EP3464283A1 - Procédé de préparation de composés hétérocycliques - Google Patents
Procédé de préparation de composés hétérocycliquesInfo
- Publication number
- EP3464283A1 EP3464283A1 EP17724598.2A EP17724598A EP3464283A1 EP 3464283 A1 EP3464283 A1 EP 3464283A1 EP 17724598 A EP17724598 A EP 17724598A EP 3464283 A1 EP3464283 A1 EP 3464283A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- formula
- alkyl group
- group
- alkyl
- compounds
- 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- Withdrawn
Links
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 150000002391 heterocyclic compounds Chemical class 0.000 title description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 13
- SKCNYHLTRZIINA-UHFFFAOYSA-N 2-chloro-5-(chloromethyl)pyridine Chemical compound ClCC1=CC=C(Cl)N=C1 SKCNYHLTRZIINA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 15
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical group [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 150000001450 anions Chemical class 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 9
- -1 alkaline earth metal cation Chemical class 0.000 claims description 9
- 125000006177 alkyl benzyl group Chemical group 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052717 sulfur Inorganic materials 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 claims description 5
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 5
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 5
- 229910001415 sodium ion Inorganic materials 0.000 claims description 5
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 4
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 claims description 4
- 125000002373 5 membered heterocyclic group Chemical group 0.000 claims description 4
- 125000004070 6 membered heterocyclic group Chemical group 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 4
- 239000011593 sulfur Chemical group 0.000 claims description 4
- 125000004434 sulfur atom Chemical group 0.000 claims description 4
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 239000002635 aromatic organic solvent Substances 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims 1
- 239000003849 aromatic solvent Substances 0.000 abstract description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000003513 alkali Substances 0.000 description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 5
- WTUAWWLVVCGTRG-UHFFFAOYSA-N 4,5-dihydro-1,3-thiazol-2-ylcyanamide Chemical compound N#CNC1=NCCS1 WTUAWWLVVCGTRG-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000003586 protic polar solvent Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 1
- VXLYOURCUVQYLN-UHFFFAOYSA-N 2-chloro-5-methylpyridine Chemical compound CC1=CC=C(Cl)N=C1 VXLYOURCUVQYLN-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
Definitions
- the present invention relates to a novel process for the preparation of known heterocyclic compounds of the formula I.
- EP 1024140 describes the reaction of compounds of the formula (II)
- One aspect of the present invention relates to a process for the preparation of compounds of the formula (I)
- R 1 represents a hydrogen atom or an alkyl group, preferably a C 1 -C 4 -alkyl group,
- A is an ethylene group which may be substituted by alkyl, preferably C 1 -C 4 -alkyl, or a trimethylene group which may be substituted by alkyl, preferably C 1 -C 4 -alkyl,
- X is an oxygen or sulfur atom or the groups
- - LH or -CH-R 3 in which represents a hydrogen atom or an alkyl group, preferably a C 1 -C 4 alkyl group, and
- Z denotes an optionally substituted 5- or 6-membered heterocyclic group which contains at least two heteroatoms selected from oxygen, sulfur and nitrogen atoms, or denotes an optionally substituted 3- or 4-pyridyl group, characterized in that compounds of the formula (II )
- n depending on the counterion (M n + ) can be one or two
- a phase transfer catalyst preferably an ammonium salt, more preferably a quaternary ammonium salt, with 2 -Chloro-5-chloromethylpyridine.
- phase transfer catalyst is an ammonium salt of the formula - N-R5 anion
- R6 wherein R4, R5, R6 is hydrogen or a Ci-Ci 2 alkyl group, or benzyl or alkylbenzyl stand, preferably a Ci-Ci 2 -alkyl group (for clarity, is in -N (-NR4R5R6) "1" the well-known shorthand notation for a methyl group, (-NR4R5R6) "1" is the short notation of (Me-NR4R5R6) + ), and
- R6 wherein R4, R5, R6 is hydrogen or a Ci-Ci 2 alkyl group, or benzyl or - alkylbenzyl (preferably C 12 - alkylbenzyl) are provided and R7 is a Ci-Ci 2 alkyl group, or - benzyl or alkylbenzyl is , preferably a Ci-Ci 2 alkyl group are, and anion "OH, chloride, bromide, iodide or cyanide is, preferably represents chloride.
- a preferred embodiment relates to a process according to the invention, in which the organic-soluble quaternary ammonium salt is Aliquat 336 (methyltri-n-octylammonium chloride).
- a preferred embodiment relates to a process according to the invention in which the solvent is selected from benzene, toluene, xylene, mixtures thereof or hexane, cyclohexane, methylcyclohexane and mixtures thereof.
- a preferred embodiment relates to a process according to the invention, wherein the solvent is toluene.
- a preferred embodiment relates to a method according to the invention, wherein M + represents a Na + ion.
- a preferred embodiment relates to a process according to the invention, wherein the compound of the formula (I) is the compound of the formula (Ia)
- Ci-C / t-alkyl group is an ethylene group which may be substituted by alkyl, preferably by a Ci-C / t-alkyl, or a trimethylene group, which is alkyl, preferably by a C 1 -C 4 alkyl, may be substituted, represents an oxygen or sulfur atom or the groups or -CH-R 3 , in which
- R 3 is a hydrogen atom or an alkyl group, preferably a Ci-C / t-alkyl group, and
- Z is an optionally substituted 5- or 6-membered heterocyclic group containing at least two heteroatoms selected from oxygen, sulfur and nitrogen atoms, or denotes an optionally substituted 3- or 4-pyridyl group, obtained by reacting compounds of the formula (II ) or ammonium, alkali or alkaline earth metal salts of the compound of formula IIa
- n depending on the counterion (M n + ), can be one or two
- R 1 is preferably hydrogen or a C 1 -C 3 -alkyl group, more preferably hydrogen;
- A is preferably an ethylene or trimethylene group, which may each be substituted by a C 1 -C 3 -alkyl group, particularly preferably an ethylene group;
- X is preferably an oxygen or sulfur atom or the group
- Z preferably represents a halogenated, 5- or 6-membered heterocyclic group which contains 2 hetero atoms selected from the group consisting of oxygen, sulfur and nitrogen or a halogenated 3- or 4-pyridyl group, more preferably a halogenated thiazolyl or 3-pyridyl group , most preferably 2-chloro-pyrid-5-yl.
- a very particularly preferred embodiment is directed to a process for preparing a compound of formula (Ia),
- (IIb) is obtained with an inorganic base and in the presence of a nonpolar aliphatic or aromatic organic solvent, preferably an aromatic hydrocarbon such as toluene or xylene, and by subsequent reaction with 2-chloro-5-chloromethylpyridine, particularly preferably, wherein the reaction in the presence a phase transfer catalyst, or by reacting the compound of formula (IIc)
- Preferred inorganic bases are ammonium-containing bases, or alkali or alkaline earth metal, particularly preferably NaOH.
- solvents it is possible to use all nonpolar aliphatic or aromatic solvents or mixtures thereof.
- aromatic solvents which may be mentioned are: benzene, toluene or xylene or mixtures thereof; Hexane, cyclohexane, methylcycolohexane or mixtures thereof; and mixtures of aliphatic and aromatic solvents. Particularly preferred is toluene.
- phase transfer catalysts such as
- R4, R5, R6 is hydrogen or a Ci-Ci 2 alkyl group or benzyl or alkylbenzyl (methyl-N (R4, R5, R6) + anion " , or
- R6 wherein R4, R5, R6 is hydrogen or a Ci-Ci 2 alkyl group, or benzyl or alkylbenzyl stand and R7 is a Ci-Ci 2 alkyl group, or benzyl or alkylbenzyl group, preferably a C 1 -C 12 - alkyl group stands,
- anion " for OH, chloride, bromide, iodide, or cyanide, particularly preferably chloride is used.
- phase transfer catalysts are organic löslische quaternary ammonium salts, particularly preferred quaternary Ci-Ci 2 alkyl ammonium halide salts, particularly preferably C 1 -C 12 - alkyl ammonium chloride salts, such as Aliquat 336 (methyl-tri-n-octylammonium chloride).
- the process is carried out in a pH range between 6 and 14.
- the range is preferably between pH 10 and pH 13.
- the reaction may be carried out at temperatures of 10 ° C to 130 ° C such as 15 ° C to 130 ° C, optionally in vacuo or under pressure. Preference is 40 to 80 ° C.
- the reaction is conveniently carried out under atmospheric pressure, but it is also possible to work under reduced or elevated pressure.
- the reaction time is between 0.1 and 12 hours, preferably 1 to 5 hours.
- the phases can also be separated first.
- the separation of the organic phase takes place at 50 ° C to 120 ° C, preferably at 40 to 80 ° C.
- the mixture is then cooled as described above and the precipitated active ingredient is isolated, washed and optionally recrystallized.
- the compounds of the formula (I) are suitable, for example, for use as insecticides (EP A2 0235 752, EP A2 0259 738).
- CCMP (2-chloro-5-chloromethylpyridine) were initially charged in 260 g of 1-butanol together with 5 g of Aliquat 336 (methyltri-n-octylammonium chloride) and heated to 70.degree. Within one hour, 250 g of a 29.8% solution of 2-Cyaniminothiazolidin-Na salt (0.5 mol) were metered into water for this purpose. Thereafter, until the complete conversion of Cyaniminothiazolidins was stirred. The mixture was then cooled to 10 ° C and filtered.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pyridine Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
- Catalysts (AREA)
Abstract
La présente invention concerne un procédé de préparation de composés de formule (I) dans laquelle R1, A, X et Z ont les correspondances indiquées dans la description, par conversion de composés de formule (II) ou de leurs sels avec de la 2-chlor-5-chlorméthylpyridine dans un solvant aromatique ou aliphatique apolaire en présence d'un catalyseur de transfert de phase.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP16173126 | 2016-06-06 | ||
| PCT/EP2017/062731 WO2017211594A1 (fr) | 2016-06-06 | 2017-05-26 | Procédé de préparation de composés hétérocycliques |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP3464283A1 true EP3464283A1 (fr) | 2019-04-10 |
Family
ID=56132768
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP17724598.2A Withdrawn EP3464283A1 (fr) | 2016-06-06 | 2017-05-26 | Procédé de préparation de composés hétérocycliques |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US11161840B2 (fr) |
| EP (1) | EP3464283A1 (fr) |
| JP (1) | JP6946354B2 (fr) |
| KR (1) | KR102380911B1 (fr) |
| CN (1) | CN109311866B (fr) |
| BR (1) | BR112018075237B1 (fr) |
| IL (1) | IL263091B (fr) |
| MX (1) | MX2018015178A (fr) |
| TW (1) | TWI750181B (fr) |
| WO (1) | WO2017211594A1 (fr) |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PH23283A (en) | 1986-02-26 | 1989-06-30 | Eisai Co Ltd | Piperidine derivative, pharmaceutical composition containing the same and method of use thereof |
| JPH0717621B2 (ja) * | 1986-03-07 | 1995-03-01 | 日本バイエルアグロケム株式会社 | 新規ヘテロ環式化合物 |
| JPH07121909B2 (ja) | 1986-09-10 | 1995-12-25 | 日本バイエルアグロケム株式会社 | 新規複素環式化合物及び殺虫剤 |
| KR0143512B1 (ko) * | 1994-06-28 | 1998-07-15 | 한경우 | 배양된 영지버섯 균사체로부터의 면역활성물질의 추출정제방법 및 그로부터 추출된 면역활성물질 |
| JP2721805B2 (ja) * | 1994-07-22 | 1998-03-04 | 日本バイエルアグロケム株式会社 | 新規ヘテロ環式化合物 |
| DE19904310A1 (de) * | 1999-01-28 | 2000-08-03 | Bayer Ag | Verfahren zur Herstellung heterocyclischer Verbindungen |
| MXPA02007060A (es) | 2000-01-19 | 2003-01-28 | Bayer Ag | Procedimiento para la obtencion de compuestos heterociclicos. |
| CN1401646A (zh) * | 2001-08-08 | 2003-03-12 | 南通江山农药化工股份有限公司 | 一种杀虫化合物及生产方法 |
| EP3350172A1 (fr) | 2015-09-15 | 2018-07-25 | Bayer Cropscience LP | Procédé pour la préparation de 2-cyanoimino -1,3-thiazolidine |
-
2017
- 2017-05-26 EP EP17724598.2A patent/EP3464283A1/fr not_active Withdrawn
- 2017-05-26 JP JP2018563683A patent/JP6946354B2/ja active Active
- 2017-05-26 MX MX2018015178A patent/MX2018015178A/es unknown
- 2017-05-26 CN CN201780034983.2A patent/CN109311866B/zh active Active
- 2017-05-26 BR BR112018075237-1A patent/BR112018075237B1/pt active IP Right Grant
- 2017-05-26 US US16/306,180 patent/US11161840B2/en active Active
- 2017-05-26 KR KR1020187037167A patent/KR102380911B1/ko active IP Right Grant
- 2017-05-26 WO PCT/EP2017/062731 patent/WO2017211594A1/fr unknown
- 2017-06-03 TW TW106118387A patent/TWI750181B/zh active
-
2018
- 2018-11-18 IL IL263091A patent/IL263091B/en active IP Right Grant
Also Published As
| Publication number | Publication date |
|---|---|
| MX2018015178A (es) | 2019-04-24 |
| CN109311866A (zh) | 2019-02-05 |
| WO2017211594A1 (fr) | 2017-12-14 |
| TWI750181B (zh) | 2021-12-21 |
| KR102380911B1 (ko) | 2022-03-30 |
| US20210261536A1 (en) | 2021-08-26 |
| JP2019517535A (ja) | 2019-06-24 |
| US11161840B2 (en) | 2021-11-02 |
| TW201819373A (zh) | 2018-06-01 |
| CN109311866B (zh) | 2022-12-09 |
| BR112018075237B1 (pt) | 2022-08-23 |
| KR20190015339A (ko) | 2019-02-13 |
| IL263091B (en) | 2021-06-30 |
| IL263091A (en) | 2018-12-31 |
| JP6946354B2 (ja) | 2021-10-06 |
| BR112018075237A2 (pt) | 2019-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1856024B2 (fr) | Procede de fabrication de biphenyls substitues | |
| DE202007018473U1 (de) | 9-Hydroxy-Risperidon (Paliperidon) | |
| EP1616863A1 (fr) | Procédé pour la préparation des composés aromatiques fluorés | |
| EP1899337B1 (fr) | Procede pour realiser des composes de 3,7-diaza-bicyclo[3.3.1]nonane | |
| DE60035109T2 (de) | Verfahren zur herstellung von thiamethoxam | |
| EP2079705B1 (fr) | Procédé de production de carbonates quaternaires | |
| EP2212289B1 (fr) | Procédé de préparation de dérivés de 2,2-difluoréthylamine par hydratation d'amides | |
| DE3514450A1 (de) | Verfahren zur herstellung von imidaten sowie neue arylsubstituierte imidate | |
| DE102009022830A1 (de) | Verbessertes Verfahren zum Herstellen von Diaminopyridinen | |
| EP3464283A1 (fr) | Procédé de préparation de composés hétérocycliques | |
| EP0004623B1 (fr) | Procédé pour la préparation d'amines aromatiques | |
| WO1999065861A1 (fr) | Procede de disubstitution symetrique et asymetrique d'amides d'acide carboxylique avec des organotitanates et des reactifs de grignard | |
| EP0370325B1 (fr) | Procédé pour la déshalogénation réductive de composés aromatiques | |
| EP1252159B1 (fr) | Procede de production de composes heterocycliques | |
| DE60011427T2 (de) | Verfahren zur herstellung von 2-pyridylpiperidin-derivaten | |
| DE19904310A1 (de) | Verfahren zur Herstellung heterocyclischer Verbindungen | |
| EP3577105B1 (fr) | Préparaton d'hydroxylamines aromatiques n-substituées | |
| DE69924702T2 (de) | Difluormethoxybenzolderivate und ihre verwendung als zwischenprodukte | |
| DE19632643C1 (de) | Katalysierte Kopplung von Arylmagnesiumhalogeniden und Bromarylcarbonsäureverbindungen zur Herstellung von Biphenylcarbonsäuren | |
| EP1442010B1 (fr) | Procede de production de biphenyl-4-carbonitrile | |
| DE3534827A1 (de) | Verfahren zur herstellung von 5-(2-chlorobenzyl)-4,5,6,7-tetrahydrothieno(3,2-c)pyridin | |
| EP1675851B1 (fr) | Procede pour produire des 3beta-aminonortropanes n-substitues | |
| CH482712A (de) | Verfahren zur Herstellung von 3-Amino-1,2,5-thiadiazolen | |
| AT366059B (de) | Verfahren zur herstellung von neuen phosphoniumimidazolverbindungen und von deren saeureadditionssalzen | |
| DE1940704C3 (de) | Verfahren zur Herstellung von 2-Mercaptoinosin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: UNKNOWN |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
| 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 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
| 17P | Request for examination filed |
Effective date: 20190107 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
| AX | Request for extension of the european patent |
Extension state: BA ME |
|
| DAV | Request for validation of the european patent (deleted) | ||
| 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: EXAMINATION IS IN PROGRESS |
|
| 17Q | First examination report despatched |
Effective date: 20200320 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
| 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: GRANT OF PATENT IS INTENDED |
|
| INTG | Intention to grant announced |
Effective date: 20230208 |
|
| 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: 20230620 |