JPH0224817B2 - - Google Patents
Info
- Publication number
- JPH0224817B2 JPH0224817B2 JP8556681A JP8556681A JPH0224817B2 JP H0224817 B2 JPH0224817 B2 JP H0224817B2 JP 8556681 A JP8556681 A JP 8556681A JP 8556681 A JP8556681 A JP 8556681A JP H0224817 B2 JPH0224817 B2 JP H0224817B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- salt
- indoxyl
- mol
- phenylglycine
- 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.)
- Expired
Links
- PCKPVGOLPKLUHR-UHFFFAOYSA-N indoxyl Chemical group C1=CC=C2C(O)=CNC2=C1 PCKPVGOLPKLUHR-UHFFFAOYSA-N 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- NPKSPKHJBVJUKB-UHFFFAOYSA-N N-phenylglycine Chemical class OC(=O)CNC1=CC=CC=C1 NPKSPKHJBVJUKB-UHFFFAOYSA-N 0.000 claims description 11
- -1 alkali metal amide Chemical class 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 10
- 229940097275 indigo Drugs 0.000 description 10
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 10
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- CZNJCUMJHDYOHK-UHFFFAOYSA-N 2-anilinoacetic acid;potassium Chemical compound [K].OC(=O)CNC1=CC=CC=C1 CZNJCUMJHDYOHK-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- HTUCJWIGUOMFRO-UHFFFAOYSA-N 1-phenoxy-2,3-diphenylbenzene Chemical class C=1C=CC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)C=1OC1=CC=CC=C1 HTUCJWIGUOMFRO-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000003181 co-melting Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000005331 phenylglycines Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Indole Compounds (AREA)
Description
【発明の詳細な説明】
本発明は不活性な高沸点の有機溶媒存在下にＮ
−フエニルグリシン塩とアルカリ金属アミドとの
反応によるインドキシルの製造方法に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for producing nitrogen in the presence of an inert high-boiling organic solvent.
- A method for producing indoxyl by reacting a phenylglycine salt with an alkali metal amide.
インドキシルはインジゴ染料の重要な中間体で
あり、インジゴ（CI.Vat BIue １）は染料とし
て重要な化合物である。 Indoxyl is an important intermediate for indigo dyes, and indigo (CI.Vat BIue 1) is an important compound as a dye.
インジゴは1870年にはじめて合成されて以来、
種々の合成方法が知られている。KirK Othmer
著「Encyclopedia of Chemical TechnoIogy」
２版、11巻、565−567頁には約30種の合成法があ
ると記載されているが、現在工業的なインジゴの
製造法はＮ−フエニルグリシン塩を、アルカリ金
属アミドと高温でアルカリ熔融することによる閉
環反応でインドキシルを得、これを酸化するいわ
ゆる、ホイマン−ブフレーガー法が採用されてい
る。 Since indigo was first synthesized in 1870,
Various synthetic methods are known. KirK Othmer
Author "Encyclopedia of Chemical TechnoIogy"
The 2nd edition, volume 11, pages 565-567 states that there are approximately 30 synthetic methods, but the current industrial method for producing indigo is to combine N-phenylglycine salt with an alkali metal amide at high temperatures. The so-called Heuman-Buffleger method is employed, in which indoxyl is obtained through a ring-closing reaction by alkali melting, and then oxidized.
この方法は、Ｎ−フエニルグリシン塩とアルカ
リ金属アミドとの反応を大量の水酸化カリウムと
水酸化ナトリウムの混合物を、溶融反応溶媒とし
て使用して、混合物の共溶融点より若干高い210
℃付近で実施し、反応終了後は混合物溶融液中に
溶融している生成インドキシル塩を、水に排出し
て溶解したインドキシル塩水溶液を酸化してイン
ジゴを得る方法である。この方法の大きな欠点は
反応時に大量の水酸化カリウムと水酸化ナトリウ
ムを使用せねばならないことである。したがつ
て、反応終了後水で稀釈された稀薄な濃度のアル
カリ混合水溶液から、水酸化カリウムと水酸化ナ
トリウムとを回収、再利用しようとすれば水分が
なくなるまで濃縮せねばならないので、そのため
多大のエネルギーおよび装置が必要である。 This method involves the reaction of an N-phenylglycine salt with an alkali metal amide using a large amount of a mixture of potassium hydroxide and sodium hydroxide as a melting reaction solvent at a temperature slightly higher than the co-melting point of the mixture.
This is a method in which the reaction is carried out at around 100°C, and after the completion of the reaction, the produced indoxyl salt dissolved in the mixture melt is discharged into water, and the dissolved indoxyl salt aqueous solution is oxidized to obtain indigo. A major drawback of this method is that large amounts of potassium hydroxide and sodium hydroxide must be used during the reaction. Therefore, if potassium hydroxide and sodium hydroxide are to be recovered and reused from a dilute alkali mixed aqueous solution diluted with water after the reaction is completed, it must be concentrated until the water disappears, which requires a large amount of waste. energy and equipment required.
本発明者等は上記欠点を改良すべく鋭意検討の
結果本発明に到達したものである。 The present inventors have arrived at the present invention as a result of intensive studies to improve the above-mentioned drawbacks.
すなわち、本発明方法は、Ｎ−フエニルグリシ
ン塩とアルカリ金属アミドとの反応を不活性な高
沸点の有機溶媒の共存下反応させるものであり、
本方法により水酸化カリウムおよび／または水酸
化ナトリウムを全く使用する必要はなく、反応は
温和な条件下で収率よく実施できる。 That is, the method of the present invention involves reacting an N-phenylglycine salt and an alkali metal amide in the presence of an inert high-boiling organic solvent,
This method does not require the use of potassium hydroxide and/or sodium hydroxide at all, and the reaction can be carried out in good yield under mild conditions.
本発明で使用するＮ−フエニルグリシン塩とは
ナトリウム塩、カリウム塩またはナトリウム塩と
カリウム塩混合物の通常使用されているＮ−フエ
ニルグリシン塩であり本発明で使用する不活性な
高沸点有機溶媒とは、180℃以上好ましくは200℃
以上の沸点をもつものがあげられ、本反応に対し
て安定なものなら全て使用できる。通常熱媒とし
て使用されているものが特に好ましく、例えば、
エツソサーム５００（エツソスタンダード石油）
として市販されている石油系の脂肪族炭化水素系
化合物、KSKOiL−330（綜研化学）として市販
されているアルキルナフタリン系化合物、その他
トリアリルジメタン系、ジフエニール−ジフエニ
ールエーテル系、ジフエニール系、テトラリン
系、デカリン系、鉱油系など、通常入手できる熱
媒なら本発明方法の溶媒として使用できる。 The N-phenylglycine salt used in the present invention is a commonly used N-phenylglycine salt such as a sodium salt, a potassium salt, or a mixture of sodium and potassium salts, and is an inert high-boiling organic salt used in the present invention. Solvent means 180℃ or higher, preferably 200℃
Those having a boiling point higher than the above can be mentioned, and all can be used as long as they are stable for this reaction. Particularly preferred are those commonly used as heating media, for example:
Etsutherm 500 (Etsuso Standard Oil)
Petroleum-based aliphatic hydrocarbon compounds commercially available as KSKOiL-330 (Soken Chemical), alkylnaphthalene compounds commercially available as KSKOiL-330 (Soken Chemical), other triallyl dimethane compounds, diphenyl-diphenyl ether compounds, diphenyl compounds, and tetralin. Any commonly available heating medium can be used as the solvent in the method of the present invention, such as fluorine, decalin, mineral oil, and the like.
本発明方法において、高沸点有機溶媒を使用す
るのはＮ−フエニルグリシン塩とアルカリ金属ア
ミドの反応を円滑に進めるためであり、高温反応
（180−3000℃）のため、不活性有機溶媒自体の蒸
気圧が低いものを選ぶことが好ましい。通常使用
されているアルカリ溶媒は必要ないが、少量併用
してもかまわない。 In the method of the present invention, a high boiling point organic solvent is used to facilitate the reaction between N-phenylglycine salt and alkali metal amide. It is preferable to choose one with a low vapor pressure. A commonly used alkaline solvent is not necessary, but a small amount may be used in combination.
不活性有機溶媒の回収は、閉環反応終了後熔融
反応物を水に排出した場合、生成インドキシル塩
の含まれる水層と有機溶媒層に容易に分液される
ので、水層の反応物と分離後、循環再使用でき
る。本発明方法では以下のようにして実施する。 In order to recover the inert organic solvent, if the molten reaction product is discharged into water after the completion of the ring-closing reaction, it will be easily separated into an aqueous layer containing the produced indoxyl salt and an organic solvent layer, so the inert organic solvent will be separated from the reactant in the aqueous layer. After separation, it can be recycled and reused. The method of the present invention is carried out as follows.
Ｎ−フエニルグリシン塩１重量部に対し１〜
100重量部、好ましくは２〜10重量部の不活性な
高沸点の有機溶媒中に、Ｎ−フエニルグリシン塩
１モルに対してアルカリ金属アミド２〜20モル好
ましくは２〜４モルを、180゜〜300℃好ましくは
220゜〜260℃に熔融し、この熔融物中にＮ−フエ
ニルグリシン塩を添加し、１〜20時間好ましくは
１〜５時間、200〜300℃好ましくは220〜250℃を
保つて反応させる。この時発生するアンモニアガ
スは随時抜き取り反応時の圧力を０〜10Kg／cm2Ｇ
好ましくは２〜５Kg／cm2Ｇに保持して反応をおこ
なう。反応終了後生成したインドキシルを水に溶
解し、溶解液をインドキシル水層と熱媒層に分液
してインドキシルを酸化するとインジゴが得られ
る。 1 to 1 part by weight of N-phenylglycine salt
2 to 20 mol, preferably 2 to 4 mol of alkali metal amide per mol of N-phenylglycine salt in 100 parts by weight, preferably 2 to 10 parts by weight of an inert high-boiling organic solvent, 180゜~300℃ preferably
Melt at 220° to 260°C, add N-phenylglycine salt to this melt, and react by maintaining the temperature at 200 to 300°C, preferably 220 to 250°C, for 1 to 20 hours, preferably 1 to 5 hours. . The ammonia gas generated at this time is extracted at any time and the pressure during the reaction is adjusted to 0 to 10 kg/cm 2 G.
Preferably, the reaction is carried out while maintaining the pressure at 2 to 5 Kg/cm 2 G. After the reaction is completed, the indoxyl produced is dissolved in water, the solution is separated into an aqueous indoxyl layer and a heat transfer layer, and the indoxyl is oxidized to obtain indigo.
本発明の方法によれば従来公知のＮ−フエニル
グリシン塩のアルカリ熔融法に比較して混合アル
カリを全く使用しないですむので無公害および省
エネルギー省力化が可能であり工業的に有利に実
施できる。また、得られたインドキシルを酸化す
ることによつて高品質のインジゴを収率よく得る
ことができる。 According to the method of the present invention, compared to the conventional alkali melting method of N-phenylglycine salt, there is no need to use a mixed alkali at all, so pollution-free, energy-saving and labor-saving are possible, and it can be carried out industrially advantageously. . Moreover, high quality indigo can be obtained in good yield by oxidizing the obtained indoxyl.
以下、本発明の方法を実施例により具体的に説
明する。 Hereinafter, the method of the present invention will be specifically explained with reference to Examples.
実施例 １
アルキルナフタリン系熱媒KSKOiL−330（綜
研化学）142.5gとソーダアマイド26.4g（0.677モ
ル）を熔融釜に装入し撹拌しながら内温を220〜
250℃に保つた。そして撹拌を続けながら常圧で
Ｎ−フエニルグリシンカリウム31.85g（0.168モ
ル）を分割装入し、７時間で装入を終了した。そ
の後２時間常圧で250℃で熟成を行なつた。反応
が終了したら溶融釜内容物を冷水に排出し、50〜
60℃にて１時間、撹撩してインドキシル溶液を得
た。この溶解液から有機溶媒層を分液し、水層
（インドキシル層）を80℃で空気酸化した。酸化
液を別乾燥し、青色の粉末12.2g（0.0465モル）
を得た。この物質はIRスペクトル染色試験によ
り混合アルカリ中で熔融して得られたインジゴと
同等のものである事が確認された。Example 1 142.5 g of alkylnaphthalene heating medium KSKOiL-330 (Soken Chemical) and 26.4 g (0.677 mol) of soda amide were charged into a melting pot and the internal temperature was raised to 220 to 220 mol while stirring.
It was kept at 250℃. Then, 31.85 g (0.168 mol) of N-phenylglycine potassium was charged in portions at normal pressure while continuing to stir, and the charging was completed in 7 hours. Thereafter, aging was carried out at 250°C under normal pressure for 2 hours. When the reaction is finished, drain the contents of the melting pot into cold water and boil for 50~
The mixture was stirred at 60°C for 1 hour to obtain an indoxyl solution. The organic solvent layer was separated from this solution, and the aqueous layer (indoxyl layer) was air oxidized at 80°C. Separately dry the oxidizing solution to produce 12.2g (0.0465mol) of blue powder.
I got it. This material was confirmed by IR spectroscopy to be equivalent to indigo obtained by melting in mixed alkali.
実施例 ２
石油系脂肪族炭化水素系熱媒エツソサーム500
（エツソスタンダード石油）142.5gとソーダアマ
イド26.4g（0.677モル）を溶解釜に装入し実施例
１同様の操作、温度でＮ−フエニルグリシンカリ
31.85g（0.168モル）を分割装入し７時間で装入を
終了した。その後は実施例１と同様の操作を行な
いインジゴ10.1g（0.0385モル）が得られた。Example 2 Petroleum-based aliphatic hydrocarbon heat medium Etsotherm 500
(Etsuo Standard Oil) 142.5g and 26.4g (0.677mol) of soda amide were charged into a melting pot, and N-phenylglycine potassium was heated in the same manner and temperature as in Example 1.
31.85 g (0.168 mol) was charged in portions and the charging was completed in 7 hours. Thereafter, the same operation as in Example 1 was carried out to obtain 10.1 g (0.0385 mol) of indigo.
実施例 ３
アルキルナフタリン系熱媒KSKOiL330 142.5g
とソーダアマイド（0.677モル）をガス排出弁を
設置した密閉型の熔融釜に装入し撹拌しながら内
温を220〜250℃に保つた。撹拌を続けながらＮ−
フエルルグリシンカリウム31.85g（0.168モル）を
分割装入し、７時間で装入を終了した。装入中は
発生するアンモニアガスによつて常に熔融釜内圧
を3.0Kg／cm2Ｇに保つた。反応後の溶解、酸化、
乾燥処理は実施例１同様に行いインジゴ18.8g
（0.0725モル）が得られた。Example 3 Alkylnaphthalene heating medium KSKOiL330 142.5g
and soda amide (0.677 mol) were charged into a closed melting pot equipped with a gas discharge valve, and the internal temperature was maintained at 220 to 250°C while stirring. N- while continuing to stir
31.85 g (0.168 mol) of ferruglycine potassium was charged in portions, and the charging was completed in 7 hours. During charging, the internal pressure of the melting pot was always maintained at 3.0 Kg/cm 2 G by the generated ammonia gas. Dissolution after reaction, oxidation,
The drying process was carried out in the same manner as in Example 1, and 18.8g of indigo was obtained.
(0.0725 mol) was obtained.
Claims (1)
ドとの反応でインドキシルを製造する方法におい
て、180℃以上の沸点を有する不活性高沸点有機
溶媒の存在下で実施することを特徴とするインド
キシルの製造方法。1. A method for producing indoxyl by the reaction of an N-phenylglycine salt and an alkali metal amide, characterized in that the method is carried out in the presence of an inert high-boiling organic solvent having a boiling point of 180°C or higher. Production method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8556681A JPS57200362A (en) | 1981-06-05 | 1981-06-05 | Preparation of indoxyl |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8556681A JPS57200362A (en) | 1981-06-05 | 1981-06-05 | Preparation of indoxyl |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57200362A JPS57200362A (en) | 1982-12-08 |
| JPH0224817B2 true JPH0224817B2 (en) | 1990-05-30 |
Family
ID=13862356
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8556681A Granted JPS57200362A (en) | 1981-06-05 | 1981-06-05 | Preparation of indoxyl |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57200362A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SI1567492T1 (en) | 2002-11-28 | 2013-07-31 | Suven Life Sciences Limited | N-arylsulfonyl-3-aminoalkoxyindoles |
| AU2003289648A1 (en) * | 2002-12-25 | 2004-07-22 | Beijing Wisdom Yingli Pharmaceutical Technology Developing Co., Ltd. | A process for dyeing directly a textile fabric in situ |
-
1981
- 1981-06-05 JP JP8556681A patent/JPS57200362A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57200362A (en) | 1982-12-08 |
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