Copper-promoted oxidative-fluorination of arylphosphine under mild conditions

Liu, Na; Mao, Liu‐Liang; Yang, Bin; Yang, Shang‐Dong

doi:10.1039/c4cc04830j

Cited by 54 publications

(30 citation statements)

References 32 publications

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“…7, to model the CIP, 4 water molecules are connected to the proton donor group of BOH so that the structure of the hydrated proton is similar to that of the Eigen cation (H 9 O 4 + ), where a H 3 O + core is symmetrically surrounded by 3 water molecules in room-temperature aqueous acidic solutions [42]; the butyl group is simplified as methyl to reduce computational costs. Also, since hydrogen bonding may play an important role in regulating the fluorescence property of a dye [43][44][45][46][47], the hydrogen bonding interactions between water molecules and the carbonyl groups of BOH (B 1 The TDDFT method has proven useful to theoretically investigate the hydrogen bonding interactions that occur in the excited-state [40,43]. As shown in Table 3 Table 3 Bond lengths of the optimized structures of the CIP models depicted in Fig.…”

Section: Spectra In Aqueous Solutions Of Hclmentioning

confidence: 99%

Excited-state proton transfer of 4-hydroxyl-1, 8-naphthalimide derivatives: A combined experimental and theoretical investigation

Zhang

Wang

et al. 2016

Journal of Luminescence

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The photophysical properties of N-butyl-4-hydroxyl-1, 8-naphthalimide (BOH) and N-(morpholinoethyl)-4-hydroxy-1, 8-naphthalimide (MOH) in various solvents are presented and the density functional theory (DFT) / time-dependent density functional theory (TDDFT) methods at the B3LYP/TZVP theoretical level are adopted to investigate the UV-visible absorption and emission data. An efficient intermolecular excited-state proton transfer (ESPT) reaction occurs for both compounds in DMSO, methanol and water. In aqueous solution, both BOH and MOH can be used as ratiometric pH probes and perform as strong photoacids with pKa* = −2.2, −2.4, respectively. Most interestingly, in the steady-state fluorescence spectra of BOH and MOH in concentrated HCl, an unexpected blue-shifted band is observed and assumed to originate from the contact ion pair (CIP) formed by hydronium ion and the anionic form of the photoacid resulted from ESPT. Theoretical calculations are used to simulate the CIP in the case of BOH, which afford reasonable results compared with the experimental data. Keywords: Naphthalimide Excited-state proton transfer Photoacid Contact ion pair Time-dependent density functional theory 1. Introduction Upon photoexcitation, aromatic alcohols (ROH) such as naphthols, hydroxyquinolines, and hydroxypyrenes may increase the acidity dramatically. Research on this photoinduced deprotonation is first described by Fὅrster in 1949 [1] and still attracting intensive attention in the field of biology and physical chemistry [2-11]. The Eigen-Weller model for proton transfer is used to depict this process, where the initial short-range proton transfer forms a contact ion pair (CIP) as a reaction intermediate followed by diffusion controlled separation of the ions [12-13]. © 2016. This manuscript version is made available under the Elsevier user license http://www.elsevier.com/open-access/userlicense/1.0/Recently, Brouwer and coworkers synthesized and characterized some hydroxy-substituted 1, 8-naphthalimide derived "super" photoacids, where the hydroxyl group is located at the 3 or 6 position of the naphthalimide ring [6,14]. However, for 4-hydroxyl-1, 8-naphthalimide derivatives, which are extensively used for designing turn-on or rationmetric fluorescent indicators for bioimaging [15][16][17][18][19][20][21][22][23][24][25][26][27][28][29], the photophysical properties and the excited-state proton transfer (ESPT) reactions are rarely studied [30].In this contribution, the steady-state absorption and emission spectra of two 4-hydroxyl-1, 8-naphthalimide derivatives (BOH and MOH, Scheme 1) in organic solvents and water with various pH values are recorded. The density functional theory (DFT) / time-dependent density functional theory (TDDFT) methods at B3LYP/TZVP theoretical level are adopted to investigate the UV-visible absorption and emission data. In the study of the ESPT of 5-cyano-2-naphthol in sub-and supercritical water, Kobayashi and coworkers [31] found that the band of their excited neutral (ROH*) and anionic (RO − *) species...

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Section: Spectra In Aqueous Solutions Of Hclmentioning

confidence: 99%

Excited-state proton transfer of 4-hydroxyl-1, 8-naphthalimide derivatives: A combined experimental and theoretical investigation

Zhang

Wang

et al. 2016

Journal of Luminescence

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“…(3)叔膦(R 3 P, R＝芳基、烷基)的反应由 path b 生成氧化产物 [11] ; (4)烷氧基苯基膦则可以经过两种反应途径生成氟化和氧化两种产物; (5)其它亚磷酸酯类化合物的反应效果较差. 二苯基磷酰氟(2a) [9] : 得 70 mg 淡黄色油状液体, 收率 79%. 1 H NMR (400 MHz, CDCl 3 ) δ: 7.86～7.77 (m, 4H), 7.63～7.57 (m, 2H), 7.53～7.46 (m, 4H); 31 P NMR (162 MHz, CDCl 3 ) δ: 40.90 (d, J＝1020 Hz); 19 F NMR (376 MHz, CDCl 3 ) δ: -75.15 (d, J＝1020 Hz); 13 C NMR (100 MHz, CDCl 3 ) δ: 133.4 (d,J＝2.3 Hz), 131.4 (dd, J＝ 11.3, 1.9 Hz), 128.9 (d,J＝14.1 Hz),128.8 (dd,J＝140.0,22.3 Hz).…”

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“…二对甲苯基磷酰氟(2b) [9] : 得 72 mg 淡黄色油状液体, 收率 72%. 1 H NMR (400 MHz, CDCl 3 ) δ: 7.73～7.65 (m, 4H), 7.32～7.27 (m, 4H), 2.40 (s, 6H); 31 P NMR (162 MHz, CDCl 3 ) δ: 42.02 (d, J＝1014 Hz); 19 F NMR (376 MHz, CDCl 3 ) δ: -74.36 (d, J＝1014 Hz); 13 C NMR (100 MHz, CDCl 3 ) δ: 144.0 (d,J＝2.3 Hz), 131.4 (dd, J＝11.7, 1.8 Hz), 129.5 (d,J＝14.5 Hz), 125.8 (dd, J＝143.0, 22.0 Hz), 21.7.…”

mentioning

confidence: 99%

“…1 H NMR (400 MHz, CDCl 3 ) δ: 7.73～7.65 (m, 4H), 7.32～7.27 (m, 4H), 2.40 (s, 6H); 31 P NMR (162 MHz, CDCl 3 ) δ: 42.02 (d, J＝1014 Hz); 19 F NMR (376 MHz, CDCl 3 ) δ: -74.36 (d, J＝1014 Hz); 13 C NMR (100 MHz, CDCl 3 ) δ: 144.0 (d,J＝2.3 Hz), 131.4 (dd, J＝11.7, 1.8 Hz), 129.5 (d,J＝14.5 Hz), 125.8 (dd, J＝143.0, 22.0 Hz), 21.7. 二间甲苯基磷酰氟(2c) [9] : 得 75 mg 无色油状液体, 收率 76%. 1 H NMR (400 MHz 二邻甲苯基磷酰氟(2d) [9] : 得 70 mg 白色固体, 收率二(1-萘基)磷酰氟(2e) [10] : 得 94 mg 白色固体, 收率 73%.…”

unclassified

“…二间甲苯基磷酰氟(2c) [9] : 得 75 mg 无色油状液体, 收率 76%. 1 H NMR (400 MHz 二邻甲苯基磷酰氟(2d) [9] : 得 70 mg 白色固体, 收率二(1-萘基)磷酰氟(2e) [10] : 得 94 mg 白色固体, 收率 73%. 1 H NMR (400 MHz, CDCl 3 ) δ: 8.55～8.54 (m, 2H), 8.10 (d, J＝8.2 Hz, 2H), 8.03 (dd, J＝17.0, 7.1 Hz, 2H), 7.94～7.92 (m, 2H), 7.57～7.50 (m, 6H); 31 P NMR (162 MHz, CDCl 3 ) δ: 44.48 (d, J＝1019 Hz); 19 F NMR (376 MHz, CDCl 3 ) δ: -67.96 (d, J＝1019 Hz); 13 C NMR (100 MHz, CDCl 3 ) δ: 134.7 (d,J＝3.1 Hz), 134.0 (dd, J＝12.0, 3.9 Hz), 133.7 (d, J＝11.3 二(3,5-二甲基苯基)磷酰氟(2h) [10] : 得 80 mg 白色固有机化学研究论文体, 收率 72%.…”

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Fluorination Reaction of P(Ⅲ) Compounds with the Electrophilic Fluorinating Reagent Selectfluor

Huang¹,

Chen²

2017

Chin. J. Org. Chem.

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A fluorination reaction of P(III) compounds with the electrophilic fluorinating reagent Selectfluor is described. The reaction proceeded in acetonitrile/water at room temperature for 15～60 min to afford phosphoric fluorides in 34%～81% yields. Keywords P(III) compound; electrophilic fluorinating reagent; fluorination reaction; phosphoric fluoride 有机磷化合物广泛应用于有机合成 [1] 、功能材料 [2] 、药物化学 [3] 、配位化学 [4] 和阻燃剂 [5] 等领域中. 其中, 含有磷-氟键的化合物在酶促反应中可作为抑制剂或机理研究的探针分子, 具有广泛的应用性 [6]. 例如, 磷酰氟类化合物能有效地抑制乙酰胆碱酯酶(acetyl cholinesterase)等多种蛋白酶和酯酶.

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Copper‐Catalyzed Cycloaddition between Secondary Phosphine Oxides and Alkynes: Synthesis of Benzophosphole Oxides

Gao

Zhang

et al. 2016

Adv Synth Catal

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Benzophosphole derivatives have attracted significant attention as promising organic optoelectronic materials. We have successfully developed a copper (2 mol%)/tert‐butyl hydroperoxide (2 equiv.) catalyst system for reaction of readily available secondary phosphine oxides and alkynes in acetonitrile at 60 °C under air, which provides a rapid access to a structurally diverse array of benzophosphole oxides in moderate to good yields within 30 min. The method can be easily used for a large‐scale preparation. Preliminary mechanistic studies revealed that the addition of a phosphoryl radical onto a triple bond followed by cyclization on the phenyl moiety of the secondary phosphine oxide might occur to form the benzophosphole oxide.magnified image

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Copper-promoted oxidative-fluorination of arylphosphine under mild conditions

Cited by 54 publications

References 32 publications

Excited-state proton transfer of 4-hydroxyl-1, 8-naphthalimide derivatives: A combined experimental and theoretical investigation

Excited-state proton transfer of 4-hydroxyl-1, 8-naphthalimide derivatives: A combined experimental and theoretical investigation

Fluorination Reaction of P(Ⅲ) Compounds with the Electrophilic Fluorinating Reagent Selectfluor

Copper‐Catalyzed Cycloaddition between Secondary Phosphine Oxides and Alkynes: Synthesis of Benzophosphole Oxides

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