- 3 -
The synthesis of the thiol firstly requiresthe synthesis of the analogous bromo compound2-(7-bromoheptyl)-9-methyl-1,10-phenanthroline(Figure 4).
Figure 4. 2-(7-bromoheptyl)-9-methyl-1,10- phenanthroline
The synthesised thiol will then be testedfor complexation with a range of metal ions insolution by recording SERRS spectra. A noticeableenhancement or change from the spectrum of theblank thiol is good evidence for complexation, andfurther SERRS spectra will be recorded of promising thiol-metal combinations with a view toinvestigating the suitability of the technique for thedetection of small amounts of that metal ion.
Lithium diisopropylamide 2.0 M in cyclohexane(LDA; Aldrich), 2,9-dimethyl-1,10-phenanthroline
(Aldrich) and 1,6-dibromohexane (Aldrich) wereused as received without further purificationLaboratory grade solvents were used unlessotherwise specified. Dry tetrahydrofuran wasobtained by distillation under N
from sodium withbenzophenone as indicator.
H NMR spectra were recorded on a Bruker DPX300 and DRX500 using the solvent as an internalreference. Raman spectra were recorded on aRamanStation (Avalon Instruments). CHN analysisand E.I mass spectroscopy were performed byA.S.E.P., The School of Chemistry, The Queen'sUniversity of Belfast.
Synthesis of 2-(7-bromoheptyl)-9-methyl-1,10- phenanthroline
2,9-dimethyl-1,10-phenanthroline (0.500g, 2.401 mmol) was added to dry tetrahydrofuran(20 ml) under a nitrogen atmosphere and cooled to-78 °C. Lithium diisopropylamide (1.60 ml, 1.8 M,2.882 mmol) was added dropwise and the mixturestirred for 2 hours. After this time, 1,6-dibromohexane (5.828 g, 24.01 mmol) was addedquickly to the mixture, and stirred for a further 20hours. Water (3 ml) was added to the mixture(turning it from brown to bright yellow in colour),and the mixture removed from the nitrogenatmosphere. The crude product was extracted usingdichloromethane (2 x 10 ml). The organic layerswere combined and dried over anhydrousmagnesium sulfate. The mixture was thenevaporated at 40
C.The mixture was separated using flashchromatography with a 6:4:1 petroleum ether:ethyl acetate : triethylamine eluent. Fractions wereanalysed by thin layer chromatography (TLC). Thefractions identified as the required monobromoproduct were combined and evaporated to leave adark yellow liquid.Yield 296 mg; 33.2%.
): 8.12–8.15 (2H, m, H
), 7.71 (2H, s, H
), 7.52 (2H, m, H
), 7.27 (CHCl
), 3.42 (7H,m,
impurity from 1,6-dibromohexane
), 3.27 (2H,m, H
), 2.95 (3H
), 2.18 (25H
),1.88 (9H, m, H
), 1.65 (6H, s,
m, includes H
). Rf of required fractions 0.6-0.8 using 6:4:1 petroleumether: ethyl acetate : triethylamine solvent.
Synthesis of 7-(9-methyl-1,10-phenanthrolin-2- yl)heptane-1-thiol
The substance prepared above (thought to be2-(7-bromoheptyl)-9-methyl-1,10-phenanthroline)(0.2960 g, 0.797 mmol) was placed in a roundbottomed flask equipped with stirrer andcondenser. Ethanol (10 ml) and thiourea (0.0631 g,0.797) was added to the flask and the mixturestirred and heated under reflux for 20 hours. Themixture was cooled to room temperature andpotassium hydroxide solution (1.43 M, (0.08 gpellet dissolved in 1 cm
water)) was added. Theresulting mixture was heated under reflux for 2hours. The organic layer was separated andretained. The remaining aqueous layer wasacidified with sulfuric acid (0.6 cm
, 2M) and thenextracted with hexane (2 x 10 cm
). The organic
HHH HHHabcd e