JPH0912520A - Production of n-methyl tertiary amine - Google Patents
Production of n-methyl tertiary amineInfo
- Publication number
- JPH0912520A JPH0912520A JP7158906A JP15890695A JPH0912520A JP H0912520 A JPH0912520 A JP H0912520A JP 7158906 A JP7158906 A JP 7158906A JP 15890695 A JP15890695 A JP 15890695A JP H0912520 A JPH0912520 A JP H0912520A
- Authority
- JP
- Japan
- Prior art keywords
- amine
- formula
- acid
- general formula
- represented
- 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
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
【０００１】[0001]
【産業上の利用分野】本発明は界面活性剤、乳化剤、分
散剤、防錆剤、殺菌剤、柔軟剤、染料、ポリマー等の製
造原料として有用な、Ｎ−メチル第３級アミンの製造方
法に関する。FIELD OF THE INVENTION The present invention relates to a method for producing an N-methyl tertiary amine useful as a raw material for producing a surfactant, an emulsifier, a dispersant, a rust preventive, a bactericide, a softener, a dye, a polymer and the like. Regarding
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】アミン
を還元メチル化してＮ−メチル化アミンを得る方法とし
ては、例えば特開平２−２４３６５４号公報に、ニッケ
ル触媒等の還元メチル化触媒を用いて第１級アミンを還
元メチル化して該当する第３級アミンを得る製造方法が
開示されている。しかし、この還元メチル化反応では、
反応率がなお十分に高くなく、目的とする物質以外に原
料などが製品中に存在すると、各用途における性能の低
下につながる場合がある。2. Description of the Related Art As a method for reductively methylating an amine to obtain an N-methylated amine, a reductive methylation catalyst such as a nickel catalyst is used in JP-A-2-243654. A method for producing a corresponding tertiary amine by reductively methylating a primary amine is disclosed. However, in this reductive methylation reaction,
If the reaction rate is not sufficiently high and raw materials other than the target substance are present in the product, the performance in each application may be deteriorated.
【０００３】従って、本発明の目的は、Ｎ−メチル第３
級アミンを高収率で得ることができる製造方法を提供す
ることにある。Therefore, an object of the present invention is the N-methyl tertiary
It is an object of the present invention to provide a method for producing a primary amine in high yield.
【０００４】[0004]
【課題を解決するための手段】本発明者らは上記課題を
解決するために鋭意検討の結果、第２級アミンを還元メ
チル化してＮ−メチル第３級アミンを得る際に、低級脂
肪酸存在下で反応を行うことにより、上記目的を達成し
うることを見出し、本発明を完成するに至った。即ち、
本発明は、一般式（ＩＩ）As a result of intensive studies to solve the above problems, the present inventors have found that when a secondary amine is reductively methylated to obtain an N-methyl tertiary amine, a lower fatty acid is present. It was found that the above object can be achieved by carrying out the reaction under the conditions described above, and the present invention has been completed. That is,
The present invention has the general formula (II)
【０００５】[0005]
【化３】 Embedded image
【０００６】〔式中、 Ｒは炭素数７〜21のアルキル基
又はヒドロキシアルキル基を示し、ｍ及びｎは同一又は
異なって１〜６の整数を示す。〕で表される第２級アミ
ンを、ホルムアルデヒド及び水素化触媒の存在下で還元
メチル化し、一般式（Ｉ）[In the formula, R represents an alkyl group having 7 to 21 carbon atoms or a hydroxyalkyl group, and m and n are the same or different and each represents an integer of 1 to 6. ] The secondary amine represented by the formula (I) is reductively methylated in the presence of formaldehyde and a hydrogenation catalyst.
【０００７】[0007]
【化４】 Embedded image
【０００８】〔式中、 R, ｍ及びｎは前記と同様の意味
を示す。〕で表されるＮ−メチル第３級アミンを製造す
るに際し、一般式(III) R'COOH (III) 〔式中、R'は H又は炭素数１〜７のアルキル基もしくは
ヒドロキシアルキル基を示す。〕で表される低級脂肪酸
の存在下に還元メチル化を行うことを特徴とする、Ｎ−
メチル第３級アミンの製造方法を提供するものである。[In the formula, R, m and n have the same meanings as described above. ] In producing the N-methyl tertiary amine represented by the following general formula (III) R'COOH (III) [In the formula, R'is H or an alkyl group having 1 to 7 carbon atoms or a hydroxyalkyl group. Show. ] Reductive methylation is performed in the presence of a lower fatty acid represented by
A method for producing a methyl tertiary amine is provided.
【０００９】本発明で使用される一般式（II）で表され
る第２級アミンにおいて、R は炭素数７〜21のアルキル
基又はヒドロキシアルキル基を示すが、炭素数11〜19の
アルキル基が好ましい。また、ｍ及びｎは同一又は異な
って１〜６の整数を示すが、好ましくは１〜３の整数で
あり、特に好ましくは２である。一般式（II）で表され
る第２級アミンの具体例としては、例えば、Ｎ−（２−
ヒドロキシエチル）−Ｎ−（２−ステアロイルアミノエ
チル）アミン、Ｎ−（２−ヒドロキシエチル）−Ｎ−
（２−パルミトイルアミノエチル）アミン、Ｎ−（３−
ヒドロキシプロピル）−Ｎ−（２−ステアロイルアミノ
エチル）アミン、Ｎ−（３−ヒドロキシプロピル）−Ｎ
−（２−パルミトイルアミノエチル）アミン、Ｎ−（２
−ヒドロキシエチル）−Ｎ−（３−ステアロイルアミノ
プロピル）アミン、Ｎ−（２−ヒドロキシエチル）−Ｎ
−（３−パルミトイルアミノプロピル）アミン、Ｎ−
（３−ヒドロキシプロピル）−Ｎ−（３−ステアロイル
アミノプロピル）アミン、Ｎ−（３−ヒドロキシプロピ
ル）−Ｎ−（３−パルミトイルアミノプロピル）アミン
等が挙げられる。In the secondary amine represented by the general formula (II) used in the present invention, R represents an alkyl group having 7 to 21 carbon atoms or a hydroxyalkyl group, and an alkyl group having 11 to 19 carbon atoms. Is preferred. Further, m and n are the same or different and represent an integer of 1 to 6, preferably an integer of 1 to 3, and particularly preferably 2. Specific examples of the secondary amine represented by the general formula (II) include N- (2-
Hydroxyethyl) -N- (2-stearoylaminoethyl) amine, N- (2-hydroxyethyl) -N-
(2-palmitoylaminoethyl) amine, N- (3-
Hydroxypropyl) -N- (2-stearoylaminoethyl) amine, N- (3-hydroxypropyl) -N
-(2-palmitoylaminoethyl) amine, N- (2
-Hydroxyethyl) -N- (3-stearoylaminopropyl) amine, N- (2-hydroxyethyl) -N
-(3-palmitoylaminopropyl) amine, N-
(3-Hydroxypropyl) -N- (3-stearoylaminopropyl) amine, N- (3-hydroxypropyl) -N- (3-palmitoylaminopropyl) amine and the like can be mentioned.
【００１０】本発明で用いられるホルムアミドとして
は、ホルムアルデヒドそれ自体以外に、例えば、トリオ
キサン及びパラ−ホルムアルデヒドのような、使用され
る反応条件下で分解してホルムアルデヒドとなる物質を
用いてもよい。またホルムアルデヒドは、ホルムアルデ
ヒド水溶液（ホルマリン）又はホルムアルデヒドメタノ
ール溶液として用いてもよい。溶液中のホルムアルデヒ
ド濃度は30〜60重量％が好ましく、35〜37重量％ホルム
アルデヒド水溶液として用いるのが特に好ましい。用い
られるホルムアルデヒドの量は、一般式（II）で表され
る第２級アミンに対して少なくとも等モル量であり、1.
0 〜 1.2倍モルの範囲が好ましい。As the formamide used in the present invention, other than formaldehyde itself, substances such as trioxane and para-formaldehyde which decompose to formaldehyde under the reaction conditions used may be used. Further, formaldehyde may be used as an aqueous formaldehyde solution (formalin) or a formaldehyde methanol solution. The formaldehyde concentration in the solution is preferably 30 to 60% by weight, and particularly preferably 35 to 37% by weight as an aqueous formaldehyde solution. The amount of formaldehyde used is at least an equimolar amount with respect to the secondary amine represented by the general formula (II), and 1.
The range of 0 to 1.2 times mol is preferable.
【００１１】本発明で用いられる水素化触媒としては、
ニッケル、ラネーニッケル、ラネーコバルト白金黒、酸
化白金、パラジウム、パラジウム／活性炭、パラジウム
黒など一般に用いられる水素化触媒のいずれを用いても
良いが、ラネーニッケルを用いるのが好ましい。なお、
これらを活性炭、シリカ、アルミナ、活性白土等各種担
体に担持させたものを用いても良い。水素化触媒の添加
量は、一般式（II）で表される第２級アミンに対して
0.1〜10重量％が好ましく、更に好ましくは１〜５重量
％である。The hydrogenation catalyst used in the present invention includes:
Any commonly used hydrogenation catalyst such as nickel, Raney nickel, Raney cobalt platinum black, platinum oxide, palladium, palladium / activated carbon, and palladium black may be used, but Raney nickel is preferably used. In addition,
What carried these on various carriers, such as activated carbon, silica, alumina, and activated clay, may be used. The amount of hydrogenation catalyst added is based on the secondary amine represented by the general formula (II).
It is preferably 0.1 to 10% by weight, more preferably 1 to 5% by weight.
【００１２】本発明で用いられる一般式(III) で表され
る低級脂肪酸としては、蟻酸、酢酸、プロピオン酸、酪
酸、吉草酸、カプロン酸、カプリル酸、グリコール酸等
が挙げられ、好ましくは蟻酸、酢酸、プロピオン酸、酪
酸であり、特に好ましくは酢酸である。一般式(III) で
表される低級脂肪酸の添加量は、一般式（II) で表され
る第２級アミンに対し、 0.1〜10重量％が好ましく、更
に好ましくは 0.5〜５重量％である。Examples of the lower fatty acid represented by the general formula (III) used in the present invention include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid and glycolic acid, and preferably formic acid. , Acetic acid, propionic acid, and butyric acid, and particularly preferably acetic acid. The amount of the lower fatty acid represented by the general formula (III) added is preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight, based on the secondary amine represented by the general formula (II). .
【００１３】本発明において、還元メチル化の温度は50
〜 200℃が好ましく、更に好ましくは80〜 150℃であ
る。水素圧は５〜 100kg/cm2Ｇ（ゲージ）が好ましく、
10〜30kg/cm2Ｇ（ゲージ）が更に好ましい。還元メチル
化を行う時間は、およそ２〜15時間程度である。還元メ
チル化を行った後、通常の方法で触媒を濾過し、溶媒を
留去することにより、高純度の一般式（Ｉ）で表される
Ｎ−メチル第３級アミンを高収率で得ることができる。In the present invention, the temperature of reductive methylation is 50.
~ 200 ° C is preferable, and more preferably 80-150 ° C. The hydrogen pressure is preferably 5 to 100 kg / cm 2 G (gauge),
More preferably, it is 10 to 30 kg / cm 2 G (gauge). The time for performing the reductive methylation is about 2 to 15 hours. After performing the reductive methylation, the catalyst is filtered by a usual method and the solvent is distilled off to obtain a highly pure N-methyl tertiary amine represented by the general formula (I) in a high yield. be able to.
【００１４】[0014]
【実施例】以下、実施例により本発明を更に詳細に説明
するが、本発明はこれらの実施例に限定されるものでは
ない。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
【００１５】実施例１ １リットルオートクレーブに、Ｎ−（２−ヒドロキシエ
チル）−Ｎ−（２−ステアロイルアミノエチル）アミン
250ｇ、50％含水ラネーニッケル12ｇ、酢酸1.6ｇを入
れ、密閉した。オートクレーブ内を窒素、水素で順次置
換した後、反応系内の圧力を15kg/cm2にして 110℃まで
昇温した。圧入ポンプを用いて、37％ホルムアルデヒド
水溶液60ｇを約５分かけて圧入した。その後その状態で
８時間反応を進行させた。反応後はオートクレーブから
内容物を取り出し、定法によって触媒濾過を行い、水分
を留去して、Ｎ−メチル−Ｎ−（２−ヒドロキシエチ
ル）−Ｎ−（２−ステアロイルアミノエチル）アミンを
得た。Example 1 A 1-liter autoclave was charged with N- (2-hydroxyethyl) -N- (2-stearoylaminoethyl) amine.
250 g, 50% water-containing Raney nickel 12 g, and acetic acid 1.6 g were put and sealed. After the inside of the autoclave was sequentially replaced with nitrogen and hydrogen, the pressure inside the reaction system was set to 15 kg / cm 2 and the temperature was raised to 110 ° C. Using a press-fitting pump, 60 g of 37% aqueous formaldehyde solution was press-fitted over about 5 minutes. Then, the reaction was allowed to proceed for 8 hours in that state. After the reaction, the content was taken out from the autoclave, the catalyst was filtered by a conventional method, and water was distilled off to obtain N-methyl-N- (2-hydroxyethyl) -N- (2-stearoylaminoethyl) amine. .
【００１６】比較例１ 酢酸を用いずに実施例１と同じ操作を行って、Ｎ−メチ
ル−Ｎ−（２−ヒドロキシエチル）−Ｎ−（２−ステア
ロイルアミノエチル）アミンを得た。Comparative Example 1 N-Methyl-N- (2-hydroxyethyl) -N- (2-stearoylaminoethyl) amine was obtained by performing the same operation as in Example 1 without using acetic acid.
【００１７】実施例２ Ｎ−（２−ヒドロキシエチル）−Ｎ−（２−ステアロイ
ルアミノエチル）アミンの代わりにＮ−（２−ヒドロキ
シエチル）−Ｎ−（２−パルミトイルアミノエチル）ア
ミンを用いて実施例１と同様の操作を行って、Ｎ−メチ
ル−Ｎ−（２−ヒドロキシエチル）−Ｎ−（２−パルミ
トイルアミノエチル）アミンを得た。Example 2 N- (2-hydroxyethyl) -N- (2-palmitoylaminoethyl) amine was used in place of N- (2-hydroxyethyl) -N- (2-stearoylaminoethyl) amine. The same operation as in Example 1 was performed to obtain N-methyl-N- (2-hydroxyethyl) -N- (2-palmitoylaminoethyl) amine.
【００１８】比較例２ 酢酸を用いずに実施例２と同じ操作を行って、Ｎ−メチ
ル−Ｎ−（２−ヒドロキシエチル）−Ｎ−（２−パルミ
トイルアミノエチル）アミンを得た。Comparative Example 2 The same operation as in Example 2 was carried out without using acetic acid to obtain N-methyl-N- (2-hydroxyethyl) -N- (2-palmitoylaminoethyl) amine.
【００１９】実施例３〜５ 酢酸の代わりに表１に示す各種低級脂肪酸を用いて実施
例１と同じ操作を行って、Ｎ−メチル−Ｎ−（２−ヒド
ロキシエチル）−Ｎ−（２−ステアロイルアミノエチ
ル）アミンを得た。Examples 3 to 5 N-Methyl-N- (2-hydroxyethyl) -N- (2-) was used in the same manner as in Example 1 except that various lower fatty acids shown in Table 1 were used instead of acetic acid. Stearoylaminoethyl) amine was obtained.
【００２０】実施例１〜５及び比較例１〜２の反応原料
及び反応結果をまとめて表１に示す。The reaction raw materials and reaction results of Examples 1 to 5 and Comparative Examples 1 and 2 are summarized in Table 1.
【００２１】[0021]
【表１】 [Table 1]
【００２２】注） *1 化合物IV：Ｎ−（２−ヒドロキシエチル）−Ｎ−
（２−ステアロイルアミノエチル）アミン *2 化合物Ｖ：Ｎ−（２−ヒドロキシエチル）−Ｎ−
（２−パルミトイルアミノエチル）アミン *3 分析方法：ガスクロマトグラフィーにて分析Note) * 1 Compound IV: N- (2-hydroxyethyl) -N-
(2-Stearoylaminoethyl) amine * 2 Compound V: N- (2-hydroxyethyl) -N-
(2-palmitoylaminoethyl) amine * 3 Analytical method: Analyzed by gas chromatography
【００２３】[0023]
【発明の効果】本発明によれば、界面活性剤、乳化剤、
分散剤、防錆剤、殺菌剤、柔軟剤、染料、ポリマー等の
製造原料として有用な、Ｎ−メチル第３級アミンを高収
率で合成できる。According to the present invention, a surfactant, an emulsifier,
N-methyl tertiary amine useful as a raw material for manufacturing dispersants, rust preventives, bactericides, softeners, dyes, polymers and the like can be synthesized in high yield.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 外谷 孝四郎 和歌山県和歌山市湊1334 花王株式会社研 究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Koshiro Sotoya 1334 Minato Minato, Wakayama, Wakayama Kao Research Laboratory
Claims (3)
アルキル基を示し、ｍ及びｎは同一又は異なって１〜６
の整数を示す。〕で表される第２級アミンを、ホルムア
ルデヒド及び水素化触媒の存在下で還元メチル化し、一
般式（Ｉ） 【化２】 〔式中、 R, ｍ及びｎは前記と同様の意味を示す。〕で
表されるＮ−メチル第３級アミンを製造するに際し、一
般式(III) R'COOH (III) 〔式中、R'は H又は炭素数１〜７のアルキル基もしくは
ヒドロキシアルキル基を示す。〕で表される低級脂肪酸
の存在下に還元メチル化を行うことを特徴とする、Ｎ−
メチル第３級アミンの製造方法。1. A compound represented by the general formula (II): [In the formula, R represents an alkyl group having 7 to 21 carbon atoms or a hydroxyalkyl group, and m and n are the same or different and are 1 to 6
Indicates an integer. ] The secondary amine represented by the following formula is reductively methylated in the presence of formaldehyde and a hydrogenation catalyst to give a compound represented by the general formula (I): [In the formula, R, m and n have the same meanings as described above. ] In producing the N-methyl tertiary amine represented by the following general formula (III) R'COOH (III) [In the formula, R'is H or an alkyl group having 1 to 7 carbon atoms or a hydroxyalkyl group. Show. ] Reductive methylation is performed in the presence of a lower fatty acid represented by
Method for producing methyl tertiary amine.
蟻酸、酢酸、プロピオン酸又は酪酸である請求項１記載
の製造方法。2. The lower fatty acid represented by the general formula (III) is
The method according to claim 1, which is formic acid, acetic acid, propionic acid or butyric acid.
加量が、一般式（II)で表される第２級アミンに対し、
0.1〜10重量％であることを特徴とする請求項１又は２
記載の製造方法。3. The addition amount of the lower fatty acid represented by the general formula (III) relative to the secondary amine represented by the general formula (II).
0.1 to 10% by weight, characterized in that 1 or 2
The manufacturing method as described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7158906A JPH0912520A (en) | 1995-06-26 | 1995-06-26 | Production of n-methyl tertiary amine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7158906A JPH0912520A (en) | 1995-06-26 | 1995-06-26 | Production of n-methyl tertiary amine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0912520A true JPH0912520A (en) | 1997-01-14 |
Family
ID=15681946
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7158906A Pending JPH0912520A (en) | 1995-06-26 | 1995-06-26 | Production of n-methyl tertiary amine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0912520A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7633407B2 (en) | 2006-12-27 | 2009-12-15 | Fujitsu Limited | Vehicle communication device and memory product |
-
1995
- 1995-06-26 JP JP7158906A patent/JPH0912520A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7633407B2 (en) | 2006-12-27 | 2009-12-15 | Fujitsu Limited | Vehicle communication device and memory product |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2524909B1 (en) | Preparation method of 4-aminomethylbenzoic acid | |
| JPH0912520A (en) | Production of n-methyl tertiary amine | |
| EP1044976B1 (en) | Process for the preparation of pirlindole hydrochloride | |
| JP5675826B2 (en) | Process for the preparation of 2,2-difluoroethylamine by hydrogenating 1,1-difluoro-2-nitroethane | |
| JPH06298709A (en) | Production of n-substituted n'-phenyl-p-phenylene diamine | |
| FI85010B (en) | FRAMEWORK FOR FRAMSTAELLNING AV RIMANTADIN. | |
| KR100362706B1 (en) | A method for reducing nitro group to amine group using indium | |
| HU214942B (en) | Process for preparing n-substituted glycine esters and glycinic and from these indoxile and indigo derivatives | |
| CN1330625A (en) | Method for preparing polyhalogenated paratriefluoromethylanilines | |
| US20030065223A1 (en) | Process for preparing vanillylamine hydrochloride | |
| EP0760360B1 (en) | Method of manufacturing alkylaniline compounds | |
| JP2951790B2 (en) | Method for producing N- [3-amino-propyl] amine | |
| JP3224922B2 (en) | Method for producing N- [3-amino-propyl] amine | |
| JP2010504928A (en) | Method for preparing amines | |
| CN116987512A (en) | Amido-containing heterocyclic surfactant, and preparation method and application thereof | |
| US6995270B2 (en) | Hydrogenation process | |
| US6307103B1 (en) | Process for the preparation of 1,1,1-trifluoro-2-aminoalkanes | |
| NO179324B (en) | Process for the preparation of 5-chloroxindole | |
| US6362372B2 (en) | Process for producing trifluoromethylbenzylamines | |
| JP2727359B2 (en) | 4,4'-Difluorodibenzylamine and process for producing the same | |
| US6384272B2 (en) | Method for preparing aspartylcyclohexyla laninamide | |
| EP2279998A1 (en) | Synthesis of iodixanol in propyleneglycol | |
| US8962886B2 (en) | Synthesis of iodixanol in methanol | |
| US20030013768A1 (en) | Process for the production of sertraline and intermediates useful therefor | |
| EP1044960B1 (en) | Process for the preparation of 1,1,1-trifluoro-2-aminoalkanes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20040810 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20040817 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20041013 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20060822 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20061023 |
|
| A911 | Transfer of reconsideration by examiner before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20061107 |
|
| A912 | Removal of reconsideration by examiner before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A912 Effective date: 20080118 |