JPS63264558A - Purification of n,n-diethylaminophenol - Google Patents
Purification of n,n-diethylaminophenolInfo
- Publication number
- JPS63264558A JPS63264558A JP62099047A JP9904787A JPS63264558A JP S63264558 A JPS63264558 A JP S63264558A JP 62099047 A JP62099047 A JP 62099047A JP 9904787 A JP9904787 A JP 9904787A JP S63264558 A JPS63264558 A JP S63264558A
- Authority
- JP
- Japan
- Prior art keywords
- diethylaminophenols
- solvent
- diethylaminophenol
- crude
- aminophenol
- 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.)
- Granted
Links
- 238000000746 purification Methods 0.000 title description 3
- YOIQWFZSLGRZJX-UHFFFAOYSA-N 2-(diethylamino)phenol Chemical compound CCN(CC)C1=CC=CC=C1O YOIQWFZSLGRZJX-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 25
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims abstract description 22
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000005932 reductive alkylation reaction Methods 0.000 claims abstract description 10
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 18
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000975 dye Substances 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 229910052786 argon Inorganic materials 0.000 abstract description 2
- 239000007850 fluorescent dye Substances 0.000 abstract description 2
- 229910052763 palladium Inorganic materials 0.000 abstract description 2
- 229910052697 platinum Inorganic materials 0.000 abstract description 2
- 239000001018 xanthene dye Substances 0.000 abstract 1
- 238000004821 distillation Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 7
- 238000007796 conventional method Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- -1 Aliphatic alcohols Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- LRFVTYWOQMYALW-UHFFFAOYSA-N 9H-xanthine Chemical compound O=C1NC(=O)NC2=C1NC=N2 LRFVTYWOQMYALW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 2
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 2
- 229940008406 diethyl sulfate Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229960003750 ethyl chloride Drugs 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- INDIALLCZKIHFF-UHFFFAOYSA-N 4-(diethylamino)phenol Chemical compound CCN(CC)C1=CC=C(O)C=C1 INDIALLCZKIHFF-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- ITQVBFRUYGGPCU-UHFFFAOYSA-N n-ethylethanamine;phenol Chemical class CC[NH2+]CC.[O-]C1=CC=CC=C1 ITQVBFRUYGGPCU-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 229940075420 xanthine Drugs 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、 Ｎ、Ｎ−ジエチルアミノフェノール類の精
製法に関する。Ｎ、Ｎ−ジエチルアミノフェノール類は
、感熱・感圧紙用染料、キサンチン系染料、蛍光染料等
の中間物として工業的に極めて重要な化合物である。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for purifying N,N-diethylaminophenols. N,N-diethylaminophenols are industrially extremely important compounds as intermediates for heat-sensitive and pressure-sensitive paper dyes, xanthine dyes, fluorescent dyes, and the like.
〈従来の技術〉
従来、 Ｎ、Ｎ−ジエチルアミノフェノール類の合成法
として
■ ニトロベンゼンを出発原料とし、〆タニル酸ソーダ
を得、これをエチルクロライド又はジエチル硫酸でエチ
ル化した後、アルカリフー−ジ冒ンして目的物を得る方
法。<Prior art> Conventionally, as a method for synthesizing N,N-diethylaminophenols, ■ nitrobenzene is used as a starting material, sodium tanylate is obtained, this is ethylated with ethyl chloride or diethyl sulfate, and then treated with an alkali fume. How to get what you want.
■ 二価フェノール類を酸触媒の存在下にジエチルアミ
ンと反応させて、目的物を得る方法。■ A method to obtain the desired product by reacting dihydric phenols with diethylamine in the presence of an acid catalyst.
■ アミノフェノール類をアルカリ塩の存在下にエチル
クロライド又はジエチル硫酸でエチル化して、目的物を
得る方法。■ A method of ethylating aminophenols with ethyl chloride or diethyl sulfate in the presence of an alkali salt to obtain the desired product.
などが知られている。etc. are known.
■の方法は、いわゆるアルカリフー−ジ１ン法であり、
多量の排水と多量のスラッジが発生し、工程も長く、工
業的には極めて魅力の乏しい方法である。Method (2) is the so-called alkaline food method,
This method generates a large amount of waste water and sludge, and the process is long, making it extremely unattractive from an industrial perspective.
■の方法は、酸触媒の存在下、高温・加圧下に過剰量の
ジエチルアミンを用いて反応する方法であるが、 Ｎ
、Ｎ−ジエチルアミノフェノール類の収率が低く、副生
物が多い。又、過剰のジエチルアミンを回収する必要が
あり、さらに材質腐食の問題もあって、工業的には極め
て困難な方法である。Method (2) is a method in which the reaction is carried out using an excess amount of diethylamine in the presence of an acid catalyst at high temperature and pressure.
, the yield of N-diethylaminophenols is low, and there are many by-products. In addition, it is necessary to recover excess diethylamine, and there is also the problem of material corrosion, making this method extremely difficult from an industrial perspective.
、／／
■の方法は、′焼酸剤としてアルカリ塩を使用している
ものの、材質の腐食を伴なうこと、又反応終了後に生成
する塩化物と生成するＮ、Ｎ −ジエチルアミノツーノ
ール類との分離が困難で。, // Method (2) uses an alkali salt as a sintering agent, but is accompanied by corrosion of the material, and chlorides and N,N-diethylaminotunols are produced after the reaction is completed. Difficult to separate from.
精製に多量の排水が発生することで、工程がかなり煩雑
になっている。The refining process generates a large amount of wastewater, making the process quite complicated.
又、■■■いずれの方法も、 Ｎ、Ｎ−ジエチルアミノ
フェノール類を回収する際、酸又はアルカリによる中和
処理が必ず必要であり、アミノ基含有化合物のため、中
和の終点が判定が困難であり、又精製する場合、 Ｎ、
Ｎ−ジエチルアミノツーノール類の熱的な不安定さのた
めに、蒸留による方法を採ることができなかった。従っ
て自スから、 Ｎ、Ｎ−ジエチルアミノフェノール類の
品質にも限界があった。In addition, in both methods, neutralization treatment with acid or alkali is always required when recovering N,N-diethylaminophenols, and because the compounds contain amino groups, it is difficult to determine the end point of neutralization. And when refining, N,
Due to the thermal instability of N-diethylaminotunols, a distillation method could not be used. Therefore, there was a limit to the quality of N,N-diethylaminophenols produced in-house.
即ち，従来法で得られるＮ，Ｎ−ジエチルアミノフェノ
ール類の外観は一般に，少量のタール分（重質分）を含
むため褐色を呈しており，従来しばしば商品価値をそこ
ねていた。That is, N,N-diethylaminophenols obtained by conventional methods generally have a brown appearance because they contain a small amount of tar (heavy content), which often impairs their commercial value.
又，アミノフェノール類とアセトアルデヒドの還元アル
キル化反応後，蒸留によって留出回収したＮ，Ｎ−ジエ
チルアミノフェノール類は。In addition, N,N-diethylaminophenols were recovered by distillation after the reductive alkylation reaction of aminophenols and acetaldehyde.
■〜■の方法に比べれば格段に改良された製品として得
ることができるが，近年， Ｎ，Ｎ−ジエチルアミノフ
ェノール類の感熱・感圧紙用染料としての需要の伸びと
相俟って必ずしも満足できる品質ではなく，用途によっ
てはより高純度でしかも，着色の少ないＮ，Ｎ−ジエチ
ルアミノフェノール類の要望が高まってきた。Although it is possible to obtain a product that is much improved compared to methods ① to ③, in recent years, combined with the growth in demand for N,N-diethylaminophenols as dyes for heat-sensitive and pressure-sensitive paper, this method is not always satisfactory. Depending on the intended use, there has been a growing demand for N,N-diethylaminophenols with higher purity and less coloring.
〈発明が解決しようとする問題点〉
本発明は．これら従来の技術の欠点，すなわち多量の排
水やスラッジの発生，材質腐食等の問題点を解決し，し
かも従来にない高品位のＮ。<Problems to be solved by the invention> The present invention... This technology solves the drawbacks of these conventional technologies, such as large amounts of wastewater, generation of sludge, and corrosion of materials, and also provides high-quality N that has never been seen before.
Ｎ−ジエチルアミノフェノール類を高収率で得ようとす
るものである。The purpose is to obtain N-diethylaminophenols in high yield.
〈問題点を解決するための手段〉
本発明者らは，従来法にかわる高品位のＮ，Ｎ−ジエチ
ルアミノフェノール類の新しい製法につき鋭意検討した
結果，アミノフェノール類とアセトアルデヒドを還元ア
ルキル化反応させ。<Means for Solving the Problems> As a result of extensive research into a new method for producing high-grade N,N-diethylaminophenols that would replace the conventional method, the present inventors discovered that aminophenols and acetaldehyde were subjected to a reductive alkylation reaction. .
反応終了後，触媒を分離して得られる反応液から蒸留に
よって留出回収した粗Ｎ，Ｎージエチルアミノフェノー
ル類を，不活性ガス雰囲気下にＮ，Ｎ−ジエチルアミノ
フェノール類と実質的に相溶しない溶媒に接触させた後
，冷却により。After the completion of the reaction, the crude N,N-diethylaminophenols recovered by distillation from the reaction solution obtained by separating the catalyst are substantively incompatible with the N,N-diethylaminophenols under an inert gas atmosphere. After contact with the solvent, by cooling.
Ｎ，Ｎ−ジエチルアミノフェノール類を析出させて，回
収することにより工業的に極めて有利に。It is extremely advantageous industrially to precipitate and recover N,N-diethylaminophenols.
収率良くしかも高品位のＮ，Ｎ−ジエチルメタアミノフ
ェノール類が得られることを見い出した。It has been found that N,N-diethyl meta-aminophenols can be obtained with good yield and high quality.
即ち，本発明はアミノツーノール類とアセトアルデヒド
を溶媒，触媒及び水素共存下に還元アルキル化反応させ
，反応終了後，触媒を分離して得られる反応液から，蒸
留によって留出回収した粗Ｎ，Ｎージエチルアミノフェ
ノール類ヲ精製するにあたり，不活性ガス雰囲気下に，
Ｎ。That is, in the present invention, aminotunols and acetaldehyde are subjected to a reductive alkylation reaction in the presence of a solvent, a catalyst, and hydrogen, and after the reaction is completed, the catalyst is separated. From the reaction liquid obtained, crude N, which is recovered by distillation, is recovered. When purifying N-diethylaminophenols, under an inert gas atmosphere,
N.
Ｎ−ジエチルアミノフェノール類と実質的に相溶しない
溶媒と，粗Ｎ．Ｎージエチルアミノフェノール類とを接
触させた後，冷却によりＮ，Ｎ −ジエチルアミノフェ
ノール類を析出させて，回収することを特徴とするＮ，
Ｎ−ジエチルアミノフェノール類の精製法である。以下
具体的に詳述する。A solvent that is substantially incompatible with N-diethylaminophenols, and a crude N. N, characterized in that the N,N-diethylaminophenol is brought into contact with the N,N-diethylaminophenol, and then the N,N-diethylaminophenol is precipitated and recovered by cooling.
This is a method for purifying N-diethylaminophenols. This will be explained in detail below.
本発明のアミノフェノール類とは、具体的には、オルソ
アミノフェノール、メタアミノフエ／ −ＩＬ／、パラ
アミノフェノ−１し等であり、特ニメタアミノフェノー
ルが好ましい。Ｎ、Ｎ−ジエチルアミノフェノール類と
は、具体的には、Ｎ。Specifically, the aminophenols of the present invention include ortho-aminophenol, meta-aminophenol, para-aminophenol, and the like, with nimeta-aminophenol being particularly preferred. N,N-diethylaminophenols specifically refer to N.
Ｎ−ジエチルオルソアミノフェノール、Ｎ、Ｎ−ジエチ
ルメタアミノフェノール、 Ｎ、Ｎ−ジエチルパラアミ
ノフェノール等であす、 特！、−Ｎ、Ｎ −ジエチル
メタ７ミノフエノールが好ましい。N-diethyl orthoaminophenol, N,N-diethylmethaminophenol, N,N-diethylpara-aminophenol, etc. Special! , -N,N-diethylmeta-7minophenol is preferred.
本発明の方法に於いて、還元アルキル化反応は通常の方
法、即ち、アミノツーノール類、溶媒及び触媒を仕込ん
で、水素加圧下にアセトアルデヒドを連続供給すること
によって容易に行なわせることができる。通常、溶媒と
しては。In the method of the present invention, the reductive alkylation reaction can be easily carried out by a conventional method, that is, by charging the aminotunols, a solvent and a catalyst, and continuously supplying acetaldehyde under hydrogen pressure. Usually as a solvent.
脂肪族アルコール、例えばメタノール、エタノール、プ
ロパツール、触媒としては、白金、パラジウム、ニッケ
ルなど還元アルキル化能を有するものが用いられる。ア
セトアルデヒドの使用量は、アミノフェノール類１モル
に対し２通常、２，１〜４倍モル量、又、使用する溶媒
の量はアミノフェノール類１重量部に対し、１重量部〜
２０重量部、触媒の量はアミノフェノール類１重量部に
対し、 ０．００５〜０．１重量部が凧いられる。Aliphatic alcohols, such as methanol, ethanol, propatool, and catalysts that have reductive alkylation ability, such as platinum, palladium, and nickel, are used. The amount of acetaldehyde used is usually 2,1 to 4 times the mole of aminophenols, and the amount of solvent used is 1 part by weight to 1 part by weight of the aminophenols.
The amount of catalyst is 0.005 to 0.1 part by weight per 1 part by weight of aminophenols.
反応温度は、常温〜１５０°Ｃ１水素圧力は特に制限な
いが１通常２０ Ｋｑ ／ ａｄ Ｇ以下で十分である
。The reaction temperature is from room temperature to 150° C. The hydrogen pressure is not particularly limited, but 20 Kq/ad G or less is usually sufficient.
又、還元アルキル化反応液、触媒を分離して得られる反
応液から粗Ｎ、Ｎ−ジエチルアミンフェノール類を蒸留
によって、留出回収する方法は２通常、先ず缶出温度を
１６０℃以下に維持しつつ、未反応のアセトアルデヒド
及び溶媒を蒸留によって実質的に除去し１次いで未反応
のアセトアルデヒド及び溶媒を実質的に除去した後の缶
出液を２００℃以下に維持しながら、Ｎ、Ｎ−ジエチル
アミノフェノール類を蒸留によって。In addition, there are two methods for distilling and recovering crude N,N-diethylamine phenols from the reaction solution obtained by separating the reduction alkylation reaction solution and the catalyst. At the same time, unreacted acetaldehyde and the solvent are substantially removed by distillation, and then N,N-diethylaminophenol is added while maintaining the bottoms after substantially removing the unreacted acetaldehyde and the solvent at 200°C or below. by distillation.
留出させることで容易に得ることが可能である。It can be easily obtained by distillation.
以上、記述した方法によって取得した粗Ｎ、Ｎ−ジエチ
ルアミノフェノール類を精製する本発明の特徴は、不活
性ガス雰囲気下に、 Ｎ、Ｎ−ジエチルアミノフェノー
ル類と実質的に相溶しない溶媒と粗Ｎ、Ｎ−ジエチルア
ミノフェノール類とを接触させた後、冷却番こよりＮ、
Ｎ−ジエチルアミノフェノール類を析出させて回収する
こと暑こある。A feature of the present invention for purifying crude N,N-diethylaminophenols obtained by the method described above is to purify crude N,N-diethylaminophenols with a solvent that is substantially incompatible with N,N-diethylaminophenols in an inert gas atmosphere. , N-diethylaminophenols, and then cooled with N,
It is very difficult to precipitate and recover N-diethylaminophenols.
本発明に於ける。 Ｎ、Ｎ−ジエチルアミノフェノー
ル類と実質的舎こ相溶しない溶媒とは、水及び脂肪族炭
化水素類で、脂肪族炭化水素類とは例えばヘキサン、ヘ
プタン、オクタン、シクロヘキサンが好ましい。溶媒の
使用量は、粗Ｎ、Ｎ−ジエチルアミノフェノール類１重
量部当たり。In the present invention. Solvents that are substantially incompatible with N,N-diethylaminophenols include water and aliphatic hydrocarbons, and examples of aliphatic hydrocarbons are preferably hexane, heptane, octane, and cyclohexane. The amount of solvent used is per part by weight of crude N,N-diethylaminophenol.
通常１〜１０重量部で十分である。不活性ガスは通常は
、窒素、アルゴン、ヘリウムが好ましい。Usually 1 to 10 parts by weight is sufficient. The inert gas is usually preferably nitrogen, argon or helium.
本発明の粗Ｎ、Ｎ−ジエチルアミノフェノール類と溶媒
の接触は通常、蒸留で回収した溶融状の粗Ｎ、Ｎ−ジエ
チルアミノフェノール類を、予め不活性ガス雰囲気下に
なっている溶媒中に攪拌上添加することにより行なわせ
ることができる。この時溶媒の保持されている温度は、
Ｎ、Ｎ−ジエチルアミノフーノール類が溶融する温度
以上でも１未満でも良いが、好ましくは、粗Ｎ。The contact between the crude N,N-diethylaminophenols and the solvent in the present invention is usually carried out by first stirring the molten crude N,N-diethylaminophenols recovered by distillation into a solvent that has been placed under an inert gas atmosphere. This can be done by adding. The temperature at which the solvent is held at this time is
The temperature may be higher than the melting temperature of N,N-diethylaminofunols or lower than 1, but preferably crude N.
Ｎ−ジエチルアミノツーノール類を添加した後。After adding N-diethylaminotunols.
一旦Ｎ、Ｎ−ジエチルアミノフェノール類が溶融する温
度以上として、接触させた方が不純物除去の観点からよ
り好ましい。Ｎ、Ｎ−ジエチルアミノフェノール類が溶
融する温度とは、粗Ｎ、Ｎ−ジエチルアミノフェノール
類に含まれる不純物の量、 粗Ｎ、Ｎ−ジエチルアミノ
フェノール類と使用する溶媒の比率などによっても異な
るが。From the viewpoint of removing impurities, it is more preferable to bring the mixture into contact at a temperature higher than the temperature at which the N,N-diethylaminophenol melts. The temperature at which N,N-diethylaminophenols melt varies depending on the amount of impurities contained in the crude N,N-diethylaminophenols, the ratio of the crude N,N-diethylaminophenols to the solvent used, and the like.
通常は５０°Ｃ以上である。Usually the temperature is 50°C or higher.
粗Ｎ、Ｎ−ジエチルアミノフェノール類と溶媒との接触
は１回分式、連続式いずれの方法にても行なうことが可
能である。粗Ｎ、Ｎ−ジエチルアミノフーノール類と溶
媒を攪拌下に接触後。The contact between the crude N,N-diethylaminophenol and the solvent can be carried out either in a single batch method or in a continuous method. After contacting the crude N,N-diethylaminofunol and the solvent with stirring.
通常の方法で冷却することによって、 Ｎ、Ｎ−ジエチ
ルアミノフ・ノール類が結晶化し、析出する。この時、
結晶化をよりスムーズ）こ行なわせるために種晶を添加
した方がより好ましい。By cooling in a conventional manner, N,N-diethylaminophenols crystallize and precipitate. At this time,
It is more preferable to add seed crystals to achieve smoother crystallization.
析出したＮ、Ｎ−ジエチルアミノフェノール類の回収は
通常の濾過操作１例えば減圧、加圧、遠心などの方法で
行なわれる。又１回収したＮ、Ｎ−ジエチルアミノフェ
ノール類のケーキは９例えば乾燥して製品にされる。The precipitated N,N-diethylaminophenols are recovered by conventional filtration operations such as reduced pressure, increased pressure, and centrifugation. In addition, the recovered N,N-diethylaminophenol cake is dried and made into a product.
この様に本発明の方法によれば、 Ｎ、Ｎ−ジエチルア
ミノフェノール類は、従来法にみられた問題点が全くな
く、シかも収率良く、高品位の淡黄白色ないし淡紅色の
固体として取得できる様になった。As described above, according to the method of the present invention, N,N-diethylaminophenols are produced as a high-grade pale yellow-white to pale pink solid in good yield without any of the problems seen in conventional methods. Now you can get it.
次に実施例をあげて２本発明をさらに詳細に説明するが
本発明はこれに限定されるものではない。Next, the present invention will be explained in more detail with reference to two examples, but the present invention is not limited thereto.
〈実施例〉
実施例−１
（ｆｆｌＮ、Ｎ−ジエチルメタアミノフェノールの取得
）攪拌機付ＳＵＳ製５ｔのオートクレーブにメタアミノ
フェノ−ｗ １６３．７ ｇｒ （１，５モル） 。<Examples> Example-1 (Obtaining fflN, N-diethyl meta-aminophenol) Meta-aminophenol-w 163.7 gr (1.5 mol) was placed in a 5-ton SUS autoclave equipped with a stirrer.
メタノール１８１４ｇｒ、触媒として５％白金−炭素４
．１ ｇｒを仕込み、 ４０℃水素圧力１０ Ｋｆ／
ｃ＋＋ｌ Ｇ一定して、アセト４ルデヒド１６５．２
ｇｒ （３，７５モル）を５時間かけて連続供給しなが
ら、還元アルキル化反応を行なりた。アセトアルデヒド
の連続導入終了後、同温度でさらに２０分間保持した後
冷却し、触媒を濾過分離して反応液を得た。Methanol 1814 gr, 5% platinum-carbon 4 as catalyst
．． Charge 1 gr, 40℃ hydrogen pressure 10 Kf/
c++l G constant, acetyldehyde 165.2
The reductive alkylation reaction was carried out while continuously supplying gr (3.75 mol) over 5 hours. After the continuous introduction of acetaldehyde was completed, the temperature was maintained for an additional 20 minutes and then cooled, and the catalyst was separated by filtration to obtain a reaction liquid.
次に還元アルキル化反応で取得した反応液をオイルバス
中をこ入れたナシ型フラスコ中に連続的に供給しながら
、未反応アルデヒド及びメタノール除去のための減圧蒸
留を行なった。反応液は３時間かけて連続供給し供給終
了後、実質的にアルデヒド及びメタノールを除くために
バッチによる濃縮を実施した。この間、操作圧力は３０
０■地一定、又缶出液の温度は１２０℃以下の操作であ
る。缶出液温度が１２０’Ｃに到達したので蒸留を停止
した。Next, while continuously feeding the reaction solution obtained in the reductive alkylation reaction into a pear-shaped flask placed in an oil bath, vacuum distillation was performed to remove unreacted aldehyde and methanol. The reaction solution was continuously fed over a period of 3 hours, and after the feeding was completed, batchwise concentration was performed to substantially remove aldehyde and methanol. During this time, the operating pressure was 30
The operation is carried out at a constant temperature of 0°C and the temperature of the bottom liquid is 120°C or less. Distillation was stopped when the bottoms temperature reached 120'C.
引続いて、アセトアルデヒド及びメタノールを除去して
得られた缶出液から、粗Ｎ、Ｎ−ジエチルメタアミノフ
ェノールを留出１回収させるため、圧力３−セ一定のも
とバッチによる減圧。Subsequently, in order to recover crude N,N-diethylmethaminophenol by distillation from the bottoms obtained by removing acetaldehyde and methanol, the pressure was reduced by batchwise at a constant pressure of 3 centimeters.
蒸留を行なりた。缶出液の温度が１７０’Ｃになっなの
で蒸留操作を停止し、得られた液状の粗Ｎ。Distillation was carried out. Since the temperature of the bottom liquid reached 170'C, the distillation operation was stopped and the obtained liquid crude N was obtained.
Ｎ−ジエチルメタアミノフェノールを次の精製工程に供
給した。N-diethylmethaminophenol was fed to the next purification step.
（Ｎ、Ｎ−ジエチルメタアミノフェノールの精製）攪拌
機、バッフル、温度計及びコンデンサーをとりつけた１
ｔのセパラブルフラスコ中に窒素雰囲気下水４００ｇｒ
を仕込み、５０℃にセットした。この中へ液状の粗Ｎ、
Ｎ−ジエチルメタアミノフェノールＬ ００ ｇｒを仕
込み１次に内温６５′ｃまで昇温してＮ、Ｎ−ジエチル
メタアミノフェノールの溶融を確認した後、攪拌しなが
ら冷却を開始した。内温６０℃で種晶を０．１ ｇｒ添
加すると内温５７℃付近からＮ、Ｎ−ジエチルメタアミ
ノフェノールの析出がはじまった。およそ。(Purification of N,N-diethyl meta-aminophenol) 1 equipped with a stirrer, baffle, thermometer and condenser
400g of nitrogen atmosphere sewage in a separable flask
was prepared and set at 50°C. Into this, liquid crude N,
After charging L 00 gr of N-diethyl meta-aminophenol and raising the temperature to an internal temperature of 65'C to confirm melting of N,N-diethyl meta-aminophenol, cooling was started while stirring. When 0.1 gr of seed crystals were added at an internal temperature of 60°C, precipitation of N,N-diethylmethaminophenol started from around 57°C. about.
０２〜０．３℃／分の冷却速度で内温３０°Ｃまで冷却
して結晶化を終了し、減圧濾過でＮ、Ｎ−ジエチルメタ
アミノツーノールのケーキを回収した。Crystallization was completed by cooling to an internal temperature of 30° C. at a cooling rate of 0.02 to 0.3° C./min, and a cake of N,N-diethyl metaaminotunol was recovered by vacuum filtration.
得られたケーキを４０℃／ ３０ ｍｍＨｇ下で２時間
乾燥して顆粒状の製品を９８．４ｇｒ得た。ガスクロマ
トグラフィー分析（以下ＧＣ分析と称す）のＰ果、ａ度
は９９．８％、又ゲルバーミーエージ書ン分析（以下Ｇ
ＰＣ分析と称す）の結果、タール分は含まれておらず製
品の外観は淡黄白色のきれいなものであった。The resulting cake was dried at 40° C./30 mmHg for 2 hours to obtain 98.4 gr of granular product. The P result of gas chromatography analysis (hereinafter referred to as GC analysis) was 99.8%, and the gel barmy age writing analysis (hereinafter referred to as GC analysis) was 99.8%.
As a result of PC analysis (referred to as PC analysis), it was found that no tar was contained and the product had a clean pale yellowish-white appearance.
実施例−２
実施例−１と同様にして取得した粗Ｎ、Ｎ ’、；エ
チルメタアミノフェノール１００ｇｒ及び溶媒としてｎ
−へブタン４００ ｇｒを用いて実施例−１と同様にし
て、 Ｎ、Ｎ−ジエチルメタ７ミノフエノールの精製を
行なった。Example-2 Crude N, N', obtained in the same manner as in Example-1; 100 gr of ethyl meta-aminophenol and n as a solvent.
-N,N-diethylmeth-7minophenol was purified in the same manner as in Example 1 using 400 gr of hebutane.
得られたケーキを４０℃／３ｏＩＩＩＩＩＩＨｇ下で２
時間乾燥して顆粒状の製品を９８．１ｇｒ取得した。Ｇ
Ｃ分析の結果、純度は９９．７％で、又、ＧＰＣ分析の
結果、タール分は含まれておらず、製品の外観は微淡紅
色のきれいなものであった。The resulting cake was heated at 40°C/3oIIIHg for 2
After drying for several hours, 98.1 gr of a granular product was obtained. G
As a result of C analysis, the purity was 99.7%, and as a result of GPC analysis, there was no tar content, and the product had a clean, pale pink appearance.
実施例−３
実施例−１と同様にして取得した粗Ｎ、Ｎ−ジエチルメ
タアミノフェノール１００ｇｒ及び溶媒としてｎ−ヘキ
サン４００ ｇｒを用いて、 Ｎ、Ｎ−ジエチルメタア
ミノフェノールの精製を行なった。Example-3 N,N-diethyl meta-aminophenol was purified using 100 gr of crude N,N-diethyl meta-aminophenol obtained in the same manner as in Example-1 and 400 gr of n-hexane as a solvent.
Ｎ２雰囲気下、内温６０℃の中に攪拌しながら。Under N2 atmosphere with stirring at an internal temperature of 60°C.
液状の粗Ｎ、Ｎ−ジエチルメタアミノフェノールを添加
し、冷却を開始した。内温５８℃で種晶を０、１ ｇｒ
添加すると、５６℃付近からＮ、Ｎ−ジエチルメタアミ
ノフェノールの析出がはじまった。Liquid crude N,N-diethylmethaminophenol was added and cooling started. 0.1 gr of seed crystals at an internal temperature of 58°C
Upon addition, N,N-diethyl meta-aminophenol began to precipitate at around 56°C.
およそ０．２〜０．３℃／分の冷却速度で内温２５°Ｃ
まで冷却して結晶化を終了した。濾過操作でケーキを得
１次いで４０°Ｃ／ ３０ ｍＨｇ下２時間の乾燥で顆
粒状の製品９８．６ｇｒを得た。ＧＣ分析の結果、純度
は９９．５％で、又、ＧＰＣ分析の結果タール分は含ま
れておらず、製品の外観は微淡紅色のきれいなものであ
った。Internal temperature of 25°C at a cooling rate of approximately 0.2-0.3°C/min
The crystallization was completed by cooling to . A cake was obtained by filtration and then dried for 2 hours at 40°C/30 mHg to obtain 98.6 gr of a granular product. As a result of GC analysis, the purity was 99.5%, and as a result of GPC analysis, there was no tar content, and the product had a clean appearance with a pale pink color.
〈発明の効果〉
アミノフェノール類とアセトアルデヒドの還元アルキル
化反応でＮ、Ｎ−ジエチルアミノフェノール類を生成さ
せ２反応液から蒸留によって留出回収した粗Ｎ、Ｎ−ジ
エチルアミノフェノール類を、不活性ガス雰囲気下にＮ
、Ｎ−ジエチルアミノツーノール類と実質的に相溶しな
い溶媒と接触させ、冷却によりＮ、Ｎ−ジエチルアミノ
ツーノール類を析出させて１回収するＮ、Ｎ−ジエチル
アミノフェノール類の精製法は、従来法にない全く新し
いＮ、Ｎ−ジエチルアミノフェノール類の工業的製法で
ある。本発明の方法によれば、材質上の腐食の問題、多
量の排水発生の問題、製品の品質の問題環、従来法に比
べて格段に進歩し、極めて工業的に有利にＮ、Ｎ−ジエ
チルアミノフェノール類が製造可能である。<Effects of the Invention> N,N-diethylaminophenols were produced by reductive alkylation reaction of aminophenols and acetaldehyde, and the crude N,N-diethylaminophenols recovered by distillation from the two reaction liquids were collected in an inert gas atmosphere. N below
, N-diethylaminotunols are brought into contact with a solvent that is substantially incompatible with the N-diethylaminotunols, and N,N-diethylaminotunols are precipitated and recovered once by cooling, which is a conventional method. This is a completely new industrial method for producing N,N-diethylaminophenols that is not available anywhere else. According to the method of the present invention, the problem of material corrosion, the problem of generation of a large amount of wastewater, and the problem of product quality are significantly improved compared to the conventional method, and it is very industrially advantageous to use N,N-diethylaminol. Phenols can be produced.
Claims (4)
触媒及び水素共存下に還元アルキル化反応させ、反応終
了後、触媒を分離して得られる反応液から蒸留によって
留出回収した粗Ｎ，Ｎ−ジエチルアミノフェノール類を
精製するにあたり、不活性ガス雰囲気下にＮ，Ｎ−ジエ
チルアミノフェノール類と実質的に相溶しない溶媒と、
粗Ｎ，Ｎ−ジエチルアミノフェノール類とを接触させた
後、冷却によりＮ，Ｎ−ジエチルアミノフェノール類を
析出させて、回収することを特徴とするＮ，Ｎ−ジエチ
ルアミノフェノール類の精製法。(1) Aminophenols and acetaldehyde as a solvent,
A reductive alkylation reaction is carried out in the coexistence of a catalyst and hydrogen, and after the completion of the reaction, the catalyst is separated and the resulting reaction liquid is distilled and recovered.When purifying the crude N,N-diethylaminophenols, the crude N,N-diethylaminophenols are purified under an inert gas atmosphere. a solvent that is substantially incompatible with N,N-diethylaminophenols;
A method for purifying N,N-diethylaminophenols, which comprises bringing crude N,N-diethylaminophenols into contact with each other, and then precipitating and recovering N,N-diethylaminophenols by cooling.
求の範囲第１項記載のＮ，Ｎ−ジエチルアミノフェノー
ル類の精製法。(2) The method for purifying N,N-diethylaminophenols according to claim 1, wherein the solvent is water or an aliphatic hydrocarbon.
ン、シクロヘキサンである特許請求の範囲第２項記載の
Ｎ，Ｎ−ジエチルアミノフェノール類の精製法。(3) The method for purifying N,N-diethylaminophenols according to claim 2, wherein the aliphatic hydrocarbon is hexane, heptane, octane, or cyclohexane.
，Ｎ−ジエチルアミノフェノール類がＮ，Ｎ−ジエチル
メタアミノフェノールである特許請求の範囲第１項記載
のＮ，Ｎ−ジエチルアミノフェノール類の精製法。(4) Aminophenols are meta-aminophenol, N
, N-diethylaminophenol is N,N-diethylmethaminophenol.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62099047A JPS63264558A (en) | 1987-04-21 | 1987-04-21 | Purification of n,n-diethylaminophenol |
| IN213/MAS/88A IN171026B (en) | 1987-04-09 | 1988-04-05 | |
| EP19880303116 EP0287277B1 (en) | 1987-04-09 | 1988-04-07 | Production and purification of an n,n-diethylaminophenol |
| DE19883872916 DE3872916T2 (en) | 1987-04-09 | 1988-04-07 | PREPARATION AND PURIFICATION OF N, N-DIETHYLAMINOPHENOL. |
| US07/179,447 US4967004A (en) | 1987-04-09 | 1988-04-08 | Process for producing N,N-diethylaminophenols |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62099047A JPS63264558A (en) | 1987-04-21 | 1987-04-21 | Purification of n,n-diethylaminophenol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63264558A true JPS63264558A (en) | 1988-11-01 |
| JPH0438742B2 JPH0438742B2 (en) | 1992-06-25 |
Family
ID=14236623
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62099047A Granted JPS63264558A (en) | 1987-04-09 | 1987-04-21 | Purification of n,n-diethylaminophenol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63264558A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5231329A (en) * | 1975-09-04 | 1977-03-09 | Yuasa Battery Co Ltd | Battery |
| JPS6239533A (en) * | 1985-08-07 | 1987-02-20 | ヘキスト・アクチエンゲゼルシヤフト | Manufacture of aromatic dialkyldiamines |
| JPS6261955A (en) * | 1985-09-12 | 1987-03-18 | Sumitomo Chem Co Ltd | Purification of n,n-diethylaminophenol |
-
1987
- 1987-04-21 JP JP62099047A patent/JPS63264558A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5231329A (en) * | 1975-09-04 | 1977-03-09 | Yuasa Battery Co Ltd | Battery |
| JPS6239533A (en) * | 1985-08-07 | 1987-02-20 | ヘキスト・アクチエンゲゼルシヤフト | Manufacture of aromatic dialkyldiamines |
| JPS6261955A (en) * | 1985-09-12 | 1987-03-18 | Sumitomo Chem Co Ltd | Purification of n,n-diethylaminophenol |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0438742B2 (en) | 1992-06-25 |
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