JPH0334951A - Production of alcoholic derivative and method for separating and obtaining the same - Google Patents
Production of alcoholic derivative and method for separating and obtaining the sameInfo
- Publication number
- JPH0334951A JPH0334951A JP17100689A JP17100689A JPH0334951A JP H0334951 A JPH0334951 A JP H0334951A JP 17100689 A JP17100689 A JP 17100689A JP 17100689 A JP17100689 A JP 17100689A JP H0334951 A JPH0334951 A JP H0334951A
- Authority
- JP
- Japan
- Prior art keywords
- propanol
- mol
- phenoxyphenol
- formula
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 238000000034 method Methods 0.000 title claims description 7
- 230000001476 alcoholic effect Effects 0.000 title 1
- ZSBDGXGICLIJGD-UHFFFAOYSA-N 4-phenoxyphenol Chemical compound C1=CC(O)=CC=C1OC1=CC=CC=C1 ZSBDGXGICLIJGD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 20
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001298 alcohols Chemical class 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N 1-propanol Substances CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 23
- RVAHBQKJLFMRFE-UHFFFAOYSA-N 1-(4-phenoxyphenoxy)propan-2-ol Chemical compound C1=CC(OCC(O)C)=CC=C1OC1=CC=CC=C1 RVAHBQKJLFMRFE-UHFFFAOYSA-N 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 4
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- 239000002917 insecticide Substances 0.000 abstract description 2
- 239000003444 phase transfer catalyst Substances 0.000 abstract description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- -1 aliphatic amines Chemical class 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- BBBKSJXFNNKBST-UHFFFAOYSA-N 2-(4-phenoxyphenoxy)propan-1-ol Chemical compound C1=CC(OC(CO)C)=CC=C1OC1=CC=CC=C1 BBBKSJXFNNKBST-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、農園芸用殺虫剤の中間体として有用な式（１
）
で示される１−（４−フェノキシフェノキシ）−２−プ
ロパノール、さらには同じく中間体として有用な式（Ｉ
Ｉ）
で示される２−（４−フェノキシフェノキシ）（２）
１−プロパノールの製造法および両化合物の分離取得方
法に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention provides a compound of the formula (1) useful as an intermediate for agricultural and horticultural insecticides.
) 1-(4-phenoxyphenoxy)-2-propanol represented by the formula (I), which is also useful as an intermediate.
The present invention relates to a method for producing 2-(4-phenoxyphenoxy)(2) 1-propanol represented by I) and a method for separating and obtaining both compounds.
〈従来の技術〉
米国特許第４．７５１．２２５号明細書に、本発明と類
似の方法が記載されている。PRIOR ART A method similar to the present invention is described in US Pat. No. 4,751,225.
〈発明が解決しようとする課題〉
しかしながら、該方法は、相間移動触媒を必要とする等
、工業的には必ずしも有利な方法とはいえない。<Problems to be Solved by the Invention> However, this method requires a phase transfer catalyst and is not necessarily an advantageous method from an industrial perspective.
く課題を解決するための手段〉
本発明者らは、このような状況に鑑み、鋭意検討した結
果、工業的に有利な本発明に到達したものである。Means for Solving the Problems In view of the above circumstances, the inventors of the present invention have made extensive studies and have arrived at the present invention, which is industrially advantageous.
すなわち、本発明は、４−フェノキシフェノールとプロ
ピレンオキシドとを、反応溶媒として、水、アルコール
類または水とアルコール類との混合物を用い、塩基の存
在下に反応させて、式（Ｉ）で示される２−プロパノー
ル（以下、２−プロパノール（Ｉ）と略称する。）を得
る方法であるが、本方法においては、主に２−プロパノ
ール（Ｉ）が得られ（３）
るものの、該異性体である式（Ｉｆ）で示される１−プ
ロパノール（以下、１−プロパノール（Ｉｆ）と略称す
る。）も同時に得られ、したがって、所望に応じて、該
混合物を晶析処理することにより、両化合物を分離取得
することができる。That is, the present invention is directed to reacting 4-phenoxyphenol and propylene oxide in the presence of a base using water, an alcohol, or a mixture of water and alcohol as a reaction solvent to obtain a compound represented by formula (I). In this method, 2-propanol (I) is mainly obtained (3), but the isomer is 1-propanol (hereinafter abbreviated as 1-propanol (If)) represented by the formula (If) is also obtained at the same time. Therefore, if desired, by crystallizing the mixture, both compounds can be obtained. can be obtained separately.
４−フェノキシフェノールとプロピレンオキシドとを反
応させる際に、溶媒として用いられるアルコール類とし
ては、たとえばメタノール、エタノール、イソプロパノ
ール、ブタノール、エチレングリコール、グリセリン等
をあげることができる。Examples of alcohols used as a solvent when reacting 4-phenoxyphenol and propylene oxide include methanol, ethanol, isopropanol, butanol, ethylene glycol, and glycerin.
また、塩基としては、たとえば水酸化リチウム、水酸化
ナトリウム、水酸化カリウム、水酸化カルシウム等の水
酸化物類、炭酸ナトリウム、炭酸カリウム等の炭酸塩類
、炭酸水素ナトリウム等の重炭酸塩類、マグネシウムメ
トキサイド、ナトリウムメトキサイド等の金属アルコキ
シド類、水素化ナトリウム、水素化カリウム等の金属水
素化物類、トリエチルアミン等の脂肪族アミン類、ピリ
ジン、ピコリン等のピリジン類、テトラプチルアンモニ
（４）
ラムヒドロキシド等のアンモニウムヒドロキシド類ある
いはそれらの混合物をあげることができる。Examples of bases include hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and calcium hydroxide; carbonates such as sodium carbonate and potassium carbonate; bicarbonates such as sodium hydrogen carbonate; side, metal alkoxides such as sodium methoxide, metal hydrides such as sodium hydride and potassium hydride, aliphatic amines such as triethylamine, pyridines such as pyridine and picoline, tetrabutyl ammonium(4), rum hydroxide and mixtures thereof.
反応に際しては、通常、４−フェノキシフェノール１モ
ルに対してプロピレンオキシドは０．１〜１０モル、好
ましくは０．５〜８モル用いられる。In the reaction, propylene oxide is usually used in an amount of 0.1 to 10 mol, preferably 0.5 to 8 mol, per mol of 4-phenoxyphenol.
また、塩基は通常、４−フェノキシフェノール１モルに
対して０．０００１〜２モル、好ましくは０．０１〜１
．５モル用いられる。Further, the base is usually 0.0001 to 2 mol, preferably 0.01 to 1 mol, per 1 mol of 4-phenoxyphenol.
．． 5 moles are used.
反応温度は、通常０ ’Ｃ〜２００℃、好ましくは２０
℃〜７０℃であり、反応時間は通常５分〜２００時間、
好ましくは３０分〜１００時間である。反応圧力は、好
ましくは常圧であるが、０．５〜８００気圧の圧力下で
反応を行なうこともできる。The reaction temperature is usually 0'C to 200C, preferably 20
°C to 70 °C, reaction time is usually 5 minutes to 200 hours,
Preferably it is 30 minutes to 100 hours. The reaction pressure is preferably normal pressure, but the reaction can also be carried out under a pressure of 0.5 to 800 atmospheres.
２−プロパノール（Ｉ）と１−プロパノール（ＩＩ）と
の混合物を晶析処理する場合、通常溶媒が用いられ、溶
媒としては、たとえばメタノール、エタノール、イソプ
ロパノール、ブタノール、エチレングリコール、グリセ
リン等のアルコール類、ベンゼン、トルエン、クロルベ
ンゼン等の芳香族炭化水素類、（５）
ジエチルエーテル、テトラヒドロフラン、ジオキサン等
のエーテル類、ペンタン、ヘキサン、ヘプタン、シクロ
ヘキサン等の脂肪族炭化水素類、ジクロルメタン、ジク
ロルエタン、クロロホルム等のハロゲン化炭化水素類、
アセトン、メチルイソブチルケトン等のケトン類、アセ
トニトリル、ベンゾニトリル等のニトリル類、水あるい
はそれらの混合溶媒があげられる。晶析を行なう場合の
温度は、−８０°Ｃ〜２００℃、好ましくは一１０°Ｃ
〜１００℃、反応時間は８０分〜２００時間、好ましく
は８０分〜１００時間である。晶析終了後は、濾過等の
通常の操作により、両化合物を分離取得することができ
る。When a mixture of 2-propanol (I) and 1-propanol (II) is crystallized, a solvent is usually used, such as alcohols such as methanol, ethanol, isopropanol, butanol, ethylene glycol, and glycerin. , aromatic hydrocarbons such as benzene, toluene, and chlorobenzene, (5) ethers such as diethyl ether, tetrahydrofuran, and dioxane, aliphatic hydrocarbons such as pentane, hexane, heptane, and cyclohexane, dichloromethane, dichloroethane, chloroform, etc. halogenated hydrocarbons,
Examples include ketones such as acetone and methyl isobutyl ketone, nitriles such as acetonitrile and benzonitrile, water, and mixed solvents thereof. The temperature for crystallization is -80°C to 200°C, preferably -10°C.
~100°C, reaction time is 80 minutes to 200 hours, preferably 80 minutes to 100 hours. After the crystallization is completed, both compounds can be separated and obtained by normal operations such as filtration.
なお、本製造法に準じて、たとえば以下に示すような化
合物も製造することができる。In addition, according to this production method, for example, the following compounds can also be produced.
１−（４−フルオロフェノキシ）フェニル−２−プロパ
ノール
１−（８−フルオロフェノキシ）フェニル−２−プロパ
ノール
１−（８，５−ジフルオロフェノキシ）フェニ（６）
ルー２−プロパノール
１−（８−クロロフェノキシ）フェニル−２プロパノー
ル
１−（８−メチルフェノキシ）フェニル−２−プロパノ
ール
２−（４−フルオロフェノキシ）フェニル−１プロパノ
ール
２− （８−フルオロフェノキシ）フェニル−１−プロ
パノール
２−（８，５−ジフルオロフェノキシ）フェニル−Ｉ−
プロパノール
２−（８−クロロフェノキシ）フェニル−１−プロパノ
ール
２−（８−メチルフェノキシ）フェニル−１−プロパノ
ール
また、本製造法におけるプロピレンオキシドをエチレン
オキシドに替えることによって、たとえば以下に示すよ
うな化合物を製造することもできる。1-(4-fluorophenoxy)phenyl-2-propanol 1-(8-fluorophenoxy)phenyl-2-propanol 1-(8,5-difluorophenoxy)pheny(6) 2-propanol 1-(8-chloro phenoxy)phenyl-2-propanol 1-(8-methylphenoxy)phenyl-2-propanol 2-(4-fluorophenoxy)phenyl-1-propanol 2-(8-fluorophenoxy)phenyl-1-propanol 2-(8,5 -difluorophenoxy)phenyl-I-
Propanol 2-(8-chlorophenoxy)phenyl-1-propanol 2-(8-methylphenoxy)phenyl-1-propanol In addition, by replacing propylene oxide in this production method with ethylene oxide, for example, the following compounds can be produced. It can also be manufactured.
２−（４−フルオロフェノキシ）フェニル−１（７）
エタノール
２−（３−フルオロフェノキシ）フェニル−１−エタノ
ール
２−（８，５−ジフルオロフェノキシ）フェニル−１−
エタノール
２−（８−クロロフェノキシ）フェニル−１エタノール
２−（８−メチルフェノキシ）フェニル−１−エタノー
ル
等の化合物を製造することもできる。2-(4-fluorophenoxy)phenyl-1(7) Ethanol 2-(3-fluorophenoxy)phenyl-1-ethanol 2-(8,5-difluorophenoxy)phenyl-1-
Compounds such as ethanol 2-(8-chlorophenoxy)phenyl-1ethanol and 2-(8-methylphenoxy)phenyl-1-ethanol can also be produced.
〈実施例〉
以下、製造例で本発明をさらに詳しく説明するが、本発
明はこれらに限定されるものではない。<Examples> The present invention will be explained in more detail below using production examples, but the present invention is not limited thereto.
製造例１
室温、窒素気流下で、４−フェノキシフェノール１５Ｆ
（０，０８１モル）、プロピレンオキシド５．１５ Ｐ
（０，０８９モル）および水酸化ナトリウム０．８２
Ｐ （０，００８モル）を、７０％メタノール水５０
ノに溶解した。反応液を攪拌下、５０〜５５℃に加温し
、常圧下で２時間熟成させた。さ（８）
らにプロピンオキシド５．１５ Ｐ （０，０８９モル
）を滴下し、４時間、５０〜５５℃で熟成させた。Production Example 1 4-phenoxyphenol 15F at room temperature under a nitrogen stream
(0,081 mol), propylene oxide 5.15 P
(0,089 mol) and sodium hydroxide 0.82
P (0,008 mol) in 70% methanol water 50
It was dissolved in . The reaction solution was heated to 50 to 55° C. with stirring and aged for 2 hours under normal pressure. Further, 5.15 P (0,089 mol) of propylene oxide was added dropwise to the mixture, and the mixture was aged at 50 to 55°C for 4 hours.
ついで反応混合液を水浴につけ、０〜５℃で８０分間攪
拌した。析出した結晶を枦取し、冷７０％メタノール水
で洗浄し、減圧下に結晶を乾燥することによって、１−
（４−フェノキシフェノキシ）−２−プロパノール１５
．８Ｐを得た。The reaction mixture was then placed in a water bath and stirred at 0-5°C for 80 minutes. The precipitated crystals were collected, washed with cold 70% methanol water, and dried under reduced pressure to obtain 1-
(4-phenoxyphenoxy)-2-propanol 15
．． I got 8 points.
製造例２
４−フェノキシフェノール１５９（０，０８１モル）、
水酸化ナトリウム１．８ Ｆ （０，０８２モル）およ
び水５０ｍ／を仕込み、攪拌、溶解後、窒素気流下で、
プロピレンオキシド１０．８ Ｐ （０，１８５モル）
を２０〜２５℃で滴下し、常圧下、同温度で１０時間熟
成させた。この反応混合液に、トルエン１ＯＯｒｎｌを
加えて抽出し、水（２０ｒｎｌ×２回）で洗浄後、減圧
下に濃縮することによって、１−（４−フェノキシフェ
ノキシ）−２−プロパノールと２−（４−フェノキシフ
ェノキシ）−１−プロパノールとの混合物１９．６ Ｆ
を得た。この混合物に、５ＱＷ／Ｗにｎ−へブタン−ト
ルエン溶液８５（９）
２を加えて、５０〜６０℃で加温溶解後、攪拌下に０〜
５°Ｃに冷却し、同温度で８０分間攪拌した。Production example 2 4-phenoxyphenol 159 (0,081 mol),
After charging 1.8 F (0,082 mol) of sodium hydroxide and 50 m of water, stirring and dissolving, under a nitrogen stream,
Propylene oxide 10.8 P (0,185 mol)
was added dropwise at 20 to 25°C, and the mixture was aged at the same temperature under normal pressure for 10 hours. This reaction mixture was extracted by adding 100 rnl of toluene, washed with water (20 rnl x 2), and concentrated under reduced pressure. -phenoxyphenoxy)-1-propanol mixture 19.6 F
I got it. To this mixture, add n-hebutane-toluene solution 85(9) 2 to 5QW/W, dissolve by heating at 50-60°C, and then stir at 0-60°C.
The mixture was cooled to 5°C and stirred at the same temperature for 80 minutes.
析出した結晶をｔ戸数し、減圧下に結晶を乾燥すること
によって、１−（４−フェノキシフェノキシ）２−プロ
パノール１７． Ｉ Ｐを得た。1-(4-phenoxyphenoxy)2-propanol 17. The precipitated crystals were separated and dried under reduced pressure. I got IP.
製造例８
室温、窒素気流下で、４−フェノキシフェノール１５５
４（０，０８１モル）、プロピレンオキシド５．１５
Ｐ （０，０８７モル）および水酸化ナトリウム０．８
２９ （０，００８モル）を７０％メタノール水５０ノ
に溶解した。反応液を攪拌下、５０〜５５℃に加温し、
常圧下で２時間熟成させた。さらにプロピレンオキシド
５．１５ Ｆ （０，０８７モル）を滴下し、４時間、
５０〜５５℃で熟成させた。ついで反応混合液を氷水８
００−に注加し、酢酸エチル５０−で２回抽出した。有
機層を合し、飽和塩化ナトリウム水溶液１００−で１回
洗浄し、無水硫酸マグネシウムで脱水した後、減圧下に
濃縮することにより、１−（４−フェノキシフェノキシ
）−２−プロパノールと２−（４−フェノキシフェ（ｌ
Ｏ）
ノキシ）−１−プロパノールとの混合物１８．５９を得
た。Production Example 8 4-phenoxyphenol 155 at room temperature under a nitrogen stream
4 (0,081 mol), propylene oxide 5.15
P (0,087 mol) and sodium hydroxide 0.8
29 (0,008 mol) was dissolved in 50 volumes of 70% methanol water. The reaction solution was heated to 50 to 55°C while stirring,
It was aged for 2 hours under normal pressure. Further, 5.15 F (0,087 mol) of propylene oxide was added dropwise, and the mixture was heated for 4 hours.
It was aged at 50-55°C. Then, the reaction mixture was diluted with ice water.
00- and extracted twice with ethyl acetate 50-. The organic layers were combined, washed once with saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to form 1-(4-phenoxyphenoxy)-2-propanol and 2-( 4-phenoxyfe (l
O) 18.59 of a mixture with noxy)-1-propanol was obtained.
製造例４
室温、窒素気流下で、４−フェノキシフェノール１５Ｆ
（０，０８１モル）、プロピレンオキシド５．１５１ｉ
’ （０，０８７モル）および水酸化カリウム０．４５
Ｐ （０，００８モル）を３０％メタノール水５０ノ
に溶解した。反応液を攪拌下、５０〜５５°Ｃに加温し
、常圧下で２時間熟成させた。さらに、プロピレンオキ
シド５．１５ Ｐ （０，０８７モル）を滴下し、６５
時間、５０〜５５℃で熟成させた。以後、製造例８と同
様の処理を行なうことにより、１−（４−フェノキシフ
ェノキシ）−２−プロパノールと２−（４−フェノキシ
フェノキシ）−１＝プロパノールとの混合物１８．１！
ｉ’を得た。Production Example 4 4-phenoxyphenol 15F at room temperature under a nitrogen stream
(0,081 mol), propylene oxide 5.151i
' (0,087 mol) and potassium hydroxide 0.45
P (0,008 mol) was dissolved in 50 volumes of 30% methanol water. The reaction solution was heated to 50 to 55°C while stirring and aged for 2 hours under normal pressure. Furthermore, 5.15 P (0,087 mol) of propylene oxide was added dropwise, and 65
It was aged at 50-55°C for an hour. Thereafter, by performing the same treatment as in Production Example 8, a mixture of 1-(4-phenoxyphenoxy)-2-propanol and 2-(4-phenoxyphenoxy)-1=propanol 18.1!
I got i'.
製造例５
室温、窒素気流下で、４−フェノキシフェノール１５Ｐ
（０，０８１モル）、プロピレンオキシド５．１５ Ｐ
（０，０８９モル）および炭酸カリウム１１．１８１
（０，１１８モル）を、メタノール８５２に溶解した。Production Example 5 4-phenoxyphenol 15P at room temperature under a nitrogen stream
(0,081 mol), propylene oxide 5.15 P
(0,089 mol) and potassium carbonate 11.181
(0,118 mol) was dissolved in methanol 852.
反応液を攪拌下、５０〜５５℃に加温し、常圧下で８時
間熟成させた。さらに、プロピレンオキシド５．１５
Ｆ （０，０８９モル）を滴下し、手毒毒１７時間、５
０〜５５℃で熟成させた。The reaction solution was heated to 50 to 55° C. with stirring and aged for 8 hours under normal pressure. Furthermore, propylene oxide 5.15
F (0,089 mol) was dropped into the hand for 17 hours, 5
It was aged at 0-55°C.
以後、製造例８と同様の処理を行なうことにより、１−
（４−フェノキシフェノキシ）−２−プロパノールと２
−（４−フェノキシフェノキシ）−１−プロパノールと
の混合物１６．８Ｐを得た。Thereafter, by performing the same treatment as in Production Example 8, 1-
(4-phenoxyphenoxy)-2-propanol and 2
16.8P of a mixture with -(4-phenoxyphenoxy)-1-propanol was obtained.
製造例６
室温、窒素気流下で、４−フェノキシフェノール１５Ｐ
（０，０８１モル）、プロピレンオキシド５．１５ Ｆ
（０，０８９モル）および水酸化リチウム０．１８Ｆ
（０，００７５モル）を、５０％メタノール水５０９に
溶解した。反応液を攪拌下、５０〜５５℃に加温し、常
圧下で５時間熟成させた。さらにプロピレンオキシド５
．１５ Ｌ！（０，０８９モル）を滴下し、４時間、５
０〜５５℃で熟成させた。Production Example 6 4-phenoxyphenol 15P at room temperature under a nitrogen stream
(0,081 mol), propylene oxide 5.15 F
(0,089 mol) and lithium hydroxide 0.18F
(0,0075 mol) was dissolved in 509 50% methanol water. The reaction solution was heated to 50 to 55° C. with stirring and aged for 5 hours under normal pressure. Furthermore, propylene oxide 5
．． 15 L! (0,089 mol) was added dropwise for 4 hours.
It was aged at 0-55°C.
以後、製造例８と同様の処理を行なうことにより、１−
（４−フェノキシフェノキシ）−２−プロパノールと２
−（４−フェノキシフェノキシ）−１−ブロパノールと
の混合物１７．２ノを得た。Thereafter, by performing the same treatment as in Production Example 8, 1-
(4-phenoxyphenoxy)-2-propanol and 2
-(4-phenoxyphenoxy)-1-propanol 17.2 g of a mixture was obtained.
製造例７
室温、窒素気流下で、４−フェノキシフェノール１５ｇ
（０，０８１モル）、プロピレンオキシド５．１５ Ｆ
（０，０８９モル）および水酸化カルシウム１．１７
Ｐ（０，０２０モル）を４０％メタノール水８０グに溶
解した。反応液を攪拌下、４０〜４５℃に加温し、常圧
下で８時間熟成させた。さらにプロピレンオキシド５．
１５ｇＬ（０，０８９モル）を滴下し、６時間、４０〜
４５℃で熟成させた。以後、製造例３と同様の処理を行
なうことにより、１−（４−フェノキシフェノキシ）−
２−プロパノールと２−（４−フェノキシフェノキシ）
−１−プロパノールとの混合物１６．８Ｓ’を得た。Production Example 7 15 g of 4-phenoxyphenol at room temperature under a nitrogen stream
(0,081 mol), propylene oxide 5.15 F
(0,089 mol) and calcium hydroxide 1.17
P (0,020 mol) was dissolved in 80 g of 40% methanol water. The reaction solution was heated to 40 to 45°C with stirring and aged for 8 hours under normal pressure. Furthermore, propylene oxide5.
15 gL (0,089 mol) was added dropwise and the mixture was heated for 6 hours at 40~
It was aged at 45°C. Thereafter, by performing the same treatment as in Production Example 3, 1-(4-phenoxyphenoxy)-
2-propanol and 2-(4-phenoxyphenoxy)
-16.8S' of a mixture with 1-propanol was obtained.
〈発明の効果〉
本発明の製造法は、従来法に比し、工業的にすぐれた方
法である。<Effects of the Invention> The production method of the present invention is industrially superior to conventional methods.
（１８完）(18 completed)
Claims (2)
とを、水、アルコール類または水とアルコール類との混
合物から選ばれた溶媒中で、塩基の存在下に反応させる
ことを特徴とする式 ▲数式、化学式、表等があります▼ で示される１−（４−フェノキシフェノキシ）−２−プ
ロパノールの製造法。(1) A formula characterized by reacting 4-phenoxyphenol and propylene oxide in the presence of a base in a solvent selected from water, alcohols, or a mixture of water and alcohols ▲ Mathematical formula, chemical formula There are tables, etc. ▼ Production method of 1-(4-phenoxyphenoxy)-2-propanol.
ロパノールと式 ▲数式、化学式、表等があります▼ で示される２−（４−フェノキシフェノキシ）−１−プ
ロパノールとの混合物を晶析処理することによる、両化
合物の分離取得方法。(2) 1-(4-phenoxyphenoxy)-2-propanol shown by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and 2-(4-phenoxy) shown by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. A method for separating and obtaining both compounds by crystallizing a mixture with phenoxy)-1-propanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17100689A JPH0334951A (en) | 1989-06-30 | 1989-06-30 | Production of alcoholic derivative and method for separating and obtaining the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17100689A JPH0334951A (en) | 1989-06-30 | 1989-06-30 | Production of alcoholic derivative and method for separating and obtaining the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0334951A true JPH0334951A (en) | 1991-02-14 |
Family
ID=15915357
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17100689A Pending JPH0334951A (en) | 1989-06-30 | 1989-06-30 | Production of alcoholic derivative and method for separating and obtaining the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0334951A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1380342A1 (en) * | 2001-04-18 | 2004-01-14 | Sumitomo Chemical Company Limited | Complex catalyst, process for producing the complex catalyst, and process for producing alcohol derivative with the complex catalyst |
| CN108276255A (en) * | 2018-02-08 | 2018-07-13 | 盐城辉煌化工有限公司 | The method for selective synthesis of Nylar intermediate ether alcohol |
| CN112174784A (en) * | 2019-07-03 | 2021-01-05 | 江苏龙灯化学有限公司 | Crystal form A of 1- (4-phenoxyphenoxy) -2-propanol and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5088037A (en) * | 1973-11-27 | 1975-07-15 | ||
| JPS514977A (en) * | 1974-07-01 | 1976-01-16 | Iwatsu Electric Co Ltd | Zetsuensono keiseihoho |
| JPS59199673A (en) * | 1983-04-25 | 1984-11-12 | Sumitomo Chem Co Ltd | Nitrogen-containing heterocyclic compound, its preparation and pesticide containing the same |
-
1989
- 1989-06-30 JP JP17100689A patent/JPH0334951A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5088037A (en) * | 1973-11-27 | 1975-07-15 | ||
| JPS514977A (en) * | 1974-07-01 | 1976-01-16 | Iwatsu Electric Co Ltd | Zetsuensono keiseihoho |
| JPS59199673A (en) * | 1983-04-25 | 1984-11-12 | Sumitomo Chem Co Ltd | Nitrogen-containing heterocyclic compound, its preparation and pesticide containing the same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1380342A1 (en) * | 2001-04-18 | 2004-01-14 | Sumitomo Chemical Company Limited | Complex catalyst, process for producing the complex catalyst, and process for producing alcohol derivative with the complex catalyst |
| CN108276255A (en) * | 2018-02-08 | 2018-07-13 | 盐城辉煌化工有限公司 | The method for selective synthesis of Nylar intermediate ether alcohol |
| CN112174784A (en) * | 2019-07-03 | 2021-01-05 | 江苏龙灯化学有限公司 | Crystal form A of 1- (4-phenoxyphenoxy) -2-propanol and preparation method and application thereof |
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