CN109081773A - The manufacturing method of 3- alkoxy -3- methyl-1-butanol - Google Patents
The manufacturing method of 3- alkoxy -3- methyl-1-butanol Download PDFInfo
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- CN109081773A CN109081773A CN201811139648.1A CN201811139648A CN109081773A CN 109081773 A CN109081773 A CN 109081773A CN 201811139648 A CN201811139648 A CN 201811139648A CN 109081773 A CN109081773 A CN 109081773A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
- C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
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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
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Abstract
A kind of method that the present invention provides high selectivity and manufactures 3- alkoxy -3- methyl-1-butanol in high yield.Specifically, the present invention provides a kind of manufacturing method of 3- alkoxy -3- methyl-1-butanol, it is to make to react selected from least one of 3- methyl-3-butene-1-alcohol and 3-M2BOL methyl butenol with the primary alconol of carbon atom number 1~5 in the presence of acid, method to manufacture 3- alkoxy -3- methyl-1-butanol, it is characterized in that, the moisture control in reaction mixture is reacted below 0.3 mass %.
Description
The application is the " system of 3- alkoxy -3- methyl-1-butanol entitled filed on March 15th, 2013
Make method ", national application number be 201380015567.X application for a patent for invention divisional application.
Technical field
The present invention relates to as medicine, pesticide intermediate, various detergent the useful 3- alkoxy -3- such as raw material
The manufacturing method of methyl-1-butanol.
Background technique
It is known in 3- methyl-3-butene-1-alcohol (hereinafter, sometimes referred to as IPEA.) or 3- methyl-2-butene-
1- alcohol is (hereinafter, sometimes referred to as PNA.) in the reacting of primary alconol, by sulfuric acid, phosphoric acid, sulfonic acid, cationic system ion exchange
Implement in the presence of the acid such as resin, can inhibit isomerization reaction, dehydration and hydroxyl to the addition reaction of double bond etc.
Manufacture 3- alkoxy -3- methyl-1-butanol simultaneously (referring to patent document 1).
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Application 50-59309 bulletin.
Summary of the invention
Problems to be solved by the invention
However, in the method recorded in patent document 1, although high conversion rate, 3- alkoxy -3- methyl-1-butanol
Selection rate it is insufficient, in order to obtain 3- alkoxy -3- methyl-1-butanol with higher yield, exist further improve it is remaining
Ground.
Therefore, 3- alkoxy -3- methyl-is manufactured the issue of the present invention is to provide high selectivity and in high yield
The method of n-butyl alcohol.
Means for solving the problems
The inventors of the present invention have made intensive studies, as a result, it has been found that, in the reacting of IPEA or PNA in presence of an acid and primary alconol, by
Water is generated in side reaction, if the moisture content in reaction mixture is greater than certain value, 3- alkoxy-3- methyl-1-fourth
The selection rate of alcohol reduces.Based on above-mentioned experience, the inventors of the present invention's discovery, by one side by the moisture control in reaction mixture
It is reacted on one side below certain value, can solve the above subject, so as to complete the present invention.
That is, the present invention provides following [1]~[4].
[1] manufacturing method of 3- alkoxy -3- methyl-1-butanol is made in the presence of acid selected from 3- first
At least one of base -3- butene-1-ol and 3-M2BOL methyl butenol is with carbon atom number
1~5 primary alconol reaction, the method to manufacture 3- alkoxy -3- methyl-1-butanol, which is characterized in that mix reaction
Moisture control in liquid is reacted below 0.3 mass %.
The manufacturing method of the 3- alkoxy -3- methyl-1-butanol of [2] above-mentioned [1], wherein above-mentioned carbon atom number is
1~5 primary alconol is methanol, ethyl alcohol or normal propyl alcohol.
The manufacturing method of the 3- alkoxy -3- methyl-1-butanol of [3] above-mentioned [1] or [2], wherein relative to choosing
It rubs from least one of 3- methyl-3-butene-1-alcohol and 3-M2BOL methyl butenol 1
You, the usage amount for the primary alconol that above-mentioned carbon atom number is 1~5 is 0.5~40 mole.
[4] manufacturing method of the 3- alkoxy -3- methyl-1-butanol of any one of above-mentioned [1]~[3], wherein
Above-mentioned acid is selected from least one of natural zeolite, synthetic zeolite and acid cation exchange resin solid acid.
Invention effect
It through the invention, can be to manufacture 3- alkoxy-3- methyl-1-than previous higher selection rate and higher yield
Butanol.
Detailed description of the invention
[Fig. 1] is the skeleton diagram of reaction unit used in embodiment 1.
Specific embodiment
Firstly, in the present specification, it can be optionally with preferred regulation, it can be by the combination between preferred regulation
Referred to as more preferably.
[manufacturing method of 3- alkoxy -3- methyl-1-butanol]
It is a feature of the present invention that ought make to be selected from 3- methyl-3-butene-1-alcohol (IPEA) and 3- first in the presence of acid
When the methyl butenol of at least one of base -2- butene-1-ol (PNA) is reacted with the primary alconol that carbon atom number is 1~5,
It is reacted while by the moisture control in reaction mixture below 0.3 mass %.
If primary alconol is expressed as R-CH2The alkyl that OH(R indicates hydrogen atom or carbon atom number is 1~4.), then it is of the invention
Manufacturing method can be indicated with chemical equation below.
[changing 1]
(in formula, 2 carbon-carbon bonds formed by solid line and dotted line indicate that one party forms carbon-to-carbon double bond.).
(primary alconol that carbon atom number is 1~5)
The primary alconol for being 1~5 as carbon atom number used in method of the invention, can enumerate methanol, ethyl alcohol, normal propyl alcohol, positive fourth
Alcohol, isobutanol etc..Wherein, from the viewpoint of the selection rate of 3- alkoxy -3- methyl-1-butanol and yield, preferably
Methanol, ethyl alcohol, normal propyl alcohol.It should be noted that if replace primary alconol using secondary alcohol (such as isopropanol) or the tertiary alcohol, then 3- alkane
The selection rate and yield of oxygroup -3- methyl-1-butanol are greatly reduced.
Relative to 1 mole of methyl butenol selected from least one of IPEA and PNA, the primary alconol that carbon atom number is 1~5
Usage amount be preferably 0.5~40 mole, more preferably 0.7~30 mole, further preferably 0.8~25 mole.Especially,
Use relative to the primary alconol that 1 mole of methyl butenol of the carbon atom number selected from least one of IPEA and PNA is 1~5
The lower limit value of amount, from the viewpoint of conversion ratio, on the basis of above-mentioned lower limit value, more preferably 2 moles, further preferably
5 moles.If make the primary alconol of carbon atom number 1~5 relative to IPEA, PNA be it is excessive, primary alconol itself is also used as solvent to play function
Can, become not needing in addition to use solvent, can efficiently be reacted, be preferred.
It should be noted that in method of the invention, it is possible to use solvent.As solvent, such as hexane, heptan can be enumerated
The aliphatic hydrocarbons such as alkane, octane；The aromatic hydrocarbons such as benzene,toluene,xylene, mesitylene；Ether, dipropyl ether, dibutyl ethers, four
Hydrogen furans, dioxane, 1,2- dimethoxy-ethane, diethylene glycol dimethyl ether (diethylene glycol dimethyl ether, diglyme),
Triethylene glycol dimethyl ether (triglyme, triglyme), tetraethylene glycol dimethyl ether (tetraethylene glycol dimethyl ether,
) etc. tetraglyme ethers etc. will not cause dysgenic solvent to reaction of the invention.Solvent can be used alone,
It can be used in combination of two or more, when the solvent is used, preferably be used after being sufficiently carried out dehydrating.
(acid)
Method of the invention carries out in the presence of acid.As acid, preferably strong acid or strong acid generates substance, can enumerate such as sulphur
The inorganic acids such as acid, phosphoric acid；The organic acid of sulfonic acid etc.；The solid acids such as natural zeolite, synthetic zeolite, acid cation exchange resin
Deng.Wherein, it is preferable to use solid acid from the viewpoint of separation easiness after reaction.
It should be noted that such as β type, A type, X-type, Y type, L-type, ZSM-5 type, mercerising can be enumerated as synthetic zeolite
Zeolite (mordenite) type, ferrierite (ferrierite) type etc., are not particularly limited.Zeolite can be proton type (H-type)
Or ammonium ion type (NH4 +Type), it is also possible to by alkali metal such as sodium, potassium；The alkaline-earth metal such as magnesium, calcium；8th race's metal such as iron；Cobalt etc.
9th race's metal；10th race's metal such as nickel etc. substituted " metal substituted type ".
For the usage amount of acid, when using above-mentioned inorganic acid, organic acid, so that acid in reaction mixture is dense
Degree is preferably 0.01~40 mass %, more preferably 0.1~15 mass %.It should be noted that when using above-mentioned solid acid
When, preferably reacted with fixed bed, at this point, as described later, the LHSV(Liquid Hourly Space of IPEA and/or PNA
Velocity；Liquid hourly space velocity (LHSV)；hr-1) be important.On the other hand, when use solid acid, using fluidized bed, suspension bed or
When moving bed is reacted, relative to raw material (IPEA and/or PNA) 1 mass parts, the usage amount of solid acid is preferably 0.001~
10 mass parts, more preferably 0.01~3 mass parts.
It in the method for the invention, will in order to improve the selection rate and yield of 3- alkoxy -3- methyl-1-butanol
Moisture control in reaction mixture is important below 0.3 mass %.Moisture content in reaction mixture is preferably 0.25
Quality % or less, more preferably 0.2 mass % or less, further preferably 0.15 mass % or less.In the method for the invention, lead to
It crosses the moisture control in reaction mixture within the above range, 3- alkoxy-3- methyl-1-fourth can be greatly improved
The selection rate and yield of alcohol.
It should be noted that the lower limit value as the moisture content in reaction mixture, is preferably 0 mass % certainly, but because
Water is generated due to side reaction, so reality is cannot to be 0 mass %.Therefore, moisture content is controlled even if as described above, as
The lower limit value, it may be said that preferably 0.04 mass % or so.
For for the dewatering of the moisture control in reaction mixture within the above range to be not particularly limited,
But the method that (1) contacts reaction mixture with dehydrating agent can be enumerated；(2) it utilizes and has used polyimide film, zeolite membrane etc.
The method that reaction mixture is dehydrated by membrane separation process；(3) method for being dehydrated reaction mixture by distillation；(4) selected from above-mentioned
(1) at least two combination etc. in~(3).
As the method for above-mentioned (1), the method for thering is (1-1) to be reacted in the presence of dehydrating agent；And (1-2) from anti-
The reaction mixture for extracting in device and contacting and carried out a part of reaction with acid is answered, contacts it with dehydrating agent, then by it
The method of the original reactor returned.As dehydrating agent, preferably using such as molecular sieve (3A, 4A, 5A, 13X), oxidation
Aluminium, calcium chloride, calcium sulfate, anhydrous magnesium sulfate, anhydrous sodium sulfate, calcium hydride, sodium hydroxide, potassium hydroxide, potassium carbonate, bicarbonate
The dehydrating agent usually used in the dehydration of the organic compound or mixture of liquid such as sodium.
In the membrane separation process of above-mentioned (2), divided using following pervaporation method (pervaporation) etc.
From: it contacts liquid mixture with the unilateral side (supply side) of seperation film, opposite side (penetrating side) decompression makes specific as a result,
Liquid (penetrating substance) is vaporized and is isolated.Such membrane separation process is mixed by distilling the azeotropic being easily separated for failing
The separation of the close mixture of the small boiling point of the separation of conjunction object, relative volatility is effective.
In the distillation of above-mentioned (3), the separation of water and primary alconol etc. is not easy to carry out sometimes, thus, it is preferable to carry out multistage steaming
It evaporates.Additionally, it is preferred that and method or (2) with the method for above-mentioned (3) and above-mentioned (1) method.
It should be noted that the moisture content in reaction mixture can be measured by karl Fischer moisture teller.
Reaction temperature when implementing method of the invention is preferably generally 40~100 DEG C, more preferably 40~80 DEG C.For
Reaction pressure is not particularly limited, in general, implement to be easy under normal pressure, thus preferably.
The embodiment of the manufacturing method of 3- alkoxy -3- methyl-1-butanol of the invention is not limited especially
System, for example, can be using method well known to batch mode, semi continuous mode, continuation mode etc..Hereinafter, illustrating based on each side
The preferred embodiment of formula, but do not limited by these embodiments particularly.
When implementing method of the invention using batch mode, for example, be packed into reactor whole IPEA and/or
PNA, primary alconol, acid (preferably above-mentioned inorganic acid or organic acid), dehydrating agent and solvent as needed, are heated to regulation temperature
Degree, is stirred.Reaction time is not particularly limited, but is turned suitably with the tracking such as gas chromatography IPEA, PNA
Rate is reacted until conversion ratio becomes preferably 55% or more, more preferable 60% or more, further preferred 70% or more, especially excellent
Select 80% or more.
When implementing method of the invention using semi continuous mode, for example, being packed into IPEA's and/or PNA into reactor
At least partially, at least part of primary alconol, acid (preferably above-mentioned inorganic acid or organic acid), dehydrating agent and as needed
Solvent at least part, on one side be stirred at the specified temperature to be reacted, on one side continually or intermittently to anti-
It answers and supplies IPEA and/or PNA, primary alconol and solvent as needed in device.It, can be with the feelings of above-mentioned batch mode about the reaction time
Condition similarly illustrates.
It should be noted that either batch mode or semi continuous mode, then can add dehydrating agent.
When implementing method of the invention using continuation mode, for example, reacting dress to the cast with sheath (jacket)
Middle filled solid acid is set as acid, simultaneously adds dehydrating agent with above-mentioned solid acid, or separately connection is filled with the pipe of dehydrating agent
Type reaction unit.The heating agent for flowing predetermined temperature in above-mentioned sheath on one side, is preferably on one side 0.1~70hr with LHSV-1, it is more excellent
It is selected as 0.1~50hr-1, further preferably 1~50hr-1Mode, make IPEA and/or PNA, with the mixed liquor of primary alconol upper
It states and is filled with the cast reaction unit circulation of solid acid, it is then made to circulate in the cast reaction unit for being filled with dehydrating agent,
It circulates alternatively, being filled with it at the same time in the cast reaction unit of solid acid and dehydrating agent.The continuation mode is using " one
It is secondary pass through (one pass) formula " implement, " circulating " can also be used to implement, " once the passing through formula " be make IPEA and/
Or PNA, be filled in the cast reaction unit of solid acid and dehydrating agent and only circulate 1 time at the same time with the mixed liquor of primary alconol, it is described
" circulating " is made to circulate in the cast reaction unit for being filled with solid acid then in the cast reaction dress for being filled with dehydrating agent
At least part or whole of reaction mixture obtained from circulation are set, is circulated in the cast reaction unit again, according to
It needs to repeat aforesaid operations.It should be noted that when using once by formula to implement, for being filled in pipe jointly
For solid acid and dehydrating agent (preferably molecular sieve) in type reaction unit, the two can be mixed, be also possible to " solid acid
The layer-by-layer state of layer-dehydration oxidant layer-solid acid layer-dehydration oxidant layer-... " mode.
When using continuation mode with once by formula to carry out method of the invention, from dehydration efficiency, IPEA and/or
From the viewpoint of the conversion ratio of PNA, the selection rate of 3- alkoxy -3- methyl-1-butanol, IPEA and/or PNA and primary alconol
The LHSV of mixed liquor be preferably 0.1~5hr-1.On the other hand, when with circulating progress, from aqueous in reaction mixture
The control of rate, the conversion ratio of IPEA and/or PNA, 3- alkoxy -3- methyl-1-butanol the viewpoint of selection rate etc. examine
Consider, LHSV is preferably 3~70hr-1, more preferably 5~50hr-1, further preferably 10~50hr-1, particularly preferably 20~
40hr-1。
Either in batch mode, semi continuous mode and continuation mode in formula, above-mentioned dewatering can be used
It replaces the above-mentioned method for contacting reaction mixture with dehydrating agent, can also not only be contacted with dehydrating agent, but also using above-mentioned de-
Water method.
It should be noted that if implementing method of the invention using continuation mode, then there is 3- alkoxy -3- first
The tendency that base-n-butyl alcohol selection rate improves.
It after reaction, can be by applying well known separation method to obtained reaction mixture, to separate 3- alcoxyl
Base -3- methyl-1-butanol.It can be by further implementing column color to obtained 3- alkoxy -3- methyl-1-butanol
The purification process such as spectrometry, distillation, to improve its purity.
Embodiment
Hereinafter, specifically describing the present invention using embodiment etc., but the present invention is not restricted by the embodiments.It needs
Bright, the gas chromatography determination condition in each embodiment is as described below.
(gas chromatography determination condition)
Device: GC-14B(Shimadzu Scisakusho Ltd system)
Use column: G-300(internal diameter 1.2mm × long 20m), chemical substance evaluation study mechanism corporation
Analysis condition: 240 DEG C of inlet temperature, 240 DEG C of detector temperature
Column temperature: 230 DEG C are warming up to 5 DEG C/min from 80 DEG C
Detector: hydrogen flame ionization detector (FID).
1 > continuation mode (circulating) of < embodiment, uses ethyl alcohol
As shown in Figure 1, filling strong-acid ion exchange resin " ダ イ ヤ イ オ Application into the cast reaction unit with sheath
PK212LH " (Mitsubishi chemical Co., Ltd's system) 100mL(hereinafter referred to as solid acid layer A), to the other cast with sheath
In reaction unit, filling molecular sieve 3a 100mL(is hereinafter referred to as dehydrated oxidant layer), the two is connected.To filled with highly acid
The warm water (heating agent) of 50 DEG C of circulation in the sheath of the cast reaction unit of ion exchange resin is being filled with above-mentioned molecular sieve 3a
Circulate about 10 DEG C of cooling water (refrigerant) in the sheath of cast reaction unit.
Then, with LHSV30hr-1By ethyl alcohol 460g(9.99mol dehydrated using molecular sieve 3a in advance) and 3- first
Base -3- butene-1-ol (IPEA) 86g(0.998mol) mixed liquor [ethyl alcohol/IPEA=10(molar ratio)] successively supply
To solid acid layer A and dehydration oxidant layer, make the total overall reaction mixed liquor as obtained from solid acid layer A and dehydration oxidant layer again using pump
It is secondary with LHSV30hr-1It then circulates in dehydration oxidant layer in solid acid layer A and makes its circulation, carried out while recycling anti-
It answers.
Gas chromatography analysis is utilized to carry out the reaction mixture after reaction in 10 hours, as a result, the conversion ratio of IPEA is
The yield of 91.1%, 3- ethyoxyl -3- methyl-1-butanol is 62.9%.Show the result in table 1.In addition, every 1 hour,
It to by being dehydrated oxidant layer, is supplied again to the reaction mixture before solid acid layer A and is sampled recycling it with pump, used
Karl Fischer moisture teller " AQV-7 " (Ping Zhao Industry Co., Ltd system) analyzes the moisture content in reaction mixture, as a result such as
Shown in table 2, moisture content is always below 0.14 mass %.Exist it should be noted that concluding to describe below including by-product
The structure and selection rate of interior each product.
1 > continuation mode (circulating) of < comparative example, using ethyl alcohol, no dehydration
In embodiment 1, it is not provided with dehydration oxidant layer, solid acid layer A is only used and in addition to this grasps similarly to Example 1
Make, has carried out operation.Show the result in table 1.The moisture content in reaction mixture after reaction in 10 hours is 0.83 matter
Measure %.It should be noted that concluding each product selectivity described including by-product below.
2 > continuation mode (circulating) of < embodiment, uses ethyl alcohol
In embodiment 1, the usage amount of IPEA is changed to 43g(0.499mol) [ethyl alcohol/IPEA=20(molar ratio)], remove this
Except, it operates similarly with example 1, has carried out operation.Show the result in table 1.In addition, every 1 hour, with implementation
The same method of example 1 samples reaction mixture, analyzes moisture content, and the results are shown in Table 2, and moisture content is 0.10 always
Quality % or less.It should be noted that concluding each product selectivity described including by-product below.
2 > continuation mode (circulating) of < comparative example, using ethyl alcohol, no dehydration
In example 2, it is not provided with dehydration oxidant layer, solid acid layer A is only used and in addition to this grasps similarly to Example 1
Make, has carried out operation.Show the result in table 1.The moisture content in reaction mixture after reaction in 10 hours is 0.35 matter
Measure %.It should be noted that concluding each product selectivity described including by-product below.
3 > continuation mode (circulating) of < embodiment, uses methanol
In example 2, ethyl alcohol 460g(9.99mol is replaced using methanol 320g(9.99mol)), in addition to this, with implementation
Example 2 operates in the same way, and has carried out operation.In the reaction, the moisture content in reaction mixture be always 0.15 mass % with
Under.Show the result in table 1.
3 > continuation mode (circulating) of < comparative example, using methanol, no dehydration
In embodiment 3, it is not provided with dehydration oxidant layer, solid acid layer A is only used and in addition to this grasps similarly to Example 3
Make, has carried out operation.The moisture content in reaction mixture after reaction in 10 hours is 0.36 mass %.Show the result in table
1。
4 > continuation mode (circulating) of < embodiment, uses normal propyl alcohol
In example 2, normal propyl alcohol 600g(9.99mol has been used) replace ethyl alcohol 460g(9.99mol), in addition to this, with
Embodiment 2 operates in the same way, and has carried out operation.In the reaction, the moisture content in reaction mixture is 0.15 mass % always
Below.Show the result in table 1.
4 > continuation mode (circulating) of < comparative example, using normal propyl alcohol, no dehydration
In example 4, it is not provided with dehydration oxidant layer, solid acid layer A is only used and in addition to this grasps similarly to Example 1
Make, has carried out operation.The moisture content in reaction mixture after reaction in 10 hours is 0.35 mass %.Show the result in table
1。
5 > continuation mode (circulating) of < comparative example, uses isopropanol
In example 2, isopropanol 600g(9.99mol has been used) replace ethyl alcohol 460g(9.99mol), in addition to this, with
Embodiment 2 operates in the same way, and has carried out operation.In the reaction, the moisture content in reaction mixture is 0.15 mass % always
Below.Show the result in table 1.
As shown in Table 1, when having used the isopropanol as secondary alcohol to replace primary alconol, by will be aqueous in reaction mixture
The selection rate improvement effect that rate maintains the following bring 3- alkoxy -3- methyl-1-butanol of 0.3 mass % cannot be abundant
It presents.
[table 1]
[table 2]
* 1: the moisture content in reaction mixture
* 2: undetermined.
[changing 2]
[changing 3]
6 > continuation mode (once passing through formula) of < comparative example, using ethyl alcohol, no dehydration
In embodiment 1, it is not provided with dehydration oxidant layer, solid acid layer A is used only, and LHSV is changed into 1.5hr-1, using only
1 time primary of circulation implements to react by formula, in addition to this, operates similarly with example 1, has carried out operation.It will
As a result it is shown in table 3.In addition, the mixed liquor before reaction and the moisture content in reaction mixture after reaction are shown in table 4.
7 > continuation mode of < comparative example (once passes through formula 2 times), using ethyl alcohol, insufficient dehydration
In comparative example 6, LHSV is changed into 3.0hr-1, 10 mass % are added into the reaction mixture obtained after reaction
Molecular sieve 3a, stand 4 hours to be dehydrated, with LHSV3.0hr at 0 DEG C-1The reaction mixture is supplied to solid
Acid layer A, once to be reacted by formula.Show the result in table 3.In addition, being analyzed using karl Fischer moisture teller
The moisture content in reaction mixture before reaction and after reaction, shows the result in table 4.
[table 3]
[table 4]
* 1: the moisture content in reaction mixture.
By table 3 and table 4 it is found that not by under moisture control to 0.3 mass % situation below, 3- alkoxy -3-
The selection rate and yield of methyl-1-butanol reduce.
5 > continuation mode (circulating) of < embodiment, uses PNA
In example 2, using PNA43g(0.499mol) replace IPEA43g(0.499mol) [ethyl alcohol/PNA=20(moles
Than)], it in addition to this, operates similarly to Example 2, has carried out operation.In the reaction, aqueous in reaction mixture
Rate is 0.15 mass % or less always.Show the result in table 5.
8 > continuation mode (circulating) of < comparative example, using PNA, no dehydration
In embodiment 5, it is not provided with dehydration oxidant layer, solid acid layer A is only used and in addition to this grasps similarly to Example 5
Make, has carried out operation.The moisture content in reaction mixture after 10 hours is 0.36 mass %.Show the result in table 5.
[table 5]
6 > continuation mode (circulating) of < embodiment, uses ethyl alcohol, zeolite beta
In example 2, using granular zeolite beta " BEA-25 " (ズ ー De ケ ミ ー catalyst Co. Ltd. system) 100mL carrys out generation
For strong-acid ion exchange resin " ダ イ ヤ イ オ Application PK212LH " (hereinafter referred to as solid acid layer B), grain will be filled at this
The temperature of the warm water (heating agent) to circulate in the sheath of the cast reaction unit of shape zeolite beta is set as 70 DEG C, in addition to this, with reality
It applies example 2 to operate in the same way, has carried out operation.In the reaction, the moisture content in reaction mixture be always 0.15 mass % with
Under.Show the result in table 6.
9 > continuation mode (circulating) of < comparative example, using ethyl alcohol, zeolite beta, no dehydration
In embodiment 6, it is not provided with dehydration oxidant layer, solid acid layer B is only used and in addition to this grasps similarly to Example 6
Make, has carried out operation.Show the result in table 6.The moisture content in reaction mixture after reaction in 10 hours is 0.35 matter
Measure %.
7 > continuation mode (circulating) of < embodiment, uses ethyl alcohol, zeolite beta
In example 2, using granular zeolite beta " BEA-150 " (ズ ー De ケ ミ ー catalyst Co. Ltd. system) 100mL carrys out generation
For strong-acid ion exchange resin " ダ イ ヤ イ オ Application PK212LH " (hereinafter referred to as solid acid layer C), β type will be filled at this
The temperature of the warm water (heating agent) to circulate in the sheath of the cast reaction unit of zeolite is set as 70 DEG C, in addition to this, with embodiment 2
It operates in the same way, has carried out operation.In reaction, the moisture content in reaction mixture is 0.15 mass % or less always.It will knot
Fruit is shown in table 6.
10 > continuation mode (circulating) of < comparative example, using ethyl alcohol, zeolite beta, no dehydration
In embodiment 7, it is not provided with dehydration oxidant layer, solid acid layer C is only used and in addition to this grasps similarly to Example 7
Make, has carried out operation.Show the result in table 6.The moisture content in reaction mixture after reaction in 10 hours is 0.34 matter
Measure %.
[table 6]
Industrial feasibility
3- alkoxy -3- the methyl-1-butanol that obtains by means of the present invention is as medicine, pesticide intermediate, various
The raw material of detergent etc. is useful.
Description of symbols
1 solid acid layer
2 dehydration oxidant layer
3 pumps.
Claims (4)
- The manufacturing method of 1.3- alkoxy-3- methyl-1-butanol is made in the presence of acid selected from 3- methyl-3- butene-1- At least one of alcohol and 3-M2BOL methyl butenol react to manufacture with the primary alconol that carbon atom number is 1~5 The method of 3- alkoxy -3- methyl-1-butanol, which is characterized in that make selected from 3- methyl-3-butene-1-alcohol and 3- methyl -2- fourth The mixed liquor for the primary alconol that the pure and mild carbon atom number of at least one of alkene -1- alcohol methyl butene is 1~5 is in the pipe for being filled with solid acid It circulates in type reaction unit, it is then made to circulate in the cast reaction unit for being filled with dehydrating agent, or fill out it at the same time It circulates in cast reaction unit filled with solid acid and dehydrating agent, on one side by the moisture control in reaction mixture in 0.3 matter Amount % or less is reacted on one side.
- 2. the manufacturing method of 3- alkoxy -3- methyl-1-butanol according to claim 1, wherein make reaction temperature 40 ~80 DEG C, and make reaction pressure normal pressure, it reacts in a continuous manner.
- 3. the manufacturing method of 3- alkoxy -3- methyl-1-butanol according to claim 1 or 2, wherein the carbon atom Number is selected from least one of methanol, ethyl alcohol and normal propyl alcohol for 1~5 primary alconol.
- 4. the manufacturing method of 3- alkoxy -3- methyl-1-butanol according to claim 1 or 2, wherein relative to being selected from 1 mole of at least one of 3- methyl-3-butene-1-alcohol and 3-M2BOL methyl butenol, the carbon atom Number is 0.5~40 mole for the usage amount of 1~5 primary alconol.
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| CN201380015567.XA CN104203890A (en) | 2012-03-27 | 2013-03-15 | Method for producing 3-alkoxy-3-methyl-1-butanol |
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|---|---|---|---|---|
| CN1543449A (en) * | 2001-06-28 | 2004-11-03 | �ձ�������ʽ���� | Solvents containing cycloalkyl alkyl ethers and process for production of the ethers |
| CN102206142A (en) * | 2011-03-23 | 2011-10-05 | 中国科学院山西煤炭化学研究所 | Method for preparing 3-methoxyl-3-methyl-1-butanol |
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| JPS5736258B2 (en) * | 1973-10-04 | 1982-08-03 | ||
| JPS5424808A (en) * | 1977-07-27 | 1979-02-24 | Kuraray Co Ltd | Preparation of 3-methyl-3-methoxybutanol |
| JPH11349512A (en) * | 1998-06-04 | 1999-12-21 | Nippon Shokubai Co Ltd | Production of (poly)alkylene glycol monoalkyl ether |
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2013
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| CN1543449A (en) * | 2001-06-28 | 2004-11-03 | �ձ�������ʽ���� | Solvents containing cycloalkyl alkyl ethers and process for production of the ethers |
| CN102206142A (en) * | 2011-03-23 | 2011-10-05 | 中国科学院山西煤炭化学研究所 | Method for preparing 3-methoxyl-3-methyl-1-butanol |
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| WO2013146390A1 (en) | 2013-10-03 |
| JP6097278B2 (en) | 2017-03-15 |
| JPWO2013146390A1 (en) | 2015-12-10 |
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