CN108484394A - A kind of preparation method of n-octyl alcohol ester and its n-octyl alcohol - Google Patents
A kind of preparation method of n-octyl alcohol ester and its n-octyl alcohol Download PDFInfo
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- CN108484394A CN108484394A CN201810321005.2A CN201810321005A CN108484394A CN 108484394 A CN108484394 A CN 108484394A CN 201810321005 A CN201810321005 A CN 201810321005A CN 108484394 A CN108484394 A CN 108484394A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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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
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/095—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of organic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
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Abstract
The invention discloses the preparation method of a kind of n-octyl alcohol ester and its n-octyl alcohol, solves the problems, such as that catalyst synthesis is complicated, of high cost in existing n-octyl alcohol preparation process, hydrogen pressure is high, industrialization is difficult and realize.The present invention passes through double catalytic action of metal salts of trifluoromethane sulphonic acid and hydrogenation catalyst with the condensation product A of furfural and acetone, accurately controls open loop, efficiently generates n-octyl alcohol ester, and the n-octyl alcohol ester generates n-octyl alcohol using saponification.The advantages that present invention has a product yield high, and catalyst is efficient and repeatable utilization, and simple for process, reaction condition is mild, environmental-friendly, and industrialization degree is high.
Description
Technical field
The present invention relates to organic chemical intermediates preparing technical fields, and in particular to a kind of n-octyl alcohol ester and its n-octyl alcohol
Preparation method.
Background technology
N-octyl alcohol is a kind of colourless liquid, there is strong impulse smell, density 0.83, refractive index 1.430, fusing point -16
DEG C, 196 DEG C of boiling point.It is water-immiscible but miscible with ethyl alcohol, ether, chloroform.For essence processed, cosmetics, and as solvent,
Antifoaming agent, plasticizer, antifreezing agent, lube oil additive etc..It is from the lauric by-product of coconut oil system.It also can be by ethylene through urging
Change after control polymerize again through hydrolyzing, being isolated.
N-octyl alcohol is used as the intermediate of solvent and fragrance mainly for the production of plasticizer, extractant, stabilizer.Octanol sheet
Body also serves as fragrance, concocts rose, the floral perfumes such as lily, as soap perfume.The product are that Chinese GB2760-86 is defined as permitting
Perhaps the flavorant used.Mainly preparing coconut, pineapple, peach, chocolate and Citrus essence.
N-octyl alcohol can be obtained by the simple saponification of n-octyl alcohol ester.
The existing method for preparing n-octyl alcohol and its n-octyl alcohol ester has following several：First, using octanoic acid in rhenium as catalysis
Reduction hydrogenation obtains octanol and octanol ether under conditions of agent, but the preparation method makees catalyst using rhenium metal, expensive
And the hydrogen pressure needed is higher；Second is that generating octanol and octanol ether, the preparation side under the action of ruthenium-containing catalyst by furfural acetone
Catalyst used in method is expensive and synthesis is complex；Third, using furfural acetone in the catalyst action containing precious metal palladium
Synthesis octanol in next step, but the synthesis of the catalyst of the preparation method is more complex and required hydrogen pressure is higher.The above existing preparation
The method of octanol, which exists, is difficult to industrialized problem, for this reason, it is necessary to invent a kind of simple, high and low cost of yield, suitable of preparing
Close the preparation method of large-scale industrial production.
Invention content
The invention solves practical problem be：Catalyst efficiency is low in the existing method for preparing n-octyl alcohol, hydrogen pressure is high, no
It is suitble to large-scale industrial production.
The present invention is accomplished by the following way：
The preparation method of a kind of n-octyl alcohol ester and its n-octyl alcohol is raw material in alkaline matter catalytic action using furfural and acetone
Lower generation condensation reaction generates the double catalytic action of condensation product A, the condensation product A through ring opening catalyst and hydrogenation catalyst
Occur plus hydrogen ring-opening reaction obtains n-octyl alcohol ester, the ring opening catalyst is metal salts of trifluoromethane sulphonic acid.
The present invention design principle be：Furfural can generate condensation product A with acetone by Aldol condensation reactions.It is described
Condensation product A is under double catalytic action of ring opening catalyst metal salts of trifluoromethane sulphonic acid and hydrogenation catalyst in condensation product A
Furan nucleus is hydrogenated saturation first, and carbonyl is hydrogenated generation hydroxyl later, and hydroxyl is esterified as ester in Organic Acid System.With
By open loop under the action of metal salts of trifluoromethane sulphonic acid, the hydroxyl that open loop generates equally is esterified to obtain three tetrahydrofuran ring afterwards
Ester.Two ester groups of non-segment are sloughed under the action of ring opening catalyst, finally obtain n-octyl alcohol ester.N-octyl alcohol ester passes through saponification
Corresponding n-octyl alcohol is obtained by the reaction, i.e., by being condensed and adding hydrogen ring-opening reaction two-step method to prepare octanol ester, as follows.
It is described condensation production A structural formula be：
The present invention, as ring opening catalyst, can accurately control furans by using acid suitable metal salts of trifluoromethane sulphonic acid
The ring-opening reaction of ring, overcomes acid too strong generation alkane, it is acid not enough can not then succeed open loop the problem of.
Preferably, the metal state in the metal salts of trifluoromethane sulphonic acid is+1-+6 valences, the metal salts of trifluoromethane sulphonic acid
Dosage be the condensation product A 0.1-10mol%.
Preferably, the dosage of the metal salts of trifluoromethane sulphonic acid is the 0.3-5mol% of the condensation product A.
Preferably, the dosage of the metal salts of trifluoromethane sulphonic acid is the 0.5-5mol% of the condensation product A.
Preferably, the dosage of the metal salts of trifluoromethane sulphonic acid be the condensation product A 0.2mol%,
0.4mol%, 0.6mol%, 0.7mol%, 0.9mol%, 1mol%, 1.3mol%, 1.7mol%, 1.9mol%,
2.2mol%, 2.5mol%, 2.7mol%, 2.9mol%, 3.5mol%, 3.7mol%, 4mol%, 4.5mol%,
4.8mol%, 5.3mol%, 5.8mol%, 6.2mol%, 6.9mol%, 7.1mol%, 8.3mol%, 8.8mol% or
9.5mol%.
Preferably, the metal salts of trifluoromethane sulphonic acid is W (OTf)6、Zr(OTf)4、Al(OTf)3、Sc(OTf)3、Nb
(OTf)5、Cu(OTf)2、Sc(OTf)2、Hf(OTf)2, it is one or more in AgOTf.
Preferably, the metal salts of trifluoromethane sulphonic acid is Sc (OTf)3。
Preferably, the hydrogenation catalyst is the catalyst containing the VIIIth group 4 transition metal element；The hydrogenation catalyst
Additive amount be the condensation product A 0.01-10mol%.
Preferably, the hydrogenation catalyst is one kind of palladium carbon or platinum carbon.
The condensation reaction the specific steps are：The ratio between amount by substance is 1:1 to 1:50 furfural with acetone and with
The alkaline matter of 0.01-1mol% on the basis of furfural is added in reactor and mixes, and 2- is stirred under conditions of 10-30 DEG C of temperature
Obtain condensation product A within 20 hours.
Described plus hydrogen ring-opening reaction the specific steps are：By the condensation product A, hydrogenation catalyst, trifluoromethanesulfonic acid metal
Salt and acidic organic solvent, which are added in reactor, is mixed to get mixture, hydrogen is passed through, by the mixture in 2-15MPa hydrogen
Pressure, reacts 10min-24h under 50-250 DEG C and stirring condition, and postcooling obtains the reaction solution of the ester containing n-octyl alcohol to 10-30 DEG C.
Preferably, the hydrogen pressure is 2-5MPa.
Preferably, described plus hydrogen ring-opening reaction temperature is 80-220 DEG C.
Preferably, described plus hydrogen ring-opening reaction temperature is 100-180 DEG C.
Preferably, described plus hydrogen ring-opening reaction temperature be 90 DEG C, 95 DEG C, 110 DEG C, 120 DEG C, 130 DEG C, 140 DEG C,
One in 150 DEG C, 160 DEG C, 170 DEG C, 185 DEG C, 190 DEG C, 200 DEG C, 205 DEG C and 215 DEG C.
Preferably, the described plus hydrogen ring-opening reaction time is 30min-4h.
Preferably, described plus hydrogen ring-opening reaction time be 30min, 35min, 40min, 45min, 50min, 55min,
60min、70min、80min、90min、100min、120min。
Preferably, described plus hydrogen ring-opening reaction stir speed (S.S.) is 100-800r/min.
Preferably, the acidic organic solvent is carboxylic acid.
Preferably, the carboxylic acid is one kind of formic acid, acetic acid, propionic acid.
Preferably, the preparation method of the n-octyl alcohol ester further includes being isolated and purified to the n-octyl alcohol ester, described point
From purifying the specific steps are：The reaction solution is adjusted to PH=7-9, using ethyl acetate as extractant, using anhydrous sulphur
Sour sodium obtains the n-octyl alcohol ester of alcohol as drier, finally vacuum distillation.
Preferably, the preparation method further includes the recycling of ring opening catalyst and hydrogenation catalyst, the specific steps are：
By the n-octyl alcohol ester after reaction solution separation, ring opening catalyst and hydrogenation catalyst are left in the reactor, then again
The condensation product A is added and acidic organic solvent carries out plus hydrogen ring-opening reaction.
Preferably, the recycling of the ring opening catalyst and hydrogenation catalyst, the specific steps are：Also by hydrogenation catalyst
It is that ring opening catalyst is carried on the carrier surface of aluminium oxide, silica gel or activated carbon, is reloaded into reactor, by the condensation
Product A is continuously added to from one end of the reactor, and the reaction solution of n-octyl alcohol ester is released by the other end of the reactor, described
The ring opening catalyst and hydrogenation catalyst left in reactor continues to be catalyzed, and realizes the repeated recycling utilize to catalyst,
The reactor is fixed-bed tube reactor.
A method of n-octyl alcohol being prepared using the n-octyl alcohol ester, with alkali saponification, which is occurred, for the n-octyl alcohol ester obtains
To n-octyl alcohol.
The advantageous effect that the present invention obtains：
1. the present invention is condensed to yield condensation product A, and in hydrogenation catalyst under alkaline condition using furfural and acetone as raw material
Occur under agent and double catalytic action of metal salts of trifluoromethane sulphonic acid plus hydrogen ring-opening reaction obtains n-octyl alcohol ester, hydrogen forces down, catalysis
Agent is without synthesis, abundance, at low cost, high catalytic efficiency and the repeatable utilization of catalyst.
2. the present invention uses organic carboxyl acid as reaction solution, environmentally protective.
3. the present invention is by isolating and purifying, obtained n-octyl alcohol ester yield is high, and purity is high.
Specific implementation mode
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is only to aid in the understanding present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1：
100mg furfurals, 200mg acetone are added in 50ml round-bottomed flasks, are added on the basis of furfural later
The NaOH solution of the 0.1mol/L of 0.1mol% is as catalyst, and 300r/min is stirred overnight at a temperature of 20 DEG C, obtains condensation production
Condensation product A is added in reaction vessel, adds the Sc (OTf) of the 0.1mol% on the basis of the condensation product A by object A3
With the palladium carbon of 0.01mol%, be eventually adding 5ml formic acid, be passed through hydrogen replace 5 times after, in the stirring condition of rate 300r/min
Under be warming up to 150 DEG C of constant temperature, hydrogen presses 2MPa, and ring-opening reaction 2h is kept the temperature under conditions of formic acid is organic solvent, and heat preservation open loop is anti-
It should keep stirring in the process.The reaction solution is adjusted to PH=7 by the reaction solution that the ester containing n-octyl alcohol is obtained after being cooled to room temperature, with
Ethyl acetate is extractant, using anhydrous sodium sulfate as drier, then is evaporated under reduced pressure to obtain octyl formate.
Sampling dilution, it is 88% to measure octyl acetate yield by gas chromatography (GC), purity 99%.Wherein gas phase
Testing conditions：Hitachi GC2014System, chromatographic column WAX, 220 DEG C, detector FID of column temperature, sample introduction：1:50 shuntings, into
80 DEG C of sample temperature, carrier gas：N2, flow velocity 30L/min.
Embodiment 2：
100mg furfurals, 400mg acetone are added in 50ml round-bottomed flasks, are added on the basis of furfural later
The NaOH solution of the 0.1mol/L of 0.1mol% is stirred overnight as catalyst, room temperature 300r/min, obtains condensation product A, will
Condensation product A is added in reaction vessel, adds the Sc (OTf) of the 0.5mol% on the basis of the condensation product A3With
The palladium carbon of 0.2mol% is eventually adding 5ml acetic acid, be passed through hydrogen replace 5 times after, risen under the stirring condition of rate 600r/min
Temperature to 135 DEG C of constant temperature, hydrogen presses 2MPa, and ring-opening reaction 0.5h is kept the temperature under conditions of acetic acid is organic solvent, keeps the temperature ring-opening reaction
It keeps stirring in the process.The reaction solution is adjusted to PH=7, with second by the reaction solution that the ester containing n-octyl alcohol is obtained after being cooled to room temperature
Acetoacetic ester is extractant, using anhydrous sodium sulfate as drier, then is evaporated under reduced pressure to obtain octyl acetate.
The NaOH of 1mol% is added into reaction gained octyl acetate, flow back 6h under the conditions of 80 °, obtains n-octyl alcohol.
Sampling dilution, it is 80% to measure octyl acetate yield by gas chromatography (GC), purity 99%.
Embodiment 3：
100mg furfurals, 800mg acetone are added in 50ml round-bottomed flasks, are added on the basis of furfural later
The NaOH solution of the 0.1mol/L of 0.1mol% is stirred overnight as catalyst, room temperature 300r/min, obtains condensation product A, will
Condensation product A is added in reaction vessel, adds the Al (OTf) of the 4mol% on the basis of the condensation product A3And 2mol%
Palladium carbon, be eventually adding 5ml acetic acid, be passed through hydrogen replace 5 times after, be warming up to 150 under the stirring condition of rate 800r/min
DEG C constant temperature, hydrogen press 3MPa, and ring-opening reaction 2h is kept the temperature under conditions of acetic acid is organic solvent, is not stopped during heat preservation ring-opening reaction
Stirring.The reaction solution is adjusted to PH=7 by the reaction solution that the ester containing n-octyl alcohol is obtained after being cooled to room temperature, and is extraction with ethyl acetate
Agent is taken, using anhydrous sodium sulfate as drier, then is evaporated under reduced pressure to obtain octyl acetate.
Sampling dilution, it is 85% to measure octyl acetate yield by gas chromatography (GC), purity 99%.
Embodiment 4：
100mg furfurals, 2g acetone are added in 50ml round-bottomed flasks, are added the 0.1mol%'s on the basis of furfural later
The NaOH solution of 0.1mol/L is stirred overnight as catalyst, room temperature 300r/min, obtains condensation product A, and condensation product A is added
Enter in reaction vessel, adds the Sc (OTf) of the 4mol% on the basis of the condensation product A3With the palladium carbon of 8mol%, finally
Be added 5ml acetic acid, be passed through hydrogen replace 5 times after, 100 DEG C of constant temperature, hydrogen pressure are warming up under the stirring condition of rate 100r/min
5MPa keeps the temperature ring-opening reaction 3h under conditions of acetic acid is organic solvent, is kept stirring during heat preservation ring-opening reaction.It is cooled to
The reaction solution is adjusted to PH=7, using ethyl acetate as extractant, with anhydrous by the reaction solution that the ester containing n-octyl alcohol is obtained after room temperature
Sodium sulphate is drier, then is evaporated under reduced pressure to obtain octyl acetate.
Sampling dilution, it is 87% to measure octyl acetate yield by gas chromatography (GC), purity 99%.
Embodiment 5：
100mg furfurals, 2g acetone are added in 50ml round-bottomed flasks, are added the 0.1mol%'s on the basis of furfural later
The NaOH solution of 0.1mol/L is stirred overnight as catalyst, room temperature 300r/min, obtains condensation product A, and condensation product A is added
Enter in reaction vessel, adds the Cu (OTf) of the 6mol% on the basis of the condensation product A2With the palladium carbon of 1.5mol%, most
Afterwards be added 5ml acetic acid, be passed through hydrogen replace 5 times after, 150 DEG C of constant temperature, hydrogen are warming up under the stirring condition of rate 600r/min
2.5MPa is pressed, ring-opening reaction 1h is kept the temperature under conditions of acetic acid is organic solvent, is kept stirring during heat preservation ring-opening reaction.It is cold
But to the reaction solution of the ester containing n-octyl alcohol is obtained after room temperature, the reaction solution is adjusted to PH=7, using ethyl acetate as extractant, with
Anhydrous sodium sulfate is drier, then is evaporated under reduced pressure to obtain octyl acetate.
Sampling dilution, it is 84% to measure octyl acetate yield by gas chromatography (GC), purity 99%.
Embodiment 6：
100mg furfurals, 1g acetone are added in 50ml round-bottomed flasks, are added the 0.1mol%'s on the basis of furfural later
The NaOH solution of 0.1mol/L is stirred overnight as catalyst, room temperature 300r/min, obtains condensation product A, and condensation product A is added
Enter in reaction vessel, adds the Hf (OTf) of the 2mol% on the basis of the condensation product A4With the palladium carbon of 1.5mol%, most
Afterwards be added 5ml acetic acid, be passed through hydrogen replace 5 times after, 150 DEG C of constant temperature, hydrogen are warming up under the stirring condition of rate 500r/min
2MPa is pressed, ring-opening reaction 4h is kept the temperature under conditions of acetic acid is organic solvent, is kept stirring during heat preservation ring-opening reaction.It is cooling
The reaction solution is adjusted to PH=7, using ethyl acetate as extractant, with nothing by the reaction solution that the ester containing n-octyl alcohol is obtained after to room temperature
Aqueous sodium persulfate is drier, then is evaporated under reduced pressure to obtain octyl acetate.
Sampling dilution, it is 90% to measure octyl acetate yield by gas chromatography (GC), purity 99%.
Embodiment 7：
100mg furfurals, 2g acetone are added in 50ml round-bottomed flasks, are added the 0.1mol%'s on the basis of furfural later
The NaOH solution of 0.1mol/L is stirred overnight as catalyst, room temperature 300r/min, obtains condensation product A, and condensation product A is added
Enter in reaction vessel, adds the Sc (OTf) of the 6mol% on the basis of the condensation product A3With the palladium carbon of 2mol%, finally
Be added 5ml butyric acid, be passed through hydrogen replace 5 times after, 150 DEG C of constant temperature, hydrogen pressure are warming up under the stirring condition of rate 400r/min
2MPa keeps the temperature ring-opening reaction 4h under conditions of butyric acid is organic solvent, is kept stirring during heat preservation ring-opening reaction.It is cooled to
The reaction solution is adjusted to PH=7, using ethyl acetate as extractant, with anhydrous by the reaction solution that the ester containing n-octyl alcohol is obtained after room temperature
Sodium sulphate is drier, then is evaporated under reduced pressure to obtain n-octyl butyrate.
The NaOH of 1mol% is added into reaction gained n-octyl butyrate, flow back 12h under the conditions of 90 degree, obtains n-octyl alcohol.
Sampling dilution, it is 95% to measure octyl acetate yield by gas chromatography (GC), purity 99%.
Embodiment 8：
100mg furfurals, 2g acetone are added in 50ml round-bottomed flasks, are added the 0.1mol%'s on the basis of furfural later
The NaOH solution of 0.1mol/L is stirred overnight as catalyst, room temperature 300r/min, obtains condensation product A, and condensation product A is added
Enter in reaction vessel, adds the Sc (OTf) of the 6mol% on the basis of the condensation product A3With the palladium carbon of 10mol%, most
Afterwards be added 5ml acetic acid, be passed through hydrogen replace 5 times after, 150 DEG C of constant temperature, hydrogen are warming up under the stirring condition of rate 400r/min
8MPa is pressed, ring-opening reaction 3h is kept the temperature under conditions of acetic acid is organic solvent, is kept stirring during heat preservation ring-opening reaction.It is cooling
The reaction solution is adjusted to PH=7, using ethyl acetate as extractant, with nothing by the reaction solution that the ester containing n-octyl alcohol is obtained after to room temperature
Aqueous sodium persulfate is drier, then is evaporated under reduced pressure to obtain octyl acetate.
Sampling dilution, it is 92% to measure octyl acetate yield by gas chromatography (GC), purity 99%.
Embodiment 9：
100mg furfurals, 2g acetone are added in 50ml round-bottomed flasks, are added the 0.1mol%'s on the basis of furfural later
The NaOH solution of 0.1mol/L is stirred overnight as catalyst, room temperature 300r/min, obtains condensation product A, and condensation product A is added
Enter in reaction vessel, adds the W (OTf) of the 4mol% on the basis of the condensation product A6With the palladium carbon of 3mol%, finally
Be added 5ml propionic acid, be passed through hydrogen replace 5 times after, 135 DEG C of constant temperature, hydrogen pressure are warming up under the stirring condition of rate 400r/min
3MPa keeps the temperature ring-opening reaction 3h under conditions of propionic acid is organic solvent, is kept stirring during heat preservation ring-opening reaction.It is cooled to
The reaction solution is adjusted to PH=7, using ethyl acetate as extractant, with anhydrous by the reaction solution that the ester containing n-octyl alcohol is obtained after room temperature
Sodium sulphate is drier, then is evaporated under reduced pressure to obtain octyl propionate.
Sampling dilution, it is 81% to measure octanol propyl ester yield by gas chromatography (GC), purity 99%.
Embodiment 10：
100mg furfurals, 2g acetone are added in 50ml round-bottomed flasks, are added the 0.1mol%'s on the basis of furfural later
As catalyst, 300r/min is stirred overnight the NaOH solution of 0.1mol/L at a temperature of 25 DEG C, is obtained condensation product A, will be condensed
Product A is added in reaction vessel, adds the Sc (OTf) of the 4mol% on the basis of the condensation product A3With the platinum of 2mol%
Carbon is eventually adding 5ml acetic acid, be passed through hydrogen replace 5 times after, 135 DEG C of perseverances are warming up under the stirring condition of rate 800r/min
Temperature, hydrogen press 4MPa, and ring-opening reaction 3h is kept the temperature under conditions of propionic acid is organic solvent, does not stop to stir during heat preservation ring-opening reaction
It mixes.The reaction solution is adjusted to PH=7 by the reaction solution that the ester containing n-octyl alcohol is obtained after being cooled to room temperature, and is extraction with ethyl acetate
Agent using anhydrous sodium sulfate as drier, then is evaporated under reduced pressure to obtain octyl acetate.
Sampling dilution, it is 82% to measure octyl acetate yield by gas chromatography (GC), purity 99%.
Specific implementation mode has been further described the purpose of the present invention, technical solution and advantageous effect, institute
It should be understood that the foregoing is merely the specific implementation mode of the present invention, it is not intended to limit the scope of protection of the present invention,
All within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should be included in the present invention's
Within protection domain.
Claims (9)
1. a kind of preparation method of n-octyl alcohol ester, under alkaline matter catalytic action occurs to be condensed instead using furfural and acetone as raw material
Condensation product A should be generated, which is characterized in that double catalytic action of the condensation product A through ring opening catalyst and hydrogenation catalyst
Occur plus hydrogen ring-opening reaction obtains n-octyl alcohol ester, the ring opening catalyst is metal salts of trifluoromethane sulphonic acid.
2. the preparation method of n-octyl alcohol ester according to claim 1, which is characterized in that in the metal salts of trifluoromethane sulphonic acid
Metal state be+1~+6 valences, the dosage of the metal salts of trifluoromethane sulphonic acid is the 0.1- of the condensation product A
10mol%.
3. preparation method according to claim 2, which is characterized in that the metal salts of trifluoromethane sulphonic acid is W (OTf)6、Zr
(OTf)4、Al(OTf)3、Sc(OTf)3、Nb(OTf)5、Cu(OTf)2、Sc(OTf)2、Hf(OTf)2, one kind or more in AgOTf
Kind.
4. according to the preparation method of claim 1-3 any one of them n-octyl alcohol esters, which is characterized in that the hydrogenation catalyst
For the catalyst containing the VIIIth group 4 transition metal element, the additive amount of the hydrogenation catalyst is the 0.01- of the condensation product A
10mol%.
5. according to the preparation method of claim 1-3 any one of them n-octyl alcohol esters, which is characterized in that described plus hydrogen open loop is anti-
It should be the specific steps are：The condensation product A, hydrogenation catalyst, metal salts of trifluoromethane sulphonic acid and acidic organic solvent are added anti-
It answers and is mixed to get mixture in device, be passed through hydrogen, by the mixture in 2-15MPa hydrogen pressures, under 50-250 DEG C and stirring condition
10min-24h is reacted, postcooling obtains the reaction solution of the ester containing n-octyl alcohol to 10-30 DEG C.
6. the preparation method of n-octyl alcohol ester according to claim 5, which is characterized in that the acidic organic solvent is carboxylic
Acid.
7. according to the preparation method of claim 1-3 or 6 any one of them n-octyl alcohol esters, which is characterized in that further include to institute
N-octyl alcohol ester is stated to be isolated and purified, it is described isolate and purify the specific steps are：The reaction solution is adjusted to PH=7-9, is used
Ethyl acetate is as extractant, and using anhydrous sodium sulfate as drier, finally vacuum distillation obtains the n-octyl alcohol ester of alcohol.
8. according to the preparation method of claim 1-3 or 6 any one of them n-octyl alcohol esters, which is characterized in that the preparation side
Method further includes the recycling of ring opening catalyst and hydrogenation catalyst, the specific steps are：By the n-octyl alcohol ester from the reaction
After liquid separation, ring opening catalyst and hydrogenation catalyst are left in the reactor, then rejoin the condensation product A and acidity to have
Solvent carries out plus hydrogen ring-opening reaction.
9. a kind of method preparing n-octyl alcohol using claim 1-3 or 6 any one of them n-octyl alcohol esters, which is characterized in that
Saponification is occurred into for the n-octyl alcohol ester and alkali and obtains n-octyl alcohol.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265400A (en) * | 2013-05-28 | 2013-08-28 | 华东理工大学 | Environment-friendly novel method for preparing primary alcohol from furan or tetrahydrofuran derivatives |
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