JPH1180063A - Production of ethers - Google Patents
Production of ethersInfo
- Publication number
- JPH1180063A JPH1180063A JP9256083A JP25608397A JPH1180063A JP H1180063 A JPH1180063 A JP H1180063A JP 9256083 A JP9256083 A JP 9256083A JP 25608397 A JP25608397 A JP 25608397A JP H1180063 A JPH1180063 A JP H1180063A
- Authority
- JP
- Japan
- Prior art keywords
- alkali metal
- palladium
- tertiary
- group
- formula
- 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
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]
【発明の属する技術分野】本発明は、アルカリ金属アル
コキシドと芳香族系塩化物との反応による第３級ブチル
エーテル類の新規な製造法に関するものである。TECHNICAL FIELD The present invention relates to a novel method for producing tertiary butyl ethers by reacting an alkali metal alkoxide with an aromatic chloride.
【０００２】本発明により提供される第３級ブチルエー
テル類は、それ自身または第３級ブチル基を脱保護して
得られるフェノール誘導体として、医薬・農薬類、染料
等の合成に用いられる有用な物質である。The tertiary butyl ethers provided by the present invention are useful as phenol derivatives obtained by deprotecting the tertiary butyl group by themselves or useful as compounds used in the synthesis of pharmaceuticals, agricultural chemicals, dyes and the like. It is.
【０００３】[0003]
【従来の技術】芳香族系塩化物をアルカリ金属アルコキ
シドでエーテル化することからなる第３級ブチルエーテ
ル類の合成は容易でなく、穏和な条件下に進行する例は
知られていない。2. Description of the Related Art The synthesis of tertiary butyl ethers comprising etherifying an aromatic chloride with an alkali metal alkoxide is not easy, and there is no known example of proceeding under mild conditions.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、アルカリ金
属第３級ブトキシドと芳香族系塩化物との反応による第
３級ブチルエーテル類の新規かつ効率的な製造方法を提
供することを目標とするものである。SUMMARY OF THE INVENTION An object of the present invention is to provide a novel and efficient method for producing tertiary butyl ethers by reacting an alkali metal tertiary butoxide with an aromatic chloride. Things.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、前記目的
を達するために鋭意研究の結果、パラジウム触媒および
アルカリ金属第３級ブトキシドの存在下において、芳香
族系塩化物のエーテル化が容易に進行し、酸素原子に芳
香族系の基が結合した第３級ブチルエーテルが得られる
という新規な事実を見いだし、それに基づいて本発明を
完成するに至った。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and have found that etherification of an aromatic chloride can be easily performed in the presence of a palladium catalyst and an alkali metal tertiary butoxide. The present inventors have found a novel fact that a tertiary butyl ether in which an aromatic group is bonded to an oxygen atom is obtained, and based on this, have completed the present invention.
【０００６】すなわち、本発明によれば、芳香族系塩化
物とアルカリ金属第３級ブトキシドの反応による第３級
ブチルエーテルの新規かつ効率的な製造法が提供され
る。That is, the present invention provides a novel and efficient method for producing tertiary butyl ether by reacting an aromatic chloride with an alkali metal tertiary butoxide.
【０００７】本発明において原料の一つとして用いるア
ルカリ金属第３級ブトキシドは、一般式 ｔ−ＢｕＯＭ (I) （式中ｔ−Ｂｕは第３級ブチル基を示し、Ｍはアルカリ
金属を示す。）で表されるものである。Ｍの具体例とし
ては、リチウム、ナトリウム、カリウム、ルビジウム、
セシウム、フランシウムが挙げられるが、反応性および
入手性の観点からカリウムの場合が最も好ましい。The alkali metal tertiary butoxide used as one of the raw materials in the present invention is represented by the general formula t-BuOM (I) (where t-Bu represents a tertiary butyl group and M represents an alkali metal). ). Specific examples of M include lithium, sodium, potassium, rubidium,
Cesium and francium are mentioned, but potassium is most preferable from the viewpoint of reactivity and availability.
【０００８】一方、本発明の反応において用いられる芳
香族系塩化物は、一般式 ＲＣｌ (II) （式中Rはアリール基またはヘテロアリール基を示す）
で表されるものである。これらのアリール基またはヘテ
ロアリール基はアルキル基、アラルキル基、シクロアル
キル基、アリール基等の炭化水素基で置換されていても
良く、また、これらのアリール基またはヘテロアリール
基、およびその置換基であるアルキル基、アラルキル
基、シクロアルキル基、アリール基等の炭化水素基は、
アルコキシ基、シアノ基、ジアルキルアミノ基、シリル
基等の官能基で置換されていても良い。具体例として
は、フェニル基、ナフチル基、チエニル基、フリル基、
シアノフェニル基、トリル基等を挙げることができる。On the other hand, the aromatic chloride used in the reaction of the present invention has a general formula RCl (II) (wherein R represents an aryl group or a heteroaryl group)
It is represented by These aryl groups or heteroaryl groups may be substituted with a hydrocarbon group such as an alkyl group, an aralkyl group, a cycloalkyl group, and an aryl group, and the aryl group or the heteroaryl group, and a substituent thereof. Certain alkyl groups, aralkyl groups, cycloalkyl groups, hydrocarbon groups such as aryl groups,
It may be substituted with a functional group such as an alkoxy group, a cyano group, a dialkylamino group and a silyl group. Specific examples include a phenyl group, a naphthyl group, a thienyl group, a furyl group,
Examples include a cyanophenyl group and a tolyl group.
【０００９】用いるアルカリ金属アルコキシドと芳香族
系塩化物の比率は、モル比で１：１ないし３：１の範囲
が好ましい。The molar ratio of the alkali metal alkoxide to the aromatic chloride is preferably in the range of 1: 1 to 3: 1.
【００１０】本発明の反応の生起には、パラジウム触媒
の使用は必須であり、触媒が存在しない場合には、第３
級ブチルエーテルは全く生成しない。パラジウム触媒と
しては種々の構造のものを用いることが出来るが、好適
なものは、いわゆる低原子価のパラジウム錯体であり、
特に３級ホスフィンを配位子とする錯体が好ましく、具
体的には、ジクロロビス（トリエチルホスフィン）パラ
ジウム、ジクロロ（トリメチルホスフィン）パラジウ
ム、ジクロロビス（トリシクロヘキシルホスフィン）パ
ラジウム、ジブロモ（トリイソプロピルホスフィン）パ
ラジウム、ジクロロビス（フェニルジシクロヘキシルホ
スフィン）パラジウム等が例示される。また、第３級ホ
スフィンを配位子として含まない錯体と３級ホスフィン
を反応系中で混合し、第３級ホスフィンを配位子とする
パラジウム錯体を発生させてそのまま触媒として用いる
方法も好ましい態様である。この方法で有利な性能を発
揮する第３級ホスフィンを例示すると、トリメチルホス
フィン、トリエチルホスフィン、ジフェニルシクロヘキ
シルホスフィン、フェニルジシクロヘキシルホスフィ
ン、トリシクロヘキシルホスフィン、トリイソプロピル
ホスフィン、ジｔｅｒｔ−ブチルフェンニルホスフィン
等が挙げられる。これに組み合わせて用いられる、第３
級ホスフィンを配位子として含まない錯体としては、酢
酸パラジウム、塩化パラジウム、ジクロロ（１，５−シ
クロオクタジエン）パラジウム、ビス（ジベンジリデン
アセトン）パラジウム、トリス（ジベンジリデンアセト
ン）二パラジウム、ジクロロビス（ベンゾニトリル）パ
ラジウム、ジブロモビス（ベンゾニトリル）パラジウ
ム、ジクロロビス（アセトニトリル）パラジウム、ジ-
μ-クロロビス（π-アリル）二パラジウム、ジクロロビ
ス（ピリジン）パラジウム等が例示される。In order for the reaction of the present invention to occur, the use of a palladium catalyst is essential.
No butyl ether is formed. Although various structures can be used as the palladium catalyst, preferred are so-called low-valent palladium complexes,
Particularly, a complex having a tertiary phosphine as a ligand is preferable. Specifically, dichlorobis (triethylphosphine) palladium, dichloro (trimethylphosphine) palladium, dichlorobis (tricyclohexylphosphine) palladium, dibromo (triisopropylphosphine) palladium, dichlorobis (Phenyldicyclohexylphosphine) palladium and the like. Further, a preferred embodiment is a method in which a complex containing no tertiary phosphine as a ligand and a tertiary phosphine are mixed in a reaction system to generate a palladium complex having a tertiary phosphine as a ligand and to be used as a catalyst as it is. It is. Examples of tertiary phosphines that exhibit advantageous performance in this method include trimethylphosphine, triethylphosphine, diphenylcyclohexylphosphine, phenyldicyclohexylphosphine, tricyclohexylphosphine, triisopropylphosphine, ditert-butylfenylphosphine, and the like. . The third used in combination with this
Complexes that do not contain primary phosphine as a ligand include palladium acetate, palladium chloride, dichloro (1,5-cyclooctadiene) palladium, bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, dichlorobis ( Benzonitrile) palladium, dibromobis (benzonitrile) palladium, dichlorobis (acetonitrile) palladium, di-
Examples thereof include μ-chlorobis (π-allyl) dipalladium and dichlorobis (pyridine) palladium.
【００１１】これらのパラジウム錯体の使用量はいわゆ
る触媒量で良く、アルカリ金属第３級ブトキシドに対し
て２０モル％以下であり、一般的には５モル％以下で十
分である。The amount of the palladium complex used may be a so-called catalytic amount, which is 20 mol% or less, and generally 5 mol% or less, based on the alkali metal tertiary butoxide.
【００１２】反応は特に溶媒を用いなくてもよいが、必
要に応じて溶媒中で実施することもできる。溶媒として
は、炭化水素系もしくはエーテル系の溶媒が一般的に用
いられる。反応温度は、芳香族系塩化物の構造によるが
一般には５０℃以上に加熱するのが好ましく、通常は８
０〜2２００℃の範囲から選ばれる。本反応の中間体は
酸素に敏感であり、反応の実施は、窒素やアルゴン、メ
タン等の不活性ガス雰囲気で行うのが好ましい。反応混
合物からの精製物の分離は、クロマトグラフィー、蒸留
または再結晶によって容易に達成される。The reaction does not need to use a solvent, but can be carried out in a solvent if necessary. As the solvent, a hydrocarbon-based or ether-based solvent is generally used. The reaction temperature depends on the structure of the aromatic chloride, but it is generally preferable to heat it to 50 ° C. or higher, and usually to 8 ° C.
The temperature is selected from the range of 0 to 2200 ° C. The intermediate of this reaction is sensitive to oxygen, and the reaction is preferably performed in an atmosphere of an inert gas such as nitrogen, argon, or methane. Separation of the purified product from the reaction mixture is easily achieved by chromatography, distillation or recrystallization.
【００１３】[0013]
【実施例】本発明を以下の実施例によってさらに具体的
に説明するが、実施態様は実施例に限定されるものでは
ない。The present invention will be described more specifically with reference to the following examples, but the embodiments are not limited to the examples.
【００１４】実施例１ クロロベンゼン（０．５ｍｍｏｌ）、カリウム第３級ブ
トキシド（０．７ｍｍｏｌ）、ジクロロビス（トリエチ
ルホスフィン）パラジウム（０．０２ｍｍｏｌ）、およ
び、トルエン（１ｍｌ）の混合物を、窒素雰囲気下、１
２０℃で４８時間撹拌した。反応液のＮＭＲ測定によ
り、第３級ブチルフェニルエーテルが７４％の収率で生
成していることが判明した。Example 1 A mixture of chlorobenzene (0.5 mmol), potassium tertiary butoxide (0.7 mmol), dichlorobis (triethylphosphine) palladium (0.02 mmol) and toluene (1 ml) was placed in a nitrogen atmosphere. 1
Stirred at 20 ° C. for 48 hours. NMR measurement of the reaction solution revealed that tertiary butyl phenyl ether was produced in a yield of 74%.
【００１５】実施例２ ｐ−クロロトルエン（０．５ｍｍｏｌ）、カリウム第３
級ブトキシド（０．７ｍｍｏｌ）、ジクロロビス（トリ
エチルホスフィン）パラジウム（０．０２ｍｍｏｌ）、
および、トルエン（１ｍｌ）の混合物を、窒素雰囲気
下、１２０℃で４８時間撹拌した。反応液のNMR測定に
より、第３級ブチルトリルエーテルが５０％の収率で生
成していることが判明した。Example 2 p-chlorotoluene (0.5 mmol), potassium tertiary
Butoxide (0.7 mmol), dichlorobis (triethylphosphine) palladium (0.02 mmol),
Then, a mixture of toluene (1 ml) was stirred at 120 ° C. for 48 hours under a nitrogen atmosphere. NMR measurement of the reaction solution revealed that tertiary butyl tolyl ether was produced in a yield of 50%.
【００１６】実施例３ ｐ−クロロアニソール（０．５ｍｍｏｌ）、カリウム第
３級ブトキシド（０．７ｍｍｏｌ）、ジクロロビス（ト
リエチルホスフィン）パラジウム（０．０２ｍｍｏ
ｌ）、および、トルエン（１ｍｌ）の混合物を、窒素雰
囲気下、１２０℃で４８時間撹拌した。反応液のNMR測
定により、第３級ブチルアニシルエーテルが５５％の収
率で生成していることが判明した。Example 3 p-Chloroanisole (0.5 mmol), potassium tert-butoxide (0.7 mmol), dichlorobis (triethylphosphine) palladium (0.02 mmol)
l) and a mixture of toluene (1 ml) was stirred at 120 ° C for 48 hours under a nitrogen atmosphere. NMR measurement of the reaction solution revealed that tertiary butyl anisyl ether was produced in a yield of 55%.
【００１７】[0017]
【発明の効果】本発明の方法により、医薬・農薬・染料
の合成に有用な第３級ブチルエーテル類を、アルカリ金
属第３級ブトキシドおよび芳香族系塩化物から効率的か
つ安全に製造でき、その分離精製も容易である。従っ
て、本発明は工業的に多大の効果をもたらす。According to the method of the present invention, tertiary butyl ethers useful for the synthesis of medicines, agricultural chemicals and dyes can be produced efficiently and safely from alkali metal tertiary butoxide and aromatic chlorides. Separation and purification are also easy. Therefore, the present invention has a great effect industrially.
Claims (1)
コキシドの存在下において、一般式 ｔ−ＢｕＯＭ (I) （式中ｔ−Ｂｕは第３級ブチル基を示し、Ｍはアルカリ
金属を示す。）で表されるアルカリ金属第３級ブトキシ
ドを、一般式 ＲＣｌ (II) （式中Ｒはアリール基またはヘテロアリール基を示す）
で表される塩化物と反応させることを特徴とする一般式 ｔ−ＢｕＯＲ (III) （Ｒは、前記一般式IIで示されるものと同じ。）で表さ
れる第３級ブチルエーテル類の製造法。1. In the presence of a palladium catalyst and an alkali metal alkoxide, represented by the general formula t-BuOM (I) (where t-Bu represents a tertiary butyl group and M represents an alkali metal). An alkali metal tertiary butoxide represented by the general formula RCl (II) (wherein R represents an aryl group or a heteroaryl group)
A method for producing a tertiary butyl ether represented by the general formula t-BuOR (III) (R is the same as that represented by the general formula II), characterized by reacting with a chloride represented by the following formula: .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9256083A JP2920522B2 (en) | 1997-09-04 | 1997-09-04 | Method for producing ethers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9256083A JP2920522B2 (en) | 1997-09-04 | 1997-09-04 | Method for producing ethers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1180063A true JPH1180063A (en) | 1999-03-23 |
| JP2920522B2 JP2920522B2 (en) | 1999-07-19 |
Family
ID=17287663
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9256083A Expired - Lifetime JP2920522B2 (en) | 1997-09-04 | 1997-09-04 | Method for producing ethers |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2920522B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7923587B2 (en) | 2004-07-23 | 2011-04-12 | Polnox Corporation | Anti-oxidant macromonomers and polymers and methods of making and using the same |
| US8691933B2 (en) | 2004-12-03 | 2014-04-08 | Polnox Corporation | Stabilized polyolefin compositions |
| US8927472B2 (en) | 2005-12-02 | 2015-01-06 | Polnox Corporation | Lubricant oil compositions |
| US9193675B2 (en) | 2006-07-06 | 2015-11-24 | Polnox Corporation | Macromolecular antioxidants comprising differing antioxidant moieties: structures, methods of making and using the same |
| US9388120B2 (en) | 2005-02-22 | 2016-07-12 | Polnox Corporation | Nitrogen and hindered phenol containing dual functional macromolecular antioxidants: synthesis, performances and applications |
| US10294423B2 (en) | 2013-11-22 | 2019-05-21 | Polnox Corporation | Macromolecular antioxidants based on dual type moiety per molecule: structures, methods of making and using the same |
| US11578285B2 (en) | 2017-03-01 | 2023-02-14 | Polnox Corporation | Macromolecular corrosion (McIn) inhibitors: structures, methods of making and using the same |
-
1997
- 1997-09-04 JP JP9256083A patent/JP2920522B2/en not_active Expired - Lifetime
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7923587B2 (en) | 2004-07-23 | 2011-04-12 | Polnox Corporation | Anti-oxidant macromonomers and polymers and methods of making and using the same |
| US8691933B2 (en) | 2004-12-03 | 2014-04-08 | Polnox Corporation | Stabilized polyolefin compositions |
| US8846847B2 (en) | 2004-12-03 | 2014-09-30 | Polnox Corporation | Macromolecular antioxidants based on sterically hindered phenols and phosphites |
| US9388120B2 (en) | 2005-02-22 | 2016-07-12 | Polnox Corporation | Nitrogen and hindered phenol containing dual functional macromolecular antioxidants: synthesis, performances and applications |
| US8927472B2 (en) | 2005-12-02 | 2015-01-06 | Polnox Corporation | Lubricant oil compositions |
| US9523060B2 (en) | 2005-12-02 | 2016-12-20 | Polnox Corporation | Lubricant oil compositions |
| US9193675B2 (en) | 2006-07-06 | 2015-11-24 | Polnox Corporation | Macromolecular antioxidants comprising differing antioxidant moieties: structures, methods of making and using the same |
| US9950990B2 (en) | 2006-07-06 | 2018-04-24 | Polnox Corporation | Macromolecular antioxidants comprising differing antioxidant moieties: structures, methods of making and using the same |
| US10294423B2 (en) | 2013-11-22 | 2019-05-21 | Polnox Corporation | Macromolecular antioxidants based on dual type moiety per molecule: structures, methods of making and using the same |
| US10683455B2 (en) | 2013-11-22 | 2020-06-16 | Polnox Corporation | Macromolecular antioxidants based on dual type moiety per molecule: structures, methods of making and using the same |
| US11060027B2 (en) | 2013-11-22 | 2021-07-13 | Polnox Corporation | Macromolecular antioxidants based on dual type moiety per molecule: structures, methods of making and using the same |
| US11578285B2 (en) | 2017-03-01 | 2023-02-14 | Polnox Corporation | Macromolecular corrosion (McIn) inhibitors: structures, methods of making and using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2920522B2 (en) | 1999-07-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Caddick et al. | An improved synthesis of bis (1, 3-di-N-tert-butylimidazol-2-ylidene) palladium (0) and its use in C–C and C–N coupling reactions | |
| US6057456A (en) | Transition metal-catalyzed process for preparing alpha-arylated carbonyl-containing compounds | |
| US6248892B1 (en) | Process for preparing arylpyridines | |
| JP2920522B2 (en) | Method for producing ethers | |
| Warad et al. | Synthesis, spectroscopic characterization and catalytic significance of Palladium (II) complexes derived from 1, 1 bis (diphenylphosphinomethyl) ethane | |
| ES2283850T3 (en) | NEW CARBEN-NICKEL COMPLEXES, -PALADIO AND -PLATINO, ITS PRODUCTION AND USE IN CATALYTIC REACTIONS. | |
| US7485744B2 (en) | Iron-catalyzed allylic alkylation | |
| Munir et al. | Synthesis of new Pro-PYE ligands as co-catalysts toward Pd-catalyzed Heck–Mizoroki cross coupling reactions | |
| Mendoza et al. | Trialkylsilyl triflimides as easily tunable organocatalysts for allylation and benzylation of silyl carbon nucleophiles with non-genotoxic reagents | |
| US20020016512A1 (en) | Heterogeneously catalyzed process for cross coupling aryl chlorides with aryl boronic acids | |
| JP2002020396A (en) | Immobilized palladium complex | |
| Yiğit et al. | Synthesis of silver (I) and palladium (II) N-heterocyclic carbene complexes and their use as catalysts for the direct C5 arylation of heteroaromatic compounds | |
| Correa-Ayala et al. | Dipalladium (I) complexes of ortho-and para-functionalized 1, 3-bis (aryl) triazenide ligands: Synthesis, structure and catalytic activity | |
| OCHIAI et al. | Umpolung of Reactivity of Allylsilane, Allylgermane, and Allylstannane: Allylation of Aromatic Compounds with Allylmetal and Arylthallium Bis (trifluoroacetate) | |
| JP2003183187A (en) | N-heterocyclic carbene complex and its use | |
| CN111423351A (en) | Chiral copper compound and preparation method and application thereof | |
| Li et al. | N-Heterocyclic carbene adducts of cyclopalladated ferrocenylimines: Synthesis, characterization and catalytic activity for the Suzuki–Miyaura reaction | |
| US20020128478A1 (en) | Process for a carbon-carbon coupling reaction of aryl halides with olefins by heterogeneous catalysts | |
| JP2017132738A (en) | Manufacturing method of bipyridyl compound | |
| CN109320538B (en) | Synthesis method of 3-bromo-5-aryl-2- (trimethylsilyl) -1- (N, N-dimethyl sulfonamide) pyrrole | |
| CN111116666A (en) | Preparation and application of triphenylphosphine allyl palladium halide compound and derivative thereof | |
| JPH10218830A (en) | Production of carboxylic acid ester or carboxylic acid | |
| CN110003062B (en) | N-phenyl-N-p-toluenesulfonyl difluoroacetamide and application thereof | |
| CN113754544B (en) | Preparation method of polysubstituted (E) -trifluoromethyl olefin | |
| JPH115769A (en) | Production of tertiary amines |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| EXPY | Cancellation because of completion of term |