摘要:

AbstractThe skeletal rearrangement of 1,4‐benzodiazepines to other heterocyclic systems are reviewed together with a discussion of possible mechanisms. Simple rearrangements involving migrations without skeletal changes are included for the sake of completenes

ISSN:0022-152X    

DOI:10.1002/jhet.5570090401

出版商:Wiley‐Blackwell    

年代:1972

数据来源: WILEY

摘要:

Abstract2 Various4‐diamino‐6‐(phenoxy, naphthyloxy, and phenalkoxy)quinazolines (VIII, XIV) were synthesized for antimalarial and antibacterial evaluation. Treatment of the anion of the requisite phenol or naphthol with 5‐chloro‐2‐nitrobenzonitrile (V) gave the corresponding 2‐nitro‐5‐(phenoxy and naphthyloxy)benzonitriles (VI) (33–78%). Alternatively, alkylation of 5‐hydroxy‐2‐nitrobenzaldehyde (IX) with the appropriate phenalkyl halide afforded the 2‐nitro‐5‐(phenalkoxy)benzaldehydes (X) (27–62%), which were converted to the 2‐nitro‐5‐(phenalkoxy)benzonitriles (XII)viathe intermediate oximes XI (62–87% overall). Reduction of the 2‐nitrobenzonitriles (VI, XII) with stannous chloride‐hydrochloric acid provided the corresponding 2‐amino‐5‐(phenoxy, naphthyloxy, and phenalkoxy)benzonitriles (VII, XIII) (30–83%), which upon cyclization with chloroformamidine hydrochloride gave the 2,4‐diaminoquinazolines VIII and XIV (12–85%). AgainstPlasmodium bergheiin mice, eleven compounds were active orally at doses ranging from 6.3 to 174 mg./kg./day for 6 days, while seven substances displayed activity subcutaneously following single doses of 40–640 mg./kg. Fifteen compounds exhibitedin vitroantibacterial activity againstStreptococcus faecalis(MGH‐2), normal (UC‐76) and drug‐resistant (S18713)Staphylococcus aureus, Escherichia coli(Vogel), andShigella sonnei(C‐10) with MIC's ranging from<0.25 to 20 μg./ml. (gradient plate). Data on the inhibitory effects of representative compounds againstStreptococcus faecalisR (S. faeciumvar.durans), S. faecalisA (amino‐pterin, methotrexate‐resistant), andLactobacillus plantaruma

ISSN:0022-152X    

DOI:10.1002/jhet.5570090402

出版商:Wiley‐Blackwell    

年代:1972

数据来源: WILEY

摘要:

Abstract2,4‐Diamino‐5,7‐dihydro‐6H‐thiopyrano[4′,3′:4,5]thieno[2,3‐d]pyrirnidine, 2,4‐diamino‐9H‐mdeno[1′,2′:4,5]thieno[2,3‐d]pyrimidine, 2,4‐diamino‐5H‐indeno[2′,1′:4,5]thieno[2,3‐d]pyrimidine, 9,11‐diamino‐5,6‐dihydronaphtho[1′,2′:4,5]thieno[2,3‐d]pyrimidine, 7,9‐diamino‐5,6‐dihydronaphtho[2′,1′:4,5]thieno[2,3‐d]pyrimidine, 2,4‐diamino‐7‐benzy]‐5,6,7,8‐tetrahydropyrido[4′,3′:4,5]thieno[2,3‐d]pyrimidine, and various 2,4‐diamino‐5,6,7,8‐tetrahydro‐[1]benzothieno[2,3‐d]pyrimidines were synthesized by cyclization of the requisite fused 2‐aminothio‐phenene‐3‐carbonitriles utilizing chloroformamidine hydrochloride in diglyme. Several compounds exhibited strong inhibitory effects againstStreptococcus faecalis(MGH‐2),Staphylococcus aureus(UC‐76),Streptococcus faecium(ATCC 8043),Lactobacillus casei(ATCC 7469), andPediococcus cerevisiae(ATCC 8081)in vitro, and three compound

ISSN:0022-152X    

DOI:10.1002/jhet.5570090403

出版商:Wiley‐Blackwell    

年代:1972

数据来源: WILEY

摘要:

Abstract4‐Aminopyrylium derivatives were prepared from secondary amines and 4‐methoxy‐2,6‐dimethylpyrylium perchlorate (1a) and the corresponding 2,6‐diphenyl derivative. Excess amine or elevated temperature resulted in the addition of two equivalents of amine to1a. The reactions of the aminopyrylium salts with hydroxide, ammonia, primary amines, hydrazines, cyanoacetamides, ethyl cyanoacetate, malononitrile, nitromethane, sodium sulfide, and a Grignard reagent are

ISSN:0022-152X    

DOI:10.1002/jhet.5570090404

出版商:Wiley‐Blackwell    

年代:1972

数据来源: WILEY

摘要:

AbstractA comprehensive kinetic investigation of reactions occurring in the formation of styryl‐quinolines has been conducted. Specific rate data such as rate equations, rate constants, and thermodynamic activation values have been determined and utilized in a study of which factors are of greatest importance in the reactions forming 2‐styrylquinolines. A mechanism has been proposed for the condensation reaction which agrees with rate relationships found. Gas‐liquid partition chromatography was used to follow the kinetics of the condensation reactions. A rate constant of 5.41 × 10−2M−1min−1was found for the reaction of benzaldehyde with 2‐methyl‐quinoline using zinc chloride as a catalyst at 104.0°. Rate constants of 1.28 × 10−2MT−1min−1and 1.05 × 10−2M−1min−1were found for the reactions ofp‐methylbenzaldehyde andp‐methoxybenzaldehyde with quinaldine to form 2‐(p‐methylstyryl)quinoline and 2‐(p‐methoxystyryl)‐quinoline, respectively at 92.4°. A linear relationship was found using the Hammett equation. An Arrhenius plot was constructed from rate constants determined at five different temperatures for the reaction of benzaldehyde and quinaldine to form 2‐styrylquinoline, using zinc chloride as a catalyst. The energy of activation, Ea, was found to be 22.2 kcal/mole for this reaction. The enthalpy of activation, ΔH‡, free energy of activation, ΔF‡, and entropy of activation, ΔS‡, were found to be 21.4 kcal/mole, 27.7 kcal/mole and ‐16.7 eu/mole, respectively, at 104.0°. The mechanism proposed in the formation of 2‐styrylquinoline involves the fast formation of a carbanion‐zinc chloride complex, which then attacks, in the rate determining step, the aldehyde utilized in the reaction. The lack of reaction of certain methylquinolines is attributed to the inadequacy of the carbanion formed and not to t

ISSN:0022-152X    

DOI:10.1002/jhet.5570090405

出版商:Wiley‐Blackwell    

年代:1972

数据来源: WILEY

摘要:

AbstractNitration of anthyridine‐2,6‐dione (I) gave 7‐nitroanthyridine‐2,6‐dione (II). Treatment of this compound with phosphorus pentasulfide afforded 7‐aminoanthyridine‐2,6‐dithione (III). Desulfurization of the thioderivative III with Raney Nickel and subsequent aromatization of 3‐amino‐5,10‐dihydroanthyridine (VI) in boiling nitrobenzene, gave 3‐aminoanthyridine (VII) in satisfactory yield. The structure of 3‐aminoanthyridine was demonstrated and its physico‐chemical features are not in agreement with that previously reported in literature. The preparation of 3‐aminoanthyridine

ISSN:0022-152X    

DOI:10.1002/jhet.5570090406

出版商:Wiley‐Blackwell    

年代:1972

数据来源: WILEY

摘要:

Abstract6,7‐Dimethoxy‐2‐naphthylethylamine, prepared by the diborane reduction of 6,7‐dimethoxy‐2‐naphtlialeneacetamide, underwent a Pictet‐Spengler cyclization to form 8,9‐dimethoxy‐1,2,3,4‐tetrahydrobenz[h]isoquinoline. This compound is identical with that obtained by reduction of the corresponding dihydrobenzisoquinoline prepared from formamide cyclization. 6,7‐Dialkoxy‐2‐naphthaleneacetic acids, the key intermediates for the preparation of these amides, were obtained from 6,7‐dialkoxy‐2‐acetonaphthones by

ISSN:0022-152X    

DOI:10.1002/jhet.5570090407

出版商:Wiley‐Blackwell    

年代:1972

数据来源: WILEY

摘要:

Abstract2 Four3,10,11‐tetraalkoxy‐substituted 5,6,15,15a‐tetrahydro‐8H‐benzo[a]naphtho[1,2‐g]‐quinolizines were prepared by the Pictet‐Spengler cyclization of the respective 1‐(6,7‐dialkoxy‐2‐naphthylmethyl)‐6,7‐dialkoxy‐1,2,3,4‐tetrahydroisoquinolines. The latter compounds were obtained by a chemical reduction of the corresponding dihydro compounds, which, in turn, were formed by a Bischler‐Napieralski cycl

ISSN:0022-152X    

DOI:10.1002/jhet.5570090408

出版商:Wiley‐Blackwell    

年代:1972

数据来源: WILEY

摘要:

AbstractThe report that the dipole moment in the five‐membered heterocyclic rings, furan, thiophene, and pyrrole has the positive pole on the heteroatom is contradicted with arguments based on reactivity data, theoretical calculations and moment values of substituted derivatives.In actuality, the dipole moment in furan and thiophene is directed from the ring (positive pole) to the heteroatom (negative pole

ISSN:0022-152X    

DOI:10.1002/jhet.5570090409

出版商:Wiley‐Blackwell    

年代:1972

数据来源: WILEY

摘要:

AbstractN1‐(2‐Methoxy‐4‐pyrimidyl)sulfanilamide was successfully prepared through three alternative routes. Namely, the above compound was obtained by condensation of 4‐amino‐2‐methoxy‐pyrimidine (III) withp‐acetaminobenzenesulfonyl chloride andp‐nitrobenzenesulfonyl chloride and by direct condensation

ISSN:0022-152X    

DOI:10.1002/jhet.5570090410

出版商:Wiley‐Blackwell    

年代:1972

数据来源: WILEY