JPH01230549A - Method for purifying n,n-diethyl-m-aminophenol - Google Patents
Method for purifying n,n-diethyl-m-aminophenolInfo
- Publication number
- JPH01230549A JPH01230549A JP63057730A JP5773088A JPH01230549A JP H01230549 A JPH01230549 A JP H01230549A JP 63057730 A JP63057730 A JP 63057730A JP 5773088 A JP5773088 A JP 5773088A JP H01230549 A JPH01230549 A JP H01230549A
- Authority
- JP
- Japan
- Prior art keywords
- aminophenol
- crude
- diethylmethaminophenol
- diethyl
- dithionite
- 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
- WAVOOWVINKGEHS-UHFFFAOYSA-N 3-(diethylamino)phenol Chemical compound CCN(CC)C1=CC=CC(O)=C1 WAVOOWVINKGEHS-UHFFFAOYSA-N 0.000 title claims abstract 7
- 238000000034 method Methods 0.000 title claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims abstract description 4
- HEZHYQDYRPUXNJ-UHFFFAOYSA-L potassium dithionite Chemical compound [K+].[K+].[O-]S(=O)S([O-])=O HEZHYQDYRPUXNJ-UHFFFAOYSA-L 0.000 claims abstract description 3
- 230000002378 acidificating effect Effects 0.000 claims description 15
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 11
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 10
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical class [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 claims description 8
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 5
- 238000005932 reductive alkylation reaction Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 5
- 238000004040 coloring Methods 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000007850 fluorescent dye Substances 0.000 abstract description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 abstract 2
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 abstract 1
- 235000019252 potassium sulphite Nutrition 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 235000010265 sodium sulphite Nutrition 0.000 abstract 1
- 239000000047 product Substances 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000000746 purification Methods 0.000 description 7
- 238000002835 absorbance Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000007796 conventional method Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CYQBIIIAQYFGOP-UHFFFAOYSA-N 3-amino-2,4-diethylphenol Chemical compound CCC1=CC=C(O)C(CC)=C1N CYQBIIIAQYFGOP-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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 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
- 230000000694 effects Effects 0.000 description 2
- 229960003750 ethyl chloride Drugs 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000012535 impurity Substances 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
- 239000007787 solid Substances 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 101100441097 Dictyostelium discoideum crlG gene Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 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
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- RDYMFSUJUZBWLH-UHFFFAOYSA-N endosulfan Chemical class C12COS(=O)OCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl RDYMFSUJUZBWLH-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 230000000007 visual effect Effects 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−ジエチルメタアミノフェノールの精
製方法に関する。Ｎ、Ｎ−ジエチルメタアミノフェノー
ルは、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-diethylmethaminophenol. N,N-diethylmethaminophenol is an industrially extremely important compound as an intermediate for heat-sensitive and pressure-sensitive paper dyes, xanthine dyes, fluorescent dyes, and the like.
〈従来の技術〉
従来、Ｎ、Ｎ−ジエチルメタアミノフェノールの合成法
として
■ ニトロベンゼンを出発原料とし、メタニル酸ソーダ
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、アルカリフユージョンして目的物を得る方
法、
■レゾルシン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、
■メタアミノフェノール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、
などが知られている。<Prior art> Conventionally, as a method for synthesizing N,N-diethyl metaaminophenol, nitrobenzene is used as a starting material to obtain sodium methanate, which is ethylated with ethyl chloride or diethyl sulfate and then subjected to alkali fusion to obtain the desired product. A method for obtaining the desired product; ■ A method for obtaining the desired product by reacting resorcin with diethylamine in the presence of an acid catalyst. ■ A method for obtaining the desired product by ethylating meta-aminophenol with ethyl chloride or diethyl sulfate in the presence of an alkali salt. How to obtain it is known.
■■■いずれの方法も、Ｎ、Ｎ−ジエチルメタアミノフ
ェノールを回収する際、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
エチルメタアミノフェノール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
ずから、Ｎ、Ｎ−ジエチルメタアミノフェノールの品質
にも限界があった。■■■ In either method, neutralization treatment with acid or alkali is always required when recovering N,N-diethyl metaaminophenol, and because it is a compound containing an amino group, it is difficult to determine the end point of neutralization. However, due to the thermal instability of N,N-diethylmethaminophenol, it has not been possible to use a distillation method for purification. Therefore, there was naturally a limit to the quality of N,N-diethylmethaminophenol.
即ち、従来法で得られるＮ、Ｎ−ジエチルメタアミノフ
ェノールの外観は一般に、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-diethyl meta-aminophenol obtained by conventional methods generally has a brown appearance because it contains a small amount of tar (heavy content), which has often impaired its commercial value.
又、メタアミノフェノール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
エチルメタアミノフェノールは、■〜■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−ジエチルメタアミノフェノールの感熱・感
圧紙用染料としての用途に対して必ずしも満足できる品
質ではなく、より高純度でしかも長期間にわたって保存
した場合でも着色の少ないＮ、Ｎ−ジエチルメタアミノ
フェノールの要望が高まってきた。Furthermore, after the reductive alkylation reaction of meta-aminophenol and acetaldehyde, N,N-diethyl meta-aminophenol, which is distilled and recovered, can be obtained as a product that is significantly improved compared to methods ① to ②. In recent years, the quality of N,N-diethylmethaminophenol is not necessarily satisfactory for use as a dye for heat-sensitive and pressure-sensitive paper, and N,N-diethylmethaminophenol has been developed with higher purity and less coloring even when stored for a long period of time. Demand for diethyl meta-aminophenol has been increasing.
く本発明が解決しようとする課題〉
本発明は、従来法では得られない高品位のＮ、 Ｎ−ジ
エチルメタアミノフェノールを得ようとするものである
。Problems to be Solved by the Present Invention The present invention aims to obtain high-quality N,N-diethyl meta-aminophenol that cannot be obtained by conventional methods.
〈課題を解決するための手段〉
本発明者らは、従来法に変わるＮ、Ｎ−ジエチルメタア
ミノフェノールの新しい精製方法について、鋭意検討し
た結果、不活性ガス雰囲気下に粗Ｎ、Ｎ−ジエチルメタ
アミノフェノールと水を接触させて、粗Ｎ、Ｎ−ジエチ
ルメタアミノフェノールを精製する際に、酸性亜硫酸塩
及び／又は亜二チオン酸塩を添加することにより極めて
工業的に有利に収率良＜、シかも高品位のＮ、Ｎ−ジエ
チルメタアミノフェノールが得られることを見出した。<Means for Solving the Problems> As a result of intensive studies on a new purification method for N,N-diethyl meta-aminophenol to replace the conventional method, the present inventors found that crude N,N-diethyl When purifying crude N,N-diethylmethaminophenol by contacting meta-aminophenol with water, adding acidic sulfite and/or dithionite can produce a highly industrially advantageous and high-yield product. It has been found that high quality N,N-diethyl meta-aminophenol can be obtained.
即ち、本発明は、不活性ガス雰囲気下に粗Ｎ、 Ｎ−ジ
エチルメタアミノフェノールと水を接触させて１［Ｎ、
Ｎ−ジエチルメタアミノフェノールを精製スる際に、１
種又は２種以上の酸性亜硫酸塩及び／又は亜二チオン酸
塩を添加することを特徴とするＮ。That is, in the present invention, 1[N,
When purifying N-diethylmethaminophenol, 1
N characterized by adding a species or two or more acidic sulfites and/or dithionites.
Ｎ−ジエチルメタアミノフェノールの精製方法である。This is a method for purifying N-diethylmethaminophenol.
以下具体的に詳述する。This will be explained in detail below.
本発明に於いて粗Ｎ、Ｎ−ジエチルメタアミノフェノー
ルと水を接触させ粗Ｎ、Ｎ−ジエチルメタアミノフェノ
ールを精製する際に、添加する酸性亜硫酸塩とは、酸性
亜硫酸ナトリウム及び酸性亜硫酸カリウムであり、又、
亜二チオン酸塩とは亜二チオン酸ナトリウム及び亜二チ
オン酸カリウムである。In the present invention, when crude N,N-diethylmethaminophenol is brought into contact with water to purify crude N,N-diethylmethaminophenol, the acidic sulfite to be added is sodium acidic sulfite and potassium acidic sulfite. Yes, also
Dithionite is sodium dithionite and potassium dithionite.
酸性亜硫酸塩、亜二チオン酸塩の添加量は粗Ｎ。The amount of acidic sulfite and dithionite added is crude N.
Ｎ−ジエチルメタアミノフェノール１００重量部当たり
０．１〜１０重量部、好ましくは０．５〜７．５重量部
の範囲である。添加量が０．１重量部未満では、精製し
て得られる製品の経時的な着色防止が十分でなく、１０
重量部をこえると製品中に残留する量が多くなり、製品
純度の低下となるので好ましくない。The amount ranges from 0.1 to 10 parts by weight, preferably from 0.5 to 7.5 parts by weight, per 100 parts by weight of N-diethylmethaminophenol. If the amount added is less than 0.1 part by weight, the product obtained by purification will not be sufficiently prevented from discoloring over time;
If the amount exceeds 1 part by weight, the amount remaining in the product will increase, resulting in a decrease in product purity, which is not preferable.
添加方法としては特に制限はなく、酸性亜硫酸ニ
塩及び／又は、亜Ｉチオン酸塩は固体粉末として添加し
ても良く、又、水添液など液状で添加しても良い。There is no particular restriction on the method of addition, and the acidic di-sulfite and/or I-thionite may be added in the form of a solid powder, or in a liquid form such as a hydrogenated solution.
この際、各々酸性亜流酸塩、亜二チオン酸塩は単独でも
又、２種以上混合して用いても何ら差しつかえない。In this case, each of the acidic sulfites and dithionites may be used alone or in combination of two or more without any problem.
本発明の粗Ｎ、Ｎ−ジエチルメタアミノフェノールは、
メタアミノフェノール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−ジエチルメタアミノフェノールであ
る。The crude N,N-diethylmethaminophenol of the present invention is
Meta-aminophenol 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 and the resulting reaction liquid is distilled and recovered using crude N,N-diethyl meta-aminophenol. be.
この様な方法で得られる粗Ｎ、Ｎ−ジエチルメタアミノ
フェノールは、実質的に重質分を含まないので、本発明
効果が顕著で、特に製品の着色経時変化が抑制され、長
期間の保存においても、良好な品質を維持することが可
能となる。Since the crude N,N-diethyl meta-aminophenol obtained by such a method does not substantially contain heavy components, the effects of the present invention are remarkable, and in particular, the coloring of the product is suppressed over time, and it can be stored for a long period of time. It is also possible to maintain good quality.
又、粗Ｎ、Ｎ−ジエチルメタアミノフェノールと水の接
触は通常、蒸留で回収した溶融状の粗〜、Ｎ−ジエチル
メタアミノフェノールを、予め不活性ガス雰囲気下にな
っている溶媒中に攪拌下添加することにより行わせるこ
とができる。In addition, the contact between crude N,N-diethyl meta-aminophenol and water is usually carried out by stirring the molten crude N,N-diethyl meta-aminophenol recovered by distillation into a solvent that is previously under an inert gas atmosphere. This can be done by adding the following.
この時水の保持されている温度は、Ｎ、Ｎ−ジエチルメ
タアミノフェノールが溶融する温度以上でも、未満でも
良いが、好ましくは、粗Ｎ、Ｎ−ジエチルメタアミノフ
ェノールを添加した後、−旦Ｎ、Ｎ−ジエチルメタアミ
ノフェノール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
ルメタアミ／フェノールが溶融する温度とは、粗Ｎ、Ｎ
−ジエチルメタアミノフェノールに含まれる不純物の量
、粗Ｎ、Ｎ−ジエチルメタアミノフェノールと使用する
水の比率などによっても異なるが、通常は５０℃以上で
ある。The temperature at which the water is maintained at this time may be higher than or lower than the temperature at which N,N-diethylmethaminophenol melts, but preferably, after adding the crude N,N-diethylmethaminophenol, - From the viewpoint of removing impurities, it is more preferable to bring the mixture into contact at a temperature equal to or higher than the temperature at which N,N-diethylmethaminophenol melts. The temperature at which N,N-diethylmethamine/phenol melts is the temperature at which crude N,N
Although it varies depending on the amount of impurities contained in -diethyl meta-aminophenol, the ratio of crude N, N-diethyl meta-aminophenol and water used, etc., the temperature is usually 50°C or higher.
粗Ｎ、Ｎ−ジエチルメタアミノフェノールと水との接触
は、回分式、連続式いずれの方法にても行うことが可能
である。The contact between crude N,N-diethyl meta-aminophenol and water can be carried out either batchwise or continuously.
酸性亜硫酸塩及び／又は亜二チオン酸塩を添加して粗Ｎ
、Ｎ−ジエチルメタアミノフェノールと水を攪拌下に接
触後、通常の方法で冷却することによって、Ｎ、Ｎ−ジ
エチルメタアミノフェノールが結晶化し、析出する。こ
の時、結晶化をよりスムーズに行わせるために種晶を添
加した方がより好ましい。Crude N by adding acidic sulfite and/or dithionite
, N-diethyl meta-aminophenol and water are brought into contact with water under stirring, and then cooled in a conventional manner to crystallize and precipitate N,N-diethyl meta-aminophenol. At this time, it is more preferable to add seed crystals for smoother crystallization.
析出したＮ、Ｎ−ジエチルメタアミノフェノールの回収
は通常の濾過操作、例えば減圧、加圧、遠心などの方法
で行われ、又、必要に応じてＮ、Ｎ−ジエチルメタアミ
ノフェノールのケーキは酸性亜硫酸塩及び／又は亜二チ
オン酸塩を溶解した水でリンス洗浄又はリパルプ洗浄が
行われる。回収したＮ。The precipitated N,N-diethylmethaminophenol is recovered by normal filtration operations, such as reduced pressure, pressurization, and centrifugation.If necessary, the N,N-diethylmethaminophenol cake is acidified. Rinsing or repulping is performed with water in which sulfite and/or dithionite is dissolved. Recovered N.
Ｎ−ジエチルメタアミノフェノールのケーキは、例えば
乾燥して製品にされる。The N-diethylmethaminophenol cake is, for example, dried to form a product.
この様に本発明の方法によれば、Ｎ、Ｎ−ジエチルメタ
アミノフェノールは、従来法にみられた問題点が全くな
く、しかも収率良く、高品位の淡黄白色ないし淡紅色の
固体として取得でき、この製品は、着色経時変化が抑制
され長期間良好な品質を維持することが可能になった。As described above, according to the method of the present invention, N,N-diethyl meta-aminophenol is produced as a high-grade pale yellowish white to pale pink solid without any of the problems seen in the conventional method, and in good yield. This product has been able to suppress color change over time and maintain good quality for a long period of time.
次に実施例をあげて、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 Examples, but the present invention is not limited thereto.
なお、着色の評価方法は、本発明の方法で取得した、製
品Ｎ、Ｎ−ジエチルメタアミノフェノールをプラスチッ
ク容器に入れ、空気中、室内暗所に保存し、着色経時変
化を調べた。The coloring was evaluated by placing the N,N-diethylmethaminophenol product obtained by the method of the present invention in a plastic container, storing it in the air in a dark room, and examining the change in coloration over time.
また着色度の測定は、スペクトロフォトメーター（日立
製）で、波長５７０ｎｍの吸光度を求め下記に示す式に
従って、モル吸光度を算出し評価し吸光度；サンプル１
．５ｇを塩酸（１＋１溶）５−に溶解してイソプロピル
アルコールで１００−とする。１０ｍｍ石英セルに前記
溶液を入れて吸光度を測定する。To measure the degree of coloration, use a spectrophotometer (manufactured by Hitachi) to measure the absorbance at a wavelength of 570 nm, calculate and evaluate the molar absorbance according to the formula shown below.Absorbance: Sample 1
．． Dissolve 5 g in hydrochloric acid (1+1 solution) 5- and make 100- with isopropyl alcohol. The solution is placed in a 10 mm quartz cell and the absorbance is measured.
Ｗ；サンプル重量（ｇｒ）
１６５．２ ；Ｎ、Ｎ−ジエチルメタアミノフェノー
ルの分子量
製品の純度；ジアゾ値純度（％）
〈実施例〉
実施例−１
（粗Ｎ、Ｎ−ジエチルメタアミノフェノールの取得）攪
拌機付ＳＯ３製５Ｉｌのオートクレーブにメタアミノフ
ェノール１６３．７ｇｒ （１，５モル）、メタノー
ル１８１４ｇｒ、触媒として５％の白金−炭素４．１ｇ
ｒを仕込み、４０℃水素圧力１０ｋｇ／ｃｒｌＧ一定し
て、アセトアルデヒド１６５．２ｇｒ （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
応を行った。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。W: Sample weight (gr) 165.2; Molecular weight of N,N-diethyl meta-aminophenol Purity of product; Diazo value purity (%) <Example> Example-1 (Crude N, N-diethyl meta-aminophenol Obtained) Meta-aminophenol 163.7g (1.5 mol), methanol 1814g, and 5% platinum-carbon 4.1g as a catalyst in a 5Il autoclave made of SO3 with a stirrer.
A reductive alkylation reaction was carried out while continuously supplying 165.2 gr (3.75 mol) of acetaldehyde over 5 hours at a constant hydrogen pressure of 10 kg/crlG at 40°C. 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
中に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３００ｍ
ｍ Ｈｇ −定、又缶出液の温度は１２０℃以下の操作
である。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 is 300m
m Hg - constant, and the temperature of the bottoms is 120°C or lower.
缶出液温度が１２０℃に到達したので蒸留を停止した。Distillation was stopped when the temperature of the bottoms 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、回収させるため、圧力３ｍｍＨｇ一定
のもとバッチによる減圧、蒸留を行った。缶出液の温度
が１７０℃になったので蒸留操作を停止し、得られた液
状の粗Ｎ、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。Subsequently, in order to distill and recover crude N,N-diethylmethaminophenol from the bottoms obtained by removing acetaldehyde and methanol, batch vacuum distillation was performed under a constant pressure of 3 mmHg. . When the temperature of the bottoms reached 170°C, the distillation operation was stopped, and the obtained liquid crude N,N-diethyl metaaminophenol was supplied 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
１１のセパラブルフラスコ中に窒素雰囲気下水４００ｇ
ｒを仕込み、次いで亜二チオン酸ナトリウム２．５ｇ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１００ｇｒを仕込み、
次に内温６５℃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０．１ｇｒｉ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、０．２〜０．３℃／分
の冷却速度で内温３０℃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フェノールのケ
ーキを回収した。(Purification of N, N-diethylmethaminophenol) 400 g of sewage water under nitrogen atmosphere was placed in 11 separable flasks equipped with a stirrer, baffles, thermometer, and condenser.
Then, 2.5 g of sodium dithionite was charged, and the temperature was set at 50°C. Liquid crude N, N
- Prepare 100g of diethyl meta-aminophenol,
Next, the internal temperature was raised to 65° C., and after confirming that N,N-diethyl meta-aminophenol had melted, cooling was started while stirring. When 0.1gri of seed crystals was added at an internal temperature of 60°C, precipitation of N,N-diethylmethaminophenol started from around 57°C. The crystallization is completed by cooling to an internal temperature of 30 °C at a cooling rate of approximately 0.2 to 0.3 °C/min,
A cake of N,N-diethylmethaminophenol was collected by vacuum filtration.
得られたケーキを４０℃／３０ｍｍＨｇ下で２時間乾燥
して頚粒状の製品を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）の結果、純度は９
９．８％であり、又ゲルパーミュエーション分析（以下
ＧＰＣ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 a neck-like product. As a result of gas chromatography analysis (hereinafter referred to as GC analysis), the purity was 9.
9.8%, and as a result of gel permeation analysis (hereinafter referred to as GPC analysis), it contained no tar and the product had a clean pale yellowish-white appearance.
（着色経時変化テスト）
空気中、室温、冷暗所にて製品の着色経時変化を調べた
。(Test on color change over time) The color change over time of the product was examined in air, at room temperature, and in a cool, dark place.
製品取得後の、モル吸光度０．１に対し２ケ月後では０
．５（微淡紅色）と良好であった。After obtaining the product, the molar absorbance was 0.1, but after 2 months it was 0.
．． 5 (slight pink), which was good.
実施例−２〜６、比較例−１
粗Ｎ、Ｎ−ジエチルメタアミノフェノールの精製時に添
加する添加剤の量及び種類をかえたほかは実施例−１と
同様な操作を行い、製品の着色経時変化をテストした。Examples 2 to 6, Comparative Example 1 The same operation as Example 1 was carried out except that the amount and type of additives added during purification of crude N,N-diethyl meta-aminophenol were changed, and the coloring of the product was We tested changes over time.
結果を表−１に示す。The results are shown in Table-1.
備考）
■）添加量；粗Ｎ、Ｎ−ジエチルメタアミノフェノール
１００ｇ当たりの量。Notes) ■) Amount added: Amount per 100 g of crude N,N-diethyl metaaminophenol.
２）モル吸光度値と目視の対応
・ 〜０．４；淡黄白色〜微淡紅色
−０，４〜１．０；微淡紅色〜淡褐色
・１．０〜 ；淡褐色〜褐色〜黒褐色概ね上記の目安
であり目標は淡褐色の０．１以内である。2) Correspondence between molar absorbance value and visual observation - ~0.4; pale yellowish white to slightly pink - 0.4 to 1.0; slightly pale pink to light brown, 1.0 to ; pale brown to brown to blackish brown in general The above guideline and target is light brown within 0.1.
３）比較例−１の２ケ月後は黒褐色である。3) The color of Comparative Example-1 after 2 months is blackish brown.
表−２から明らかなごとく比較例−１は黒褐色に経度し
たのに対し、実施例−２〜６は、微淡紅色〜微淡褐色で
あり、非常に満足すべき結果であった。゛
〈発明の効果〉
不活性ガス雰囲気下に粗Ｎ、Ｎ−ジエチルメタアミノフ
ェノールと水を接触させて、粗Ｎ、Ｎ−ジエチルメタア
ミノフェノールを精製する際に酸性亜硫酸塩及び／又は
亜二チオン酸塩を添加して精製すると従来法に比べて製
品の着色経時変化が抑制され極めて高品位のＮ、Ｎ−ジ
エチルメタアミノフェノールを得ることが可能である。As is clear from Table 2, Comparative Example 1 had a blackish brown color, whereas Examples 2 to 6 had a slightly pale pink to slightly pale brown color, which was a very satisfactory result. <Effects of the Invention> When crude N,N-diethylmethaminophenol is purified by contacting the crude N,N-diethylmethaminophenol with water in an inert gas atmosphere, acidic sulfites and/or dinitrite are purified. Purification by adding a thionate salt suppresses the color change of the product over time compared to conventional methods, making it possible to obtain extremely high-quality N,N-diethylmethaminophenol.
＼ ＼ ＼ ゝ＼、 ゝ＼ ＼ ＼、 ＼ ＼ ＼ ＼、 ＼ ＼\ \ \ ゝ＼、 ゝ＼ \ \、 \ \ \ \、 \ \
Claims (4)
アミノフェノールと水を接触させて、粗Ｎ，Ｎ−ジエチ
ルメタアミノフェノールを精製する際に、１種又は２種
以上の酸性亜硫酸塩及び／又は亜二チオン酸塩を添加す
ることを特徴とするＮ，Ｎ−ジエチルメタアミノフェノ
ールの精製方法。(1) When purifying crude N,N-diethylmeta-aminophenol by contacting crude N,N-diethylmeta-aminophenol with water in an inert gas atmosphere, one or more types of acidic sulfites are added. A method for purifying N,N-diethylmethaminophenol, which comprises adding a salt and/or a dithionite salt.
アミノフェノール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
媒を分解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−ジエチルメタアミノフェノールである請
求項１記載のＮ，Ｎ−ジエチルメタアミノフェノールの
精製方法。(2) Crude N,N-diethyl meta-aminophenol is obtained by subjecting meta-aminophenol and acetaldehyde to a reductive alkylation reaction in the presence of a solvent, a catalyst and hydrogen, and after the reaction is completed, the catalyst is decomposed and the resulting reaction liquid is distilled by distillation. The method for purifying N,N-diethylmethaminophenol according to claim 1, which is the recovered crude N,N-diethylmethaminophenol.
硫酸カリウム、又亜二チオン酸塩が亜ニチオン酸ナトリ
ウム、亜二チオン酸カリウムである請求項１記載のＮ，
Ｎ−ジエチルメタアミノフェノールの精製方法。(3) N according to claim 1, wherein the acidic sulfite is sodium acidic sulfite or potassium acidic sulfite, and the dithionite is sodium dithionite or potassium dithionite;
A method for purifying N-diethylmethaminophenol.
が粗Ｎ，Ｎ−ジエチルメタアミノフェノール１００重量
部当たり０．１〜１０重量部であることを特徴とする請
求項１記載のＮ，Ｎ−ジエチルメタアミノフェノールの
精製方法。(4) The method according to claim 1, characterized in that the amount of acidic sulfite and/or dithionite added is 0.1 to 10 parts by weight per 100 parts by weight of crude N,N-diethylmethaminophenol. A method for purifying N,N-diethylmethaminophenol.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63057730A JPH01230549A (en) | 1988-03-10 | 1988-03-10 | Method for purifying n,n-diethyl-m-aminophenol |
| IN213/MAS/88A IN171026B (en) | 1987-04-09 | 1988-04-05 | |
| DE19883872916 DE3872916T2 (en) | 1987-04-09 | 1988-04-07 | PREPARATION AND PURIFICATION OF N, N-DIETHYLAMINOPHENOL. |
| EP19880303116 EP0287277B1 (en) | 1987-04-09 | 1988-04-07 | Production and purification of an n,n-diethylaminophenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63057730A JPH01230549A (en) | 1988-03-10 | 1988-03-10 | Method for purifying n,n-diethyl-m-aminophenol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01230549A true JPH01230549A (en) | 1989-09-14 |
Family
ID=13064037
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63057730A Pending JPH01230549A (en) | 1987-04-09 | 1988-03-10 | Method for purifying n,n-diethyl-m-aminophenol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01230549A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015501798A (en) * | 2011-11-22 | 2015-01-19 | タミンコ | Stabilized choline solution and method for preparing the same |
| US9527799B2 (en) | 2013-04-11 | 2016-12-27 | Taminco | Process for choline hydroxide |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS617239A (en) * | 1984-06-20 | 1986-01-13 | Mitsui Petrochem Ind Ltd | Preparation of aminophenol |
-
1988
- 1988-03-10 JP JP63057730A patent/JPH01230549A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS617239A (en) * | 1984-06-20 | 1986-01-13 | Mitsui Petrochem Ind Ltd | Preparation of aminophenol |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015501798A (en) * | 2011-11-22 | 2015-01-19 | タミンコ | Stabilized choline solution and method for preparing the same |
| US9527799B2 (en) | 2013-04-11 | 2016-12-27 | Taminco | Process for choline hydroxide |
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