JPH09143163A - Production of nitrogen-containing heteroaromatic amides - Google Patents
Production of nitrogen-containing heteroaromatic amidesInfo
- Publication number
- JPH09143163A JPH09143163A JP7310436A JP31043695A JPH09143163A JP H09143163 A JPH09143163 A JP H09143163A JP 7310436 A JP7310436 A JP 7310436A JP 31043695 A JP31043695 A JP 31043695A JP H09143163 A JPH09143163 A JP H09143163A
- Authority
- JP
- Japan
- Prior art keywords
- group
- nitrogen
- amines
- lewis acid
- formula
- 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.)
- Pending
Links
- -1 nitrogen-containing heteroaromatic amides Chemical class 0.000 title claims abstract description 63
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 150000001412 amines Chemical class 0.000 claims abstract description 28
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 24
- 239000002841 Lewis acid Substances 0.000 claims abstract description 22
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 22
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 15
- 125000003118 aryl group Chemical group 0.000 claims abstract description 11
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract description 18
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 abstract description 15
- 239000012299 nitrogen atmosphere Substances 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 5
- FQYYIPZPELSLDK-UHFFFAOYSA-N ethyl pyridine-2-carboxylate Chemical compound CCOC(=O)C1=CC=CC=N1 FQYYIPZPELSLDK-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003905 agrochemical Substances 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 3
- 239000000975 dye Substances 0.000 abstract 1
- GVBHRBMWXDCRHZ-UHFFFAOYSA-N n-phenylpyridine-2-carboxamide Chemical compound C=1C=CC=NC=1C(=O)NC1=CC=CC=C1 GVBHRBMWXDCRHZ-UHFFFAOYSA-N 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 12
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 9
- 125000001424 substituent group Chemical group 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 238000007098 aminolysis reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- BWZVCCNYKMEVEX-UHFFFAOYSA-N 2,4,6-Trimethylpyridine Chemical compound CC1=CC(C)=NC(C)=C1 BWZVCCNYKMEVEX-UHFFFAOYSA-N 0.000 description 4
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2-methyl-5-methylpyridine Natural products CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 125000004434 sulfur atom Chemical group 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 150000003931 anilides Chemical class 0.000 description 3
- 150000004982 aromatic amines Chemical class 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 2
- WGCYRFWNGRMRJA-UHFFFAOYSA-N 1-ethylpiperazine Chemical compound CCN1CCNCC1 WGCYRFWNGRMRJA-UHFFFAOYSA-N 0.000 description 2
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 2
- CZZZABOKJQXEBO-UHFFFAOYSA-N 2,4-dimethylaniline Chemical compound CC1=CC=C(N)C(C)=C1 CZZZABOKJQXEBO-UHFFFAOYSA-N 0.000 description 2
- FECNOIODIVNEKI-UHFFFAOYSA-N 2-[(2-aminobenzoyl)amino]benzoic acid Chemical class NC1=CC=CC=C1C(=O)NC1=CC=CC=C1C(O)=O FECNOIODIVNEKI-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 2
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- 238000007112 amidation reaction Methods 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 2
- 125000005110 aryl thio group Chemical group 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000000269 nucleophilic effect Effects 0.000 description 2
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 2
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 150000003222 pyridines Chemical class 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- XOAAWQZATWQOTB-UHFFFAOYSA-N taurine Chemical compound NCCS(O)(=O)=O XOAAWQZATWQOTB-UHFFFAOYSA-N 0.000 description 2
- 125000004149 thio group Chemical group *S* 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 125000006701 (C1-C7) alkyl group Chemical group 0.000 description 1
- MBIZXFATKUQOOA-UHFFFAOYSA-N 1,3,4-thiadiazole Chemical compound C1=NN=CS1 MBIZXFATKUQOOA-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-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
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 1
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 1
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 1
- GAWAYYRQGQZKCR-UHFFFAOYSA-N 2-chloropropionic acid Chemical compound CC(Cl)C(O)=O GAWAYYRQGQZKCR-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- SDNXQWUJWNTDCC-UHFFFAOYSA-N 2-methylsulfonylethanamine Chemical compound CS(=O)(=O)CCN SDNXQWUJWNTDCC-UHFFFAOYSA-N 0.000 description 1
- IMLAIXAZMVDRGA-UHFFFAOYSA-N 2-phenoxyethanamine Chemical compound NCCOC1=CC=CC=C1 IMLAIXAZMVDRGA-UHFFFAOYSA-N 0.000 description 1
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- BNDAZCFXFGOYSK-UHFFFAOYSA-N 3-(2,4-dipentylphenoxy)propan-1-amine Chemical compound CCCCCC1=CC=C(OCCCN)C(CCCCC)=C1 BNDAZCFXFGOYSK-UHFFFAOYSA-N 0.000 description 1
- ALYNCZNDIQEVRV-PZFLKRBQSA-N 4-amino-3,5-ditritiobenzoic acid Chemical compound [3H]c1cc(cc([3H])c1N)C(O)=O ALYNCZNDIQEVRV-PZFLKRBQSA-N 0.000 description 1
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 1
- KNILZINKISHVIQ-UHFFFAOYSA-N 4-azaniumylbutane-1-sulfonate Chemical compound NCCCCS(O)(=O)=O KNILZINKISHVIQ-UHFFFAOYSA-N 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- 125000002373 5 membered heterocyclic group Chemical group 0.000 description 1
- KFKNOWKJWCLXRA-UHFFFAOYSA-N 5-aminonaphthalene-1,7-disulfonic acid Chemical compound C1=CC=C2C(N)=CC(S(O)(=O)=O)=CC2=C1S(O)(=O)=O KFKNOWKJWCLXRA-UHFFFAOYSA-N 0.000 description 1
- 125000004070 6 membered heterocyclic group Chemical group 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- KPKLLSYGFIFTJR-UHFFFAOYSA-N N-(3-pentadecylphenoxy)propan-1-amine Chemical compound CCCCCCCCCCCCCCCC1=CC=CC(ONCCC)=C1 KPKLLSYGFIFTJR-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- HOPRXXXSABQWAV-UHFFFAOYSA-N anhydrous collidine Natural products CC1=CC=NC(C)=C1C HOPRXXXSABQWAV-UHFFFAOYSA-N 0.000 description 1
- 150000001448 anilines Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- UTBIMNXEDGNJFE-UHFFFAOYSA-N collidine Natural products CC1=CC=C(C)C(C)=N1 UTBIMNXEDGNJFE-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- NISGSNTVMOOSJQ-UHFFFAOYSA-N cyclopentanamine Chemical compound NC1CCCC1 NISGSNTVMOOSJQ-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010644 ester aminolysis reaction Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 1
- VLDUBDZWWNLZCU-UHFFFAOYSA-N ethyl 5-methyl-1h-imidazole-4-carboxylate Chemical compound CCOC(=O)C=1NC=NC=1C VLDUBDZWWNLZCU-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- VGNWOZHANVNVGF-UHFFFAOYSA-N n-(4-nitrophenyl)pyridine-2-carboxamide Chemical compound C1=CC([N+](=O)[O-])=CC=C1NC(=O)C1=CC=CC=N1 VGNWOZHANVNVGF-UHFFFAOYSA-N 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
- 125000001624 naphthyl group Chemical group 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- KQOATKAFTRNONV-UHFFFAOYSA-N oxolan-2-amine Chemical compound NC1CCCO1 KQOATKAFTRNONV-UHFFFAOYSA-N 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-M picolinate Chemical compound [O-]C(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-M 0.000 description 1
- 229940081066 picolinic acid Drugs 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- IKNCGYCHMGNBCP-UHFFFAOYSA-N propan-1-olate Chemical compound CCC[O-] IKNCGYCHMGNBCP-UHFFFAOYSA-N 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- LJXQPZWIHJMPQQ-UHFFFAOYSA-N pyrimidin-2-amine Chemical compound NC1=NC=CC=N1 LJXQPZWIHJMPQQ-UHFFFAOYSA-N 0.000 description 1
- 125000000246 pyrimidin-2-yl group Chemical group [H]C1=NC(*)=NC([H])=C1[H] 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229950000244 sulfanilic acid Drugs 0.000 description 1
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 description 1
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- ZUZPOSNHFCUOMQ-UHFFFAOYSA-N thiolan-2-amine Chemical compound NC1CCCS1 ZUZPOSNHFCUOMQ-UHFFFAOYSA-N 0.000 description 1
- GLQWRXYOTXRDNH-UHFFFAOYSA-N thiophen-2-amine Chemical compound NC1=CC=CS1 GLQWRXYOTXRDNH-UHFFFAOYSA-N 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
Landscapes
- Thiazole And Isothizaole Compounds (AREA)
- Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
- Pyridine Compounds (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は染料中間体、医薬、
農薬などに有用な含窒素ヘテロ芳香族アミド類の製造方
法に関し、さらに詳しくは、ルイス酸を活性化剤として
用いて、含窒素ヘテロ芳香族エステル化合物とアミン類
から含窒素ヘテロ芳香族アミド類を製造する方法に関す
る。TECHNICAL FIELD The present invention relates to dye intermediates, pharmaceuticals,
Regarding a method for producing a nitrogen-containing heteroaromatic amide useful for agricultural chemicals, more specifically, a Lewis acid is used as an activator to produce a nitrogen-containing heteroaromatic amide from a nitrogen-containing heteroaromatic ester compound and amines. It relates to a method of manufacturing.
【0002】[0002]
【従来の技術】窒素原子の隣接位にカルバモイル基を有
する含窒素ヘテロ芳香族アミド類は例えば、染料中間
体、医薬、農薬などの骨格として有用な化合物である。
(特開昭51−77327、同63−139949、特
開平6−211852、J.Med.Chem.,3
7,2445(1984)など)2. Description of the Related Art Nitrogen-containing heteroaromatic amides having a carbamoyl group adjacent to a nitrogen atom are compounds useful as a skeleton for dye intermediates, pharmaceuticals, agricultural chemicals and the like.
(JP-A-51-77327, JP-A-63-139949, JP-A-6-212852, J. Med. Chem., 3
7, 2445 (1984) etc.)
【0003】含窒素ヘテロ芳香族アミド類の合成方法
は、従来、いくつか知られているが、一般的にはエステ
ルのアミノリシスによるものである(特開昭63−13
9949、特開平6−211852、J.Med.Ch
em.,37,2445(1984)など)。しかし、
アミンがモルホリンやアニリンのように求核性が低下し
た二級アミンや芳香族アミンの場合、高温、長時間の反
応条件が必要であり、工業的な製造方法には適さないも
のであった。Although several methods for synthesizing nitrogen-containing heteroaromatic amides have been known in the past, they are generally based on aminolysis of esters (JP-A-63-13).
9949, JP-A-6-212852, J. Med. Ch
em. , 37, 2445 (1984)). But,
When the amine is a secondary amine or aromatic amine having a reduced nucleophilicity such as morpholine or aniline, the reaction conditions of high temperature and long time are required, which is not suitable for the industrial production method.
【0004】エステルのアミノリシスによらない含窒素
ヘテロ芳香族アミド類の合成方法もいくつか知られてい
る。例えば、カルボキシ体とスルホン酸塩化物誘導体を
反応させ、混合酸無水物を経てアミド化する方法などで
ある。しかし多段階の工程を余分に必要とするため、コ
ストアップにつながるという欠点を有するものである。Several methods for synthesizing nitrogen-containing heteroaromatic amides that do not rely on ester aminolysis are also known. For example, a method in which a carboxy derivative is reacted with a sulfonic acid chloride derivative, and amidation is performed via a mixed acid anhydride, etc. However, this method has the drawback of increasing costs because it requires additional multi-step processes.
【0005】エステルのアミノリシスによるアミド化反
応にルイス酸を用いる方法は、ルイス酸とアミン類が反
応し、アミン類が消費されたりルイス酸性が低下したり
するために一般にはあまり用いられる事はない。しか
し、少数ではあるが次の例が知られている。 R.D. Gless, Jr., Synth. Comm., 16, 633 (1986) 2−クロロプロピオン酸エステルのアミノリシス F. Porta, M. Pizzotti, C. Crotti and S. Cenini,
Gazz. Chim. Ital.,118, 475 (1988) 酢酸またはプロピオン酸エチルの一級アミンによるアミ
ノリシス J.I. Levin, E. Turos and S.M. Weinreb, Synth. Co
mm., 12, 989 (1982) アルキルアルミニウムを用いるアミノリシスThe method of using a Lewis acid in the amidation reaction by aminolysis of an ester is not generally used because the Lewis acid and amines react with each other and the amines are consumed or the Lewis acidity decreases. . However, the following examples are known, albeit in small numbers. RD Gless, Jr., Synth. Comm., 16, 633 (1986) Aminolysis of 2-chloropropionate F. Porta, M. Pizzotti, C. Crotti and S. Cenini,
Gazz. Chim. Ital., 118, 475 (1988) Aminolysis with a primary amine of acetic acid or ethyl propionate JI Levin, E. Turos and SM Weinreb, Synth. Co
mm., 12, 989 (1982) Aminolysis using alkylaluminum.
【0006】しかし、とでは、基質がごく一部の脂
肪族エステルとアミン類に限られるうえでは例えばア
ニリンのような求核性に乏しい芳香族アミンとは反応し
がたく、また、は種々のエステル類に応用されている
ものの、試薬として用いられるトリメチルアルミニウム
が発火性禁水性化合物であり、工業的製造方法としては
問題のある方法であった。However, in the case of and, since the substrates are limited to a small part of aliphatic esters and amines, it is difficult to react with aromatic amines having poor nucleophilicity such as aniline, and Although applied to esters, trimethylaluminum used as a reagent is a flammable water-prohibiting compound, which is a problematic industrial production method.
【0007】[0007]
【発明が解決しようとする課題】従って本発明の目的
は、有用な含窒素ヘテロ芳香族アミド類を高収率で合成
する工業的に有効な製造方法を提供することにある。SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide an industrially effective production method for synthesizing useful nitrogen-containing heteroaromatic amides in high yield.
【0008】[0008]
【課題を解決するための手段】本発明者は、含窒素ヘテ
ロ芳香族エステルをアミノリシスすることで該含窒素ヘ
テロ芳香族アミドを合成する方法を研究した。その結
果、含窒素ヘテロ芳香族エステルのアミン類によるアミ
ノリシスが、ルイス酸を活性化剤として用いることによ
って容易に進行し、該含窒素ヘテロ芳香族アミドが製造
できることを見いだした。さらに、本発明者は、上記活
性化に用いられるルイス酸は、触媒として作用すること
を見いだした。このことは、工業的に製造する上で、反
応後の後処理や生産物の取り出し、環境保全の観点から
きわめて有意義なことである。The present inventors have studied a method for synthesizing a nitrogen-containing heteroaromatic amide by aminolyzing the nitrogen-containing heteroaromatic ester. As a result, they have found that aminolysis of nitrogen-containing heteroaromatic ester with amines easily proceeds by using Lewis acid as an activator, and the nitrogen-containing heteroaromatic amide can be produced. Furthermore, the present inventor has found that the Lewis acid used for the above activation acts as a catalyst. This is extremely significant in industrial production from the viewpoint of post-treatment after reaction, removal of product, and environmental protection.
【0009】すなわち、本発明の目的は、一般式(A)
で表される化合物をルイス酸存在下、下記一般式(B)
で表されるアミン類と反応させることを特徴とする下記
一般式(C)で表される含窒素ヘテロ芳香族アミド類の
製造方法によって達成された。That is, the object of the present invention is to formula (A)
The compound represented by the following general formula (B) in the presence of a Lewis acid
It was achieved by a method for producing a nitrogen-containing heteroaromatic amide represented by the following general formula (C), which comprises reacting with an amine represented by
【0010】[0010]
【化2】 Embedded image
【0011】(式中、Xは5または6員環ヘテロ芳香環
を形成し得る原子群を表し、R1はアルキル基を表し、
R2 およびR3 はそれぞれ、水素原子、アルキル基、ア
リール基、または複素環基を表し、互いに結合して環を
形成してもよい。)(In the formula, X represents an atomic group capable of forming a 5- or 6-membered heteroaromatic ring, R 1 represents an alkyl group,
R 2 and R 3 each represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and may combine with each other to form a ring. )
【0012】次に一般式(A)について詳細に説明す
る。Xは炭素原子、窒素原子、酸素原子、または硫黄原
子から構成される5または6員環ヘテロ芳香環を形成し
得る原子団で、これらの原子団は、炭素原子、酸素原
子、窒素原子、または硫黄原子で連結される有機置換基
や水酸基、ハロゲン原子、スルホン酸基などの置換基を
有していてもよい。これらの有機置換基は、例えば、ア
ルキル基、アリール基、複素環基、シアノ基、アシル
基、カルボキシル基、アリールオキシ基、アルコキシ
基、複素環オキシ基、アミノ基、スルファモイルアミノ
基、スルホンアミド基、アルキルチオ基、アリールチオ
基、複素環チオ基、スルファモイル基、スルホニル基、
スルフィニル基である。Next, the general formula (A) will be described in detail. X is an atomic group capable of forming a 5- or 6-membered heteroaromatic ring composed of a carbon atom, a nitrogen atom, an oxygen atom, or a sulfur atom, and these atomic groups are a carbon atom, an oxygen atom, a nitrogen atom, or It may have an organic substituent linked by a sulfur atom or a substituent such as a hydroxyl group, a halogen atom or a sulfonic acid group. These organic substituents include, for example, alkyl groups, aryl groups, heterocyclic groups, cyano groups, acyl groups, carboxyl groups, aryloxy groups, alkoxy groups, heterocyclic oxy groups, amino groups, sulfamoylamino groups, sulfones. Amide group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfonyl group,
It is a sulfinyl group.
【0013】Xで形成される5または6員環ヘテロ芳香
環はその置換基同士が結合してさらに縮環していてもよ
い Xで形成される5または6員環ヘテロ芳香環を具体的に
説明する。Xで形成される5または6員環ヘテロ芳香環
は例えば、ピリジン、ピリミジン、ピラジン、ピリダジ
ン、トリアジン類、イミダゾール、トリアゾール類、オ
キサゾール、イソキサゾール、チアゾール、イソチアゾ
ール、オキサジアゾール、チアジアゾール、キノリン、
ベンゾピリミジン、ベンズイミダゾール、ベンズオキサ
ゾール、プリンなどである。The 5- or 6-membered heteroaromatic ring formed by X may have its substituents bonded to each other to be further condensed. explain. The 5- or 6-membered heteroaromatic ring formed by X is, for example, pyridine, pyrimidine, pyrazine, pyridazine, triazines, imidazole, triazoles, oxazole, isoxazole, thiazole, isothiazole, oxadiazole, thiadiazole, quinoline,
Examples include benzopyrimidine, benzimidazole, benzoxazole and purine.
【0014】Xで形成される5または6員環ヘテロ芳香
環は炭素原子と窒素原子のみから形成される5または6
員環ヘテロ芳香環、または炭素原子と窒素原子と硫黄原
子のみから形成される5員環ヘテロ芳香環、またはベン
ズオキサゾールが好ましく、ピリジン、ピリミジン、ピ
ラジン、ピラゾール、イミダゾール、キノリン、チアゾ
ール、イソチアゾール、1,3,4−チアジアゾールが
さらに好ましく、ピリジン、イミダゾールが最も好まし
い。The 5- or 6-membered heteroaromatic ring formed by X is a 5- or 6-membered heteroaromatic ring formed by only carbon and nitrogen atoms.
A membered heteroaromatic ring, or a 5-membered heteroaromatic ring formed only from a carbon atom, a nitrogen atom and a sulfur atom, or benzoxazole is preferable, and pyridine, pyrimidine, pyrazine, pyrazole, imidazole, quinoline, thiazole, isothiazole, 1,3,4-thiadiazole is more preferable, and pyridine and imidazole are the most preferable.
【0015】R1はアルキル基を表すが、置換されてい
てもよく、詳しくは、炭素数1から12の直鎖または分
岐鎖のアルキル基であり、具体的には、メチル、エチ
ル、プロピル、イソプロピル、n−ブチル、s−ブチ
ル、1−(2−エチルヘキシル)、デシル、ドデシル、
シクロペンチル、シクロヘキシル基などである。R 1 represents an alkyl group, but it may be substituted, and more specifically, it is a linear or branched alkyl group having 1 to 12 carbon atoms, specifically, methyl, ethyl, propyl, Isopropyl, n-butyl, s-butyl, 1- (2-ethylhexyl), decyl, dodecyl,
Examples include cyclopentyl and cyclohexyl groups.
【0016】R1は好ましくは、炭素数1から6のアル
キル基であり、さらに好ましくは、炭素数1から4の直
鎖アルキル基であり、特に好ましいのはメチル基、また
はエチル基である。R 1 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a linear alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group.
【0017】次に一般式(A)で表される5または6員
環ヘテロ環芳香族エステル類の具体例を示すが、もちろ
ん、これらに限定されることはない。Next, specific examples of the 5- or 6-membered heterocyclic aromatic ester represented by the general formula (A) are shown, but of course, the present invention is not limited thereto.
【0018】[0018]
【化3】 Embedded image
【0019】次に一般式(B)について詳細に説明す
る。本発明で用いられる一般式(B)で表されるアミン
類は、一般式(C)で表される5または6員環含窒素ヘ
テロ芳香環アミド類のR2,R3で表される基を有するア
ンモニア、または、一級もしくは二級のアミン類であ
る。Next, the general formula (B) will be described in detail. The amines represented by the general formula (B) used in the present invention are the groups represented by R 2 and R 3 of the 5- or 6-membered nitrogen-containing heteroaromatic amides represented by the general formula (C). Is ammonia or a primary or secondary amine.
【0020】R2、R3について詳しく述べる。R2、R3
は水素原子、アルキル基、アリール基、または複素環基
を表すが、それらはいずれも置換されていてもよく、詳
しく述べるとアルキル基は炭素数1から12の直鎖また
は分岐鎖のアルキル基を表し、R2とR3のアルキル基が
互いに連結して環を形成していてもよい。アリール基は
炭素数6から10のフェニル基、またはナフチル基を表
し、複素環基は5から7員環の飽和または不飽和の複素
環基を表す。これらの基は、炭素原子、酸素原子、窒素
原子、または硫黄原子で連結される有機置換基や水酸
基、ハロゲン原子、スルホン酸基などの置換基を有して
いてもよい。これらの有機置換基は、例えば、アルキル
基、アリール基、複素環基、シアノ基、アシル基、カル
ボキシル基、アリールオキシ基、アルコキシ基、複素環
オキシ基、アミノ基、スルファモイルアミノ基、スルホ
ンアミド基、アルキルチオ基、アリールチオ基、複素環
チオ基、スルファモイル基、スルホニル基、スルフィニ
ル基である。R 2 and R 3 will be described in detail. R 2 , R 3
Represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and any of them may be substituted. More specifically, the alkyl group is a straight chain or branched chain alkyl group having 1 to 12 carbon atoms. The alkyl groups of R 2 and R 3 may be linked to each other to form a ring. The aryl group represents a phenyl group having 6 to 10 carbon atoms or a naphthyl group, and the heterocyclic group represents a saturated or unsaturated heterocyclic group having a 5- to 7-membered ring. These groups may have a substituent such as an organic substituent linked by a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom, a hydroxyl group, a halogen atom, and a sulfonic acid group. These organic substituents include, for example, alkyl groups, aryl groups, heterocyclic groups, cyano groups, acyl groups, carboxyl groups, aryloxy groups, alkoxy groups, heterocyclic oxy groups, amino groups, sulfamoylamino groups, sulfones. An amide group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, a sulfonyl group, and a sulfinyl group.
【0021】R2,R3で表される置換基を具体的にさら
に詳しく説明する。R2,R3で表されるアルキル基は、
例えば、メチル、エチル、プロピル、イソプロピル、n
−ブチル、s−ブチル、シクロペンチル、シクロヘキシ
ル、メトキシエチル、2−ヒドロキシエチル、カルボキ
シメチル、フェノキシエチル、メタンスルホニルエチ
ル、(3−ペンタデシルフェノキシ)プロピル、3−
(2,4−ジアミルフェノキシ)プロピル、2−スルホ
エチル、4−スルホブチル、2’−スルホベンジル基な
どである。The substituents represented by R 2 and R 3 will be specifically described in more detail. The alkyl group represented by R 2 and R 3 is
For example, methyl, ethyl, propyl, isopropyl, n
-Butyl, s-butyl, cyclopentyl, cyclohexyl, methoxyethyl, 2-hydroxyethyl, carboxymethyl, phenoxyethyl, methanesulfonylethyl, (3-pentadecylphenoxy) propyl, 3-
(2,4-diamylphenoxy) propyl, 2-sulfoethyl, 4-sulfobutyl, 2'-sulfobenzyl group and the like.
【0022】R2,R3で表されるアルキル基が互いに連
結して形成する環は、5、または6員環で、さらに詳し
く説明すれば、例えば、ピロリジン、ピペリジン、4−
メチルピペラジン、4−エチルピペラジン、モルホリン
などである。R2、R3で表されるアリール基は、例え
ば、フェニル、4−トリル、4−メトキシフェニル、
2,4−キシリル、2−クロロフェニル、4−カルボキ
シフェニル、4−スルホフェニル、2,5−ジスルホフ
ェニル、1−ナフチル、1−(3,5−ジスルホナフチ
ル)基などである。The ring formed by connecting the alkyl groups represented by R 2 and R 3 to each other is a 5- or 6-membered ring, and more specifically, for example, pyrrolidine, piperidine, 4-
Examples include methylpiperazine, 4-ethylpiperazine, morpholine and the like. The aryl group represented by R 2 and R 3 includes, for example, phenyl, 4-tolyl, 4-methoxyphenyl,
2,4-xylyl, 2-chlorophenyl, 4-carboxyphenyl, 4-sulfophenyl, 2,5-disulfophenyl, 1-naphthyl, 1- (3,5-disulfonaphthyl) groups and the like.
【0023】R2、R3で表される複素環基は、例えば、
2−テトラヒドロフラニル、2−テトラヒドロチエニ
ル、1−ピペリジノ、2−ピリジル、1−ピラゾリル、
2−チエニル、2−ピリミジニル、2−ベンゾチアゾリ
ル、3−(1,1−ジオキソテトラヒドロチエニル)基
などである。The heterocyclic group represented by R 2 and R 3 is, for example,
2-tetrahydrofuranyl, 2-tetrahydrothienyl, 1-piperidino, 2-pyridyl, 1-pyrazolyl,
2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl, 3- (1,1-dioxotetrahydrothienyl) group and the like.
【0024】R2、R3のアルキル基は、好ましくは、炭
素数1から7のアルキル基であり、さらに好ましくは、
カルボキシル基、スルホ基、アルコキシ基、または水酸
基で置換された炭素数1から7のアルキル基か無置換の
メチル基である。R2、R3で表されるアルキル基が互い
に連結して形成する環は、好ましくはピロリジン、ピペ
リジン、4−メチルピペラジン、モルホリンであり、さ
らに好ましくは、モルホリンである。The alkyl group of R 2 and R 3 is preferably an alkyl group having 1 to 7 carbon atoms, and more preferably
It is a C1-C7 alkyl group substituted with a carboxyl group, a sulfo group, an alkoxy group, or a hydroxyl group, or an unsubstituted methyl group. The ring formed by connecting the alkyl groups represented by R 2 and R 3 to each other is preferably pyrrolidine, piperidine, 4-methylpiperazine or morpholine, and more preferably morpholine.
【0025】R2、R3で表されるアリール基は好ましく
は、フェニル基であり、さらに好ましくは、カルボキシ
ル基、またはスルホ基で置換されたフェニル基である。The aryl group represented by R 2 and R 3 is preferably a phenyl group, and more preferably a phenyl group substituted with a carboxyl group or a sulfo group.
【0026】R2、R3は、水素原子、メチル基、カルボ
キシエチル基、スルホ基で置換された炭素数2から4の
直鎖アルキル基、4−スルホフェニル基、2,5−ジス
ルホフェニル基、または、R2、R3が互いに連結して形
成するモルホリノ基が特に好ましく、モルホリノ基が最
も好ましい。R 2 and R 3 are each a hydrogen atom, a methyl group, a carboxyethyl group, a linear alkyl group having 2 to 4 carbon atoms substituted with a sulfo group, a 4-sulfophenyl group, or a 2,5-disulfophenyl group. A group or a morpholino group formed by connecting R 2 and R 3 to each other is particularly preferable, and a morpholino group is most preferable.
【0027】次に本発明で用いられるアミン類について
説明する。本発明で用いられるアミン類は、アンモニ
ア、置換又は無置換の、一級又は二級の、アルキル、ア
リール、又は複素環基を有するアミンであり、これらの
アルキル、アリール、又は複素環基は、化合物(B)の
R2、R3で表わされる置換基である。Next, the amines used in the present invention will be described. The amines used in the present invention are ammonia, amines having a substituted or unsubstituted primary or secondary alkyl, aryl, or heterocyclic group, and these alkyl, aryl, or heterocyclic groups are compounds. It is a substituent represented by R 2 and R 3 of (B).
【0028】本発明で用いられるアミン類を具体例で更
に詳しく説明すれば、例えば、アンモニア、メチルアミ
ン、エチルアミン、プロピルアミン、イソプロピルアミ
ン、n−ブチルアミン、s−ブチルアミン、シクロペン
チルアミン、シクロヘキシルアミン、メトキシエチルア
ミン、2−ヒドロキシエチルアミン、グリシン、フェノ
キシエチルアミン、メタンスルホニルエチルアミン、
(3−ペンタデシルフェノキシ)プロピルアミン、3−
(2,4−ジアミルフェノキシ)プロピルアミン、2−
スルホエチルアミン、4−スルホブチルアミン、2’−
スルホベンジルアミン、ジメチルアミン、ジエチルアミ
ン、ジプロピルアミン、ジn−ブチルアミン、ジ(メト
キシエチル)アミン、ジ(2−ヒドロキシエチル)アミ
ン、グリシン、ピロリジン、ピペリジン、4−メチルピ
ペラジン、4−エチルピペラジン、モルホリンなどのア
ルキルアミン、アニリン、4−トルイジン、4−アニシ
ジン、2,4−ジメチルアニリン、2−クロロアニリ
ン、4−ニトロアニリン、4−アミノ安息香酸、4−ア
ミノベンゼンスルホン酸、2−アミノベンゼン−1,4
−ジスルホン酸、1−ナフチルアミン、1−アミノ−ナ
フタレン−3,5−ジスルホン酸などのアリールアミ
ン、2−テトラヒドロフラニルアミン、2−テトラヒド
ロチエニルアミン、2−ピリジルアミン、ピラゾール、
2−チエニルアミン、2−ピリミジニルアミン、2−ベ
ンゾチアゾリルアミン、3−(1,1−ジオキソテトラ
ヒドロチエニル)アミンなどの複素環アミンである。The amines used in the present invention will be described in more detail with reference to specific examples. For example, ammonia, methylamine, ethylamine, propylamine, isopropylamine, n-butylamine, s-butylamine, cyclopentylamine, cyclohexylamine, methoxy. Ethylamine, 2-hydroxyethylamine, glycine, phenoxyethylamine, methanesulfonylethylamine,
(3-pentadecylphenoxy) propylamine, 3-
(2,4-Diamylphenoxy) propylamine, 2-
Sulfoethylamine, 4-sulfobutylamine, 2'-
Sulfobenzylamine, dimethylamine, diethylamine, dipropylamine, di-n-butylamine, di (methoxyethyl) amine, di (2-hydroxyethyl) amine, glycine, pyrrolidine, piperidine, 4-methylpiperazine, 4-ethylpiperazine, Alkylamines such as morpholine, aniline, 4-toluidine, 4-anisidine, 2,4-dimethylaniline, 2-chloroaniline, 4-nitroaniline, 4-aminobenzoic acid, 4-aminobenzenesulfonic acid, 2-aminobenzene -1,4
Arylamines such as disulfonic acid, 1-naphthylamine, 1-amino-naphthalene-3,5-disulfonic acid, 2-tetrahydrofuranylamine, 2-tetrahydrothienylamine, 2-pyridylamine, pyrazole,
Heterocyclic amines such as 2-thienylamine, 2-pyrimidinylamine, 2-benzothiazolylamine, and 3- (1,1-dioxotetrahydrothienyl) amine.
【0029】次に本発明で用いられるルイス酸について
説明する。電子受容体として働くルイス酸の中心元素
は、ホウ素、アルミニウム、珪素、スズなどの典型元
素、または、チタン、鉄、ニッケル、銅、亜鉛などの第
四周期の遷移金属元素である。Next, the Lewis acid used in the present invention will be described. The central element of the Lewis acid that acts as an electron acceptor is a typical element such as boron, aluminum, silicon, tin or the like, or a transition metal element of the fourth period such as titanium, iron, nickel, copper and zinc.
【0030】ルイス酸の配位子は、塩化物イオン、フッ
化物イオンなどのハロゲン化物イオン、エトキシド、プ
ロポキシド、ブトキシドなどのアルコキシイオンであ
り、ルイス酸の中心元素に対し、これらの配位子は、一
種類でもよいが、二種類以上を組み合わせてもよい。ル
イス酸が二種類以上の配位子を持つ場合、そのようなル
イス酸は予め調製してもよいが、よく知られた方法で、
in−situで配位子交換反応によって合成してもよ
い(富士薫、野出学、有機合成化学、42,194(1
984))。The Lewis acid ligand is a halide ion such as chloride ion and fluoride ion, and an alkoxy ion such as ethoxide, propoxide and butoxide, and these ligands are used for the central element of the Lewis acid. May be one kind, or may be a combination of two or more kinds. When the Lewis acid has two or more kinds of ligands, such Lewis acid may be prepared in advance, but by a well-known method,
It may be synthesized by in-situ ligand exchange reaction (Fuji Kaoru, Node Manabu, Synthetic Organic Chemistry, 42, 194 (1
984)).
【0031】本発明で用いられるルイス酸は、具体的に
は、三フッ化ホウ素や三塩化ホウ素、三臭化ホウ素など
の三ハロゲン化ホウ素、塩化アルミニウムや臭化アルミ
ニウムなどの三ハロゲン化アルミニウム、四塩化スズな
どの四ハロゲン化スズ、二塩化スズなどの二ハロゲン化
スズ、四塩化チタンなどの四ハロゲン化チタン、三塩化
チタンなどの三ハロゲン化チタン、チタンイソプロポキ
シドなどのチタンアルコキシド、二塩化鉄などの二ハロ
ゲン化鉄、三塩化鉄などの三ハロゲン化鉄、二塩化ニッ
ケルなどの二ハロゲン化ニッケル、塩化亜鉛や臭化亜鉛
などのハロゲン化亜鉛などである。The Lewis acid used in the present invention is specifically boron trihalide such as boron trifluoride, boron trichloride or boron tribromide, aluminum trihalide such as aluminum chloride or aluminum bromide, Tin tetrahalides such as tin tetrachloride, tin dihalides such as tin dichloride, titanium tetrahalides such as titanium tetrachloride, titanium trihalides such as titanium trichloride, titanium alkoxides such as titanium isopropoxide, Examples include iron dihalides such as iron chloride, iron trihalides such as iron trichloride, nickel dihalides such as nickel dichloride, and zinc halides such as zinc chloride and zinc bromide.
【0032】ルイス酸としてより好ましくは、三ハロゲ
ン化ホウ素、三ハロゲン化アルミニウム、四ハロゲン化
スズ、四ハロゲン化チタン、チタンアルコキシド、三ハ
ロゲン化鉄、ハロゲン化亜鉛であり、さらに好ましく
は、三塩化鉄、塩化アルミニウム、チタンイソプロポキ
シド、四塩化チタン、塩化亜鉛であり、最も好ましいの
は塩化アルミニウムである。The Lewis acid is more preferably boron trihalide, aluminum trihalide, tin tetrahalide, titanium tetrahalide, titanium alkoxide, iron trihalide or zinc halide, and more preferably trichloride. Iron, aluminum chloride, titanium isopropoxide, titanium tetrachloride, zinc chloride, most preferably aluminum chloride.
【0033】本発明で用いられるルイス酸は任意の量を
用いることが出来るが、その範囲はアミン類に対し、
0.0005当量から、1当量である。更に、触媒とし
て用いることが好ましく、その場合、0.0005当量
から0.35当量が好ましく、0.005等量から0.
2等量が特に好ましい。本発明の反応では、ルイス酸の
反応性を調節する目的で、非求核性のアミンを加えても
よい。そのようなアミンとはトリエチルアミンなどの三
級アミン類、ジエチルアニリンなどの三級アニリン類、
ピリジン、コリジンなどのピリジン類、DBUなどであ
る。The Lewis acid used in the present invention can be used in any amount, but the range is based on amines.
From 0.0005 equivalent to 1 equivalent. Further, it is preferably used as a catalyst, and in this case, 0.0005 equivalent to 0.35 equivalent is preferable, and 0.005 equivalent to 0.
Two equivalents are particularly preferred. In the reaction of the present invention, a non-nucleophilic amine may be added for the purpose of adjusting the reactivity of the Lewis acid. Such amines include tertiary amines such as triethylamine, tertiary anilines such as diethylaniline,
Pyridines such as pyridine and collidine, DBU and the like.
【0034】非求核性アミンの中で、ピリジン類が好ま
しく、2−メチルピリジン、2,6−ルチジン、γ−コ
リジンがより好ましく、2,6−ルチジン、γ−コリジ
ンが最も好ましい。Among the non-nucleophilic amines, pyridines are preferable, 2-methylpyridine, 2,6-lutidine and γ-collidine are more preferable, and 2,6-lutidine and γ-collidine are most preferable.
【0035】本発明の反応では種々の溶媒を用いること
が出来る。例えば、トルエン、キシレンなどの芳香族炭
化水素溶媒、クロロホルム、クロルベンゼン、o−ジク
ロルベンゼンなどのハロゲン化炭化水素溶媒、テトラヒ
ドロフラン、ジメトキシエタンなどのエーテル溶媒、ジ
メチルスルホキシド、スルホランなどである。また、ア
ミン類を過剰に用い、それ自身を溶媒としてもよい。Various solvents can be used in the reaction of the present invention. Examples thereof include aromatic hydrocarbon solvents such as toluene and xylene, halogenated hydrocarbon solvents such as chloroform, chlorobenzene and o-dichlorobenzene, ether solvents such as tetrahydrofuran and dimethoxyethane, dimethyl sulfoxide and sulfolane. Further, amines may be used in excess and used as a solvent itself.
【0036】溶媒のうち、好ましくは、トルエン、キシ
レン、クメン、クロルベンゼン、o−ジクロルベンゼ
ン、ジメトキシエタン、スルホラン、過剰のアミンそれ
自身であり、さらに好ましくは、トルエン、キシレン、
クロルベンゼン、または、過剰のアミンそれ自身であ
り、過剰のアミンを用いるのが最も好ましい。Of the solvents, preferred are toluene, xylene, cumene, chlorobenzene, o-dichlorobenzene, dimethoxyethane, sulfolane, and excess amine itself, and more preferred are toluene, xylene, and
Chlorobenzene or excess amine itself, with the excess amine being most preferred.
【0037】反応温度は、0℃から200℃であり、な
かでも20℃から150℃が好ましく、モルホリンと反
応させる場合、80℃から130℃がさらに好ましい。
反応は、生成物が酸化されることを防ぐために窒素雰囲
気下で行うことが好ましい。次に本発明で合成されるヘ
テロ芳香族アミド類の具体例を示すが、もちろん、これ
らに限定されるものではない。The reaction temperature is 0 ° C to 200 ° C, preferably 20 ° C to 150 ° C, and more preferably 80 ° C to 130 ° C in the case of reacting with morpholine.
The reaction is preferably carried out under a nitrogen atmosphere to prevent the product from being oxidized. Next, specific examples of the heteroaromatic amides synthesized in the present invention are shown, but of course, the present invention is not limited to these.
【0038】[0038]
【化4】 Embedded image
【0039】[0039]
【実施例】以下実施例によって本発明を更に詳細に説明
する。 実施例1〔ピコリン酸アニリドC−1の合成〕 ピコリン酸エチル3.02g(20mmol)とアニリ
ン14.6g(160mmol)と塩化アルミニウム
0.27g(2mmol)を窒素雰囲気下、110℃で
3時間20分撹拌した。冷却後、酢酸エチル100ml
で希釈し、2規定塩酸で洗い、さらに、重曹水と食塩水
で洗った。酢酸エチルをエバポレートして目的とするピ
コリン酸アニリドを得た。3.74g(94%)、融点
(イソプロパノール)76−77℃。The present invention will be described in more detail with reference to the following examples. Example 1 [Synthesis of anilide picolinate C-1] 3.02 g (20 mmol) of ethyl picolinate, 14.6 g (160 mmol) of aniline, and 0.27 g (2 mmol) of aluminum chloride were placed in a nitrogen atmosphere at 110 ° C for 3 hours 20. Stir for minutes. After cooling, 100 ml of ethyl acetate
The mixture was diluted with, washed with 2N hydrochloric acid, and further washed with aqueous sodium hydrogen carbonate and brine. Ethyl acetate was evaporated to obtain the desired anilide picolinate. 3.74 g (94%), melting point (isopropanol) 76-77 ° C.
【0040】比較例1 塩化アルミニウムを加えない以外は実施例と全く同一の
条件下反応を行った。目的とするピコリン酸アニリドの
生成は全く認められなかった。Comparative Example 1 The reaction was carried out under the same conditions as in Example except that aluminum chloride was not added. The desired formation of anilide picolinate was not observed at all.
【0041】実施例2〔ピコリン酸アニリドC−1の合
成〕 ピコリン酸エチル0.76g(5mmol)とアニリン
0.51g(5.5mmol)と塩化アルミニウム67
mg(0.5mmol)と2,6−ルチジン0.27g
(2.5mmol)とクロルベンゼン9mlを窒素雰囲
気下、100℃で7時間撹拌した。冷却後、酢酸エチル
15mlで希釈し、0.5規定塩酸で洗い、さらに、重
曹水と食塩水で洗った。酢酸エチルをエバポレートして
目的とするピコリン酸アニリドを得た。0.93g(9
3%)。Example 2 [Synthesis of anilide picolinic acid C-1] 0.76 g (5 mmol) of ethyl picolinate, 0.51 g (5.5 mmol) of aniline and aluminum chloride 67
mg (0.5 mmol) and 0.27 g of 2,6-lutidine
(2.5 mmol) and 9 ml of chlorobenzene were stirred at 100 ° C. for 7 hours under a nitrogen atmosphere. After cooling, it was diluted with 15 ml of ethyl acetate, washed with 0.5N hydrochloric acid, and further washed with aqueous sodium hydrogen carbonate and brine. Ethyl acetate was evaporated to obtain the desired anilide picolinate. 0.93 g (9
3%).
【0042】実施例3〔ピコリン酸4−ニトロアニリド
C−2の合成〕 ピコリン酸エチル0.76g(5mmol)とp−ニト
ロアニリン0.76g(5.5mmol)と塩化アルミ
ニウム67mg(0.5mmol)と2,6−ルチジン
0.27g(2.5mmol)とクロルベンゼン9ml
を窒素雰囲気下、120℃で8時間撹拌した。冷却後、
酢酸エチル800mlで希釈し、2規定塩酸で洗い、さ
らに、重曹水と食塩水で洗った。酢酸エチルをエバポレ
ートして得られた粘稠なオイル0.98gにエタノール
5mlを加えると結晶化し、目的とするピコリン酸4−
ニトロアニリドが得られた。0.71g(58%)。融
点236−237℃。Example 3 [Synthesis of 4-nitroanilide C-2 picolinate] 0.76 g (5 mmol) of ethyl picolinate, 0.76 g (5.5 mmol) of p-nitroaniline and 67 mg (0.5 mmol) of aluminum chloride. And 2,6-lutidine 0.27 g (2.5 mmol) and chlorobenzene 9 ml
Was stirred at 120 ° C. for 8 hours under a nitrogen atmosphere. After cooling,
The mixture was diluted with 800 ml of ethyl acetate, washed with 2N hydrochloric acid, and further washed with aqueous sodium hydrogen carbonate and brine. To 0.98 g of a viscous oil obtained by evaporating ethyl acetate, 5 ml of ethanol was added to crystallize the desired picolinic acid 4-
Nitroanilide was obtained. 0.71 g (58%). Melting point 236-237 [deg.] C.
【0043】実施例4〔4−メチル−5−イミダゾール
カルボキソアニリドC−7の合成〕 4−メチル−5−イミダゾールカルボン酸エチル3.0
8g(20mmol)とアニリン14.6g(160m
mol)と塩化アルミニウム0.27g(2mmol)
を窒素雰囲気下、110℃で1.5時間撹拌した。冷却
後、エタノールで希釈し、析出物を濾取して目的とする
アニリドを得た。4.1g(定量的)、融点258−2
59℃。Example 4 [Synthesis of 4-methyl-5-imidazolecarboxoanilide C-7] Ethyl 4-methyl-5-imidazolecarboxylate 3.0
8 g (20 mmol) and aniline 14.6 g (160 m
mol) and aluminum chloride 0.27 g (2 mmol)
Was stirred at 110 ° C. for 1.5 hours under a nitrogen atmosphere. After cooling, it was diluted with ethanol and the precipitate was collected by filtration to obtain the desired anilide. 4.1 g (quantitative), melting point 258-2
59 ° C.
【0044】[0044]
【発明の効果】本発明の、含窒素ヘテロ芳香族エステル
化合物をルイス酸存在下アミン類と反応させることを特
徴とする含窒素ヘテロ芳香族アミド類の製造方法は反応
温度を低く設定でき、また、反応時間も短縮することが
出来、含窒素ヘテロ芳香族アミド類の合成に広く用いる
ことが出来る。The method for producing nitrogen-containing heteroaromatic amides of the present invention, which comprises reacting a nitrogen-containing heteroaromatic ester compound with amines in the presence of a Lewis acid, can set a low reaction temperature, and Also, the reaction time can be shortened and it can be widely used for the synthesis of nitrogen-containing heteroaromatic amides.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 FI 技術表示箇所 C07D 277/68 C07D 239/55 285/12 285/12 B ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location C07D 277/68 C07D 239/55 285/12 285/12 B
Claims (2)
ロ芳香族エステル化合物をルイス酸存在下、下記一般式
(B)で表されるアミン類と反応させることを特徴とす
る下記一般式(C)で表される含窒素ヘテロ芳香族アミ
ド類の製造方法。 【化1】 (式中、Xは5または6員環ヘテロ芳香環を形成し得る
原子群を表し、R1はアルキル基を表し、R2 およびR
3 はそれぞれ、水素原子、アルキル基、アリール基、ま
たは複素環基を表し、互いに結合して環を形成してもよ
い。)1. A nitrogen-containing heteroaromatic ester compound represented by the following general formula (A) is reacted with an amine represented by the following general formula (B) in the presence of a Lewis acid. A method for producing a nitrogen-containing heteroaromatic amide represented by the formula (C). Embedded image (In the formula, X represents an atomic group capable of forming a 5- or 6-membered heteroaromatic ring, R 1 represents an alkyl group, R 2 and R
Each 3 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, which may be bonded to each other to form a ring. )
05当量から0.35当量用いることを特徴とする請求
項1記載のヘテロ芳香族アミド類の製造方法。2. The Lewis acid relative to amines is 0.00
The method for producing a heteroaromatic amide according to claim 1, which is used in an amount of from 05 equivalent to 0.35 equivalent.
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Family
ID=18005230
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