JP2005200381A - Method for refining crystalline aminophenols - Google Patents
Method for refining crystalline aminophenols Download PDFInfo
- Publication number
- JP2005200381A JP2005200381A JP2004010246A JP2004010246A JP2005200381A JP 2005200381 A JP2005200381 A JP 2005200381A JP 2004010246 A JP2004010246 A JP 2004010246A JP 2004010246 A JP2004010246 A JP 2004010246A JP 2005200381 A JP2005200381 A JP 2005200381A
- Authority
- JP
- Japan
- Prior art keywords
- aminophenols
- crystalline
- crystals
- ethers
- 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
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000007670 refining Methods 0.000 title claims abstract 4
- 239000013078 crystal Substances 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 238000002425 crystallisation Methods 0.000 claims abstract description 12
- 230000008025 crystallization Effects 0.000 claims abstract description 12
- 150000002170 ethers Chemical class 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 5
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 claims description 20
- 229940018563 3-aminophenol Drugs 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 238000004040 coloring Methods 0.000 description 10
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 7
- 229940018564 m-phenylenediamine Drugs 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 230000006837 decompression Effects 0.000 description 3
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- -1 aliphatic ethers Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本発明は、結晶性アミノフェノール類の精製方法に関するものである。更に詳しくは、本発明は、空気中に保存しても、経時的に着色しにくいという点で優れた効果を有する結晶性アミノフェノール類の精製方法に関するものである。 The present invention relates to a method for purifying crystalline aminophenols. More specifically, the present invention relates to a method for purifying crystalline aminophenols, which has an excellent effect in that it is difficult to color over time even when stored in air.
アミノフェノール類は、医薬、農薬、アゾ染料、酸化防止剤又は写真現像薬などの中間体等の分野に広く使用されており、産業上有用な化学製品である。アミノフェノール類の製造方法は、特許文献１等に開示されている。 Aminophenols are widely used in fields such as pharmaceuticals, agricultural chemicals, azo dyes, intermediates such as antioxidants or photographic developers, and are industrially useful chemical products. A method for producing aminophenols is disclosed in Patent Document 1 and the like.
しかしながら、従来の方法で製造したアミノフェノール類は、経時的に着色することがあるという問題点を有している（特許文献２参照）。着色までの期間は、化合物、製造条件、保存環境等に依存するが、通常数日〜数ヶ月の間に徐々に着色することが多い。 However, aminophenols produced by conventional methods have a problem that they may be colored over time (see Patent Document 2). Although the period until coloring depends on the compound, production conditions, storage environment, etc., it is usually gradually colored for several days to several months.
かかる状況において、本発明が解決しようとする課題は、空気中に保存しても、経時的に着色しにくいという点でという点で優れた効果を有する結晶性アミノフェノール類の精製方法を提供する点にある。 In such a situation, the problem to be solved by the present invention is to provide a method for purifying crystalline aminophenols, which has an excellent effect in that it is difficult to color over time even when stored in the air. In the point.
すなわち、本発明は、アミノフェノール類を晶析操作して得た結晶を濾過し、溶剤を用いて洗浄した後に、減圧操作終了まで、結晶を４０℃以下にて乾燥する工程を含む結晶性アミノフェノール類の精製方法に係るものである。 That is, the present invention relates to a crystalline amino acid comprising a step of filtering crystals obtained by crystallization operation of aminophenols, washing with a solvent, and drying the crystals at 40 ° C. or lower until the completion of the pressure reduction operation. The present invention relates to a method for purifying phenols.
本発明により、空気中に保存しても、経時的に着色しにくいという点で優れた効果を有する結晶性アミノフェノール類の精製方法を提供することができる。 INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a method for purifying crystalline aminophenols, which has an excellent effect in that it is difficult to color over time even when stored in the air.
本発明の精製方法に付されるアミノフェノール類としては、ｍ−アミノフェノール、ｐ−アミノフェノール等を例示することができる。 Examples of aminophenols subjected to the purification method of the present invention include m-aminophenol and p-aminophenol.
本発明の精製方法に付される結晶性アミノフェノール類の具体的で好ましい製造方法としては、以下の工程を含む方法をあげることができる。
工程（Ａ）：２価フェノールとアンモニアの反応工程
工程（Ｂ）：アミノフェノール類をエーテル類を溶媒とする晶析操作に付する工程
工程（Ｃ）：工程（Ｂ）後のアミノフェノール類の結晶を濾過する工程
工程（Ａ）は、２価フェノールとアンモニアの反応工程である。
As a specific and preferable method for producing crystalline aminophenols subjected to the purification method of the present invention, a method including the following steps can be mentioned.
Step (A): Reaction step of dihydric phenol and ammonia Step (B): Step of subjecting aminophenols to crystallization operation using ethers as solvents Step (C): Aminophenols after step (B) Step of filtering crystals Step (A) is a reaction step of dihydric phenol and ammonia.
工程（Ｂ）は、アミノフェノール類をエーテル類を溶媒とする晶析操作に付する工程である。エーテル類としては、例えばジブチルエーテルをあげることができる。 Step (B) is a step of subjecting aminophenols to a crystallization operation using ethers as solvents. Examples of ethers include dibutyl ether.
工程（Ｃ）は、工程（Ｂ）後のアミノフェノール類の結晶を濾過する工程である。本工程においては、減圧・加圧・遠心方法等を用いた濾過操作をあげることができる。 Step (C) is a step of filtering the aminophenol crystals after step (B). In this step, a filtration operation using a reduced pressure / pressurization / centrifugation method or the like can be given.
本発明は、アミノフェノール類を晶析操作して得た結晶を濾過し、溶剤を用いて洗浄した後に、減圧操作終了まで、結晶を４０℃以下にて乾燥する工程を含む点に最大の特徴を有する。 The present invention is characterized in that it includes a step of drying a crystal at 40 ° C. or lower until the completion of pressure reduction operation after filtering the crystal obtained by crystallization operation of aminophenols, washing it with a solvent, and then ending the pressure reduction operation. Have
晶析および洗浄に用いる溶剤の好ましい具体例として、水または水とエーテル類の混合液をあげることができる。水とエーテル類の混合液を用いる場合の水／
エーテル類の重量混合比率は１０／１〜１／１０である。
Preferable specific examples of the solvent used for crystallization and washing include water or a mixed solution of water and ethers. Water when using a mixture of water and ethers /
The weight mixing ratio of ethers is 10/1 to 1/10.
エーテル類の好ましい例として、ジブチルエーテルをあげることができる。 A preferred example of ethers is dibutyl ether.
溶剤を用いて洗浄する方法としては、例えば遠心濾過する最中に洗浄する方法がある。 As a method of washing using a solvent, for example, there is a method of washing during centrifugal filtration.
本発明においては、減圧操作終了まで、結晶を４０℃以下にて乾燥する必要がある。乾燥温度が高すぎる場合は、得られた結晶性アミノフェノール類が、空気中に保存すると着色しやすくなる場合がある。好ましい乾燥温度は４０〜２０℃である。乾燥温度が低すぎる場合は乾燥に必要な時間が長くなることがある。 In the present invention, it is necessary to dry the crystals at 40 ° C. or lower until the decompression operation is completed. When the drying temperature is too high, the obtained crystalline aminophenols may be easily colored when stored in the air. A preferable drying temperature is 40 to 20 ° C. If the drying temperature is too low, the time required for drying may increase.
乾燥方法としては、結晶を攪拌しながら加熱する方法がある。 As a drying method, there is a method of heating the crystals while stirring.
減圧操作は、大気圧から４ｋＰａＡであることが好ましい。圧力は低すぎると低い圧力を維持するための設備の費用が大きくなる場合があり、一方圧力が高すぎると乾燥温度が高くなり、得られた結晶性アミノフェノール類が、空気中に保存すると着色しやすくなる場合がある。 The pressure reducing operation is preferably from atmospheric pressure to 4 kPaA. If the pressure is too low, the cost of equipment for maintaining the low pressure may increase, while if the pressure is too high, the drying temperature will increase, and the resulting crystalline aminophenols will become colored when stored in air. May be easier to do.
次に本発明を実施例により説明する。 Next, the present invention will be described with reference to examples.
ｍ−フェニレンジアミンの濃度と着色度の関係
本件出願人は、ｍ−フェニレンジアミンの濃度と着色度の関係について特許出願をしている（特願２００３−０５０７６２号)。その要点は、下記のとおりである。
下記の工程により、結晶性アミノフェノール類の経時的着色を予測することができる。
工程（１）：結晶性アミノフェノール類の外表面を溶媒に溶解させる工程
工程（２）：工程（１）で得た溶液について、着色の原因物質を定量分析する工程
工程（１）は、結晶性アミノフェノール類の外表面を溶媒に溶解させる工程である。溶媒は、アミノフェノール類の結晶の表面のみを選択的に溶解できるものを選ぶ必要があり、脂肪族エーテル類が好ましい。工程（１）は具体的には、結晶性アミノフェノール類をその０．１〜１０重量倍の脂肪族エーテル類に常温にて０．１〜６０分間静置することで行うことができる。
工程（２）は、工程（１）で得た溶液について、着色の原因物質を定量分析する工程である。たとえば、アミノフェノール類がｍ−アミノフェノールの場合、着色の原因物質であるｍ−フェニレンジアミンを定量分析すればよい。ｍ−フェニレンジアミンを定量分析方法は、例えば、液クロマトグラフィー等を用いることができる。
工程（２）で得られた結果と予め作成しておいた着色の原因物質の濃度と経時着色の実績の相関をまとめた検量線（図１）等を使用して、着色の程度を予測すればよい。
Relationship between the concentration of m-phenylenediamine and the degree of coloring The applicant has filed a patent application regarding the relationship between the concentration of m-phenylenediamine and the degree of coloring (Japanese Patent Application No. 2003-050762). The main points are as follows.
The coloration with time of crystalline aminophenols can be predicted by the following steps.
Step (1): Step of dissolving the outer surface of crystalline aminophenols in a solvent Step (2): Step of quantitatively analyzing the causative substance of coloring in the solution obtained in Step (1) Step (1) is a step of This is a step of dissolving the outer surface of the hydrophilic aminophenol in a solvent. It is necessary to select a solvent that can selectively dissolve only the surface of aminophenol crystals, and aliphatic ethers are preferred. Specifically, the step (1) can be carried out by allowing crystalline aminophenols to stand in 0.1 to 10 times by weight of aliphatic ethers at room temperature for 0.1 to 60 minutes.
Step (2) is a step of quantitatively analyzing the causative substance of the coloration of the solution obtained in step (1). For example, when the aminophenol is m-aminophenol, m-phenylenediamine, which is a causative substance for coloring, may be quantitatively analyzed. As a quantitative analysis method of m-phenylenediamine, for example, liquid chromatography can be used.
Use the calibration curve (Figure 1) that summarizes the correlation between the results obtained in step (2) and the concentration of the causative substances that have been prepared in advance and the results of coloration over time. That's fine.
実施例１
以下の工程を含む方法により得られたｍ−アミノフェノールを用いた。
工程（Ａ）：２価フェノールとアンモニアの反応工程
工程（Ｂ）：アミノフェノール類をエーテル類を溶媒とする晶析操作に付する工程
工程（Ｃ）：工程（Ｂ）後のアミノフェノール類の結晶を濾過する工程
工程（Ｃ）で得られたｍ−アミノフェノールを晶析操作して得た結晶を濾過し、溶剤を用いて洗浄した後に、減圧操作終了まで、結晶を４０℃以下にて乾燥させた。
晶析に用いる溶剤としては水とエーテル類の混合液（ケーキに対して４重量倍のエーテル、１重量倍の水）を用いた。洗浄は、エーテルを用いて洗浄した後、水で洗浄した（ケーキに対して１重量倍のエーテル、その後１重量倍の水）。
エーテル類としては、ジブチルエーテルを用いた。溶剤を用いて洗浄する方法としては、遠心濾過する最中に洗浄する方法を用いた。乾燥方法としては、結晶を攪拌しながら加熱する方法を用いた。減圧操作は大気圧から４ｋＰａＡまでとした。その結果得られたｍ−アミノフェノールの結晶１ｇを、ｎ−ジブチルエーテル１ｍｌに溶解させて、溶媒中のｍ−フェニレンジアミンの濃度を測定したところ、１．２０７ｗｔ％であった。該ｍ−フェニレンジアミンの濃度と着色度の関係を図１に示した（詳細は、特願２００３−０５０７６２号明細書参照。）。
Example 1
The m-aminophenol obtained by the method including the following steps was used.
Step (A): Reaction step of dihydric phenol and ammonia Step (B): Step of subjecting aminophenols to crystallization operation using ethers as solvents Step (C): Aminophenols after step (B) Step of filtering crystals After crystallizing the m-aminophenol obtained in step (C), the crystals were filtered and washed with a solvent, and then the crystals were kept at 40 ° C or lower until the end of the decompression operation. Dried.
As a solvent used for crystallization, a mixed solution of water and ethers (4 times as much ether and 1 times as much water as the cake) was used. Washing was carried out with ether and then with water (1 weight ether with respect to the cake, then 1 weight water).
Dibutyl ether was used as the ether. As a method of washing using a solvent, a method of washing during centrifugal filtration was used. As a drying method, a method of heating the crystals while stirring was used. The decompression operation was performed from atmospheric pressure to 4 kPaA. 1 g of the resulting m-aminophenol crystal was dissolved in 1 ml of n-dibutyl ether, and the concentration of m-phenylenediamine in the solvent was measured and found to be 1.207 wt%. The relationship between the concentration of m-phenylenediamine and the degree of coloring is shown in FIG. 1 (for details, see Japanese Patent Application No. 2003-050762).
比較例１
ｍ−アミノフェノールを晶析操作して得た結晶を濾過し、溶剤を用いて洗浄した後に、減圧操作終了まで、結晶を５３℃にて乾燥させたとしたこと以外、実施例１と同様に行った。その結果得られたｍ−アミノフェノールの結晶１ｇを、ｎ−ジブチルエーテル１ｍｌに溶解させて、溶媒中のｍ−フェニレンジアミンの濃度を測定したところ、１．７２９ｗｔ％であった。
Comparative Example 1
Crystals obtained by crystallization of m-aminophenol were filtered, washed with a solvent, and then the same as in Example 1 except that the crystals were dried at 53 ° C. until completion of the pressure reduction operation. It was. As a result, 1 g of the resulting m-aminophenol crystal was dissolved in 1 ml of n-dibutyl ether, and the concentration of m-phenylenediamine in the solvent was measured and found to be 1.729 wt%.
Claims (6)
工程（Ａ）：２価フェノールとアンモニアの反応工程
工程（Ｂ）：アミノフェノール類をエーテル類を溶媒とする晶析操作に付する工程
工程（Ｃ）：工程（Ｂ）後のアミノフェノール類の結晶を濾過する工程 The production method according to claim 1, wherein the aminophenols subjected to the method according to claim 1 are obtained from a method comprising the following steps.
Step (A): Reaction step of dihydric phenol and ammonia Step (B): Step of subjecting aminophenols to crystallization operation using ethers as solvents Step (C): Aminophenols after step (B) Filtering the crystals
The method according to claim 1, wherein the pressure reducing operation according to claim 1 is from atmospheric pressure to 4 kPaA.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004010246A JP4442230B2 (en) | 2004-01-19 | 2004-01-19 | Method for purifying crystalline aminophenols |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004010246A JP4442230B2 (en) | 2004-01-19 | 2004-01-19 | Method for purifying crystalline aminophenols |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005200381A true JP2005200381A (en) | 2005-07-28 |
| JP4442230B2 JP4442230B2 (en) | 2010-03-31 |
Family
ID=34823032
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004010246A Expired - Lifetime JP4442230B2 (en) | 2004-01-19 | 2004-01-19 | Method for purifying crystalline aminophenols |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4442230B2 (en) |
-
2004
- 2004-01-19 JP JP2004010246A patent/JP4442230B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP4442230B2 (en) | 2010-03-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2275354C2 (en) | Methods for preparing nateglynide crystal of b-type | |
| RU2373193C2 (en) | Method of purifying mesotrione | |
| JP4442230B2 (en) | Method for purifying crystalline aminophenols | |
| CN113956274A (en) | Design and synthesis method of fluorescent probe capable of responding to viscosity and peroxynitrite change in epileptic diseases | |
| JP4545911B2 (en) | Method for producing camostat mesylate | |
| JP2017095453A (en) | High-purity fluorescein sodium | |
| EP1192224B1 (en) | Purification of aqueous dye solutions | |
| CN110372587A (en) | Salicylic acid azo 8-hydroxyquinoline and its preparation method and application | |
| JP2004284954A (en) | Method for preparing crystalline aminophenols | |
| JP3588544B2 (en) | Dye remover and method for removing dye from dye-containing water | |
| JPH09176115A (en) | Production of optically active n-benzyl-3-aminopyrrolidine | |
| JP5329867B2 (en) | Method for producing oxidation coloring compound | |
| JP2004256477A (en) | Method for predicting coloration of crystalline aminophenols with time | |
| CN110066242B (en) | Compound for detecting p-phenylenediamine and preparation method thereof | |
| EA010569B1 (en) | Process for the preparation of chirally-pure crystalline modification of nateglinide | |
| RU2276132C1 (en) | Solution for synthesis of 4-aminodiphenylamine, method for its preparing and method for synthesis of 4-aminodiphenylamine | |
| RU2668500C2 (en) | Method for producing paracetamol | |
| SU1018938A1 (en) | Process for preparing 1-methylamino or 1-n-acetyl-methylamino-4-aminoanthraquinones | |
| JP2002020367A (en) | Method for purifying homocystine | |
| JP2009029717A (en) | Method for producing epalrestat | |
| CN106866519B (en) | A kind of roflumilast crystal-form compound and preparation method thereof | |
| SU1721481A1 (en) | Method of quantifying remantadine | |
| JPH11228546A (en) | Production of optically active 2-(n-tert-butylcarbamoyl) piperazine | |
| JPH0827390A (en) | Method for purifying vat dye and intermediate thereof | |
| JP2012214419A (en) | Method of producing oxidation color developing compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20061023 |
|
| RD05 | Notification of revocation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7425 Effective date: 20080130 |
|
| RD05 | Notification of revocation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7425 Effective date: 20080513 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20090914 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090929 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20091127 |
|
| TRDD | Decision of grant or rejection written | ||
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20091130 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20091222 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20100104 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 4442230 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130122 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130122 Year of fee payment: 3 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| EXPY | Cancellation because of completion of term |