GB2379930A - Crystalline Calixarene Compounds - Google Patents
Crystalline Calixarene Compounds Download PDFInfo
- Publication number
- GB2379930A GB2379930A GB0122846A GB0122846A GB2379930A GB 2379930 A GB2379930 A GB 2379930A GB 0122846 A GB0122846 A GB 0122846A GB 0122846 A GB0122846 A GB 0122846A GB 2379930 A GB2379930 A GB 2379930A
- Authority
- GB
- United Kingdom
- Prior art keywords
- crystalline material
- material according
- calixarene
- crystalline
- molecules
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical class COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000002178 crystalline material Substances 0.000 claims abstract description 22
- 239000013078 crystal Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 150000002678 macrocyclic compounds Chemical class 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000003466 anti-cipated effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- NHYXMAKLBXBVEO-UHFFFAOYSA-N bromomethyl acetate Chemical compound CC(=O)OCBr NHYXMAKLBXBVEO-UHFFFAOYSA-N 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000008863 intramolecular interaction Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000004492 methyl ester group Chemical group 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
- C07C69/708—Ethers
- C07C69/712—Ethers the hydroxy group of the ester being etherified with a hydroxy compound having the hydroxy group bound to a carbon atom of a six-membered aromatic ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J45/00—Ion-exchange in which a complex or a chelate is formed; Use of material as complex or chelate forming ion-exchangers; Treatment of material for improving the complex or chelate forming ion-exchange properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/20—Organic adsorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/30—Physical properties of adsorbents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A crystalline material comprising calixarene molecules wherein the molecules pack together to form a columnar structure thus defining a substantially tubular cavity in the crystal. The invention also provides a method of filtering a contaminated atmosphere comprising passing said atmosphere through the said crystalline material.
Description
<Desc/Clms Page number 1>
Novel calixarene structures The present invention relates to novel crystalline structures formed by calixarene molecules, particularly, but not exclusively those that may be used to filter fluidic atmospheres.
Calixarenes are cyclic molecules that often have an ability to chelate with certain metallic species, the exact structure of the calixarenes determining the preferred metallic species to be chelated. Like many organic compounds, calixarenes may be recrystallised to form various crystalline structures. The nature of the structure formed will depend on numerous factors such as, inter alia, the solvent used, the speed of recrystallisation, the molecular structure of the calixarene, any metallic species present and the presence of impurities. The properties of the resulting crystal will depend to a large extent on the structure of the crystal. The present invention provides a crystalline material having a particular structure of interest. According to the present invention, a crystalline material comprising calixarene molecules wherein the molecules pack together to form a columnar structure thus defining a substantially tubular cavity in the crystal. This provides a material that may remove unwanted species from a fluidic environment.
The columnar structures may pack together to form a hexagonal or rectangular lattice.
This forms a dense array of such tubular structures. The mean plane of the macrocycles may be approximately parallel to the hexagonal or rectangular lattice.
This maximises the effective diameter of the tubular cavity for the particular macrocycle used.
The crystalline structure may comprise 6n molecules in each unit cell, wherein n=l to 10. It is preferred that n=l to 4 and more preferred that n=3.
It is preferred that the tubular cavity has a mean diameter of greater than approximately 4 . Such a cavity allows capture and possible retention of certain chemical species.
<Desc/Clms Page number 2>
The long axis of the tubular cavity may be substantially parallel to one of the axes of the unit cell.
It is preferred that the crystalline material comprises a lattice that is trigonal on hexagonal, wherein a=1200, y=900 and c=lO-30 . Lattice parameter a may preferably be 10-50 .
It is preferred that the crystalline structure is formed in the absence of a metallic species.
It is also preferred that the crystalline structure comprises a calixarene of structure (1) :
In a second aspect of the invention, a method of filtering a contaminated atmosphere comprising passing said atmosphere through a crystalline material according to the present invention.
The present invention is described by way of example only with reference to the following figures of which: Figure 1 shows the chemical structure of a calixarene 1 that forms a crystalline structure in accordance with the present invention; Figure 2 shows the conformational structure of calixarene 1 in a crystalline structure in accordance with the present invention; and Figure 3 shows the supramolecular structure of 1 in a crystal in accordance with the present invention.
<Desc/Clms Page number 3>
Synthesis of 1 Calixarene 1 (see figure 1) was synthesised by the reaction ofcalix [4] arene with bromomethylacetate according to Aoki et al. (J. Chem. Soc. Chem. Commun., 1992, 9, 730-732).
Recrystallisation of 1 Calixarene 1 was recrystallised into a crystalline material in accordance with the present invention from a methanol/chlorofonn mixture.
Determination of structure of calixarene 1 The crystal structure of calixarene 1 in accordance with the present invention was determined using conventional x-ray diffraction apparatus and techniques. A Nonius Kappa CCD area detector diffractometer was used, with Mo K-a radiation (k = o 0. 71073 A). The cell parameters were extracted from 13396 reflections using the following parameters : 6=1. 02-30. 51 h=-42-33 k=-30-42 1=-17-18 adsorption correction using multi-scan SORTAU, Blessing (1997, J Appl. Cryst., 30, 421-429) Refinement R (F) =0. 0436 mR (P2) =0. 1136 s=1. 04 (ö./cr) max=0. 002 O q Apmax = 0. 243eA O q Ap=-0. 197eAextinction correction by SHELXL extinction co-efficient 0. 00040 (7) scattering factors from International Tables for Crystallography (Vol. C)
<Desc/Clms Page number 4>
Crystal structure Hexagonal lattice, a=32. 840 (5) , c=13. 918 (3) , a=90 , y=1200 V=13000 (4) 3 Z=18 Dx=1. 307Mg m-3 The structure of the crystalline material formed by calixarene 1 in accordance with the present invention is now described with reference to figures 2 and 3. The calixarene molecules pack together to form tubular, columnar structures. The tubular structures pack together in a hexagonal lattice as shown in Figure 3. It may be said the crystal structure is of a honeycomb in nature. Each tubular structure is formed by the stacking of three calixarenes one upon another, alternately offset by 60 , giving overall C3 symmetry. The three stacked molecules give a dimension c of 13. 9 ISA. The tubular orifice defined by the columnar packed calixarene molecules has an internal diameter of 4. 83 (9) . The driving force for the formation of this structure is probably the pi-pi stacking/interlocking between the calixarene rings and dipole-dipole interactions between the lower rim methyl ester groups. This is demonstrated by the head-to-tail arrangement of the carbonyl groups on the lower rim. The angles about the meso C atoms (C (l), C (8), C (17) and C (24) ) are reasonably close to ideal tetrahedral geometry indicating a macrocycle that is substantially strain-free. The upper rim of
calixarene 1 forms a cavity with separations between meso carbon atoms of 5. 067 (6), 5. 075 (6), 5. 079 (8) and 5. 070 (7) A. Cross-ring distances between meso carbon atoms are 7. 312 (7) and 7. 031 (6) A. The asymmetry of the macrocycle is caused by the lower rim substituents which form a number of intramolecular hydrogen bonds with each other. The angles of the aromatic rings with respect to the mean plane of the macrocycle (defined by the meso carbon atoms) are 71.70 (4) and 68.46 (3) for the alkyl ester functionalised rings whilst those for the hydroxyl substituted rings are 42.35 (4) and 37.86 (5) . Thus the hydroxyl substituted rings are allowed to lie more in the plane of the macrocycle due to their relatively small functional groups on their lower rims that due to the intramolecular interactions in which they are involved.
The pendant ester groups are locked in position by strong hydrogen bonding between the hydroxyl substituent and the oxy-linkage between the calixarene and the ester.
There is a further interaction between the carbonyl group of the ester and the hydroxyl
<Desc/Clms Page number 5>
substituent, making it a bifurcated donor. The relevant hydrogen bonding parameters are shown in Table 1 :
D-H...A D-H( ) H...A( ) D...A( ) Angle (DH... A) 01-HI... 06 0. 84 1. 92 2. 7262 (14) 159.9 05-H5A... 02 0. 84 1. 99 2. 7987 (15) 160.6 01-HIA... 07 0. 84 2. 88 3. 4142 (16) 123.7 05-H5A... 03 0. 84 2. 90 3. 4434 (16) 124. 3 Table 1-hydrogen bonding parameters for calixarene 1 in a crystal structure in accordance with the present invention It is anticipated that the crystalline structure of the present invention as illustrated by the structure formed by calixarene 1 will be useful in the removal of unwanted species from fluidic, particularly gaseous, atmospheres. It is anticipated that the tubular orifices formed by the calixarenes will be able to entrap the unwanted species and thus remove them from the fluid to be filtered.
It is anticipated that calixarenes having a molecular structure different from that of calixarene 1 will form similar structures having substantially tubular cavities therein.
Non-uptake of recrystallisation solvent is believed to be key in the formation of such structures.
Claims (14)
- Claims 1. A crystalline material comprising calixarene molecules wherein the molecules pack together to form a columnar structure thus defining a substantially tubular cavity in the crystal.
- 2. A crystalline material according to claim 1 wherein the columnar structures pack together to form a hexagonal or rectangular lattice.
- 3. A crystalline material according to claim 2 wherein the mean plane of the macrocycles are approximately parallel to the hexagonal or rectangular lattice.
- 4. A crystalline material according to any one preceding claim comprising 6n molecules in each unit cell, wherein n= 1 to 10.
- 5. A crystalline material according to claim 4 wherein n=l to 4.
- 6. A crystalline material according to claim 4 wherein n=3.
- 7. A crystalline material according to any one preceding claim wherein the tubular cavity has a mean diameter of greater than approximately 4 .
- 8. A crystalline material according to any one preceding claim wherein the long axis of the tubular cavity is substantially parallel to one of the axes of the unit cell.
- 9. A crystalline material according to any one preceding claim wherein the lattice istrigonal on hexagonal, wherein a=120 , y=90 and c=10-30A.
- 10. A crystalline material according to claim 9 wherein a= 1 0-50 .
- 11. A crystalline material according to any one preceding claim wherein the crystalline structure is formed in the absence of a metallic species.<Desc/Clms Page number 7>
- 12. A crystalline material according to any one preceding claim comprising a calixarene of structure (I) :
- 13. A crystalline material substantially as hereinbefore described with reference to figures 1,2 and 3.
- 14. A method of filtering a contaminated atmosphere comprising passing said atmosphere through a crystalline material according to any one preceding claim.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0122846A GB2379930B (en) | 2001-09-22 | 2001-09-22 | Novel calixarene structures |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0122846A GB2379930B (en) | 2001-09-22 | 2001-09-22 | Novel calixarene structures |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB0122846D0 GB0122846D0 (en) | 2001-11-14 |
| GB2379930A true GB2379930A (en) | 2003-03-26 |
| GB2379930B GB2379930B (en) | 2004-10-13 |
Family
ID=9922507
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB0122846A Expired - Fee Related GB2379930B (en) | 2001-09-22 | 2001-09-22 | Novel calixarene structures |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2379930B (en) |
-
2001
- 2001-09-22 GB GB0122846A patent/GB2379930B/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| J. Chem. Soc., Perkin Trans. 1 (1986), (2), 211-14 New metal cation-selective ionophores ISSN :0300-922X * |
Also Published As
| Publication number | Publication date |
|---|---|
| GB0122846D0 (en) | 2001-11-14 |
| GB2379930B (en) | 2004-10-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| ES2996282T3 (en) | Method for purifying reclaimed polypropylene | |
| ES2996258T3 (en) | Method for purifying reclaimed polyethylene | |
| Loiseau et al. | MIL-96, a porous aluminum trimesate 3D structure constructed from a hexagonal network of 18-membered rings and μ 3-oxo-centered trinuclear units | |
| ES2991913T3 (en) | Method to purify regenerated polymers | |
| Felder et al. | A liquid crystalline supramolecular complex of C60 with a cyclotriveratrylene derivative | |
| US7687432B2 (en) | Mesh-adjustable molecular sieve | |
| US11517878B2 (en) | Selective, adsorbate-induced spin state changes in transition metal-based metal-organic frameworks | |
| CN104370950B (en) | Triazole Cd(II) complex with two-dimensional planar porous framework structure and synthesis method and application thereof | |
| Fayad et al. | A Rational Approach to the Ionothermal Synthesis of an AlPO4 Molecular Sieve with an LTA‐Type Framework | |
| CN109718746A (en) | A kind of ultramicropore flexibility MOFs material ZnBD-SCUT and the preparation method and application thereof | |
| Gallagher et al. | Self inclusion in a calix [5] arene structure; structure of the cone conformer of a pentahydroxy-p-tert-butylcalix [5] arene | |
| GB2379930A (en) | Crystalline Calixarene Compounds | |
| Do et al. | Syntheses of heterotetranuclear metallocarboranes containing a planar M2Cu2 (M= Mo, W) rhomb and BH-Cu bridges: structure of [Mo2Cu2 (. mu.-CO) 4 (CO) 2 (. mu.-H) 2 (C2B9H10) 2] 2 | |
| Wheatley et al. | Cyclam as a structure-directing agent in the crystallization of aluminophosphate open framework materials from fluoride media | |
| Halouani et al. | Synthesis, conformations and extraction properties of new chromogenic calix [4] arene amide derivatives | |
| Che et al. | Eco-friendly synthesis of kaolin-based chabazite for CO2 capture | |
| Adams et al. | Cleavage of metal-metal bonds in heteronuclear clusters. The reaction of Os3 (. mu. 3-S)(. mu. 3-. eta. 2-SCH2)(CO) 8PMe2Ph with Me3SnH and the crystal and molecular structures of HOs3 (. mu. 3-S)(. mu. 3-. eta. 2-SCH2)(CO) 7 (PMe2Ph)(SnMe3) and H2Os3 (. mu. 3-S)(. mu. 3-. eta. 2-SCH2)(CO) 7 (PMe2Ph) | |
| Wang et al. | Synthesis and characterization of two new organically templated indium phosphites built from one-dimensional ladders | |
| Takjoo et al. | Effect of solvents in mixed-ligand supramolecular self-assembly architectures | |
| Zhang et al. | Stable hydrogen-bonded spherical capsules formed from self-assembly of pyrogallol [4] arenes | |
| Burrows et al. | The synthesis and structural characterization of a penta-palladium cluster,[Pd5 (μ-SO2) 3 (μ-CNXyl) 2 (CNXyl) 5], with linear bridging isocyanide ligands | |
| US4960745A (en) | Layered aluminum compounds containing phosphorus or arsenic and pendant organic groups | |
| Hill et al. | The synthesis of high cobalt-containing CoAPO-34 | |
| Hamada et al. | Channel structure for guest inclusion based on hexameric assembly of thiacalix [4] arene analogue | |
| Bret et al. | Nuclear quadrupole resonance of several copper (I) complexes with heterocyclic thioamido ligands. Crystal structure of chlorobis [tetrahydro-1 H-pyrimidine-2-thione] copper (I) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 20130922 |