JPH0311030A - Production of alkylenedioxydiphenols - Google Patents
Production of alkylenedioxydiphenolsInfo
- Publication number
- JPH0311030A JPH0311030A JP14761589A JP14761589A JPH0311030A JP H0311030 A JPH0311030 A JP H0311030A JP 14761589 A JP14761589 A JP 14761589A JP 14761589 A JP14761589 A JP 14761589A JP H0311030 A JPH0311030 A JP H0311030A
- Authority
- JP
- Japan
- Prior art keywords
- water
- solvent
- formula
- dihaloalkane
- general formula
- 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 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 239000012046 mixed solvent Substances 0.000 claims abstract description 6
- 125000001424 substituent group Chemical group 0.000 claims abstract 2
- 125000002947 alkylene group Chemical group 0.000 claims description 10
- 150000005205 dihydroxybenzenes Chemical class 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims 2
- 125000001246 bromo group Chemical group Br* 0.000 claims 1
- 125000001309 chloro group Chemical group Cl* 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 15
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002904 solvent Substances 0.000 abstract description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 abstract description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 abstract 3
- 150000001875 compounds Chemical class 0.000 abstract 3
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 23
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 16
- 238000000034 method Methods 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- IBYHHJPAARCAIE-UHFFFAOYSA-N 1-bromo-2-chloroethane Chemical compound ClCCBr IBYHHJPAARCAIE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-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
- 238000006959 Williamson synthesis reaction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- YHRUOJUYPBUZOS-UHFFFAOYSA-N 1,3-dichloropropane Chemical compound ClCCCCl YHRUOJUYPBUZOS-UHFFFAOYSA-N 0.000 description 1
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- KJDRSWPQXHESDQ-UHFFFAOYSA-N 1,4-dichlorobutane Chemical compound ClCCCCCl KJDRSWPQXHESDQ-UHFFFAOYSA-N 0.000 description 1
- LBKDGROORAKTLC-UHFFFAOYSA-N 1,5-dichloropentane Chemical compound ClCCCCCCl LBKDGROORAKTLC-UHFFFAOYSA-N 0.000 description 1
- OVISMSJCKCDOPU-UHFFFAOYSA-N 1,6-dichlorohexane Chemical compound ClCCCCCCCl OVISMSJCKCDOPU-UHFFFAOYSA-N 0.000 description 1
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 1
- -1 3-hydroxyphenoxy Chemical group 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 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、アルキレンジオキシジフェノール類の製造方
法に関するものである。更に詳しくハ、ジヒドロキシベ
ンゼン類とジハロアルカンとを原料とし、高収率で経済
的なアルキレンジオキシジフェノール類の製造方法に関
するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Field of Application> The present invention relates to a method for producing alkylene dioxydiphenols. More specifically, the present invention relates to a high-yield, economical method for producing alkylene dioxydiphenols using dihydroxybenzenes and dihaloalkanes as raw materials.
本発明によりて得られるアルキレンジオキシジフェノー
ル類は、たとえば、感熱記録材料及び感圧記録材料をは
じめとする各種の記録材料用資材として用いられる（た
とえば、特開昭５７−８１９４号公報、特開昭６１−４
０１８６号公報及び特開昭６１−１３００８８号公報参
照）。The alkylene dioxydiphenols obtained by the present invention are used, for example, as materials for various recording materials including heat-sensitive recording materials and pressure-sensitive recording materials (for example, JP-A-57-8194; Kaisho 61-4
0186 and JP-A-61-130088).
〈従来の技術〉
ハロゲン化アルキル類とフェノール類とからエーテル類
を合成する方法は、従来から。<Prior art> There is a conventional method for synthesizing ethers from alkyl halides and phenols.
Ｗｉｌｌｉａｍｓｏｎ合成として知られている。This is known as Williamson synthesis.
また、有機合成化学協会誌（第３４巻、第５８０頁。Also, Journal of the Society of Organic Synthetic Chemistry (Vol. 34, p. 580).
１９７６年）には２本発明と同じ（、ジヒドロキシベン
ゼン類とジハロアルカンからアルキレンジオキシジフェ
ノール類を製造する方法が記載されている。(1976) describes a method for producing alkylene dioxydiphenols from dihydroxybenzenes and dihaloalkanes, which is the same as the present invention.
〈発明が解決しようとする課題〉
しかし、従来、 Ｗｉｌｌｉａｍｓｏｎ合成において反
応を十分に進行させるためには、溶媒としては、非プロ
トン性で極性の高い溶媒、たとえば、ＤＭＦ （Ｎ、
Ｎ−ジメチルホルムアミド）、ＤＭＳＯ（ジメチルスル
ホオキシド）、ＤＭＥ （ジメトキエタン）又はＴＨＦ
（テトラヒドロフラン）などを用いるべきであること
が知られている（たとえば、新実験化学講座、第１４巻
、第５６９頁。<Problems to be Solved by the Invention> However, conventionally, in order for the reaction to proceed sufficiently in Williamson synthesis, aprotic and highly polar solvents such as DMF (N,
N-dimethylformamide), DMSO (dimethyl sulfoxide), DME (dimethoxyethane) or THF
It is known that (tetrahydrofuran) etc. should be used (for example, New Experimental Chemistry Course, Vol. 14, p. 569).
丸善参照）。ところが、従来の方法においては。(See Maruzen). However, in the conventional method.
前記の溶媒は、いずれも高価であり、しかも。All of the above solvents are expensive.
かかる溶媒は水に可溶性であるため２反応に″より副生
ずる無機塩を除去するための反応後の後処理工程におい
て、高価な溶媒が洗浄水中に溶解してしまい、その後の
溶媒の回収・再使用が困難になるといった欠点がある。Since such solvents are soluble in water, expensive solvents are dissolved in the washing water during the post-treatment process after the reaction to remove inorganic salts produced as by-products in the second reaction, making it difficult to recover and recycle the solvents. The drawback is that it is difficult to use.
更１コ、前記の有機合成化学協会誌に開示されている方
法においては、高価なりＭＦ又はＤＭＳＯが好ましい溶
媒として使用されていると共に、原料であるジハロアル
カンとジヒドロキシベンゼンは、２．５〜２．６／１（
ただし、ジハロアルカン／ジヒドロキシベンゼン モル
比）の割合で使用されている。Furthermore, in the method disclosed in the above-mentioned Journal of the Society of Organic Synthetic Chemistry, expensive MF or DMSO is used as the preferred solvent, and the raw materials dihaloalkane and dihydroxybenzene are .6/1(
However, it is used at a ratio of (dihaloalkane/dihydroxybenzene molar ratio).
化学量論に基づく上記の比が、０．５／１であることを
考慮すると、ここに開示された方法は。Considering that the above ratio based on stoichiometry is 0.5/1, the method disclosed herein.
化学量論的に要求される量より大過剰のジハロアルカン
を必要とするものであり、このため。For this reason, a large excess of dihaloalkane is required over the stoichiometrically required amount.
本方法におけるシバ、ロアルカン当たりのアルキレンジ
オキシジフェノールの収率は、わずか２０％にも満たな
いという欠点を有している。This method has a drawback in that the yield of alkylene dioxydiphenol per Siba-loalkane is only less than 20%.
く課題を解決するための手段〉
かかる現状に鑑み９本発明者らは、前記のような高価な
溶媒を使用する必要がなり、シかも。Means for Solving the Problems> In view of the current situation, the inventors of the present invention may have to use an expensive solvent as described above.
高収率下にアルキレンジオキシフェノールを製造する方
法を提供することを主たる目的として。The main objective is to provide a method for producing alkylene dioxyphenols in high yield.
鋭意検討した。その結果、塩基の存在下において、水及
び水、と相互に溶解しない有機溶媒からなる混合溶媒中
で反応を行なうことにより、かかる目的が達成され得る
ことを見い出し９本発明に到達した。I considered it carefully. As a result, the present inventors have found that the above object can be achieved by carrying out the reaction in the presence of a base in a mixed solvent consisting of water and an organic solvent that is not mutually soluble in water, resulting in the present invention.
すなわち１本発明は。In other words, one aspect of the present invention is.
一般式（Ｉｌで示されるジヒドロキシベンゼン類と。Dihydroxybenzenes represented by the general formula (Il).
Ｈ 一般式（ｎ）で示されるジハロアルカンとを。H and a dihaloalkane represented by general formula (n).
Ｘ （ＣＨ２）ｎ Ｙ ｆｍ（式中、Ｘ及び
Ｙは塩素原子及び臭素原子よりなる群から選択された同
−又は異なる置換基を表わし、ｎは２〜６の整数を表わ
す。）塩基の存在下１こおいて、水及び水と相互に溶解
しない有機溶媒からなる混合溶媒中で反応させることを
特徴とする。一般式＋Ｉ［＋で示されるアルキレンジオ
キシジフェノール類の製造方法に係るものである。Presence of a base The method below is characterized in that the reaction is carried out in a mixed solvent consisting of water and an organic solvent that is not mutually soluble in water. This invention relates to a method for producing alkylene dioxydiphenols represented by the general formula +I[+.
（式中、ｎは前記一般式（ＩＩＩのものと同じ。）以下
に９本発明１こついて、詳しく説明する。(In the formula, n is the same as that of the general formula (III).) Below, nine aspects of the present invention will be explained in detail.
本発明における前記の一般式（Ｉｌで示されるジヒドロ
キシベンゼン類は、カテコール、レゾルシン又はハイド
ロキノンである。The dihydroxybenzenes represented by the general formula (Il) in the present invention are catechol, resorcinol, or hydroquinone.
本発明（こおけるジハロアルカンは、前記の一般式（［
１で示されるものであり、たとえば、ジハロアルカンと
しては、１．２−ジクロルエタン、１゜２−ジブロムエ
タン、ｌ、３−ジクロルプロパン。In the present invention, the dihaloalkane is represented by the general formula ([
For example, dihaloalkanes include 1,2-dichloroethane, 1°2-dibromoethane, and 1,3-dichloropropane.
１．３−ブロムプロパン、１．４−ジクロルブタン。1,3-bromopropane, 1,4-dichlorobutane.
１．４−ジブロムブタン、ｔ、ｓ−ジクロルペンタン、
１５−ジブロムペンタン、１．６−ジクロルヘキサン、
１，６−シブロムヘキサン、１−ブロム−２−クロルエ
タン、１−７’ロム−５−クロルペンタンなどがあげら
れる。1.4-dibromobutane, t,s-dichloropentane,
15-dibromopentane, 1,6-dichlorohexane,
Examples include 1,6-cybromohexane, 1-bromo-2-chloroethane, and 1-7' rom-5-chloropentane.
反応に用いられるジハロアルカンとジヒドロキンベンゼ
ンの使用量（仕込量、以下同じ。）は、ジヒドロキシベ
ンゼン／ジハロアルカンのモル比が２０／１〜２／１．
更に好ましくは８／１〜２／１である。The amounts of dihaloalkane and dihydroquinebenzene used in the reaction (charged amounts, the same hereinafter) are such that the molar ratio of dihydroxybenzene/dihaloalkane is 20/1 to 2/1.
More preferably, it is 8/1 to 2/1.
本発明おける塩基としては、水酸化ナトリウム、水酸化
カリウム、炭酸ソーダ、炭酸カリウムなどが好ましいも
のとして用いられる。塩基の使用量は、塩基／ジハロア
ルカンのモル比で４／１〜１／１．更に好ましくは３／
１〜２／１である。As the base in the present invention, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. are preferably used. The amount of the base to be used is in a molar ratio of base/dihaloalkane of 4/1 to 1/1. More preferably 3/
It is 1 to 2/1.
本発明における水と相互に溶解しない有機溶媒としては
９反応条件において水と混合した場合に二層に分離する
ものであればよ（、たとえば、ベンゼン、トルエン、キ
シレン、エチルベンゼン、クメンなどの芳香族炭化水素
；ヘキサン、ヘプタン、オクタン、シクロヘキサンなど
の脂肪族炭化水素；モノクロルベンゼン、ジクロルベン
ゼンなどのハロゲン化炭化水素及ヒメチルエチルケトン
、メチルイソブチルケトンなどのケトン類があげられる
。In the present invention, organic solvents that are not mutually soluble in water include those that separate into two layers when mixed with water under 9 reaction conditions (for example, aromatic solvents such as benzene, toluene, xylene, ethylbenzene, cumene, etc.). Hydrocarbons; aliphatic hydrocarbons such as hexane, heptane, octane, and cyclohexane; halogenated hydrocarbons such as monochlorobenzene and dichlorobenzene; and ketones such as hismethyl ethyl ketone and methyl isobutyl ketone.
水及び水と相互に溶解しない有機溶媒の使用量は、水／
水と相互１こ溶解しない有機溶媒の容量比で１０／１〜
１／１０．更に好ましくは２／１〜１／２である。また
、水及び水と相互に溶解しない有機溶媒からなる混合溶
媒全体の使用量は、ジハロアルカン１モルに対して０．
１〜１０リツトル、更に好ましくは０．２〜２リツトル
である。The amount of water and organic solvents that are not mutually soluble in water and
Volume ratio of organic solvent that does not dissolve in water and water is 10/1~
1/10. More preferably, it is 2/1 to 1/2. The amount of the entire mixed solvent consisting of water and an organic solvent that is not mutually soluble in water is 0.00% per mole of dihaloalkane.
The amount is 1 to 10 liters, more preferably 0.2 to 2 liters.
本発明の反応温度は、１００〜２２０℃、更に好ましく
は１３０〜１８０ ’Ｃであり１反応圧力は２反応系が
液層を保つ範囲であれば、特に制限されない。The reaction temperature of the present invention is 100 to 220°C, more preferably 130 to 180'C, and the reaction pressure is not particularly limited as long as the two reaction systems maintain a liquid phase.
かかる条件において２反応は９通常１〜１０時間で終了
する。−
本発明の方法は、たとえば２次のように実施される。所
定量のジヒドロキシベンゼン、塩基。Under these conditions, the two reactions are usually completed in 1 to 10 hours. - The method of the invention is carried out, for example, in the following way. A given amount of dihydroxybenzene, base.
水及び水と相互に溶解しない有機溶媒を反応器に仕込み
、所定の反応温度に昇温し、その後。Water and an organic solvent that does not dissolve in water are charged into a reactor, heated to a predetermined reaction temperature, and then.
ジハロアルカンを反応系に加え、撹拌しながら。Add the dihaloalkane to the reaction system while stirring.
反応を終了させる。反応終了後２反応混合物を冷却した
後、酸を添加することにより反応混合物を酸性とすると
、目的のアルキレンジオキシジフェノールが析出してく
るので、これをろ過・採取する。更に純度の高いアルキ
レンジオキシジフェノールを得たい場合は、再結晶法に
より、その目的が達っせられる。Terminate the reaction. After the reaction mixture is cooled, an acid is added to make the reaction mixture acidic, and the desired alkylenedioxydiphenol precipitates out, which is filtered and collected. If it is desired to obtain alkylene dioxydiphenol with even higher purity, the recrystallization method can achieve this purpose.
〈実施例〉
次に１本発明を実施例にて更に具体的に説明するが、こ
れによって本発明が限定されるものではない。<Example> Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.
実施例１
２００ ｍｌのオートクレーブに、レゾルシン２２ｇ（
０，２ｍｏｌ） 、水酸化ナトリウム２．２ｇ（０，０
５５ｍｏｌ）。Example 1 In a 200 ml autoclave, 22 g of resorcinol (
0.2 mol), sodium hydroxide 2.2 g (0.0
55 mol).
水４０ｍ０１及びモノクロルベンゼン−２５ｍ１ヲ仕込
んだ。耐圧滴下ロートに１．５−ジクロルペンタン３．
５３ ｇ（０，０２５ｍｏ！ ）を入れ、上記のオート
クレーブに装着した。オートクレーブを撹拌しながら１
００’Ｃ１ζ加熱した。ついで、耐圧滴下ロートから１
゜５−ジクロルペンタンを＋ １０ｋｇ／ｃｍ２の窒素
圧で３０分かけて滴下した。滴下終了後、オートクレー
ブの温度を１６０℃にし、その温度で４時間保持した。40 ml of water and 25 ml of monochlorobenzene were charged. 1.5-dichloropentane in a pressure-resistant dropping funnel 3.
53 g (0,025 mo!) was placed in the autoclave described above. 1 while stirring the autoclave.
00'C1ζ was heated. Next, from the pressure-resistant dropping funnel, 1
5-Dichloropentane was added dropwise over 30 minutes under a nitrogen pressure of +10 kg/cm2. After completion of the dropwise addition, the temperature of the autoclave was raised to 160°C and maintained at that temperature for 4 hours.
反応終了後、オートクレーブを室温まで冷却、シ１反応
混合物をオートクレーブより取り出した。反応混合物を
３Ｎ塩酸で酸性にし。After the reaction was completed, the autoclave was cooled to room temperature, and the reaction mixture S1 was taken out from the autoclave. The reaction mixture was made acidic with 3N hydrochloric acid.
５０ ｍｌのエーテルで三回抽出した。抽出して得た全
てのエーテル層は合一し、ガスクロで組成分析をした。Extracted three times with 50 ml of ether. All the ether layers obtained by extraction were combined and analyzed for composition by gas chromatography.
その結果、レゾルシンの転化率は２７．６％、１．５−
ビス（３−ヒドロキシフェノキシ）ペンタン（以下ＰＢ
Ｒと記載する）の収率ｉ−１７６，８％であり、５−（
３−ヒドロキシフェノキシ）ペンタン−１−オール（以
下Ｐ−６ト記載する）の収率は５．０％であった。なお
、転化率及び収率は次のようにして計算した。As a result, the conversion rate of resorcinol was 27.6%, 1.5-
Bis(3-hydroxyphenoxy)pentane (PB
The yield of 5-(
The yield of 3-hydroxyphenoxy)pentan-1-ol (hereinafter referred to as P-6) was 5.0%. Note that the conversion rate and yield were calculated as follows.
使用したレゾルシン（ｍｏｌ） ガスクロによる分析条件を次に示す。Resorcinol used (mol) The analysis conditions by gas chromatography are shown below.
カラム：３％０Ｖ−１７／Ｃｈｒｏｍｏｓｏｒｂ ＡＷ
−ＤＭＣ８１，１ｍ温 度：１７０°Ｃ（４分保持）か
ら２６０°Ｃに昇温、昇温速度３２℃／ｍｉｎ
また、ＰＢＲ及びＰ−６の構造は２次のとおり。Column: 3% 0V-17/Chromosorb AW
-DMC81,1m Temperature: Increased temperature from 170°C (held for 4 minutes) to 260°C, temperature increase rate 32°C/min Moreover, the structures of PBR and P-6 are as follows.
機器分析により決定した。Determined by instrumental analysis.
Ｐ ＢＲ； ＧＣ−ＭＳ ； ｍＡ２８８ （Ｍ”）Ｎ
ＭＲ；δ６．９８（ｔ、ＩＨ）、 ６．３０（ｄ、２Ｈ
）、 ６．２７（ｓ、ＩＨ）。PBR; GC-MS; mA288 (M”)N
MR; δ6.98 (t, IH), 6.30 (d, 2H
), 6.27 (s, IH).
３．８９（ｔ、４Ｈ）、 ３．３４（ｓ、ＩＨ）、 １
．７（ｍ、６Ｈ）ＩＲ；３４００ｃｍ ’
ｍｐ；１１１〜１１２℃
Ｐ−６；ＧＣ−ＭＳ；ｍ／ｅ ２１４（Ｍ”）、 ２１
６（Ｍ”）実施例２〜１ル
ゾルシン、１．５−ジクロルペンタン、水酸化ナトリウ
ムの仕込比及び水と相互に溶解しない有機溶媒を表１記
載のものとした以外は、実施例１と同様に１反応、後処
理１分析を行い。3.89 (t, 4H), 3.34 (s, IH), 1
．． 7 (m, 6H) IR; 3400 cm'mp; 111-112°C P-6; GC-MS; m/e 214 (M"), 21
6 (M'') Examples 2 to 1 Same as Example 1 except that the charging ratio of lusorcin, 1.5-dichloropentane, and sodium hydroxide and the organic solvent that is not mutually soluble in water were as shown in Table 1. Similarly, one reaction and one post-treatment analysis were performed.
表１の結果を得た。The results shown in Table 1 were obtained.
実施例１２〜１６
１．５−ジクロルペンタンを表２記載のジハロアルカン
とし、実施例２と同様に２反応、後処理２分析を行い表
２の結果を得た。なお、生成物の同定はＧＯ−ＭＳ分析
により行った。Examples 12 to 16 Using 1,5-dichloropentane as the dihaloalkane listed in Table 2, two reactions and two post-treatments and two analyzes were performed in the same manner as in Example 2 to obtain the results shown in Table 2. Note that the product was identified by GO-MS analysis.
実施例１７〜１８
実施例２のレゾルシンをカテコール又はハイドロキノン
とした以外は実施例２と同様に１反応、後処理９分析を
行い１表３の結果を得た。Examples 17 to 18 One reaction and nine post-treatments were carried out in the same manner as in Example 2, except that catechol or hydroquinone was used as the resorcinol in Example 2, and the results shown in Table 3 were obtained.
なお、生成物の同定はＧＯ−ＭＳ分析により行った。Note that the product was identified by GO-MS analysis.
比較例１
実施例１において、水酸化ナトリウムを使用しなかった
こと以外は、実施例１と同様に行った。その結果、レゾ
ルシンの転化率、ＰＢＲの収率及びＰ−６の収率は全て
０％であった。Comparative Example 1 The same procedure as in Example 1 was conducted except that sodium hydroxide was not used. As a result, the conversion rate of resorcinol, the yield of PBR, and the yield of P-6 were all 0%.
比較例２
実施例ＩＩζおいて、水を使用せず、力入つ、モノクロ
ルベンゼンを６５ｍ１としたこと以外は、実流側１と同
様に行った。その結果、レゾルシンの転化率は７１．５
％、ＰＢＲの収率は１３．５％、Ｐ−６の収率は６．７
％であった。Comparative Example 2 In Example IIζ, the same procedure as Actual Flow Side 1 was carried out, except that water was not used and monochlorobenzene was added to 65 ml. As a result, the conversion rate of resorcinol was 71.5
%, the yield of PBR is 13.5%, the yield of P-6 is 6.7
%Met.
比較例３
実施例１において、モノクロルベンゼンを使用せず、か
つ、水を６５ｍ１としたこと以外は、実施例１と同様に
行った。その結果、レゾルシンの転化率は１８．５％、
ＰＢＲの収率は４５．９％、Ｐ−６の収率は８．９％で
あった。Comparative Example 3 The same procedure as in Example 1 was conducted except that monochlorobenzene was not used and the amount of water was 65 ml. As a result, the conversion rate of resorcinol was 18.5%,
The yield of PBR was 45.9% and the yield of P-6 was 8.9%.
〈発明の効果〉
以上説明したように２本発明１こより、高価な溶媒を使
用することなく、かつ、高収率を達成できるアルキレン
ジオキシジフェノール類の製造方法が提供できた。<Effects of the Invention> As explained above, the present invention provides a method for producing alkylene dioxydiphenols that does not require the use of expensive solvents and can achieve high yields.
以上that's all
Claims (1)
類と、 ▲数式、化学式、表等があります▼（ I ） 一般式（II）で示されるジハロアルカンとを、Ｘ−（Ｃ
Ｈ＿２）ｎ−Ｙ（II） （式中、Ｘ及びＹは塩素原子及び臭素原子よりなる群か
ら選択された同一又は異なる置換基を表わし、ｎは２〜
６の整数を表わす。）塩基の存在下において、水及び水
と相互に溶解しない有機溶媒からなる混合溶媒中で反応
させることを特徴とする、一般式（III）で示されるア
ルキレンジオキシジフェノール類の製造方法。 ▲数式、化学式、表等があります▼（III） （式中、ｎは前記一般式（II）のものと同じ。）(1) Dihydroxybenzenes represented by the general formula (I) and dihaloalkanes represented by the general formula (II) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I)
H_2)n-Y(II) (wherein, X and Y represent the same or different substituents selected from the group consisting of chlorine atoms and bromine atoms, and n is 2 to
Represents an integer of 6. ) A method for producing alkylene dioxydiphenols represented by general formula (III), which comprises reacting in a mixed solvent consisting of water and an organic solvent that is not mutually soluble in water in the presence of a base. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, n is the same as in the general formula (II) above.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14761589A JPH0311030A (en) | 1989-06-08 | 1989-06-08 | Production of alkylenedioxydiphenols |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14761589A JPH0311030A (en) | 1989-06-08 | 1989-06-08 | Production of alkylenedioxydiphenols |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0311030A true JPH0311030A (en) | 1991-01-18 |
Family
ID=15434330
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14761589A Pending JPH0311030A (en) | 1989-06-08 | 1989-06-08 | Production of alkylenedioxydiphenols |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0311030A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005306693A (en) * | 2004-04-26 | 2005-11-04 | Toshiba Mach Co Ltd | Glass forming apparatus |
| WO2006103748A1 (en) * | 2005-03-29 | 2006-10-05 | Tokyo Institute Of Technology | Resorcinol derivative and crown ether resin synthesized using the same |
| JP2006274087A (en) * | 2005-03-29 | 2006-10-12 | Tokyo Institute Of Technology | Crown ether resin synthesized using resorcinol derivative and its synthetic method |
-
1989
- 1989-06-08 JP JP14761589A patent/JPH0311030A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005306693A (en) * | 2004-04-26 | 2005-11-04 | Toshiba Mach Co Ltd | Glass forming apparatus |
| JP4580677B2 (en) * | 2004-04-26 | 2010-11-17 | 東芝機械株式会社 | Glass forming equipment |
| WO2006103748A1 (en) * | 2005-03-29 | 2006-10-05 | Tokyo Institute Of Technology | Resorcinol derivative and crown ether resin synthesized using the same |
| JP2006274087A (en) * | 2005-03-29 | 2006-10-12 | Tokyo Institute Of Technology | Crown ether resin synthesized using resorcinol derivative and its synthetic method |
| JP4570040B2 (en) * | 2005-03-29 | 2010-10-27 | 国立大学法人東京工業大学 | Crown ether resin synthesized using resorcinol derivative and synthesis method thereof |
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