An Efficient Method for Selective Syntheses of Sodium Selenide and Dialkyl Selenides
Abstract
:1. Introduction
2. Results and Discussion
2.1. Optimization for the Reaction Conditions
2.2. Reaction Pathways
2.3. Synthesis of Dialkyl Selenides 1
2.4. Solvent Studies
3. Experimental
3.1. General
3.2. General Procedure for the Synthesis of Dialkyl Monoselenides 1
3.2.1. 1,2-Dibenzyl Selenide (1a) [2]
3.2.2. 1,2-Bis(2-phenylethyl) Selenide (1b) [2]
3.2.3. 1,2-Diallyl Selenide (1c) [22]
3.2.4. 1,2-Di-n-butyl Selenide (1d) [19]
3.2.5. 1,2-Di-n-pentyl Selenide (1e) [2]
3.2.6. 1,2-Di-n-hexyl Selenide (1f) [19]
3.2.7. 1,2-Di-n-octyl Selenide (1g) [23]
3.2.8. 1,2-Di-c-pentyl Selenide (1h) [24]
3.2.9. 1,2-Di-c-hexyl Selenide (1i) [25]
3.2.10. 1,2-Bis(3-pentyl) Selenide (1j) [22]
3.2.11. 1,2-Bis(4-heptyl) Selenide (1k)
3.2.12. 1,3-Dihydrobenzo[c]Selenophene (1l) [26]
3.2.13. Tetrahydro-3,4-Selenophenediol (1m) [27]
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
Sample Availability
References
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Entry | Na2Se Formation | 1a Formation (Reaction with BnBr) | Product | Side Product | |
---|---|---|---|---|---|
NaBH4 (eq) | Time (h) | Time (h) | 1a Yield b (%) | 2a Yield b (%) | |
1 | 1.0 | 1 | 2 | 25 | 40 |
2 | 1.5 | 1 | 2 | 27 | 40 |
3 | 2.0 | 0.5 | 1 | 59 | 8 |
4 | 1 | 2 | 44 | 34 | |
5 | 2 | 2 | 49 | 25 | |
6 | 4 | 2 | 28 | 56 | |
7 | 8 | 2 | c | 34 | |
8 | 3.0 | 0.5 | 1 | 80 | c |
9 | 1 | 2 | 87 | 2 | |
10 | 2 | 2 | 76 | c | |
11 | 4 | 2 | 79 | c | |
12 | 8 | 2 | 80 | c |
Entry | Reaction with RX | Product | Yields (%) | |||
---|---|---|---|---|---|---|
RX | RX (eq) | Time (h) | Temp (°C) | |||
1 b | BnBr | 2.4 | 2 | rt | 87 | |
2 | PhCH2CHBr | 2.4 | 5 | rt | 66 | |
3 | allylBr | 2.4 | 25 | rt | 66 | |
4 | n-BuBr | 2.4 | 3 | rt | n-Bu–Se-Bu-n1d | 93 |
5 | n-PenBr | 2.4 | 3 | rt | n-Pen–Se-Pen-n1e | 82 |
6 | n-HexBr | 2.4 | 5 | rt | n-Hex–Se-Hex-n1f | 85 |
7 | n-OctBr | 2.4 | 5 | rt | n-Oct–Se-Oct-n1g | 85 |
8 | 2.4 | 3 | 50 | 50 | ||
9 | 2.4 | 8 | 50 | 48 | ||
10 | 2.4 | 5 | 50 | 31 | ||
11 | 2.4 | 25 | 50 | 35 | ||
12 b | 1.0 | 24 | rt | 65 | ||
13 b | 1.0 | 48 | rt | 51 |
Entry | Na2Se Formation | Reaction with BnBr | Product | Side Product | ||
---|---|---|---|---|---|---|
Solvent | Temp (°C) | Time (h) | Time (h) | 1a Yields b (%) | 2a Yields b (%) | |
1 | H2O-THF | 25 | 1 | 2 | 87 | 2 |
2 | EtOH | 25 | 1 | 2 | 81 | c |
3 | MeCN | 25 | 2 | 2 | 80 | c |
4 | THF | 50 | 1 | 48 | 50 | c |
5 | DME | 25 | 1 | 47 | 30 | 22 |
Entry | RX | Product | Yields (%) b | |
---|---|---|---|---|
Solvent (H2O-THF) | Solvent (MeCN) | |||
1 | BnBr | 87% | 80% | |
2 | BnCl | 79% | 70% | |
3 | PhCH2CH2Br | 66% | 20% | |
4 | PhCH2CH2Cl | 32% | 38% | |
5 | n-HexBr | n-Hex–Se-Hex-n | 85% | 63% |
6 | n-HexCl | 21% | 21% | |
7 | n-OctBr | n-Oct–Se-Oct-n | 85% | 56% |
8 | n-OctCl | 24% | 21% | |
9 | c-HexBr | 48% | 24% | |
10 | c-HexCl | 3% | c % |
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Shin, N.H.; Lim, Y.J.; Kim, C.; Kim, Y.E.; Jeong, Y.R.; Cho, H.; Park, M.-S.; Lee, S.H. An Efficient Method for Selective Syntheses of Sodium Selenide and Dialkyl Selenides. Molecules 2022, 27, 5224. https://doi.org/10.3390/molecules27165224
Shin NH, Lim YJ, Kim C, Kim YE, Jeong YR, Cho H, Park M-S, Lee SH. An Efficient Method for Selective Syntheses of Sodium Selenide and Dialkyl Selenides. Molecules. 2022; 27(16):5224. https://doi.org/10.3390/molecules27165224
Chicago/Turabian StyleShin, Na Hye, Yoo Jin Lim, Chorong Kim, Ye Eun Kim, Yu Ra Jeong, Hyunsung Cho, Myung-Sook Park, and Sang Hyup Lee. 2022. "An Efficient Method for Selective Syntheses of Sodium Selenide and Dialkyl Selenides" Molecules 27, no. 16: 5224. https://doi.org/10.3390/molecules27165224