JPS63216861A - Production of 4-hydroxyindolines - Google Patents
Production of 4-hydroxyindolinesInfo
- Publication number
- JPS63216861A JPS63216861A JP4870287A JP4870287A JPS63216861A JP S63216861 A JPS63216861 A JP S63216861A JP 4870287 A JP4870287 A JP 4870287A JP 4870287 A JP4870287 A JP 4870287A JP S63216861 A JPS63216861 A JP S63216861A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- diazotization
- sulfuric acid
- acid
- aminoindolines
- 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 abstract description 5
- OWWAUBQOFLVUMS-UHFFFAOYSA-N 2,3-dihydro-1h-indol-4-ol Chemical class OC1=CC=CC2=C1CCN2 OWWAUBQOFLVUMS-UHFFFAOYSA-N 0.000 title description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 20
- 238000006193 diazotization reaction Methods 0.000 abstract description 13
- 150000001875 compounds Chemical class 0.000 abstract description 9
- MXXKDNVTCQXXHU-UHFFFAOYSA-N 2,3-dihydro-1h-indol-4-amine Chemical class NC1=CC=CC2=C1CCN2 MXXKDNVTCQXXHU-UHFFFAOYSA-N 0.000 abstract description 8
- NLMQHXUGJIAKTH-UHFFFAOYSA-N 4-hydroxyindole Chemical class OC1=CC=CC2=C1C=CN2 NLMQHXUGJIAKTH-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- RXQNKKRGJJRMKD-UHFFFAOYSA-N 5-bromo-2-methylaniline Chemical compound CC1=CC=C(Br)C=C1N RXQNKKRGJJRMKD-UHFFFAOYSA-N 0.000 abstract description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 abstract description 2
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 125000003545 alkoxy group Chemical group 0.000 abstract description 2
- 229960003116 amyl nitrite Drugs 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000011707 mineral Substances 0.000 abstract description 2
- CSDTZUBPSYWZDX-UHFFFAOYSA-N n-pentyl nitrite Chemical compound CCCCCON=O CSDTZUBPSYWZDX-UHFFFAOYSA-N 0.000 abstract description 2
- 150000007524 organic acids Chemical class 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- 238000009283 thermal hydrolysis Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 10
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000004982 aromatic amines Chemical class 0.000 description 3
- 239000012954 diazonium Substances 0.000 description 3
- 150000001989 diazonium salts Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 2
- -1 naphthylamine Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- PMZDQRJGMBOQBF-UHFFFAOYSA-N quinolin-4-ol Chemical compound C1=CC=C2C(O)=CC=NC2=C1 PMZDQRJGMBOQBF-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 125000003387 indolinyl group Chemical group N1(CCC2=CC=CC=C12)* 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical group 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate 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４−ハイドロオキシインドリン類の製造法に関
する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for producing 4-hydroxyindolines.
従来の技術
４−ハイドロオキシインドリン類は脱水素反応により４
−ハイドロオキシインドール類に導かれるものであり医
薬、農薬用の重要な中間体である。Conventional technology 4-Hydroxyindolines are converted into 4 by dehydrogenation reaction.
-It is derived from hydroxyindoles and is an important intermediate for pharmaceuticals and agricultural chemicals.
４−ハイドロオキシインドリン類の合成法は従来あまり
知られておらず、わずかに特開昭５９−６５，０７２に
おいて、４−ハイドロオキシインドールからの合成法が
開示されているにすム存注下に脱アンモニア反応する（
プッハラー反応）方法、アミン基をジアゾイヒした後、
水の存在下に加熱加水分解するいわゆるジアゾ分解ｍ法
等が知られている。しかしながらこれらのうち前者はナ
フチルアミンのような特別な芳香族アミンの場合には優
れた方法であるが汎用性がなく４−アミノインドリン類
に適用することは出来ない。又、後者は種々の芳香族ア
ミンについて行われるが、一般に多くの色素成分の副成
を伴い好収率に目的物を得ることは難しい。殊に４−ア
ミノインドリン類のように分子ンの場合はこのような副
性成物の生成の他にジアゾ化時に２級アミン基がニトロ
フ化反応を起こしそれが為にアミン基（−Ｎ）Ｔｌｚ）
のジアゾ化がうけにくくなるという傾向がある。The method for synthesizing 4-hydroxyindolines is not well known, and only a method for synthesizing from 4-hydroxyindole is disclosed in JP-A-59-65072. Ammonia removal reaction (
Puchler reaction) method, after diazoising the amine group,
The so-called diazolysis method, which involves heating and hydrolysis in the presence of water, is known. However, although the former is an excellent method for special aromatic amines such as naphthylamine, it is not versatile and cannot be applied to 4-aminoindolines. Although the latter method is carried out using various aromatic amines, it is generally difficult to obtain the desired product in a good yield due to the formation of many dye components as by-products. In particular, in the case of molecules such as 4-aminoindolines, in addition to the formation of such by-products, the secondary amine group undergoes a nitrophation reaction during diazotization, which causes the amine group (-N) to form. Tlz)
tends to be less susceptible to diazotization.
発明が解決しようとする問題点
純度のだかい４−ハイドロオキシインドリン類を高収率
で製造する方法の確立が望まれている。Problems to be Solved by the Invention It is desired to establish a method for producing 4-hydroxyindolines of high purity in high yield.
問題点を解決する為の手段
本発明者らは前記したような問題点を解決すべく鋭意研
究を重ねた結果、意外にもインドリン環の２級アミノ基
を保護することなく４−アミノインドリン類をジアゾ化
し次いでジアゾ分解することによって好収率で目的とす
る４−・・イドロオキシインドリン類が得られることを
見い出し、本発明に至った。即ち、本発明は式（１）（
式（１）においてＸは水素原子、ニトロ基、水酸基、Ｃ
Ｉ〜４のアルコキシ基又はノ・ロゲン原子を表す）
で示される４−アミノインドリン類をジアゾ化し次いで
加熱することを特徴とする式（２）（式（２）において
Ｘは前記と同じ意味を表す）で示される４−ノ・イドロ
オキシインドリン類の製造法を提供する。Means for Solving the Problems The present inventors have conducted intensive research to solve the above-mentioned problems, and as a result, surprisingly, 4-aminoindolines were prepared without protecting the secondary amino group of the indoline ring. It has been discovered that the desired 4-... idroxyindolines can be obtained in good yields by diazotizing and then diazolyzing, leading to the present invention. That is, the present invention provides formula (1) (
In formula (1), X is a hydrogen atom, a nitro group, a hydroxyl group, a C
Formula (2) is characterized by diazotizing and then heating 4-aminoindolines represented by I to 4 (representing an alkoxy group or a norogen atom) (in formula (2), X has the same meaning as above). The present invention provides a method for producing 4-hydrooxiindolines represented by the following formula.
本発明の方法において原料として用いられる式（１）の
化合物の具体例としては次のものが挙げられる。Specific examples of the compound of formula (1) used as a raw material in the method of the present invention include the following.
式（１）の４−アミノインドリン類のジアゾ化は芳香族
アミン類のジアゾ化に通常用いられる方法によって行う
ことが出来る。例えば鉱酸、有機酸又はこれらの混合物
中で式（１）で示される化合物に亜硝酸塩の金属塩、ニ
トロシル硫酸、亜硝酸アミルなとのジアゾ化試剤を当モ
ル−若干過剰モルを反応させる（ジアゾ化）ことにより
行われる。ジアゾ化における反応温度は通常−１０〜５
０℃好ましくは０〜１０℃、同じく灰中で行われること
から硫酸水溶液中でジアゾ化するのが好ましい。ジアゾ
化によってえられたジアゾニウム塩は単離あるいはその
ままで次の加水分解反応にかけられる。又必要ならジア
ゾ化終了後、スルフアミン酸、尿素等を加えて未反応の
亜硝酸イオンを分解してから用いる。Diazotization of the 4-aminoindoline of formula (1) can be carried out by a method commonly used for diazotization of aromatic amines. For example, the compound represented by formula (1) is reacted with a diazotization reagent such as a metal salt of nitrite, nitrosyl sulfuric acid, or amyl nitrite in an equimolar amount to a slight excess molar amount of the compound represented by formula (1) in a mineral acid, an organic acid, or a mixture thereof ( diazotization). The reaction temperature in diazotization is usually -10 to 5
Diazotization is preferably carried out at 0°C, preferably from 0 to 10°C, in an aqueous sulfuric acid solution since it is also carried out in ash. The diazonium salt obtained by diazotization is isolated or directly subjected to the next hydrolysis reaction. If necessary, after diazotization is completed, sulfamic acid, urea, etc. are added to decompose unreacted nitrite ions before use.
次に前記のようにして得られた式（１）で示される化合
物のジアゾニウム塩の加水分解は硫酸水溶液中で行われ
る。硫酸濃度は加水分解反応の収率に大きく影響を及ぼ
すため重要な要素であり重１にパーセントで４０〜８０
％より好ましくは５０〜７０％で行うのが良い。文相い
る硫酸水溶液は反応基質に対して２〜２０倍より好まし
くは５〜１０倍（重量比）である。又、反応媒体として
有機溶媒を共存させ均−或いは不均一系で行っても良い
。加水分解における反応温度は４０〜１５０℃、より好
ましくは５０〜ｌＯＯ℃で行うのが良い。反応時間は、
硫酸濃度、反応温度によって変化するが大体２〜４０時
間である。加水分解が終了したら、反応液を弱アルカリ
−弱酸性に調整してから抽出・沖過等通常の操作を行う
ことにより目的物を単離することが出来る。得られた目
的化合物は所望によりカラムクロマトグラフィーで分離
精製したり、酢酸エチル、ジクロルメタン等の有機溶媒
で再結晶してより純度の高い目的化合物を得ることも出
来る。Next, the diazonium salt of the compound represented by formula (1) obtained as described above is hydrolyzed in an aqueous sulfuric acid solution. The sulfuric acid concentration is an important factor because it greatly affects the yield of the hydrolysis reaction, and it is 40 to 80% by weight.
%, more preferably 50 to 70%. The amount of the sulfuric acid aqueous solution used is 2 to 20 times, preferably 5 to 10 times (weight ratio) to the reaction substrate. Alternatively, the reaction may be carried out in a homogeneous or heterogeneous system in the presence of an organic solvent as a reaction medium. The reaction temperature in hydrolysis is preferably 40 to 150°C, more preferably 50 to 100°C. The reaction time is
Although it varies depending on the sulfuric acid concentration and reaction temperature, it is approximately 2 to 40 hours. When the hydrolysis is completed, the target product can be isolated by adjusting the reaction solution to be weakly alkaline or weakly acidic and then performing conventional operations such as extraction and filtration. The obtained target compound can be separated and purified by column chromatography, if desired, or recrystallized from an organic solvent such as ethyl acetate or dichloromethane to obtain a higher purity target compound.
実施例 実施例によって本発明を更に詳細に説明する。Example The present invention will be explained in more detail by way of Examples.
実施例１゜
反応器に６５ ｗｔ／ｗｔ％硫酸水溶液１１ｇと４−ア
ミノインドリンＩＩＩＩＴとを加え、かきまぜて４−ア
ミノインドリンを溶解する。これに４ ｗｔ ／て４０
分を要して滴下し、同温で１０時間かきまぜた。その後
スルフアミン酸１１．３１Ｎ、を加えさらに１時間かき
まぜた。これによって得たジアゾニウム塩溶液（硫酸濃
度５７重量％）を６５〜７５０Ｃに・１時間加熱し加水
分解反応を行った。冷却後反応液が中性を呈するまで１
０ ｗｔ／ｖｏ１％水酸化ナトリウム水溶液を加え、次
に酢酸エチルで抽出し有機層を無水芒硝で乾燥した後、
酢酸エチルを留去した。侭査をシリカゲルカラムを用い
、酢酸エチル−〇−ヘキサン溶剤で分離精製することに
より４−ハイドロオキシインドリン８６．４１Ｔ１ｇ（
収率７６．９％、ｍ、ｐ、ｌ ３９−１４０’Ｃ）を得
た。Example 1 11 g of a 65 wt/wt% aqueous sulfuric acid solution and 4-aminoindoline IIIT are added to a reactor and stirred to dissolve the 4-aminoindoline. 4 wt/te 40 for this
The mixture was added dropwise over several minutes and stirred at the same temperature for 10 hours. Thereafter, 11.31N of sulfamic acid was added and stirred for an additional hour. The diazonium salt solution thus obtained (sulfuric acid concentration: 57% by weight) was heated at 65 to 750C for 1 hour to carry out a hydrolysis reaction. 1 until the reaction solution becomes neutral after cooling.
After adding 0 wt/vo 1% aqueous sodium hydroxide solution and then extracting with ethyl acetate and drying the organic layer with anhydrous sodium sulfate,
Ethyl acetate was distilled off. The sample was separated and purified using a silica gel column with an ethyl acetate-〇-hexane solvent, yielding 86.41 T1g of 4-hydroxyindoline (
A yield of 76.9%, m, p, l 39-140'C) was obtained.
実施例２〜５゜
実施例１において加水分解時の硫酸濃度（５７重量％）
を第１表に示される濃度に水又は硫酸によって調整する
以外は実施例１と同様に反応を行って４−ハイドロオキ
シキノリンを同表に示される収率で得た。Examples 2 to 5゜Sulfuric acid concentration during hydrolysis in Example 1 (57% by weight)
The reaction was carried out in the same manner as in Example 1, except that the concentration of 4-hydroxyquinoline was adjusted to the concentration shown in Table 1 with water or sulfuric acid, and 4-hydroxyquinoline was obtained in the yield shown in Table 1.
第 １ 表
実施例６〜１３゜
第２表の■欄に示される原料化合物を用いて、同表に示
されるジアゾ化条件、加水分解条件によってｎ欄に示さ
れる目的化合物を得た。その時の収率な１ｍ欄に示した
。Table 1 Examples 6 to 13 Using the starting compounds shown in column 2 of Table 2, the target compounds shown in column n were obtained under the diazotization conditions and hydrolysis conditions shown in the same table. The yield at that time is shown in the 1m column.
発明の効果Effect of the invention
Claims (1)
Ｃ＿１＿〜＿４のアルコキシ基又はハロゲン原子を表す
） で示される４−アミノインドリン類をジアゾ化し次いで
加熱することを特徴とする式（２）▲数式、化学式、表
等があります▼（２） （式（２）においてＸは前記と同じ意味を表す）で示さ
れる４−ハイドロオキシインドリン類の製造法[Claims] 1 Formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) (In formula (1), X is a hydrogen atom, a nitro group, a hydroxyl group,
Formula (2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(2) (Formula (2), X represents the same meaning as above)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4870287A JPS63216861A (en) | 1987-03-05 | 1987-03-05 | Production of 4-hydroxyindolines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4870287A JPS63216861A (en) | 1987-03-05 | 1987-03-05 | Production of 4-hydroxyindolines |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63216861A true JPS63216861A (en) | 1988-09-09 |
Family
ID=12810643
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4870287A Pending JPS63216861A (en) | 1987-03-05 | 1987-03-05 | Production of 4-hydroxyindolines |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63216861A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2760012A1 (en) * | 1997-02-26 | 1998-08-28 | Oreal | COMPOSITIONS FOR DYEING KERATINIC FIBERS CONTAINING PARA-AMINOPHENOLS, DYEING METHOD, NOVEL PARA-AMINOPHENOLS AND PREPARING METHOD THEREOF |
| US6673122B1 (en) | 1997-02-26 | 2004-01-06 | L'oréal | Compositions for dyeing keratin fibers containing para-aminophenols, dyeing process, novel para-aminophenols and process for their preparation |
-
1987
- 1987-03-05 JP JP4870287A patent/JPS63216861A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2760012A1 (en) * | 1997-02-26 | 1998-08-28 | Oreal | COMPOSITIONS FOR DYEING KERATINIC FIBERS CONTAINING PARA-AMINOPHENOLS, DYEING METHOD, NOVEL PARA-AMINOPHENOLS AND PREPARING METHOD THEREOF |
| EP0861835A1 (en) * | 1997-02-26 | 1998-09-02 | L'oreal | Para-aminophenols containing compositions for dyeing of keratin fibres, dyeing process, para-aminophenols and a method for their preparation |
| US6203580B1 (en) * | 1997-02-26 | 2001-03-20 | L'oreal | Compositions for dyeing keratin fibers containing para-aminophenols, dyeing process, and para -aminophenols |
| US6673122B1 (en) | 1997-02-26 | 2004-01-06 | L'oréal | Compositions for dyeing keratin fibers containing para-aminophenols, dyeing process, novel para-aminophenols and process for their preparation |
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