Synthesis and Characterization of a New Organoselenium and Organotellurium Compounds Depending on 9-Chloro-10-Nitro-9,10-Dihydroanthracene
Wiaam M. Ahmed1, NuhaH. Al-Saadawy2, Mohammed I. Abowd3
1,2,3
Department of Chemistry, College of Science, University of Thi-Qar, Thi-Qar, Iraq.
[email protected] , [email protected], [email protected]
Abstract
The present work refers to the preparation of novel organoselenocyanate and organotellurocyanate that occurs in two reaction steps: the first one is the synthesis of potassium selenocyanate and potassium tellurocyanate obtained by the reaction of selenium and tellurium metal with potassium cyanide in dimethyl sulphoxide as a solvent under nitrogen gas of interest. The second one is the synthesis of selenocyanate and tellurocyanate derivatives which is from the reaction between the synthesized potassium selenocyanate and potassium tellurocyanate and 9-chloro-10-nitro-9,10- dihydroanthracene. all the compounds were characterized by 1-H NMR, infrared (IR), and mass spectroscopy (MS).
Keywords: organoselenium, organotellurium , selenium metal,tellurium metal , anthracene and sodium cyanide
Introduction
Organic synthesis, materials science, food chemistry, medical chemistry, and biology all benefit from organoselenium and organotellurium compounds1.Since Sharpless' seminal research on the ring opening reaction of epoxides with selenium nucleophiles in 19732, the use of chalcogens in nucleophilic ring opening reactions (NRORs) has piqued chemists' interest3.A variety of procedures for transforming strained heterocycles into functionalized valuable chalcogen-containing molecules, such as b-hydroxy-, b-aminoselenides, and tellurides, have been developed based on this foundation4.A number of chalcogen-mediated functional-group transformations have also been identified and used in organic synthesis and organocatalysis. For the production of b-hydroxy and b-amino chalcogenides, NRORs of epoxides and aziridines are the preferred process.These important compounds are versatile reagents with a wide range of applications in organic synthesis due to their ability to selectively functionalize the carbon–chalcogen bond.Complete synthesis of lycorine,5 (-)-galanthamine, 6(+)-7- deoxypancratistatin7, and plumisclerin8, for example, all have a selenium-mediated ring opening reaction as a main phase.Furthermore, functionalized organoselenides and organotellurides are effective drug candidates with potential uses in medicinal chemistry due to their biological properties9.The current range of ring-opening reactions for the synthesis of functionalised
11036 organoselenium and organotellurium compounds is reviewed in this Perspective.
2. EXPERIMENTAL
2.1 Chemicals and Apparatus
Chemicals acquired from Sigma-Aldrich, Fluka and BDH utilized without filtration. Liquefying point was dictated by utilizing open hairlike tube dissolving point mechanical assembly. 1H NMR spectra was recorded onBruker DRX System AL (500 MHz )with TMS as an inner reference utilizing DMSO- d6 dissolvable. Infra-red spectra were recorded with KBr circles utilizing a FT- IR spectrophotometer Shimadzu model 8400 S in reach 4000- 250 cm-1. Dissolving purposes of every single strong compound were resolved utilizing a MPS10 electrically warmed liquefying point mechanical assembly.
2.2 [9- nitro-10-selenocyanato-9-10-dihydroanthracene]:
Put in a round with two neck (0.005 mol, 0.44 g) of finely ground and dried selenium with (0.006 mol, 0.33 g) of finely ground and dried potassium cyanide, then add 15 mL of freshly distilled dimethyl sulfoxide and heat the mixture for one hour at a temperature of 100 ° C. In an inert atmosphere of nitrogen, then 15 ml of distilled dimethyl sulfoxide was added to the hot converter and then left to cool at room temperature where a pale yellow solution was added. Then (0.0056 mol, 1.33 g) of the compound (9-chloro-10-nitro-9, 10-dihydroanthracene) was added and repelled back under nitrogen for two hours at a temperature of 100 ° C. The solution was filtered while it was hot and left until it cooled to laboratory temperature. Then the filtrate was poured into a baker containing 250 ml of cold distilled water, and reddish-brown crystals were observed10. The solution was filtered to obtain crystals, then washed with distilled water and ethanol and recrystallized with ethanol. (The resulting weight was 0.8 g, the reaction yield was 47%, its melting point: 110-112 d)
2.3 [9- nitro-10-tellurocyanato-9-10-dihydroanthracene]:
Put in a round with two neck (0.005 mol, 0.63 g) of finely ground and dried tellurium with (0.006 mol, 0.33 g) of well ground and dried potassium cyanide, then add 15 mL of freshly distilled dimethyl sulfoxide and heat the mixture for one hour at 100 ° C in An inert atmosphere of nitrogen, then 15 ml of distilled dimethyl sulfoxide was added to the hot transformer and then left to cool at room temperature where a pale yellow solution was added. Then (0.0056 mol, 1.33 g) of the compound(9- chloro-10-nitro-9,10-dihydroanthracene) was added to it and rose back under nitrogen for two hours at a temperature of 100 ° C. The solution was filtered while it was hot and left until it cooled to the laboratory temperature. Then the filtrate was poured into a baker containing 250 ml of cold distilled water and the appearance of greenish-yellow crystals was observed11. The solution was filtered to obtain crystals, then washed with distilled water and ethanol and recrystallized with ethanol. (Yield weight 0.67 g, reaction yield 35%, melting point: 107-105 d)
Table (1) Physical data for organoselenium and organotrllurium compounds
No Molecular formula M.Wt Color m.p. C◦ Yield %
1 C15H10N2O2Se 329.21 Reddish brown 110-112D 47%
2 C15H10N2O2Te 377.85 Greenish yellow 105-107D 35%
3. RESULTS AND DISCUSSION
The compound 9-chloro-10-nitro-9,10-dihydroanthracene is formed by the reaction between anthracene and nitric acid, acetic acid then with hydrochloric acid 12, these step reaction gave a great yield of starting material. [9- nitro-10-selenocyanato-9-10-dihydroanthracene] and [9- nitro-10-tellurocyanato- 9-10-dihydroanthracene] have been obtained by reacting between 9-chloro-10-nitro-9,10- dihydroanthracene and potassium selenocyanate and potassium tellurocyanate respectively in DMSO under N2 gas, as shown in Scheme (1)
Scheme (1) preparation of compounds [9- nitro-10-selenocyanato-9-10-dihydroanthracene] and [9- nitro-10-tellurocyanato-9-10-dihydroanthracene]
The spectral measurements of 1HNMR for [9- nitro-10-selenocyanato-9-10-dihydroanthracene]as shown in Figure (1) and Table (2),showed Different bundles appear in the aromatic region extending between ( 7.68 – 9.01 ppm). Where there appeared multiple beams extending between (7.68 – 7.9 ppm) the integration of 8 protons belonging to the symmetric rings at the ends of the intermediate ring. He
11038 also showed beams extending between ( 8.21 – 8.3 ppm) and the integration of 2 protons belonging to the protons of the intermediate ring(13-14).
The spectral measurements of 1HNMR for [9- nitro-10-tellurocyanato-9-10-dihydroanthracene] as shown in Figure (2) and Table (2),showed Different bundles appear in the aromatic region extending between ( 7.68 – 9.01 ppm ). Where there appeared multiple beams extending between ( 7.68 – 7.95 ppm ) and the integration of 8 protons belonging to the symmetric rings at the ends of the intermediate ring. He also showed beams extending between ( 8.21 – 9.01ppm ) and the integration of 2 protons belonging to the protons of the intermediate ring(13-14).
Table (2) 1H NMR Spectral Data for Selected Compounds
Structure for comp. 1H NMR (DMSO-d6); TMS
= 0 ppm
1 7.68 - 7.95 (m, 8H, Ar-H);
8.21 – 9.01 (m, 2H,Alph-H)
2 7.68 – 7.95 (m, 8H, Ar-H);
8.21 – 9.01 (m, 2H,Alph - H);
Figure (1): 1H NMR spectrum for [9- nitro-10-selenocyanato-9-10-dihydroanthracene]
Figure (2): 1H NMR spectrum for [9- nitro-10-tellurocyanato-9-10-dihydroanthracene]
IR spectra for all compounds displayed common features in certain regions and characteristic bands in the fingerprint and other regions.IR spectra for all compounds displayed common features in certain regions and characteristic bands in the fingerprint and other regions.The IR spectra confirm the suggested structure for organoselenium compound(13-14).As shown in Figure (3) , Table (3). In the IR spectrum, we observe a clear beam at (1944 cm-1) respectively refer to C Ξ N(13-14), the appearance of a band at ( 1674cm-1) respectively indicated to C=C bond for, ,while the NO2 group shows a very clear band at (1513 cm-1), andthe C-N group shows a very clear band at (1162 cm-1), band appeared at (515 cm- 1)(13-14).respectively respectively for C - Se .
The IR spectra confirm the suggested structure for organotellurium compounds.(13-14).As shown in Figure (4) , Table (3). In the IR spectrum, we observe a clear beam at (2208 cm-1) respectively refer to C Ξ N (13-14).,the appearance of a band at ( 1584cm-1) respectively indicated to C=C bond for , ,while the NO2 group shows a very clear band at (1565 cm-1), and the C-N group shows a very clear band at (1166 cm-1) band appeared at (520 cm- 1)(13-14).respectively respectively for C - Te .
Table (3) FT - IR Spectral Data for Selected Compounds C≡N Aromatic
C=C
NO2 C-N C-Se
C-Te
1944 1674 1513 1162 515 __
2208 1584 1565 1166 __ 520
11040 Figure (3): IR spectrum for [9- nitro-10-selenocyanato-9-10-dihydroanthracene]
Figure (4): IR spectrum for [9- nitro-10-tellurocyanato-9-10-dihydroanthracene]
The mass spectrum of compound 9- nitro-10-selenocyanato-9-10-dihydroanthracene showed us the parent ion beam at 327 m/z , which represents the molecular weight of the compound, and the appearance of a relatively high abundance beam at 176 m/z belonging to group C10H11NO2•+
in addition to other packages.
The mass spectrum of compound 9- nitro-10-tellurocyanato-9-10-dihydroanthracene showed us the
parent ion beam at 377 m/z , which represents the molecular weight of the compound, and the appearance of a relatively high abundance beam at 80 m/z belonging to group C6H6•+ in addition to other packages.fragments shown as Figure (5), Figure (6), Scheme (2) and Scheme (3) respectively.
Figure (5): Mass spectrum for [9- nitro-10-selenocyanato-9-10-dihydroanthracene]
Figure (6): Mass spectrum for [9- nitro-10-tellurocyanato-9-10-dihydroanthracene]
11042
\
Scheme (2) mechanism for fragmentation for [9- nitro-10-selenocyanato-9-10-dihydroanthracene
Scheme (3) mechanism for fragmentation for [9- nitro-10-tellurocyanato-9-10- dihydroanthracene]
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