1-Alkyl-1-piperidino

In Poland, various 5-cycloaminornetbyl-6-(p-chlorophenyl)-4,5-dihydro-3(2//)-pyridazinones (89, R1 = pyrrolidino, piperidino, morpholino, etc. R2 = H, substituted alkyl, aryl) have been prepared in search of biologically active pyridazines some of these compounds have been reported to exhibit immunosuppressive activity [180, 284, 285]. 

R, R R. R = H. alkyl, aryl, hrtaiyl R = piperidino, pyrrolidino, moipholino Scheme 4... 

Die analoge Reaktion von Organo-magnesiumhalogeniden mit dem aus 3-Chlor-propan-saure-piperidid, Natrium und Chlor-trimethyl-silan leicht zuganglichcn 1 -Methoxy-1 -pi-peridino-cyclopropan ergibt in guten Ausbeuten 1-Alkyl-, l-(l-Alkenyl)- bzw. 1-Aryl-l-piperidino-cyclopropane3. 

NR2 = NMe2, NEt2, N(CH2Ph)2, pyrrolidino, piperidino, or morpholino R = alkyl or halogen... 

An amino alcohol was found to accelerate the addition reaction of diethlylzinc to aldehyde [8], and then chiral amino alcohols were proved to be efficient chiral catalysts for asymmetric alkylation by using dialkylzinc reagents [9], Oguni reported a remarkable asymmetric amplification in chiral amino alcohol-promoted alkylation (Scheme 9.4). In the presence of (-)-l-piperidino-3,3-dimethyl-2-butanol (5) of 11% ee, benzaldehyde is alkylated enantioselectively to give (/ )-l-phenylpropanol with 82% ee [10]. Asymmetric amplification was also observed by Noyori using partially resolved (2.S )-3-exo-(dimethylamino)isobomeol (6) [11]. 

Alkylations may be followed by subsequent reactions, e.g. cycliza-tion. Thus, treatment of o>,o/-dihalogenoalkanes with 1-pyrrolidino-l-eyclohexene, followed by hydrolysis, affords, in addition to other products, bicyclic ketones.232 An interesting cyclization was described by Parcell233 in connection with the alkylation of 1-piperidino-l-... 

Photoinduced forms of all derivatives of 1-methyl-9,10-anthraquinones studied (Table 7.1) exhibited a long-wavelength absorption band located, as a rule, in the 580-600 nm range.17,18,26,36 Compounds with phenyl groups in 1-alkyl-substituted and 4-piperidino-l-methyl-9,10-anthraquinone (Figure 7.3) were characterized by a red shift of the absorption band (617-635 nm)26,36 The absorption band of the photoinduced form of 4-oxy-derivatives of 1-methyl-9,10-anthraquinone was shifted to the blue region to 472-478 nm. 

A facile preparation of F-alkyl enaminones F-MeCOCH=CHNRR1 in 90% yield involves refluxing MeCOCH2CH(OMe)2 with amines RRXNH (R = R1 = H, Me, Et R = Me, R1 = Ph, PhCH2 or RRXN = 1-pyrrolidino, piperidino, morpholino)593. 

The central ring systems found to yield antiviral compounds have included fluorene (fluorenone), dibenzofuran, dibenzothiophene, fluoranthene, anthraquinone, acenaphthene, xanthene, thioxanthene, phenothiazine, carbazole, phenanthrene and others. The side chains were represented by basic ethers, basic ketones, basic esters plus carboxamides, sulphonamides, alkanols, methylene and others attached to the various ring systems. The amine function was usually substituted to the tertiary amine with various alkyl substituents although a few ring types (e.g., pyrrole or piperidino) were synthesized. 

Reaction of 2-naphthol with N-piperidino-mcthyl and N-morpholinomcihyl alkyl ethers,... 

Both /ranj-selectivity and enantioselectivity depend on the structure of the terminal amino group, six-membered ring amines represented by piperidino 8g and morpholino 8h generally being most selective [71]. Substituted aromatic aldehydes, a,i -unsaturated aldehydes, and secondary and tertiary alkyl aldehydes can be converted into the corresponding /ranj-oxazolines with high enantioselectivity. Enantiomeric purities and transjcis ratios obtained for the aldol reaction of several aldehydes in the presence of Au/(R)-(S)-8h are shown in Scheme 2-51. The gold-catalyzed aldol reaction of isocyanoacetate has been applied to the synthesis... 

The empirical SARs could be construed tn suggest that the 4-aryl piperidino moiety is superimpo.sable on the 2-phcnylethylamino moiety of dopamine and. accordingly, cuuld promote affinity for D and Dj receptors. The long V alkyl substituent could help promote receptor affinity and mxiuce receptor antagonism activity und/or inverse ago-nism.. 

Both cyclic and acyclic enamines are oxidized very easily, at potentials smaller than that of A. jY-dimethylaniline ( + 0.7 V vs SCE), The ease of oxidation is affected by many factors, such as the length of the n system, the degree and nature of substitution at the enamine function (alkyl groups lower the potentials considerably, aryl group much less) and the steric interactions. Mainly, however, it depends on the number of amino groups linked to the double bond , and then on the electron-donating power of the amino-component. Pyrrolidino enamines are oxidized more easily than piperidino and morpholine ones. The yields also depend on the oxidation potential, since they decrease with increasing ease of electrolytic oxidation . ... 

Pyrazoles and Isoxazoles Consistent with the finding that certain pyrazoles exhibit ERa-selective agonism, the University of Illinois reported that attachment of a BSC to these pyrazoles provided ERa-selective antagonists [171, 172]. Thus, 220-fold ERa selectivity was observed for pyrazole 137 (methyl-piperidino-pyrazole). It was found that the combination of a methyl group at C4 and piperidine as part of the BSC were key elements that direct ERa selectivity. Although larger alkyl groups had little effect... 

Nitro-phcnyl)-2-(3-pyridyl-amino)-171 5-Nitro-2-piperidino- 244 5-Nitro-2-(pyrazin-2-yloxy)- 290 5-Nitro-2-(2-pyridylamino)- 244 5-Nitro-2-[2-(2-pyridyl)-ethenyl]- 272, 312 2-Organothio-5-thiocyanat- 252 2-(2-Oxo-alkyl)- 198, 340... 

Piperidino-mcthyl)- 224 Pyridyl- 299 2-(2-Pyridyl)- 299 2-(2-Pyridylamino)- 109, 285 2-(2-Pyridylamino)-5-sulfo- 250 2-(l-Silyloxy-alkyl)- 307 Stannyl- 305... 

A mixture of diethylacetonitrile and chlorobenzene added with stirring at 35-40 to Na in benzene, after 5 hrs. 180 gm. ethyl diphenylacetate added with cooling at 40°, stirred several hrs., warmed 0.5 hr. at 60 , cooled to 10-20 , 110 gm. piperidinoethyl chloride dropped in below 40°, and, after 2 hrs., refluxed for 1 hr. 212 gm. ethyl y-piperidino-a,a-diphenylbutyrate.—It may be preferable not to use the very active phenyl-Na for the alkylation, particularly if the compounds contain several reactive groups, but an intermediate, less reactive Na-carrier, in this case, diethylacetonitrile. (F. e. s. M. Boekmtihl and G. Ehrhart, A. 561, 52 (1948).)... 

A study has correlated the reactivities of different onium salts based on HOXt [66]. The nature of the different reagents, phosphonium versus aminium or uronium, iV-alkyl substituents (R), and OAt versus OBt influences were investigated. HXTU, HAPyU, PyXOP, XOP, the piperidino derivative, 0-(7-azabenzotriazol-1 -yl)-1,1,3,3-bis(pentamethylene)uronium hexafluorophosphate (32) (HAPipU), both dihydroimidazole derivatives, 0-(7-azabenzotriazol- 1-yl)-1,3-dimethyl-1,3-dimethyleneuronium hexaflu-... 

The competition between the N- and the C-protonation in weakly acid media is likely to occur for N,N-dimethyl-m-phenylenediamine as well There is an indication that the protonation of l,3,5-tris(dialkylamino)benzenes depends on the alkyl substituents. Thus, l,3,5-tris(pyrrolidino)benzcne in CDClj attaches the proton to the unsubstituted ring position, whereas l,3,5-tris(piperidino)benzene under the same conditions is protonated at the amino group. 

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