JP2952702B2 - Method for producing 3-amino-1-benzylpyrrolidine - Google Patents
Method for producing 3-amino-1-benzylpyrrolidineInfo
- Publication number
- JP2952702B2 JP2952702B2 JP27372690A JP27372690A JP2952702B2 JP 2952702 B2 JP2952702 B2 JP 2952702B2 JP 27372690 A JP27372690 A JP 27372690A JP 27372690 A JP27372690 A JP 27372690A JP 2952702 B2 JP2952702 B2 JP 2952702B2
- Authority
- JP
- Japan
- Prior art keywords
- benzylpyrrolidine
- amino
- reaction
- benzyl
- pyrrolidinone
- 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 - Lifetime
Links
Landscapes
- Pyrrole Compounds (AREA)
- Catalysts (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、3−アミノ−1−ベンジルピロリジンの製
造法に関する。Description: TECHNICAL FIELD The present invention relates to a method for producing 3-amino-1-benzylpyrrolidine.
従来技術 3−アミノ−1−ベンジルピロリジンは、医薬、農薬
合成用中間体として多様な用途が期待される有用な化合
物である。BACKGROUND ART 3-Amino-1-benzylpyrrolidine is a useful compound expected to have various uses as an intermediate for synthesizing pharmaceuticals and agricultural chemicals.
従来、3−アミノ−1−ベンジルピロリジン類の製造
法としては、1,2,4−トリ置換−ブタン類(置換基
は、ハロゲン又はアルキルスルホニル基を示す)にベン
ジルアミンを反応させ、次いでアンモニアを反応させる
方法(特開昭63−41452号公報)、1−ベンジル−3
−ピロリン−2,5−ジオン類をアンモニアと反応させた
後カルボニル基を還元する方法(特開平1−106862号公
報)、1−ベンジル−3−ピロリジノンオキシム類を
還元する方法(特開昭53−28161号公報)、1−ベン
ジル−3−フタルイミドピロリジン類とヒドラジンを反
応させる方法(J.Med.Chem.,Vol.11,1034(1968)等が
知られている。Conventionally, 3-amino-1-benzylpyrrolidines are produced by reacting 1,2,4-trisubstituted-butanes (substituents represent halogen or alkylsulfonyl groups) with benzylamine, and then reacting with ammonia. (JP-A-63-41452), 1-benzyl-3
A method of reacting -pyrroline-2,5-diones with ammonia and then reducing the carbonyl group (JP-A-1-106686), and a method of reducing 1-benzyl-3-pyrrolidinone oximes (JP-A-5353) -28161) and a method of reacting 1-benzyl-3-phthalimidopyrrolidine with hydrazine (J. Med. Chem., Vol. 11, 1034 (1968)).
発明が解決しようとする問題点 しかしながら、上記従来の製造法のうちの方法及び
の方法では、工程が長い上に低収率(の方法では33
%、の方法では31.1%)であり、の方法では、使用
原料であるオキシムが不安定であり、またの方法では
使用原料であるヒドラジンが有害であり、工業的に製造
するには危険を伴う。従って上記〜のいずれの場合
も工業的製造法として充分なものとは言い難い。Problems to be Solved by the Invention However, in the methods and methods of the above-mentioned conventional production methods, the steps are long and the yield is low.
%, The method is 31.1%). In the method, the starting material oxime is unstable, and in the other method, the starting material hydrazine is harmful and involves danger for industrial production. . Therefore, it is difficult to say that any of the above cases is sufficient as an industrial production method.
本発明の目的はかかる欠点を克服し、工業的に有利な
3−アミノ−1−ベンジルピロリジンの製造法を提供す
ることにある。An object of the present invention is to overcome the above drawbacks and provide an industrially advantageous method for producing 3-amino-1-benzylpyrrolidine.
問題点を解決するための手段 本発明者らは1−ベンジル−3−ピロリジノンのアミ
ノ化について研究を重ねた結果、アンモニア及び還元触
媒の存在下に1−ベンジル−3−ピロリジノンを水素に
よって接触還元する際に、特定の温度に昇温後、水素を
加えて反応を行うことにより3−アミノ−1−ベンジル
ピロリジンを一工程でしかも高収率で製造できることを
見出し本発明を完成した。Means for Solving the Problems The present inventors have repeated studies on the amination of 1-benzyl-3-pyrrolidinone and found that 1-benzyl-3-pyrrolidinone is catalytically reduced with hydrogen in the presence of ammonia and a reduction catalyst. In doing so, it was found that 3-amino-1-benzylpyrrolidine can be produced in one step and in a high yield by raising the temperature to a specific temperature and then performing a reaction by adding hydrogen to complete the present invention.
即ち本発明は、1−ベンジル−3−ピロリジノンをア
ンモニア及び還元触媒の存在下、90〜200℃に昇温した
後、水素を加えて還元することを特徴とする3−アミノ
−1−ベンジルピロリジンの製造法に係る。That is, the present invention is characterized in that 1-benzyl-3-pyrrolidinone is heated to 90 to 200 ° C. in the presence of ammonia and a reduction catalyst, and then reduced by adding hydrogen, to 3-amino-1-benzylpyrrolidine. Pertaining to the production method.
上記本発明製造法によれば、3−アミノ−1−ベンジ
ルピロリジンを簡単に且つ高収率で得ることができる。According to the above-mentioned production method of the present invention, 3-amino-1-benzylpyrrolidine can be obtained easily and in high yield.
以下、本発明の具体的な方法について説明する。本発
明で使用する還元触媒は接触還元に使用される一般的な
金属触媒でよく、例えばラネ−ニッケル、ラネ−コバル
ト、パラジウムカーボン、白金カーボン等が挙げられ、
通常これらの触媒を原料化合物に対して0.5〜100wt%、
好ましくは1〜20wt%用いるのがよい。Hereinafter, a specific method of the present invention will be described. The reduction catalyst used in the present invention may be a general metal catalyst used for catalytic reduction, for example, Raney-nickel, Raney-cobalt, palladium carbon, platinum carbon, and the like.
Usually, these catalysts are used in an amount of 0.5 to 100% by weight based on the starting compound.
Preferably, 1 to 20% by weight is used.
1−ベンジル−3−ピロリジノンのアミノ化反応は、
通常オートクレーブ中でキシレン、トルエン、メタノー
ル、エタノール、水等の単一或は混合溶媒系中で行なう
ことができる。The amination reaction of 1-benzyl-3-pyrrolidinone comprises
Usually, the reaction can be carried out in a single or mixed solvent system of xylene, toluene, methanol, ethanol, water and the like in an autoclave.
アンモニアは原料化合物に対して、通常1〜50倍モ
ル、好ましくは1.0〜20倍モル使用し、接触還元に用い
る水素は、アンモニア及び還元触媒の存在下、特定の温
度に昇温した後、オートクレーブ中に加えられる。即
ち、本発明製造法によれば、原料化合物として1−ベン
ジル−3−ピロリジノンを使用する場合、反応開始前に
水素を加える方法では副生物である3−ヒドロキシ−1
−ベンジルピロリジンが増加し、目的物の収率が低下す
るため、昇温し特定の反応温度に到達してから水素を加
える方法が採用される。Ammonia is usually used in a molar amount of 1 to 50 times, preferably 1.0 to 20 times the molar amount of the starting compound.Hydrogen used for catalytic reduction is heated to a specific temperature in the presence of ammonia and a reduction catalyst, and then autoclaved. Added inside. That is, according to the production method of the present invention, when 1-benzyl-3-pyrrolidinone is used as the starting compound, 3-hydroxy-1 which is a by-product is not added by the method of adding hydrogen before the start of the reaction.
-Benzylpyrrolidine increases and the yield of the target product decreases, so a method is employed in which the temperature is raised to reach a specific reaction temperature and then hydrogen is added.
反応温度としては、90〜200℃の範囲内が採用され
る。また、反応圧としては、通常は常圧以上、好ましく
は5〜40kg/cm2である。反応時間は、通常30分〜3時間
で完結する。また原料の1−ベンジル−3−ピロリジノ
ンは、昇温後オートクレーブ中に圧入することにより反
応させてもよい。The reaction temperature is in the range of 90 to 200 ° C. The reaction pressure is usually not lower than normal pressure, preferably 5 to 40 kg / cm 2 . The reaction time is usually completed in 30 minutes to 3 hours. Alternatively, the starting material 1-benzyl-3-pyrrolidinone may be reacted by pressurizing the autoclave after heating.
反応後、触媒を別し、液を蒸留することにより目
的物が得られる。After the reaction, the target substance is obtained by separating the catalyst and distilling the liquid.
発明の効果 従来の3−アミノ−1−ベンジルピロリジンの製造法
は、工程数が長いか、使用原料が危険物である等の理由
により、工業的製法としては数々の問題があった。これ
に対して、1−ベンジル−3−ピロリジノンの3位のカ
ルボニルとアンモニアとの脱水反応、及び水素による接
触還元を同一反応系内で行なう本発生の製造法は入手の
容易な原料を用い一工程でしかも高収率で3−アミノ−
1−ベンジルピロリジンを得ることができる工業的に有
利な方法である。Effects of the Invention The conventional method for producing 3-amino-1-benzylpyrrolidine has a number of problems as an industrial production method because the number of steps is long or the raw materials used are dangerous substances. In contrast, the production method of the present invention in which the dehydration reaction of 3-position carbonyl of 1-benzyl-3-pyrrolidinone with ammonia and the catalytic reduction with hydrogen in the same reaction system are carried out using easily available raw materials. 3-amino-
This is an industrially advantageous method by which 1-benzylpyrrolidine can be obtained.
尚、3−アミノ−1−ベンジルピロリジンは、その構
造から予想される様に、医薬・農薬等の生理活性物質の
合成原料として用いられる。例えば、3−アミノ−1−
ベンジルピロリジン・2塩酸塩をパラジウムカーボン存
在下で接触還元すると脱ベンジル化して、高収率で3−
アミノピロリジン・2塩酸塩が得られるが、この3−ア
ミノピロリジンは、医薬・農薬の合成原料として有用で
ある。As expected from the structure, 3-amino-1-benzylpyrrolidine is used as a raw material for synthesizing a physiologically active substance such as a medicine or an agricultural chemical. For example, 3-amino-1-
When benzylpyrrolidine dihydrochloride is catalytically reduced in the presence of palladium carbon, it is debenzylated to give 3-yield in high yield.
Aminopyrrolidine dihydrochloride is obtained, and this 3-aminopyrrolidine is useful as a raw material for synthesizing medicines and agricultural chemicals.
実 施 例 以下に実施例を示して本発明を説明するが、本発明は
これらの実施例に限定されるものではない。EXAMPLES Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.
実施例1 1−ベンジル−3−ピロリジノン131g、キシレン262
g、メタノール75g、ラネ−ニッケル26g及びアンモニア1
9gをオートクレーブ中に加え、温度120℃で水素を加え
内圧40kg/cm2で1時間30分撹拌した。反応中に消費され
る水素を供給しながら内圧を40kg/cm2に維持した。触媒
を別し、液を濃縮した後蒸留して、沸点133〜135℃
/10mmHgの3−アミノ−ベンジルピロリジン117g(GC%:
98.5%、3−ヒドロキシ−1−1−ベンジルピロリジン
1.4%含有)を得た。(収率:87.3%) NMR(CDCl3):δppm 7.42(s.5H)、3.55(s.2H)、3.25〜3.72(m.1H) 1.95〜2.90(m.6H)、1.30(s.2H) IR(KBr) 3350,3250,2770,1600 1490,1450,880cm-1 実施例2 1−ベンジル−3−ピロリジノン131g、キシレン262
g、ラネ−ニッケル26g及びアンモニア19gをオートクレ
ーブ中に加え、温度120℃で水素を加え内圧40kg/cm2で
1時間撹拌した。反応中に消費される水素を供給しなが
ら内圧を40kg/cm2に維持した。反応液を実施例1と同様
に処理して、3−アミノ−1−ベンジルピロリジン111g
(GC%:96.9%、3−ヒドロキシ−1−ベンジルピロリ
ジン3.1%含有)を得た。(収率:81.5%) 実施例3 ラネ−ニッケルの使用量を13gとする以外は全て実施
例1と同様に処理して、3−アミノ−1−ベンジルピロ
リジン117g(GC%:98.8%、3−ヒドロキシ−1−ベン
ジルピロリジン1.1%含有)を得た。(収率:87.5%) 実施例4 1−ベンジル−3−ピロリジノン131g、メタノール26
2g、ラネ−ニッケル26g及びアンモニア127gをオートク
レーブ中に加え、温度120℃で水素を加え内圧40kg/cm2
で4時間撹拌した。反応中に消費される水素を供給しな
がら内圧を40kg/cm2に維持した。反応液を実施例1と同
様に処理して3−アミノ−ベンジルピロリジン133g(GC
%:61.4%、3−ヒドロキシ−1−1ベンジルピロリジ
ン28.0%含有)を得た。(収率:61.9%) 実施例5 触媒をラネ−ニッケルから5%Pd−カーボンに変え5
%Pd−カーボンを3.3g使用する以外は全て実施例1と同
様に処理して、3−アミノ−1−ベンジルピロリジン86
g(GC%:96.2%、3−ヒドロキシ−1−ベンジルピロリ
ジン3.8%含有)を得た。(収率:62.7%) 実施例6 1−ベンジル−3−ピロリジノン131g、キシレン262
g、メタノール75g、ラネーニッケル26g及びアンモニア1
9gをオートクレーブ中に投入し、水素で内圧を40kg/cm2
にした。その後120℃に昇温し、1.5時間撹拌した。反応
中に消費される水素を供給しながら内圧を40kg/cm2に維
持した。反応液を実施例1と同様に処理して3−アミノ
−1−ベンジルピロリジン130g(GC%:70.7%、3−ヒ
ドロキシ−1−ベンジルピロリジン27.8%含有)を得
た。(収率:69.7%) 実施例7 1−ベンジル−2−メチル−3−ピロリジノン94.5
g、キシレン315g、メタノール50g、ラネーニッケル18.9
g及びアンモニア12.8gをオートクレーブ中に投入し、水
素で内圧を20kg/cm2にした。その後140℃に昇温し、3
時間撹拌した。反応中に消費される水素を供給しながら
内圧を20kg/cm2に維持した。反応終了後、触媒を別
し、液を濃縮した後蒸留して、1−ベンジル−2−メ
チル−3−アミノピロリジン86.0g(GC%:98.6%、3−
ヒドロキシ−1−ベンジルピロリジン0.7%含有)を得
た。(収率:89.3%) NMR(CDCl3):δppm 7.2(s.5H)、1.7〜4.2(m.8H)、1.38(s.2H) 1.0〜1.3(d.d.3H) IR(KBr) 3350,3250,2770,1600 1490,1450cm-1 Example 1 1-benzyl-3-pyrrolidinone 131 g, xylene 262
g, methanol 75 g, Raney-nickel 26 g and ammonia 1
9 g was added into an autoclave, hydrogen was added at a temperature of 120 ° C., and the mixture was stirred at an internal pressure of 40 kg / cm 2 for 1 hour and 30 minutes. The internal pressure was maintained at 40 kg / cm 2 while supplying hydrogen consumed during the reaction. The catalyst is separated, the liquid is concentrated and then distilled, and the boiling point is 133 to 135 ° C.
117 g of 3-amino-benzylpyrrolidine at / 10 mmHg (GC%:
98.5%, 3-hydroxy-1-benzylpyrrolidine
1.4%). (Yield: 87.3%) NMR (CDCl 3 ): δ ppm 7.42 (s.5H), 3.55 (s.2H), 3.25 to 3.72 (m.1H) 1.95 to 2.90 (m.6H), 1.30 (s.2H) IR) (KBr) 3350,3250,2770,1600 1490,1450,880 cm -1 Example 2 131 g of 1-benzyl-3-pyrrolidinone, xylene 262
g, 26 g of Raney-nickel and 19 g of ammonia were added into an autoclave, hydrogen was added at a temperature of 120 ° C., and the mixture was stirred at an internal pressure of 40 kg / cm 2 for 1 hour. The internal pressure was maintained at 40 kg / cm 2 while supplying hydrogen consumed during the reaction. The reaction solution was treated in the same manner as in Example 1 to give 3-amino-1-benzylpyrrolidine (111 g).
(GC%: 96.9%, containing 3-hydroxy-1-benzylpyrrolidine 3.1%). (Yield: 81.5%) Example 3 Except that the amount of Raney-nickel used was changed to 13 g, the same treatment as in Example 1 was carried out to obtain 117 g of 3-amino-1-benzylpyrrolidine (GC%: 98.8%, 3%). -Hydroxy-1-benzylpyrrolidine containing 1.1%). (Yield: 87.5%) Example 4 131 g of 1-benzyl-3-pyrrolidinone, 26 of methanol
2 g, Raney-nickel 26 g and ammonia 127 g were added to the autoclave, hydrogen was added at a temperature of 120 ° C., and the internal pressure was 40 kg / cm 2.
For 4 hours. The internal pressure was maintained at 40 kg / cm 2 while supplying hydrogen consumed during the reaction. The reaction solution was treated in the same manner as in Example 1 to obtain 133 g of 3-amino-benzylpyrrolidine (GC
%: 61.4%, containing 28.0% of 3-hydroxy-1-benzylpyrrolidine). (Yield: 61.9%) Example 5 The catalyst was changed from Raney-nickel to 5% Pd-carbon.
Except for using 3.3 g of% Pd-carbon, the same treatment as in Example 1 was carried out to give 3-amino-1-benzylpyrrolidine 86
g (GC%: 96.2%, containing 3-hydroxy-1-benzylpyrrolidine 3.8%). (Yield: 62.7%) Example 6 131 g of 1-benzyl-3-pyrrolidinone, 262 of xylene
g, methanol 75g, Raney nickel 26g and ammonia 1
9 g is charged into the autoclave, and the internal pressure is increased to 40 kg / cm 2 with hydrogen.
I made it. Thereafter, the temperature was raised to 120 ° C., and the mixture was stirred for 1.5 hours. The internal pressure was maintained at 40 kg / cm 2 while supplying hydrogen consumed during the reaction. The reaction solution was treated in the same manner as in Example 1 to obtain 130 g of 3-amino-1-benzylpyrrolidine (GC%: 70.7%, containing 37.8% of 3-hydroxy-1-benzylpyrrolidine). (Yield: 69.7%) Example 7 1-benzyl-2-methyl-3-pyrrolidinone 94.5
g, xylene 315 g, methanol 50 g, Raney nickel 18.9
g and 12.8 g of ammonia were charged into an autoclave, and the internal pressure was adjusted to 20 kg / cm 2 with hydrogen. Then, the temperature was raised to 140 ° C
Stirred for hours. The internal pressure was maintained at 20 kg / cm 2 while supplying hydrogen consumed during the reaction. After completion of the reaction, the catalyst was separated, and the solution was concentrated and distilled.
(Hydroxy-1-benzylpyrrolidine 0.7%). (Yield: 89.3%) NMR (CDCl 3 ): δ ppm 7.2 (s.5H), 1.7-4.2 (m.8H), 1.38 (s.2H) 1.0-1.3 (dd3H) IR (KBr) 3350,3250, 2770,1600 1490,1450cm -1
───────────────────────────────────────────────────── フロントページの続き (72)発明者 江川 彰彦 大阪府大阪市鶴見区鶴見3丁目13番32― 807号 (56)参考文献 特開 昭55−22699(JP,A) 特開 昭63−41452(JP,A) (58)調査した分野(Int.Cl.6,DB名) C07D 207/00 - 207/50 CA(STN) CAOLD(STN) REGISTRY(STN)──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Akihiko Egawa 3-13-32-807, Tsurumi, Tsurumi-ku, Osaka-shi, Osaka (56) References JP-A-55-22699 (JP, A) JP-A-63- 41452 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) C07D 207/00-207/50 CA (STN) CAOLD (STN) REGISTRY (STN)
Claims (1)
ニア及び還元触媒の存在下、90〜200℃に昇温した後、
水素を加えて還元することを特徴とする3−アミノ−1
−ベンジルピロリジンの製造法。1. After heating 1-benzyl-3-pyrrolidinone to 90 to 200 ° C. in the presence of ammonia and a reducing catalyst,
3-amino-1 characterized by reduction by adding hydrogen
-A process for producing benzylpyrrolidine.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP27356389 | 1989-10-19 | ||
JP1-273563 | 1989-10-19 |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH03204854A JPH03204854A (en) | 1991-09-06 |
JP2952702B2 true JP2952702B2 (en) | 1999-09-27 |
Family
ID=17529548
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP27372690A Expired - Lifetime JP2952702B2 (en) | 1989-10-19 | 1990-10-12 | Method for producing 3-amino-1-benzylpyrrolidine |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2952702B2 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114369052A (en) * | 2021-12-21 | 2022-04-19 | 赤峰万泽药业股份有限公司 | Synthetic method of 3-aminopyrrolidine dihydrochloride |
-
1990
- 1990-10-12 JP JP27372690A patent/JP2952702B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPH03204854A (en) | 1991-09-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP3001685B2 (en) | Diamine production method | |
JP2952702B2 (en) | Method for producing 3-amino-1-benzylpyrrolidine | |
IE843116L (en) | Preparation of glyoxals and acetals | |
JPH01193246A (en) | Production of 2,3-dichloropyridine | |
JP2577405B2 (en) | Method for producing 2,4,5-triamino-6-hydroxypyrimidine | |
JP3038271B2 (en) | Method for producing 3-aminopropanol | |
JPH02147A (en) | Synthesis of n,n-dialkylhydroxylamine | |
US4582922A (en) | Process for the preparation of methyl N-methylanthranilate | |
JP3282372B2 (en) | Piperonal manufacturing method | |
JP3031727B2 (en) | Process for producing aminomethylpyridines having a chlorine atom at the α-position | |
US4161614A (en) | Process for the preparation of cyclohexane dione-(1,4)-tetramethyl diketal | |
JPH08109170A (en) | Production of hexahydropyridazine | |
US4978792A (en) | Process for producing aminobenzylamine | |
JPS61251659A (en) | Production of 2-or 3-aminomethylpiperidine | |
JP2537528B2 (en) | Process for producing 2- (0-aminophenyl) ethanol | |
JPH0816101B2 (en) | Process for producing 3,5-dichloropyridine | |
JPH03133954A (en) | Production of 3-aminopyrrolidine | |
US4204076A (en) | Hydroquinone dimethyl ether | |
JPH078839B2 (en) | Method for producing N, N, N ', N'-tetramethyl-1.6-hexanediamine | |
JPS6056707B2 (en) | Method for producing 2-pyrrolidone | |
JPS63174947A (en) | Production of gamma-hydroxybutyric acid | |
JPH0597778A (en) | Production of 2-aminoindane and its salts | |
JPH03127752A (en) | Production of methylcyclohexanone | |
JPS62161765A (en) | Production of 1-substituted-imidazole | |
JP2702425B2 (en) | Method for producing 2-imidazolidinones |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080716 Year of fee payment: 9 |
|
FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080716 Year of fee payment: 9 |
|
FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 10 Free format text: PAYMENT UNTIL: 20090716 |
|
FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100716 Year of fee payment: 11 |