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DOI: 10.1055/a-1730-8186
Room Temperature, Metal-Free, Regioselective Arylselenation of Anilines Using Diselenides as Selenium Source
The Council of Scientific and Industrial Research [No. 02(0341)/18/EMR-II] and SERB-DST, New Delhi (CRG/2020/003634).
This work is dedicated to Professor Deevi Basavaiah (University of Hyderabad) on his 71st birthday.
Abstract
A metal-free direct C–H selenation of aniline derivatives via an iodine-catalyzed C–Se bond formation using diselenides as a selenium source at ambient temperature is described. A variety of aniline derivatives underwent regioselective C–H selenation with different diselenides to afford the corresponding aryl selenoethers in good to excellent yields.
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Recent years have witnessed an exponential growth in the development of green, sustainable, and metal-free organic transformation for carbon–carbon and carbon–heteroatom bond constructions.[1] A variety of catalytic systems such as oxidant catalysis, photocatalysis, and electrocatalysis have significantly substituted the traditional transition metal catalysis.[2] Meanwhile, due to versatile applications in the area of chemical biology,[3] asymmetric catalysis,[4] [5] cross-coupling reactions,[6] organic synthesis,[7–9] materials science,[10] and natural products,[11] the preparation of the organoselenium frameworks has attracted much attention of synthetic and medicinal chemists in recent years.
Although several synthetic protocols have been developed for the construction of C–Se bonds using different catalytic systems and selenium surrogates, the transition-metal-catalyzed aryl–selenium bond construction is still one of the most conventional, common methods.[12] Moreover, the C–Se bond formation between aniline derivatives and diselenides under sustainable conditions is less explored. A copper-catalyzed arylselenation of anilines via C–H bond cleavage followed by C–Se bond formation using diselenides as selenide source was reported by Alves and co-workers (Path A, Scheme [1]).[13] Fang et al. have developed a FeF3/I2-catalyzed C–Se bond formation between aryl amines and diselenides (Path B, Scheme [1]).[14] In both these cases, higher temperature, namely 110 and 80 °C, respectively, is required for the reaction to happen. A microwave-assisted C–Se bond formation between aniline and diselenide was reported by Braga and co-workers (Path C, Scheme [1]).[15] Thurow et al. have reported a metal- and base-free synthesis of arylselanyl anilines in glycerol by using anilines and arylselanyl chlorides as reaction partners.[16] Ranu and co-workers[17] have reported a visible light photocatalyzed C–Se bond formation between anilines and diselenides in the presence of t BuONO using eosin Y as photocatalyst providing diaryl selenides (Path D, Scheme [1]). Simultaneously, Lee and co-workers[18] have also performed the same reaction under the influence of t BuONO without any photocatalyst. However, in both the Ranu and Lee conditions amino functionality was removed. Zhou et al. have developed a KI-mediated C–Se bond formation on aniline framework using SeO2 as selenium source and aryl boronic acids as aryl counterpart (Path E, Scheme [1]).[19] Zhou and He have reported iodine-catalyzed regioselective arylselenation of N,N-disubstituted aniline derivatives using diaryl selenides as selenium source (Path F, Scheme [1]).[20] As per our long-term plan to develop metal-free organic synthetic protocols,[21] we herein report a metal-free, iodine-catalyzed regioselective C–Se bond formation between anilines and diselenides.
a Reaction conditions: Aniline (1a; 2.0 mmol), diphenyl diselenide (2a; 0.5 mmol), and I2 were reacted in the presence of 4 Å molecular sieves (100 mg) in solvent (3.0 mL) in open air.
b Isolated yields based on 2a. NR: No reaction.
For optimization, we chose aniline (1a; 2.0 mmol) and diphenyl diselenide (2a; 0.5 mmol) as model substrates (Table [1]). Initially, the reaction between 1a and 2a was carried out under the influence of I2 (1.0 mmol) in the presence of 4 Å molecular sieves using DMSO + DMF solvent system at 120 °C, which after 6 hours afforded the desired product 3a in 50% yield (Table [1], entry 1). When we switched to water as a solvent, 48% of 3a was obtained (entry 2). Lowering the reaction temperature resulted into the enhancement of yield of 3a (entries 3–5). MeCN as solvent could not provide superior results (entry 6). Lowering the amount of I2 diminished the yield of 3a (entries 7–9). Based on our previous experience,[21a] [b] reaction was also performed on silica gel at room temperature, which provided 60% of 3a (entry 10). TBAI as catalyst could not yield the desired product 3a (entry 11). No product formation was observed under catalyst-free conditions (entry 12). Low yield was obtained under solvent-free conditions (entry 13). Increasing the amount of I2 from 1.0 to 2.0 mmol at room temperature provided the 98% of 3a after 1 hour, hence considered as optimized reaction conditions (entry 14).
With the optimized reaction conditions (Table [1], entry 14) in hand, first, we employed aniline (1a) and o-substituted anilines 1b–e for regioselective monoselenation using a variety of diselenides 2 under the influence of I2 to provide the desired para-selenoethers 3b–p in 14–95% yields (Table [2]). Diaryl diselenide possessing different substrates were well tolerated under the reaction conditions employed. However, no monoselenation products were obtained when the reaction was performed using dialkyl diselenides and the aniline got converted into corresponding iodoanilines.
a Aniline 1 (2 mmol), diselenide 2 (0.50 mmol), and I2 (2 mmol) were reacted in DMF (3 mL) in the presence of MS 4Å.
b Isolated yields of 3 are based on 2.
c Formation of 4-iodoaniline was observed.
Next, we employed p-substituted anilines 1f–j for the monoselenation with different aryl diselenides under the influence of I2 using optimized reaction conditions and the results are presented in Table [3]. Again, the C–Se coupling between a variety of substrates possessing both electron-rich and electron-deficient group proceeded well to afford the corresponding o-selenoethers 4a–r in 22–97% yields. It is worthy to mention here that in this case also alkyl diselenides could not provide encouraging results.
a Aniline 1 (2 mmol), diselenide 2 (0.50 mmol), and I2 (2 mmol) were reacted in DMF (3 mL) in the presence of MS 4Å.
b Isolated yields of 4 are based on 2.
To find out the plausible mechanism, we have performed control experiments as shown in Scheme [2]. The reaction between 1a and 2a was carried out in the presence of 5.0 equivalents of TEMPO (2,2,6,6-tetramethylpiperidine 1-oxyl) following optimized reaction conditions under the influence of I2; no effect on the formation of product was observed, that is, 96% of 3a was obtained. This experiment ruled out the possibility of a radical mechanism. Also, when we treated 2a with I2 in DMF at room temperature under air for 30 minutes, we could observe the formation of PhSeI. We then added 1a to this reaction mixture and after stirring at room temperature for 30 minutes isolated the product 3a. On the basis of above experiments, a plausible mechanism for the C–H selenation on aniline (1a) with diphenyl diselenide (2a) is presented in Scheme [3]. Initially, I2 reacts with diselenide to generate the active electrophilic species PhSeI. PhSeI on reaction with aniline generates intermediate species A, which on removal of HI provided the desired product 3a.
In conclusion, we have developed a metal-free, simple protocol for the regioselective monoselenation of different aniline derivatives using diselenides as selenide surrogates at room temperature. The substrate scope is studied well and substrates possessing different substitutes were well tolerated under the reaction conditions employed.
All chemicals were purchased from commercial suppliers and used without further purification. NMR spectra were recorded on a JEOL Resonance-400 instrument using CDCl3 solvent. Chemical shifts are reported in parts per million (ppm) and referenced to the residual solvent resonance. Coupling constant (J) are reported in hertz (Hz). Standard abbreviations indicating multiplicity were used.
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4-(Phenylselanyl)aniline (3a);[13] Typical Procedure (Table [1])
Aniline (1a; 0.186 g, 2 mmol), diphenyl diselenide (2a; 0.156 g, 0.5 mmol), and catalyst were mixed using different solvents in an open flask (Table [1]). Then the reaction mixture was stirred or heated at various temperatures. After complete conversion, workup was done, solvent was evaporated, and the residue thus obtained was purified by column chromatography (silica gel, 5% EtOAc in hexanes) to afford product 3a as a yellowish liquid.
Table [1], entry 14; yield: 0.244 g (98%).
IR (film): 3447, 3358, 1607, 1486 cm–1.
1H NMR (400 MHz, CDCl3): δ = 3.56 (s, 2 H), 6.46–6.49 (m, 2 H), 6.64–6.68 (m, 1 H), 7.15–7.30 (m, 3 H), 7.39–7.41 (m, 3 H).
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Arylselenation of Anilines; General Procedure
Aniline 1 (2 mmol), diselenide 2 (0.50 mmol) and I2 (0.506 g, 2 mmol) were mixed in DMF (3 mL), then MS 4Å (100.0 mg) were added. The reaction mixture was stirred at rt for 1–2 h under an open atmosphere. After completion of the reaction, the workup was done by extracting with EtOAc and washing the combined EtOAc layers with brine. After drying (Na2SO4) the combined EtOAc layers, the solvent was evaporated. The crude product thus obtained was purified by column chromatography using silica gel (5% EtOAc in hexanes) to afford the corresponding product 3 or 4 (Tables 2 and 3).
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4-[(4-Methoxyphenyl)selanyl]aniline (3b)[22a]
Yellowish liquid; yield: 0.224 g (81%).
IR (film): 3454, 3360, 1632, 1485 cm–1.
1H NMR (400 MHz, CDCl3): δ = 3.67 (s, 5 H), 6.47–6.50 (m, 2 H), 6.68–6.71 (m, 2 H), 7.21–7.27 (m, 4 H).
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4-(o-Tolylselanyl)aniline (3c)
Yellowish liquid; yield: 0.224 g (86%).
IR (film): 3452, 3360, 1624, 1485 cm–1.
1H NMR (400 MHz, CDCl3): δ = 2.28 (s, 3 H), 3.68 (s, 2 H), 6.54–6.57 (m, 2 H), 6.89–6.94 (m, 2 H), 6.99 (td, J = 2.0, 7.2 Hz, 1 H), 7.04–7.06 (m, 1 H), 7.27–7.29 (m, 2 H).
13C NMR (100 MHz, CDCl3): δ = 21.7, 115.6, 116.2, 126.0, 126.5, 129.7, 129.9, 134.9, 137.2, 137.4, 146.9.
HRMS (ESI): m/z (M + H) calcd for C13H13NSe + H: 264.0291; found: 264.0266.
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4-(p-Tolylselanyl)aniline (3d)[19]
Yellowish liquid; yield: 0.228 g (87%).
IR (film): 3450, 3359, 1621, 1485 cm–1.
1H NMR (400 MHz, CDCl3): δ = 2.28 (s, 3 H), 3.72 (s, 2 H), 6.61 (dd, J = 2.0, 6.4 Hz, 2 H), 7.01 (d, J = 8.0 Hz, 2 H), 7.22–7.25 (m, 2 H), 7.36 (dd, J = 2.0, 6.4 Hz, 2 H).
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4-[(4-Bromophenyl)selanyl]aniline (3e)
Yellowish liquid; yield: 0.281 g (86%).
IR (film): 3454, 3362, 1610, 1488 cm–1.
1H NMR (400 MHz, DMSO-d 6): δ = 5.48 (s, 2 H), 6.57 (d, J = 8.4 Hz, 2 H), 7.09 (d, J = 8.4 Hz, 2 H), 7.25 (d, J = 8.4 Hz, 2 H), 7.39 (d, J = 8.4 Hz, 2 H).
13C NMR (100 MHz, CDCl3): δ = 115.8, 116.1, 119.9, 131.5, 132.0, 133.3, 137.3, 147.1.
HRMS (ESI): m/z (M + H) calcd for C12H10BrNSe + H: 327.9240; found: 327.9298.
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4-(Pyridin-3-ylselanyl)aniline (3f)
Yellowish liquid; yield: 0.0346 g (14%).
IR (film): 3428 (br), 2254, 2129, 1649 cm–1.
1H NMR (400 MHz, DMSO-d 6): δ = 6.67 (d, J = 8.0 Hz, 2 H), 7.33 (d, J = 8.0 Hz, 2 H), 7.37 (dd, J = 5.2, 8.4 Hz, 1 H), 7.71 (d, J = 8.0 Hz, 1 H), 8.42 (d, J = 4.8 Hz, 1 H), 8.47 (s, 1 H).
13C NMR (100 MHz, DMSO-d 6): δ = 116.7, 125.2, 132.1, 136.8, 138.0, 139.2, 145.5, 147.1, 147.8.
HRMS (ESI): m/z (M + H) calcd for C11H10N2Se + H: 251.0087; found: 251.0059.
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2-Fluoro-4-(phenylselanyl)aniline (3g)
Yellowish liquid; yield: 0.218 g (82%).
IR (film): 3468, 3372, 1610, 1476 cm–1.
1H NMR (400 MHz, CDCl3): δ = 3.76 (s, 2 H), 6.66 (t, J = 8.4 Hz, 1 H), 7.08–7.17 (m, 5 H), 7.23–7.26 (m, 2 H).
13C NMR (100 MHz, CDCl3): δ = 117.3 (d, 3 J C,F = 6.0 Hz), 117.6 (d, 3 J C,F = 3.0 Hz), 122.0 (d, 2 J C,F = 18.0 Hz), 126.6, 129.2, 130.9, 131.6 (d, 4 J C,F = 3.0 Hz), 132.9, 134.4 (d, 2 J C,F = 12.0 Hz), 151.4 (d, 1 J C,F = 242.0 Hz).
19F NMR (376 MHz, CDCl3): δ = –133.3.
HRMS (ESI): m/z (M + H) calcd for C12H10FNSe + H: 268.0041; found: 268.0056.
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2-Chloro-4-(p-tolylselanyl)aniline (3h)[22b]
Yellowish liquid; yield: 0.196 g (66%).
IR (film): 3466, 3375, 1611, 1475 cm–1.
1H NMR (400 MHz, DMSO-d 6): δ = 2.24 (s, 3 H), 5.54 (br s, 2 H), 6.77 (dd, J = 1.6, 8.4 Hz, 1 H), 7.09 (d, J = 8.4 Hz, 2 H), 7.17–7.23 (m, 3 H), 7.36 (t, J = 2.0 Hz, 1 H).
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2-Chloro-4-(phenylselanyl)aniline (3i)[22b]
Yellowish liquid; yield: 0.238 g (84%).
IR (film): 3465, 3374, 1610, 1476 cm–1.
1H NMR (400 MHz, DMSO-d 6): δ = 5.70 (br s, 2 H), 6.81 (dd, J = 1.6, 8.4 Hz, 1 H), 7.18–7.22 (m, 1 H), 7.24–7.27 (m, 5 H), 7.41 (d, J = 1.6 Hz, 1 H).
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2-Bromo-4-[(4-methoxyphenyl)selanyl]aniline (3j)
Yellowish liquid; yield: 0.182 g (51%).
IR (film): 3472, 3376, 1614, 1477 cm–1.
1H NMR (400 MHz, CDCl3): δ = 3.71 (s, 3 H), 6.60 (d, J = 8.0 Hz, 1 H), 6.73 (dd, J = 6.8, 2.0 Hz, 2 H), 7.16 (dd, J = 8.0, 2.0 Hz, 1 H), 7.30 (dd, J = 6.8, 2.0 Hz, 2 H), 7.49 (d, J = 2.0 Hz, 1 H).
13C NMR (100 MHz, CDCl3): δ = 55.3, 109.7, 115.0, 116.4, 119.9, 122.1, 134.0, 134.3, 137.3, 143.5, 159.2.
HRMS (ESI): m/z (M + H) calcd for C13H12BrNOSe + H: 357.9346; found: 357.9300.
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2-Bromo-4-(phenylselanyl)aniline (3k)
Yellowish liquid; yield: 0.307 g (93%).
IR (film): 3469, 3375, 1612, 1478 cm–1.
1H NMR (400 MHz, DMSO-d 6): δ = 5.65 (br s, 2 H), 6.80 (d, J = 8.0 Hz, 1 H), 7.20–7.30 (m, 6 H), 7.55 (d, J = 1.6 Hz, 1 H).
13C NMR (100 MHz, CDCl3): δ = 107.4, 113.1, 116.2, 126.3, 129.4, 129.6, 133.4, 136.0, 138.8, 146.6.
HRMS (ESI): m/z (M + H) calcd for C12H10BrNSe + H: 327.9240; found: 327.9196.
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2-Iodo-4-[(4-methoxyphenyl)selanyl]aniline (3l)
Yellowish liquid; yield: 0.250 g (62%).
IR (film): 3455, 3365, 1608, 1479 cm–1.
1H NMR (400 MHz, CDCl3): δ = 3.78 (s, 5 H), 6.64 (d, J = 8.0 Hz, 1 H), 6.80 (dd, J = 1.6, 8.8 Hz, 2 H), 7.25–7.27 (m, 1 H), 7.35–7.37 (m, 2 H), 7.80 (d, J = 2.0 Hz, 1 H).
13C NMR (100 MHz, CDCl3): δ = 55.3, 84.4, 115.0, 115.2, 120.0, 122.3, 134.1, 135.2, 143.7, 146.4, 159.2.
HRMS (ESI): m/z (M + H) calcd for C13H12INOSe + H: 405.9207; found: 405.9161.
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2-Iodo-4-(p-tolylselanyl)aniline (3m)
Yellowish liquid; yield: 0.348 g (90%).
IR (film): 3454, 3362, 1607, 1476 cm–1.
1H NMR (400 MHz, CDCl3): δ = 2.21 (s, 3 H), 4.08 (s, 2 H), 6.56 (d, J = 8.4 Hz, 1 H), 6.96 (d, J = 8.0 Hz, 2 H), 7.16 (d, J = 8.0 Hz, 2 H), 7.23 (dd, J = 2.0, 8.4 Hz, 1 H), 7.78 (d, J = 2.0 Hz, 1 H).
13C NMR (100 MHz, CDCl3): δ = 21.1, 84.3, 115.2, 118.7, 129.2, 130.0, 131.3, 136.2, 136.6, 144.7, 146.7.
HRMS (ESI): m/z (M + H) calcd for C13H12INSe + H: 389.9258; found: 389.9274.
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2-Iodo-4-(phenylselanyl)aniline (3n)
Yellowish liquid; yield: 0.354 g (95%).
IR (film): 3454, 3362, 1631, 1470 cm–1.
1H NMR (400 MHz, CDCl3): δ = 4.10 (s, 2 H), 6.56 (d, J = 8.4 Hz, 1 H), 7.06–7.15 (m, 4 H), 7.21 (dd, J = 2.0, 8.4. Hz, 1 H), 7.26 (dd, J = 2.0, 8.4 Hz, 1 H), 7.81 (d, J = 2.0 Hz, 1 H).
13C NMR (100 MHz, CDCl3): δ = 4.3, 115.2, 117.7, 126.4, 129.2, 130.4, 133.4, 136.8, 145.3, 147.0.
HRMS (ESI): m/z (M + H) calcd for C12H10INSe + H: 375.9101; found: 375.9060.
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4-[(4-Bromophenyl)selanyl]-2-iodoaniline (3o)
Yellowish liquid; yield: 0.341 g (75%).
IR (film): 3459, 3364, 1635, 1474 cm–1.
1H NMR (400 MHz, DMSO-d 6): δ = 5.62 (s, 2 H), 6.78 (d, J = 1.6 Hz, 1 H), 7.16 (dd, J = 1.6, 8.4 Hz, 2 H), 7.31 (d, J = 8.4 Hz, 1 H), 7.44 (dd, J = 2.0, 8.4 Hz, 2 H), 7.77 (s, 1 H).
13C NMR (100 MHz, DMSO-d 6): δ = 83.3, 113.1, 115.1, 119.3, 131.2, 132.1, 133.3, 136.9, 145.3, 149.6.
HRMS (ESI): m/z (M + H) calcd for C12H9BrINSe + H: 453.8207; found: 453.8198.
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2-Iodo-4-(pyridin-3-ylselanyl)aniline (3p)
Yellowish liquid; yield: 0.126 g (34%).
IR (film): 3433 (br), 2264, 2138, 1656 cm–1.
1H NMR (400 MHz, DMSO-d 6): δ = 5.61 (s, 2 H), 6.76 (d, J = 8.4 Hz, 1 H), 7.29 (dd, J = 4.8, 8.0 Hz, 1 H), 7.34 (d, J = 8.4 Hz, 1 H), 7.65 (dd, J = 2.0, 7.6, 1 H), 7.79 (s, 1 H), 8.39 (d, J = 4.8 Hz, 1 H), 8.46 (d, J = 2.0 Hz, 1 H).
13C NMR (100 MHz, DMSO-d 6): δ = 83.3, 112.8, 115.1, 124.6, 130.8, 136.7, 137.6, 145.1, 147.4, 149.6, 149.8.
HRMS (ESI): m/z calcd for C11H9IN2Se + H (M + H): 376.9054; found: 376.9002.
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2-[(4-Methoxyphenyl)selanyl]-4-methylaniline (4a)[19]
Yellowish liquid; yield: 0.244 g (84%).
IR (film): 3452, 1613, 1490 cm–1.
1H NMR (400 MHz, CDCl3): δ = 2.21 (s, 3 H), 3.74 (s, 3 H), 4.11 (s, 2 H), 6.67 (d, J = 8.0 Hz, 1 H), 6.75–6.79 (m, 2 H), 6.97–6.99 (m, 1 H), 7.23–7.27 (m, 2 H), 7.35 (d, J = 2.8 Hz, 1 H).
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4-Methyl-2-(o-tolylselanyl)aniline (4b)[19]
Yellowish liquid; yield: 0.244 g (89%).
IR (film): 3460, 3368, 1617, 1492 cm–1.
1H NMR (400 MHz, CDCl3): δ = 2.23 (s, 3 H), 2.40 (s, 3 H), 6.74 (dd, J = 1.6, 8.4 Hz, 1 H), 6.85 (dd, J = 1.6, 7.6 Hz, 1 H), 6.95–6.99 (m, 1 H), 7.04–7.09 (m, 2 H), 7.14 (d, J = 7.6 Hz, 1 H), 7.36 (d, J = 2.4 Hz, 1 H).
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4-Methyl-2-(p-tolylselanyl)aniline (4c)[19]
Yellowish liquid; yield: 0.258 g (94%).
IR (film): 3459, 3366, 1613, 1492 cm–1.
1H NMR (400 MHz, CDCl3): δ = 2.21 (s, 3 H), 2.26 (s, 3 H), 3.90 (s, 2 H), 6.69 (d, J = 8.0 Hz, 1 H), 6.99–7.02 (m, 3 H), 7.15 (dd, J = 2.0, 6.8 Hz, 2 H), 7.38 (q, J = 1.2 Hz, 1 H).
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4-Methyl-2-(phenylselanyl)aniline (4d)[13]
Yellowish liquid; yield: 0.254 g (97%).
IR (film): 3458, 3365, 1611, 1490 cm–1.
1H NMR (400 MHz, CDCl3): δ = 2.15 (s, 3 H), 3.81 (s, 2 H), 6.63 (d, J = 8.4 Hz, 1 H), 6.95 (dt, J = 1.6, 8.4 Hz, 1 H), 7.06–7.16 (m, 5 H), 7.32 (d, J = 2.0 Hz, 1 H).
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2-[(4-Bromophenyl)selanyl]-4-methylaniline (4e)
Yellowish liquid; yield: 0.135 g (40%).
IR (film): 3464, 3368, 16181, 1497 cm–1.
1H NMR (400 MHz, DMSO-d 6): δ = 2.15 (s, 3 H), 5.18 (s, 2 H), 6.76 (d, J = 8.0 Hz, 1 H), 7.01 (d, J = 7.6 Hz, 1 H), 7.13 (dd, J = 1.6, 8.4 Hz, 2 H), 7.26 (s, 1 H), 7.43 (dd, J = 1.6, 8.4 Hz, 2 H).
13C NMR (100 MHz, DMSO-d 6): δ = 19.6, 110.2, 114.9, 119.2, 125.7, 131.0, 131.2, 131.9, 132.0, 137.9, 147.4.
HRMS (ESI): m/z (M + H) calcd for C13H12BrNSe + H: 341.9397; found: 341.9302.
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4-Ethyl-2-[(4-methoxyphenyl)selanyl]aniline (4f)
Yellowish liquid; yield: 0.264 g (86%).
IR (film): 3462, 3361, 1617, 1486 cm–1.
1H NMR (400 MHz, CDCl3): δ = 1.17 (t, J = 7.6 Hz, 3 H), 2.51 (q, J = 7.6 Hz, 2 H), 3.74 (s, 3 H), 4.11 (s, 2 H), 6.69 (d, J = 8.0 Hz, 1 H), 6.77 (d, J = 8.8 Hz, 2 H), 7.01 (dd, J = 2.0, 8.0 Hz, 1 H), 7.25 (d, J = 8.8 Hz, 2 H), 7.37 (d, J = 2.0 Hz, 1 H).
13C NMR (100 MHz, CDCl3): δ = 15.8, 27.8, 55.3, 115.1, 116.7, 121.1, 128.1, 129.9, 132.7, 136.5, 136.7, 143.1, 158.9.
HRMS (ESI): m/z (M + H) calcd for C15H17NOSe + H: 308.0554; found: 308.0508.
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4-Ethyl-2-(o-tolylselanyl)aniline (4g)
Yellowish liquid; yield: 0.270 g (93%).
IR (film): 3457, 3360, 1612, 1490 cm–1.
1H NMR (400 MHz, CDCl3): δ = 1.18 (t, J = 7.6 Hz, 3 H), 2.40 (s, 3 H), 2.53 (q, J = 7.6 Hz, 2 H), 3.86 (s, 2 H), 6.76 (d, J = 8.0 Hz, 1 H), 6.85 (dd, J = 1.6, 8.0 Hz, 1 H), 6.97 (td, J = 1.6, 8.0 Hz, 1 H), 7.04–7.09 (m, 2 H), 7.14 (dd, J = 1.6, 7.6 Hz, 1 H), 7.38 (d, J = 2.0 Hz, 1 H).
13C NMR (100 MHz, CDCl3): δ = 15.8, 21.5, 27.7, 111.8, 115.2, 125.9, 126.7, 128.0, 130.1, 130.7, 132.4, 135.0, 136.8, 137.8, 146.7.
HRMS (ESI): m/z (M + H) calcd for C15H17NSe + H: 292.0604; found: 292.0648.
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4-Ethyl-2-(p-tolylselanyl)aniline (4h)
Radish yellow liquid; yield: 0.264 g (91%).
IR (film): 3456, 3360, 1611, 1489 cm–1.
1H NMR (400 MHz, CDCl3): δ = 1.18 (t, J = 7.6 Hz, 3 H), 2.26 (s, 3 H), 2.52 (q, J = 7.6 Hz, 2 H), 3.93 (s, 2 H), 6.71 (d, J = 8.0 Hz, 1 H), 7.02–7.05 (m, 3 H), 7.15 (d, J = 8.0 Hz, 2 H), 7.40 (d, J = 2.0 Hz, 1 H).
13C NMR (100 MHz, CDCl3): δ = 15.8, 21.0, 27.7, 113.3, 115.1, 127.8, 129.7, 130.1, 130.4, 134.7, 136.1, 137.3, 146.2.
HRMS (ESI): m/z (M + H) calcd for C15H17NSe + H: 292.0604; found: 292.0664.
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4-Ethyl-2-(phenylselanyl)aniline (4i)
Yellowish liquid; yield: 0.262 g (95%).
IR (film): 3455, 3359, 1610, 1489 cm–1.
1H NMR (400 MHz, CDCl3): δ = 1.18 (t, J = 7.6 Hz, 3 H), 2.52 (q, J = 7.6 Hz, 2 H), 4.12 (s, 2 H), 6.72 (d, J = 8.0 Hz, 1 H), 7.05 (dd, J = 2.0, 8.4 Hz, 1 H), 7.13–7.23 (m, 5 H), 7.41 (d, J = 2.4 Hz, 1 H).
13C NMR (100 MHz, CDCl3): δ = 15.8, 27.7, 112.6, 115.1, 126.0, 129.1, 129.2, 130.6, 131.8, 134.7, 137.5, 146.4.
HRMS (ESI): m/z (M + H) calcd for C14H15NSe + H: 278.0448; found: 278.0411.
#
4-Chloro-2-(o-tolylselanyl)aniline (4j)
Yellowish liquid; yield: 0.240 g (80%).
IR (film): 3464, 3376, 1611, 1478 cm–1.
1H NMR (400 MHz, CDCl3): δ = 2.39 (s, 3 H), 4.08 (s, 2 H), 6.73 (d, J = 8.8 Hz, 1 H), 6.90 (dd, J = 1.6, 8.0 Hz, 1 H), 6.98–7.02 (m, 1 H), 7.11 (td, J = 1.6, 7.6 Hz, 1 H), 7.15–7.19 (m, 2 H), 7.49 (d, J = 2.8 Hz, 1 H).
13C NMR (100 MHz, CDCl3): δ = 21.6, 113.2, 115.9, 122.7, 126.6, 126.9, 128.7, 130.3, 130.8, 131.4, 137.2, 137.3, 147.3.
HRMS (ESI): m/z (M + H) calcd for C13H12ClNSe + H: 297.9902; found: 297.9841.
#
4-Chloro-2-(p-tolylselanyl)aniline (4k)
Yellowish liquid; yield: 0.138 g (93%).
IR (film): 3463, 3375, 1610, 1477 cm–1.
1H NMR (400 MHz, CDCl3): δ = 2.29 (s, 3 H), 4.25 (s, 2 H), 6.69 (d, J = 8.4 Hz, 1 H), 7.04 (d, J = 8.0 Hz, 2 H), 7.13 (dd, J = 2.4, 8.8 Hz, 1 H), 7.17–7.20 (m, 2 H), 7.52 (d, J = 2.4 Hz, 1 H).
13C NMR (100 MHz, CDCl3): δ = 21.9, 114.7, 115.8, 122.5, 126.7, 130.3, 130.4, 130.5, 136.80, 136.89, 146.8.
HRMS (ESI): m/z (M + H) calcd for C13H12ClNSe + H: 297.9902; found: 297.9871.
#
4-Chloro-2-(phenylselanyl)aniline (4l)[19]
Yellowish liquid; yield: 0.194 g (69%).
IR (film): 3461, 3372, 1608, 1473 cm–1.
1H NMR (400 MHz, CDCl3): δ = 4.05 (s, 2 H), 6.69 (d, J = 8.4 Hz, 1 H), 7.14 (dd, J = 2.8, 8.8 Hz, 1 H), 7.17–7.26 (m, 5 H), 7.54 (d, J = 2.4 Hz, 1 H).
#
2-[(4-Bromophenyl)selanyl]-4-chloroaniline (4m)
Yellowish liquid; yield: 0.081 g (22%).
IR (film): 3468, 3379, 1610, 1476 cm–1.
1H NMR (400 MHz, DMSO-d 6): δ = 5.58 (s, 2 H), 6.89 (d, J = 8.8 Hz, 1 H), 7.26 (d, J = 8.4 Hz, 3 H), 7.47 (d, J = 2.4 Hz, 1 H), 7.53 (dd, J = 2.4, 7.2 Hz, 2 H).
13C NMR (100 MHz, DMSO-d 6): δ = 111.4, 115.9, 118.9, 119.8, 130.3, 130.7, 131.6, 132.2, 136.1, 148.9.
HRMS (ESI): m/z (M + H) calcd for C12H9BrClNSe + H: 361.8850; found: 361.8802.
#
4-Bromo-2-(phenylselanyl)aniline (4n)
Yellowish liquid; yield: 0.149 g (45%).
IR (film): 3464, 3376, 1612, 1476 cm–1.
1H NMR (400 MHz, DMSO-d 6): δ = 5.43 (s, 2 H), 6.73 (d, J = 8.8 Hz, 1 H), 7.19–7.25 (m, 6 H), 7.44 (d, J = 2.4 Hz, 1 H).
13C NMR (100 MHz, DMSO-d 6): δ = 106.1, 112.9, 116.3, 126.7, 129.5, 130.0, 130.7, 133.1, 138.5, 149.1.
HRMS (ESI): m/z (M + H) calcd for C12H10BrNSe + H: 327.9240; found: 327.9198.
#
4-Bromo-2-(pyridin-3-ylselanyl)aniline (4o)
Yellowish liquid; yield: 0.116 g (35%).
IR (film): 3433, 2264, 2138, 1656 cm–1.
1H NMR (400 MHz, DMSO-d 6): δ = 5.59 (s, 2 H), 6.76 (d, J = 8.8 Hz, 1 H), 7.27–7.32 (m, 2 H), 7.54 (s, 1 H), 7.66 (d, J = 7.6 Hz, 1 H), 8.42 (d, J = 4.8 Hz, 1 H), 8.48 (s, 1 H).
13C NMR (100 MHz, DMSO-d 6): δ = 106.0, 111.7, 116.4, 124.7, 128.2, 133.4, 137.9, 138.7, 147.5, 149.3, 150.1.
HRMS (ESI): m/z (M + H) calcd for C11H9BrN2Se + H: 328.9193; found: 328.9208.
#
2-(o-Tolylselanyl)-4-(trifluoromethyl)aniline (4p)
Yellowish liquid; yield: 0.310 g (93%).
IR (film): 3483, 3380, 3101, 1622, 1490 cm–1.
1H NMR (400 MHz, CDCl3): δ = 2.31 (s, 3 H), 4.46 (s, 2 H), 6.69 (d, J = 8.8 Hz, 1 H), 6.75 (d, J = 8.0 Hz, 1 H), 6.90 (td, J = 2.0, 8.0 Hz, 1 H), 6.99–7.08 (m, 2 H), 7.35 (dd, J = 2.8, 8.8 Hz, 1 H), 7.71 (s, 1 H).
13C NMR (100 MHz, CDCl3): δ = 21.5, 111.2, 114.1, 120.4 (q, 2 J C,F = 33.0 Hz), 124.3 (q, 1 J C,F = 269 Hz), 126.6, 126.9, 128.2 (q, 3 J C,F = 4.0 Hz), 128.3, 130.4, 131.1, 135.9 (q, 3 J C,F = 4.0 Hz), 137.1, 151.5.
19F NMR (376 MHz, CDCl3): δ = –61.0.
HRMS (ESI): m/z (M + H) calcd for C14H12F3NSe + H: 332.0165; found: 332.0102.
#
2-(p-Tolylselanyl)-4-(trifluoromethyl)aniline (4q)
Yellowish liquid; yield: 0.320 g (97%).
IR (film): 3482, 3378, 3101, 1620, 1489 cm–1.
1H NMR (400 MHz, CDCl3): δ = 2.27 (s, 3 H), 4.56 (s, 2 H), 6.73–6.76 (m, 1 H), 7.04 (d, J = 8.4 Hz, 2 H), 7.17 (d, J = 8.0 Hz, 2 H), 7.39–7.42 (m, 1 H), 7.83 (t, J = 1.2 Hz, 1 H).
13C NMR (100 MHz, CDCl3): δ = 21.0, 112.8, 114.1, 120.2 (q, 2 J C,F = 33.0 Hz), 124.3 (q, 1 J C,F = 270 Hz), 126.5, 127.9 (q, 3 J C,F = 4.0 Hz), 130.1, 130.2, 132.3, 135.3 (q, 3 J C,F = 4.0 Hz), 135.9, 151.0.
19F NMR (376 MHz, CDCl3): δ = –60.9.
HRMS (ESI): m/z (M + H) calcd for C14H12F3NSe + H: 332.0165; found: 332.0196.
#
2-(Phenylselanyl)-4-(trifluoromethyl)aniline (4r)
Yellowish liquid; yield: 0.300 g (95%).
IR (film): 3481, 3376, 3199, 1616, 1487 cm–1.
1H NMR (400 MHz, CDCl3): δ = 4.50 (s, 2 H), 6.73 (d, J = 8.4 Hz, 1 H), 7.16–7.23 (m, 5 H), 7.41 (dd, J = 2.4, 8.4 Hz, 1 H), 7.84 (d, J = 2.4 Hz, 1 H).
13C NMR (100 MHz, CDCl3): δ = 112.0, 114.1, 120.2 (q, 2 J C,F = 33.0 Hz), 124.3 (q, 1 J C,F = 270 Hz), 126.7, 128.1 (q, 3 J C,F = 4.0 Hz), 129.5, 129.6, 130.5, 135.7 (q, 3 J C,F = 4.0 Hz), 151.2.
19F NMR (376 MHz, CDCl3): δ = –60.8.
HRMS (ESI): m/z (M + H) calcd for C13H10F3NSe + H: 318.0009; found: 317.9973.
#
#
Conflict of Interest
The authors declare no conflict of interest.
Acknowledgment
R.B. thanks the CSIR-India and SERB – India for a fellowship. We thank MRC-MNIT Jaipur for NMR data collection and BITS Pilani, Pilani campus for HRMS data collection.
Supporting Information
- Supporting information for this article is available online at https://doi-org.accesdistant.sorbonne-universite.fr/10.1055/a-1730-8186.
- Supporting Information
-
References
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- 18 Shieh Y.-C, Du K, Basha RS, Xue Y.-J, Shih B.-H, Li L, Lee C.-F. J. Org. Chem. 2019; 84: 6223
- 19 Ren Y, Xu B, Zhong Z, Pittman CU. Jr, Zhou A. Org. Chem. Front. 2019; 6: 2023
- 20 Zhou Z, He X. Synth. Commun. 2018; 48: 2553
- 21a Choudhary R, Singh P, Bai R, Sharma MC, Badsara SS. Org. Biomol. Chem. 2019; 17: 9757
- 21b Badsara SS, Singh P, Choudhary R, Bai R, Sharma MC. New J. Chem. 2019; 43: 11045
- 21c Choudhary R, Bai R, Singh P, Sharma MC, Badsara SS. SynOpen 2018; 2: 213
- 21d Bai R, Choudhary R, Singh P, Thakuria R, Sharma MC, Badsara SS. ChemistrySelect 2018; 3: 3221
- 21e Singh P, Bai R, Choudhary R, Sharma MC, Badsara SS. RSC Adv. 2017; 7: 30594
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Corresponding Author
Publication History
Received: 03 August 2021
Accepted after revision: 04 January 2022
Accepted Manuscript online:
04 January 2022
Article published online:
08 March 2022
© 2022. Thieme. All rights reserved
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-
References
- 1a Sun C.-L, Shi Z.-J. Chem. Rev. 2014; 114: 9219
- 1b Mehta VP, Punji B. RSC Adv. 2013; 3: 11957
- 1c Liu W, Li J, Querard P, Li C.-J. J. Am. Chem. Soc. 2019; 141. 6755
- 2a Wang H, Gao X, Lv Z, Abdelilah T, Lei A. Chem. Rev. 2019; 119: 6769
- 2b Guo W, Tao K, Tan W, Zhao M, Zheng L, Fan X. Org. Chem. Front. 2019; 6: 2048
- 2c Sauermann N, Meyer TH, Tian C, Ackermann L. J. Am. Chem. Soc. 2017; 139: 18452
- 2d Ackermann L. Acc. Chem. Res. 2020; 53: 84
- 2e Yan M, Kawamata Y, Baran PS. Chem. Rev. 2017; 117: 13230
- 2f Yoshida J.-i, Shimizu A, Hayashi R. Chem. Rev. 2018; 118: 4702
- 3a Shamberger RJ. Biochemistry of Selenium . Plenum Press; New York: 1983
- 3b Klayman DL, Gunter WH. H. Organoselenium Compounds: Their Chemistry and Biology . Wiley-Interscience; New York: 1973
- 3c Rotruck JT, Pope AL, Ganther HE, Swanson AB, Hafeman DG, Hoekstra WG. Science 1973; 179: 588
- 3d Nogueira CW, Zeni G, Rocha JB. T. Chem. Rev. 2004; 104: 6255
- 3e Mugesh G, du Mont WW, Sies H. Chem. Rev. 2001; 101: 2125
- 3f Mugesh G, Singh HB. Chem. Soc. Rev. 2000; 29: 347
- 4a Braga AL, Vargas F, Sehnem JA, Braga RC. J. Org. Chem. 2005; 70: 9021
- 4b Schwab RS, Soares LC, Dornelles L, Rodrigues OE. D, Paixao MW, Godoi M, Braga AL. Eur. J. Org. Chem. 2010; 3574
- 5a Wirth T. Tetrahedron 1999; 55: 1
- 5b Wirth T. Angew. Chem. Int. Ed. 2000; 39: 3740
- 5c Godoi M, Paixao MW, Braga AL. Dalton Trans. 2011; 40: 11347
- 6 Perin G, Lenardao EJ, Jacob RG, Panatieri RB. Chem. Rev. 2009; 109: 1277
- 7a Topics in Current Chemistry in Organoselenium Chemistry. Wirth T. Springer; Heidelberg: 2000: 208
- 7b Krief A. In Comprehensive Organometallic Chemistry II, Vol. 11. Abel EV, Stone FG. A, Wilkinson G. Pergamon Press; New York: 1995: 515
- 7c Paulmier C. Selenium Reagents and Intermediates in Organic Synthesis, Organic Chemistry Series 4. Baldwin JE. Pergamon Press; Oxford: 1986
- 8 Freudendahl DM, Iwaoka M, Wirth T. Eur. J. Org. Chem. 2010; 3934
- 9a Keck GE, Grier MC. Synlett 1999; 1657
- 9b Chen C, Crich D, Papadatos A. J. Am. Chem. Soc. 1992; 114: 8313
- 9c Boger DL, Mathvink RJ. J. Org. Chem. 1992; 57: 1429
- 9d Hiiro T, Morita Y, Inoue T, Kambe N, Ogawa A, Ryuand I, Sonoda N. J. Am. Chem. Soc. 1990; 112: 455
- 10 Yamada J.-i, Akutsu H, Nishikawa H, Kikuchi K. Chem. Rev. 2004; 104: 5057
- 11 Inoue M, Yamahita S, Ishihara Y, Hirama M. Org. Lett. 2006; 8: 5805
- 12a Kundu D. RSC Adv. 2021; 11: 6682
- 12b Rodrigues J, Saba S, Joussef AC, Rafique J, Braga AL. Asian J. Org. Chem. 2018; 7: 1819
- 12c Kumaraswamy G, Ramesh V, Gangadhar M, Vijaykumar S. Asian J. Org. Chem. 2018; 7: 1689
- 13 Ricordi VG, Thurow S, Penteado F, Schumacher RF, Perin G, Lenardão EJ, Alves D. Adv. Synth. Catal. 2015; 357: 933
- 14 Fang X.-L, Tanga R.-Y, Zhang X.-G, Li J.-H. Synthesis 2011; 1099
- 15 Saba S, Rafique J, Braga AL. Catal. Sci. Technol. 2016; 6: 3087
- 16 Thurow S, Penteado F, Perin G, Jacob RG, Alves D, Lenardão EJ. Green Chem. 2014; 16: 3854
- 17 Kundu D, Ahammed S, Ranu BC. Org. Lett. 2014; 16: 1814
- 18 Shieh Y.-C, Du K, Basha RS, Xue Y.-J, Shih B.-H, Li L, Lee C.-F. J. Org. Chem. 2019; 84: 6223
- 19 Ren Y, Xu B, Zhong Z, Pittman CU. Jr, Zhou A. Org. Chem. Front. 2019; 6: 2023
- 20 Zhou Z, He X. Synth. Commun. 2018; 48: 2553
- 21a Choudhary R, Singh P, Bai R, Sharma MC, Badsara SS. Org. Biomol. Chem. 2019; 17: 9757
- 21b Badsara SS, Singh P, Choudhary R, Bai R, Sharma MC. New J. Chem. 2019; 43: 11045
- 21c Choudhary R, Bai R, Singh P, Sharma MC, Badsara SS. SynOpen 2018; 2: 213
- 21d Bai R, Choudhary R, Singh P, Thakuria R, Sharma MC, Badsara SS. ChemistrySelect 2018; 3: 3221
- 21e Singh P, Bai R, Choudhary R, Sharma MC, Badsara SS. RSC Adv. 2017; 7: 30594
- 21f Choudhary R, Bai R, Singh P, Sharma MC, Badsara SS. Tetrahedron 2017; 73: 4323
