UNSATURATED NITROGEN-COMPOUNDS CONTAINING FLUORINE .15. THE REACTIONS OF 2,5-DICHLORO-1,1,1,6,6,6-HEXAFLUORO-3,4-DIAZAHEXA-2,4-DIENE AND ITS 2-AMINO DERIVATIVE WITH ENAMINES

Reaction of the title dichloroazine (1) with the enamines CH2(CH2)(n)CH=CNR(2)[(4), NR(2)=NEt(2),n=2; (6), NR(2)=NEt(2), n=3; (7), NR(2)=N(CH2)(2)OCH2H2, n=2] gives initially the 2-substituted enamines CH2(CH2)C(NR(2))=CC(CF3)=NN= CClCF3 (19a-c) which can undergo tautomerisation to the rearranged enamines R(2)NC=CH(CH2)(n)C=C(CF3)NHN=CClCF3 (20a-c). Further reaction of amine 20a takes place with dichloroazine 1 to afford the bicyclic compound CF3CCl=NNHCH(CF3)C=CNEtCHMeN(N=CClCF3)C(CF3)=CCH2CH2 (5) (34%). All the other isolated products are formed via hydrolysis on attempted purification on silica gel, i.e. 19a-->Et(2)NCH(CH2)(3)C=C(CF3)N=NCOCF3(9) (23%); 19b-->O=C(CH2)(4)CHC(CF3)=NN=CRCF(3) [R=NEt(2) (11) (21%); R=NHEt (12) (17%)]; 19c-->O=C(CH2)(3)C=C(CF3)NHN-CClCF3 (15) (21%) and CH2CH2O(CH2)(3)C=C(CF3)N=NCOCF3 (17) (9%); 20b-->O=C(CH2)(4)CHCH(CF3)NHN=CClCF3 (10) (28%) and CH(CH2)(4)C=C(CF3)NHNCOF3 (13) (9%>; 20c-->CF3CCl=NN=C(CF3)C=C-O-CH(CH2)(3)N=NC(CF3)=CCH2CH2 CH2(H-2)(2)C(NCH2CH2OCH2CH2)=CC(CF3)=NNHC(CF3)=C(CH2)2CH[C(CF3)=NN=CCLCF(3)]C=O (16) (18%). Reaction of the 2-aminoazine 8 with enamine 4 affords the 2-substituted enamine CH2(CH2)(2)C(NEt(2))=CC(CF3)=NN=C(NH2)CF3) (18) (36%) on separation on neutral alumina, but on silica gel the hydrolysis product O=C(CH2)(3)CHC(CF3)=NN=C(NH2)CF3 (37) (38%) is formed. The amides 9, 13 and 17 resulting from hydrolysis of a CF3CCl=N grouping are unexpected products. Compounds 9, 14 and 17 are fully conjugated and in cases where the products could contain a carbonyl group conjugated with an olefinic double bond or a conjugated azine grouping, the isolated products have the former conjugation i.e. compounds 15 and 16, except if an amino or substituted amino substituent is present when the azine conjugation is preferred, i.e., compounds 11, 12 and 37.