CN105218312B - Method for continuously preparing linalool from allylic alcohol by isomerization process - Google Patents
Method for continuously preparing linalool from allylic alcohol by isomerization process Download PDFInfo
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- CN105218312B CN105218312B CN201510734564.2A CN201510734564A CN105218312B CN 105218312 B CN105218312 B CN 105218312B CN 201510734564 A CN201510734564 A CN 201510734564A CN 105218312 B CN105218312 B CN 105218312B
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/56—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by isomerisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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Abstract
The invention provides a method for continuously preparing linalool from allylic alcohol by an isomerization process. The method comprises the following steps: preparing a vanadium-amine complex catalyst, adding a reacting product and a catalyst, controlling isomerization reaction conditions, constantly adding the reacting product, and constantly rectifying, wherein the vanadium-amine complex catalyst is prepared by adding 1 part by weight of xylene, 0.01-0.1 part by weight of a vanadium compound and 0.01-0.1 part by weight of nitrogen base, starting to stir and heat, insulating for 1-3 hours at 140 DEG C, cooling to below 50 DEG C, and filtering to reclaim the catalyst. According to the method, the catalyst system has high reaction selectivity, the selectivity of linalool is 93.2-96.2 percent, the yield of linalool is 92.7-94.5 percent, the scrap rate is 2.7-4.0 percent, and the linalool content is 98.5-98.7 percent. The catalyst has low unit consumption.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to a kind of allyl alcohol Jing isomerization process continuously prepares Lignum cinnamomi camphorae
The method of alcohol.
Background technology
Linalool (Linaloo1) also known as linalool, linalool.Scientific name is 3,7- dimethyl -1,6- octadiene -3- alcohol.Virtue
The Camphor tree alcohol and its ester fragrance of a flower fragrance of happiness mostly with grace, it occupies important ground in the composition of many odor types
Position, can be used to allocate the various essence such as Bulbus Lilii, Flos Caryophylli, orange blossom, or the important source material of synthesis Wei Shengsuo E, A.
The isomerization reaction of allyl alcohol is 1, the 3- migrations of corresponding hydroxyl and the movement of corresponding double bond, geraniol/orange
Flower alcohol isomerization reaction equation is as follows：
The catalyst for being presently available for allyl alcohol isomery mainly has following several：
1st, acid catalyst
Patent EP0012198, document [Journal of the Indian Chemical Society, 1998,
Vol. 75, # 10-12 p. 688-689] and document [Bulletin de la Societe Chimique de
France, 1919 , vol. <4>25, p. 68] report and catalyst is done using liquid acid or solid acid, by geraniol/orange
The method that flower alcohol directly tautomerizes to linalool, the shortcoming of the method is in acid condition, side reaction dehydration and cyclisation account for master
Reaction is led, the selectivity of linalool is relatively low.
2nd, W-Sn deposits
Patent WO2001/042177 and patent WO2003/048091 describe one kind and use tungsten oxide and part to constitute
Catalyst system and catalyzing be used for the isomerization reaction of allyl alcohol, done using the citral transformation of geraniol/nerol mixture that obtains of hydrogenation
Raw material, semi-continuous reaction 30h obtain the yield that content is 98% linalool and are about 92%.The advantage of the method is reaction yield
Higher, shortcoming is that catalyst price is higher, prepares difficulty larger.
3rd, vanadium series catalyst.
Document [Bulletin of the Chemical Society of Japan, 1985, vol. 58, # 3
P. 844-849] describe using bis-acetylacetonate vanadyl and double trimethyl silicane peroxide catalysis under, nerol isomery
Selectivity for linalool is 70%.The catalyst that patent 4006193 describes formula VO (OR) 3 is anti-to the isomery of allyl alcohol
The effect answered, with linalool as raw material, (i-Bu)3VO is catalyst, and 4h is reacted at 190 DEG C, and conversion ratio is 37.6%, is prepared fragrant
Folic alcohol/nerol selectivity is up to 98.4%.Document [Tetrahedron, 1977,33,
1775-1783] description isomerization reaction of the vanadium series catalyst to allyl alcohols, using tetrahydrolinalool ortho-vanadic acid
Ester is catalyst, and after linalool reacts 1.5h at 160 DEG C, conversion ratio is 30%, and selectivity is 85%.The advantage of the method is vanadium system
Catalyst is cheap, advantageously reduces cost, and shortcoming is that reaction conversion ratio is relatively low, and reaction temperature is higher（More than 160 DEG C）,
Cause heel rate higher.
The content of the invention
The present invention is solution above technical problem, there is provided a kind of allyl alcohol Jing isomerization process continuously prepares the side of linalool
Method, the present invention with geraniol, nerol one or two as raw material, the vanadium amine prepared in vanadium sub-group compound and nitrogenous base coordinates
Under thing catalyst action, by the method for reactive distillation, linalool is continuously prepared.
The present invention realizes following goal of the invention：
（1）The inventive method, the catalyst system reaction selectivity for using are high, and linalool high income, heel rate are low, Lignum cinnamomi camphorae
Alcohol content is up to more than 98.5%.
（2）The inventive method, technique is reactive distillation processes, continuous feed, continuous discharge, the high conversion rate of raw material, and
It is easy to operate.
（3）Catalyst price of the present invention is low, prepares simply, and long service life, unit consumption are low.
To solve the above problems, the present invention is employed the following technical solutions：
A kind of method that allyl alcohol Jing isomerization process continuously prepares linalool, including preparing vanadium amine complex catalyst,
Add reactant, catalyst, the control of isomerization reaction condition to be continuously added into reactant, continue rectification.
The following is the further restriction to above-mentioned technical proposal：
It is described to prepare vanadium amine complex catalyst, the dimethylbenzene of 1 weight portion is added, the vanadium of 0.01～0.1 weight portion is added
The nitrogen base of based compound and 0.01～0.1 weight portion, starts stirring and heats up, 140 DEG C of 1～3h of insulation, cools to less than 50 DEG C, mistake
Catalyst is reclaimed in filter.
The vanadium sub-group compound is vanadic anhydride, Vanadium sesquioxide, one or more in ammonium metavanadate.
The nitrogen base is one or more of primary, secondary, tertiary monoamine, polyamine, amino alcohol.
The nitrogen base is methylamine, ethamine, propylamine, aniline, dimethylamine, diethylamine, dibutyl amine, piperidines, morpholine, front three
One or more in amine, triethylamine, tricyclohexyltin amine, pyridine, quinoline, N- crassitudes, ethylenediamine, pyrazine, ethanolamine.
The vanadium sub-group compound is 1 with the mol ratio of nitrogen base:0.5～3.
The addition reactant, catalyst, it is 0.003～0.05 that catalyst accounts for the mass ratio of reactant:1.
The reactant is allyl alcohol；The allyl alcohol is geraniol, one or two in nerol.
The control of the isomerization reaction condition, by adjusting vacuum degree control kettle temperature at 140-180 DEG C, vacuum degree control
In 6000～15000Pa, and the linalool for generating is steamed from tower top, reflux ratio is controlled for 3～5:1, maintain top temperature constant,
Top temperature maintains 110～135 DEG C.
The kettle temperature, preferably 140～160 DEG C.
Described to continue rectification, control top temperature is constant, and top temperature maintains 110～125 DEG C, and reflux ratio is gradually adjusted to 10:1,
Continue rectification until during tower top Lignum cinnamomi camphorae alcohol content ＜ 90.0%, vacuum is turned down to 1000Pa or so, leftover materials are steamed, kettle
Temperature control system is within 110 DEG C.
When the by-product accumulated in kettle is more, when the formation speed of linalool is decreased obviously, suitably can add a certain amount of
Catalyst.
The present invention is intended to provide a kind of method that allyl alcohol Jing isomerization process continuously prepares linalool, with prior art phase
Than beneficial effects of the present invention are：
（1）The inventive method, the catalyst system reaction selectivity for using are high, and the selectivity of linalool is 93.2-
96.2%, linalool yield is 92.7-94.5%, and heel rate is 2.7-4.0%, and Lignum cinnamomi camphorae alcohol content is 98.5-98.7%.
（2）The inventive method, technique are reactive distillation processes, and continuous feed, continuous discharge are easy to operate.
（3）Catalyst price of the present invention is low, prepares simple, long service life, operates continuously 48h, and activity has no substantially drop
Low, catalyst consumption is about 0.0015-0.006 g/g linalool finished products.
Specific embodiment
Hereinafter the preferred embodiments of the present invention are illustrated, it will be appreciated that preferred embodiment described herein is only used
In the description and interpretation present invention, it is not intended to limit the present invention.
The method that a kind of 1 allyl alcohol Jing isomerization process of embodiment continuously prepares linalool
（1）Prepare vanadium amine complex catalyst
500.0g dimethylbenzene is added in the there-necked flask with thermometer, condensing tube and churned mechanically 1000ml, plus
Enter 5.0g (0.0274mol) vanadic anhydrides and 5g（0.0494mol）Triethylamine, opens mechanical agitation intensification, is incubated 1 at 140 DEG C
Hour, cooling is filtered by sand core funnel, and filter cake is washed twice with ether, obtains vanadium amine complex catalyst, about 5.9g.
（2）Add reactant, catalyst
500.0g Herba Pelargonii Graveolentiss are added in the there-necked flask of the 1000ml for being furnished with thermometer, 60cm rectifying columns and magnetic stirring apparatuss
The transformation of geraniol/nerol mixture that alcohol content is 63.5% and orange blossom alcohol content is 35.6%, adds vanadium amine complex catalyst
5.9g。
（3）The control of isomerization reaction condition
Stirring heats up, and opens vacuum pump pulling vacuum, by adjusting vacuum degree control kettle temperature at 140 DEG C or so, vacuum degree control
In 6000Pa or so, and the linalool for generating is steamed from tower top, reflux ratio is controlled for 3～5:1, maintain top temperature constant, top
Temperature maintains 110～115 DEG C.
（4）It is continuously added into reactant
Linalool is continuously produced with the speed for being about 75g/h, while the Lignum cinnamomi camphorae with extraction is continuously added in there-necked flask
The transformation of geraniol/nerol mixture of the roughly the same amount of alcohol, adds speed to be about 78g/h, to keep the perseverance of inventory in reactor
It is fixed.After continuous and quantitative Deca 48h, transformation of geraniol/nerol mixture addition is 3623.8g, stops Deca.
（5）Continue rectification
Continue control top temperature constant, push up temperature and maintain 110～115 DEG C, adjust reflux ratio, reflux ratio is gradually adjusted to 10:
1, continue rectification until during tower top Lignum cinnamomi camphorae alcohol content ＜ 90.0%, vacuum is turned down to 1000Pa or so, by leftover materials in flask
Steam, kettle temperature is controlled within 110 DEG C.
It is 98.8% linalool to steam 3896.9g contents, and 100.3g Herba Pelargonii Graveolentiss alcohol content is that 42.5%, orange blossom alcohol content is
15.6% and the mixture of Lignum cinnamomi camphorae alcohol content 30.4%, 105.8g heavy constituent heels.The selectivity for calculating linalool is 96.2%, is received
Rate is 94.5%, and heel rate is 2.7%, and catalyst consumption is about 0.0015 g/g linalool finished products.
The method that a kind of 2 allyl alcohol Jing isomerization process of embodiment continuously prepares linalool
（1）Prepare catalyst vanadium amine complex
500.0g dimethylbenzene is added in the there-necked flask with thermometer, condensing tube and churned mechanically 1000ml, plus
Enter 20g（0.133mol）Vanadium sesquioxide and 8.5g (0.144mol) n-propylamine, open mechanical agitation intensification, are incubated 2 at 140 DEG C
Hour, cooling is filtered by sand core funnel, and filter cake is washed twice with ether, obtains vanadium amine complex catalyst about 25.2g.
（2）Add reactant, catalyst
500.0g contents are added in the there-necked flask of the 1000ml for being furnished with thermometer, 60cm rectifying columns and magnetic stirring apparatuss
For 98.7% geraniol, vanadium amine complex catalyst 25.2g is added.
（3）The control of isomerization reaction condition
Stirring heats up, and opens vacuum pump pulling vacuum, by adjusting vacuum degree control kettle temperature at 150 DEG C or so, vacuum degree control
In 9000Pa or so, and the linalool for generating is steamed from tower top, reflux ratio is controlled for 3～5:1, maintain top temperature constant, top
Temperature maintains 115～120 DEG C.
（4）It is continuously added into reactant
Linalool is continuously produced with the speed for being about 100g/h, while the Lignum cinnamomi camphorae with extraction is continuously added in there-necked flask
The transformation of geraniol/nerol mixture of the roughly the same amount of alcohol, adds speed to be about 104g/h, to keep the perseverance of inventory in reactor
It is fixed.After continuous and quantitative Deca 48h, transformation of geraniol/nerol mixture addition is 4925.7g, stops Deca.When what is accumulated in kettle
By-product is more, when the formation speed of linalool is decreased obviously, can suitably add a certain amount of catalyst.
（5）Continue rectification
Continue control top temperature constant, push up temperature and maintain 115～120 DEG C, adjust reflux ratio, reflux ratio is gradually adjusted to 10:
1, continue rectification until during tower top Lignum cinnamomi camphorae alcohol content ＜ 90.0%, vacuum is turned down to 1000Pa or so, by leftover materials in flask
Steam, kettle temperature is controlled within 110 DEG C.
It is 98.7% linalool to steam 5029.6g contents, and it is 3.7% that 165.3g Herba Pelargonii Graveolentiss alcohol content is 70.1%, orange blossom alcohol content
With the mixture of Lignum cinnamomi camphorae alcohol content 20.6%, 200.7g heavy constituent heels.The selectivity for calculating linalool is about 93.2%, and yield is about
For 92.7%, heel rate is about 4.0%, and catalyst consumption is about 0.005 g/g linalool finished products.
The method that a kind of 3 allyl alcohol Jing isomerization process of embodiment continuously prepares linalool
（1）Prepare vanadium amine complex catalyst
500.0g dimethylbenzene is added in the there-necked flask with thermometer, condensing tube and churned mechanically 1000ml, plus
Enter 30g（0.256mol）Ammonium metavanadate and 10.5g (0.172mol) ethanolamine, open mechanical agitation intensification, little in 140 DEG C of insulations 2
When, cooling is filtered by sand core funnel, and filter cake is washed twice with ether, obtains vanadium amine complex catalyst about 33.6g.
（2）Add reactant, catalyst
500.0g contents are added in the there-necked flask of the 1000ml for being furnished with thermometer, 60cm rectifying columns and magnetic stirring apparatuss
For 98.0% nerol, vanadium amine complex catalyst 33.6g is added.
（3）The control of isomerization reaction condition
Stirring heats up, and opens vacuum pump pulling vacuum, by adjusting vacuum degree control kettle temperature at 160 DEG C or so, vacuum degree control
In 12000Pa or so, and the linalool for generating is steamed from tower top, reflux ratio is controlled for 3～5:1, maintain top temperature constant, top
Temperature maintains 120～125 DEG C.
（4）It is continuously added into reactant
Linalool is continuously produced with the speed for being about 110g/h, while the Lignum cinnamomi camphorae with extraction is continuously added in there-necked flask
The transformation of geraniol/nerol mixture of the roughly the same amount of alcohol, adds speed to be about 112g/h, to keep the perseverance of inventory in reactor
It is fixed.After continuous and quantitative Deca 48h, transformation of geraniol/nerol mixture addition is 5270.6g, stops Deca.When what is accumulated in kettle
By-product is more, when the formation speed of linalool is decreased obviously, can suitably add a certain amount of catalyst.
（5）Continue rectification
Continue control top temperature constant, push up temperature and maintain 120～125 DEG C, adjust reflux ratio, reflux ratio is gradually adjusted to 10:
1, continue rectification until during tower top Lignum cinnamomi camphorae alcohol content ＜ 90.0%, vacuum is turned down to 1000Pa or so, by leftover materials in flask
Steam, kettle temperature is controlled within 110 DEG C.
It is 98.5% linalool to steam 5403.7g contents, and it is 51.4% that 120.0g Herba Pelargonii Graveolentiss alcohol content is 20%, orange blossom alcohol content
With the mixture of Lignum cinnamomi camphorae alcohol content 20.6%, 219.4g heavy constituent heels.The selectivity for calculating linalool is about 95.9%, and yield is about
For 93.6%, heel rate is about 4.0%, and catalyst consumption is about 0.006g/g linalool finished products.
Unless otherwise stated, the percent employed in the present invention is percetage by weight, ratio of the present invention,
For mass ratio.
The ultimate principle and principal character and advantages of the present invention of the present invention has been shown and described above.The skill of the industry
Simply explanation of the art personnel it should be appreciated that the present invention is not restricted to the described embodiments, described in above-described embodiment and description
The principle of the present invention, without departing from the spirit and scope of the present invention, the present invention also has various changes and modifications, these
Changes and improvements are both fallen within scope of the claimed invention.The claimed scope of the invention by appending claims and
Its equivalent thereof.
Claims (6)
1. a kind of method that allyl alcohol Jing isomerization process continuously prepares linalool, it is characterised in that：Coordinate including vanadium amine is prepared
Thing catalyst, adds reactant, catalyst, the control of isomerization reaction condition to be continuously added into reactant, continues rectification；
The vanadium amine complex catalyst, including vanadium sub-group compound and nitrogen base；The weight part ratio of the vanadium sub-group compound and nitrogen base
Example be：0.1：0.01～0.1；
Described vanadium sub-group compound is vanadic anhydride, Vanadium sesquioxide, one or more in ammonium metavanadate；
The nitrogen base is methylamine, ethamine, propylamine, aniline, dimethylamine, diethylamine, dibutyl amine, piperidines, morpholine, trimethylamine, three second
One or more in amine, tricyclohexyltin amine, pyridine, quinoline, N- crassitudes, ethylenediamine, pyrazine, ethanolamine；
The control of the isomerization reaction condition, control kettle temperature is at 140-160 DEG C；
The addition reactant, catalyst, it is 0.003～0.05 that catalyst accounts for the mass ratio of reactant:1；
It is described to be continuously added into reactant, continuous and quantitative dropwise reaction thing 48h.
2. the method that a kind of allyl alcohol Jing isomerization process according to claim 1 continuously prepares linalool, its feature exist
In：It is described to prepare vanadium amine complex catalyst, the dimethylbenzene of 1 weight portion is added, the vanadium system chemical combination of 0.01～0.1 weight portion is added
The nitrogen base of thing and 0.01～0.1 weight portion, starts stirring and heats up, 140 DEG C of 1～3h of insulation, cools to less than 50 DEG C, is recovered by filtration
Catalyst.
3. the method that a kind of allyl alcohol Jing isomerization process according to claim 2 continuously prepares linalool, its feature exist
In：Prepare in vanadium amine complex catalyst process, the vanadium sub-group compound is 1 with the mol ratio of nitrogen base:0.5～3.
4. the method that a kind of allyl alcohol Jing isomerization process according to claim 1 continuously prepares linalool, its feature exist
In：The control of the isomerization reaction condition, vacuum degree control is in 6000～15000Pa, and causes the linalool for generating from tower
Top steams, and controls reflux ratio for 3～5:1, maintain top temperature constant, top temperature maintains 110～135 DEG C.
5. the method that a kind of allyl alcohol Jing isomerization process according to claim 1 continuously prepares linalool, its feature exist
In：The reactant is allyl alcohol；The allyl alcohol is geraniol, one or two in nerol.
6. the method that a kind of allyl alcohol Jing isomerization process according to claim 1 continuously prepares linalool, its feature exist
In：Described to continue rectification, control top temperature is constant, and top temperature maintains 110～125 DEG C, and reflux ratio is gradually adjusted to 10:1, continue essence
Evaporate until during tower top Lignum cinnamomi camphorae alcohol content ＜ 90.0%, vacuum is turned down to 1000Pa or so, leftover materials are steamed, kettle temperature control
Within 110 DEG C.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3925485A (en) * | 1968-12-30 | 1975-12-09 | Rhone Poulenc Sa | Process for the preparation of allylic alcohols |
| CN1402699A (en) * | 1999-12-06 | 2003-03-12 | 巴斯福股份公司 | Method for isomerising allyl alcohols |
| CN1461291A (en) * | 2000-09-20 | 2003-12-10 | 巴斯福股份公司 | Method for isomerisation of alcohols |
| CN1599644A (en) * | 2001-12-07 | 2005-03-23 | 巴斯福股份公司 | Method for isomerizing allyl alcohols |
| CN104024201A (en) * | 2011-12-26 | 2014-09-03 | 公益财团法人相模中央化学研究所 | Method for producing farnesal using vanadium complex |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57139027A (en) * | 1981-02-24 | 1982-08-27 | Dainippon Ink & Chem Inc | Preparation of secondary or tertiary allyl alcohol |
-
2015
- 2015-11-03 CN CN201510734564.2A patent/CN105218312B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3925485A (en) * | 1968-12-30 | 1975-12-09 | Rhone Poulenc Sa | Process for the preparation of allylic alcohols |
| CN1402699A (en) * | 1999-12-06 | 2003-03-12 | 巴斯福股份公司 | Method for isomerising allyl alcohols |
| CN1461291A (en) * | 2000-09-20 | 2003-12-10 | 巴斯福股份公司 | Method for isomerisation of alcohols |
| CN1599644A (en) * | 2001-12-07 | 2005-03-23 | 巴斯福股份公司 | Method for isomerizing allyl alcohols |
| CN104024201A (en) * | 2011-12-26 | 2014-09-03 | 公益财团法人相模中央化学研究所 | Method for producing farnesal using vanadium complex |
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