Host behaviour of related compounds, TETROL and DMT, in the presence of two different classes of aromatic guest compounds

Barton, Benita; Jager, Lize de; Dorfling, Sasha-Lee; Hosten, Eric C.; McCleland, Cedric W.; Pohl, Pieter L.

doi:10.1016/j.tet.2018.07.044

Cited by 7 publications

(4 citation statements)

References 19 publications

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“…In fact, the three complexes are isostructural with nearly identical unit cell axes lengths and angles. Remarkably, H2 only ever crystallized with the same host packing irrespective of whether the guests were xylenes and ethylbenzene, 2 anilines and N-methylated anilines, 20 toluidines, 21 alkylbenzenes, 22 nitroaromatics, 23 and anisoles. 24 The unit cell for these inclusion compounds is provided in Fig.…”

Section: Single Crystal X-ray Diffraction (Scxrd) Experimentsmentioning

confidence: 99%

An investigation of the selectivity behaviour of host compound (R,R)-(−)-2,3-dimethoxy-1,1,4,4-tetraphenylbutane-1,4-diol in mixed cresols

2023

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Section: Single Crystal X-ray Diffraction (Scxrd) Experimentsmentioning

confidence: 99%

An investigation of the selectivity behaviour of host compound (R,R)-(−)-2,3-dimethoxy-1,1,4,4-tetraphenylbutane-1,4-diol in mixed cresols

2023

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“…A comparison of these results with the observations made with host compounds from previous investigations, − ((2 R ,3 R )-(−)-2,3-dimethoxy-1,1,4,4-tetraphenylbutane-1,4-diol (DMT), N , N’ -bis(9-phenyl-9-thioxanthenyl)ethylenediamine, trans-N , N’ -bis(9-phenyl-9-xanthenyl)cyclohexane-1,4-diamine, trans-N , N’ -bis(9-phenyl-9-thioxanthenyl)cyclohexane-1,4-diamine, trans-N , N’ -bis(9-phenyl-9-xanthenyl)cyclohexane-1,2-diamine, and trans-N , N’ -bis(9-phenyl-9-thioxanthenyl)cyclohexane-1,2-diamine), showed that, indeed, the structure of the host compound has a profound effect on the host selectivity behavior: while CUM was never a preferred guest in the present investigation, this guest was preferentially enclathrated by trans-N , N’ -bis(9-phenyl-9-xanthenyl)cyclohexane-1,2-diamine.…”

Section: Resultsmentioning

confidence: 51%

“…It was noted that different host compounds oftentimes possessed different affinities in such mixtures. For example, the tartaric acid host derivative, (2 R ,3 R )-(−)-2,3-dimethoxy-1,1,4,4-tetraphenylbutane-1,4-diol (DMT), usually selected EB, while N , N’ -bis(9-phenyl-9-thioxanthenyl)ethylenediamine was overwhelmingly in favor of TOL; related host compounds trans-N , N ′-bis(9-phenyl-9-xanthenyl)cyclohexane-1,4-diamine, trans-N , N′ -bis(9-phenyl-9-thioxanthenyl)cyclohexane-1,4-diamine, trans-N , N′ -bis(9-phenyl-9-xanthenyl)cyclohexane-1,2-diamine, and trans-N , N′ -bis(9-phenyl-9-thioxanthenyl)cyclohexane-1,2-diamine behaved complementarily, the first of these favoring CUM, the second and third TOL, and the last EB . In the present investigation, we presented the four host compounds with mixtures of these guests and report on our findings now.…”

Section: Introductionmentioning

confidence: 99%

Crystal Growth of Host Compound DED and Derivatives in Alkylbenzenes

Barton,

Caira,

Senekal

et al. 2024

Crystal Growth & Design

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Crystal growth of host compound trans-9,10-dihydro-9,10-ethanoanthracene-11,12-dicarboxylic acid (H1, DED) and three derivatives thereof (H2–H4) from potential guest solvents toluene (TOL), ethylbenzene (EB), and cumene (CUM) revealed that each one has the ability to enclathrate one, some, or all of these guest species. In equimolar TOL/CUM mixtures, H4 displayed an increased affinity for TOL (86.1%) compared with H2 (62.4%), while these selectivities for this guest species were only moderate when crystallization was from the equimolar mixed ternary guests (56.9 and 51.1%, respectively). H1 and H3, on the other hand, formed a mixed complex only in the equimolar TOL/EB solution, the remaining experiments furnishing a guest-free apohost compound only. Importantly, since various procedures in the industry yield mixtures of these alkylbenzenes, H4 was shown to be a likely candidate for the separation of both TOL from the TOL/CUM and EB from EB/CUM mixtures (the averaged selectivity coefficients, K, were high, 13.7 and 12.1, respectively). SCXRD experiments showed that EB in 3H3·EB experienced a significantly shorter (host)C–H···π(guest) interaction (2.50 Å) than TOL in its complex with H3 (2.87, 2.66 Å), in accordance with the higher affinity of H3 for EB relative to that for TOL. The H4·TOL and H4·EB complexes experienced analogous host···host interactions, but host···guest contacts could not be compared since the SQUEEZE function in PLATON was required during the refinement of the crystal structure of H4·EB to deal with severe guest disorder. Thermal analyses showed that the preferred guest of H3 (EB) formed a complex with a greater relative thermal stability compared with less favored TOL. Finally, this investigation has shown that the size of the alkyl group bonded to the aromatic ring of the guest species affects the selectivity behavior of each host compound. CUM, which has the largest alkyl substituent of the three guest species, was not ever preferred by any of the four host compounds investigated here.

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“…(+)-(2 R ,3 R )-1,1,4,4-Tetraphenylbutane-1,2,3,4-tetraol (TETROL, Scheme ), a host compound that only possesses temporary interstitial cavities in the presence of the guest compound and only in the solid state (hence known as a clathrand , with its complexes termed as clathrates ) has demonstrated rich host–guest chemistry in ongoing investigations in our laboratory. This tartaric acid-derived compound displayed selectivity when crystallized from mixed pyridines, cyclohexanones, − alkyl aromatics and anilines (both C - and N -alkylated), − and both saturated and unsaturated six-membered heterocyclic compounds . In the present work, we have considered the behavior of TETROL as a host compound in the presence of potential guests γ-butyrolactone (GBL), 2-pyrrolidone (NP), N -methyl-2-pyrrolidone (NMP), and N -ethyl-2-pyrrolidone (NEP) (Scheme ), which are important organic solvents and also find application in both drug actives and drug formulations.…”

Section: Introductionmentioning

confidence: 99%

Host Ability of (+)-(2R,3R)-1,1,4,4-Tetraphenylbutane-1,2,3,4-tetraol (TETROL) in the Presence of γ-Butyrolactone-, 2-Pyrrolidone-, and N-Alkyl-substituted 2-Pyrrolidones

Barton,

Caira,

Adam

et al. 2023

Crystal Growth & Design

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In the present work, (+)-(2R,3R)-1,1,4,4-tetraphenylbutane-1,2,3,4-tetraol (TETROL) was assessed for its host ability in γ-butyrolactone (GBL), 2-pyrrolidone (NP), N-methyl-2-pyrrolidone (NMP), N-ethyl-2-pyrrolidone (NEP), and mixtures of these. These compounds are often present as mixtures in the synthesis of NMP and NEP. TETROL formed crystalline inclusion compounds with each compound, with the exception of GBL, which was not enclathrated. In mixed guests, TETROL was revealed to behave extremely selectively, especially when these mixtures were binary and equimolar in nature and had present GBL; GBL/NP, GBL/NMP and GBL/NEP furnished crystals with 93.8%, 84.8%, and 93.2% NP, NMP, and NEP, respectively. The ternary equimolar mixture, GBL/NP/NEP, also saw TETROL absorb significant amounts of NEP (89.9%). In these particular cases, TETROL may therefore serve as an ideal separatory agent for such mixtures. Data from single crystal X-ray diffraction (SCXRD) analyses revealed the H-bonding motifs present in all of these crystal structures . Hirshfeld surfaces and guest packing in the voids of the complexes were, furthermore, analyzed, and thermal experiments were also carried out; the peak temperature of the endotherm for the guest release process for the NMPcontaining complex (the favored guest) was greater than those in the remaining two complexes.

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Host behaviour of related compounds, TETROL and DMT, in the presence of two different classes of aromatic guest compounds

Cited by 7 publications

References 19 publications

An investigation of the selectivity behaviour of host compound (R,R)-(−)-2,3-dimethoxy-1,1,4,4-tetraphenylbutane-1,4-diol in mixed cresols

An investigation of the selectivity behaviour of host compound (R,R)-(−)-2,3-dimethoxy-1,1,4,4-tetraphenylbutane-1,4-diol in mixed cresols

Crystal Growth of Host Compound DED and Derivatives in Alkylbenzenes

Host Ability of (+)-(2R,3R)-1,1,4,4-Tetraphenylbutane-1,2,3,4-tetraol (TETROL) in the Presence of γ-Butyrolactone-, 2-Pyrrolidone-, and N-Alkyl-substituted 2-Pyrrolidones

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