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Josephine Bicknell ; Sidhaesh A. Agarwal ; Kyle J. Petersen , et al. Cryst. Growth Des.,2024,24(12):5222-5230. DOI: 10.1021/acs.cgd.4c00457
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Abstract: Lipophilic aggregation using adamantanes is a widely exploited molecular property in medicinal and materials chemistry. Adamantanes are traditionally installed to molecular units via covalent bonds. However, the noncovalent installation of adamantanes has been relatively underexplored and presents the potential to bring properties associated with adamantanes to molecules without affecting their intrinsic properties (e.g., pharmacophores). Here, we systematically study a series of adamantanecarboxylic acids with varying substitution levels of methyl groups and their cocrystals with bipyridines. Specifically, single-crystal X-ray diffraction shows that while the directionality of single-component adamantanes is notably sensitive to changes in methyl substitution, hydrogen-bonded cocrystals with bipyridines show consistent and robust packing due to π-stacking predominance. Our observations are supported by Hirshfeld surface and energy framework analyses. The applicability of cocrystal formation of adamantanes bearing carboxylic acids was used to generate the first cocrystals of adapalene, an adamantane-bearing retinoid used for treating acne vulgaris. We envisage our study to inspire noncovalent (i.e., cocrystal) installation of adamantanes to generate lipophilic aggregation in multicomponent systems.
Purchased from AmBeed: 106685-40-9 ; 828-51-3 ; 14670-94-1 ; 2632-99-7 ; 4916-57-8 ; 15291-66-4
CAS No. : | 4916-57-8 | MDL No. : | MFCD00006451 |
Formula : | C12H12N2 | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | DQRKTVIJNCVZAX-UHFFFAOYSA-N |
M.W : | 184.24 | Pubchem ID : | 78630 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | |
Hazard Statements: | H315-H319-H335 | Packing Group: | |
GHS Pictogram: |
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* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
42% | With sodium hydroxide; In ethanol; water; at 130℃; for 72h;pH 5.5;Autoclave; | A mixture of Zn(NO3)36H2O (0.2 mmol) and H2mip (0.2 mmol)and bpe (0.2 mmol) were added to 10 ml H2O/EtOH (1:1 volumeratio). The pH value was adjusted to 5.5 with 1.0 mmol L1 NaOHsolution. It was then sealed in a 25 mL Teflon-lined stainless steelautoclave and heated at 130 C for 3 days and then slowly cooled toroom temperature. Colorless block crystals were collected by filtrationand washed with distilled water in 42percent yield based on bpe.Anal. Calcd. for C21H18N2O4Zn (percent): C, 58.96; H, 4.24; N, 6.55. Found(percent): C, 59.12; H, 4.39; N, 6.38. IR (KBr, cm1): 3392(s), 1612(s),1550(s), 1432(s), 1370(s), 1106(w), 726 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
A mixture of zinc perchlorate hexahydrate (0.1169 g, 0.3139 mmol), 2-thiophenepropionic acid (0.200 g, 1.2820 mmol), bpa (0.1031 g, 0.5603 mmol) water (30 mL) and ethanol (30 mL). This mixture was stirred for 30 min and stoichiometrically neutralized with sodium hydroxide. This solution was sealed in a polyfluoroethylene-lined stainless steel bomb, heated to 90 C in 6 h and kept at 90 C under autogenous pressure for 72 h. After cooling at a ramp of 0.77 C/h to room temperature, the solution was transferred to a beaker and then suitable single crystals were obtained after a few days and separated by filtration. Elemental analysis for compound 2: Anal. Calc: C25H25ClN3O6SZn: C, 50.35%; H, 4.23%; N, 7.05%. Found: C, 51.93%; H, 4.33%; N, 6.93%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
A mixture of 2-thiophenepropionic acid (0.0118 g,0.0756 mmol), bpa (0.0135 g, 0.0733 mmol) and of KOH (0.0029 g, 0.0517 mmol) was dissolved in ethanol (10 mL) and stirredfor 30 min resulting in a homogeneous colorless solution; tothis solution was added by slow diffusion 5 mL of an aqueous solutioncontaining zinc perchlorate hexahydrate (0.026 g,0.0698 mmol). Suitable single crystals were obtained after a fewdays and separated by filtration. Elemental analysis for compound3: Anal. Calc. C76H77Cl2N8O16S4Zn3: C, 52.05%; H, 4.43%; N, 6.39%.Found C, 52.01%; H, 4.35% N, 7.07%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | In water; at 80℃; for 72h;High pressure; Sealed tube; | CdSO4·8H2O (63 mg, 0.18 mmol), dpe (68 mg, 0.37 mmol) and tricarballylicacid (33 mg, 0.19 mmol) were placed into 5 mL distilled H2Oin a 15 mL screw-cap glass vial. The vial was sealed and heated in an oilbath at 80 C for 72 hrs, whereupon it was cooled slowly to 25 C.Colorless blocks of 1 (66 mg, 78% yield based on Cd) were isolated afterwashing with distilled water and acetone, and drying in air. Anal. Calc.for C36H36Cd2N4O12 1: C, 45.92; H, 3.85; N, 5.95% Found: C, 45.77; H,3.73; N, 5.89%. IR ( ): 3251 (w, br), 1702 (m), 1612 (m), 1579 (s),1426 (w), 1397 (s), 1312 (w), 1258 (w), 1226 (w), 1098 (w), 1018 (w),832 (m), 808 (w), 722 (w), 675 (w) cm-1. |
[ 30532-36-6 ]
3-(Pyridin-4-yl)propan-1-amine
Similarity: 0.91
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