EP1781594A1 - Procédé de stabilisation de choline base et composition comprenant de la choline base - Google Patents

Procédé de stabilisation de choline base et composition comprenant de la choline base

Info

Publication number
EP1781594A1
EP1781594A1 EP05758588A EP05758588A EP1781594A1 EP 1781594 A1 EP1781594 A1 EP 1781594A1 EP 05758588 A EP05758588 A EP 05758588A EP 05758588 A EP05758588 A EP 05758588A EP 1781594 A1 EP1781594 A1 EP 1781594A1
Authority
EP
European Patent Office
Prior art keywords
choline
sulfite
stabilizer
composition
solution
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.)
Withdrawn
Application number
EP05758588A
Other languages
German (de)
English (en)
Inventor
Reinhard Broucek
Hendrikus A. Workel
Johannes Wilhelmus Franciscus Lucas Seetz
Gerrit Jan Oudendijk
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Akzo Nobel NV
Original Assignee
Akzo Nobel NV
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Akzo Nobel NV filed Critical Akzo Nobel NV
Priority to EP05758588A priority Critical patent/EP1781594A1/fr
Publication of EP1781594A1 publication Critical patent/EP1781594A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C215/40—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton with quaternised nitrogen atoms bound to carbon atoms of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/55—Boron-containing compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/07—Nitrogen-containing compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/11—Halides

Definitions

  • the present invention relates to a composition comprising choline hydroxide, a stabilizer, and a solvent, to a process to prepare the composition, and to the use thereof.
  • Choline hydroxide also known as choline base or (2-hydroxyethyl) trimethyl- ammonium hydroxide, is a well-known organic base suitable for many uses.
  • compositions of choline hydroxide are subject to a gradual decomposition process.
  • the main reason for this decomposition is thought to be the tendency of choline base to attack itself, as a result of which the products of this decomposition are reacted further.
  • the underlying chemistry of this degradation is quite complex and not fully understood yet, but it results in choline base solutions turning brown to black during longer storage and developing precipitates.
  • US 4,294,911 discloses the addition of a stabilizing concentration of a sulfite to an aqueous choline hydroxide composition.
  • Sulfite is normally added as the inexpensive and readily available sodium sulfite salt.
  • a disadvantage of using sodium sulfite is that concentrated choline base solutions still darken in a relatively short period of time, which is believed to be due to a low solubility of the sodium sulfite in concentrated choline base solutions. For example, in a 45 wt% aqueous choline base solution less than 0.5 wt% sodium sulfite is soluble. More soluble sulfites exist, but these are much more expensive and/or not readily available.
  • US 4,686,002 discloses the addition of a stabilizing concentration of formaldehyde to an aqueous choline hydroxide composition. Formaldehydes are banned from many applications due to environmental issues.
  • the object of the present invention is to provide a stabilized composition of choline hydroxide free of the above drawbacks.
  • composition comprising choline hydroxide, a solvent, and one or more stabilizers selected from the group consisting of a hydride and choline sulfite.
  • the stabilizer used in the composition of the present invention causes the composition to retain its white colour for a longer period of time compared to sodium sulfite.
  • the stabilizers of the present invention further have the advantage that they generally introduce less salt into the composition; a lower amount of the hydride is generally required to prevent darkening of the composition as compared to conventional compositions comprising sodium sulfite salt, and choline sulfite does not introduce any salt into the composition.
  • the solvent is water or an alcohol, more preferred is water or methanol, most preferred is water. However, also a mixture of these solvents can be used.
  • the invention relates to a composition comprising choline hydroxide and a borohydride compound wherein the amount of borohydride compound is smaller than the amount of choline hydroxide on a weight basis.
  • composition according to the invention comprises 10 to 60 wt% choline hydroxide, based on the total weight of the composition. In a more preferred embodiment the composition comprises 20 to 55 wt% choline hydroxide, based on the total weight of the composition, and in a most preferred embodiment it comprises 30 to 50 wt%.
  • the composition according to the invention comprises a hydride as stabilizer in an amount of 1 ppm to 1,000 ppm, preferably 10 ppm to 500 ppm, and most preferably 50 ppm to 200 ppm.
  • the stabilizer is choline sulfite
  • the composition according to the invention comprises 0.1 to 19 wt%, based on the total weight of the composition, preferably 0.2 to 5 wt%, and most preferably 0.5 to 1 wt% of choline sulfite.
  • compositions comprising these amounts of stabilizer reveal a higher colour stability than conventional choline base compositions containing sodium sulfite as stabilizer.
  • the present invention further pertains to a masterbatch comprising 10 to 60 wt% of choline hydroxide, 5 to 20 wt% of one or more stabilizers selected from the group consisting of a hydride and choline sulfite, with the remaining part being solvent, based on the total weight of choline hydroxide, stabilizer, and solvent.
  • a masterbatch which typically comprises a large quantity of stabilizer, can be added to a choline hydroxide solution in the desired amount in order to stabilize the solution.
  • Such masterbatches preferably comprise 8 to 15 wt% of stabilizer and most preferably between 10 and 12 wt%, based on the total weight of the masterbatch.
  • the stabilizer of the present invention is selected from the group consisting of hydrides and choline sulfite.
  • the hydride generally is a strong reducing agent and can be any hydride known to the man skilled in the art. Suitable examples of hydrides are lithium hydrides, aluminium hydrides, and borohydrides. The preferred hydrides are borohydrides.
  • borohydride refers to any compound, or mixture of compounds, comprising a molecule of boron and hydrogen, also known as hydroborons, with the formula B x Hy, x and y being integers >0, such as B 2 H 6 (boroethane), B4H10 (borobutane), B 5 Hg, and B1 0 H14 (borodecane), and anions derived therefrom such as BH 4 " .
  • Gaseous borohydrides are less preferred, as they are difficult to handle and may impose safety risks.
  • Preferred borohydrides comprise one or more anions derived from borohydride.
  • the preferred borohydride is a BH 4 " salt and particularly preferred are alkali metal borohydride salts.
  • a preferred alkali metal borohydride salt because of its commercial availability and the fact that it is relatively safe to make, handle, and use is sodium borohydride (NaBH 4 ).
  • the composition comprises a hydride, and in particular a borohydride compound, which is fixed to a polymer carrier.
  • a borohydride compound which is fixed to a polymer carrier.
  • the use of such a (boro)hydride compound has the advantage that the (boro)hydride stabilizer may be easily removed from the choline base solution when desired, for example when the choline base solution is used in an application where the (boro)hydride or the inorganic counterion has a detrimental effect.
  • the composition comprises one or more additional stabilizing compounds.
  • additional stabilizing compounds include sulfites, formaldehyde, hydroxylamines, derivatives and mixtures thereof.
  • the second stabilizing compound is a sulfite or a sulfite derivative.
  • Sulfite derivatives include for example dithionites.
  • the sulfite is sodium sulfite.
  • two or more additional stabilizing compounds are used.
  • the stabilizer and in particular of the borohydrides, are their reducing power and their compatibility with the choline base production process. Because of their reducing power the choline base solution is clear and paper white.
  • the hydrides, and in particular the borohydride compounds can even be added to a choline base mixture that is already yellowed and still provide a clear and white solution.
  • stabilizers of the invention are stable under strongly alkaline conditions. This means that the concentration of the stabilizer in choline base can be increased to amounts sufficiently high to combine the desired properties of both choline hydroxide and stabilizer. This is particularly advantageous when borohydrides are used as stabilizer.
  • the process further pertains to a process for preparing the composition according to any one of claims 1-5 by combining one or more stabilizers selected from the group consisting of a hydride and choline sulfite with a choline hydroxide solution.
  • the current invention also relates to a process for preparing the composition of the invention comprising the steps of reacting ethylene oxide with trimethylamine in the presence of one or more stabilizers selected from the group consisting of a hydride and choline sulfite, said stabilizer being added to the ethylene oxide, the trimethyl amine and/or the reaction mixture.
  • This process for preparing choline base is generally carried out by reacting ethylene oxide with trimethyl amine in an inert atmosphere at a temperature of 0 to 70 0 C.
  • choline sulfite is used as the stabilizer, it is also envisaged to prepare the choline sulfite in situ by subjecting the choline hydroxide solution produced by reacting ethylene oxide and trimethyl amine to sulfur dioxide.
  • the resulting amount of choline sulfite in the chlorine hydroxide solution will depend on the period of time the choline hydroxide solution is subjected to the sulfur dioxide.
  • the resulting amount of choline sulfite can be set as desired.
  • the stabilizer in particular a borohydride
  • the stabilizer is used in an amount such that 1-1,000 ppm, preferably 10-500 ppm, more preferably 50-200 ppm of borohydride is present on the total weight of the final product solution.
  • the stabilizer is used in an amount such that 5 to 20 wt%, preferably 8-15 wt%, and most preferably 10-12 wt% is present on the total weight of the final product solution.
  • the choline base is prepared at a temperature between 10 and 5O 0 C and an inert atmosphere is created by flushing the reactor and the solution with an inert gas, while a safety pressure of the inert gas - normally nitrogen - is maintained during the reaction step.
  • the. .temperature is between 15 and 45°C, most preferred is a temperature of about room temperature.
  • compositions according to the present invention are suitable for many applications. As already indicated above, as the amount of stabilizer in a choline base can be relatively high, the compositions can also be used in applications where the stabilizer is active as well. In this respect, the stabilizers of the invention, and in particular borohydride, are particularly suitable for use in the production and bleaching of paper.
  • a method to bleach paper pulp is also covered by the present application.
  • paper pulp is contacted with the compositions according to the present invention.
  • Aqueous compositions comprising a borohydride salt are known for bleaching paper and are disclosed, e.g., in WO 88/10334.
  • aqueous compositions comprising choline hydroxide and a borohydride salt for bleaching paper are not disclosed for this use.
  • borohydride solutions known to be used in applications where borohydride is active often are solutions of borohydride in caustic, which often makes them less suitable for applications that are not compatible with a caustic solution, such as the production of paper.
  • a solution of choline base in water is prepared in a 1 -litre pressure autoclave by reacting 116 g of ethylene oxide with a solution of 150 g of trimethylamine in 417 g of water. By using a cooling jacket the temperature during the reaction is kept between 15 and 45 0 C. Before starting the reactor is flushed with nitrogen and a safety pressure of 2-3 bar nitrogen is maintained during the ethoxylation step.,. The resulting solution of 45 wt% of choline base in water is used in Examples 1 - 3 below.
  • a solution of choline sulfite is prepared by adding gaseous sulfur dioxide in a stoichiometric amount to the 45 wt% aqueous choline base solution of Prep.
  • Example A The resulting 53 wt% solution of choline sulfite is used in Examples 1 , 2, 5, and 6 below.
  • a solution of sodium borohydride in choline base is prepared by adding solid sodium borohydride to a 45 wt% aqueous choline base solution of Prep. Example A until a concentration of 12 wt% borohydride is reached. The resulting aqueous composition is used in Preparation Example D below.
  • a solution of choline base in water is made in a 1 -litre pressure autoclave by reacting 116 g ethylene oxide and 15O g of trimethylamine in 417 g of water. By using a cooling jacket the temperature during the reaction is kept between 15 and 45 0 C. Before starting the reactor is flushed with nitrogen and a safety pressure of 2-3 bar of nitrogen is maintained during the ethoxylation step. Before starting the reaction 0.85g of the borohydride solution described in Example C is added. The resulting aqueous composition is used in Examples 4 and 5 below.
  • Example A Two samples of 110 g of the choline base solution of Prep.
  • Example A were drawn into 100 ml sample bottles under flushing with nitrogen. Choline sulfite solution of preparation example B was added till the total concentration of choline sulfite in the sample was 0.2 wt%.
  • the sample bottles were closed and stored under ambient conditions. After 4 months the solutions were slightly yellow but still clear (i.e. free of precipitates).
  • Example A Two samples of 110 g of the choline base solution of Prep.
  • Example A were drawn into 100 ml sample bottles under flushing with nitrogen.
  • Choline sulfite solution of preparation Example B was added till the total concentration of choline sulfite in the sample was 0.4 wt%.
  • the sample bottles were closed and stored under ambient conditions. After 4 months the solutions were slightly yellow but still clear. Comparative Example 3
  • Example A Two samples of 110 g of the choline base solution of Prep. Example A were drawn into 100 ml sample bottles under flushing with nitrogen. Paraformaldehyde was added till the total concentration of paraformaldehyde in the sample was 0.4 wt%. The sample bottles were closed and stored under ambient conditions. After 4 months the solutions were darkened and a layer of brown precipitates had formed on the bottom of the sample bottles
  • Example D Two samples of 110 g of the choline base solution of Prep. Example D were drawn into 100 ml sample bottles under flushing with nitrogen. The sample bottles were closed and stored under ambient conditions. After 4 months the solutions were still clear and paper white.
  • Example D Two samples of 110 g of the choline base solution of Prep. Example D were drawn into 100 ml sample bottles under flushing with nitrogen. Choline sulfite solution of preparation Example B was added till the total concentration of choline sulfite in both samples was 0.4 wt%. The sample bottles were closed and stored under ambient conditions. After 4 months the solutions were still clear and paper white.
  • Example D Two samples of 110 g of the choline base solution of Prep. Example D were drawn into 100 ml sample bottles under flushing with nitrogen. Choline sulfite solution of preparation Example B was added till the total concentration of choline sulfite in both samples was 2.6 wt%. The sample bottles were closed and stored under ambient conditions. After 4 months the solutions were still clear and paper white.
  • Example D Two samples of 110 g of the choline base solution of Prep. Example D were drawn into 100 ml sample bottles under flushing with nitrogen. Sodium sulfite was added till the total concentration of sodium sulfite in both samples was 0.5 wt%. The sample bottles were closed and stored under ambient conditions. After 4 months the solutions were still clear and paper white, but a white layer of unsolved sodium sulfite had formed on the bottom of the sample bottle.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Paper (AREA)

Abstract

La présente invention a trait à une composition comportant de la choline hydroxyde, un solvant, et un ou des agents stabilisateurs choisis parmi le groupe constitué d'un hydrure et de sulfite de choline.
EP05758588A 2004-07-09 2005-07-04 Procédé de stabilisation de choline base et composition comprenant de la choline base Withdrawn EP1781594A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP05758588A EP1781594A1 (fr) 2004-07-09 2005-07-04 Procédé de stabilisation de choline base et composition comprenant de la choline base

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP04076991 2004-07-09
US60735004P 2004-09-07 2004-09-07
EP05758588A EP1781594A1 (fr) 2004-07-09 2005-07-04 Procédé de stabilisation de choline base et composition comprenant de la choline base
PCT/EP2005/053160 WO2006005692A1 (fr) 2004-07-09 2005-07-04 Composition comportant de la choline hydroxyde et son procede de preparation

Publications (1)

Publication Number Publication Date
EP1781594A1 true EP1781594A1 (fr) 2007-05-09

Family

ID=34928350

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05758588A Withdrawn EP1781594A1 (fr) 2004-07-09 2005-07-04 Procédé de stabilisation de choline base et composition comprenant de la choline base

Country Status (8)

Country Link
US (1) US20070193708A1 (fr)
EP (1) EP1781594A1 (fr)
JP (1) JP2008505867A (fr)
CN (1) CN1984875A (fr)
CA (1) CA2573213A1 (fr)
MX (1) MX2007000298A (fr)
RU (1) RU2007104939A (fr)
WO (1) WO2006005692A1 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140329184A1 (en) * 2011-11-22 2014-11-06 Taminco Stabilized choline solutions and methods for preparing the same
WO2013077855A1 (fr) * 2011-11-22 2013-05-30 Taminco N.V. Solutions de choline stabilisées et leurs procédés de préparation
CN104066711B (zh) * 2011-12-29 2017-04-19 塔明克公司 生产氢氧化胆碱的方法
IN2014DN05702A (fr) * 2012-01-19 2015-04-10 Dow Agrosciences Llc
CN107325009B (zh) * 2012-04-13 2022-03-18 亨斯迈石油化学有限责任公司 使用新颖的胺来稳定化季三烷基烷醇胺
MX353852B (es) 2013-04-11 2018-01-30 Taminco Procedimiento mejorado para preparar hidróxido de colina.
KR102338550B1 (ko) 2013-06-06 2021-12-14 엔테그리스, 아이엔씨. 질화 티타늄의 선택적인 에칭을 위한 조성물 및 방법
JP7036212B2 (ja) * 2018-04-26 2022-03-15 栗田工業株式会社 第四級トリアルキルアルカノールアミン水酸化物を含む組成物の安定化
CN109503395B (zh) * 2018-12-26 2021-11-16 济南蓬勃生物技术有限公司 一种稳定的胆碱溶液及其制备方法
CN109748808B (zh) * 2018-12-26 2021-12-24 济南蓬勃生物技术有限公司 一种胆碱碳酸氢盐和碳酸盐的制备方法
CN113548973A (zh) * 2021-07-28 2021-10-26 上海德迈世欧化工有限公司 一种电子级氢氧化胆碱溶液的制备方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1397732A (en) * 1971-07-26 1975-06-18 Mundipharma Ag Stabilized choline salicylate compounds
IT975184B (it) * 1971-10-06 1974-07-20 Weyerhaeuser Co Rivestimento elettroconduttivo particolarmente per la copiatura elettrostatografica e procedimen to per la sua preparazione ed im piego
US4294911A (en) * 1979-06-18 1981-10-13 Eastman Kodak Company Development of light-sensitive quinone diazide compositions using sulfite stabilizer
GB2153373A (en) * 1984-01-30 1985-08-21 Procter & Gamble Process for minimizing color formation during base catalyzed ethoxylation of 2- hydroxyethylamines
US4686002A (en) * 1986-07-18 1987-08-11 Syntex (U.S.A.) Inc. Stabilized choline base solutions
DE69608669T2 (de) * 1995-12-19 2001-03-01 Fsi International Chaska Stromloses aufbringen von metallfilmen mit sprayprozessor
US20030211618A1 (en) * 2001-05-07 2003-11-13 Patel Gordhandhai Nathalal Color changing steam sterilization indicator

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2006005692A1 *

Also Published As

Publication number Publication date
WO2006005692A1 (fr) 2006-01-19
CA2573213A1 (fr) 2006-01-19
CN1984875A (zh) 2007-06-20
JP2008505867A (ja) 2008-02-28
US20070193708A1 (en) 2007-08-23
RU2007104939A (ru) 2008-08-20
MX2007000298A (es) 2007-04-02

Similar Documents

Publication Publication Date Title
US20070193708A1 (en) Composition Comprising Choline Hydroxide And Process For Preparing The same
KR101563247B1 (ko) 테트라플루오로 붕산 리튬 용액의 제조 방법
EP2782899B1 (fr) Solutions de choline stabilisées et leurs procédés de préparation
AU2014253067C1 (en) Improved process for preparing choline hydroxide
CA2485228A1 (fr) Procede de preparation de solutions concentrees d'hypobromites stabilises
US6781005B1 (en) Process for the fluorination of boron hydrides
KR20070031397A (ko) 콜린 수산화물을 포함하는 조성물 및 이를 제조하는 방법
US9079829B2 (en) Method of preparing powder of a solid carbazic acid derivative
EP3541782B1 (fr) Procédé de fabrication de n-(fluorosulfonyl) diméthylamine
CN104557770A (zh) 以次氯酸钠为氧化剂合成橡胶硫化促进剂ns的方法
CN114835605A (zh) 二苯甲酮腙的合成方法
US20140329184A1 (en) Stabilized choline solutions and methods for preparing the same
KR20200135212A (ko) 고체 아민을 활용한 페로브스카이트 유기-무기 복합 소재의 제조 방법
EP2984068B1 (fr) Procédé amélioré pour préparer l'hydroxyde de choline
JP2014065638A (ja) ヨウ化リチウム水溶液の製造方法及びその利用
CN101948417A (zh) 一种橡胶硫化促进剂二硫化二异丁基秋兰姆(TiBTD)的制备方法
US20200317603A1 (en) Process for stabilization of at least monoalkyl-substituted diaminocyclohexanes
CN109503395A (zh) 一种稳定的胆碱溶液及其制备方法
WO2022089774A8 (fr) Procédé de préparation de 1,2-benzisothiazoline-3-one
US3445198A (en) Atmosphere regenerants and method of preparing same
WO2005044806A1 (fr) Procede de preparation d'un trifluoromethylthioether
CN105175286A (zh) 一种盐酸烷基胍盐的制备方法
KR20070022639A (ko) 시클로알킬-히드라진의 엑소시클릭 유도체 및헤테로시클로알킬-히드라진의 엑소시클릭 유도체의합성방법

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20061214

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20100202