WO2003011844A2 - Reactif et procede pour la perfluoroalcoylation - Google Patents
Reactif et procede pour la perfluoroalcoylation Download PDFInfo
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- WO2003011844A2 WO2003011844A2 PCT/FR2002/002424 FR0202424W WO03011844A2 WO 2003011844 A2 WO2003011844 A2 WO 2003011844A2 FR 0202424 W FR0202424 W FR 0202424W WO 03011844 A2 WO03011844 A2 WO 03011844A2
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- 0 CC(C)[C@](C)*C(*)(C(F)(F)F)O Chemical compound CC(C)[C@](C)*C(*)(C(F)(F)F)O 0.000 description 1
- KZJRKRQSDZGHEC-UHFFFAOYSA-N O=C(C(F)(F)F)c1ccccc1 Chemical compound O=C(C(F)(F)F)c1ccccc1 KZJRKRQSDZGHEC-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
- C07D295/182—Radicals derived from carboxylic acids
- C07D295/185—Radicals derived from carboxylic acids from aliphatic carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
- C07C233/04—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C233/05—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/12—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by halogen atoms or by nitro or nitroso groups
- C07C233/13—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by halogen atoms or by nitro or nitroso groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/64—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by simultaneous introduction of -OH groups and halogens
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C313/00—Sulfinic acids; Sulfenic acids; Halides, esters or anhydrides thereof; Amides of sulfinic or sulfenic acids, i.e. compounds having singly-bound oxygen atoms of sulfinic or sulfenic groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C313/02—Sulfinic acids; Derivatives thereof
- C07C313/04—Sulfinic acids; Esters thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C313/00—Sulfinic acids; Sulfenic acids; Halides, esters or anhydrides thereof; Amides of sulfinic or sulfenic acids, i.e. compounds having singly-bound oxygen atoms of sulfinic or sulfenic groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C313/02—Sulfinic acids; Derivatives thereof
- C07C313/06—Sulfinamides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/22—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with hetero atoms directly attached to ring nitrogen atoms
- C07D295/26—Sulfur atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H11/00—Compounds containing saccharide radicals esterified by inorganic acids; Metal salts thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H13/00—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids
- C07H13/02—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids
- C07H13/04—Compounds containing saccharide radicals esterified by carbonic acid or derivatives thereof, or by organic acids, e.g. phosphonic acids by carboxylic acids having the esterifying carboxyl radicals attached to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
- C07C2603/18—Fluorenes; Hydrogenated fluorenes
-
- C—CHEMISTRY; METALLURGY
- C40—COMBINATORIAL TECHNOLOGY
- C40B—COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES
- C40B40/00—Libraries per se, e.g. arrays, mixtures
Definitions
- the subject of the present invention is a new reagent and a method of using the latter to produce perfluoroalkylations. It relates more particularly to a perfluoroalkylation technique in which everything happens as if a perfluoroalkyl anion attacked an electrophile.
- Ruppert's reagent which is none other than a persilylated trifluoromethyl radical, makes it possible to obtain trifluoromethylated derivatives easily and with generally good yields.
- this reagent has the major drawback of being difficult to manufacture and therefore extremely expensive.
- one of the aims of the present invention is to provide a perfluoroalkylation technique which is capable of giving good results at temperatures close to ambient, and more generally at temperatures between 0 ° C and 100 °. C approx.
- Another object of the present invention is to provide a process which allows the use of a fairly wide variety of solvents.
- composition which comprises: a) at least one of the compounds of formula (I):
- Rf- Z (0) n -Y where Z represents a metalloid atom chosen from sulfur, selenium and carbon; where Y represents an OR group, an N (R ') R group or an R "group; R,
- R'and R " are chosen from hydrocarbyl groups, that is to say groups comprising both carbon and hydrogen and the free bond of which is carried by a carbon; where n is an integer chosen from the values 1 or 2, with the condition that when Z is carbon, n is always equal to 1; b) a basic system containing or capable of producing an alcoholate; with the condition that the group R ", does not carry hydrogen on the carbon carrying the bond with the atom Z.
- R and R ' can be the same or different.
- composition constitutes a perfluoroalkylation reagent and also advantageously comprises an aprotic polar solvent. It is preferable that the reagent is as little protic as possible, so as to avoid parasitic reactions.
- the concentration of mobile hydrogen that is to say hydrogen corresponding to acid forms whose pKa is less than 18, preferably less than 20, is at most equal to 10% of the concentration expressed in mole of the compound of formula 1.
- the hydrogens there will be counted for two those which constitute a molecule of water.
- the amount of base used, or generated in situ is advantageously at least equal to 0.8, preferably once, more preferably 1.2 times the amount expressed in moles of the compound of formula 1.
- the basic system is advantageously a alcoholate, preferably secondary, more preferably tertiary.
- the alcoholate can be generated in situ by the various techniques known to those skilled in the art, for example the simultaneous addition of alcohol and a stronger base than alcohol or better still by the addition of a fluoride ion (F " ) on a silylated alcohol.
- the cations associated with the alcoholates are preferably relatively large or made coarse cations. Thus, it is preferable to use alkalis of rank at least equal to that of sodium and preferably to less equal to that of potassium.
- Rf covers a family of radicals which is larger than the perfluoroalkyl radicals sensus stricto, c 'that is to say to the radicals of formula C n F 2n + ⁇ .
- Rf is meant a radical of formula:
- X similar or different, represent a chlorine, a fluorine or a radical of formula C n F 2n + 1 with n integer at most equal to 5 preferably to 2, with the condition that at least one of the X is fluorine, fluorine advantageously carried by the carbon connected to the sulfur;
- GEA represents an electro-attractor group (ie sigma p greater than zero, advantageously 0.1, preferably 0.2), the possible functions of which are inert under the conditions of the reaction, advantageously fluorine or a perfluorinated residue of formula C n F 2n + 1 with n integer at most equal to 8, advantageously 5.
- the total number of Rf carbons is advantageously between 1 and 15, preferably between 1 and 10.
- n it is preferable that n be equal to 1.
- Z it should be noted that the case where Z is sulfur leads to compounds of formula 1 which are more reactive but slightly more fragile than in the case where Z is carbon.
- Y is an amino function disubstituted to form an amide with the group Z (0) n .
- the presence of oxygen and especially of a nitrogen in the gamma, delta or epsilon position, relative to Z improves the reactivity of the reagent, in particular so is the case of the amides corresponding to piperazine 1, 4. It is preferable, in the compounds of formula 1, that there are no hydrogen-carrying amines. As for solvents, they are very often a source of improvement in results, and even sometimes necessary when the compounds are not liquid or are not miscible at ambient temperatures.
- ⁇ is advantageously at least equal to about 5.
- ⁇ is less than or equal to 50 (position zeros are not considered to be significant figures in the present description unless it specified otherwise) and greater than or equal to 5.
- the solvents of the invention are capable of well solvating the cations (which is often linked to the basicity of the solvent), which can be coded by the donor index D of these solvents. It is thus preferable that the donor index D of these solvents is between 10 and 30.
- the donor index the "donor number” or “donor number”
- DN the nucleophilic nature of the solvent and reveals its ability to give its doublet.
- the reagent does not have acidic hydrogen on the polar solvent or solvents that it uses.
- the polar character of the solvent (s) is obtained by the presence of electron-attracting groups, it is desirable that there is no hydrogen in alpha of the electron-attractive function.
- the pKa corresponding to the first acidity of the solvent is at least equal to approximately 20 (“approximately” emphasizing that only the first digit is significant), advantageously at least equal to 25, preferably between 25 and 35.
- the components of the reaction medium are at least partially, preferably completely, soluble in the medium constituting the reagent.
- the solvents which give good results can in particular be solvents of amide type.
- the amides one also includes amides of a particular character such as tetrasubstituted ureas and monosubstituted lactams.
- the amides are preferably substituted (disubstituted for ordinary amides). Mention may be made, for example, of pyrrolidone derivatives, such as N-methylpyrrolidone, or also N, N-dimethylformamide, or N, N-dimethylacetamide.
- ethers Another particularly interesting category of solvents is constituted by ethers, whether they are symmetrical or non-symmetrical, whether they are open or not.
- ethers In the category of ethers must be incorporated the different derivatives of glycol ethers such as the different glymes, diglyme for example.
- ethers in particular cyclic, such as THF or polyfunctional such as glymes
- amides which, such as DMF or DAAU (N, N'-DiAlcoylAlcoylèneUrée) such as DMEU (N, N'- DiMethylEthylène-Urée) or DMPU (N, N'-DiMéthylPropylèneUrée) do not have hydrogen acid.
- DAAU N, N'-DiAlcoylAlcoylèneUrée
- DMEU N, N'- DiMethylEthylène-Urée
- DMPU N, N'-DiMéthylPropylNonethelessUrée
- Heterocycles with a basic character, such as pyridine can be used without constituting a class of preferred solvents.
- diluents there may be mentioned aliphatic or aromatic hydrocarbons, such as alkanes or aryl derivatives. Mention must be made of arylmethanes which can both serve as a diluent (because inert under the conditions of the reaction) and as basic sources when the latter is made beforehand in situ.
- the implementation of the reagents and compositions according to the invention is easy to carry out by placing the target substrate for perfluoroalkylation in the presence of the reagent at temperatures between -10 ° C and 100 ° C, preferably between 0 ° C and 70 ° C, more preferably between ambient and 50 ° C.
- the target substrates are essentially electrophiles. The best results are those obtained with target substrates capable of acting by addition between the electrophile and the nucleophile.
- this reagent as perhaloalkylating agent, is done simply by adding said reagent to the target substrate considered or vice versa, the amide derivatives constitute to date the best reagents (formula IV).
- the target substrates are advantageously chosen from those carrying at least one electrophilic function by addition.
- the reaction takes place, in any case on a temporary basis, by addition to a function having a double bond (naturally including that of donor acceptor type) or a doublet belonging to a metalloid of period of rank at least. equal to 3.
- the reaction is disadvantaged in the case where the chalcogen carries a hindered radical (secondary and especially tertiary radical) and / or whose carbocation is stabilized (radical of benzyl or tertioalkyl type).
- a hindered radical secondary and especially tertiary radical
- carbocation radical of benzyl or tertioalkyl type
- the reagent also advantageously reacts with a compound chosen from carbonyl compounds of the ketone, aldehyde, activated ester or (or even acid halide) type, by carrying out an addition on the carbonyl function.
- the reaction product is an alcohol (ate) in which the carbon atom carrying the hydroxyl function is substituted by a substituted difluoromethyl group.
- the electrophilic function of the substrate risks giving reactions of transesterification type with the base
- the basicity of the leaving group is then desirable for the basicity of the leaving group to be similar to or greater than that of the base initially used as reactant.
- the compounds of formula 1 advantageously have at most 50 carbon atoms, preferably at most 30 carbon atoms and more preferably at most 20 carbon atoms.
- 6.6 g of ephedrine are introduced into a flask fitted with an isobaric dropping funnel then purged with nitrogen. After the introduction of 40 ml of CH 2 CI 2 , the reaction mixture is cooled to 0 ° C. and then 6 ml of N-trimethylsilylimidazole are introduced, the whole being maintained at 0 ° C for 40 min. The reaction is kept stirring at AT for 2 h. 7.2 ml of DIEA are added and then the reaction mixture is cooled to 0 ° C. A solution of 5.6 ml of trifluoroacetic anhydride in 16 ml of CH 2 CI 2 is poured through the ampoule in 1.5 hours. At the end of the pouring, the mixture is kept at 0 ° C for 10 min and then at RT for 5 h.
- reaction medium is then washed with an aqueous solution of NaHCO ⁇ (6%)
- organic phase is dried with Na 2 S0 4 , filtered and evaporated.
- the expected product is then purified by chromatography on silica gel (eluent Ep / Et 2 0 9/1).
- acetamide derived from ephedrine 1 mmol of acetamide derived from ephedrine is introduced into a flask and dissolved in 1 ml of glyme (DME). 1 mmol of carbonyl compound is then added and the whole is stirred. CsF is introduced in a catalytic amount (10%) and the medium is kept stirring for the times indicated in the table, at the given temperature.
- the crude reaction product is hydrolyzed with 1 M HCl, then extracted with ether and dried with Na 2 S0 4 .
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Biotechnology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2002330561A AU2002330561A1 (en) | 2001-07-10 | 2002-07-10 | Reagent and method for perfluoroalkylation |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0109144A FR2827285B1 (fr) | 2001-07-10 | 2001-07-10 | Reactif et procede pour la perfluoroalcoylation |
FR0109144 | 2001-07-10 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2003011844A2 true WO2003011844A2 (fr) | 2003-02-13 |
WO2003011844A3 WO2003011844A3 (fr) | 2003-09-25 |
Family
ID=8865319
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR2002/002424 WO2003011844A2 (fr) | 2001-07-10 | 2002-07-10 | Reactif et procede pour la perfluoroalcoylation |
Country Status (3)
Country | Link |
---|---|
AU (1) | AU2002330561A1 (fr) |
FR (1) | FR2827285B1 (fr) |
WO (1) | WO2003011844A2 (fr) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010041748A1 (fr) * | 2008-10-10 | 2010-04-15 | 日本たばこ産業株式会社 | Composé de fluorène et utilisation de celui-ci pour des applications médicales |
WO2014142291A1 (fr) * | 2013-03-15 | 2014-09-18 | 日本たばこ産業株式会社 | Composé hydrate de fluor et cristaux de celui-ci |
WO2014142290A1 (fr) * | 2013-03-15 | 2014-09-18 | 日本たばこ産業株式会社 | Composé de pyrazole-amide et utilisations médicinales s'y rapportant |
US10981877B2 (en) | 2016-07-29 | 2021-04-20 | Japan Tobacco Inc. | Production method for pyrazole-amide compound |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10216998A1 (de) * | 2002-04-18 | 2003-11-13 | Merck Patent Gmbh | Verfahren zur Herstellung von Perfluoralkylphosphinen und deren Verwendung als Perfluoralkylierungsreagenzien |
WO2012148772A1 (fr) | 2011-04-28 | 2012-11-01 | University Of Southern California | Trifluorométhylations directes à l'aide de trifluorométhane |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IL117534A0 (en) * | 1995-03-24 | 1996-07-23 | Rhone Poulenc Agrochimie | Reagent and process which are useful for grafting a substituted difluoromethyl group onto a compound containing at least one electrophilic function |
HU222504B1 (hu) * | 1995-11-23 | 2003-07-28 | Rhodia Chimie | Perfluor-alkilezésnél felhasználásra kerülő eljárás és az eljárásnál felhasznált reagensek |
JP2001506593A (ja) * | 1996-11-15 | 2001-05-22 | ローディア シミ | ペルハロゲノアルキル化に有用な化合物及びこれらの化合物に使用するための試薬並びにこれらの化合物を得るための合成方法 |
-
2001
- 2001-07-10 FR FR0109144A patent/FR2827285B1/fr not_active Expired - Fee Related
-
2002
- 2002-07-10 WO PCT/FR2002/002424 patent/WO2003011844A2/fr not_active Application Discontinuation
- 2002-07-10 AU AU2002330561A patent/AU2002330561A1/en not_active Abandoned
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8871934B2 (en) | 2008-10-10 | 2014-10-28 | Japan Tobacco Inc. | Fluorene compound and pharmaceutical use thereof |
JP2011079801A (ja) * | 2008-10-10 | 2011-04-21 | Japan Tobacco Inc | フルオレン化合物及びその医薬用途 |
US8343994B2 (en) | 2008-10-10 | 2013-01-01 | Japan Tobacco Inc. | Fluorene compound and pharmaceutical use thereof |
JP2016053055A (ja) * | 2008-10-10 | 2016-04-14 | 日本たばこ産業株式会社 | フルオレン化合物及びその医薬用途 |
WO2010041748A1 (fr) * | 2008-10-10 | 2010-04-15 | 日本たばこ産業株式会社 | Composé de fluorène et utilisation de celui-ci pour des applications médicales |
JP2014185159A (ja) * | 2008-10-10 | 2014-10-02 | Japan Tobacco Inc | フルオレン化合物及びその医薬用途 |
US9040717B2 (en) | 2013-03-15 | 2015-05-26 | Japan Tobacco Inc. | Pyrazole-amide compounds and pharmaceutical use thereof |
JP2015024984A (ja) * | 2013-03-15 | 2015-02-05 | 日本たばこ産業株式会社 | ピラゾール−アミド化合物およびその医薬用途 |
WO2014142290A1 (fr) * | 2013-03-15 | 2014-09-18 | 日本たばこ産業株式会社 | Composé de pyrazole-amide et utilisations médicinales s'y rapportant |
CN105051015A (zh) * | 2013-03-15 | 2015-11-11 | 日本烟草产业株式会社 | 吡唑-酰胺化合物和其医药用途 |
WO2014142291A1 (fr) * | 2013-03-15 | 2014-09-18 | 日本たばこ産業株式会社 | Composé hydrate de fluor et cristaux de celui-ci |
AU2014230569B2 (en) * | 2013-03-15 | 2017-11-23 | Japan Tobacco Inc. | Pyrazole-amide compound and medicinal uses therefor |
JP2018021061A (ja) * | 2013-03-15 | 2018-02-08 | 日本たばこ産業株式会社 | ピラゾール−アミド化合物およびその医薬用途 |
EP3348545A1 (fr) * | 2013-03-15 | 2018-07-18 | Japan Tobacco Inc. | Composé de pyrazole-amide et utilisations médicinales s'y rapportant |
EP3805205A1 (fr) * | 2013-03-15 | 2021-04-14 | Japan Tobacco Inc. | Composé de pyrazole-amide et utilisations médicinales s'y rapportant |
US10981877B2 (en) | 2016-07-29 | 2021-04-20 | Japan Tobacco Inc. | Production method for pyrazole-amide compound |
Also Published As
Publication number | Publication date |
---|---|
WO2003011844A3 (fr) | 2003-09-25 |
AU2002330561A1 (en) | 2003-02-17 |
FR2827285B1 (fr) | 2003-12-05 |
FR2827285A1 (fr) | 2003-01-17 |
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