Directed ortho Metalation Studies on Podocarpic Acid Derivatives: Advantageous Use of a LICKOR Base

1991 ◽  
Vol 44 (10) ◽  
pp. 1465 ◽  
Author(s):  
RC Cambie ◽  
PI Higgs ◽  
KC Lee ◽  
MR Metzler ◽  
PS Rutledge ◽  
...  
Keyword(s):  
Amide Group ◽  
Dynamic Features ◽  
Tertiary Amide ◽  
Ortho Metalation ◽  
Derivatives Of ◽  
Oxazoline Derivatives

Methyl 13-(N,N- diethylcarbamoyl )-12-methoxypodocarpa-8,11,13-trien-19-oate (2), 13-(N,N- diethylcarbamoyl )-12,19-dimethoxypodocarpa-8,11,13-triene (8) and N,N-diethyl-2-methoxy-4,5-dimethylbenzamide (15) were prepared for studies involving lithiation directed ortho to the tertiary amide group, in which the use of a LICKOR base was advantageous. Some dynamic features of the n.m.r. spectra of the amides are discussed. Oxazoline derivatives of both tile monocyclic and diterpenoid compounds were synthesized.

The Ion Associates of Methyl-, Ethyl- and Isopropyl Derivatives of Dialkylaminoethyl Dialkylamidofluorophosphate with Bromophenol Blue

1992 ◽  
Vol 57 (1) ◽  
pp. 56-63 ◽  
Author(s):  
Emil Halámek ◽  
Zbyněk Kobliha
Keyword(s):  
Extraction Efficiency ◽  
Ion Pairs ◽  
Amino Nitrogen ◽  
Ion Pair ◽  
Amide Group ◽  
Bromophenol Blue ◽  
Amino Group ◽  
Methyl Ethyl ◽  
Derivatives Of

Nine new Tammelin esters were studied on the basis of the chloroform extracts of their ion associates with bromophenol blue. A study was made of the effect of the alkyl on the amino and amido groups of dialkylaminoethyl dialkylamidofluorophosphate and on the extraction efficiency of the ion pair. An increase in the number of carbon atoms on the amide group leads to the increase in the extraction efficiency of the ion pairs as a consequence of the increasing hydrophobicity. A further contribution to the increase in the extraction efficiency with increasing number of carbon atoms in the alkyls of the amino nitrogen is clearly retarded by the increasing basicity of the amino group. An extraction spectrophotometric determination of the test derivatives of dialkylaminoethyl dialkylamidofluorophosphate was developed and the interferences from precursors in the synthesis were examined.

Pseudoacids. II. 2-Acylbenzoic Acid Derivatives

1998 ◽  
Vol 54 (3) ◽  
pp. 264-276 ◽  
Author(s):  
E. J. Valente ◽  
S. B. Martin ◽  
L. D. Sullivan
Keyword(s):  
Bond Length ◽  
Tertiary Amide ◽  
Derivatives Of

Structures of derivatives of cyclic o-acylbenzoic acids, including the chloride, endo- and exocyclic amides, esters and anhydrides, are examined. 3-Chloro-1(3H)-isobenzofuranone (1), orthorhombic, Pbca, a = 11.616 (5), b = 8.120 (3), c = 15.640 (9) Å; 3-methoxy-3-phenyl-1(3H)-isobenzofuranone (3), orthorhombic, P212121, a = 6.923 (2), b = 8.291 (4), c = 21.551 (8) Å; 3-hydroxy-3-phenyl-N-propyl-1(3H)-isoindolone (4), orthorhombic, P212121, a = 8.662 (4), b = 9.551 (7), c = 17.649 (14) Å; 3-(N-morpholino)-1(3H)-isobenzofuranone (5), triclinic, P1¯, a = 6.172 (4), b = 11.163 (7), c = 17.33 (2) Å, α = 105.91 (6), β = 99.85 (6), γ = 97.57 (5)°; 3-(2′-benzoylbenzoyloxy)-3-phenyl-1(3H)-isobenzofuranone (7), triclinic, P1¯, a = 9.694 (3), b = 10.505 (4), c = 11.163 (4) Å, α = 80.58 (3), β = 80.41 (3), γ = 76.49 (3)°; bis[1(3H)-isobenzofuranone-3-yl]ether (8), monoclinic, I2/a, a = 15.31 (2), b = 6.111 (12), c = 28.30 (5) Å, β = 101.61 (12)°. An open oxoacid tertiary amide is also described: N-morpholino 2′-benzoylbenzamide (6): monoclinic, P21/c, a = 6.844 (4), b = 15.696 (8), c = 14.154 (7) Å, β = 99.43 (4)°. Pseudoacid derivatives form planar isobenzofuran and isoindole rings, and the former aldehyde/ketone carbon–heteroatom endocyclic and exocyclic bond distances show bond length variations which correlate with the relative basicities of the attached groups. Structures of both endocyclic and exocyclic nitrogen pseudoamides are reported as well as examples of the normal–pseudoanhydride and the dipseudoanhydride.

scholarly journals Microwave-assisted synthesis of biologically active amide derivatives of naphthenic acids under neat conditions

2018 ◽  
Vol 37 (1) ◽  
pp. 13 ◽  
Author(s):  
Ljubica Grbović ◽  
Bojana Radovan Vasiljević ◽  
Ksenija Pavlović ◽  
Timea Hajnal-Jafari ◽  
Simonida Đurić ◽  
...  
Keyword(s):  
Naphthenic Acid ◽  
Growth Stimulation ◽  
Naphthenic Acids ◽  
Biologically Active ◽  
Microwave Assisted Synthesis ◽  
Tertiary Amide ◽  
Amide Derivatives ◽  
Temperature Heating ◽  
Derivatives Of ◽  
Solvent Free Synthesis

Within the field of green chemistry, a noticeable results were obtained in the solvent-free synthesis of amide derivatives of naphthenic acids under microwave irradiation. Naphthenic acid amides, anilides, and morpholides were synthesized directly from free carboxylic acids and amines in the absence of solvent and catalyst under high-temperature heating in a closed-vessel system of microwave reactor. With this new and efficient method, different primary, secondary, and tertiary amide derivatives of naphthenic acids were obtained in good to excellent yields. Synthesized derivatives were assayed as plant rooting agents for their stimulative effects on the formation of adventitious roots in sunflower cuttings and susceptibility for growth stimulation of Pseudomonas sp. strains.

Substituent Interactions in Di- and Tri-acyl Derivatives of cis- and trans- 2-Hydrazinocyclopentanol

1973 ◽  
Vol 51 (10) ◽  
pp. 1587-1597 ◽  
Author(s):  
J. A. Campbell ◽  
Donald Mackay
Keyword(s):  
Acetyl Derivative ◽  
Ester Group ◽  
Major Product ◽  
Amide Group ◽  
Acid Mixture ◽  
Tosyl Chloride ◽  
Cis And Trans ◽  
Work Up ◽  
Derivatives Of ◽  
Acyl Derivatives

The action of thionyl chloride followed by an alkaline work-up quantitatively isomerizes trans-1,2-dibenzoyl-1-(2-hydroxylcyclopentyl)hydrazine(5) to cis-2-benzoyl-1-(2-benzoyloxycyclopentyl)hydrazine (3). One equivalent of tosyl chloride in pyridine converts 5 to an intermediate which can be hydrolyzed to a mixture of 3 and 5 or can be transformed to the N-tosyl derivative 13 by tosylation and then hydrolysis. Oxazolidine structures are suggested as intermediates for these reactions.The alcohol 2 can also be isomerized to 3, using 0.8 N aqueous ethanolic hydrochloric acid, to which 5 is inert. The ester 3 is again the major product in the hydrolysis by this acid mixture of the cis-tribenzoyl derivative 17, the cis-N1-p-anisoyl derivative 21a and the cis-N1-acetyl derivative 21b, the amide group being cleaved much more rapidly than the ester, especially in the case of 21b. A mechanism involving ester participation by way of an oxazolidinium cation is proposed for these amide hydrolyses, and this is supported by tracer studies.The trans-esters 24a and b hydrolyze mainly at the ester group with retention of configuration.Polymorphism is a common phenomenon among the title compounds.

Kinetics and mechanism of base-catalyzed cyclization of substituted amides and nitriles of hydantoic acid

1987 ◽  
Vol 52 (1) ◽  
pp. 140-155 ◽  
Author(s):  
Vladimír Macháček ◽  
Gabriela Svobodová ◽  
Vojeslav Štěrba
Keyword(s):  
Rate Constant ◽  
Acid Amide ◽  
Phenyl Group ◽  
Reaction Rate Constant ◽  
Amide Group ◽  
Cyclization Reaction ◽  
Hydrolysis Rate ◽  
Cyclization Reactions ◽  
Hydrolysis Of ◽  
Derivatives Of

Rates of base-catalyzed cyclizations of 8 substituted derivatives of hydantoic acid amide type R3-NH(5)-CO(4)-NR2(3)-CH2(2)-CO(1)-NHR1 and 9 nitriles type R3-NH(5)-CO(4)-NR2(3)-CHR1(2)-CN have been measured in aqueous and methanolic media. The cyclization of the amides in aqueous medium is also accompanied by hydrolysis of the hydantoins formed. In some cases the hydrolysis rate constant is greater than the corresponding cyclization reaction rate constant. With the least reactive amides, the cyclization is also accompanied by hydrolysis of the amide group. The rate of the cyclization reactions in water is higher than that in methanol (at the same concentration of the lyate ions) by the factor of 10-100. Substitution of hydrogen at 3 and 5 positions by methyl or phenyl groups causes an acceleration of the cyclization reaction, whereas a substitution in the amide group causes a considerable retardation. The greatest acceleration of the cyclization (by as much as 4 orders) is caused by introduction of phenyl group to the N(5) position, which is due to a substantial increase of concentration of the reactive anion.

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