2/5/24, 8:48 PM JP3271904B2 - Method for producing halohydrin ether and method for producing glycidyl ether - Google

g glycidyl ether - Google Patents

Patents JP3271904

Method for producing halohydrin ether and method for producing glycidyl ether

Classifications
JP3271904B2
Y02P20/52 Improvements relating to the production of bulk chemicals using catalysts, e.g. Japan
selective catalysts

Find Prior Art Similar

Other languages: Japanese

Inventor: 宗尚 奥津, 智人 木附, 克己 喜多

Current Assignee : Kao Corp

Worldwide applications

1996 JP

【請求項６】 触媒(A)をアルコール類に対し0.001〜0.
Application JP19184396A events
1モル倍、触媒(B)を触媒(A)に対し1.0〜3.0モル倍使用
する請求項１〜５のいずれかに記載の製造方法。
1996-07-22 Application filed by Kao Corp

1996-07-22 Priority to JP19184396A

1998-02-10 Publication of JPH1036307A

2002-04-08 Application granted

2002-04-08 Publication of JP3271904B2

2016-07-22 Anticipated expiration

Status Expired - Fee Related

Info: Cited by (4), Legal events, Similar documents, Priority and

Related Applications

External links: Espacenet, Global Dossier, Discuss

Claims (8) Hide Dependent

translated from Japanese

(57) [Claims] 1. A method for producing a halohydrin ether by reacting an alcohol with α-epihalohydrin,
A process for producing a halohydrin ether, comprising using (A) an aluminum alkoxide and (B) a phenol or sulfonic acid as a catalyst. 2. An alcohol represented by the following
general formula (1) R- (OA) n -OH (1) wherein R is a saturated or unsaturated linear or branched chain having 1 to 36 carbon atoms in total. A represents an alkylene group having 2
to 4 carbon atoms, and n represents a number of 0 to 100. The method according to claim 1, wherein 3. The method according to claim 1, wherein the catalyst (A) is an aluminum
trialkoxide. 4. The process according to claim 1, wherein the catalyst (A) is aluminum triisopropoxide. 5. The catalyst (B) comprises phenol or naphthol optionally substituted with a
halogen atom, or a compound having 1 carbon atom.
The method according to any one of claims 1 to 4, wherein the alkyl group or the hydroxyl group is a benzenesulfonic acid or a naphthalenesulfonic acid which may be substituted.
6. The catalyst (A) may be used in an amount of 0.001 to 0.1 with respect to alcohols.
The production method according to any one of claims 1 to 5, wherein the catalyst (B) is used at a molar ratio of 1.0 to 3.0 times as much as the catalyst (A). 7. A glycidyl ether
produced by producing a halohydrin ether by the method according to claim 1 and then adding an alkali to remove the halogen without removing the catalyst. Manufacturing
method. 8. An alcohol is added to the alcohol in an amount of 1.0 to 4.0.
8. The production method according to claim 7, which is used in a molar amount.

Description translated from Japanese

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing halohydrin ether and a method for producing glycidyl ether with high selectivity and high yield.

[0002]

2. Description of the Related Art Conventionally, the following two methods are mainly known as methods for producing glycidyl ether. That is, alcohols and α-
epihalohydrin, for example, 4
A one-step method in which an alkali is reacted in the presence of a phase transfer catalyst such as a quaternary ammonium salt, and an alcohol and α-epihalohydrin are
reacted in the presence of an acid catalyst to form a halohydrin ether, followed by ring closure with an alkali This is a two-step method.

[0003]

However, the one-step method has a problem that it is necessary to use an excessive amount of α-epihalohydrin in order to avoid further addition of alcohols to the
produced glycidyl ether. In the two-step method, the conversion rate of alcohols is low when the acid catalyst is sulfuric acid or the like, and when the Lewis acid catalyst
such as BF 3 or SnCl 4 is used, α-epihalohydrin to the formed halohydrin ether is used. An excessive addition reaction of the alcohol tends to occur, and in order to avoid
this, it is necessary to use an alcohol in excess of α-epihalohydrin. Further, when the Lewis acid catalyst is a metal chloride, there is a problem that a free chlorine group

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2/5/24, 8:48 PM JP3271904B2 - Method for producing halohydrin ether and method for producing glycidyl ether - Google Patents
reacts with α-epihalohydrin. Further, there is another problem that a hydrophilic solvent or a phase transfer catalyst must be used in order to efficiently perform ring
closure of the halohydrin ether with an alkali.

Accordingly, the present invention relates to alcohols and α-

A method in which the conversion ratio of alcohols is high and the halohydrin ether can be produced in high yield even when the use ratio of epihalohydrin is almost
equimolar, and the subsequent ring closure reaction can proceed efficiently to produce glycidyl ether in high yield. The purpose is to provide.

[0005]

Under these circumstances, the present inventors have conducted intensive studies, and as a result, they have been able to use (A) aluminum alkoxide and (B) phenols or
sulfonic acids in combination as acid catalysts. It was found that the conversion rate of alcohols was high and that halohydrin ethers were obtained in extremely high
yields, and that the subsequent ring-closing reaction with alkali also proceeded well, and that glycidyl ethers could be produced in high yields. Completed the invention.

That is, the present invention is characterized in that (A) aluminum alkoxide and (B) phenols or sulfonic acids are used as catalysts in the production of halohydrin ethers
by reacting alcohols with α-epihalohydrin. After producing a halohydrin ether by the method and halohydrin ether by the method,
An object of the present invention is to provide a method for producing glycidyl ether, which comprises adding an aqueous alkaline solution to remove hydrogen halide
without removing a catalyst.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The alcohol used in the present invention is not particularly limited, but for example, the following general formula (1)

R- (OA) n -OH (1)

[Wherein, R represents a saturated or unsaturated linear or branched hydrocarbon group having a total of 1 to 36 carbon atoms, A represents an alkylene group having 2
【請求項６】 触媒(A)をアルコール類に対し0.001〜0.
to 4 carbon atoms, and n represents 0 to 0. Indicates the number of 100. ]
1モル倍、触媒(B)を触媒(A)に対し1.0〜3.0モル倍使用
[0010] Specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol,する請求項１〜５のいずれかに記載の製造方法。
undecanol,
In addition to aliphatic saturated alcohols such as dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol,
2-ethylhexanol, 3,5-dimethylhexanol, and oleyl alcohol And aliphatic unsaturated alcohols such as linole alcohol and alkylene oxide adducts thereof.
As such an alkylene oxide adduct, an ethylene oxide adduct (A is ethylene in the general formula (1)) is preferable, and the number of moles added (n in the general
formula (1)) is 0.
To 20 are preferable, and alcohols to which no alkylene oxide is added (n = 0 in the general formula (1)) are preferable.

The α-epihalohydrin used in the present invention includes α-epichlorohydrin, α-epibromohydrin, α-epiiodohydrin and the like.
-Epichlorohydrin is preferred.

The aluminum alkoxide which is the catalyst (A) used in the present invention may be any of a mono-, di- and trialkoxide compound, but a trialkoxide compound is more
preferable and the alkoxyl group has 1 carbon atom. ~ 4
Is preferred. More specifically, aluminum trimethoxide as aluminum trialkoxide,
Examples thereof include aluminum triethoxide, aluminum triisopropoxide, and aluminum tributoxide, with aluminum triisopropoxide being particularly preferred. These
may be commercially available products, or may be a mixture of a mono-, di-, or trialkoxide compound obtained by reacting an aluminum trihalide or a trialkylaluminum
with an alcohol. In this case as well, it is preferable to select conditions that increase the content of the trialkoxide compound.

The phenols or sulfonic acids which are the catalyst (B) used in the present invention are not particularly limited as long as they have a phenolic hydroxyl group or a
sulfonic acid group. Examples thereof include phenol and chlorophenol. , Dichlorophenol, 2,4,6-trichlorophenol, 1-naphthol, 2-naphthol, hydroquinone, 2,2-
Bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, binaphthol, methanesulfonic acid, p-toluenesulfonic acid, phenolsulfonic acid,
Dodecylbenzenesulfonic acid, naphthalenesulfonic acid and the like can be mentioned. As the (B) catalyst, phenol or naphthol which may be substituted with a halogen
atom, or benzenesulfonic acid or naphthalenesulfonic acid which may be substituted with an alkyl group or a hydroxyl group having 1 to 12 carbon atoms is preferable,
and further, 2,4,6-Trichlorophenol, 1-naphthol and phenolsulfonic acid are preferred, and phenolsulfonic acid is particularly preferred.

In the halohydrin etherification reaction between alcohols and α-epihalohydrin, α-epihalohydrin is used in an amount of 0.5 to 1.5 moles, especially 1.0 to 1.2 moles,
relative to the alcohol, and the catalyst (A) is used. The catalyst (B) is used in an amount of 1.0 to 3.0 mole times, particularly preferably 0.01 to 0.05 mole times the
amount of the alcohols, particularly 0.01 to 0.05 times the moles of the alcohol (A).
It is preferable to use 2.0 to 3.0 mole times. The reaction temperature is
The temperature is preferably 10 to 120 ° C, particularly preferably 70 to 110 ° C, and the reaction is preferably performed for 1 to 5 hours.

In order to produce glycidyl ether from the halohydrin ether obtained by the above reaction, an alkali may be added and the ring may be closed by a dehydrohalogenation
reaction without removing the catalyst from the reaction mixture.

Examples of the alkali used here include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide and alkaline earth metal hydroxides such as calcium
hydroxide and barium hydroxide. Sodium and potassium hydroxide are preferred.

In the ring-closing reaction of the halohydrin ether, it is preferable to use 1.0 to 4.0 mol times, particularly 1.5 to 2.5 mol times of the alkali with respect to the charged
amount of the alcohol, for example, as a 10 to 50% aqueous solution. It is preferred to add. The reaction temperature is preferably 80 to 100 ° C, and the reaction is
preferably performed for several hours.

The glycidyl ether thus obtained can be separated and purified by known separation and purification means, specifically, distillation, recrystallization,
It can be isolated and purified by column chromatography and the like.

[0019]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited
thereto.

Example 1 11.7 g (0.09 mol) of octyl alcohol, 0.36 g (1.77 mmol) of aluminum triisopropoxide and 0.94 g (5.40 mmol) of p-phenolsulfonic acid were put into a 100 ml
four-necked flask, and nitrogen was introduced. The temperature was raised to 95 ° C. while stirring. Next, 10.0 g (0.108 mol) of epichlorohydrin was added dropwise over
10 minutes, and the mixture was stirred for 3 hours. The yield of halohydrin ether determined by GLC was 87%. The residual amount of unreacted octyl alcohol was
determined by GLC and found to be 5% or less. Add 4 to this reaction mixture.
40 ml of N sodium hydroxide aqueous solution was added, and the mixture was stirred at 85 to 90 ° C. for 3 hours. After cooling to room temperature, the aqueous layer
was removed, and the mixture was further washed twice with 30 ml of water and purified by distillation under reduced pressure. 14.2 g of octyl glycidyl ether (1,2-epoxy-4-
oxadodecane) was obtained as a colorless transparent oil. (Total yield 85%).

1 H-NMR (200 MHz, CDCl

3 ): δ ppm 0.9 (3H, triplet, 12th methyl) 1.2-1.5 (10H, overlapping broad peak, 7-11th methylene) 1.51 (2H, triplet, 6.65, 2.8 (2H, each quadruple,
1st methylene) 3.18 (1H, multiplet, 2nd methine) 3.38 and 3.7, 3.45 and 3.76 (2H, each doublet, 3rd methylene) 3.5 (2H, wide multiplet, 5-position methylene) Purity (GLC):

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99.5%

Comparative Example 1 11.7 g (0.09 mol) of octyl alcohol and 0.36 g (1.77 mmol) of aluminum triisopropoxide were placed in a 100 ml four-necked flask, and the
temperature was raised to 95 ° C. while introducing nitrogen and stirring. Next, epichlorohydrin 10.0g (0.108mo
l) was added dropwise over 10 minutes, and the mixture was stirred for 3 hours. The yield of halohydrin ether was 6%, and the residual amounts of unreacted octyl
alcohol and epichlorohydrin were 90% or more.

COMPARATIVE EXAMPLE 2 11.7 g (0.09 mol) of octyl alcohol and 0.94 g of p-phenolsulfonic acid were put into a 100 ml four-necked flask, and heated to 95 ° C. while
stirring under nitrogen. Next, 10.0 g (0.108 mol) of epichlorohydrin was added dropwise over 10 minutes, and the mixture was stirred for 3 hours. The yield of halohydrin
ether is
At 22%, the remaining unreacted octyl alcohol was more than 65%.

Comparative Example 3 11.7 g (0.09 mol) of octyl alcohol and BF 3 OEt 2

0.25 g (1.77 mmol) was placed in a 100 ml four-necked flask, and 10.0 g of epichlorohydrin (0.
108 mol) was added dropwise over 30 minutes, and the mixture was stirred for 3 hours.
All epichlorohydrin was consumed, but the yield of halohydrin ether was 61%.

Example 2 21.8 g (0.09 mol) of hexadecyl alcohol was placed in a 100 ml four-necked flask and heated to 70 ° C. 0.36 g (1.77 mmol) of aluminum triisopropoxide and
0.94 g (5.40 mmol) of p-phenolsulfonic acid were added, and nitrogen was introduced.
The temperature was raised to 100 ° C. while stirring. Next, 10.0 g (0.108 mol) of epichlorohydrin was added dropwise over 10 minutes.
Stirred for hours. The yield of halohydrin ether determined by GLC was 85%. The remaining amount of unreacted octyl alcohol was 5% or less. 40 ml of a 4N aqueous
sodium hydroxide solution was added to the reaction mixture, and the mixture was heated at 85 to 95 ° C for 3 hours.
Stirred for hours. After adding 50 ml of hexane and cooling to room temperature, the aqueous layer was removed, and the mixture was further washed twice with 30 ml of
water. The solvent was distilled off, the residue was purified by silica gel column chromatography, and 22.3 g of【請求項６】 触媒(A)をアルコール類に対し0.001〜0.
hexadecylglycidyl ether (1,2-
Epoxy-4-oxaeicosane) was obtained as white crystals (83% overall yield) and identified by 1 H-NMR (200 MHz). 1モル倍、触媒(B)を触媒(A)に対し1.0〜3.0モル倍使用
GLC
More pure was 99%. する請求項１〜５のいずれかに記載の製造方法。

Example 3 11.7 g (0.09 mol) of octyl alcohol, 0.36 g (1.77 mmol) of aluminum triisopropoxide and 0.76 g (5.29 mmol) of 1-naphthol were placed in a 100 ml four-necked
flask, and stirred under nitrogen. While heating, the temperature was raised to 95 ° C. Next, 10.0 g (0.108 mol) of epichlorohydrin was added dropwise over 10 minutes,
and the mixture was stirred for 3 hours. The yield of halohydrin ether determined by GLC was 88%. The remaining amount of unreacted octyl alcohol was 4% or less.

Example 4 11.7 g (0.09 mol) of octyl alcohol, 0.36 g (1.77 mmol) of aluminum triisopropoxide and 1.04 g (5.29 mmol) of 2,4,6-trichlorophenol were placed in a 100 ml
four-necked flask. The temperature was raised to 90 ° C. with stirring while introducing nitrogen. Next, add 10.0 g (0.108 mol) of epichlorohydrin
The mixture was added dropwise over 10 minutes and stirred for 2 hours. The yield of halohydrin ether determined by GLC was 87%. The remaining amount of unreacted
octyl alcohol was 3% or less.

[0028]

According to the method of the present invention, a halohydrin ether having a high conversion rate of alcohols and an extremely high yield can be obtained, and the
subsequent ring-closure reaction with an alkali proceeds favorably to convert glycidyl ether. Can be produced in high yield.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. 7 Identification code FI C07D 301/26 C07D
301/26 303/22 303/22 // C07B 61/00 300 C07B 61/00 300 (56) References Special JP-A-52-12109 (JP, A) JP-A-2-25438 (JP, A) JP-A-52-89606 (JP, A) JP-A-54-148705
(JP, A) JP-A-2-169533 (JP JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C07C 41/03 C07C 43/13 C07D 301/26 C07D 303/22

Cited By (4)

Publication number Priority date Publication date Assignee Title

Family To Family Citations

DE69842079D1 * 1997-05-01 2011-02-10 Kao Corp Process for the preparation of an ester, acetal, ketal, ether or alkyl glycoside

JP4587549B2 * 2000-10-23 2010-11-24 高砂香料工業株式会社 1-halogeno-3-l-menthoxypropan-2-ol

JP5514492B2 * 2008-09-22 2014-06-04 三洋化成工業株式会社 Method for producing polyether compound

JP5200071B2 * 2010-08-13 2013-05-15 高砂香料工業株式会社 Process for producing 3-l-menthoxypropane-1,2-diol

* Cited by examiner, † Cited by third party, ‡ Family to family citation

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Priority Applications (1)

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JP19184396A 1996-07-22 1996-07-22 Method for producing halohydrin ether and method for producing glycidyl ether

Applications Claiming Priority (1)

Application Filing date Title

JP19184396A 1996-07-22 Method for producing halohydrin ether and method for producing glycidyl ether

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