show that its transformation efficiency is 93%.
Embodiment 3
344.52g prenol and 20% tosic acid solution 34.4g (prenol and tosic acid weight ratio 1:0.1) is dropped in 1L injection reactor, drop into isovaleric aldehyde 413.42g (prenol and isovaleric aldehyde mol ratio 1:1.2) again, circulating reaction 2h at control temperature of reaction 25 DEG C, internal circulating load control 9L/h, control after 2h to add with 35.5ml/h the prenol and 20% tosic acid mixture that mol ratio is 1:0.01 to injection reactor continuously, isovaleric aldehyde is added continuously with 45.2ml/h, control with the outside continuous discharge of 81ml/h, sampling vapor-phase chromatography detects that in compound, lily of the valley pyrans total recovery is 78%, show that its transformation efficiency is 93%.
Embodiment 4
215.33g prenol and 20% tosic acid solution 21.5g (prenol and tosic acid weight ratio 1:0.1) is dropped in 1L injection reactor, drop into isovaleric aldehyde 430.56g (prenol and isovaleric aldehyde mol ratio 1:2) again, circulating reaction 2h at control temperature of reaction 40 DEG C, internal circulating load control 9L/h, control after 2h to add with 25.6ml/h the prenol and 20% tosic acid mixture that mol ratio is 1:0.01 to injection reactor continuously, isovaleric aldehyde is added continuously with 53.8ml/h, control with the outside continuous discharge of 79.5ml/h, sampling vapor-phase chromatography detects that in compound, lily of the valley pyrans total recovery is 68%, show that its transformation efficiency is 95%.
Embodiment 5
344.52g prenol and methylsulfonic acid 17g (prenol and methylsulfonic acid weight ratio 1:0.05) is dropped in 1L injection reactor, drop into isovaleric aldehyde 378.97g (prenol and isovaleric aldehyde mol ratio 1:1.1) again, circulating reaction 2h at control temperature of reaction 25 DEG C, internal circulating load control 9L/h, control after 2h to add with 35.6ml/h the prenol and methanesulfonic acid mixture that mol ratio is 1:0.005 to injection reactor continuously, isovaleric aldehyde is added continuously with 41.4ml/h, control with the outside continuous discharge of 77ml/h, sampling vapor-phase chromatography detects that in compound, lily of the valley pyrans yield is 85%, show that its transformation efficiency is 88%.
Embodiment 6
344.52g prenol and sal enixum 17g (prenol and sal enixum weight ratio 1:0.05) is dropped in 1L injection reactor, drop into isovaleric aldehyde 378.97g (prenol and isovaleric aldehyde mol ratio 1:1.1) again, circulating reaction 2h at control temperature of reaction 25 DEG C, internal circulating load control 9L/h, control after 2h to add with 35.6ml/h the prenol and sal enixum mixture that mol ratio is 1:0.005 to injection reactor continuously, isovaleric aldehyde is added continuously with 41.4ml/h, control with the outside continuous discharge of 77ml/h, sampling vapor-phase chromatography detects that in compound, lily of the valley pyrans yield is 75%, show that its transformation efficiency is 80%.
Embodiment 7
344.52g prenol and ferric sulfate 17g (prenol and ferric sulfate weight ratio 1:0.05) is dropped in 1L injection reactor, drop into isovaleric aldehyde 378.97g (prenol and isovaleric aldehyde mol ratio 1:1.1) again, circulating reaction 2h at control temperature of reaction 25 DEG C, internal circulating load control 9L/h, control after 2h to add with 35.6ml/h the prenol and ferric sulfate mixture that mol ratio is 1:0.005 to injection reactor continuously, isovaleric aldehyde is added continuously with 41.4ml/h, control with the outside continuous discharge of 77ml/h, sampling vapor-phase chromatography detects that in compound, lily of the valley pyrans yield is 87%, show that its transformation efficiency is 60%.
Embodiment 8
344.52g prenol and Adlerika 17g (prenol and magnesium sulfate weight ratio 1:0.05) is dropped in 1L injection reactor, drop into isovaleric aldehyde 378.97g (prenol and isovaleric aldehyde mol ratio 1:1.1) again, circulating reaction 2h at control temperature of reaction 25 DEG C, internal circulating load control 9L/h, control after 2h to add with 35.6ml/h the prenol and magnesium sulfate mixture that mol ratio is 1:0.005 to injection reactor continuously, isovaleric aldehyde is added continuously with 41.4ml/h, control with the outside continuous discharge of 77ml/h, sampling vapor-phase chromatography detects that in compound, lily of the valley pyrans yield is 89%, show that its transformation efficiency is 55%.
Embodiment 9
344.52g prenol and alumina solution 17g (prenol and alumina weight are than 1:0.05) is dropped in 1L injection reactor, drop into isovaleric aldehyde 378.97g (prenol and isovaleric aldehyde mol ratio 1:1.1) again, circulating reaction 2h at control temperature of reaction 25 DEG C, internal circulating load control 9L/h, control after 2h to add with 35.6ml/h the prenol and alumina mixture that mol ratio is 1:0.005 to injection reactor continuously, isovaleric aldehyde is added continuously with 41.4ml/h, control with the outside continuous discharge of 77ml/h, sampling vapor-phase chromatography detects that in compound, lily of the valley pyrans yield is 88%, show that its transformation efficiency is 57%.
The foregoing is only embodiments of the invention; not thereby the scope of the claims of the present invention is limited; every utilize specification sheets of the present invention to do equivalent structure or the conversion of equivalent flow process, or be directly or indirectly used in other relevant technical fields, be all in like manner included in scope of patent protection of the present invention.
Claims (10)
1. a preparation technology for lily of the valley pyrans, is characterized in that, comprises the steps:
A. prenol and catalyzer are added in injection reactor, then add isovaleric aldehyde, temperature of reaction 10 ~ 60 DEG C; Circulating reaction 4 ~ 8h, 10 ~ 30min recycle to extinction controlled circulation amount; Wherein, the mol ratio of described prenol and isovaleric aldehyde is 0.5 ~ 1:1; The weight ratio of catalyzer and prenol is 1 ~ 10:100; Reactor pressure 0.1 ~ 1Mpa;
B. adding weight ratio with 1 ~ 5ml/h speed continuously to injection reactor is the prenol of 1:0.01 ~ 0.1 and the mixture of catalyzer, adds isovaleric aldehyde continuously, control mixture discharging with the speed of 3 ~ 11ml/h with 2 ~ 6ml/h speed;
C. by mixture through solvent extraction, washing, obtain lily of the valley pyrans after rectifying, described solvent is aromatic hydrocarbon or naphthenic hydrocarbon, or by it with the mixed solvent of arbitrary proportion.
2. the preparation technology of lily of the valley pyrans according to claim 1, is characterized in that, in steps A, temperature of reaction is 20 ~ 40 DEG C.
3. the preparation technology of lily of the valley pyrans according to claim 1, is characterized in that, the mol ratio of prenol described in steps A and isovaleric aldehyde is 0.7 ~ 0.9:1.
4. the preparation technology of lily of the valley pyrans according to claim 1, is characterized in that, the weight ratio 5 ~ 9:100 of catalyzer and prenol in steps A.
5. the preparation technology of lily of the valley pyrans according to claim 1, is characterized in that, reactor pressure 0.3 ~ 0.5MPa in steps A.
6. the preparation technology of lily of the valley pyrans according to claim 1, is characterized in that, solvent described in step C is toluene or hexanaphthene, or by it with the solvent of arbitrary proportion mixing.
7. the preparation technology of the lily of the valley pyrans according to aforementioned arbitrary claim, is characterized in that, described catalyzer is acidic cpd.
8. the preparation technology of lily of the valley pyrans according to claim 7, is characterized in that, described catalyzer is methylsulfonic acid, sal enixum, tosic acid, ferric sulfate, magnesium sulfate or aluminum oxide.
9. the preparation technology of lily of the valley pyrans according to claim 8, is characterized in that, described catalyzer is tosic acid.
10. the preparation technology of lily of the valley pyrans according to claim 9, is characterized in that, described catalyzer is the 20% tosic acid aqueous solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510159723.0A CN104803958A (en) | 2015-04-03 | 2015-04-03 | Preparation technique for florosa |
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| CN201510159723.0A CN104803958A (en) | 2015-04-03 | 2015-04-03 | Preparation technique for florosa |
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| CN201510159723.0A Pending CN104803958A (en) | 2015-04-03 | 2015-04-03 | Preparation technique for florosa |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105175372A (en) * | 2015-09-23 | 2015-12-23 | 山东新和成药业有限公司 | Method for compounding lily-of-the-valley pyran through reaction under static bed loaded solid superacid catalysis |
| CN109608426A (en) * | 2018-12-04 | 2019-04-12 | 万华化学集团股份有限公司 | A kind of method for synthesizing lily of the valley pyran by taking the waste liquid of producing citral as raw material |
| CN111039907A (en) * | 2019-11-27 | 2020-04-21 | 万华化学集团股份有限公司 | Method for preparing 2- (2-methylpropyl) -4-hydroxy-4-methyl tetrahydropyran |
| CN114011461A (en) * | 2021-11-24 | 2022-02-08 | 万华化学集团股份有限公司 | Heterogeneous catalyst based on eutectic solvent and application thereof |
| CN114210366A (en) * | 2022-01-12 | 2022-03-22 | 万华化学集团股份有限公司 | Supported heteropolyacid catalyst, preparation method and application thereof in preparation of lily-of-the-valley pyran |
| CN114797968A (en) * | 2021-01-18 | 2022-07-29 | 万华化学集团股份有限公司 | Supported phosphoric acid catalyst and preparation method and application thereof |
| CN119930560A (en) * | 2025-01-23 | 2025-05-06 | 浙江工业大学 | A kind of synthetic method of lily of the valley pyran |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1590384A (en) * | 2003-07-04 | 2005-03-09 | 花王株式会社 | Process for producing a pyran compound |
| JP2007154069A (en) * | 2005-12-06 | 2007-06-21 | T Hasegawa Co Ltd | Perfume ingredients and method for producing the same |
| CN201906610U (en) * | 2010-11-14 | 2011-07-27 | 潍坊兴潍科技创新咨询服务中心 | Spraying reaction device |
-
2015
- 2015-04-03 CN CN201510159723.0A patent/CN104803958A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1590384A (en) * | 2003-07-04 | 2005-03-09 | 花王株式会社 | Process for producing a pyran compound |
| JP2007154069A (en) * | 2005-12-06 | 2007-06-21 | T Hasegawa Co Ltd | Perfume ingredients and method for producing the same |
| CN201906610U (en) * | 2010-11-14 | 2011-07-27 | 潍坊兴潍科技创新咨询服务中心 | Spraying reaction device |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105175372B (en) * | 2015-09-23 | 2018-03-16 | 山东新和成药业有限公司 | A kind of method that reaction synthesizes lily of the valley pyrans under fixed bed carried solid superacid as catalyst |
| CN105175372A (en) * | 2015-09-23 | 2015-12-23 | 山东新和成药业有限公司 | Method for compounding lily-of-the-valley pyran through reaction under static bed loaded solid superacid catalysis |
| CN109608426A (en) * | 2018-12-04 | 2019-04-12 | 万华化学集团股份有限公司 | A kind of method for synthesizing lily of the valley pyran by taking the waste liquid of producing citral as raw material |
| CN109608426B (en) * | 2018-12-04 | 2020-11-24 | 万华化学集团股份有限公司 | A kind of method for synthesizing lily of the valley pyran by taking the waste liquid of producing citral as raw material |
| CN111039907A (en) * | 2019-11-27 | 2020-04-21 | 万华化学集团股份有限公司 | Method for preparing 2- (2-methylpropyl) -4-hydroxy-4-methyl tetrahydropyran |
| CN114797968B (en) * | 2021-01-18 | 2024-06-25 | 万华化学集团股份有限公司 | A supported phosphoric acid catalyst and its preparation method and use |
| CN114797968A (en) * | 2021-01-18 | 2022-07-29 | 万华化学集团股份有限公司 | Supported phosphoric acid catalyst and preparation method and application thereof |
| CN114011461A (en) * | 2021-11-24 | 2022-02-08 | 万华化学集团股份有限公司 | Heterogeneous catalyst based on eutectic solvent and application thereof |
| CN114011461B (en) * | 2021-11-24 | 2023-05-26 | 万华化学集团股份有限公司 | Heterogeneous catalyst based on eutectic solvent and application thereof |
| CN114210366A (en) * | 2022-01-12 | 2022-03-22 | 万华化学集团股份有限公司 | Supported heteropolyacid catalyst, preparation method and application thereof in preparation of lily-of-the-valley pyran |
| CN114210366B (en) * | 2022-01-12 | 2023-08-11 | 万华化学集团股份有限公司 | Supported heteropolyacid catalyst, preparation method and application thereof in preparation of convallaria |
| CN119930560A (en) * | 2025-01-23 | 2025-05-06 | 浙江工业大学 | A kind of synthetic method of lily of the valley pyran |
| CN119930560B (en) * | 2025-01-23 | 2025-10-14 | 浙江工业大学 | A kind of synthetic method of lily of the valley pyran |
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