- A solvent-free method for the preparation of phosphinates from P(O)-OH compounds with alkyl chlorides
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Herein, a new solvent-free synthetic method using P(O)-OH compound and alkyl chloride for phosphinate compounds is disclosed. This transformation proceeds smoothly under the promotion of a lone base and presents the advantages of an easily available raw material source, a simple post treatment process, good functional group tolerance and high reaction efficiency. Good yield was obtained when the reaction was magnified to gram scale, and the molar ratio of P(O)-OH compounds and alkyl chlorides can be decreased to 1:2. This protocol provides a practical method for the preparation of phosphorus derivatives. Furthermore, the reaction mechanism was explored by means of 31P NMR.
- Yuan, Huihui,Wang, Mingyue,Fan, Lei,Yang, Jia,Wang, Shuai,Zhong, Hong
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supporting information
(2021/11/17)
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- Tf2O/DMSO-Promoted P-O and P-S Bond Formation: A Scalable Synthesis of Multifarious Organophosphinates and Thiophosphates
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A Tf2O/DMSO-based system for the dehydrogenative coupling of a wide range of alcohols, phenols, thiols, and thiophenols with diverse phosphorus reagents has been developed. This metal- and strong-oxidant-free strategy provides a facile approach to a great variety of organophosphinates and thiophosphates. The simple reaction system, good functional-group tolerance, and broad substrate scope enable the application of this method to the modification of natural products and the direct synthesis of bioactive molecules and flame retardants.
- Shen, Jian,Li, Qi-Wei,Zhang, Xin-Yue,Wang, Xue,Li, Gui-Zhi,Li, Wen-Zuo,Yang, Shang-Dong,Yang, Bin
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supporting information
p. 1541 - 1547
(2021/04/05)
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- Novel method for preparing phosphonate through oxidative dehydrogenation coupled reaction of copper-catalyzed diarylphosphine oxide and alcohol
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The invention provides a method for efficiently and highly selectively synthesizing phosphonate derivatives containing different substituted functional groups. According to the method, cuprous iodideis used as a catalyst, 2,2'-dipyridyl is used as a ligand, pyridine is used as an alkali, oxygen is used as an oxidant, diarylphosphine oxide and an alcohol compound are used as reaction substrates, and an organic solvent is added into a reaction system. The method has the advantages that the catalyst and the oxidant are cheap and easily available; substrate applicability is high; reaction conditions are mild, safe and reliable; the selectivity of the obtained target products is close to 100%; and the yield of the target products is as high as 90% or above. The method overcomes the defects ofpoor reaction selectivity, complex reaction steps, low yield, need for reagents harmful to the environment and the like in the traditional synthesis of phosphonate derivatives, and has favorable industrial application prospects. The invention also provides the corresponding phosphonate derivatives containing different substituted functional groups.
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Paragraph 0015
(2020/12/14)
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- Preparation method of compound containing P-O bond or P-S bond
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The invention discloses a preparation method of a compound containing a P-O bond or a P-S bond. The method comprises the following steps: a compound containing hydroxyl or sulfydryl and a phosphorus reagent are taken as initial raw materials; then, the initial raw materials are put into an inert gas atmosphere; and under the action of trifluoromethanesulfonic anhydride (Tf2O) and dimethyl sulfoxide (DMSO), the compound containing hydroxyl or sulfydryl, the phosphorus reagent, the trifluoromethanesulfonic anhydride and the dimethyl sulfoxide in a molar ratio of (1-5): (1-2.5): (2-3): 2 react inan organic solvent at the reaction temperature of 25-100 DEG C for 6-20 hours to obtain the compound with the structural general formula (I). The reagents used in the method are low in toxicity and environmentally friendly, and use of precious metal catalysts high in price and toxicity is avoided. The reagents trifluoromethanesulfonic anhydride (Tf2O) and dimethyl sulfoxide (DMSO) used in the method are low in toxicity and very low in cost, so that the method is green, environment-friendly, high in economy and suitable for large-scale production.
- -
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Paragraph 0187-0191
(2020/09/12)
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- A phosphoryl radical-initiated Atherton-Todd-type reaction under open air
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A phosphoryl radical-initiated Atherton-Todd-type reaction using air as the radical initiator and CHCl3 as the halogenating reagent for the phosphorylation of alcohols, phenols, and amines has been developed. This novel transformation provides a highly efficient route to important phosphinates, phosphinic amides, and phosphoramidates in up to 99% yield with a broad substrate scope under very mild conditions (48 examples).
- Ou, Yingcong,Huang, Yuanting,He, Zhenlin,Yu, Guodian,Huo, Yanping,Li, Xianwei,Gao, Yang,Chen, Qian
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supporting information
p. 1357 - 1360
(2020/02/11)
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- Electrochemical Dehydrogenative Coupling of Alcohols with Hydrogen Phosphoryl Compounds: A Green Protocol for P?O Bond Formation
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This study reports the environment-friendly electrochemical transformation of structurally diverse phosphorus compounds and alcohol into phosphonates in the presence of ammonium iodide as electrolyte and redox catalyst in acetonitrile at ambient temperature. This method for P?O bond formation exhibits remarkable features, such as transition metal- and oxidant-free conditions. A reliable mechanism is proposed after control and cyclic voltammetry experiments. (Figure presented.).
- Li, Qian-Yu,Swaroop, Toreshettahally R.,Hou, Cheng,Wang, Zi-Qiang,Pan, Ying-Ming,Tang, Hai-Tao
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supporting information
p. 1761 - 1765
(2019/02/20)
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- A scalable electrochemical dehydrogenative cross-coupling of P(O)H compounds with RSH/ROH
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A practical, scalable electrochemical dehydrogenative cross-coupling of P(O)H compounds with thiols, phenols and alcohols in both an undivided cell and a continuous-flow setup is disclosed. Its broad substrate scope (>50 examples), good functional-group tolerance and scalability (>10 g) show potential for practical synthesis. A preliminary mechanistic study suggests that the phosphorus radicals are involved in the catalytic cycle.
- Li, Yujun,Yang, Qi,Yang, Liquan,Lei, Ning,Zheng, Ke
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supporting information
p. 4981 - 4984
(2019/05/21)
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- Electrochemical Dehydrogenative Phosphorylation of Alcohols for the Synthesis of Organophosphinates
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An eco-friendly and efficient method for the synthesis of organophosphinates via an electrochemical cross-dehydrogenative-coupling reaction between alcohols and secondary phosphine oxides has been developed. This electrochemical reaction was conducted at
- Deng, Lingling,Wang, Yang,Mei, Haibo,Pan, Yi,Han, Jianlin
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p. 949 - 956
(2019/01/14)
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- DCC-assisted direct esterification of phosphinic and phosphoric acids with O-nucleophiles
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A novel and efficient dicyclohexylcarbodiimide-promoted protocol for the selective and controllable esterification of P(O)OH compounds using O-nucleophiles (alcohols and phenols) as efficient esterification reagents is described. This method features a high efficiency and good functional-group tolerance, meaning a simple way to synthesize a broad spectrum of phosphinic and phosphoric acid esters from basic starting materials with moderate to excellent yields.
- Xiong, Biquan,Wang, Gang,Zhou, Congshan,Liu, Yu,Li, Jiandong,Zhang, Pangliang,Tang, Kewen
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supporting information
p. 239 - 244
(2017/11/20)
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- Perfluoroalkanosulfonyl fluoride-assisted Atherton–Todd-like reaction of diphenylphosphine oxide with alcohols under air generating diphenylphosphinate esters
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An efficient method for the synthesis of diphenylphosphinate esters via the Atherton–Todd-like reaction of diphenylphosphine oxide with alcohols assisted by perfluoroalkanosulfonyl fluoride in the presence of triethylamine under air is achieved affording the corresponding diphenylphosphinate esters in moderate to good yields of 52–78%. The protocol features the use of non-toxic and stable perfluoroalkanosulfonyl fluoride and metal-free reaction conditions.
- Wang, Wangyang,Jin, Hongai,Yan, Zhaohua,He, Mingchuang,Lin, Sen,Tian, Weisheng
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supporting information
p. 3489 - 3492
(2017/10/06)
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- Method for preparing organophosphate compound from P(O)-OH-containing compound and alcohol through efficient esterification
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The invention provides a method for efficiently and highly selectively synthesizing an organophosphate derivative containing different substitute functional groups. The method is characterized by adopting a polypeptide catalyst as a condensation reagent, taking a P(O)-OH-containing compound and alcohol as reaction substrates, and adding an organic solvent in a reaction system. The method disclosed by the invention has the advantages that the catalyst is cheap in cost and easy to obtain; the substrate applicability is high; reaction conditions are mild, safe and reliable; the selectivity of an obtained target product is close to 100 percent, and the yield is up to 90 percent or more. According to the method provided by the invention, the defects of a traditional method for synthesizing an organophosphate compound that the reaction selectivity is poor, the reaction steps are tedious, the yield is low, reagents which are harmful to the environment are required to be used, and the like are solved, and a good industrial application prospect is obtained. Meanwhile, the invention also provides the corresponding organophosphate derivative containing different substitute functional groups.
- -
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Paragraph 0034
(2017/07/21)
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- CDI-promoted direct esterification of P(O)-OH compounds with phenols
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A novel and efficient N,N′-carbonyl diimidazole-catalyzed protocol for the direct esterification of P(O)-OH compounds using phenols as efficient esterification reagents is illustrated. It is a simple way to synthesis a broad spectrum of functionalized O-aryl phosphinates, phosphonates, and phosphates from basic starting materials with moderate to excellent yields.
- Xiong, Biquan,Hu, Chenghong,Li, Haotian,Zhou, Congshan,Zhang, Pangliang,Liu, Yu,Tang, Kewen
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supporting information
p. 2482 - 2486
(2017/05/31)
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- Iron-catalyzed clean dehydrogenative coupling of alcohols with P(O)-H compounds: A new protocol for ROH phosphorylation
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An efficient oxygen-phosphoryl bond-forming reaction via iron-catalyzed cross dehydrogenative coupling has been developed. This transformation proceeds efficiently under oxidant- and halide-free reaction conditions with H2 liberation, and represents a straightforward method to prepare valuable organophosphoryl compounds from the readily available alcohols and P(O)-H compounds.
- Li, Chunya,Chen, Tieqiao,Han, Li-Biao
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supporting information
p. 14893 - 14897
(2016/10/11)
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- Electrophilic Fluorination of Secondary Phosphine Oxides and Its Application to P-O Bond Construction
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A novel and efficient electrophilic fluorination of secondary phosphine oxides with Selectfluor has been achieved. This transformation provides direct access to phosphoric fluorides in up to 92% yield under mild conditions. In addition, P-O bond construction via a one-pot coupling process of secondary phosphine oxides with water or alcohols in the presence of Selectfluor leads to the formation of phosphinic acids or phosphinates in up to 96% yield.
- Chen, Qian,Zeng, Jiekun,Yan, Xinxing,Huang, Yulin,Wen, Chunxiao,Liu, Xingguo,Zhang, Kun
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p. 10043 - 10048
(2016/11/02)
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- Nickel-catalyzed C-P cross-coupling reactions of aryl iodides with H-phosphinates
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Synthesis of aryl phosphinates was achieved through cross-coupling reactions of aryl iodides with H-phosphinates catalyzed by nickel under mild conditions. The method was applicable to various aryl iodides and H-phosphinates having defined stereochemistry
- Kinbara, Atsushi,Ito, Momoko,Abe, Tohru,Yamagishi, Takehiro
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p. 7614 - 7619
(2015/09/07)
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- Direct aerobic oxidative esterification and arylation of P(O)-OH compounds with alcohols and diaryliodonium triflates
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Copper-catalyzed aerobic oxidative esterification of P(O)-OH compounds is achieved using alcohols as efficient esterification reagents, giving the expected products with good to moderate yields. Furthermore, it is shown that the arylation of P(O)-OH compounds proceeds efficiently to produce the corresponding products via the treatment of diaryliodonium triflates under mild reaction conditions. It is a simple way to produce a broad spectrum of functionalized phosphinates, phosphonates, and phosphates from basic starting materials with good to excellent yields. The protocol is convenient for practical application. A plausible mechanism has been proposed for the reaction.
- Xiong, Biquan,Feng, Xiaofeng,Zhu, Longzhi,Chen, Tieqiao,Zhou, Yongbo,Au, Chak-Tong,Yin, Shuang-Feng
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p. 537 - 543
(2015/04/14)
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- MW-Assisted P-C Coupling Reaction Using P-Ligand-Free Pd(OAc) 2 Catalyst
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P-C coupling reactions of a variety of >P(O)H species with aryl bromides were found to take place under P-ligand-free microwave conditions.
- Jablonkai, Erzsébet,Balázs, László B.,Keglevich, Gy?rgy
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p. 660 - 663
(2015/07/20)
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- Base-promoted O-deprotonation/alkylation reaction of P(O)-OH compounds with alkyl halides
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A novel base-promoted O-deprotonation/alkylation reaction of P(O)-OH compounds with alkyl halides has been developed. The protocol is practical, representing a simple way to produce a broad spectrum of functionalized phosphinates, phosphonates, and phosphates from basic starting materials with good to excellent yields. A plausible mechanism was proposed for this reaction.
- Xiong, Biquan,Ye, Qianqian,Feng, Xiaofeng,Zhu, Longzhi,Chen, Tieqiao,Zhou, Yongbo,Au, Chak-Tong,Yin, Shuang-Feng
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p. 9057 - 9063
(2015/03/05)
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- A "green" variation of the Hirao reaction: The P-C coupling of diethyl phosphite, alkyl phenyl-H-phosphinates and secondary phosphine oxides with bromoarenes using a P-ligand-free Pd(OAc)2 catalyst under microwave and solvent-free conditions
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The P-C coupling of diethyl phosphite, alkyl phenyl-H-phosphinates, diphenylphosphine oxide and dialkylphosphine oxides with bromoarenes may be performed in the presence of a P-ligand-free Pd(OAc)2 catalyst and triethylamine under microwave-assisted (MW) and, in almost all cases, solvent-free conditions to afford diethyl arylphosphonates, alkyl diphenylphosphinates, aryldiphenylphosphine oxides and dialkylphenylphosphine oxides, respectively. This is the "greenest" accomplishment of the well-known Hirao reaction that has now been found to have general application for a broad spectrum of >P(O)H species with different reactivity and a great variety of substituted bromobenzenes. The alkyl phenyl-H-phosphinates were prepared by the MW-promoted alkylation of phenyl-H-phosphinic acid in the absence of any solvent. This journal is the Partner Organisations 2014.
- Keglevich, Gyoergy,Jablonkai, Erzsebet,Balazs, Laszlo B.
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p. 22808 - 22816
(2014/06/23)
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- Synthesis of new thiazole-2, -4, and -5-yl-(amino)methylphosphonates and phosphinates: Unprecedented cleavage of thiazole-2 derivatives under acidic conditions
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An efficient and reliable synthesis of new thiazole-(amino) methylphosphonic, phosphinic acids, and phosphine oxides is reported. The synthetic protocol is based on nucleophilic addition of phosphorous species to thiazole derived imines. Unexpectedly, it was discovered that heating of thiazole-2-yl-(amino)methylphosphonates and phosphinates with aqueous HCl leads to their decomposition resulting in a rupture of the C-P bond, rejecting of the phosphorus containing fragment and formation of the corresponding secondary N-(thiazole-2-yl-methyl)-alkylamines. Two alternative mechanisms for this cleavage are postulated.
- Olszewski, Tomasz Krzysztof,Boduszek, Bogdan
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experimental part
p. 8661 - 8666
(2011/01/04)
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- Anomalous reaction of ethyl bromofluoro- and difluoro-acetates with dialkylphosphonites
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The Michaelis-Arbuzov reaction of ethyl α-bromo-α-fluoro- and α, α-difluoro-acetates with dialkyl phenylphosphonites leads to the formation of unusual products including a fluorophosphinate. The reaction of ethyl bromofluoracetate with diisopropyl- and dimethyl-phenylphosphonites furnishes a complex mixture of eight and five compounds respectively. Five different compounds are obtained when ethyl bromodifluoroacetate is reacted with diisopropyl phenylphosphonite. Dimethyl phenylphosphonite yields three compounds when heated with bromochloromethane. The probable mechanism of formation of the compounds and their mass spectral characterization using GC-MS, tandem MS-MS and DART techniques are presented in this paper. Copyright Taylor & Francis Group, LLC.
- Durst,Rohrbaugh,Smith,Nilles,Connell,Laramee,Munavalli
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experimental part
p. 2655 - 2668
(2009/09/25)
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- Aminophosphine oxides in a pyridine series. Studies on the cleavage of pyridine-2- and pyridine-4-yl-(N-benzylamino)-methyldiphenylphosphine oxides in acidic solutions
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The synthesis and reactions of 1-(N-benzylamino)-1-(2-pyridyl)- and 1-(N-benzylamino)-1-(4-pyridyl)-methyldiphenylphosphine oxides are described. It was found that these compounds were exceptionally easy to cleave in aqueous sulfuric acid solutions to form diphenylphosphinic acid and the corresponding N-(pyridylmethyl)-benzylamines. The structure of a single diastereoisomer, that is, the (R)-(+)-1-[N-(α-methylbenzylamino)]-1-(4-pyridyl)-(S)-methyldiphen ylphosphine oxide was determined by X-ray crystallography. The acidic alcoholysis of the selected model chiral pyridine aminophosphine oxides was investigated by means of 31P NMR spectroscopy. The cleavage kinetics were also studied. On the basis of the obtained results, a mechanism of the cleavage was formulated.
- Goldeman, Waldemar,Olszewski, Tomasz K.,Boduszek, Bogdan,Sawka-Dobrowolska, Wanda
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p. 4506 - 4518
(2007/10/03)
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- Irreversibility of single electron transfer occurring from trivalent phosphorus compounds to iron(III) complexes in the presence of ethanol
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Various types of trivalent phosphorus compounds (1; Ph(3-n)P(OR)n) underwent single electron transfer (SET) to unsubstituted (2H) and 5-chloro-substituted tris(1, 10-phenanthroline)iron(III) complexes (2Cl) in the presence of ethanol in acetonitrile, resulting in the reduction of 2 to the corresponding iron(II) complexes. The rate constants (kp) for the overall SET process were determined spectrophotometrically to show that within each series of 1 with an identical alkoxy group OR, log kp correlates linearly with the difference in the half-wave potentials (ΔE1/2) between 1 and 2. The slope of each correlation line gave an α-value for each series of 1. The α-values were significantly smaller than unity, indicating that the SET step is irreversible, even though this step is endothermic. The trivalent phosphorus radical cation 1.+ generated in the SET step undergoes a rapid ionic reaction with ethanol, which is certainly the origin of the irreversibility. Upon examining the α-values more closely, it was found that the transition state of the SET step becomes earlier with increasing bulkiness of the substituent OR. It is concluded that 1 and 2 form a tight encounter complex to undergo SET from the former to the latter.
- Yasui, Shinro,Itoh, Kenji,Tsujimoto, Munekazu,Ohno, Atsuyoshi
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p. 1311 - 1318
(2007/10/03)
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- Reaction of trivalent phosphorus compounds with an Fe(III) complex in the presence of alcohol. Single electron transfer accompanied by a P-O bond formation
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Reactions of various types of trivalent phosphorus compounds with iron(III) complex in the presence of ethanol have been examined kinetically, showing that the single electron transfer from the former compounds to the latter is followed by rapid reaction of the resulting trivalent phosphorus radical cations with ethanol.
- Yasui, Shinro,Itoh, Kenji,Tsujimoto, Munekazu,Ohno, Atsuyoshi
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p. 1019 - 1020
(2007/10/03)
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- THE KINETICS AND MECHANISM OF THE REACTION OF TRICO-ORDINATE PHOSPHORUS COMPOUNDS WITH TETRACYANOQUINODIMETHANE AND TETRACYANOETHYLENE
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Trico-ordinate phosphorus compounds, ArnP(OPri)3-n where n = 0-3, react with tetracyanoquinodimethane (TCNQ) in acetonitrile in the presence of water to give the corresponding phosphoryl compounds, ArnP(O)(OPri)3-n and 1,4-bis-dicyanomethylbenzene (TCNQH2) in quantitative yield.The kinetics of these reactions are reported together with the Hammett ρ-parameters from variation of substituents in the aryl group for n = 1,2 and 3.On the basis of the available evidence, a mechanism is proposed involving one electron transfer from phosphorus (the donor) to TCNQ.A kinetic study of the reaction of triarylphosphines with TCNE in aqueous acetonitrile, however, suggests rate-limiting nucleophilic attack on nitrogen rather than the radical cation mechanism.Key words: Tricoordinate phosphorus, tetracyanoquinodimethane, tetracyanoethylene, kinetics, mechanism.
- Hall, C. D.,Beer, P. D.,Powell, R. L.,Naan, M. P.
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p. 145 - 156
(2007/10/02)
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- THE THERMAL AND PHOTO-REACTIONS OF DIPHENYLPHOSPHINITE ESTER WITH N-METHYLACRIDINIUM ION
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The thermal reaction of diphenylphosphinite esters (1b-f) with N-methylacridinium iodide (2) resulted in the formation of a phosphonium ion through a polar process.On the other hand, when isopropyl derivative (1f) was reacted with 2 under the irradiation with visible light, N-methylacridan, along with isopropyl diphenylphosphinate, was formed through single electron transfer (SET) from 1f to 2.
- Yasui, Shinro
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p. 197 - 200
(2007/10/02)
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- The Kinetics and Mechanism of the Reaction of Tricoordinate Phosphorus Compounds with Diaryl Trisulfides
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Kinetic data and activation parameters are reported for the reaction of a series of tricoordinate phosphorus compounds, , with diaryl trisulfides.The second-order rate coefficients for series of arylphosphines, phosphinites and phosphonites, correlate with the Hammett ? constants of the aryl substituents with ρ values of -1.1, -1.1 and -1.1 respectively and these results are discussed in terms of a biphilic mechanism analogous to that proposed for the reaction of tricoordinate phosphorus with S8.
- Hall, C. Dennis,Tweedy, Bruce R.,Kayhanian, Robert,Lloyd, John R.
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p. 775 - 779
(2007/10/02)
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- The Kinetics and Mechanism of the Reactions of Acyclic Trico-ordinate Phosphorus Compounds with Diethyl Peroxide
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The kinetics of the reactions of acyclic phosphinites, phosphonites, and phosphines with diethyl peroxide in benzene or acetonitrile as solvent are reported together with the activation parameters for phosphinites and phosphonites and Hammett ρ values for all three types of trico-ordinate phosphorus.The data reveal a bimolecular, non-polar transition state for each reaction with ρ values are virtually independent of the nature of the trico-ordinate phosphorus species.
- Lloyd, John R.,Lowther, Nicholas,Hall, C. Dennis
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p. 245 - 250
(2007/10/02)
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- PHOSPHORORGANISCHE VERBINDUNGEN 96. DIE SELECTIVE VERKNUEPFUNG BIOLOGISCH WICHTIGER FUNKTIONELLER GRUPPEN MIT PHOSPHORORGANISCHEN SAEUREN
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Derivatives of phosphinic, phosphonic, and phosphoric acids of the general type R1R2P(O)X show selectivity in their reactions with nucleophiles RYH (R = n-C4H9; Y = O, NR or S) according the Eq. (1); the selectivity depends on the nature of the leaving group (X = Cl, F, CN, N3 or OC6H4NO2(p)) and the base used.The nature of the ligands R1 and R2, exert a comparatively minor influence on the reaction.Method: (a) The phosphylating agent R1R2P(O)X was allowed to react with mixture of two nucleophiles RYH and RY'H in competition (Reagent ratio 1:1:1).The product mixture (R1R2P(O)YR + R1R2P(O)Y'R was then analyzed. (b) Compounds of the type HY-CH2-CH2-Y'H (serine-n-butylamide L-cysteinmethylester) were reacted with the phosphylating agent R1R2P(O)X (reagent ratio 1:1) according the Eqs. (3) and (4) respectively.The products were isolated, identified and the yields quantitatively determined.Results: For X = F, CN, OC6H4NO2 (p), the O-ester is formed virtually exclusively.For X = Cl, only amides are formed.Azides (X = N3) show no selectivity.In competition reactions using n-butylamine and n-butylthiol, the organophosphorus chlorides (X = Cl) were found to be N-selective,, whereas the corresponding cyanides (X = CN) were S-selective.In competition reactions using n-butanol and n-butylthiol, the organophosphorus fluorides (X = F) p-nitrophenylesters (X = OC6H4NO2(p)) and cyanides (X = CN) were all O-selective.
- Horner, L,Gehring, R.
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p. 157 - 176
(2007/10/02)
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