Alkylamino Substituents Research Articles

The Nucleophilic Substitution of Various Substituted Fluoroarenetricarbonylchromium Complexes with Methoxide

Abstract The tricarbonylchromium complexes of a variety of di- and trisubstituted fluoro- and difluoroarenes have been reacted in refluxing methoxide/methanol to yield SNAr-type substitution products. The reaction mixtures were analyzed by glpc and nmr. Methoxide substitution of each fluoride in the complexes occurred rapidly. These are the first examples of the substitution of two fluorides in a tricarbonylchromium complex by a nucleophile. Fluoride was displaced from arenes containing alkyl, methoxy, amino, and alkylamino substituents.

The Preparation of Aryl Alkyl Ethers from Fluoroarenetricarbonylchromium Complexes

Abstract The nucleophilic substitution of a number of di- and trisubstituted fluoroarenetricarbonylchromium complexes has been studied using the alkoxides derived from methyl, ethyl, isopropyl and t-butyl alcohols. In the first three cases the reactions proceed smoothly to give the expected aryl ethers, while in the t-butoxide case significant amounts of phenolic elimination products are also observed. Fluoride was displaced from arenes containing alkyl, methoxy, amino and alkylamino substituents.

Synthesis of 2,2,6,6-tetramethyl-a-diaminoalkylpiperidin-1-oxyls

A convenient method was developed for the production of 2,2,6,6-tetramethylpiperidin-1-oxyls with aminoalkyl substituents at position 4 of the piperidine ring. They can be used in the synthesis of spin labels with various lengths in the linking bridge for the modification of macromolecules.

Radiation-induced polymerization of styrene derivatives having alkylamino substituents

The polymerizability of styrene derivatives having alkylamino substituents, such as 1-(2-isopropylaminoethyl)-4-vinylbenzene (IPVB), 1-(2-diethylaminoethyl)-4-vinylbenzene (DEVB) and 1-(2-dimethylaminoethyl)-4-vinylbenzene (DMVB), was investigated in the range −96 to +25° with gamma-rays from a 60Co source. The glass transition temperatures were found to be −94° for IPVB, −102° for DEVB and −114° for DMVB. The polymer yield of these monomers prepared by 4 × 10 6 rad irradiation at −55° was 39.9, 10.4 and 4.9% respectively. On the other hand, the polymer yield of IPVB as a function of irradiation temperature (irradiation dose: 4 × 10 6 rad) was 2.4% at −96°, 27.4% at −78°, 39.9% at −55°, 35.7% at −37°, 36.4% at −24°, 54.8% at 0° and 71.3% at +25°. Such a trend of temperature-dependent polymer yield also decreased markedly in the order IPVB, DEVB and DMVB. The polymers prepared were soft and gummy, although polymers prepared by irradiating at the doses of 1 × 10 7 or above were hard and transparent.

ChemInform Abstract: SYNTHESIS AND PHARMACOLOGICAL ACTIVITY OF 6‐ARYL‐2‐AZABICYCLO(4.2.1)NONANES

A series of 6-phenyl-, 6-(m-methoxyphenyl)-, and 6-(m-hydroxyphenyl)-2-azabicyclo[4.2.1]nonanes was synthesized by a sequence involving alkylation of an appropriate 2-arylcyclopentanone with an aminoalkyl substituent. Subsequent ring closure at the other alpha position on the cyclopentanone ring and Wolff-Kishner reduction afforded the title compound. Several derivatives of these materials showed activity in an antinociceptive assay comparable to codeine. Most analogues were either inactive or toxic.

Synthesis and pharmacological activity of 6-aryl-2-azabicyclo[4.2.1]nonanes.

A series of 6-phenyl-, 6-(m-methoxyphenyl)-, and 6-(m-hydroxyphenyl)-2-azabicyclo[4.2.1]nonanes was synthesized by a sequence involving alkylation of an appropriate 2-arylcyclopentanone with an aminoalkyl substituent. Subsequent ring closure at the other alpha position on the cyclopentanone ring and Wolff-Kishner reduction afforded the title compound. Several derivatives of these materials showed activity in an antinociceptive assay comparable to codeine. Most analogues were either inactive or toxic.

Proton NMR studies of reduced porphyrin compounds

AbstractDetailed 1H NMR studies of ms tetraphenylchlorins (H2TPC), new amino‐ and hydroxypyrroline substituted ms tetraphenylchlorins and ms tetraphenylisobacteriochlorins (H2TPisoB) are presented and discussed. The results obtained are consistent with the general aspects of the ring current models as applied to the parent porphyrins. According to proton chemical shifts a gradual reduction in the magnitude of the ring current is observed in the order ms tetraphenylporphyrin (H2TPP) > H2TPC> ms tetraphenylbacteriochlorin (H2TPB) > H2TPisoB. The 1H NMR spectra show chemical non‐equivalence of the pyrroline ring protons due to adjacent substituents, and effects of steric constraints on the aminoalkyl substituents due to the close vicinity to the meso phenyl rings. The non‐equivalence of the methylene protons of the pyrroline ring produces geminal coupling between the two methylene protons and vicinal coupling with the adjacent pyrroline proton, more pronounced in H2TPCOH and in . Restricted configuration of the methylene groups in the ethyl groups of H2TPCC(H)(CH3)N(CH2CH3)2 produces observable geminal coupling between the methylene protons. 1H NMR reveals the difference between two types of meso phenyls in the chlorins, and three types of meso phenyls in isobacteriochlorins, as reflected in the chemical shifts of the o‐phenyl protons.

Aminofluorsilane: 1.3-Silylgruppenwanderung und gehinderte Si-N-Bindungsrotation / Aminofluorosilanes: 1.3-Migration of Silyl Groups and Si-N-Rotational Barrier

Triaminofluorosilanes with bulky amino groups are prepared by the reaction of bis- (organyl-trimethylsilyl)amino-difluorosilanes with lithiated amines. A 1,3-migration of trimethylsilyl groups from bulky alkylamino substituents to arylamino substituents is observed in these reactions. Structural isomers of the new triaminofluorosilanes were isolated. The silyl group migration depends on steric and electronic effects. Further reactions of the triaminofluorosilanes with butyllithium and trifluoroorganylsilanes lead to the formation of difluorosilyl-substituted triaminofluorosilanes and LiF. The symmetric compounds show AB-systems for the fluorine atoms of the difluorosilyl groups in the low temperature 19F NMR Spectra, due to hindered rotation about the Si-N-bond. The coalescence temperature depends on the bulkiness of the substituents and is observed at or about room temperature.

Reaction of N-acylated ?-amino acids with primary amines

1. The combined dehydration of N-acylated α-amino acids with primary aliphatic amines in the presence of POC13 results in the formation of bisoxazolyl-N-alkylamines, dihydropyrazines, tetrahydropyrazines with alkylamino, alkylimino, or keto substituents. 2. The yields of the oxazolylalkylamines and hydropyrazines depend on the relative amounts of the reactants and total from 60 to 70%.

ChemInform Abstract: SYNTHESIS OF 3‐SUBSTITUTED AND 1,3‐DISUBSTITUTED 4,7‐DIAZAINDOLES

AbstractBei der Bromierung von Diazaindol (I) sowie bei der Mannich‐Reaktion werden 3‐substituierte Derivate (II) und (V) erhalten.

ChemInform Abstract: SYNTHESIS OF 3‐AMINOCYCLOHEPTATRIENYLIDENAMINES

Abstract3‐Methoxytropon (I) wird mit überschüssigem Fluorsulfonsäuremethylester in Benzol zum Dimethoxytropyliumsalz (III) methyliert, das mit Aminen in Methanol :in Gegenwart von Kaliummethylat zu den Aminoderivaten (V) reagiert.

Synthesis of 3-substituted and 1,3-disubstituted 4,7-diazaindoles

On the basis of a study of electrophilic substitution reactions (the Mannich reaction and bromination) it was shown that 4,7-diazaindoles react with greater difficulty with “soft” electrophilic agents than indoles or 4- and 7-monoazaindoles. 3-Substituted and 1,3-disubstituted 4,7-diazaindoles containing amino(dialkylamino)alkyl substituents in the 1 or 3 positions were synthesized.

Synthesis of 3-aminocycloheptatrienylidenamines

Methylation of 3-methoxytropone with methyl fluorosulphonate to give 1,3-dimethoxytropenylium ion, folowed by reaction with primary amines in the presence of strong base gives 3-aminocycloheptatrienylidenamines which are more stable for arylamino than alkylamino substituents; a similar reaction with 1-methoxy-3-dimethylaminotropenylium ion failed.

The relationship between the chemical structure of s-triazines and fungitoxicity to Sclerotium rolfsii.

Thirty eight substituted s-triazine and three dialkyl biguanide analogs were tested for their effects on mycelial growth and the formation of sclerotia by Sclerotium rolfsii. None of the chemicals were fungicidal to the organism at a test concentration of 100 μg/ml in potato dextrose agar. One of the chemicals, ipazine, was highly fungistatic, and 11 others demonstrated a significant but lower degree of activity against mycelial growth. The formation of sclerotia was completely inhibited in the presence of only one s-triazine, 2-amino-4-chloro-6-n-propylamino-s-triazine. Eight other s-triazines were as active as atrazine, the standard test chemical, in inhibiting the formation of sclerotia, and 10 more of the s-triazines were significantly effective but at a lower level of activity than atrazine. N1,N5-bis(ethyl)biguanide was the only chemical which caused a significant increase in the number of sclerotia formed. No absolute correlation was observed between biological activity and chemical structure although in certain instances there was an apparent correlation between toxicity and the overall electron withdrawing character of the non-alkylamino substituent on the s-triazine ring, or to the steric effects caused by the configuration of the alkylamino substituents. Only those chemicals which were highly active as herbicides were significantly effective in inhibiting mycelial growth and sclerotia formation; however, not all of the herbicidally active compounds were effective in this regard.

Catalytic transformations of furan amines

1. 5-Methylfurfurylamine was obtained in 80% yield from 5-methyl-2-furaldehyde by reductive animation. 2. 1-(5-methylfuryl)-2-aminoethane was synthesized by the condensation of 5-methyl-2-furaldehyde with nitromethane and subsequent reduction of the nitro compound with lithium aluminum hydride to the corresponding amine. 3. A study was made of the catalytic hydrogenolysis of 1-(5-methylfuryl)-2-aminoethane and 5-methylfurfurylamine when they were subjected to vapor-phase hydrogenation over Pt/C catalyst at normal hydrogen pressure and a temperature of 230°. 4. Hydrogenolysis of the furan ring under these conditions proceeds mainly at the C-O bond adjacent to the aminoalkyl substituent. 5. α-Pipecoline, 2, 5-dibutylpyrazine, and 2-methylhexamethyleneimine were obtained by a new method, namely by the catalytic hydrogenolysis of 5-methylfurfurylamine and 1-(5-methylfuryl)-2-aminoethane.