- The unexpected formation of P-ylide in the reaction of 3-azido 1,4-benzodiazepine with tricyclohexylphosphine
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Reaction of substituted 3-azido 1,4-benzodiazepine with tricyclohexylphosphine is not the Staudinger reaction and unexpectedly results in P-ylide of 1,4-benzodiazepine. This is the first example of organic azides exhibiting the pseudo halide properties in the reactions of trivalent phosphorus compounds.
- Gololobov, Yu. G.,Krasnova, I. Yu.,Barabanov,Fedyanin,Andronati,Pavlovskii
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- Reactions of Ferrocenium Hexafluorophosphate with P?OR Nucleophiles Give Ring C?H Functionalization or Ring Replacement Products Depending on the Phosphorus Reagent
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Ferrocenium hexafluorophosphate reacts with different P?OR nucleophiles (PR3) in CH2Cl2 at room temperature to give either half-sandwich complexes [CpFe(PR3)3](PF6) (PR3=P(OMe)3, P(OEt)3, PhP(OMe)2) or ferrocenylphosphonium salts [CpFe(C5H4PR3)](PF6) (PR3=iPr2P(OMe), iPr2P(OEt)). Mixtures of both products are formed for some other nucleophiles (PR3=Ph2P(OMe), Ph2P(OEt), PhP(OiPr)2). The mechanism of the former reaction was established using DFT calculations. This reaction pathway is especially characteristic of π-acceptor nucleophiles, which is presumably explained by their ability to stabilize the 19e intermediates. The result of the reaction with tertiary phosphines, aminophosphines, and P?OR nucleophiles can be reliably predicted based on the values of the Tolman electronic parameter (below 2070 cm?1 – only ferrocenylphosphonium salt, in between 2073 cm?1 and 2080 cm?1 – only half-sandwich complex, and in the range from 2070 cm?1 to 2073 cm?1 – mixtures of both products).
- Chamkin, Aleksandr A.,Krivykh, Vasily V.,Kreindlin, Arkady Z.,Dolgushin, Fedor M.,Ustynyuk, Nikolai A.
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p. 1601 - 1610
(2021/04/16)
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- Silver-Catalyzed Regioselective Phosphorylation of para-Quinone Methides with P(III)-Nucleophiles
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A simple and efficient method for the silver-catalyzed regioselective phosphorylation of para-quinone methides (p-QMs) with P(III)-nucleophiles (P(OR)3, ArP(OR)2, Ar2P-OR) has been established via Michaelis-Arbuzov-type reaction. A broad range of P(III)-nucleophiles and para-quinone methides are well tolerated under the mild conditions, giving the expected diarylmethyl-substituted organophosphorus compounds with good to excellent yields. Moreover, a series of corresponding enantiomers can be obtained by employing dialkyl arylphosphonite (ArP(OR)2) as substrates. The control experiments and 31P NMR tracking experiments were also performed to gain insights for the plausible reaction mechanism. This protocol may have significant implications for the formation of C(sp3)-P bonds in Michaelis-Arbuzov-type reactions.
- Liu, Yu,Tang, Ke-Wen,Wong, Wai-Yeung,Xie, Jun,Xiong, Biquan,Xu, Shipan,Xu, Weifeng
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p. 14983 - 15003
(2021/11/12)
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- Preparation method of material compound
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The invention provides a preparation method of a diarylphosphonate compound, which comprises the following steps: in a protective gas atmosphere, taking diarylphosphonic acid and halogenated alkane as raw materials, taking heteropoly acid as a catalyst and taking an organic solvent as a solvent, and conducting reacting to obtain the diarylphosphonate compound. According to the preparation method disclosed by the invention, only an extremely small amount of catalyst is needed, the reaction temperature is relatively mild, the reaction time can be obviously shortened, the yield and purity are relatively high, and an unexpected technical effect is achieved.
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Paragraph 0044-0049; 0062-0063
(2021/04/10)
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- Efficient Synthesis of Phosphonamidates through One-Pot Sequential Reactions of Phosphonites with Iodine and Amines
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A one-pot sequential strategy to construct phosphonamidates has been developed by generating phosphonites in situ from arylmagnesium bromides and triethyl phosphite followed by treatment with iodine and amines. A variety of phosphonamidates were obtained with good to excellent yields at room temperature from easily available materials.
- Chen, Xunwei,Luo, Wenjun,Wang, Yanlin,Li, Zikang,Ma, Xiaorui,Peng, Ai-Yun
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p. 14474 - 14480
(2020/10/06)
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- New preparation method of first-class phenyl phosphine oxide initiator
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The invention provides a new preparation method of a first-class phenyl phosphine oxide initiator. The method comprises the steps that (1) benzene and aluminum trichloride are added into a reaction vessel and stirred uniformly, then phosphorus trichloride is added, the temperature is slowly increased, and after a complete reaction, the temperature is reduced to room temperature; (2) a reaction mixture obtained in the step (1) is slowly added dropwise into a solvent containing a decomplexing agent, and the temperature is controlled for decomplexing; (3) a decomplexing product obtained in the step (2) is filtered to separate solids, and filtrate is subjected to pressure reduction distillation to obtain phenyl dialkoxy phosphine or diphenyl alkoxy phosphine; (4) a product obtained in the step(3) is dissolved in a benzene or methylbenzene solvent, and a trichloromethyl acetyl compound is added dropwise for a reaction; and (5) a solution obtained after the complete reaction in the step (4)is subjected to low-pressure desolvation, and light-yellow liquid or solid, namely the phenyl phosphine oxide initiator, is obtained through crystallization, suction filtering and drying. The methodhas the advantages that raw materials are easy to obtain, cost is low, operation is easy to perform, and mass production can be realized.
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Paragraph 0045-0046
(2020/03/05)
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- Synthesis method of diphenyl hypophosphite
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The invention discloses a synthesis method of diphenyl hypophosphite, which belongs to the technical field of organic synthesis. The method comprises: by adopting N-methylimidazole as an acid-bindingagent, carrying out a reaction on diphenyl phosphorus chloride and an alcohol to obtain diphenyl hypophosphite and N-methylimidazole hydrochloride, carrying out standing and layering to remove the N-methylimidazole hydrochloride, and rectifying to obtain a finished product. The synthesis process does not need to add any solvent, is safe and environment-friendly, can remove the N-methylimidazole hydrochloride through layering, is simple to operate, mild in reaction condition, simple in wastewater and waste gas treatment, and easy to realize industrialization.
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Paragraph 0041-0048
(2020/10/04)
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- Chemoselective reduction of the phosphoryl bond of O-alkyl phosphinates and related compounds: An apparently impossible transformation
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A method is reported for the phosphoryl bond cleavage of O-alkyl phosphinates, phosphinothioates and certain phosphonamidates to furnish the corresponding P(iii) borane adducts. The two-step procedure relies upon initial activation of the phosphoryl bond with an alkyl triflate, followed by reduction of the resulting intermediate using lithium borohydride.
- Kenny, Niall P.,Rajendran, Kamalraj V.,Gilheany, Declan G.
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supporting information
p. 16561 - 16564
(2015/11/18)
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- Branched-regioselective hydroformylation with catalytic amounts of a reversibly bound directing group
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(Chemical Equation Presented) Phosphinites do the trick and work as reversibly bound catalyst-directing groups in catalytic amounts to allow for the highly regioselective hydroformylation of homo-allylic alcohols with terminal and internal alkene functions in favor of the branched product.
- Gruenanger, Christian U.,Breit, Bernhard
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supporting information; experimental part
p. 7346 - 7349
(2009/04/07)
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- Synthesis of diphenylphosphine oxide and diethyl phosphonate with 4-dimethylsila-2-hexen-6-ol moiety
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Two reagents useful for the Horner-Wittig or Wadshworth-Emmons reaction: 3-(2-hydroxyethyldimethylsila)-2-propen-1-yldiphenylphosphine oxide (5a) and diethyl 3-(2-hydroxyethyldimethylsila)-2-propen-1-ylphosphonate (5b) were synthesized from propargyl chloride and dimethylchlorosilane. The usefulness of phosphine oxide was demonstrated in the olefmation reactions of benzaldehyde and hexanal.
- Gawdzik,Wawrzenczyk
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p. 541 - 545
(2007/10/03)
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- On the reactivity of the iminodiphosphane C6H 4(o-CN)N=PPh2-PPh2: Fragmentation versus isomerisation
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The reactivity of the iminodiphosphane C6H4(o-CN)N= PPh2-PPh2, which contains an N=P-P unit, has been investigated. Reaction with small molecules, [viz. H2P/O2, H2O2,
- Fei, Zhaofu,Scopelliti, Rosario,Dyson, Paul J.
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p. 530 - 537
(2007/10/03)
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- X-H (X = C, N, O, P, S) Bond Activations Induced by β-Heterosubstituted Zirconaindenes
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The azazirconacyclopentene-substituted phosphines 3 and 4 have been found to activate the C-H bonds of acetylenic systems, such as methylpropiolate, diphenylphosphinoacetylene and phenylacetylene, or of methylene compounds, such as malonitrile and diethyl
- Cadierno, Victorio,Zablocka, Maria,Donnadieu, Bruno,Igau, Alain,Majoral, Jean-Pierre,Skowronska, Aleksandra
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p. 221 - 229
(2007/10/03)
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- Ether functionalised aminophosphines: synthesis and co-ordination chemistry of palladium(II) and platinum(II) complexes
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Ether-functionalised aminophosphines Ph2PNHR [R=CH2CH2OCH3 L1, CH2CH(OCH3)2 L2, CH2CH2CH2OCH3 L3 or C6H4OCH3-2 L4] were prepared from the reaction of Ph2PCl and the amine RNH2 in the presence of triethylamine. Reaction of L1-4 with [MCl2(cod)] (M=Pd or Pt) or [PtBr2(cod)] gave the complexes [MCl2L2] (1, M=Pd, L=L1; 2, M=Pd, L=L2; 3, M=Pd, L=L3; 4, M=Pd, L=L4; 5, M=Pt, L=L1; 6, M=Pt, L=L2; 7, M=Pt, L=L4) and [PtBr2(L1)2] 8. X-Ray crystallographic analyses of complexes 1 and 2 indicated the presence of bifurcated hydrogen bonds between the NH protons and both the chloride ligands and the ether oxygen atoms. Reaction of 1, 5 and 7 with two equivalents of AgBF4 led to formation of trans-[Pd(L1)2][BF4]2 9 and cis-[Pt(L2][BF4]2 (L=L1; 10 or L4 11) containing bidentate P,O-co-ordinated ligands whereas reaction of 1 with one equivalent of AgBF4 gave exclusively [{Pd(μ-Cl)(L1)2}2][BF4]2 12, containing only unidentate aminophosphine ligands. Reaction of 5 and 8 with NaNO2 led to formation of cis-[PtX(NO2)(L1)2] (X=Cl 13 or Br 14). Shielding of one of the NH protons with respect to 5 and 8 suggested loss of N-H...X hydrogen bonding and this was confirmed by an X-ray crystallographic analysis of 14. Reaction of L1-4 with [{M(dmba)(μ-Cl)}2] (M=Pd or Pt; Hdmba=N,N-dimethylbenzylamine) gave [M(dmba)ClL] (16, M=Pd, L=L1; 17, M=Pd, L=L2; 18, M=Pd, L=L3; 19, M=Pd, L=L4; 20, M=Pt, L=L1; 21, M=Pt, L=L2; 22, M=Pt, L=L4). The crystal structure of 16 reveals a similar bifurcated hydrogen bond to those observed in 1 and 2, whereas the structure of 18 shows the N-H...Cl interaction to be present but the N-H...O interaction absent. Reaction of 16, 20 and 22 with AgBF4 gave the bidentate P,O-co-ordinated complexes [M(dmba)L]BF4 (23, M=Pd, L=L1; 24, M=Pt, L=L1; 25, M=Pt, L=L4). Displacement of the co-ordinated ether oxygen was achieved by reaction of 24 and 25 with CO and of 25 with xylyl isocyanide and acetonitrile. Attempts to recrystallise 24 led instead to isolation of the dinuclear species [{Pt(dmba)(μ-PPh2O)}2] 30 which was characterised by X-ray crystallography.
- Burrows, Andrew D.,Mahon, Mary F.,Palmer, Mark T.
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p. 1669 - 1678
(2007/10/03)
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- Alkyl arylphosphinites
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A process for the preparation of alkyl arylphosphinites of the formula (I) STR1 in which R1 is (C1 -C16)-alkyl, cyclohexyl, cyclopentyl, aryl which can also be substituted by halogen, (C1 -C6)-alkoxy groups R2 is aryl which can also be substituted by halogen, (C1 -C6)-alkyl, (C1 -C6)-alkoxy groups, where R1 and R2 together with the phosphorous atom can also form a ring and R3 is (C1 -C4)-alkyl, which comprises reacting halo(aryl) phosphines of the formula (II) STR2 in which R1, R2 have the meaning given above and X is halogen, with ammonia-containing alcohols of the formula (III) in which R3 has the meaning given above.
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- STUDY OF THE ALKALINE CLEAVAGE OF THE P-C BOND IN PHOSPHINE OXIDES AND DERIVATIVES OF TRICHLOROMETHANEPHOSPHONATE
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A study of alkaline decomposition of aromatic phosphine oxides containing p- and o-nitrobenzyl, and trichloromethyl as leaving groups, is reported.The property of the trichloromethyl group as leaving group, and the CCl3--group's further decomposition in the hydrolysis of diethyl and disodium trichloromethanephosphonates, have also been investigated.
- Aksnes, Gunnar,Gierstae, Roald,Wulvik, Erik A.
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p. 141 - 152
(2007/10/02)
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- Studies on the Occurrence of Hydrogen Transfer, 75. Electrochemical Investigation of Raney-Nickel (Ra-Ni) Poisoned with S and P and Experiments for the Reactivation
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Ra-Ni with an artificial rest potential of -1000 mV (vs SCE) is shifted with different rates to more positive values after the addition of thioethers and carbon disulfide.Only with Na2S*9H2O a potential of -1100 mV (constant) is observed.Ra-Ni poisoned with sulfur is not reactivated neither cathodically nor anodically nor by the corrosive degradation at constant pH.Hydrogen structurally incorporated into the lattice of Ra-Ni (structural bonded hydrogen) is consumed by poisoning with thioethers and trivalent phosphorus compounds in a stoichiometric way.Ra-Ni-powder st epwise corrosively degradated up to 30 percent shows the same degree of desulfurization as the original Ra-Ni.Desactivated Ra-Ni (loss of structural bonded hydrogen) is reactivated (56 percent) by cathodical treatment.In competing reactions the P-S, C-S, and C-P-bond in thiophosphinic esters, thioethers and trivalent P-compounds are hydrogenolyzed by Ra-Ni, the C-P-bond faster than the C-S-bond. - Keywords: Structural Bonded Hydrogen, Hydrogen Transfer, Raney-Nickel, Electrochemical Investigation
- Horner, Leopold,Franz, Christoph
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p. 814 - 821
(2007/10/02)
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- ALKYL- UND ARYLKOMPLEXE DES IRIDIUMS UND RHODIUMS. XV. PHOSPHONIT- UND PHOSPHINITINDUZIERTE CO-INSERTIONS- UND C-H-ADDITIONSREAKTIONEN ortho-METHYLSUBSTITUIERTER IRIDIUMARYLE. REVERSIBLE CH3-METALLIERUNG IM PHOSPHINITKOMPLEX
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The synthesis of a series of cyclometallated hydrido-iridium(III) compounds fac- (Ar = C6H4: R = R' = OMe.Ar = C6H2Me2-4,6:R = OMe, OEt, Ph; R' = OMe, OEt) from iridium(I) aryls Ir(CO)(PPh3)2 and phosphonites or phosphinites is reported.As a result of a reversible methyl-to-metal hydrogen transfer the tris(phosphinite) complex exists in solution in an equilibrium with Ir(CO)(Ph2POMe)2 and Ph2POMe.The demetallated iridium(I) compound predominates in this equilibrium which may be shifted in favour of the metallacyclic component by addition of excess phosphinite.
- Dahlenburg, L.
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p. 215 - 222
(2007/10/02)
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- Phosphino Sulphonates, a Type of PIII-anhydride and Their Isomerisation into Phosphinoyl Sulphinates: a Novel Rearrangement in Phosphorus-Sulphur Chemistry
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The imidazolides (1) react smoothly with RSO3H to afford a novel class of trico-ordinate phosphorus anhydride, the phosphino sulphonates (2); under suitable structural circumstances the compounds (2) undergo a novel type of rearrangement, (2) -> (6), which provides the first example of a phosphinoyl sulphinate structure (6).
- Dabkowski, Wojciech,Michalski, Jan,Skrzypczynski, Zbigniew
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p. 1260 - 1261
(2007/10/02)
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- PHOSPHORORGANISCHE VERBINDUNGEN 91 Entschwefelungsstudien an optisch aktiven Thiophosphinsaerederivaten mit dem Ziele der Darstellung optisch aktiver Phosphinigsaerederivate
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Chiral phosphinous acid derivatives 4 MePhPX(X = OR, SR) were not obtained following desulphurization of optically active thiophosphinic acid esters 3(X = OR, SR), where sodium/liquid NH3, sodium-naphthalide (THF), potassium, trimethylphosphine, tributylphosphine, or cathodic fassion were employed as agents.The barrier to inversion in phosphinous acid derivatives is obviously small.
- Horner, Leopold,Jordan, Manfred
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p. 221 - 224
(2007/10/02)
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