WO2013146370A1 - Method for producing 3-alkoxy-3-methyl-1-butanol - Google Patents

Method for producing 3-alkoxy-3-methyl-1-butanol Download PDF

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WO2013146370A1
WO2013146370A1 PCT/JP2013/057481 JP2013057481W WO2013146370A1 WO 2013146370 A1 WO2013146370 A1 WO 2013146370A1 JP 2013057481 W JP2013057481 W JP 2013057481W WO 2013146370 A1 WO2013146370 A1 WO 2013146370A1
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methyl
butanol
type zeolite
alkoxy
buten
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PCT/JP2013/057481
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French (fr)
Japanese (ja)
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史彦 岡部
雄高 鈴木
矢田　和之
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株式会社クラレ
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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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  • the present invention relates to a method for producing 3-alkoxy-3-methyl-1-butanol which is useful as a raw material for intermediates for medical and agricultural chemicals and various detergents.
  • an object of the present invention is to provide a method for producing 3-alkoxy-3-methyl-1-butanol with high selectivity and high yield.
  • the present invention provides the following [1] to [4].
  • [1] At least one methylbutenol selected from 3-methyl-3-buten-1-ol and 3-methyl-2-buten-1-ol and a primary alcohol having 1 to 5 carbon atoms
  • 3-alkoxy-3-methyl-1-butanol can be produced with higher selectivity and higher yield than before.
  • the production method of the present invention is represented by the following chemical reaction formula. (In the formula, two carbon-carbon bonds consisting of a solid line and a broken line indicate that one of them is a carbon-carbon double bond.)
  • Examples of the primary alcohol having 1 to 5 carbon atoms used in the method of the present invention include methanol, ethanol, n-propanol, n-butanol, and isobutanol. Of these, methanol, ethanol, and n-propanol are preferable from the viewpoint of selectivity and yield of 3-alkoxy-3-methyl-1-butanol. If a secondary alcohol (for example, isopropanol) or a tertiary alcohol is used instead of the primary alcohol, the selectivity and yield of 3-alkoxy-3-methyl-1-butanol are greatly reduced.
  • a secondary alcohol for example, isopropanol
  • a tertiary alcohol is used instead of the primary alcohol, the selectivity and yield of 3-alkoxy-3-methyl-1-butanol are greatly reduced.
  • the amount of the primary alcohol having 1 to 5 carbon atoms is preferably 0.5 to 40 mol, more preferably 0.7 to 1 mol of at least one methylbutenol selected from IPEA and PNA. -30 mol, more preferably 0.8-25 mol.
  • the lower limit of the amount of primary alcohol having 1 to 5 carbon atoms to 1 mol of at least one methylbutenol selected from IPEA and PNA is, in addition to the lower limit, from the viewpoint of conversion, Preferably it is 2 mol, More preferably, it is 5 mol.
  • the primary alcohol having 1 to 5 carbon atoms When the primary alcohol having 1 to 5 carbon atoms is excessive with respect to IPEA or PNA, the primary alcohol itself functions as a solvent, and there is no need to use another solvent, so that the reaction can be carried out efficiently. Is preferable.
  • a solvent can also be used.
  • the solvent include aliphatic hydrocarbons such as hexane, heptane, and octane; aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxy.
  • Examples include ethane, ethers such as diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), and tetraethylene glycol dimethyl ether (tetraglyme), which do not adversely affect the reaction of the present invention.
  • a solvent may be used individually by 1 type and may use 2 or more types together.
  • ⁇ -type zeolite, Y-type zeolite The method of the present invention is carried out in the presence of at least one zeolite selected from ⁇ -type zeolite and Y-type zeolite.
  • Zeolite is a hydrous aluminosilicate having pores.
  • ⁇ -type zeolite and / or “Y-type” zeolite high-selectivity and high yield of 3- It has been found that alkoxy-3-methyl-1-butanol can be produced.
  • ⁇ -type zeolite and Y-type zeolite may be proton type (H type) or ammonium ion type (NH 4 + type); alkali metals such as sodium and potassium; alkaline earth metals such as magnesium and calcium; iron Group 8 metals such as cobalt; Group 9 metals such as cobalt; Group 10 metals such as nickel; From the viewpoint of the selectivity and yield of 3-alkoxy-3-methyl-1-butanol, it is preferable that both ⁇ -type zeolite and Y-type zeolite are proton types.
  • the SiO 2 / Al 2 O 3 (molar ratio) of the ⁇ -type zeolite is preferably 5 to 500, more preferably 10 to 450 from the viewpoint of the selectivity and yield of 3-alkoxy-3-methyl-1-butanol. More preferably, it is 15 to 400.
  • BET specific surface area of the ⁇ -type zeolite, 3-alkoxy-3-methyl-1-butanol selectivity and in terms of yield preferably 100 ⁇ 1,000m 2 / g, more preferably 150 ⁇ 800m 2 / g More preferably, it is 200 to 700 m 2 / g.
  • the pore size of ⁇ -type zeolite is preferably 0.2 to 1.0 nm, more preferably 0.4 to 0.8 nm, and still more preferably 0.5 to 0.7 nm.
  • the average particle size of ⁇ -type zeolite is preferably 1 to 100 ⁇ m, more preferably 1 to 80 ⁇ m, and still more preferably 1 to 50 ⁇ m.
  • the sodium content of the ⁇ -type zeolite is preferably 0.01 to 1% by mass, more preferably 0.01 to 0.5% by mass.
  • the SiO 2 / Al 2 O 3 (molar ratio) of the Y-type zeolite is preferably 6 to 50, more preferably 7 to 40, from the viewpoint of the selectivity and yield of 3-alkoxy-3-methyl-1-butanol. More preferably, it is 8-20.
  • the BET specific surface area of the Y-type zeolite is preferably 100 to 1,000 m 2 / g, more preferably 250 to 800 m 2 / g from the viewpoint of the selectivity and yield of 3-alkoxy-3-methyl-1-butanol. More preferably, it is 400 to 750 m 2 / g.
  • the pores of the Y-type zeolite are those in which a 12-membered ring generally called a large pore is formed from the viewpoint of selectivity and yield of 3-alkoxy-3-methyl-1-butanol. Is preferred.
  • the pore size of the Y-type zeolite is preferably 0.2 to 1.0 nm, more preferably 0.4 to 0.8 nm, and still more preferably 0.6 to 0.8 nm.
  • the acid amount of the Y-type zeolite determined by the NH 3 -TPD method is preferably 0.01 to 5 mmol / g, more preferably from the viewpoint of the selectivity and yield of 3-alkoxy-3-methyl-1-butanol.
  • the average particle size of the Y-type zeolite is preferably 1 to 100 ⁇ m, more preferably 1 to 50 ⁇ m, still more preferably 3 to 20 ⁇ m.
  • the sodium content of the Y-type zeolite is preferably 0.01 to 1% by mass, more preferably 0.01 to 0.5% by mass.
  • the reaction temperature for carrying out the method of the present invention is usually preferably 40 to 80 ° C., more preferably 50 to 80 ° C.
  • reaction pressure usually preferably 40 to 80 ° C.
  • reaction pressure usually, it is simple and preferable to implement under a normal pressure.
  • known methods such as a batch method, a semi-continuous method, and a continuous method can be applied.
  • embodiments according to the respective methods will be described in detail, but the present invention is not particularly limited thereto.
  • the reactor is charged with IPEA and / or PNA, primary alcohol, ⁇ -type zeolite and / or Y-type zeolite, and if necessary, all of the solvent, at a predetermined temperature. Heat to agitate and stir.
  • the reaction time is not particularly limited, and the conversion rate of IPEA or PNA is appropriately monitored by gas chromatography or the like, and the conversion rate is preferably 55% or more, more preferably 60% or more, still more preferably 70% or more, particularly preferably Is reacted until it reaches 80% or more.
  • the reactor is equipped with at least part of IPEA and / or PNA, at least part of primary alcohol, ⁇ -type zeolite and / or Y-type zeolite, Accordingly, at least a part of the solvent is charged, and the reaction is carried out by stirring at a predetermined temperature, while continuously or intermittently supplying IPEA and / or PNA, primary alcohol, and, if necessary, the solvent to the reactor.
  • reaction time it demonstrates similarly to the case of the said batch system.
  • a jacketed tubular reactor is filled with ⁇ -type zeolite and / or Y-type zeolite, and a heating medium of a predetermined temperature is allowed to flow through the jacket while IPEA and / or PNA.
  • the primary alcohol are mixed such that LHSV (Liquid Hourly Space Velocity; liquid space velocity; hr ⁇ 1 ) is preferably 0.1 to 70 hr ⁇ 1 , more preferably 0.1 to 50 hr ⁇ 1.
  • LHSV Liquid Hourly Space Velocity; liquid space velocity; hr ⁇ 1
  • Such a continuous system is implemented by a “one-pass system” in which a mixed solution of IPEA and / or PNA and primary alcohol is circulated only once through a tubular reactor filled with ⁇ -type zeolite and / or Y-type zeolite.
  • a “circulation type” in which at least part or all of the reaction mixture obtained by passing through the tubular reactor is circulated through the tubular reactor again and the above operation is repeated as necessary. May be implemented.
  • LHSV when carrying out in a single pass type, LHSV, from the viewpoint of conversion, preferably 0.1 ⁇ 5 hr -1, more preferably 0.1 ⁇ 3 hr -1, more preferably 0.1 ⁇ 1hr -1 is there.
  • LHSV is preferably 3 to 70 hr ⁇ 1 , more preferably 5 to 50 hr ⁇ 1 , still more preferably 10 to 50 hr ⁇ 1 , particularly preferably 15 to 40 hr from the viewpoint of conversion. -1 .
  • the selectivity for 3-alkoxy-3-methyl-1-butanol tends to increase.
  • 3-alkoxy-3-methyl-1-butanol can be separated by applying a known separation method to the resulting reaction mixture.
  • the obtained 3-alkoxy-3-methyl-1-butanol can be further purified by subjecting it to purification techniques such as column chromatography and distillation.
  • Example 1 Batch mode, ⁇ -type zeolite, ethanol use Thermometer, Dimroth condenser and 300 mL three-necked flask equipped with a stirrer were charged with 21.5 g (0.25 mol) of 3-methyl-3-buten-1-ol. , 230 g of ethanol (4.99 mol, ethanol / IPEA ⁇ 20 (molar ratio)) and ⁇ -type zeolite “BEA-25” (BET specific surface area: 250 m 2 / g, average particle size: 3.8 ⁇ m, proton type, Sudden Chemie catalyst 15g) was added, and the reaction was conducted while heating to 60 ° C and stirring.
  • Example 3 Batch system, ⁇ -type zeolite, ethanol used In Example 1, instead of ⁇ -type zeolite “BEA-25”, ⁇ -type zeolite “BEA-150” (BET specific surface area: 620 m 2 / g, average The same operation as in Example 1 was performed except that a particle size: 45 ⁇ m, proton type, manufactured by Zude Chemie Catalysts Co., Ltd.) was used. The reaction mixture after 8 hours from the start of the reaction was analyzed by gas chromatography.
  • Example 4 Batch system, use of Y-type zeolite, ethanol
  • Y-type zeolite “350HUA” BET specific surface area: 650 m 2 / g, average particle diameter
  • 6 ⁇ m proton type, manufactured by Tosoh Corporation
  • the reaction mixture after 8 hours from the start of the reaction was analyzed by gas chromatography.
  • the conversion of 3-methyl-3-buten-1-ol was 74.9% and 3-ethoxy-3-methyl-1-butanol
  • the yield was 58.0% (selectivity of 3-ethoxy-3-methyl-1-butanol was 77.5%).
  • Table 1 If the reaction is further continued, it can be said that the yield of 3-ethoxy-3-methyl-1-butanol can be further increased.
  • Example 1 Batch system, use of strong acidic ion exchange resin, ethanol
  • strongly acidic ion exchange resin “Diaion PK212LH” manufactured by Mitsubishi Chemical Corporation
  • the reaction time was 16 hours.
  • the reaction mixture after 16 hours from the start of the reaction was analyzed by gas chromatography.
  • the conversion of 3-methyl-3-buten-1-ol was 97.0% and 3-ethoxy-3-methyl-1-butanol
  • the yield was 58.0% (selectivity of 3-ethoxy-3-methyl-1-butanol 59.8%).
  • Table 1 The results are shown in Table 1. In addition, since the conversion rate was high enough, it turns out that a yield cannot be raised any more.
  • Example 2 Batch system, use of ZSM-5 type zeolite, ethanol
  • ZSM-5 type zeolite manufactured by Zude Chemie Catalysts
  • the same operation as in Example 1 was performed.
  • the reaction mixture after 8 hours from the start of the reaction was analyzed by gas chromatography.
  • the conversion of 3-methyl-3-buten-1-ol was 13.6% and 3-ethoxy-3-methyl-1-butanol
  • the yield was 4.4% (selectivity of 3-ethoxy-3-methyl-1-butanol 32.7%).
  • Table 1 The results are shown in Table 1.
  • Example 3 Batch system, use of activated clay, ethanol In Example 1, in place of ⁇ -type zeolite “BEA-25”, activated clay (manufactured by Nippon Kakuhaku Co., Ltd.) was used. The same operation was performed. When the reaction mixture after 8 hours from the start of the reaction was analyzed by gas chromatography, the conversion of 3-methyl-3-buten-1-ol was 14.8%. No 1-butanol was obtained. The results are shown in Table 1.
  • Example 4 Batch system, using niobium oxide and ethanol
  • Example 1 was used except that niobium oxide (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of ⁇ -type zeolite “BEA-25”. The same operation was performed.
  • the reaction mixture after 8 hours from the start of the reaction was analyzed by gas chromatography.
  • the conversion of 3-methyl-3-buten-1-ol was 3.4%, and 3-ethoxy-3-methyl-1-butanol
  • the yield was 0.1% (selectivity of 3-ethoxy-3-methyl-1-butanol: 3.0%).
  • Table 1 The results are shown in Table 1.
  • Example 5 Continuous type, ⁇ -type zeolite, ethanol used (circulation type) A jacketed tubular reactor was charged with 100 mL of pellet-shaped ⁇ -type zeolite “BEA-25” (manufactured by Zude Chemie Catalysts). While flowing warm water (heat medium) at 70 ° C.
  • Example 6 Continuous method, using ⁇ -type zeolite, n-propanol (circulation type)
  • Example 5 the same operation as in Example 5 was performed, except that 600 g (9.99 mol) of n-propanol was used instead of 460 g (9.99 mol) of ethanol.
  • the reaction mixture after reaction for 10 hours was analyzed by gas chromatography.
  • the conversion of 3-methyl-3-buten-1-ol was 93.5% and 3-propoxy-3-methyl-1-butanol
  • the yield was 75.0% (selectivity of 3-propoxy-3-methyl-1-butanol was 80.2%).
  • Table 2 The results are shown in Table 2.
  • Example 7 Continuous system, ⁇ -type zeolite, methanol (circulation)
  • Example 5 the same operation as in Example 5 was performed except that 320 g (9.99 mol) of methanol was used instead of 460 g (9.99 mol) of ethanol.
  • the reaction mixture after flowing for 10 hours was analyzed by gas chromatography.
  • the conversion of 3-methyl-3-buten-1-ol was 87.1%, and 3-methoxy-3-methyl-1-butanol.
  • the yield was 73.2% (selectivity of 3-methoxy-3-methyl-1-butanol 84.0%).
  • Table 2 The results are shown in Table 2.
  • Example 8 Continuous system, ⁇ -type zeolite, ethanol used (one-pass system)
  • Example 5 is the same as Example 5 except that the LHSV was changed to 0.5 hr ⁇ 1 , the one-pass system was used in which the tubular reactor was circulated only once, and the reaction mixture was not circulated by the pump. The same operation was performed. The obtained reaction mixture was analyzed by gas chromatography. The conversion of 3-methyl-3-buten-1-ol was 87.9%, and the yield of 3-ethoxy-3-methyl-1-butanol was 71.7% (selectivity of 3-ethoxy-3-methyl-1-butanol was 81.6%). The results are shown in Table 2.
  • Example 5 Continuous method, strong acidic ion exchange resin, ethanol used (circulation type)
  • a strongly acidic ion exchange resin “Diaion PK212LH” manufactured by Mitsubishi Chemical Corporation
  • the same operation as in Example 5 was performed.
  • the reaction mixture after reaction for 10 hours was analyzed by gas chromatography.
  • the conversion of 3-methyl-3-buten-1-ol was 90.9% and 3-ethoxy-3-methyl-1-butanol
  • the yield was 58.9% (selectivity of 3-ethoxy-3-methyl-1-butanol 64.8%).
  • Table 2 The results are shown in Table 2.
  • Example 9 Continuous type, ⁇ -type zeolite, PNA, ethanol used (circulation type)
  • 43 g (0.50 mol) of 3-methyl-2-buten-1-ol was used instead of 43 g (0.50 mol) of 3-methyl-3-buten-1-ol.
  • the same operation as 5 was performed.
  • the reaction mixture after the reaction for 10 hours was analyzed by gas chromatography.
  • the conversion of 3-methyl-2-buten-1-ol was 83.1% and 3-ethoxy-3-methyl-1-butanol
  • the yield was 65.6% (selectivity of 3-ethoxy-3-methyl-1-butanol 79.0%).
  • Table 3 The results are shown in Table 3.
  • Example 9 Continuous system, strong acidic ion exchange resin, PNA, ethanol used (circulation type)
  • a strongly acidic ion exchange resin “Diaion PK212LH” (manufactured by Mitsubishi Chemical Corporation) was used, and the temperature of hot water was changed to 50 ° C.
  • the same operation as in Example 9 was performed.
  • the reaction mixture after the reaction for 10 hours was analyzed by gas chromatography.
  • the conversion of 3-methyl-2-buten-1-ol was 88.2% and 3-ethoxy-3-methyl-1-butanol.
  • the yield was 55.2% (selectivity of 3-ethoxy-3-methyl-1-butanol 62.6%).
  • Table 3 The results are shown in Table 3.
  • the 3-alkoxy-3-methyl-1-butanol obtained by the production method of the present invention is useful as an intermediate for medical and agricultural chemicals and as a raw material for various cleaning agents.

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Abstract

Provided is a method for producing 3-alkoxy-3-methyl-1-butanol with high selectivity and high yield. Specifically provided is a method for producing 3-alkoxy-3-methyl-1-butanol, wherein at least one kind of methyl butenol that is selected from among 3-methyl-3-buten-1-ol and 3-methyl-2-buten-1-ol is reacted with a primary alcohol having 1-5 carbon atoms in the presence of at least one kind of zeolite that is selected from among β zeolite and Y zeolite.

Description

３－アルコキシ－３－メチル－１－ブタノールの製造方法Method for producing 3-alkoxy-3-methyl-1-butanol
　本発明は、医農薬中間体や各種洗浄剤の原料などとして有用な３－アルコキシ－３－メチル－１－ブタノールの製造方法に関する。 The present invention relates to a method for producing 3-alkoxy-3-methyl-1-butanol which is useful as a raw material for intermediates for medical and agricultural chemicals and various detergents.
　３－メチル－３－ブテン－１－オール（以下、ＩＰＥＡと称することがある。）または３－メチル－２－ブテン－１－オール（以下、ＰＮＡと称することがある。）と第一級アルコールとの反応において、硫酸、燐酸、スルホン酸、カチオン系イオン交換樹脂などの酸の存在下に実施することにより、異性化反応や脱水反応、さらに二重結合への水酸基の付加反応などを抑制しながら３－アルコキシ－３－メチル－１－ブタノールを製造し得ることが知られている（特許文献１参照）。 3-methyl-3-buten-1-ol (hereinafter sometimes referred to as IPEA) or 3-methyl-2-buten-1-ol (hereinafter sometimes referred to as PNA) and primary alcohol In the presence of acids such as sulfuric acid, phosphoric acid, sulfonic acid, and cationic ion exchange resins, to suppress isomerization and dehydration reactions, and addition of hydroxyl groups to double bonds. However, it is known that 3-alkoxy-3-methyl-1-butanol can be produced (see Patent Document 1).
特開昭５０－５９３０９号公報JP 50-59309 A
　しかしながら、特許文献１に記載の方法では、転化率は高いものの、３－アルコキシ－３－メチル－１－ブタノールの選択率が不十分であり、より高収率で３－アルコキシ－３－メチル－１－ブタノールを得るためには、更なる改良の余地があった。
　そこで、本発明の課題は、３－アルコキシ－３－メチル－１－ブタノールを高選択率および高収率で製造する方法を提供することにある。 However, in the method described in Patent Document 1, although the conversion rate is high, the selectivity of 3-alkoxy-3-methyl-1-butanol is insufficient, and 3-alkoxy-3-methyl- There was room for further improvement in order to obtain 1-butanol.
Accordingly, an object of the present invention is to provide a method for producing 3-alkoxy-3-methyl-1-butanol with high selectivity and high yield.
　本発明者らが鋭意検討した結果、ＩＰＥＡまたはＰＮＡと第一級アルコールとの反応において、特定のゼオライトを触媒として用いることにより前記課題を解決できることを見出し、本発明を完成するに至った。
　即ち、本発明は、下記［１］～［４］を提供する。
［１］３－メチル－３－ブテン－１－オールおよび３－メチル－２－ブテン－１－オールから選択される少なくとも１種のメチルブテノールと炭素数１～５の第一級アルコールとを、β型ゼオライトおよびＹ型ゼオライトから選択される少なくとも１種のゼオライトの存在下に反応させることを特徴とする、３－アルコキシ－３－メチル－１－ブタノールの製造方法。
［２］前記炭素数１～５の第一級アルコールが、メタノール、エタノールまたはｎ－プロパノールである、上記［１］の３－アルコキシ－３－メチル－１－ブタノールの製造方法。
［３］前記炭素数１～５の第一級アルコールの使用量が、３－メチル－３－ブテン－１－オールおよび３－メチル－２－ブテン－１－オールから選択される少なくとも１種のメチルブテノール１モルに対して０．５～４０モルである、上記［１］または［２］の３－アルコキシ－３－メチル－１－ブタノールの製造方法。
［４］前記β型ゼオライトおよびＹ型ゼオライトのＢＥＴ比表面積が、それぞれ、１００～１，０００ｍ2／ｇである、上記［１］～［３］のいずれかの３－アルコキシ－３－メチル－１－ブタノールの製造方法。 As a result of intensive studies by the present inventors, it has been found that the above problem can be solved by using a specific zeolite as a catalyst in the reaction of IPEA or PNA with a primary alcohol, and the present invention has been completed.
That is, the present invention provides the following [1] to [4].
[1] At least one methylbutenol selected from 3-methyl-3-buten-1-ol and 3-methyl-2-buten-1-ol and a primary alcohol having 1 to 5 carbon atoms A process for producing 3-alkoxy-3-methyl-1-butanol, characterized by reacting in the presence of at least one zeolite selected from β-type zeolite and Y-type zeolite.
[2] The process for producing 3-alkoxy-3-methyl-1-butanol according to the above [1], wherein the primary alcohol having 1 to 5 carbon atoms is methanol, ethanol or n-propanol.
[3] The use amount of the primary alcohol having 1 to 5 carbon atoms is at least one selected from 3-methyl-3-buten-1-ol and 3-methyl-2-buten-1-ol. The process for producing 3-alkoxy-3-methyl-1-butanol according to the above [1] or [2], which is 0.5 to 40 mol per 1 mol of methylbutenol.
[4] The 3-alkoxy-3-methyl- of any one of the above [1] to [3], wherein the β-type zeolite and the Y-type zeolite each have a BET specific surface area of 100 to 1,000 m 2 / g. A method for producing 1-butanol.
　本発明の製造方法によれば、３－アルコキシ－３－メチル－１－ブタノールを従来よりも高選択率および高収率で製造することができる。 According to the production method of the present invention, 3-alkoxy-3-methyl-1-butanol can be produced with higher selectivity and higher yield than before.
　まず、本明細書において、好ましいとする規定は任意に採用することができ、好ましいとする規定同士の組み合わせは、より好ましいといえる。 First, in the present specification, it is possible to arbitrarily adopt a rule that is preferable, and it can be said that a combination of rules that are preferable is more preferable.
［３－アルコキシ－３－メチル－１－ブタノールの製造方法］
　本発明の３－アルコキシ－３－メチル－１－ブタノールの製造方法では、３－メチル－３－ブテン－１－オール（ＩＰＥＡ）および３－メチル－２－ブテン－１－オール（ＰＮＡ）から選択される少なくとも１種のメチルブテノールと炭素数１～５の第一級アルコールとを、β型ゼオライトおよびＹ型ゼオライトから選択される少なくとも１種のゼオライトの存在下に反応させることに特徴を有する。第一級アルコールをＲ－ＣＨ2ＯＨ（Ｒは、水素原子または炭素数１～４のアルキル基を示す。）と表すと、本発明の製造方法は、以下の化学反応式で表される。
Figure JPOXMLDOC01-appb-C000001
 （式中、実線と破線からなる２箇所の炭素－炭素結合は、いずれか一方が炭素－炭素二重結合になっていることを示す。） [Method for producing 3-alkoxy-3-methyl-1-butanol]
In the method for producing 3-alkoxy-3-methyl-1-butanol according to the present invention, a selection is made from 3-methyl-3-buten-1-ol (IPEA) and 3-methyl-2-buten-1-ol (PNA). Characterized in that at least one methylbutenol and a primary alcohol having 1 to 5 carbon atoms are reacted in the presence of at least one zeolite selected from β-type zeolite and Y-type zeolite. . When the primary alcohol is represented by R—CH 2 OH (R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), the production method of the present invention is represented by the following chemical reaction formula.
Figure JPOXMLDOC01-appb-C000001
 (In the formula, two carbon-carbon bonds consisting of a solid line and a broken line indicate that one of them is a carbon-carbon double bond.)
（炭素数１～５の第一級アルコール）
　本発明の方法で用いる炭素数１～５の第一級アルコールとしては、メタノール、エタノール、ｎ－プロパノール、ｎ－ブタノール、イソブタノールなどが挙げられる。中でも、３－アルコキシ－３－メチル－１－ブタノールの選択率および収率の観点から、好ましくはメタノール、エタノール、ｎ－プロパノールである。なお、第一級アルコールの代わりに第二級アルコール（例えばイソプロパノール）または第三級アルコールを用いると、３－アルコキシ－３－メチル－１－ブタノールの選択率および収率が大幅に低減する。
　炭素数１～５の第一級アルコールの使用量は、ＩＰＥＡおよびＰＮＡから選択される少なくとも１種のメチルブテノール１モルに対して、好ましくは０．５～４０モル、より好ましくは０．７～３０モル、さらに好ましくは０．８～２５モルである。特に、ＩＰＥＡおよびＰＮＡから選択される少なくとも１種のメチルブテノール１モルに対する炭素数１～５の第一級アルコールの使用量の下限値は、転化率の観点から、前記下限値に加え、より好ましくは２モル、さらに好ましくは５モルである。炭素数１～５の第一級アルコールを、ＩＰＥＡやＰＮＡに対して過剰量とすると、第一級アルコール自体が溶媒としても機能し、他に溶媒を用いる必要がなくなり、効率良く反応を行なうことができて好ましい。
　なお、本発明の方法においては、溶媒を用いることもできる。溶媒としては、例えばヘキサン、ヘプタン、オクタンなどの脂肪族炭化水素；ベンゼン、トルエン、キシレン、メシチレンなどの芳香族炭化水素；ジエチルエーテル、ジプロピルエーテル、ジブチルエーテル、テトラヒドロフラン、ジオキサン、１，２－ジメトキシエタン、ジエチレングリコールジメチルエーテル（ジグライム）、トリエチレングリコールジメチルエーテル（トリグライム）、テトラエチレングリコールジメチルエーテル（テトラグライム）などのエーテルなどの、本発明の反応に悪影響を及ぼさない溶媒が挙げられる。溶媒は、１種を単独で使用してもよいし、２種以上を併用してもよい。 (Primary alcohol with 1 to 5 carbon atoms)
Examples of the primary alcohol having 1 to 5 carbon atoms used in the method of the present invention include methanol, ethanol, n-propanol, n-butanol, and isobutanol. Of these, methanol, ethanol, and n-propanol are preferable from the viewpoint of selectivity and yield of 3-alkoxy-3-methyl-1-butanol. If a secondary alcohol (for example, isopropanol) or a tertiary alcohol is used instead of the primary alcohol, the selectivity and yield of 3-alkoxy-3-methyl-1-butanol are greatly reduced.
The amount of the primary alcohol having 1 to 5 carbon atoms is preferably 0.5 to 40 mol, more preferably 0.7 to 1 mol of at least one methylbutenol selected from IPEA and PNA. -30 mol, more preferably 0.8-25 mol. In particular, the lower limit of the amount of primary alcohol having 1 to 5 carbon atoms to 1 mol of at least one methylbutenol selected from IPEA and PNA is, in addition to the lower limit, from the viewpoint of conversion, Preferably it is 2 mol, More preferably, it is 5 mol. When the primary alcohol having 1 to 5 carbon atoms is excessive with respect to IPEA or PNA, the primary alcohol itself functions as a solvent, and there is no need to use another solvent, so that the reaction can be carried out efficiently. Is preferable.
In the method of the present invention, a solvent can also be used. Examples of the solvent include aliphatic hydrocarbons such as hexane, heptane, and octane; aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxy. Examples include ethane, ethers such as diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), and tetraethylene glycol dimethyl ether (tetraglyme), which do not adversely affect the reaction of the present invention. A solvent may be used individually by 1 type and may use 2 or more types together.
（β型ゼオライト、Ｙ型ゼオライト）
　本発明の方法では、β型ゼオライトおよびＹ型ゼオライトから選択される少なくとも１種のゼオライトの存在下に実施する。ゼオライトは細孔を有した含水アルミノ系ケイ酸塩であり、その中でも、本発明では「β型」ゼオライトおよび／または「Ｙ型」ゼオライトを用いることにより、高選択的に高収率で３－アルコキシ－３－メチル－１－ブタノールを製造できることを見出した。
　β型ゼオライトおよびＹ型ゼオライトは、プロトン型（Ｈ型）またはアンモニウムイオン型（ＮＨ4 +型）であってもよく、ナトリウムやカリウム等のアルカリ金属；マグネシウムやカルシウム等のアルカリ土類金属；鉄等の８族金属；コバルト等の９族金属；ニッケル等の１０族金属などによって置換された「金属置換型」であってもよい。３－アルコキシ－３－メチル－１－ブタノールの選択率および収率の観点からは、β型ゼオライトおよびＹ型ゼオライトは、いずれもプロトン型であることが好ましい。 (Β-type zeolite, Y-type zeolite)
The method of the present invention is carried out in the presence of at least one zeolite selected from β-type zeolite and Y-type zeolite. Zeolite is a hydrous aluminosilicate having pores. Among them, in the present invention, by using “β-type” zeolite and / or “Y-type” zeolite, high-selectivity and high yield of 3- It has been found that alkoxy-3-methyl-1-butanol can be produced.
β-type zeolite and Y-type zeolite may be proton type (H type) or ammonium ion type (NH 4 + type); alkali metals such as sodium and potassium; alkaline earth metals such as magnesium and calcium; iron Group 8 metals such as cobalt; Group 9 metals such as cobalt; Group 10 metals such as nickel; From the viewpoint of the selectivity and yield of 3-alkoxy-3-methyl-1-butanol, it is preferable that both β-type zeolite and Y-type zeolite are proton types.
　β型ゼオライトのＳｉＯ2／Ａｌ2Ｏ3（モル比）は、３－アルコキシ－３－メチル－１－ブタノールの選択率および収率の観点から、好ましくは５～５００、より好ましくは１０～４５０、さらに好ましくは１５～４００である。
　β型ゼオライトのＢＥＴ比表面積は、３－アルコキシ－３－メチル－１－ブタノールの選択率および収率の観点から、好ましくは１００～１，０００ｍ2／ｇ、より好ましくは１５０～８００ｍ2／ｇ、さらに好ましくは２００～７００ｍ2／ｇである。β型ゼオライトの細孔については、３－アルコキシ－３－メチル－１－ブタノールの選択率および収率の観点から、一般的に大細孔と言われる１２員環が形成されたものであることが好ましい。また、β型ゼオライトの細孔径は、好ましくは０．２～１．０ｎｍ、より好ましくは０．４～０．８ｎｍ、さらに好ましくは０．５～０．７ｎｍである。
　β型ゼオライトの平均粒子径は、好ましくは１～１００μｍ、より好ましくは１～８０μｍ、さらに好ましくは１～５０μｍである。
　β型ゼオライトのナトリウム含有量は、好ましくは０．０１～１質量％、より好ましくは０．０１～０．５質量％である。 The SiO 2 / Al 2 O 3 (molar ratio) of the β-type zeolite is preferably 5 to 500, more preferably 10 to 450 from the viewpoint of the selectivity and yield of 3-alkoxy-3-methyl-1-butanol. More preferably, it is 15 to 400.
BET specific surface area of the β-type zeolite, 3-alkoxy-3-methyl-1-butanol selectivity and in terms of yield, preferably 100 ~ 1,000m 2 / g, more preferably 150 ~ 800m 2 / g More preferably, it is 200 to 700 m 2 / g. Regarding the pores of β-type zeolite, from the viewpoint of selectivity and yield of 3-alkoxy-3-methyl-1-butanol, a 12-membered ring generally called a large pore is formed. Is preferred. The pore size of β-type zeolite is preferably 0.2 to 1.0 nm, more preferably 0.4 to 0.8 nm, and still more preferably 0.5 to 0.7 nm.
The average particle size of β-type zeolite is preferably 1 to 100 μm, more preferably 1 to 80 μm, and still more preferably 1 to 50 μm.
The sodium content of the β-type zeolite is preferably 0.01 to 1% by mass, more preferably 0.01 to 0.5% by mass.
　Ｙ型ゼオライトのＳｉＯ2／Ａｌ2Ｏ3（モル比）は、３－アルコキシ－３－メチル－１－ブタノールの選択率および収率の観点から、好ましくは６～５０、より好ましくは７～４０、さらに好ましくは８～２０である。Ｙ型ゼオライトのＢＥＴ比表面積は、３－アルコキシ－３－メチル－１－ブタノールの選択率および収率の観点から、好ましくは１００～１，０００ｍ2／ｇ、より好ましくは２５０～８００ｍ2／ｇ、さらに好ましくは４００～７５０ｍ2／ｇである。Ｙ型ゼオライトの細孔については、３－アルコキシ－３－メチル－１－ブタノールの選択率および収率の観点から、一般的に大細孔と言われる１２員環が形成されたものであることが好ましい。また、Ｙ型ゼオライトの細孔径は、好ましくは０．２～１．０ｎｍ、より好ましくは０．４～０．８ｎｍ、さらに好ましくは０．６～０．８ｎｍである。
　Ｙ型ゼオライトのＮＨ3－ＴＰＤ法によって求めた酸量は、３－アルコキシ－３－メチル－１－ブタノールの選択率および収率の観点から、好ましくは０．０１～５ｍｍｏｌ／ｇ、より好ましくは０．０１～３ｍｍｏｌ／ｇ、さらに好ましくは０．０５～２ｍｍｏｌ／ｇである。
　Ｙ型ゼオライトの平均粒子径は、好ましくは１～１００μｍ、より好ましくは１～５０μｍ、さらに好ましくは３～２０μｍである。
　Ｙ型ゼオライトのナトリウム含有量は、好ましくは０．０１～１質量％、より好ましくは０．０１～０．５質量％である。 The SiO 2 / Al 2 O 3 (molar ratio) of the Y-type zeolite is preferably 6 to 50, more preferably 7 to 40, from the viewpoint of the selectivity and yield of 3-alkoxy-3-methyl-1-butanol. More preferably, it is 8-20. The BET specific surface area of the Y-type zeolite is preferably 100 to 1,000 m 2 / g, more preferably 250 to 800 m 2 / g from the viewpoint of the selectivity and yield of 3-alkoxy-3-methyl-1-butanol. More preferably, it is 400 to 750 m 2 / g. The pores of the Y-type zeolite are those in which a 12-membered ring generally called a large pore is formed from the viewpoint of selectivity and yield of 3-alkoxy-3-methyl-1-butanol. Is preferred. The pore size of the Y-type zeolite is preferably 0.2 to 1.0 nm, more preferably 0.4 to 0.8 nm, and still more preferably 0.6 to 0.8 nm.
The acid amount of the Y-type zeolite determined by the NH 3 -TPD method is preferably 0.01 to 5 mmol / g, more preferably from the viewpoint of the selectivity and yield of 3-alkoxy-3-methyl-1-butanol. 0.01 to 3 mmol / g, more preferably 0.05 to 2 mmol / g.
The average particle size of the Y-type zeolite is preferably 1 to 100 μm, more preferably 1 to 50 μm, still more preferably 3 to 20 μm.
The sodium content of the Y-type zeolite is preferably 0.01 to 1% by mass, more preferably 0.01 to 0.5% by mass.
　本発明の方法を実施する際の反応温度は、通常、好ましくは４０～８０℃、より好ましくは５０～８０℃である。反応圧力に特に制限はないが、通常、常圧下で実施するのが簡便であり好ましい。
　本発明の３－アルコキシ－３－メチル－１－ブタノールの製造方法の実施形態に特に制限はなく、例えば、バッチ方式、セミ連続方式、連続方式など、公知の方法を適用できる。以下に、それぞれの方式による実施形態について具体的に説明するが、特にこれらに制限されるものではない。
　本発明の方法をバッチ方式により実施する場合、例えば、反応器にＩＰＥＡおよび／またはＰＮＡ、第一級アルコール、β型ゼオライトおよび／またはＹ型ゼオライト、さらに必要に応じて溶媒を全て仕込み、所定温度に加熱して攪拌する。反応時間に特に制限はなく、適宜、ガスクロマトグラフィーなどによってＩＰＥＡやＰＮＡの転化率を追跡し、転化率が好ましくは５５％以上、より好ましくは６０％以上、さらに好ましくは７０％以上、特に好ましくは８０％以上になるまで反応を行う。
　本発明の方法をセミ連続方式により実施する場合、例えば、反応器にＩＰＥＡおよび／またはＰＮＡの少なくとも一部、第一級アルコールの少なくとも一部、β型ゼオライトおよび／またはＹ型ゼオライト、さらに必要に応じて溶媒の少なくとも一部を仕込み、所定温度で攪拌して反応を行ないながら、連続的又は断続的にＩＰＥＡおよび／またはＰＮＡ、第一級アルコール、および必要に応じ溶媒を反応器に供給する。反応時間については、前記バッチ方式の場合と同様に説明される。
　本発明の方法を連続方式により実施する場合、例えば、ジャケット付き管型反応装置にβ型ゼオライトおよび／またはＹ型ゼオライトを充填し、ジャケットに所定温度の熱媒を流しながら、ＩＰＥＡおよび／またはＰＮＡと第一級アルコールとの混合液を、ＬＨＳＶ（Ｌｉｑｕｉｄ　Ｈｏｕｒｌｙ　Ｓｐａｃｅ　Ｖｅｌｏｃｉｔｙ；液空間速度；ｈｒ-1）が好ましくは０．１～７０ｈｒ-1、より好ましくは０．１～５０ｈｒ-1となるように前記管型反応装置に流通させる。かかる連続方式は、ＩＰＥＡおよび／またはＰＮＡと第一級アルコールとの混合液を、β型ゼオライトおよび／またはＹ型ゼオライトを充填した管型反応装置に１回のみ流通させる「ワンパス式」で実施してもよいし、該管型反応装置を通過させて得られる反応混合液の少なくとも一部または全部を再び該管型反応装置に流通させ、必要に応じて前記操作を繰り返して行う「循環式」で実施してもよい。なお、ワンパス式で実施する場合、ＬＨＳＶは、転化率の観点から、好ましくは０．１～５ｈｒ-1、より好ましくは０．１～３ｈｒ-1、さらに好ましくは０．１～１ｈｒ-1である。一方、循環式で実施する場合、ＬＨＳＶは、転化率の観点から、好ましくは３～７０ｈｒ-1、より好ましくは５～５０ｈｒ-1、さらに好ましくは１０～５０ｈｒ-1、特に好ましくは１５～４０ｈｒ-1である。
　なお、本発明の方法を連続方式にて実施すると、３－アルコキシ－３－メチル－１－ブタノールの選択率が高まる傾向にある。 The reaction temperature for carrying out the method of the present invention is usually preferably 40 to 80 ° C., more preferably 50 to 80 ° C. Although there is no restriction | limiting in particular in reaction pressure, Usually, it is simple and preferable to implement under a normal pressure.
There is no particular limitation on the embodiment of the method for producing 3-alkoxy-3-methyl-1-butanol of the present invention, and known methods such as a batch method, a semi-continuous method, and a continuous method can be applied. Hereinafter, embodiments according to the respective methods will be described in detail, but the present invention is not particularly limited thereto.
When the method of the present invention is carried out in a batch mode, for example, the reactor is charged with IPEA and / or PNA, primary alcohol, β-type zeolite and / or Y-type zeolite, and if necessary, all of the solvent, at a predetermined temperature. Heat to agitate and stir. The reaction time is not particularly limited, and the conversion rate of IPEA or PNA is appropriately monitored by gas chromatography or the like, and the conversion rate is preferably 55% or more, more preferably 60% or more, still more preferably 70% or more, particularly preferably Is reacted until it reaches 80% or more.
When the process according to the invention is carried out in a semi-continuous manner, for example, the reactor is equipped with at least part of IPEA and / or PNA, at least part of primary alcohol, β-type zeolite and / or Y-type zeolite, Accordingly, at least a part of the solvent is charged, and the reaction is carried out by stirring at a predetermined temperature, while continuously or intermittently supplying IPEA and / or PNA, primary alcohol, and, if necessary, the solvent to the reactor. About reaction time, it demonstrates similarly to the case of the said batch system.
When the method of the present invention is carried out in a continuous manner, for example, a jacketed tubular reactor is filled with β-type zeolite and / or Y-type zeolite, and a heating medium of a predetermined temperature is allowed to flow through the jacket while IPEA and / or PNA. And the primary alcohol are mixed such that LHSV (Liquid Hourly Space Velocity; liquid space velocity; hr −1 ) is preferably 0.1 to 70 hr −1 , more preferably 0.1 to 50 hr −1. In the tubular reactor. Such a continuous system is implemented by a “one-pass system” in which a mixed solution of IPEA and / or PNA and primary alcohol is circulated only once through a tubular reactor filled with β-type zeolite and / or Y-type zeolite. Alternatively, a “circulation type” in which at least part or all of the reaction mixture obtained by passing through the tubular reactor is circulated through the tubular reactor again and the above operation is repeated as necessary. May be implemented. Incidentally, when carrying out in a single pass type, LHSV, from the viewpoint of conversion, preferably 0.1 ~ 5 hr -1, more preferably 0.1 ~ 3 hr -1, more preferably 0.1 ~ 1hr -1 is there. On the other hand, when carried out in a cyclic manner, LHSV is preferably 3 to 70 hr −1 , more preferably 5 to 50 hr −1 , still more preferably 10 to 50 hr −1 , particularly preferably 15 to 40 hr from the viewpoint of conversion. -1 .
When the method of the present invention is carried out in a continuous manner, the selectivity for 3-alkoxy-3-methyl-1-butanol tends to increase.
　反応終了後、得られた反応混合液に公知の分離方法を適用することにより、３－アルコキシ－３－メチル－１－ブタノールを分離できる。得られた３－アルコキシ－３－メチル－１－ブタノールは、さらにカラムクロマトグラフィーや蒸留などの精製手法に付すことにより、その純度を高めることができる。 After completion of the reaction, 3-alkoxy-3-methyl-1-butanol can be separated by applying a known separation method to the resulting reaction mixture. The obtained 3-alkoxy-3-methyl-1-butanol can be further purified by subjecting it to purification techniques such as column chromatography and distillation.
　以下、実施例などにより本発明を具体的に説明するが、本発明はこれらの実施例に限定されない。なお、各例におけるガスクロマトグラフィー測定条件は以下の通りである。
（ガスクロマトグラフィー測定条件）
　装置　　　：ＧＣ－１４Ｂ（株式会社島津製作所製）
　使用カラム：Ｇ－３００（内径１．２ｍｍ×長さ２０ｍ）、（財）化学物質評価研究機構製
　分析条件　：注入口温度２４０℃、検出器温度２４０℃
　カラム温度：８０℃から２３０℃まで５℃／分で昇温
　検出器　　：水素炎イオン化検出器（ＦＩＤ） EXAMPLES Hereinafter, although an Example etc. demonstrate this invention concretely, this invention is not limited to these Examples. In addition, the gas chromatography measurement conditions in each example are as follows.
(Gas chromatography measurement conditions)
Device: GC-14B (manufactured by Shimadzu Corporation)
Column used: G-300 (inner diameter 1.2 mm × length 20 m), manufactured by Chemicals Research Institute Analysis conditions: inlet temperature 240 ° C., detector temperature 240 ° C.
Column temperature: 80 ° C. to 230 ° C. at a rate of 5 ° C./min Detector: Hydrogen flame ionization detector (FID)
＜実施例１＞バッチ方式、β型ゼオライト、エタノール使用
　温度計、ジムロート冷却器および攪拌装置を備えた３００ｍＬ三口フラスコに、３－メチル－３－ブテン－１－オール２１．５ｇ（０．２５ｍｏｌ）、エタノール２３０ｇ（４．９９ｍｏｌ、エタノール／ＩＰＥＡ≒２０（モル比））およびβ型ゼオライト「ＢＥＡ－２５」（ＢＥＴ比表面積：２５０ｍ2／ｇ、平均粒子径：３．８μｍ、プロトン型、ズードケミー触媒株式会社製）１５ｇを入れ、６０℃に加熱して攪拌しながら反応を行った。
　反応開始から８時間後の反応混合液をガスクロマトグラフィーで分析したところ、３－メチル－３－ブテン－１－オールの転化率は８８．４％、３－エトキシ－３－メチル－１－ブタノールの収率は６６．３％（３－エトキシ－３－メチル－１－ブタノールの選択率７５．０％）であった。結果を表１に示す。 <Example 1> Batch mode, β-type zeolite, ethanol use Thermometer, Dimroth condenser and 300 mL three-necked flask equipped with a stirrer were charged with 21.5 g (0.25 mol) of 3-methyl-3-buten-1-ol. , 230 g of ethanol (4.99 mol, ethanol / IPEA≈20 (molar ratio)) and β-type zeolite “BEA-25” (BET specific surface area: 250 m 2 / g, average particle size: 3.8 μm, proton type, Sudden Chemie catalyst 15g) was added, and the reaction was conducted while heating to 60 ° C and stirring.
The reaction mixture after 8 hours from the start of the reaction was analyzed by gas chromatography. The conversion of 3-methyl-3-buten-1-ol was 88.4% and 3-ethoxy-3-methyl-1-butanol. The yield was 66.3% (selectivity of 3-ethoxy-3-methyl-1-butanol 75.0%). The results are shown in Table 1.
＜実施例２＞バッチ方式、β型ゼオライト、エタノール使用
　実施例１において、エタノールの使用量を１１５ｇ（２．５ｍｏｌ、エタノール／ＩＰＥＡ＝１０（モル比））としたこと以外は実施例１と同様の操作を行なった。
　反応開始から８時間後の反応混合液をガスクロマトグラフィーで分析したところ、３－メチル－３－ブテン－１－オールの転化率は６０．７％、３－エトキシ－３－メチル－１－ブタノールの収率は４２．９％（３－エトキシ－３－メチル－１－ブタノールの選択率７０．７％）であった。結果を表１に示す。なお、さらに反応を継続すれば、３－エトキシ－３－メチル－１－ブタノールの収率をより一層高めることができるといえる。 <Example 2> Batch system, β-type zeolite, ethanol used In Example 1, the same as Example 1 except that the amount of ethanol used was 115 g (2.5 mol, ethanol / IPEA = 10 (molar ratio)). The operation was performed.
The reaction mixture after 8 hours from the start of the reaction was analyzed by gas chromatography. The conversion of 3-methyl-3-buten-1-ol was 60.7% and 3-ethoxy-3-methyl-1-butanol The yield was 42.9% (selectivity of 3-ethoxy-3-methyl-1-butanol was 70.7%). The results are shown in Table 1. If the reaction is further continued, it can be said that the yield of 3-ethoxy-3-methyl-1-butanol can be further increased.
＜実施例３＞バッチ方式、β型ゼオライト、エタノール使用
　実施例１において、β型ゼオライト「ＢＥＡ－２５」の代わりに、β型ゼオライト「ＢＥＡ－１５０」（ＢＥＴ比表面積：６２０ｍ2／ｇ、平均粒子径：４５μｍ、プロトン型、ズードケミー触媒株式会社製）を使用したこと以外は実施例１と同様の操作を行なった。
　反応開始から８時間後の反応混合液をガスクロマトグラフィーで分析したところ、３－メチル－３－ブテン－１－オールの転化率は５９．５％、３－エトキシ－３－メチル－１－ブタノールの収率は４１．６％（３－エトキシ－３－メチル－１－ブタノールの選択率６９．９％）であった。結果を表１に示す。なお、さらに反応を継続すれば、３－エトキシ－３－メチル－１－ブタノールの収率をより一層高めることができるといえる。 <Example 3> Batch system, β-type zeolite, ethanol used In Example 1, instead of β-type zeolite “BEA-25”, β-type zeolite “BEA-150” (BET specific surface area: 620 m 2 / g, average The same operation as in Example 1 was performed except that a particle size: 45 μm, proton type, manufactured by Zude Chemie Catalysts Co., Ltd.) was used.
The reaction mixture after 8 hours from the start of the reaction was analyzed by gas chromatography. The conversion of 3-methyl-3-buten-1-ol was 59.5% and 3-ethoxy-3-methyl-1-butanol The yield was 41.6% (selectivity of 3-ethoxy-3-methyl-1-butanol 69.9%). The results are shown in Table 1. If the reaction is further continued, it can be said that the yield of 3-ethoxy-3-methyl-1-butanol can be further increased.
＜実施例４＞バッチ方式、Ｙ型ゼオライト、エタノール使用
　実施例１において、β型ゼオライト「ＢＥＡ－２５」の代わりに、Ｙ型ゼオライト「３５０ＨＵＡ」（ＢＥＴ比表面積：６５０ｍ2／ｇ、平均粒子径：６μｍ、プロトン型、東ソー株式会社製）を使用したこと以外は実施例１と同様に操作を行なった。
　反応開始から８時間後の反応混合液をガスクロマトグラフィーで分析したところ、３－メチル－３－ブテン－１－オールの転化率は７４．９％、３－エトキシ－３－メチル－１－ブタノールの収率は５８．０％（３－エトキシ－３－メチル－１－ブタノールの選択率７７．５％）であった。結果を表１に示す。なお、さらに反応を継続すれば、３－エトキシ－３－メチル－１－ブタノールの収率をより一層高めることができるといえる。 <Example 4> Batch system, use of Y-type zeolite, ethanol In Example 1, instead of β-type zeolite “BEA-25”, Y-type zeolite “350HUA” (BET specific surface area: 650 m 2 / g, average particle diameter) : 6 μm, proton type, manufactured by Tosoh Corporation) was used in the same manner as in Example 1.
The reaction mixture after 8 hours from the start of the reaction was analyzed by gas chromatography. The conversion of 3-methyl-3-buten-1-ol was 74.9% and 3-ethoxy-3-methyl-1-butanol The yield was 58.0% (selectivity of 3-ethoxy-3-methyl-1-butanol was 77.5%). The results are shown in Table 1. If the reaction is further continued, it can be said that the yield of 3-ethoxy-3-methyl-1-butanol can be further increased.
＜比較例１＞バッチ方式、強酸性イオン交換樹脂、エタノール使用
　実施例１において、β型ゼオライト「ＢＥＡ－２５」の代わりに、強酸性イオン交換樹脂「ダイヤイオンＰＫ２１２ＬＨ」（三菱化学株式会社製）を使用し、反応時間を１６時間としたこと以外は実施例１と同様の操作を行なった。
　反応開始から１６時間後の反応混合液をガスクロマトグラフィーで分析したところ、３－メチル－３－ブテン－１－オールの転化率は９７．０％、３－エトキシ－３－メチル－１－ブタノールの収率は５８．０％（３－エトキシ－３－メチル－１－ブタノールの選択率５９．８％）であった。結果を表１に示す。なお、転化率は充分に高かったため、これ以上、収率を高められないことがわかる。 <Comparative Example 1> Batch system, use of strong acidic ion exchange resin, ethanol In Example 1, instead of β-type zeolite “BEA-25”, strongly acidic ion exchange resin “Diaion PK212LH” (manufactured by Mitsubishi Chemical Corporation) Was used, and the same operation as in Example 1 was performed except that the reaction time was 16 hours.
The reaction mixture after 16 hours from the start of the reaction was analyzed by gas chromatography. The conversion of 3-methyl-3-buten-1-ol was 97.0% and 3-ethoxy-3-methyl-1-butanol The yield was 58.0% (selectivity of 3-ethoxy-3-methyl-1-butanol 59.8%). The results are shown in Table 1. In addition, since the conversion rate was high enough, it turns out that a yield cannot be raised any more.
＜比較例２＞バッチ方式、ＺＳＭ－５型ゼオライト、エタノール使用
　実施例１において、β型ゼオライト「ＢＥＡ－２５」の代わりに、ＺＳＭ－５型ゼオライト（ズードケミー触媒株式会社製）を使用したこと以外は実施例１と同様の操作を行なった。
　反応開始から８時間後の反応混合液をガスクロマトグラフィーで分析したところ、３－メチル－３－ブテン－１－オールの転化率は１３．６％、３－エトキシ－３－メチル－１－ブタノールの収率は４．４％（３－エトキシ－３－メチル－１－ブタノールの選択率３２．７％）であった。結果を表１に示す。 <Comparative Example 2> Batch system, use of ZSM-5 type zeolite, ethanol In Example 1, instead of using β type zeolite “BEA-25”, ZSM-5 type zeolite (manufactured by Zude Chemie Catalysts) was used. The same operation as in Example 1 was performed.
The reaction mixture after 8 hours from the start of the reaction was analyzed by gas chromatography. The conversion of 3-methyl-3-buten-1-ol was 13.6% and 3-ethoxy-3-methyl-1-butanol The yield was 4.4% (selectivity of 3-ethoxy-3-methyl-1-butanol 32.7%). The results are shown in Table 1.
＜比較例３＞バッチ方式、活性白土、エタノール使用
　実施例１において、β型ゼオライト「ＢＥＡ－２５」の代わりに、活性白土（日本活性白土株式会社製）を使用したこと以外は実施例１と同様の操作を行なった。
　反応開始から８時間後の反応混合液をガスクロマトグラフィーで分析したところ、３－メチル－３－ブテン－１－オールの転化率は１４．８％であったが、３－エトキシ－３－メチル－１－ブタノールは全く得られなかった。結果を表１に示す。 <Comparative Example 3> Batch system, use of activated clay, ethanol In Example 1, in place of β-type zeolite “BEA-25”, activated clay (manufactured by Nippon Kakuhaku Co., Ltd.) was used. The same operation was performed.
When the reaction mixture after 8 hours from the start of the reaction was analyzed by gas chromatography, the conversion of 3-methyl-3-buten-1-ol was 14.8%. No 1-butanol was obtained. The results are shown in Table 1.
＜比較例４＞バッチ方式、酸化ニオブ、エタノール使用
　実施例１において、β型ゼオライト「ＢＥＡ－２５」の代わりに、酸化ニオブ（和光純薬工業株式会社製）を使用したこと以外は実施例１と同様の操作を行なった。
　反応開始から８時間後の反応混合液をガスクロマトグラフィーで分析したところ、３－メチル－３－ブテン－１－オールの転化率は３．４％、３－エトキシ－３－メチル－１－ブタノールの収率は０．１％（３－エトキシ－３－メチル－１－ブタノールの選択率３．０％）であった。結果を表１に示す。 <Comparative Example 4> Batch system, using niobium oxide and ethanol In Example 1, Example 1 was used except that niobium oxide (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of β-type zeolite “BEA-25”. The same operation was performed.
The reaction mixture after 8 hours from the start of the reaction was analyzed by gas chromatography. The conversion of 3-methyl-3-buten-1-ol was 3.4%, and 3-ethoxy-3-methyl-1-butanol The yield was 0.1% (selectivity of 3-ethoxy-3-methyl-1-butanol: 3.0%). The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
＜実施例５＞連続方式、β型ゼオライト、エタノール使用（循環式）
　ジャケット付き管型反応装置に、ペレット状のβ型ゼオライト「ＢＥＡ－２５」（ズードケミー触媒株式会社製）を１００ｍＬ充填した。ジャケットに７０℃の温水（熱媒）を流しながら、エタノール４６０ｇ（９．９９ｍｏｌ）と３－メチル－３－ブテン－１－オール４３ｇ（０．５０ｍｏｌ）の混合液（エタノール／ＩＰＥＡ≒２０（モル比））を、ＬＨＳＶ３０ｈｒ-1で管型反応装置に供給し、通過させて得られた反応混合液の全量を、ポンプを用いて再び該管型反応装置に供給することにより、循環させながら反応を行った。
　１０時間反応させた後の反応混合液をガスクロマトグラフィーで分析したところ、３－メチル－３－ブテン－１－オールの転化率は８７．９％、３－エトキシ－３－メチル－１－ブタノールの収率は７２．３％（３－エトキシ－３－メチル－１－ブタノールの選択率８２．３％）であった。結果を表２に示す。 <Example 5> Continuous type, β-type zeolite, ethanol used (circulation type)
A jacketed tubular reactor was charged with 100 mL of pellet-shaped β-type zeolite “BEA-25” (manufactured by Zude Chemie Catalysts). While flowing warm water (heat medium) at 70 ° C. through the jacket, a mixed solution of ethanol 460 g (9.99 mol) and 3-methyl-3-buten-1-ol 43 g (0.50 mol) (ethanol / IPEA≈20 (mol) The ratio)) is supplied to the tubular reactor at LHSV 30 hr −1 , and the reaction mixture is circulated by supplying the entire amount of the reaction mixture obtained by passing through the tubular reactor again using a pump. Went.
The reaction mixture after the reaction for 10 hours was analyzed by gas chromatography. The conversion of 3-methyl-3-buten-1-ol was 87.9% and 3-ethoxy-3-methyl-1-butanol. The yield was 72.3% (selectivity of 3-ethoxy-3-methyl-1-butanol was 82.3%). The results are shown in Table 2.
＜実施例６＞連続方式、β型ゼオライト、ｎ－プロパノール使用（循環式）
　実施例５において、エタノール４６０ｇ（９．９９ｍｏｌ）の代わりにｎ－プロパノール６００ｇ（９．９９ｍｏｌ）を使用したこと以外は実施例５と同様の操作を行なった。
　１０時間反応させた後の反応混合液をガスクロマトグラフィーで分析したところ、３－メチル－３－ブテン－１－オールの転化率は９３．５％、３－プロポキシ－３－メチル－１－ブタノールの収率は７５．０％（３－プロポキシ－３－メチル－１－ブタノールの選択率８０．２％）であった。結果を表２に示す。 <Example 6> Continuous method, using β-type zeolite, n-propanol (circulation type)
In Example 5, the same operation as in Example 5 was performed, except that 600 g (9.99 mol) of n-propanol was used instead of 460 g (9.99 mol) of ethanol.
The reaction mixture after reaction for 10 hours was analyzed by gas chromatography. The conversion of 3-methyl-3-buten-1-ol was 93.5% and 3-propoxy-3-methyl-1-butanol The yield was 75.0% (selectivity of 3-propoxy-3-methyl-1-butanol was 80.2%). The results are shown in Table 2.
＜実施例７＞連続方式、β型ゼオライト、メタノール使用（循環式）
　実施例５において、エタノール４６０ｇ（９．９９ｍｏｌ）の代わりにメタノール３２０ｇ（９．９９ｍｏｌ）を使用したこと以外は実施例５と同様の操作を行なった。
　１０時間流通させた後の反応混合液をガスクロマトグラフィーで分析したところ、３－メチル－３－ブテン－１－オールの転化率は８７．１％、３－メトキシ－３－メチル－１－ブタノールの収率は７３．２％（３－メトキシ－３－メチル－１－ブタノールの選択率８４．０％）であった。結果を表２に示す。 <Example 7> Continuous system, β-type zeolite, methanol (circulation)
In Example 5, the same operation as in Example 5 was performed except that 320 g (9.99 mol) of methanol was used instead of 460 g (9.99 mol) of ethanol.
The reaction mixture after flowing for 10 hours was analyzed by gas chromatography. The conversion of 3-methyl-3-buten-1-ol was 87.1%, and 3-methoxy-3-methyl-1-butanol. The yield was 73.2% (selectivity of 3-methoxy-3-methyl-1-butanol 84.0%). The results are shown in Table 2.
＜実施例８＞連続方式、β型ゼオライト、エタノール使用（ワンパス式）
　実施例５において、ＬＨＳＶを０．５ｈｒ-1に変更し、管型反応装置を１回のみ流通させるワンパス式にて実施し、反応混合液をポンプで循環しなかったこと以外は実施例５と同様の操作を行なった。
　得られた反応混合液をガスクロマトグラフィーで分析したところ、３－メチル－３－ブテン－１－オールの転化率は８７．９％、３－エトキシ－３－メチル－１－ブタノールの収率は７１．７％（３－エトキシ－３－メチル－１－ブタノールの選択率８１．６％）であった。結果を表２に示す。 <Example 8> Continuous system, β-type zeolite, ethanol used (one-pass system)
Example 5 is the same as Example 5 except that the LHSV was changed to 0.5 hr −1 , the one-pass system was used in which the tubular reactor was circulated only once, and the reaction mixture was not circulated by the pump. The same operation was performed.
The obtained reaction mixture was analyzed by gas chromatography. The conversion of 3-methyl-3-buten-1-ol was 87.9%, and the yield of 3-ethoxy-3-methyl-1-butanol was 71.7% (selectivity of 3-ethoxy-3-methyl-1-butanol was 81.6%). The results are shown in Table 2.
＜比較例５＞連続方式、強酸性イオン交換樹脂、エタノール使用（循環式）
　実施例５において、β型ゼオライト「ＢＥＡ－２５」の代わりに、強酸性イオン交換樹脂「ダイヤイオンＰＫ２１２ＬＨ」（三菱化学株式会社製）を使用し、温水の温度を５０℃としたこと以外は実施例５と同様の操作を行なった。
　１０時間反応させた後の反応混合液をガスクロマトグラフィーで分析したところ、３－メチル－３－ブテン－１－オールの転化率は９０．９％、３－エトキシ－３－メチル－１－ブタノールの収率は５８．９％（３－エトキシ－３－メチル－１－ブタノールの選択率６４．８％）であった。結果を表２に示す。 <Comparative Example 5> Continuous method, strong acidic ion exchange resin, ethanol used (circulation type)
In Example 5, instead of β-type zeolite “BEA-25”, a strongly acidic ion exchange resin “Diaion PK212LH” (manufactured by Mitsubishi Chemical Corporation) was used, and the temperature of hot water was changed to 50 ° C. The same operation as in Example 5 was performed.
The reaction mixture after reaction for 10 hours was analyzed by gas chromatography. The conversion of 3-methyl-3-buten-1-ol was 90.9% and 3-ethoxy-3-methyl-1-butanol The yield was 58.9% (selectivity of 3-ethoxy-3-methyl-1-butanol 64.8%). The results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
＜実施例９＞連続方式、β型ゼオライト、ＰＮＡ、エタノール使用（循環式）
　実施例５において、３－メチル－３－ブテン－１－オール４３ｇ（０．５０ｍｏｌ）の代わりに３－メチル－２－ブテン－１－オール４３ｇ（０．５０ｍｏｌ）を使用したこと以外は実施例５と同様の操作を行なった。
　１０時間反応させた後の反応混合液をガスクロマトグラフィーで分析したところ、３－メチル－２－ブテン－１－オールの転化率は８３．１％、３－エトキシ－３－メチル－１－ブタノールの収率は６５．６％（３－エトキシ－３－メチル－１－ブタノールの選択率７９．０％）であった。結果を表３に示す。 <Example 9> Continuous type, β-type zeolite, PNA, ethanol used (circulation type)
In Example 5, 43 g (0.50 mol) of 3-methyl-2-buten-1-ol was used instead of 43 g (0.50 mol) of 3-methyl-3-buten-1-ol. The same operation as 5 was performed.
The reaction mixture after the reaction for 10 hours was analyzed by gas chromatography. The conversion of 3-methyl-2-buten-1-ol was 83.1% and 3-ethoxy-3-methyl-1-butanol The yield was 65.6% (selectivity of 3-ethoxy-3-methyl-1-butanol 79.0%). The results are shown in Table 3.
＜比較例６＞連続方式、強酸性イオン交換樹脂、ＰＮＡ、エタノール使用（循環式）
　実施例９において、β型ゼオライト「ＢＥＡ－２５」の代わりに、強酸性イオン交換樹脂「ダイヤイオンＰＫ２１２ＬＨ」（三菱化学株式会社製）を使用し、温水の温度を５０℃としたこと以外は実施例９と同様の操作を行なった。
　１０時間反応させた後の反応混合液をガスクロマトグラフィーで分析したところ、３－メチル－２－ブテン－１－オールの転化率は８８．２％、３－エトキシ－３－メチル－１－ブタノールの収率は５５．２％（３－エトキシ－３－メチル－１－ブタノールの選択率６２．６％）であった。結果を表３に示す。 <Comparative Example 6> Continuous system, strong acidic ion exchange resin, PNA, ethanol used (circulation type)
In Example 9, instead of β-type zeolite “BEA-25”, a strongly acidic ion exchange resin “Diaion PK212LH” (manufactured by Mitsubishi Chemical Corporation) was used, and the temperature of hot water was changed to 50 ° C. The same operation as in Example 9 was performed.
The reaction mixture after the reaction for 10 hours was analyzed by gas chromatography. The conversion of 3-methyl-2-buten-1-ol was 88.2% and 3-ethoxy-3-methyl-1-butanol. The yield was 55.2% (selectivity of 3-ethoxy-3-methyl-1-butanol 62.6%). The results are shown in Table 3.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　本発明の製造方法により得られる３－アルコキシ－３－メチル－１－ブタノールは、医農薬中間体や各種洗浄剤の原料などとして有用である。 The 3-alkoxy-3-methyl-1-butanol obtained by the production method of the present invention is useful as an intermediate for medical and agricultural chemicals and as a raw material for various cleaning agents.

Claims (4)

  1. 　３－メチル－３－ブテン－１－オールおよび３－メチル－２－ブテン－１－オールから選択される少なくとも１種のメチルブテノールと炭素数１～５の第一級アルコールとを、β型ゼオライトおよびＹ型ゼオライトから選択される少なくとも１種のゼオライトの存在下に反応させることを特徴とする、３－アルコキシ－３－メチル－１－ブタノールの製造方法。 Β-form comprising at least one methylbutenol selected from 3-methyl-3-buten-1-ol and 3-methyl-2-buten-1-ol and a primary alcohol having 1 to 5 carbon atoms A process for producing 3-alkoxy-3-methyl-1-butanol, characterized by reacting in the presence of at least one zeolite selected from zeolite and Y-type zeolite.
  2. 　前記炭素数１～５の第一級アルコールが、メタノール、エタノールまたはｎ－プロパノールである、請求項１に記載の３－アルコキシ－３－メチル－１－ブタノールの製造方法。 The method for producing 3-alkoxy-3-methyl-1-butanol according to claim 1, wherein the primary alcohol having 1 to 5 carbon atoms is methanol, ethanol or n-propanol.
  3. 　前記炭素数１～５の第一級アルコールの使用量が、３－メチル－３－ブテン－１－オールおよび３－メチル－２－ブテン－１－オールから選択される少なくとも１種のメチルブテノール１モルに対して０．５～４０モルである、請求項１または２に記載の３－アルコキシ－３－メチル－１－ブタノールの製造方法。 At least one methylbutenol selected from the group consisting of 3-methyl-3-buten-1-ol and 3-methyl-2-buten-1-ol, wherein the primary alcohol having 1 to 5 carbon atoms is used; The process for producing 3-alkoxy-3-methyl-1-butanol according to claim 1 or 2, wherein the amount is 0.5 to 40 mol per mol.
  4. 　前記β型ゼオライトおよびＹ型ゼオライトのＢＥＴ比表面積が、それぞれ、１００～１，０００ｍ2／ｇである、請求項１～３のいずれかに記載の３－アルコキシ－３－メチル－１－ブタノールの製造方法。 The 3-alkoxy-3-methyl-1-butanol according to any one of claims 1 to 3, wherein the β-type zeolite and the Y-type zeolite each have a BET specific surface area of 100 to 1,000 m 2 / g. Production method.
PCT/JP2013/057481 2012-03-27 2013-03-15 Method for producing 3-alkoxy-3-methyl-1-butanol WO2013146370A1 (en)

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WO2020189485A1 (en) 2019-03-15 2020-09-24 積水化成品工業株式会社 Biodegradable resin particles, biodegradable resin particle group comprising said particles, and use thereof
WO2020262509A1 (en) 2019-06-28 2020-12-30 積水化成品工業株式会社 Biodegradable resin particles and external preparation containing same
WO2021067087A1 (en) * 2019-09-30 2021-04-08 Dow Global Technologies Llc Methods of etherification
WO2021067079A1 (en) * 2019-09-30 2021-04-08 Dow Global Technologies Llc Methods of etherification
WO2021067077A1 (en) * 2019-09-30 2021-04-08 Dow Global Technologies Llc Methods of etherification
EP4234611A1 (en) 2016-07-22 2023-08-30 Sekisui Plastics Co., Ltd. Generally spherical resin particles formed of thermoplastic resin, method for producing same and use of same

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4234611A1 (en) 2016-07-22 2023-08-30 Sekisui Plastics Co., Ltd. Generally spherical resin particles formed of thermoplastic resin, method for producing same and use of same
WO2020189485A1 (en) 2019-03-15 2020-09-24 積水化成品工業株式会社 Biodegradable resin particles, biodegradable resin particle group comprising said particles, and use thereof
WO2020262509A1 (en) 2019-06-28 2020-12-30 積水化成品工業株式会社 Biodegradable resin particles and external preparation containing same
WO2021067087A1 (en) * 2019-09-30 2021-04-08 Dow Global Technologies Llc Methods of etherification
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