DK144011B - Fremgangsmaade til fremstilling af heteroaromatiske urinstofderivater - Google Patents
Fremgangsmaade til fremstilling af heteroaromatiske urinstofderivater Download PDFInfo
- Publication number
- DK144011B DK144011B DK180378AA DK180378A DK144011B DK 144011 B DK144011 B DK 144011B DK 180378A A DK180378A A DK 180378AA DK 180378 A DK180378 A DK 180378A DK 144011 B DK144011 B DK 144011B
- Authority
- DK
- Denmark
- Prior art keywords
- urea
- heteroaromatic
- chloride
- reaction
- yield
- Prior art date
Links
- 238000000034 method Methods 0.000 title description 9
- 238000002360 preparation method Methods 0.000 title description 4
- 230000002485 urinary effect Effects 0.000 title 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 18
- -1 heteroaromatic urea derivatives Chemical class 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000002841 Lewis acid Substances 0.000 description 7
- 150000007517 lewis acids Chemical class 0.000 description 7
- GGXGVZJHUKEJHO-UHFFFAOYSA-N 5-tert-butyl-1,2-oxazol-3-amine Chemical compound CC(C)(C)C1=CC(N)=NO1 GGXGVZJHUKEJHO-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 150000003672 ureas Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- JLLJHQLUZAKJFH-UHFFFAOYSA-N Isouron Chemical compound CN(C)C(=O)NC=1C=C(C(C)(C)C)ON=1 JLLJHQLUZAKJFH-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 125000001072 heteroaryl group Chemical group 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 2
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 2
- XMXLBDNVSIHRRA-UHFFFAOYSA-N 4,5-dimethyl-1,3-thiazol-2-amine Chemical compound CC=1N=C(N)SC=1C XMXLBDNVSIHRRA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- YIIMEMSDCNDGTB-UHFFFAOYSA-N Dimethylcarbamoyl chloride Chemical compound CN(C)C(Cl)=O YIIMEMSDCNDGTB-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 235000013877 carbamide Nutrition 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- SUCONPINCPEQKC-UHFFFAOYSA-N 1,1-dimethyl-3-(4-methyl-1,3-thiazol-2-yl)urea Chemical compound CN(C)C(=O)NC1=NC(C)=CS1 SUCONPINCPEQKC-UHFFFAOYSA-N 0.000 description 1
- NYDCIKWIMJJMJX-UHFFFAOYSA-N 1,1-dimethyl-3-(5-phenyl-1,2-thiazol-3-yl)urea Chemical compound S1N=C(NC(=O)N(C)C)C=C1C1=CC=CC=C1 NYDCIKWIMJJMJX-UHFFFAOYSA-N 0.000 description 1
- XRMHIRYPZQIKKK-UHFFFAOYSA-N 1,1-dimethyl-3-pyridin-2-ylurea Chemical compound CN(C)C(=O)NC1=CC=CC=N1 XRMHIRYPZQIKKK-UHFFFAOYSA-N 0.000 description 1
- UMDOQTDANJTGJY-UHFFFAOYSA-N 1,3-bis(5-tert-butyl-1,2-oxazol-3-yl)urea Chemical compound O1C(C(C)(C)C)=CC(NC(=O)NC2=NOC(=C2)C(C)(C)C)=N1 UMDOQTDANJTGJY-UHFFFAOYSA-N 0.000 description 1
- UHGULLIUJBCTEF-UHFFFAOYSA-N 2-aminobenzothiazole Chemical compound C1=CC=C2SC(N)=NC2=C1 UHGULLIUJBCTEF-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- AMIJSEIHRANBNZ-UHFFFAOYSA-N 3-(1,3-benzothiazol-2-yl)-1,1-dimethylurea Chemical compound C1=CC=C2SC(NC(=O)N(C)C)=NC2=C1 AMIJSEIHRANBNZ-UHFFFAOYSA-N 0.000 description 1
- DDURBKJYRBUVKU-UHFFFAOYSA-N 3-(4,5-dimethyl-1,3-thiazol-2-yl)-1,1-dimethylurea Chemical compound CN(C)C(=O)NC1=NC(C)=C(C)S1 DDURBKJYRBUVKU-UHFFFAOYSA-N 0.000 description 1
- PIFBWXULXGPZKO-UHFFFAOYSA-N 3-(5-tert-butyl-1,2-oxazol-3-yl)-1,1-diethylurea Chemical compound CCN(CC)C(=O)NC=1C=C(C(C)(C)C)ON=1 PIFBWXULXGPZKO-UHFFFAOYSA-N 0.000 description 1
- IMIXYLFTWDRFHY-UHFFFAOYSA-N 3-(5-tert-butyl-1,2-oxazol-3-yl)-1-methoxy-1-methylurea Chemical compound CON(C)C(=O)NC=1C=C(C(C)(C)C)ON=1 IMIXYLFTWDRFHY-UHFFFAOYSA-N 0.000 description 1
- KCIPJIIZEPMNPU-UHFFFAOYSA-N 3-(5-tert-butyl-1,2-oxazol-3-yl)-1-methyl-1-prop-2-enylurea Chemical compound C=CCN(C)C(=O)NC=1C=C(C(C)(C)C)ON=1 KCIPJIIZEPMNPU-UHFFFAOYSA-N 0.000 description 1
- OUQMXTJYCAJLGO-UHFFFAOYSA-N 4-methyl-1,3-thiazol-2-amine Chemical compound CC1=CSC(N)=N1 OUQMXTJYCAJLGO-UHFFFAOYSA-N 0.000 description 1
- VLQBYPSKWKIMPS-UHFFFAOYSA-N 5-phenyl-1,2-thiazol-3-amine Chemical compound S1N=C(N)C=C1C1=CC=CC=C1 VLQBYPSKWKIMPS-UHFFFAOYSA-N 0.000 description 1
- 125000004648 C2-C8 alkenyl group Chemical group 0.000 description 1
- CKDWPUIZGOQOOM-UHFFFAOYSA-N Carbamyl chloride Chemical compound NC(Cl)=O CKDWPUIZGOQOOM-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- XZVYDRLPXWFRIS-UHFFFAOYSA-N n-ethyl-n-methylcarbamoyl chloride Chemical compound CCN(C)C(Cl)=O XZVYDRLPXWFRIS-UHFFFAOYSA-N 0.000 description 1
- SHQJHXLWZDMQEJ-UHFFFAOYSA-N n-methoxy-n-methylcarbamoyl chloride Chemical compound CON(C)C(Cl)=O SHQJHXLWZDMQEJ-UHFFFAOYSA-N 0.000 description 1
- UEKTZPNFEQJPLZ-UHFFFAOYSA-N n-methyl-n-prop-2-enylcarbamoyl chloride Chemical compound ClC(=O)N(C)CC=C UEKTZPNFEQJPLZ-UHFFFAOYSA-N 0.000 description 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229940075930 picrate Drugs 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-M picrate anion Chemical compound [O-]C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-M 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
- C07D213/72—Nitrogen atoms
- C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
- C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
- C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
- C07D261/10—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more 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
- C07D261/14—Nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D275/00—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings
- C07D275/02—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings
- C07D275/03—Heterocyclic compounds containing 1,2-thiazole or hydrogenated 1,2-thiazole rings not condensed with other rings 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole 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
- C07D277/38—Nitrogen atoms
- C07D277/44—Acylated amino or imino radicals
- C07D277/48—Acylated amino or imino radicals by radicals derived from carbonic acid, or sulfur or nitrogen analogues thereof, e.g. carbonylguanidines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles 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 in position 2
- C07D277/82—Nitrogen 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)
- Pyridine Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Thiazole And Isothizaole Compounds (AREA)
Description
(19) DANMARK
|f| (12) FREMLÆGGELSESSKRIFT <n> 144011 B
DIREKTORATET FOR PATENT- OG VAREMÆRKEVÆSENET
(21) Ansøgning nr. 1805/78 (51) intCI* ® ® 261/14 (22) Indleveringsdag 25· apr. 1978 ® ® " eTW 1Π7« C 07 D 283/00 (24) Løbedag 25· apr. 1978 (41) Aim. tilgængelig 29* okt. 1978 (44) Fremlagt 1 6. nov. 1981 (86) International ansøgning nr. “ (86) International indleveringsdag ~ (85) Videreførelsesdag " (62) Stamansøgning nr. “
(30) Prioritet 2δ· apr. 1977# ^9^29/77# JP
(71) Ansøger _SHIONOGI & CO. LTD·# Osaka# JP · (72) Opfinder Yasuo Makisurai# JP: Takashi Sasatani# JP: Akira
Murabayashi # JP.
(74) Fuldmægtig Th. Ostenfeld Patent bureau A/S.
(54) Fremgangsmåde til fremstilling af heteroaromatiske urinstofderivater.
Den foreliggende opfindelse angår en særlig fremgangsmåde til fremstilling af heteroaromatiske urinstofderivater med formlen (I): R 1
Ar-N-CO-N (I) hvori Ar betegner en rest af en 5- eller 6-leddet heteroaromatisk ring med et eller to he te roatomer i form af nitrogen, oxygen eller svovl, R betegner hydrogen eller (C^-Cg) alkyl, R^ betegner (C^-Cg) alkyl, og ® R^ betegner (C^-Cg)alkyl, (C2~Cg)alkenyl eller (C^-Cg)alkoxy.
T- Heteroaromatiske urinstofderivater er nyttige som selektive herbi- cider. F.eks. er 5-alkylisoxazolylurinstoffer omhandlet i USA-patent
——J
nr. 4.062.861, og N-substituerede 1-(2-benzothiazolyl)urinstoffer er omhandlet i hollandsk fremlæggelsesskrift nr. 7.211.273, De kendte fremgangsmåder til fremstilling af disse urinstofderivater er imid-^ lertid mindre tilfredsstillende til industrielle formål.
2 U4011 F.eks. beskrives i USA-patentskriftet en fremgangsmåde til fremstilling af l,l-dimethyl-3-(5-t-butyl-3-isoxazolyl)urinstof, som omfatter, at 3-amino-5-t-butylisoxazol omsættes med N,N-dimethylcarbamoyl-chlorid i nærværelse af en base såsom pyridin. Denne fremgangsmåde lider af den mangel, at produktudbyttet uundgåeligt formindskes på grund af dannelsen af 1,3-bis(5-t-butyl-3-isoxazolyl)urinstof som et uønsket biprodukt.
Efter omhyggelige undersøgelser med henblik på udvikling af en forbedret fremgangsmåde til fremstilling af disse urinstofderivater (I) uden at sådanne biprodukter dannes, har det vist sig, at man ved anvendelse af en Lewis-syre i ovenstående reaktionssystem opnår, at omsætningen forløber selektivt og derved giver det største udbytte, og at udvalget af anvendelige udgangsaminer, Ar-NH-R (II) kan udvides til også at omfatte mindre reaktive heteroaromatiske aminer. Den foreliggende opfindelse er derfor med held blevet omsat til praksis.
Den foreliggende opfindelse angår således - som nævnt - en særlig fremgangsmåde til fremstilling af urinstofderivater med formlen (I): R R1
I /R
Ar-N-CO-N , (I) hvori Ar betegner en rest af en 5- eller 6-leddet heteroaromatisk ring, med et eller to heteroatomer i form af nitrogen, oxygen eller svovl, R betegner hydrogen eller (C^-Cg) alkyl, R"*" betegner (C^-Cg)-alkyl, og R2 betegner (C^-Cg)alkyl, (C2~Cg)alkenyl eller (C^-Cg)-alkoxy ved hvilken man omsætter en amin med formlen(II):
Ar-NH-R (II) hvori Ar og R har den ovenfor anførte betydning, med et carbamoyl-halogenid med formlen (III): X-CO-N (III)
^R
1 2 hvori X betegner et halogenatom, og R og R har den ovenfor anførte betydning, hvilken fremgangsmåde er ejendommelig ved, at omsætningen foretages i nærværelse af en Lewis-syre i et inert opløsningsmiddel.
Definitionen af ovenstående substituenter kan suppleres med følgende beskrivelse: 3 1UQ11
Den heteroaromatiske ring omfatter 3-isoxazolyl- (f.eks. 5-alkyl-3-isoxazolyl-, 5-phenyl-3-isoxazolyl-), 2-thiazolyl- (f.eks. 4-alkyl-2-thiazolyl-, 4,5-dialkyl-2-thiazolyl-), 3-isothiazolyl- (f.eks. 5-phenyl-3-isothiazolyl-), 2-benzothiazolyl- og 2-pyridylringe; alkyl-gruppen omfatter methyl, ethyl, propyl, i-propyl, butyl, i-butyl, t-butyl, pentyl og i-pentyl; alkenylgruppen omfatter allyl, butenyl, pentenyl og hexenyl; alkoxygruppen omfatter methoxy, ethoxy, propoxy og butoxy; halogen omfatter chlor, brom og iod, og Lewis-syren omfatter aluminiumchlorid, stannichlorid, titantetrachlorid, magnesiumchlo-rid og zinkchlorid, især aluminiumchlorid.
Omsætningen ifølge opfindelsen kan gennemføres i nærværelse af en Lewis-syre i et passende inert opløsningsmiddel (f.eks. benzen, toluen, xylen, chloroform, methylenchlorid, dichlorethan, trichlor-ethylen) under opvarmning fortrinsvis til omkring opløsningsmidlets kogepunkt. Mængden af carbamoylhalogenidet (III) i forhold til ud-gangsaminen (II) kan indstilles til ca. 1,0 til ca. 1,2 molækvivalent, fortrinsvis ca. 1,0 til ca. 1,1 molækvivalent. Forholdet mellem Lewis-syren og udgangsaminen (II) kan være ca. 1,0 til ca. 1,2 mol ækvivalent, fortrinsvis ca. 1,0 til ca. 1,1 molask vi valent.
Den industrielle fordel ved den foreliggende opfindelse i forhold til den kendte teknik er som følger: 1) Omsætningen giver kun det pågældende rene produkt i næsten kvantitativt udbytte uden sidereaktioner af betydning; 2) Omsætningens anvendelsesområde er tilstrækkelig bredt til, at der kan anvendes forskellige mindre reaktive heteroaromatiske aminer; 3) Fremgangsmåden er simpel at gennemføre, og slutproduktet kan let isoleres og renses.
Fremgangsmåden ifølge den foreliggende opfindelse illustreres hærmere i de følgende udførelseseksempler.
Eksempel 1 N,N-dimethylcarbamoylchlorid (7,91 g) og aluminiumchlorid (9,80 g) sættes til toluen (100 ml), og blandingen omrøres ved stuetemperatur i 30 minutter. Til denne blanding sættes 3-amino-5-t-butylisoxazol (9,81 g), og den opnåede blanding tilbagesvales i 6 timer under omrøring. Efter afkøling blandes reaktionsblandingen med vand, omrøres ved stuetemperatur og rystes med toluen. Det organiske lag inddampes til fjernelse af toluen, hvorved l,l-dimethyl-3-(5-t-butyl-3-isoxa-zolyl)urinstof (14,63 g) opnås. Udbyttet er 98,9%. Smeltepunktet af 4 144011 det farveløse krystallinske produkt er 119 til 120,5°C (efter om-krystallisation fra benzen).
Eksempel 2-5
Onder anvendelse af følgende Lewis-syrer i stedet for aluminium-chlorid gennemføres omsætningen som i eksempel 1 ovenfor, hvorved l,l-dimethyl-3-(5-t-butyl-3-isoxazolyl)urinstof fås i de i tabel I viste udbytter.
Tabel I
Eksempel nr. Lewis-syre Odbytte (%) 2 SnCl4 99,1 3 TiCl4 98,8 4 MgCl2 97,4 5 ZnCl2 97,4
Eksempel 6-12
Onder anvendelse af følgende udgangsmaterialer (II) og (III) gennemføres omsætningen som i eksempel 1, hvorved de tilsvarende urinstofderivater (I) fås som vist i tabel II.
R4 R1 R4 R R1
Nl-Π—NHR ClCON^ _ (III) 'Nl-Γ1 N-CO-N^ 0 •I \R2 II XR2 R3-V -> (II) (!)
Tabel II
5 144011
Eks. II__III__I _ nr* - . io Smp. (°c) eller Udbytte R R0 R R R Kp. (°C)/mm Hg (%) 6 H Me H Me Me 153-154 97,3 7 H Et H Me Me 87,5-89 98,4 8 H i-Pr H Me Me 69,5-71 98,0 9 Et Me H Me Me 105-107/0,2 95,9 10 Me t-Bu H Me Me 93-94 97,7 11 Me Ph H Me Me 165-168/0,4 97,2 12 H t-Bu Br Me Me 169,5-171 96,8 NB: Forkortelserne i Tabel II har følgende betydninger: H (hydrogen), Me (methyl), Et (ethyl).
Pr (propyl), Bu (butyl), Ph (phenyl), Br (brom), i- (iso-), t- (tertiær-)
Eksempel 13 Ν,Ν-dimethylcarbamoylchlorid (1,29 g) og aluminiumchlorid (1,60 g) opløses i toluen (40 ml), og blandingen omrøres ved stuetemperatur i 30 minutter. Til denne blanding sættes 3-amino-5-phenyl-isothiazol (1,76 g), og den opnåede blanding tilbagesvales i 6 timer under omrøring. Efter afkøling blandes reaktionsblandingen med vand og rystes med toluen. Det organiske lag fraskilles, vaskes med vand, tørres og koncentreres til tørhed til frembringelse af 1,1-dimethyl-3-(5-phenyl-3-isothiazolyl)urinstof (2,38 g). Udbytte: 96,4%. Smeltepunktet af de farveløse krystaller er 129 til 130,5°C (efter omkrystallisation fra benzen/petroleumbenzin).
Eksempel 14
En blanding af 2-amino-4-methylthiazol (1,14 g), Ν,Ν-dimethylcarbamoylchlorid (1,29 g), aluminiumchlorid (1,60 g) og xylen (40 ml) tilbagesvales i 20 timer. Reaktionsblandingen oparbejdes som i eksempel 1, hvorved der fås 1,l-dimethyl-3-(4-methyl-2-thiazolyl)urinstof (1,73 g). Udbytte: 93,5%. Smeltepunkt 97 til 98°C (rent produkt om·* krystalliseres fra ether/petroleumsether).
6 144011
Eksempel 15
Under anvendelse af 2-amino-4,5-dimethylthiazol (1,28 g), Ν,Ν-dimethylcarbamoylchlorid (1,29 g), aluminiumchlorid (1,60 g) og xylen (40 ml) forløber omsætningen som i eksempel 1, hvorved der fås l,l-dimethyl-3-(4,5-dimethyl-2-thiazolyl)urinstof (1,82 g). Udbytte: 91,5%. Smeltepunkt 202,5 til 204°C (efter omkrystallisation fra ethylacetat).
Eksempel 16
Under anvendelse af 2-aminobenzothiazol (1,50 g), Ν,Ν-dimethylcarbamoylchlorid (1,29 g), aluminiumchlorid (1,60 g) og trichlor-ethylen (40 ml) gennemføres omsætningen som i eksempel 1, bortset fra at der tilbagesvales i 40 timer. Derved fås l,l-dimethyl-3-(2-benzo-thiazolyl)urinstof (2,16 g). Udbytte: 97,7%. Smeltepunkt højere end 300°C (efter omkrystallisation fra ethanol).
Eksempel 17
En blanding af 2-aminopyridin (941 mg), Ν,Ν-dimethylcarbamoylchlorid (1,29 g), aluminiumchlorid (1,60 g) og xylen (30 ml) opvarmes under reflux i 8 timer. Efter afkøling gøres reaktionsblandingen alkalisk med natriumhydroxid og rystes med chloroform. Det organiske lag fraskilles, vaskes med vand, tørres og inddampes til fjernelse af opløsningsmidlet, hvorved der fås l,l-dimethyl-3-(2-pyridyl)urinstof (1,57 g) som et olieagtigt produkt. Picratet af dette produkt viser et smeltepunkt på 187 til 189,5°C (dekomponering).
Eksempel 18
Under anvendelse af 3-amino-5-t-butylisoxazol og N-ethyl-N-methylcarbamoylchlorid gennemføres omsætningen som i eksempel 1, hvorved der fås 1-ethyl-1-methy1-3-(5-t-butyl-3-isoxazolyl)urinstof. Udbytte: 96,1%. Smeltepunkt 88,5 til 89,5°C.
Eksempel 19
Under anvendelse af 3-amino-5-t-butylisoxazol og N-allyl-N-methylcarbamoylchlorid gennemføres omsætningen som i eksempel 1, hvorved der fås l-allyl-l-methyl-3-(5-t-butyl-3-isoxazolyl)urinstof. Udbytte: 90,5%. Smeltepunkt 90,0 til 91,0°C.
Eksempel 20 7 144011
Under anvendelse af 3-amino-5-t-butylisoxazol og N-methoxy-N-methylcarbamoylchlorid forløber omsætningen som i eksempel 1, hvorved der fås l-methoxy-l-methyl-3-(5-t-butyl-3-isoxazolyl)urinstof.
Udbytte: 94,7%. Smeltepunkt 106,0 til 107,0°C.
Eksempel 21
Under anvendelse af 3-amino-5-t-butylisoxazol og N,N-diethyl·-carbamoylchlorid gennemføres omsætningen som i eksempel 1, hvorved der fås 1,l-diethyl-3-(5-t-butyl-3-isoxazolyl)urinstof- Udbytte: 98,2%. Smeltepunkt 122,0 til 123,5°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP52049629A JPS6033109B2 (ja) | 1977-04-28 | 1977-04-28 | 尿素誘導体の合成法 |
| JP4962977 | 1977-04-28 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK180378A DK180378A (da) | 1978-10-29 |
| DK144011B true DK144011B (da) | 1981-11-16 |
| DK144011C DK144011C (da) | 1982-04-26 |
Family
ID=12836505
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK180378A DK144011C (da) | 1977-04-28 | 1978-04-25 | Fremgangsmaade til fremstilling af heteroaromatiske urinstofderivater |
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| Country | Link |
|---|---|
| US (1) | US4183856A (da) |
| JP (1) | JPS6033109B2 (da) |
| AR (1) | AR225666A1 (da) |
| AU (1) | AU513688B2 (da) |
| BE (1) | BE866581A (da) |
| BG (1) | BG33278A3 (da) |
| BR (1) | BR7802618A (da) |
| CA (1) | CA1093081A (da) |
| CH (1) | CH633542A5 (da) |
| CS (1) | CS198297B2 (da) |
| DD (1) | DD135905A5 (da) |
| DE (1) | DE2818947A1 (da) |
| DK (1) | DK144011C (da) |
| ES (1) | ES468897A1 (da) |
| FR (1) | FR2388802A1 (da) |
| GB (1) | GB1572976A (da) |
| HU (1) | HU176881B (da) |
| IE (1) | IE46769B1 (da) |
| IL (1) | IL54468A0 (da) |
| IT (1) | IT1111465B (da) |
| NL (1) | NL183513C (da) |
| PL (1) | PL110681B1 (da) |
| SE (1) | SE442867B (da) |
| SU (1) | SU1091853A3 (da) |
| YU (1) | YU40334B (da) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8422461D0 (en) * | 1984-09-05 | 1984-10-10 | Wyeth John & Brother Ltd | Pyridine derivatives |
| US4808722A (en) * | 1985-10-31 | 1989-02-28 | Fmc Corporation | Pyridinylurea N-oxide compounds and agricultural uses |
| ATE103589T1 (de) * | 1989-11-10 | 1994-04-15 | Agrolinz Agrarchemikalien | Verfahren zur herstellung reiner, unsymmetrisch disubstituierter harnstoffe. |
| DE3940261A1 (de) * | 1989-12-06 | 1991-06-13 | Agrolinz Agrarchemikalien Muen | Verfahren zur herstellung reiner, unsymmetrisch disubstituierter harnstoffe |
| PL370989A1 (en) * | 2001-12-21 | 2005-06-13 | Novo Nordisk A/S | Amide derivatives as gk activators |
| MXPA05000130A (es) * | 2002-06-27 | 2005-02-17 | Novo Nordisk As | Derivados de aril-carbonilo como agentes terapeuticos. |
| PL1723128T3 (pl) * | 2004-01-06 | 2013-04-30 | Novo Nordisk As | Pochodne heteroarylowe mocznika oraz ich zastosowanie jako aktywatory glukokinazy |
| ATE547396T1 (de) * | 2005-07-08 | 2012-03-15 | Novo Nordisk As | Dicycloalkylcarbamoyl-harnstoffe als glucokinase- aktivatoren |
| KR20080024211A (ko) * | 2005-07-08 | 2008-03-17 | 노보 노르디스크 에이/에스 | 디시클로알킬 우레아 글루코키나제 활성제 |
| US7884210B2 (en) * | 2005-07-14 | 2011-02-08 | Novo Nordisk A/S | Ureido-thiazole glucokinase activators |
| US8138185B2 (en) * | 2007-01-09 | 2012-03-20 | Novo Nordisk A/S | Urea glucokinase activators |
| EP2099777B1 (en) * | 2007-01-11 | 2015-08-12 | Novo Nordisk A/S | Urea glucokinase activators |
| EP4487909A3 (en) | 2018-06-12 | 2025-03-19 | vTv Therapeutics LLC | Therapeutic uses of glucokinase activators in combination with insulin or insulin analogs |
| US12391658B2 (en) | 2020-02-18 | 2025-08-19 | Vtv Therapeutics Llc | Sulfoxide and sulfone glucokinase activators and methods of use thereof |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2755285A (en) * | 1956-07-17 | I-xsubstituted | ||
| US2756135A (en) * | 1955-07-13 | 1956-07-24 | Du Pont | 1-methyl-3-(2-benzothiazolyl)-ureas and their use as herbicides |
| DE1209801B (de) * | 1963-05-11 | 1966-01-27 | Bayer Ag | Unkrautbekaempfung in Rueben |
| US3293257A (en) * | 1964-09-14 | 1966-12-20 | United States Borax Chem | Pyridyl urea compounds |
| FR1533184A (fr) * | 1965-04-06 | 1968-07-19 | Pechiney Saint Gobain | Dérivés du thiazole |
| DE1620448C3 (de) * | 1965-05-08 | 1974-08-29 | Schering Ag, 1000 Berlin Und 4619 Bergkamen | Harnstoff- bzw. Thioharnstoffderivate des 3-Methylisothiazols |
| US3622593A (en) * | 1967-08-09 | 1971-11-23 | Fmc Corp | 1,1-dimethyl-3-(isothiazol-5-yl)urea |
| US3547940A (en) * | 1967-10-31 | 1970-12-15 | Du Pont | Substituted ureido isoxazoles |
| GB1266769A (da) * | 1969-08-15 | 1972-03-15 | ||
| US4062861A (en) * | 1973-07-27 | 1977-12-13 | Shionogi & Co., Ltd. | 3-Isoxazolylurea derivatives |
| JPS5031039A (da) * | 1973-07-27 | 1975-03-27 | ||
| US4013706A (en) * | 1973-11-14 | 1977-03-22 | Sucreries Du Soissonnais Et Compagnie Sucriere | Derivatives of substituted urea, acyl ureas, and sulphonyl ureas, and a process for producing the same |
| US4046770A (en) * | 1974-08-30 | 1977-09-06 | Eli Lilly And Company | N-(6-acyloxybenzothiazol-2-yl)-N'-phenyl (or substituted phenyl)ureas |
| JPS5810361B2 (ja) * | 1974-10-04 | 1983-02-25 | 塩野義製薬株式会社 | ３−アルチルイソオキサゾ−ル系除草剤 |
-
1977
- 1977-04-28 JP JP52049629A patent/JPS6033109B2/ja not_active Expired
-
1978
- 1978-04-05 CA CA300,467A patent/CA1093081A/en not_active Expired
- 1978-04-05 GB GB13400/78A patent/GB1572976A/en not_active Expired
- 1978-04-10 US US05/895,105 patent/US4183856A/en not_active Expired - Lifetime
- 1978-04-10 IL IL54468A patent/IL54468A0/xx not_active IP Right Cessation
- 1978-04-11 IE IE707/78A patent/IE46769B1/en not_active IP Right Cessation
- 1978-04-18 ES ES468897A patent/ES468897A1/es not_active Expired
- 1978-04-21 SE SE7804596A patent/SE442867B/sv not_active IP Right Cessation
- 1978-04-25 DK DK180378A patent/DK144011C/da not_active IP Right Cessation
- 1978-04-26 AU AU35468/78A patent/AU513688B2/en not_active Expired
- 1978-04-27 FR FR7812529A patent/FR2388802A1/fr active Granted
- 1978-04-27 HU HU78SI1624A patent/HU176881B/hu not_active IP Right Cessation
- 1978-04-27 IT IT67959/78A patent/IT1111465B/it active
- 1978-04-27 BR BR7802618A patent/BR7802618A/pt unknown
- 1978-04-27 NL NLAANVRAGE7804550,A patent/NL183513C/xx not_active IP Right Cessation
- 1978-04-27 DD DD78205055A patent/DD135905A5/xx unknown
- 1978-04-28 DE DE19782818947 patent/DE2818947A1/de active Granted
- 1978-04-28 BG BG039586A patent/BG33278A3/xx unknown
- 1978-04-28 PL PL1978206450A patent/PL110681B1/pl unknown
- 1978-04-28 CH CH470378A patent/CH633542A5/de not_active IP Right Cessation
- 1978-04-28 SU SU782608147A patent/SU1091853A3/ru active
- 1978-04-28 YU YU1037/78A patent/YU40334B/xx unknown
- 1978-04-28 BE BE187289A patent/BE866581A/xx not_active IP Right Cessation
- 1978-04-28 CS CS782773A patent/CS198297B2/cs unknown
-
1981
- 1981-04-10 AR AR284939A patent/AR225666A1/es active
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