Primary Alkylammonium Salts Research Articles

Novel C2-Symmetric Macrocycles Bearing Diamide−Diester Groups: Synthesis and Enantiomeric Recognition for Primary Alkyl Ammonium Salts

We synthesized a series of novel macrocycles with diamide-diester groups (S,S)-1, (S,S)-2, (S,S)-3, and (R,R)-1, derived from dimethyloxalate and amino alcohols by high dilution technique, and evaluated enantiomeric recognition properties of these macrocycles toward primary alkyl ammonium salts by 1H NMR titration. Taking into account the host employed, important differences were observed in the Ka values of (R)-Am and (S)-Am for (S,S)-1 and (R,R)-1 hosts, KS/KR = 5.55 and KR/KS = 3.65, Delta Delta Go = 0.43 and -0.32 kJ mol-1, respectively. There seems a general tendency for the host to include the guests with the same absolute configuration.

Polysulfonylamines. XCI. Ethylammonium Di(benzenesulfonyl)amide 1,4,7,10,13,16-Hexaoxacyclooctadecane (1/1/1)

In the structure of the title compound, C2H8N+.C12H10NO4S2−.C12H24O6, the non-coordinating (C6H5SO2)2N− anion adopts an extended conformation with the phenyl groups lying on opposite sides of the S—N—S plane. The conformation of the macrocycle and the hydrogen-bond geometry in the complex cation closely resemble those in related adducts between 18-crown-6 and primary alkylammonium salts.

Extraction of chiral ammonium cations and transport through supported liquid membranes mediated by 1,2,4-triazole-containing podands and macrocycles

Extraction of chiral primary alkylammonium salts was achieved in the presence of 1,2,4-triazole-containing macrocycles and podands with moderate enantioselectivities. Although preferential transport of ( R)-1-naphthylethylammonium salts was always observed, significant differences in both rates and selectivities were found when bulk (CHCl 3CCl 4) or supported (microporous polypropylene film) membranes were employed. The preparation of new protonionizable chiral bistriazolo-18-crown-6 macrocycles 3c, d is described.

Factors influencing enantiomeric recognition of primary alkylammonium salts by pyridino-18-crown-6 type ligands

Equilibrium constant (K), enthalpy change (ΔH), and entropy change (ΔS) values were determined for the interactions of a series of chiral pyridino-18-crown-6 type ligands with enantiomers of several primary alkylammonium salts in various solvents. Good enantiomeric recognition in terms of Δ logK was observed in many systems with Δ logK values greater than 0.4. The extent of enantiomeric recognition and the stabilities of the chiral crown ether-ammonium salt complexes were found to depend on the rigidity of the macrocyclic frame of the ligand, the type and arrangement of the donor atoms on the ligand, the bulkiness of the substituents on the ligand's chiral centers, the location of the chiral centers on the ligand, and the solvent. The effects of these factors on the extent of enantiomeric recognition and on the stabilities of the complexes were examined for the systems studied.

Polymeric chiral crown ethers, 2. Syntheses and chiral recognition of polymers consisting of (S)‐ or (R)‐2,2′‐binaphthyl‐21‐crown‐6 units through cyclopolymerization of divinyl ethers

AbstractOptically active divinyl ethers, (−)‐(S)‐ and (+)‐(R)‐2,2′‐bis[2‐(2‐ vinyloxyethoxy)ethoxy]‐1,1′‐binaphthyl [(S)‐1 and (R)‐1], were synthesized and polymerized with cationic catalysts. The resulting polymers are composed of only cyclic constitutional units, (S)‐ and (R)‐dinaphtho‐[2,1‐r:1,2‐t]‐1,4,7,11,14,17‐hexaoxaperhydrocyclohenicosen‐8,10‐ylene. Both (S)‐ and (R)‐polymers show nearly equal values of optical rotation, but in opposite directions. The ability of chiral recognition of the (R)‐polymer towards racemic primary alkylammonium salts was investigated with salts of 1‐phenylethylamine, valine, phenylalanine and phenylglycine, and found to be very similar to that of the corresponding model crown ether.

ChemInform Abstract: The Formation of Complexes Between Aza Derivatives of Crown Ethers and Primary Alkylammonium Salts. Part 9. Bicyclic Derivatives of Diaza Crown Ethers

ChemInform Abstract: The Formation of Complexes Between Aza Derivatives of Crown Ethers and Primary Alkylammonium Salts. Part 9. Bicyclic Derivatives of Diaza Crown Ethers

The formation of complexes between aza derivatives of crown ethers and primary alkylammonium salts. Part 9. Bicyclic derivatives of diaza crown ethers

The bridged diaza-15-crown-5 derivatives (12a–c) and (16) form complexes with alkylammonium cations RNH3 in organic solvents. The 1H n.m.r. spectra of the complexes (12). RNH3 show that they are mostly of the inclusion type (3) but in a few cases a second diastereoisomeric complex, possibly (4), is also formed. These bicyclic hosts do not show particularly high selectivity in complexation on the basis of competition between pairs of guest cations.

ChemInform Abstract: FORMATION OF COMPLEXES BETWEEN AZA DERIVATIVES OF CROWN ETHERS AND PRIMARY ALKYLAMMONIUM SALTS. PART 8. 12‐CROWN‐4, 15‐CROWN‐5, 21‐CROWN‐7, AND 24‐CROWN‐8 DERIVATIVES

Chemischer InformationsdienstVolume 16, Issue 48 Heterocyclic Compounds ChemInform Abstract: FORMATION OF COMPLEXES BETWEEN AZA DERIVATIVES OF CROWN ETHERS AND PRIMARY ALKYLAMMONIUM SALTS. PART 8. 12-CROWN-4, 15-CROWN-5, 21-CROWN-7, AND 24-CROWN-8 DERIVATIVES M. R. JOHNSON, M. R. JOHNSONSearch for more papers by this authorN. F. JONES, N. F. JONESSearch for more papers by this authorI. O. SUTHERLAND, I. O. SUTHERLANDSearch for more papers by this authorR. F. NEWTON, R. F. NEWTONSearch for more papers by this author M. R. JOHNSON, M. R. JOHNSONSearch for more papers by this authorN. F. JONES, N. F. JONESSearch for more papers by this authorI. O. SUTHERLAND, I. O. SUTHERLANDSearch for more papers by this authorR. F. NEWTON, R. F. NEWTONSearch for more papers by this author First published: December 3, 1985 https://doi.org/10.1002/chin.198548226Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume16, Issue48December 3, 1985 RelatedInformation

Formation of complexes between aza derivatives of crown ethers and primary alkylammonium salts. Part 8. 12-Crown-4, 15-crown-5, 21-crown-7, and 24-crown-8 derivatives

The monoaza-crown ethers (3), (4), and (5) and the diaza-crown ethers (6), (7), (10). and (11) form complexes with primary alkylammonium thiocyanates in organic solvents. The diaza-15-crown-5 system (11) forms well defined 1:1 complexes with the cis-,cis-stereochemistry shown in (16) but the diaza-24-crown-8 derivative (7) forms a 2:1 complex (G:H ratio) with benzylammonium thiocyanate having the cis,cis,trans,trans-stereochemistry (17a). The diaza-24-crown-6 derivative (10) forms weak 1:1 complexes which apparently adopt the double nesting conformation (18).

The formation of complexes between aza derivatives of crown ethers and primary alkylammonium salts. Part 7. Chiral derivatives of aza crown ethers

A number of optically active derivatives of diaza-15-crown-5 and diaza-18-crown-6 have been synthesised using amino acids as the source of chirality. The diaza-18-crown-6 derivatives (21) show enantioselectivity in the complexation of 1-phenylethylammonium thiocyanate in methylene chloride as determined by 1H n.m.r. spectroscopy. The degree of enantioselectivity depends upon the substituents on the nitrogen atoms of the macrocycle and although the N,N-dibenzyl derivatives (21) show moderately high enantioselectivity, the N,N-dimethyl derivatives (20) do not. In the presence of water the hosts (21) apparently form hydrated complexes with guest alkylammonium cations with very little enantioselectivity.

A comparison between the solid state structures and solution behaviour of molecular complexes formed between primary alkylammonium salts and chiral crown ethers incorporating 1,2:4,6-diacetals of D-mannitol

The results of an X-ray crystallographic study of D-(1)-Me2CHNH3ClO4 and D-(2)-PhCH2NH3CIO4 reveal conformational features and a hydrogen bonding pattern in the 1:1 complexes which may be correlated with the complexaton behaviour of the 20-crown-6 derivatives D-(1), D-(2), and (3) in solution towards a range of cationic guest species.

Temperature dependent 1H Nmr studies of the complexation of synthetic macrocyclic multidentate compounds with primary alkylammonium salts. A short review

Temperature dependent ¹H Nmr studies of the complexation of synthetic macrocyclic multidentate compounds with primary alkylammonium salts. A short review

Chiral diaza-18-crown-6 derivatives

The chiral diaza-18-crown-6 derivatives (7) and (8), which are readily synthesised from the corresponding optically active α-amino-acids or derived amino-alcohols (1), form complexes with primary alkyl-ammonium salts in non-polar solvents; enantiomer recognition in complex formation depends upon the substituents R3 on the ring nitrogen atoms.

The formation of complexes between aza-derivatives of crown ethers and primary alkylammonium salts. Part 6. Bis(mono-aza)crown ethers

The bis mono-aza-crown ethers (4) form 2 : 1 (G : H ratio) complexes with benzylammonium thiocyanate. In the case of the mono-aza-15-crown-5-derivatves (4a–g) the complexes have cis,cis-stereochemistry (10) but the 2 : 1 complexes of the mono-aza-18-crown-6 derivatives (4h–m) are mixtures of the cis,cis-(10), cis,trans-(11), and trans,trans-(12) isomers. The host molecules (4a–f) form 1 : 1 complexes with the bis(primary alkylammonium)thiocyanate (14); in the cases of (4a) and (4b) only a well-defined intramolecular complex (16) is formed but in the other cases both intramolecular and intermolecular (polymeric) complexes are formed. Hosts (4h–j) also form intramolecular complexes, with probably an increasing proportion of intermolecular complex as the distance between the macrocycles increases.

The formation of complexes between aza-derivatives of crown ethers and primary alkylammonium salts. Part 5. Chiral macrocyclic diamines

Syntheses of three types of chiral macrocyclic diamines, analogous to crown ethers, are described. The chirality of these systems is based, in one case, upon the plane of chirality of paracyclophane systems and, in the other two cases, upon the axis of chirality of bridged biphenyls. Two methods are described for the measurement of chiral selectivity in the formation of complexes between these chiral macrocyclic host molecules and chiral guest primary alkylammonium salts. Both methods use n.m.r. Spectrometry, a single-phase system, a racemic chiral host and (R)- and (RS)-guest salts. The first method is suitable for both optically labile and optically stable hosts and the second method is only suitable for optically labile host species.

The formation of complexes between aza derivatives of crown ethers and primary alkylammonium salts. Part 1. Monoaza derivatives

The monoaza derivatives of crown ethers form complexes with primary alkylammonium thiocyanates analogous to those formed by the crown ethers. The n.m.r. spectra of the complexes show temperature dependence which can be analysed in terms of various types of guest exchange processes and conformational changes of the host molecules. In particular, rapid conformational changes of the host macrocycle, accompanied by changes in hydrogen bonding to the guest cation, can occur without dissociation of the complex. The complexes of the monoaza 15-crown-5 analogues involve only a single face of the host macrocycle, and the substituent on the host nitrogen atom and the guest molecule are syn-related in the complex. The monoaza 18-crown-6 analogues form two diastereomeric complexes, having syn- and anti-relationships between the guest molecule and the substituent on the nitrogen atom of the host.

The formation of complexes between aza-derivatives of crown ethers and primary alkylammonium salts. Part 3. Monobenzo-derivatives of diaza-analogues and diazametacyclophanes

The diaza-analogues of crown ethers (3b and e–g) form complexes with primary alkylammonium thiocyanates in non-polar solvents in which the binding energy is comparable with that found for the complexes of the analogous host molecules lacking the fused benzene ring substituent. These relative binding energies are based upon a kinetic method using n.m.r. line-shape techniques. The host molecule (6b) forms complexes with primary alkylammonium thiocyanates in which guest–host binding energy is significantly greater than for the [12] metacyclophane derivatives (3).

The formation of complexes between aza-derivatives of crown ethers and primary alkylammonium salts. Part 2. Diaza-derivatives of metacyclophanes

The diazametacyclophanes (6) and the derivatives (15) have been synthesised and the formation of complexes between these host macrocycles and guest primary alkylammonium salts in CD2Cl2 has been examined using n.m.r. line-shape methods. In general the strengths of the complexes for any particular guest are in the order (6b) > (6c)(6a). A detailed examination of the complexes of (6b) shows that binding is affected adversely by steric interactions between guest and host, by the presence of certain additional functional groups in the guest cation, and by the lack of lipophilic shielding of the guest NH3 group. Complex formation by the derivatives (15) is affected by the side chains containing functional groups, and in some cases the binding energy is significantly increased relative to complex formation by the diazametacyclophane (6b).

Formation of complexes between aza derivatives of crown ethers and primary alkylammonium salts. Part 4. Diaza-18-crown-6 derivatives

Diaza analogues of 18-crown-6 (7b) and (10b), benzo-18-crown-6 (8b), and dibenzo-18-crown-6 (9b) form strong complexes in methylene chloride with primary alkylammonium thiocyanates. The n.m.r. spectra of these complexes show temperature dependence which can be explained in the terms of different types of guest exchange processes. The complexes of the dibenzo-18-crown-6 analogue (9b) appear to exist in one form only but the spectra of the complexes of the other 18-crown-6 analogues (7b), (8b), and (10b) indicate that two or more different types of complex are in equilibrium. The possible nature of these closely related but different species is discussed.

Complexes of primary alkylammonium salts and secondary dialkylammonium salts with diazaparacyclophanes

Complexes of primary alkylammonium salts and secondary dialkylammonium salts with diazaparacyclophanes