DE3003653A1 - N-substd. oxazolidine-2,4-di:one derivs. prodn. - by one-pot reaction of alkali cyanate with organic halide and alpha-hydroxy carboxylic acid ester - Google Patents
N-substd. oxazolidine-2,4-di:one derivs. prodn. - by one-pot reaction of alkali cyanate with organic halide and alpha-hydroxy carboxylic acid esterInfo
- Publication number
- DE3003653A1 DE3003653A1 DE19803003653 DE3003653A DE3003653A1 DE 3003653 A1 DE3003653 A1 DE 3003653A1 DE 19803003653 DE19803003653 DE 19803003653 DE 3003653 A DE3003653 A DE 3003653A DE 3003653 A1 DE3003653 A1 DE 3003653A1
- Authority
- DE
- Germany
- Prior art keywords
- acid ester
- carbon atoms
- substituted
- substd
- halogen
- 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- Withdrawn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
- 239000003513 alkali Substances 0.000 title claims abstract description 4
- 150000004820 halides Chemical class 0.000 title claims abstract 4
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 title claims abstract 3
- 238000005580 one pot reaction Methods 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 14
- 239000012948 isocyanate Substances 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 6
- 150000002367 halogens Chemical class 0.000 claims abstract description 6
- 125000004953 trihalomethyl group Chemical group 0.000 claims abstract description 4
- 125000004104 aryloxy group Chemical group 0.000 claims abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 3
- 125000005000 thioaryl group Chemical group 0.000 claims abstract description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract 4
- 229910052794 bromium Inorganic materials 0.000 claims abstract 2
- 239000003880 polar aprotic solvent Substances 0.000 claims abstract 2
- -1 unsaturated alkyl radical Chemical class 0.000 claims description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 150000008282 halocarbons Chemical class 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002102 aryl alkyloxo group Chemical group 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 125000000449 nitro group Chemical class [O-][N+](*)=O 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 150000003903 lactic acid esters Chemical class 0.000 claims 1
- 210000000056 organ Anatomy 0.000 claims 1
- 239000000575 pesticide Substances 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 abstract description 2
- 239000000314 lubricant Substances 0.000 abstract description 2
- 239000004033 plastic Substances 0.000 abstract description 2
- 229920003023 plastic Polymers 0.000 abstract description 2
- 239000003381 stabilizer Substances 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract 2
- 125000002252 acyl group Chemical group 0.000 abstract 1
- 229910052740 iodine Inorganic materials 0.000 abstract 1
- COWNFYYYZFRNOY-UHFFFAOYSA-N oxazolidinedione Chemical compound O=C1COC(=O)N1 COWNFYYYZFRNOY-UHFFFAOYSA-N 0.000 abstract 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000000010 aprotic solvent Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229940112021 centrally acting muscle relaxants carbamic acid ester Drugs 0.000 description 2
- 150000001913 cyanates Chemical class 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000001475 oxazolidinediones Chemical class 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- AFENDNXGAFYKQO-VKHMYHEASA-N (S)-2-hydroxybutyric acid Chemical compound CC[C@H](O)C(O)=O AFENDNXGAFYKQO-VKHMYHEASA-N 0.000 description 1
- ZULBFSSEZXLFIV-UHFFFAOYSA-N 1,2,3,4,5-pentachloro-6-(chloromethyl)benzene Chemical compound ClCC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl ZULBFSSEZXLFIV-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- TZGFQIXRVUHDLE-UHFFFAOYSA-N 1-chloro-2-nitro-4-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC(C(F)(F)F)=CC=C1Cl TZGFQIXRVUHDLE-UHFFFAOYSA-N 0.000 description 1
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical group [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- IRSVDHPYXFLLDS-UHFFFAOYSA-N 2,4-dichloro-1-(chloromethyl)benzene Chemical compound ClCC1=CC=C(Cl)C=C1Cl IRSVDHPYXFLLDS-UHFFFAOYSA-N 0.000 description 1
- MONMFXREYOKQTI-UHFFFAOYSA-N 2-bromopropanoic acid Chemical compound CC(Br)C(O)=O MONMFXREYOKQTI-UHFFFAOYSA-N 0.000 description 1
- HFHAVERNVFNSHL-UHFFFAOYSA-N 2-chloro-1,3-dinitro-5-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC(C(F)(F)F)=CC([N+]([O-])=O)=C1Cl HFHAVERNVFNSHL-UHFFFAOYSA-N 0.000 description 1
- MYCXCBCDXVFXNE-UHFFFAOYSA-N 2-chloro-2-methylpropanoic acid Chemical compound CC(C)(Cl)C(O)=O MYCXCBCDXVFXNE-UHFFFAOYSA-N 0.000 description 1
- GAWAYYRQGQZKCR-UHFFFAOYSA-N 2-chloropropionic acid Chemical group CC(Cl)C(O)=O GAWAYYRQGQZKCR-UHFFFAOYSA-N 0.000 description 1
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 1
- ABEUJUYEUCCZQF-UHFFFAOYSA-N 4-chloro-2-methoxy-1-nitrobenzene Chemical compound COC1=CC(Cl)=CC=C1[N+]([O-])=O ABEUJUYEUCCZQF-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RENMDAKOXSCIGH-UHFFFAOYSA-N Chloroacetonitrile Chemical compound ClCC#N RENMDAKOXSCIGH-UHFFFAOYSA-N 0.000 description 1
- XJUZRXYOEPSWMB-UHFFFAOYSA-N Chloromethyl methyl ether Chemical compound COCCl XJUZRXYOEPSWMB-UHFFFAOYSA-N 0.000 description 1
- 229930182843 D-Lactic acid Natural products 0.000 description 1
- JVTAAEKCZFNVCJ-UWTATZPHSA-N D-lactic acid Chemical compound C[C@@H](O)C(O)=O JVTAAEKCZFNVCJ-UWTATZPHSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- VYZAHLCBVHPDDF-UHFFFAOYSA-N Dinitrochlorobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 VYZAHLCBVHPDDF-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- NGEWQZIDQIYUNV-UHFFFAOYSA-N L-valinic acid Natural products CC(C)C(O)C(O)=O NGEWQZIDQIYUNV-UHFFFAOYSA-N 0.000 description 1
- BNUHAJGCKIQFGE-UHFFFAOYSA-N Nitroanisol Chemical compound COC1=CC=C([N+]([O-])=O)C=C1 BNUHAJGCKIQFGE-UHFFFAOYSA-N 0.000 description 1
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical compound C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- JDNTWHVOXJZDSN-UHFFFAOYSA-N iodoacetic acid Chemical compound OC(=O)CI JDNTWHVOXJZDSN-UHFFFAOYSA-N 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- GSJFXBNYJCXDGI-UHFFFAOYSA-N methyl 2-hydroxyacetate Chemical compound COC(=O)CO GSJFXBNYJCXDGI-UHFFFAOYSA-N 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002917 oxazolidines Chemical class 0.000 description 1
- KGCNHWXDPDPSBV-UHFFFAOYSA-N p-nitrobenzyl chloride Chemical compound [O-][N+](=O)C1=CC=C(CCl)C=C1 KGCNHWXDPDPSBV-UHFFFAOYSA-N 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- LIGACIXOYTUXAW-UHFFFAOYSA-N phenacyl bromide Chemical compound BrCC(=O)C1=CC=CC=C1 LIGACIXOYTUXAW-UHFFFAOYSA-N 0.000 description 1
- IMACFCSSMIZSPP-UHFFFAOYSA-N phenacyl chloride Chemical compound ClCC(=O)C1=CC=CC=C1 IMACFCSSMIZSPP-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- ZVCDLGYNFYZZOK-UHFFFAOYSA-M sodium cyanate Chemical compound [Na]OC#N ZVCDLGYNFYZZOK-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D263/44—Two oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
Description
Verfahren zur Herstellung von B-substituierten Oxazolidin-Process for the preparation of B-substituted oxazolidine
dionen-(2,4) Es ist bekannt, Oxazolidindione der allgemeinen Formel (I) in der R1 und R2 Wasserstoffatome oder gegebenenfalls halogelierte Alkyl- oder Alkenylreste sind, oder gemeinsam für don Al k ylenrest stehen, durch Umsetzen von 3, 5-Oichlurphenylisocyanat mit einem α-Hydroxycarbonsäureester der Formel herzustellen (DE-PS 1 811 843; DE-OS 1 207 576).diones- (2,4) It is known that oxazolidinediones of the general formula (I) in which R1 and R2 are hydrogen atoms or optionally halogenated alkyl or alkenyl radicals, or together represent the alkylene radical, by reacting 3,5-oxychlorophenyl isocyanate with an α-hydroxycarboxylic acid ester of the formula (DE-PS 1 811 843; DE-OS 1 207 576).
Bei dieser Umsetzung werden relativ hohe Mengen an tertiären Aminen als Katalysatoren benötigt. Außerdem muß man das erforderliche Isocyanat unter Einsatz von stark toxischem Phosgen aus dem Basisanilin gewinnen.In this implementation, relatively large amounts of tertiary amines are used needed as catalysts. In addition, the required isocyanate must be used of highly toxic phosgene from the base aniline.
Ein anderes Verfahren zur Herstellung von Oxazolidin-(2,4)-dienen, bei dem Hydroxycarbonsäureester nicht mit Isocyanaten sondern mit Carbaminsöureestern umgesetzt worden (0E-0S 2 813 873), be seitigt diese Nachteile im Prinzip nicht, da die Herstellung der Carbaminsäureestor bevorzugt durch Umsetzung von Isocyßhaten mit niedermolekularen Alkoholen erfolgt, so daß im Vergleich zu den vorgenannten Reaktionen sogar eine zusätzliche Reaktions- Stufe erforderlich ist. In der DE-OS 2 827 414 ist schließlich ein Verfahren beschrieben, bei dem Harnstoffes die ja ebenfalls Folgsprodukte von Isocyanaten sind, eingesetzt werden.Another process for the preparation of oxazolidine (2,4) dienes, in the case of the hydroxycarboxylic acid ester, not with isocyanates but with carbamic acid esters has been implemented (0E-0S 2 813 873), does not eliminate these disadvantages in principle, since the production of the carbamic acid esters is preferably carried out by converting isocysshates takes place with low molecular weight alcohols, so that in comparison to the aforementioned Reactions even an additional reaction Level required is. Finally, DE-OS 2 827 414 describes a process in which urea which are also by-products of isocyanates, are used.
Es wurde nun gefunden, daß N-substituierte Oxazolidindione-(2,4) der allgemeinen Formel (II) unter welche auch die obengenannten9 bereits bekannten Oxazolidindione-(2,4) der Formel (I) fallen. auf erheblich einfachere Weise in einem einzigen Verfahrensschritt aus einem Organohalogenid und einem α-Hydroxycarbonsäureester in Anwesenheit eines Alkalicyanats herstellbar sind.It has now been found that N-substituted oxazolidinediones (2,4) of the general formula (II) which also include the above-mentioned9 already known oxazolidinediones (2,4) of the formula (I). can be prepared in a much simpler manner in a single process step from an organohalide and an α-hydroxycarboxylic acid ester in the presence of an alkali metal cyanate.
Die vorliegende Erfindung betrifft daher ein Verfahren zur HOrstellung von N-substituierten Oxazilidindionen-(2,4) der allgemeinen Formel (II) i.n der n und m die Bedeutung von null oder 1 haben, A gleich oder verschieden und H, CH3 oder C2H5 ist, R² und R³ für Wasserstoff oder einen gesättigten oder ungesättigten Alkylrest mit bis zu 4 C-Atomen, der auch halogensubstituiert sein kann oder einen Aryl-, Aralkyl- oder Cycloalkylrest mit 6 bis 10 C-Atomen stehen, und R1 eine Gruppe Y oder eino Gruppe Z bedeutet, wobei Y ein gesättigter oder ungesättigter Alkylrest mit bis zu 4 C-Atomen oder auch ein alkoxirest dor gleichen KohlenstoffzahL ist, und diese Reste' durch Halogen, Cyan, Trihalogenmethyl oder Alkoxi substituiert sein können, während Z für einen Aryl-, Aryloxi-, Thioaryl-, Aralkyl-, Aralkyloxi- oder Cycloalkylrest, der jeweils auch ein oder mehrfach durch Halogen, Cyan, Nitro, Trihologonmothyl oder Alkoxi ringsubstituiert sein kann, steht, durch Reagierenlassen eines Isocyanates der allgemeinen Formel (III) O=C=N-(CA2)n-(CO)m-R¹ (III) mit einem α-Hydroxycarbonsäureester der allgemeinen Formel (IV) in der R4 einen Alkylrest mit 1 bis 4 C-Atomen bedeutet, welches dadurch gekennzeichnet ist, daß man das Isocyanat (oil) aus Alkalicyanat und einem Organohalogenid der allgemeinen Formol (V) X-(CA2)n-(CO)m-R¹ (V) in der X = C17 Br oder J ist, in Gegenwart des α-Hydroxicarbonsaureestere (IV) in situ erzeugt, wobei das Molverhältnis von (V) : (IV) im Bereich von 2 : 1 bis 1 : 10 10 liegen soll, die Reaktionstemperatur 20 bis 200 e beträgt und man in An- oder Abwesenheit eines polaren, aprotischon Lösungsmittels arbeitet.The present invention therefore relates to a process for the preparation of N-substituted oxazilidinedione- (2,4) of the general formula (II) in which n and m have the meanings zero or 1, A is identical or different and H, CH3 or C2H5, R² and R³ represent hydrogen or a saturated or unsaturated alkyl radical with up to 4 carbon atoms, which can also be halogen-substituted or are an aryl, aralkyl or cycloalkyl radical with 6 to 10 carbon atoms, and R1 is a group Y or a group Z, where Y is a saturated or unsaturated alkyl radical with up to 4 carbon atoms or an alkoxy radical with the same number of carbon atoms , and these radicals' can be substituted by halogen, cyano, trihalomethyl or alkoxy, while Z represents an aryl, aryloxy, thioaryl, aralkyl, aralkyloxy or cycloalkyl radical, each of which is also one or more times by halogen, cyano, nitro , Trihologonmothyl or Alkoxi ring-substituted, by reacting an isocyanate of the general formula (III) O = C = N- (CA2) n- (CO) m -R¹ (III) with an α-hydroxycarboxylic acid ester of the general formula (IV ) in which R4 denotes an alkyl radical with 1 to 4 carbon atoms, which is characterized in that the isocyanate (oil) is obtained from alkali metal cyanate and an organohalide of the general formula (V) X- (CA2) n- (CO) m-R¹ (V) in which X = C17 Br or J, generated in situ in the presence of the α-hydroxycarboxylic acid ester (IV), the molar ratio of (V): (IV) being in the range from 2: 1 to 1:10 , the reaction temperature is 20 to 200 e and one works in the presence or absence of a polar, aprotic solvent.
Da aus der Literatur bekannt ist, daß austauschfähiges Halogen enthaltende Verbindungen beim Umsatz mit alkalicyanaten unter Überspringe der Stufe des monomeren Cyanats unmittelbar zu Isocyanuraten trimerisieren, war die Entstehung von Verbindungen vom Typ (II) beim Umsatz von Organohalogeniden des Typs (V) mit Alkalicyanat nicht zu erwarten. Es war vielmetir damit zu rechnen, daß die zunachst gebildeten Isocyanate der Formel (III), bevor sie mit den Hydroxicarbonsäureestern (IV) reagieren, ebenfalls in Isocyanurate übergehen, zudem ja bekannt ist, daß Alkohole, welche die gleiche OH-Funktionalität aufweisen wie die Verbindungen der StoffklAsse (IV)9 bei der llerstellung von Isocyanuraten aus Halogencarbonsäureestern als Lösungsmittel dienen können n (vgl. DE-PS 812 312). Für den Fachmann völlig unerwartet ergab oich jedoch, daß die Isocyanuratbildung in dem vorliegenden System praktisch völlig unterbleibt, Des erfindungsgemäße Verfahren wird in An- oder Abwesenheit eines aprotischen Lösungemittels durchgeführt. Beim Arbeiten in Abwesenheit eines Lösungsmittels setzt man bevorzugt den α-Hydroxicarbonsäurester (IV) zwecks Erhöhung der Polarität der Reaktionslösung im Überschuß ein. Diese Arbeitsweise ist besondare vorteilhaft, weil das Reaktionsgleichgewicht günstig beeinflußt wird. im allgemeinen soll das Molverhältnis von (V) : (VI) zwischen 2 : 1 und 1 : 10 vorzugsweise 1 : 1 und 1 : 10 liegen. Als polare, aprotische Lösungsmittel eignen sich z. 0. Dioxan, Glykoldimethylether, Diglykoldimethylether, Tetrahydrofuran, Dimethylsulfoxid, Dimethylformamid und Phosphorsäure-tris-dimethylamid.Since it is known from the literature that containing exchangeable halogen Compounds in the reaction with alkali cyanates, skipping the monomer stage Trimerizing cyanates directly to isocyanurates was the formation of compounds of type (II) in the reaction of organohalides of type (V) with alkali metal cyanate not expected. It was to be expected that the isocyanates initially formed of the formula (III), before they react with the hydroxycarboxylic acid esters (IV), likewise pass into isocyanurates, moreover it is known that alcohols, which are the same Have OH functionality like the compounds of substance class (IV) 9 when they are produced of isocyanurates from halocarboxylic acid esters can serve as solvents n (see DE-PS 812 312). However, completely unexpectedly for the person skilled in the art, I found that the isocyanurate formation in the present system is practically completely absent, The process according to the invention is carried out in the presence or absence of an aprotic solvent carried out. When working in the absence of a solvent, preference is given to using the α-hydroxycarboxylic acid ester (IV) for the purpose of increasing the polarity of the reaction solution in excess one. This procedure is particularly advantageous because the reaction equilibrium is favorably influenced. in general, the molar ratio of (V): (VI) should be between 2: 1 and 1:10, preferably 1: 1 and 1:10. As polar, aprotic solvents are suitable e.g. 0. Dioxane, glycol dimethyl ether, diglycol dimethyl ether, tetrahydrofuran, Dimethyl sulfoxide, dimethylformamide and phosphoric acid tris-dimethylamide.
Das Molverhältnis Alkalicyanat : Organohalogenid bewegt sich zwischen 1 : 1 und 2 . 1, wobei im allgemeinen ein geringer Überschuß an Alkalicyanat, entsprechend einem Molverhältnis von 1,1 : 1, genügt.The molar ratio of alkali metal cyanate: organohalide ranges between 1: 1 and 2. 1, whereby in general a small excess of alkali metal cyanate, accordingly a molar ratio of 1.1: 1 is sufficient.
Die Umsetzung wird bei Tamperaturen zwischun 20 und 200, vorzugsweise zwischen 50 und 150 und insbesondere zwischun 50 und 100 °C durchgeführt und ist, sofern nicht unter Druck gearbeitet wird, durch den Siedepunkt der am niedrigsten siedenden Reaktionskomponente bzw. des mitverwendeten aprotischen Lösungs mittels begrenzt. Zuweilen ist es zweckmäßig, bei der Reaktion geringe Mengen (0,01 bis 3 gew.-%, bezogen auf Komponente V) sekundärer oder tertiärer Amine als Katalysatoren zuzusetzen.The implementation is at temperatures between 20 and 200, preferably between 50 and 150 and in particular between 50 and 100 ° C carried out and is, if not working under pressure, the lowest due to the boiling point boiling reaction component or the concomitantly used aprotic solvent means limited. Sometimes it is useful to use small amounts (0.01 to 3% by weight, based on component V), of secondary or tertiary amines as catalysts to add.
Geeignete α-Hydroxicarbonsäureester (IV) sind z. B. Methyl-, Ethyl-, Propyl-, Isopropyl-, n-Butyl- und Iosbutylester der Glykol-, Milch- und Mandulsäure, sowie von Derivaten dieser Säuren. Hierzu zählen: α-Hydroxipropion-, α-Hydroxy-n-buttersäure, α-Hydroxiisobuttersäure, a-Vinyl-, a-1 -Bromvinyl-, α-Propan-1-yl, α-2-Brompropen-1-yl, α-3-Brom-propen-1-yl-, α-2,2-Dimethylvinyl-, α,ß,ß-Trimethyl- und ß,ß,ß-Trimethylmilchsäure.Suitable α-hydroxycarboxylic acid esters (IV) are, for. B. methyl, Ethyl, propyl, isopropyl, n-butyl and isobutyl esters of the glycol, milk and Mandulic acid, as well as derivatives of these acids. These include: α-Hydroxipropion-, α-hydroxy-n-butyric acid, α-hydroxyisobutyric acid, a-vinyl, a-1 -bromovinyl, α-propan-1-yl, α-2-bromopropen-1-yl, α-3-bromo-propen-1-yl-, α-2,2-dimethylvinyl-, α, ß, ß-trimethyl and ß, ß, ß-trimethyl lactic acid.
Unter Organohalogeniden, die durch die Formel (V) charakterisiert sind, werden verstanden: Monohalogenierungsprodukte von gerad- und verzweigtkettigen, gesättigten und ungesättigten Alkanon oder Cycloalkenen, die Nethyl-, Ethyl-, Propyl-, Isopropyl-, n-Dutyl- und Isobutylester der Chlorameinsäure sowie anderer Halogenfettsäuren namentlich der Chlor-, Bro- und Jodessigsäure, der α-Chlor- und α-Brompropionsäure und der a-Chlor-n- hzw. α-Chlor-isobuttersäure. Genannt seien ferner z. B. Monochloracetonitril, Monochlordimethylether, Brom- und Jodbenzol, 2-Nitro- und 2,4-Dinitrochlorbenzol, 2-Nitro-4-trifluormethyl-chlorbenzol, 4-Nitro- und 5-Chlor-2-nitroanisol, 2,6-Dinitro-4-trifluormethyl-chlorbenzol, 2,4-Dichlorbenzylchlorid, 2,3,4,5,6-Pentachlorbenzylchlorid, α-Chlor- und α-Bromacetophenon.Among organohalides, which are characterized by the formula (V) are understood as: monohalogenation products of straight and branched chain, saturated and unsaturated alkanone or cycloalkenes, the ethyl, ethyl, propyl, Isopropyl, n-dutyl and isobutyl esters of chloramic acid and other halogen fatty acids namely chloro, bromo and iodoacetic acid, α-chloro and α-bromopropionic acid and the a-chlorine-n- hzw. α-chloro-isobutyric acid. Also mentioned are z. B. Monochloroacetonitrile, monochlorodimethyl ether, bromobenzene and iodobenzene, 2-nitro and 2,4-dinitrochlorobenzene, 2-nitro-4-trifluoromethylchlorobenzene, 4-nitro- and 5-chloro-2-nitroanisole, 2,6-dinitro-4-trifluoromethyl-chlorobenzene, 2,4-dichlorobenzyl chloride, 2,3,4,5,6-pentachlorobenzyl chloride, α-chloro- and α-bromoacetophenone.
Von den nach dem erfindungegemäßen Verfahren erhältlichen verbindungen der Formel (II) sind, wie bereits erwähnt, einige bekannt, neu sind jedoch dia, in denen n für null oder 1, in für 1 und R1 für O-Alkyl oder Alkyl mit 1 bis 4 C-Atomcn steht.Of the compounds obtainable by the process according to the invention of the formula (II), as already mentioned, some are known, but the following are new, in which n stands for zero or 1, in for 1 and R1 for O-alkyl or alkyl with 1 to 4 carbon atoms.
Die Verfahrensprodukte eignen sich zum Einsatz auf dem Schädlingsbekämpfungs- und Pharmasektor, als Stabilisatoren für das Kunststoffgebiet sowie als Veradlungszusätze zu Schmiermitteln.The process products are suitable for use on the pest control and the pharmaceutical sector, as stabilizers for the plastics sector and as additives to lubricants.
Des weiteren können sie als Zwischenprodukte zur Synthese von weiteren Schädlingsbekämpfungsmitteln und pharmazeutischer Präparaten Verwendung finden.They can also be used as intermediates for the synthesis of other Find pesticides and pharmaceutical preparations use.
Beispiel 1 In einern mit Rührer, Thermometer und Rückflußkühler mit Ga¢abgang versehenen 1-l~Rührkolben wird eine Suspension aus 71,5 g = 1,1 ol Natriumcyanat und 40090 9 Acetonitril vorgelegt. In dieee Suspollsion tritt man unter Rühren nacheinander 9090 9 = 1 Mol Glykolsäuromethylesters 12295 g = 1 Mol Monochloressigsäsureethylester und nachfolgend 490 g Triethylamin ( = 1 % bezogen auf Acetonitril) ein.Example 1 In one with stirrer, thermometer and reflux condenser A 1 liter stirred flask provided with the outlet becomes a suspension of 71.5 g = 1.1 mol of sodium cyanate and 40090 9 presented acetonitrile. The suspension is stepped one after the other with stirring 9090 9 = 1 mole of methyl glycolate 12295 g = 1 mole of ethyl monochloroacetate and then 490 g of triethylamine (= 1% based on acetonitrile).
Die Suspension wird 22 Stunden bei 80 °C gerührt. Die Ionen chlorbestimmung im salzhaltigen Bodenkörper zeigte mit 5292 % eine vollständige Umsetzung an.The suspension is stirred at 80 ° C. for 22 hours. The ion chlorine determination in the salty soil body showed a complete conversion with 5292%.
Es wird filtriert, der Salzrückstand auf dem Filter zweimal mit Je 65 g Acetonitril gewaschen und das Filtrat einschließlich der Waschaflüssigkeiten im Rotationsunrdampfer eingeengt. Der zunächst pastöse Rückstand verfestigt sich beitn Stehen. Man extrahiert ihn mit 50 %igem Ethanol und aus diesem kristallisieren dann insgesamt 114,8 g, bei 62 bis 65 °C schmelzendes 3-Carbnthoxj.-mothyl-oxazolidin-dion--(2,4) der Formel % C: 44,9 (Th: 45,2); % H: 5,4 (Th: 5,4); % N: 14,8 (Th: 15,0) Beispiel 2 Es wurde wie in Beispiel 1 verfahren, jedoch anstelle des Glykolsäuremethylesters 118,13 g = 1 Mol d,1-Milchsäureethylester eingesetzt.It is filtered, the salt residue on the filter is washed twice with 65 g of acetonitrile each time and the filtrate, including the washing liquids, is concentrated in a rotary evaporator. The initially pasty residue solidifies when standing. It is extracted with 50% ethanol and then a total of 114.8 g of 3-carbnthoxj.-mothyl-oxazolidin-dione - (2,4) of the formula which melts at 62 to 65 ° C. crystallize out of this % C: 44.9 (Th: 45.2); % H: 5.4 (Th: 5.4); % N: 14.8 (Th: 15.0) Example 2 The procedure was as in Example 1, except that 118.13 g = 1 mol of d, 1-lactic acid ethyl ester were used instead of the methyl glycolate.
Die Reaktionsdauer betrug 8 1/2 Stunden bei 80 oC.The reaction time was 8 1/2 hours at 80 oC.
Das wie in Beispiel 1 isolierte Rohrprodukt ist eine bräunlichn, viskose Flüssigkeit, die einer Vakuumdestillation bei ca.The pipe product isolated as in Example 1 is a brownish, viscous one Liquid that can be subjected to vacuum distillation at approx.
0,3 mbar unterwerfen wird. Man erhält das bei Raumtemperatur flüssige 3-Carbethoxymethyl-5-methyl-oxazolidin-dion-(2,4) in einer Ausbeute von nahezu 100%. Kp0,3: ca. 114°C % C: 47,9 (Th: 47,8); % H: 5,8 (Th: 5,6); % N: N: 7,3 (Th: 6,gjr) Beispiel 3 Es wurde wie in Beispiel 2 gearbeitet, jedoch anstelle von Monochloressigsäureethylester 1 Mol = 126,6 g Bonzylchlori(d einem setzt.0.3 mbar is subjected. The liquid at room temperature is obtained 3-Carbethoxymethyl-5-methyl-oxazolidin-dione- (2,4) in a yield of almost 100%. Bp 0.3: about 114 ° C% C: 47.9 (Th: 47.8); % H: 5.8 (Th: 5.6); % N: N: 7.3 (Th: 6, gjr) Example 3 The procedure was as in Example 2, but instead of ethyl monochloroacetate 1 mol = 126.6 g of Bonzylchlori (d one sets.
Nach der gemäß Beispiel 1 erfolgten Aufarbeitung verbleiben als Rückstand 180,6 g einer leicht rötlich gefärbten, beim Stehen allmählich kristallisierenden Flüssigkeit, die sich als geringfügig verunreinigtes 3-Benzyl5-methyl-oxazolidin-dion-(2,4) erwies (Ausbaute ca. 88,1 %). Fp. nach Umkristallisation aus Ethanol: 75 bis 77 'C.After the work-up carried out according to Example 1, the residue remains 180.6 g of a slightly reddish color that gradually crystallizes on standing Liquid which turns out to be slightly contaminated 3-Benzyl5-methyl-oxazolidin-dione- (2,4) proved (expansion approx. 88.1%). M.p. after recrystallization from ethanol: 75 to 77 'C.
% C: 64,4 (Th: 64,3);% H: 5,4 (Th: 5,4); % N: 6,9 (Th: G,8) Beispiel 4 Der Ansatz des Beispiels 1 wurde derart abgeändert, daß anstelle von 1 Mol Monochloressigsäureethylester 1 Mol p-Nitrobenzylchlorid zum Einsatz kam.% C: 64.4 (Th: 64.3);% H: 5.4 (Th: 5.4); % N: 6.9 (Th: G, 8) Example 4 The approach of Example 1 was modified in such a way that instead of 1 mol of ethyl monochloroacetate 1 mole of p-nitrobenzyl chloride was used.
Nach alfstündiger Reaktionsdauer bei 80 tC wurde wie beschrieben aufgearbeitet. Es verblieben 218.7 g einer eckerfarbenen teilkristallinen Paste, die durch Austreiben mit 150 ml eines Cemisches aus 5 volumenteilen Diethylether und 1 Uolumentsil Acetonitril zu einem Pulver zerfiel. Der Fp desselben betrug nach dom Trocknen 123 bis 140 °C. Nach der Rekristallisation aus Ethanol besaß das derart erhaltene 3-p-Nitrobenzyl-oxazolidin-dien-(2,4) einen Fp von 156 bis 159 °C.After a reaction time of eleven hours at 80 ° C., work-up was carried out as described. There remained 218.7 g of a corner-colored, partially crystalline paste, which was removed by expelling with 150 ml of a mixture of 5 parts by volume of diethyl ether and 1 uolumentsil acetonitrile disintegrated into a powder. The melting point of the same was 123 to 140 ° C. after dom drying. After recrystallization from ethanol, the 3-p-nitrobenzyl-oxazolidine-diene- (2,4) obtained in this way had mp 156-159 ° C.
% C : 50,7 (Th: 50,8); % H: 3,4 (Th: 3,4): % N: 11,9 (Th: 11,9) Beispiel 5 In einem 0,5-1-Rundkolben, der entsprechend Beispiel 1 ausgerüstet war, wurde eine Suspension aus 20090 9 = 22,2 ol Glykolsauremethylester und 35,7 g = 095 Mol zuzüglich 10 % Natriumcyun vorgelegt.% C: 50.7 (Th: 50.8); % H: 3.4 (Th: 3.4):% N: 11.9 (Th: 11.9) Example 5 In a 0.5-1 round bottom flask, which was equipped according to Example 1, was a suspension of 20090 9 = 22.2 ol methyl glycolate and 35.7 g = 095 mol submitted plus 10% sodium cyun.
Unter Rühren trug man allmählich eine Lösung von 77,3 g = 0,5 Mol #-Chloracetophenon in 45,3 g = 0,5 Mol Glykolsäuremethylester ein.A solution of 77.3 g = 0.5 mol was gradually added with stirring # -Chloroacetophenone in 45.3 g = 0.5 mol of glycolic acid methyl ester.
Nach einer Reaktionszeit von 15/4 Stunden bei 80°C war die Umsetzung beendet.After a reaction time of 15/4 hours at 80 ° C., the reaction was complete completed.
Das bei Raumtemperatur feste Rohprodukt wurde mit 70 g Acetonitril versetzt, auf 50 °C erwärmt und druckfiltriert. Nach dem Einengen des Filtrats im Rotationsverdampfer verblieben 129,4 9 einer rötlich-braun gefärbten kristallinen Masse, aus der beim Umkristallisieren aus Ethanol 47,8 g reines 3-Phenacyloxazolidin-dion-(S,4) isoliert werden konnten, entsprechend einer Ausbeute von 43,7 % d. Th.; Fp: 128 bis 130°C.The crude product, which was solid at room temperature, was treated with 70 g of acetonitrile added, heated to 50 ° C and pressure filtered. After concentrating the filtrate in Rotary evaporator remained 129.4 9 of a reddish-brown colored crystalline Mass from which, when recrystallized from ethanol, 47.8 g of pure 3-phenacyloxazolidine-dione (S, 4) could be isolated, corresponding to a yield of 43.7% of theory. Th .; Mp: 128 up to 130 ° C.
% C: 59,9 (Th: 60,2); % H: 4,1 (Th: 4,1)) % N: 6,3 (Th: 6,4)% C: 59.9 (Th: 60.2); % H: 4.1 (Th: 4.1)% N: 6.3 (Th: 6.4)
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19803003653 DE3003653A1 (en) | 1980-02-01 | 1980-02-01 | N-substd. oxazolidine-2,4-di:one derivs. prodn. - by one-pot reaction of alkali cyanate with organic halide and alpha-hydroxy carboxylic acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19803003653 DE3003653A1 (en) | 1980-02-01 | 1980-02-01 | N-substd. oxazolidine-2,4-di:one derivs. prodn. - by one-pot reaction of alkali cyanate with organic halide and alpha-hydroxy carboxylic acid ester |
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| Publication Number | Publication Date |
|---|---|
| DE3003653A1 true DE3003653A1 (en) | 1981-08-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19803003653 Withdrawn DE3003653A1 (en) | 1980-02-01 | 1980-02-01 | N-substd. oxazolidine-2,4-di:one derivs. prodn. - by one-pot reaction of alkali cyanate with organic halide and alpha-hydroxy carboxylic acid ester |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6518434B2 (en) | 2000-02-07 | 2003-02-11 | Astrazeneca Ab | Coupling process |
| JP2006517218A (en) * | 2003-01-23 | 2006-07-20 | サノフィ−アベンティス | Preparation of arylalkyl carbamate derivatives and their therapeutic use |
-
1980
- 1980-02-01 DE DE19803003653 patent/DE3003653A1/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6518434B2 (en) | 2000-02-07 | 2003-02-11 | Astrazeneca Ab | Coupling process |
| JP2006517218A (en) * | 2003-01-23 | 2006-07-20 | サノフィ−アベンティス | Preparation of arylalkyl carbamate derivatives and their therapeutic use |
| CN101058564B (en) * | 2003-01-23 | 2010-05-26 | 赛诺菲安万特 | Production of arylalkyl carbamate derivatives and their use in therapy |
| AU2004207657B2 (en) * | 2003-01-23 | 2010-09-16 | Sanofi-Aventis | Aryl alkyl carbamate derivatives production and use thereof in therapy |
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