EP1216220A1 - Verfahren zur herstelung von substituierten alkynischen mischethern - Google Patents

Verfahren zur herstelung von substituierten alkynischen mischethern

Info

Publication number
EP1216220A1
EP1216220A1 EP00966235A EP00966235A EP1216220A1 EP 1216220 A1 EP1216220 A1 EP 1216220A1 EP 00966235 A EP00966235 A EP 00966235A EP 00966235 A EP00966235 A EP 00966235A EP 1216220 A1 EP1216220 A1 EP 1216220A1
Authority
EP
European Patent Office
Prior art keywords
group
carbon atoms
linear
groups
branched
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Withdrawn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
EP00966235A
Other languages
English (en)
French (fr)
Inventor
Roland Jacquot
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.)
Rhodia Chimie SAS
Original Assignee
Rhodia Chimie SAS
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 Rhodia Chimie SAS filed Critical Rhodia Chimie SAS
Publication of EP1216220A1 publication Critical patent/EP1216220A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation

Definitions

  • the present invention relates to a process for preparing substituted alkynic mixed ethers.
  • the invention relates more particularly to the preparation of mixed ethers derived from a benzyl alcohol and a substituted alkynic alcohol
  • the benzyl alcohol used has the following general formula:
  • - A symbolizes the remainder of a cycle forming all or part of a carbocyclic or heterocyclic, aromatic, monocyclic or polycyclic system
  • - R represents one or more substituents, identical or different
  • R- R- ⁇ and R identical or different, represent a hydrogen atom, a functional group or a hydrocarbon group having from 1 to 24 carbon atoms,
  • benzyl alcohol denotes not only an aromatic carbocycle but also an aromatic heterocycle of which a directly attached hydrogen atom the aromatic nucleus is replaced by a group I
  • R5 represents a hydrocarbon group having from 1 to 24 carbon atoms, which can be a saturated or unsaturated, linear or branched acyclic aliphatic group; a saturated, unsaturated or aromatic cycloaliphatic group; a saturated or unsaturated, linear or branched aliphatic group, carrying a cyclic substituent.
  • the ether of the benzyl alcohol of formula (F1) and of the alcohol of formula (F2) obtained can (F3).
  • unsaturated alcohols such as substituted alkynic alcohols, in particular 2-butyn-1 -ol represented by the formula CH 3 -C ⁇ C-CH 2 -OH .
  • the object of the present invention is to provide an inexpensive process for preparing an ether derived from an alcohol of the benzyl type and from a substituted alkynic alcohol, that is to say that the hydrogen atom of the function alkyne is substituted by a hydrocarbon group.
  • - R represents one or more substituents, identical or different
  • - Ri and R 2 identical or different, represent a hydrogen atom, a functional group or a hydrocarbon group having from 1 to 24 carbon atoms, which can be a saturated or unsaturated, linear or branched acyclic aliphatic group; a saturated, unsaturated or aromatic, monocyclic or polycyclic cycloaliphatic group; a saturated or unsaturated, linear or branched aliphatic group, carrying a cyclic substituent, - R3 and R4, identical or different, represent a hydrogen atom or a hydrocarbon group having from 1 to 12 carbon atoms,
  • - n is a number less than or equal to 5
  • - x is a number ranging from 1 to 10. preferably from 1 to 5.
  • the mixed alkynic ether which is involved in the process of the invention corresponds to formula (I) in which R ⁇ and R 2 represent an acyclic aliphatic group, saturated or unsaturated, linear or branched.
  • R-, and R 2 represent a linear or branched alkyl group having from 1 to 12 carbon atoms, preferably from 1 to 6 carbon atoms: the hydrocarbon chain can possibly be interrupted by a heteroatom (for example, l 'oxygen), by a functional group (for example -CO-) and / or carrying a substituent (for example, a halogen).
  • a heteroatom for example, l 'oxygen
  • a functional group for example -CO-
  • a substituent for example, a halogen
  • the acyclic, saturated or unsaturated, linear or branched aliphatic group may optionally carry a cyclic substituent.
  • cycle is preferably meant a carbocyclic or heterocyclic, saturated, unsaturated or aromatic, preferably cycloaliphatic or aromatic, in particular cycloaliphatic, cycle comprising 6 carbon atoms in the benzene ring.
  • the acyclic aliphatic group can be linked to the cycle by a valential link, a heteroatom or a functional group and examples are given above.
  • the ring can be optionally substituted and, by way of examples of cyclic substituents, it is possible to envisage, among others, the substituents such as R, the meaning of which is specified below.
  • R 1 and R 2 may also represent a carbocyclic group saturated or comprising 1 or 2 unsaturations in the ring, generally having from 3 to 8 carbon atoms, preferably 6 carbon atoms in the ring; said cycle possibly being substituted by substituents such as R.
  • R 1 and R 2 may also represent an aromatic carbocyclic group, preferably a monocyclic group generally having at least 4 carbon atoms, preferably 6 carbon atoms in the ring; said cycle possibly being substituted by substituents such as R.
  • and R 2 can represent a group CF 3 .
  • the invention applies in particular to mixed alkynic ethers corresponding to formula (I) in which A is the residue of a cyclic compound, preferably having at least 4 atoms in the ring, preferably 5 or 6, optionally substituted, and representing at least one of the following cycles: - an aromatic, monocyclic or polycyclic carbocycle,
  • an aromatic, monocyclic or polycyclic heterocycle comprising at least one of the heteroatoms O, N and S,
  • the optionally substituted residue A represents, the remainder: - of a monocyclic, carbocyclic, aromatic compound, such as, for example, benzene or toluene,
  • naphthalene a polycyclic, condensed, aromatic compound, such as, for example, naphthalene
  • - a monocyclic, heterocyclic, aromatic compound, such as, for example, pyridine, furan, thiophene.
  • the residue A of the mixed alkynic ether of formula (I) can carry one or more substituents insofar as they do not react with the anionization reagent.
  • the number of substituents present on the cycle depends on the carbon condensation of the cycle and on the presence or not of unsaturations on the cycle.
  • substituents are given below, but this list is not limiting. Mention may in particular be made of: the linear or branched alkyl groups preferably having from 1 to 6 carbon atoms and even more preferably from 1 to 4 carbon atoms,
  • cycloalkyl groups having from 3 to 6 carbon atoms, preferably the cyclohexyl group,
  • R5-O- or thioether R5-S- in which R 5 represents a linear or branched alkyl group having from 1 to 6 carbon atoms and even more preferably from 1 to 4 carbon atoms or the phenyl group,
  • R 6 - -N- (R 6 ) 2 groups in which the identical or different R 6 groups represent a hydrogen atom, a linear or branched alkyl group having from 1 to 6 carbon atoms and even more preferably from 1 to 4 atoms carbon or a phenyl group,
  • two R groups and the two successive atoms of the aromatic ring can be linked together by an alkylene, alkenylene or alkenylidene group having from 2 to 4 carbon atoms to form a saturated, unsaturated or aromatic heterocycle having 5 to 7 carbon atoms.
  • One or more carbon atoms can be replaced by another heteroatom, preferably oxygen.
  • the R groups can represent a methylenedioxy or ethylenedioxy group.
  • Preferred substituents are selected from electron donor groups.
  • electron donor group is understood to mean a group as defined by HC BROWN in the work of Jerry MARCH - Advanced Organic Chemistry, chapter 9, pages 243 and 244 (1985).
  • R 3 and R in formula (I) they more particularly represent a hydrogen atom or a linear or branched alkyl group having from 1 to 12 carbon atoms, preferably from 1 to 4 .
  • R 3 and R 4 represent a hydrogen atom, a methyl, ethyl, propyl or isopropyl group.
  • R 3 and R 4 represent a hydrogen atom.
  • x is a number equal to 1, 2 or 3.
  • - n is a number less than or equal to 4, preferably equal to 1 or 2,
  • - x is a number equal to 1, 2 or 3,
  • the group or groups R are an electron-donor group, preferably an alkyl or alkoxy group having 1 or 4 carbon atoms or methylenedioxy or ethylenedioxy,
  • an alkyl group linear or branched, having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl,.
  • a cycloalkyl group having 3 to 8 carbon atoms, preferably a cyclopentyl or cyclohexyl group,.
  • R 3 and R 4 which are identical or different, represent a hydrogen atom or a linear or branched alkyl group having from 1 to 4 carbon atoms.
  • - n is a number equal to 1 or 2
  • - x is a number equal to 1, 2 or 3
  • the groups R which are identical or different, represent an alkyl or alkoxy group having 1 or 4 carbon atoms or methylenedioxy or ethylene dioxy,
  • an alkyl group linear or branched, having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl.
  • the groups R 3 and R 4 which are identical or different, represent a hydrogen atom or a linear or branched alkyl group having from 1 to 4 carbon atoms.
  • - n is a number equal to 1 or 2
  • the group or groups R represent an alkyl or alkoxy group having from 1 to 4 carbon atoms or methylenedioxy
  • the group R- represents a hydrogen atom or an alkyl group, linear or branched, having from 1 to 4 carbon atoms.
  • the compounds of formula (I) can be prepared according to the teaching of application PCT / FR / 98/01472 according to a process which consists in reacting, in the presence of a zeolite:
  • R, R *), R 2 ⁇ A and n have the meaning given above.
  • R 3 , R 4 and x have the meaning given above.
  • Compounds (II) and (III) are reacted in the presence of a zeolite.
  • a zeolite is used such as: the mordenite with an Si / Ai molar ratio of 5 to 150, preferably of 10 to 100 and even more preferably of 10 to 25,
  • - ⁇ zeolites with an Si / Ai molar ratio greater than 8, preferably between 10 to 100, and even more preferably from 12 to 50,
  • the reaction of the benzyl alcohol of formula (II) with the unsaturated alcohol of formula (III) can be carried out in the presence or in the absence of an organic solvent, one of the reagents being able to be used as solvent reaction.
  • solvents suitable for the present invention there may be mentioned, without limitation, aliphatic, cycloaliphatic or aromatic ether-oxides and, more particularly, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl oxide, methyltertiobutylether, dipentyl oxide, diisopentyl oxide, phenyl oxide, benzyl oxide; dioxane, tetrahydrofuran (THF).
  • the catalyst can represent, by weight relative to the faulty reagent, from 2 to 50%, preferably from 5 to 20%.
  • the process is carried out continuously, for example by reacting a mixture of the benzyl alcohol and unsaturated alcohol on a fixed bed of catalyst, these catalyst / benzyl alcohol ratios are meaningless and at a given time, there may be an excess weight of catalyst relative to the starting benzyl alcohol.
  • the amount of unsaturated alcohol of formula (III) expressed in moles. of unsaturated alcohol per mole of benzyl alcohol of formula (II) can also vary within wide limits.
  • the molar ratio of unsaturated alcohol of formula (III) / benzyl alcohol of formula (II) can vary between 1 and 30.
  • the upper bound is not critical, but however for economic reasons, there is no point in exceeding it .
  • the temperature of the etherification reaction can vary widely. It is chosen, advantageously between 50 ° C and 200 ° C and even more preferably between 50 ° C and 100 ° C.
  • reaction is carried out at atmospheric pressure, but higher pressures may also be suitable, ranging from 1 to 50 bar, preferably from 1 to 25 bar.
  • pressures may also be suitable, ranging from 1 to 50 bar, preferably from 1 to 25 bar.
  • inert gases such as nitrogen or rare gases, for example argon.
  • the duration of the reaction can be very variable. It is most often between 15 minutes and 10 hours, preferably between 30 minutes and 5 hours.
  • the process can be carried out batchwise or continuously.
  • the catalyst it is possible to charge the catalyst, the unsaturated alcohol of formula (III), optionally an organic solvent, then the alcohol of the benzyl type is introduced.
  • a preferred mode of the invention consists in gradually introducing the benzyl alcohol, continuously or in fractions, then the reaction mixture is brought to the desired temperature.
  • the other variant of the invention consists in carrying out the reaction continuously, in a tubular reactor comprising the solid catalyst placed in a fixed bed.
  • the benzyl alcohol and the unsaturated alcohol are preferably introduced separately. They can also be introduced into a solvent as mentioned above.
  • the residence time of the material flow on the catalytic bed varies, for example, between 15 min and 10 hours, and preferably between 30 min and 5 hours.
  • a liquid phase comprising the alcohol of the etherified benzyl type corresponding to formula (I) which can be recovered in a conventional manner.
  • the C-alkylation reaction of the compound of formula (I), previously obtained, is carried out using an alkylating agent.
  • a first class of alkylating agents which can be used in the process of the invention are dialkylsulfates.
  • dialkyl sulphates of the formula may be used:
  • dimethyl sulphate is preferred.
  • Another class suitable for the invention are the halide type compounds, in particular those represented by the following formula:
  • R 8 represents a hydrocarbon group having from 1 to 20 carbon atoms which can be a saturated or unsaturated, linear or branched acyclic aliphatic group; a saturated, unsaturated or aromatic, monocyclic or polycyclic cycloaliphatic group; a saturated or unsaturated, linear or branched aliphatic group carrying a cyclic substituent;
  • - X represents a bromine, chlorine or iodine atom.
  • ring is preferably understood to mean a carbocyclic or heterocyclic, saturated, unsaturated or aromatic, preferably cycloaliphatic or aromatic, in particular cycloaliphatic, ring comprising 6 carbon atoms in the ring or benzene.
  • R 8 represents a linear or branched C 1 to C 10 alkyl group, C 3 to C 10 cycloalkyl, C 6 to C 12 aryl or C arylalkyl 7 to C 15 such as for example a benzyl group.
  • halide of formula (IVb) it is preferred to use those corresponding to formula (IVb) in which X is a chlorine or iodine atom and R 8 is a linear or branched alkyl group having from 1 to 4 atoms. carbon.
  • methyl iodide methyl chloride, chloroethane, methyl bromide and bromoethane are used.
  • the amount of alkylating agent used is equal to or greater than the stoichiometric amount necessary to alkylate the hydrogen atom of the alkyne function
  • the alkylating agent is used in an amount such that the ratio between the number of moles of the alkylating agent and the number of hydrogen atoms replaced by an alkyl group Rg (Rg representing R 7 or R 3 ), varies between 1 and 2, preferably between 1, 1 and 1, 3.
  • the mixed alkynic ether of formula (I) and the alkylating agent are reacted in the presence of a reagent of anionization of the alkyne function thus making it possible to transform it into G ⁇ C function ".
  • An organic base of amide type can be used, for example lithium diisopropylamide, lithium hexamethyldisilazane prepared or used in situ by the action of a strong lithiated base on the corresponding amine, but it is preferred to use a mineral salt, preferably an alkali metal amide and more particularly sodium or potassium amide.
  • alkali metal alcoholate preferably a sodium or potassium alcoholate, preferably sodium or potassium methylate, ethylate or tert-butoxide. It is also possible to use an alkali metal, preferably sodium or potassium.
  • the amount of anionization reagent is at least equal to the required stoichiometric amount but it is generally used in an excess of up to 20%.
  • the reaction is carried out in an organic solvent inert with respect to the anionization reagent. Mention may in particular be made of aliphatic or aromatic hydrocarbons.
  • aliphatic hydrocarbons there may be mentioned more particularly paraffins such as in particular, hexane, heptane, octane, nonane, decane, undecane, dodecane, tetradecane or cyclohexane , and aromatic hydrocarbons and more particularly aromatic hydrocarbons such as in particular benzene, toluene, xylenes, cumene, petroleum fractions consisting of a mixture of alkylbenzenes, in particular cuts of the Solvesso® type.
  • aromatic hydrocarbons such as in particular benzene, toluene, xylenes, cumene, petroleum fractions consisting of a mixture of alkylbenzenes, in particular cuts of the Solvesso® type.
  • solvents toluene is preferably used.
  • the amount of organic solvent used can vary widely. Thus, it is such that the weight concentration of the compound of formula is advantageously between 5 and 50%, preferably between 20 and 30%.
  • the temperature to which the process of the invention is carried out is generally chosen between 20 ° C. and the reflux temperature of the reaction mixture, preferably between 50 and 80 ° C.
  • the reaction pressure is chosen by a person skilled in the art depending on the nature of the alkylating agent. It can be between 10 ⁇ 2 and 50 bars, preferably atmospheric pressure.
  • the method of the invention is easy to implement since it does not require the use of specific apparatus.
  • reaction mixture The various constituents of the reaction mixture are loaded into the chosen apparatus. There is no critical order of introduction.
  • the compound of formula (I) is brought into contact with the anionization reagent.
  • the reaction medium is brought to the desired temperature and then the alkylating agent is added.
  • the desired product is then recovered in a conventional manner.
  • reaction medium is brought to 20 ° C. and 126 g of methyl sulfate are poured in over 15 min.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP00966235A 1999-09-29 2000-09-29 Verfahren zur herstelung von substituierten alkynischen mischethern Withdrawn EP1216220A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9912146A FR2798928B1 (fr) 1999-09-29 1999-09-29 Procede de preparation d'ethers mixtes alcyniques substitues
FR9912146 1999-09-29
PCT/FR2000/002704 WO2001023338A1 (fr) 1999-09-29 2000-09-29 Procede de preparation d'ethers mixtes alcyniques substitues

Publications (1)

Publication Number Publication Date
EP1216220A1 true EP1216220A1 (de) 2002-06-26

Family

ID=9550372

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00966235A Withdrawn EP1216220A1 (de) 1999-09-29 2000-09-29 Verfahren zur herstelung von substituierten alkynischen mischethern

Country Status (7)

Country Link
US (1) US6881869B1 (de)
EP (1) EP1216220A1 (de)
JP (1) JP2003510301A (de)
AU (1) AU7669300A (de)
FR (1) FR2798928B1 (de)
HU (1) HUP0202831A3 (de)
WO (1) WO2001023338A1 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB201104156D0 (en) 2011-03-11 2011-04-27 Rothamstead Res Ltd Compositions and methods for controlling pesticide resistant pests
US8747639B2 (en) 2011-03-31 2014-06-10 Pratt & Whitney Canada Corp. Metal plating method and apparatus
EP3208863B1 (de) * 2016-02-22 2019-10-23 Novaled GmbH Ladungsübertragendes halbleitermaterial und elektronische vorrichtung damit

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1190714B (it) * 1982-03-04 1988-02-24 Montedison Spa Processo per la preparazione del composto 1-decilossi-4-((7-ossa-4-ottinil)-ossi)-benzene
HU220697B1 (hu) * 1995-11-21 2002-04-29 AGRO-CHEMIE Növényvédőszer Gyártó, Értékesítő és Forgalmazó Kft. Arthropodicid hatóanyagok, eljárás előállításukra és ezeket a hatóanyagokat tartalmazó készítmények
FR2765870B1 (fr) * 1997-07-09 1999-09-03 Rhodia Chimie Sa Procede d'etherification d'un alcool de type benzylique

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SLOCUM W. ET AL: "Metalation in hydrocarbon solvents: the mechanistic aspects of substrate-promoted ortho-metalations", TETRAHEDRON LETTERS, vol. 59, 2003, pages 8275 - 8284, XP004458584, DOI: doi:10.1016/j.tet.2003.07.010 *

Also Published As

Publication number Publication date
WO2001023338A1 (fr) 2001-04-05
FR2798928A1 (fr) 2001-03-30
US6881869B1 (en) 2005-04-19
HUP0202831A2 (hu) 2002-12-28
FR2798928B1 (fr) 2003-04-11
JP2003510301A (ja) 2003-03-18
HUP0202831A3 (en) 2003-11-28
AU7669300A (en) 2001-04-30

Similar Documents

Publication Publication Date Title
WO2005082820A1 (fr) Procedure de preparation d'un compose fluoroaromatique a partir d'un compose aminoaromatique.
CH636848A5 (fr) Procede de production de n,n-di(ethyl)-meta-toluamide.
EP2139853A1 (de) Verfahren zur herstellung von carbenvorläufern des caac-typs und ihre verwendung zur herstellung besagter carbene
EP0877726B1 (de) Verfahren zur acylierung einer aromatischen verbindung
WO1996035656A1 (fr) Procede d'acylation d'ethers aromatiques
EP1234811B1 (de) Verfahren zur Herstellung von Monoarylalkylethern
EP1910256A2 (de) Verfahren für die c-alkylierung aromatischer hydroxylverbindungen
WO2001023338A1 (fr) Procede de preparation d'ethers mixtes alcyniques substitues
FR2486069A2 (fr) Procede pour la preparation de 2-methylene-aldehydes
CA2471463C (fr) Composes (aryl) (amino)boranes, procede pour leur preparation
WO2005095307A1 (fr) Procede de formation d'une liaison carbone-carbone comprenant une reaction d’un arenediazoether
EP1255715A1 (de) Verfahren zur herstellung von polyaromatischen verbindungen
EP1095035B1 (de) Verfahren zur herstellung vom 4-(3-pyridinyl)-1h-imidazol und die zugehörigen zwischenprodukte
EP0091385A1 (de) Verfahren zur Herstellung von p-Hydroxybenzylnitrilen oder p-Hydroxybenzylaminen
EP0876340B1 (de) Verfahren zur acylierung von aromatischen thioethern
EP1250303A1 (de) Verfahren zur herstellung von alpha-halogenierten ketonen
EP0127536B1 (de) Verfahren zur Herstellung von alpha-delta-diethylenischen Carbonylverbindungen
FR2730731A1 (fr) Procede de carboxylation d'un ether aromatique
FR2793792A1 (fr) Procede d'alpha-metallation d'un derive heterocyclique, monocyclique ou polycyclique et possedant au moins un heterocycle a 5 atomes, insature ou aromatique
WO2003010156A1 (fr) Procede de preparation de alpha-halogenoalkylarylcetones et de leurs produits intermediaires halogenes de type cetal cyclique
FR2787787A1 (fr) Procede de preparation de thioethers aromatiques de type diphenyle
WO2003048145A2 (fr) Procede de preparation d'un compose de type aminobenzofuranne.
EP1663914A2 (de) Verfahren zur bildung einer kohlenstoff-kohlenstoff- oder kohlenstoff-heteroatom-bindung
KR20060096427A (ko) 1-[시아노(페닐)메틸]-사이클로헥사놀 화합물의 제조 방법
FR2461704A1 (fr) Compose basique de styrene et procede pour sa preparation

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: 20020213

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

17Q First examination report despatched

Effective date: 20030610

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

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: 20050614