METHOD FOR PRODUCING 2-(3,6-DIHALOPYRIDIN-2-YL)-3H-IMIDAZOL[4,5-C]PYRIDINE DERIVATIVES AND RELATED COMPOUNDS BY REACTION OF THE 3H-IMIDAZOL[4,5-C]PYRIDINE DERIVATIVE WITH AN ORGANOMETALLIC ZINC-AMINE BASEThe invention relates to a method for producing halogenated pyridine derivatives of formula (II) from compounds of the Q-H structure via intermediate steps of formula (IIIa) or (IIIb) in which Q is astructural element, where the character # indicates the binding to the radical of the molecule and A, Q1, Q2, Q3, Q4, Q5 and Q6 have the designations provided in the description, W is halogen, and Y is halogen, CO2R1 or NO2, where R1 is (C1-C6) alkyl or (C1-C6) haloalkyl, and R2 is halogen or -O-pivaloyl.The method for preparing the compound of formula (ii)whereinq is structural elementwherein symbol # indicates the connecting key with the rest part of molecule, andq1for n or cr6,q2for n or cr6,q3for n or c,q4for o, s, n or nr7,q5for n or c,q6for n or ch,r6for hydrogen, (c1-c4) alkyl, (c1-c4) halogenated alkyl, (c1-c4) cyanoalkyl, (c1-c4) hydroxyalkyl, (c1-c4) alcoxyl base-(c1-c4) alkyl, (c1-c4) halogenated alkoxy-(c1-c4) alkyl, (c2-c4) alkenyl, (c2-c4) alkenyloxy group-(c1-c4) alkane base, (c2-c4) haloalkenyloxy-(c1-c4) alkyl, (c2-c4) halogenated alkenyl, (c2-c4) cyano alkenyl, (c2-c4) alkynyl, (c2- c4) alkynyloxy group-(c1-c4) alkyl, (c2-c4) halo alkynyl, (c3-c6) naphthenic base, (c3-c6) naphthenic base-(c3-c6) naphthenic base, (c1-c4) alkyl-(c3-c6) naphthenic base, halogenated (c3-c6) naphthenic base, (c1-c4) alkylthio group-(c1-c4) alkyl, (c1-c4) alkyl sulfinyl-(c1-c4) alkyl, (c1-c4) alkyl sulphonyl-(c1-c4) alkyl or (c1-c4) alkyl-carbonyl-(c1-c4) alkyl,r7for (c1-c4) alkyl, (c1-c4) halogenated alkyl, (c1-c4) cyanoalkyl, (c1-c4) hydroxyalkyl, (c1-c4) alkoxy- (c1-c4) alkyl, (c1-c4) halogenated alkoxy-(c1-c4) alkyl, (c2-c4) alkenyl, (c2-c4) alkenyloxy group-(c1-c4) alkyl, (c2-c4) haloalkenyloxy-(c1-c4) alkyl, (c2-c4) halogenated alkenyl, (c2-c4) cyano alkenyl, (c2-c4) alkynyl, (c2-c4) alkynyloxy group-(c1-c4) alkyl, (c2-c4) halo alkynyl, (c3-c6) naphthenic base, (c3-c6) naphthenic base-(c3-c6) naphthenic base, (c1- c4) alkyl-(c3-c6) naphthenic base, halogenated (c3-c6) naphthenic base, (c1-c4) alkylthio group-(c1-c4) alkyl, (c1-c4) alkyl asia sulphur acyl group-(c1-c4) alkyl, (c1-c4) alkyl sulphonyl-(c1-c4) alkyl or (c1-c4) alkyl-carbonyl-(c1-c4) alkyl, anda is hydrogen, cyano, halogen, (c1-c4) alkyl, (c1-c4) halogenated alkyl, (c2-c4) alkenyl, (c2-c4) halogenated alkenyl, (c2- c4) alkynyl, (c2-c4) halo alkynyl, (c3-c6) naphthenic base, (c3-c6) naphthenic base-(c3-c6) naphthenic base, (c1-c4) alkyl- (c3-c6) naphthenic base, (c1-c4) alkoxy, (c1-c4) halogenated alkoxy, (c1-c4) alkoximino, (c1-c4) alkylthio group, (c1-c4) halogenated alkylthio, (c1-c4) alkyl sulphinyl, (c1-c4) alkylsulfinyl, (c1-c4) alkyl sulphonyl, (c1-c4) halogenated alkyl sulfonyl, (c1-c4) alkylsulfonyloxy, (c1-c4) alkyl-carbonyl, (c1-c4) halogenated alkyl carbonyl, ammonia base carbonyl, (c1-c4) alkyl amino-carbonyl, two (c1-c4) alkyl amino-carbonyl, (c1-c4) alkyl sulfonyl-amino, (c1-c4) alkane base amino, two (c1-c4) alkyl amino, amino-sulfonyl, (c1-c4) alkyl amino sulfonyl or two (c1-c4) alkyl amino sulphur acyl group,or a is-o-cf2- o-, and and q1and its carbon atom of bonding is formed together 5 member rings, wherein q1for carbon,w is halogen, andy is halogen, co2r1or no2, wherein r1for (c1-c6)-alkyl or (c1-c6)-halogenated alkyl,it is characterized in that, in first method step a), wherein q compound q-h as defined above and structure (nr3r4)-zn- r2or (nr3r4)2the organic zinc alkali of-zn reacts, and obtains the compound of formula (iiia) or formula (iiib), whereinr2for halogen or-o- valeryl, andr3and r4it is formed together-(ch2)4-、-(ch2)5or-(ch2)2o(ch2)2group, wherein each of these groups can optionally by 1,2,3 or 4 r5group replaces, and r5selected from methyl, ethyl, n-propyl and isopropyl,q-zn-q (iiib),wherein q and r2respectively there is definition given above,and compound of the compound of the formula (iiia) or (iiib) in second method step b) with formula (i) is in catalyst in the presence of react, obtain the compound of formula (ii)wherein x is halogen, and w and y respectively have definition given above.
3H-이미다졸[4,5-c]피리딘 유도체와 유기금속 아연-아민 염기의 반응에 의한 2-(3,6-디할로피리딘-2-일)-3H-이미다졸[4,5-c]피리딘 유도체 및 관련 화합물의 제조 방법 본 발명은 화합물 Q-H로부터 출발하여 (IIIa) 또는 (IIIb)의 중간체를 거쳐 화학식 (II)의 할로겐화 피리딘 유도체를 제조하는 방법에 관한 것이다:[이미지][이미지] 상기 식에서, Q는[이미지] 의 구조 성분이고, 여기서 기호 #는 나머지 분자와의 결합을 나타내며, A, Q1, Q2, Q3, Q4, Q5 및 Q6은 명세서에 주어진 정의를 가지며, W는 할로겐이고, Y는 할로겐, CO2R1 또는 NO2이고, 여기서 R1은 (C1-C6)-알킬 또는 (C1-C6)-할로알킬이고, R2는 할로겐 또는 -O-피발로일이다.제1 방법 단계 a)에서, Q가 하기 정의되는 바와 같은 화합물 Q-H를 구조 (NR3R4)-Zn-R2 또는 (NR3R4)2-Zn의 유기 아연 염기 (여기서, R2는 할로겐 또는 -O-피발로일이고, R3 및 R4는 함께 각각 1, 2, 3 또는 4개의 R5 라디칼에 의해 임의로 치환될 수 있는 -(CH2)4-, -(CH2)5- 또는 -(CH2)2O(CH2)2- 그룹을 형성하고, R5는 메틸, 에틸, n-프로필 및 i-프로필로 구성된 그룹중에서 선택됨)와 반응시켜 화학식 (IIIa) 또는 화학식 (IIIb)의 화합물을 수득하고,제2 방법 단계 b)에서 상기 수득한 화학식 (IIIa) 또는 화학식 (IIIb)의 화합물을 촉매의 존재하에 화학식 (I)의 화합물과 반응시켜 화학식 (II)의 화합물을 수득하는 것을 특징으로 하는,화학식 (II)의 화합의 제조 방법:[이미지][이미지][이미지]상기 식에서,Q는[이미지]의 구조 성분이고,여기서 기호 #는 나머지 분자와의 결합을 나타내며,Q1은 N 또는 CR6이고,Q2는 N 또는 CR6이고,Q3는 N 또는 C이고,Q4는 O, S, N 또는 NR7이고,Q5는 N 또는 C이고,Q6은 N 또는 CH이고,R6은 수소, (C1-C4)알킬, (C1-C4)할로알킬, (C1-C4)시아노알킬, (C1-C4)하이드록시알킬, (C1-C4)알콕시-(C1-C4)알킬, (C1-C4)할로알콕시-(C1-C4)알킬, (C2-C4)알케닐, (C2-C4)알케닐옥시-(C1-C4)알킬, (C2-C4)할로알케닐옥시-(C1-C4)알킬, (C2-C4)할로알케닐, (C2-C4)시아노알케닐, (C2-C4)알키닐, (C2-C4)알키닐옥시-(C1-C4)알킬, (C2-C4)할로알키닐, (C3-C6)사이클로알킬, (C3-C6)사이클로알킬-(C3-C6)사이클로알킬, (C1-C4)알킬-(C3-C6)사이클로알킬, 할로(C3-C6)사이클로알킬, (C1-C4)알킬티오-(C1-C4)알킬, (C1-C4)알킬설피닐-(C1-C4)알킬, (C1-C4)알킬설포닐-(C1-C4)알킬 또는 (C1-C4)알킬카보닐-(C1-C4)알킬이고,R7은 (C1-C4)알킬, (C1-C4)할로알킬, (C1-C4)시아노알킬, (C1-C4)하이드록시알킬, (C1-C4)알콕시-(C1-C4)알킬, (C1-C4)할로알콕시-(C1-C4)알킬, (C2-C4)알케닐, (C2-C4)알케닐옥시-(C1-C4)알킬, (C2-C4)할로알케닐옥시-(C1-C4)알킬, (C2-C4)할로알케닐, (C2-C4)시아노알케닐, (C2-C4)알키닐, (C2-C4)알키닐옥시-(C1-C4)알킬, (C2-C4)할로알키닐, (C3-C6)사이클로알킬, (C3-C6)사이클로알킬-(C3-C6)사이클로알킬, (C1-C4)알킬-(C3-C6)사이클로알킬, 할로(C3-C6)사이클로알킬, (C1-C4)알킬티오-(C1-C4)알킬, (C1-C4)알킬설피닐-(C1-C4)알킬, (C1-C4)알킬설포닐-(C1-C4)알킬 또는 (C1-C4)알킬카보닐-(C1-C4)알킬이고,A는 수소, 시아노, 할로겐, (C1-C4)알킬, (C1-C4)할로알킬, (C2-C4)알케닐, (C2-C4)할로알케닐, (C2-C4)알키닐, (C2-C4)할로알키닐, (C3-C6)사이클로알킬, (C3-C6)사이클로알킬-(C3-C6)사이클로알킬, (C1-C4)알킬-(C3-C6)사이클로알킬, (C1-C4)알콕시, (C1-C4)할로알콕시, (C1-C4)알콕시이미노, (C1-C4)알킬티오, (C1-C4)할로알킬티오, (C1-C4)알킬설피닐, (C1-C4)할로알킬설피닐, (C1-C4)알킬설포닐, (C1-C4)할로알킬설포닐, (C1-C4)알킬설포닐옥시, (C1-C4)알킬카보닐, (C1-C4)할로알킬카보닐, 아미노카보닐, (C1-C4)알킬아미노카보닐, 디-(C1-C4)알킬아미노카보닐, (C1-C4)알킬설포닐아미노, (C1-C4)알킬아미노, 디-(C1-C4)알킬아미노, 아미노설포닐, (C1-C4)알킬아미노설포닐 또는 디-(C1-C4)알킬아미노설포닐이거나, 또는A는 -O-CF2-O-이고, Q1 및 결합된 탄소 원자와 함께 5-원 환을 형성하고 여기서 Q1은 탄소이고,W는 할로겐이고,Y는 할로겐, CO2R1 또는 NO2이고, 여기서 R1은 (C1-C6)-알킬 또는 (C1-C6)-할로알킬이다.