Palladium-Catalyzed Hydrophosphorylation of Allenes Leading to Regio- and Stereoselective Formation of Allylphosphonates

The aims of this study were to investigate the photoinitiation behaviors of acylphosphine oxide (APO) and bisacylphosphine oxide (BAPO) derivatives in comparison to D,L-camphorquinone (CQ)/tertiary amine (EDAB) system. Fifty six kinds of experimental unfilled, light-cured resins were prepared using APO, BAPO, CQ, EDAB, resin monomers, and adhesive monomers. The measurements of ultraviolet-visible (UV-VIS) spectroscopy, photopolymerization with differential scanning calorimeter (photo-DSC) and degree of conversion (DC) determination were performed. Results showed that the UV-VIS spectra of all APO and BAPO derivatives possessed λmax ranging between 365 and 416 nm. Their photoinitiation behaviors were not influenced by acidic adhesive monomers formulated in unfilled Bis-GMA-based resins (p<0.05). Although BAPO exhibited higher reactivity than CQ/EDAB in unfilled 6-methacryloyloxyhexcyl phosphonoacetate (6-MHPA)/ 2-hydroxyethyl methacrylate (HEMA) and 6-MHPA/glycerol monomethacrylate (GM)-based resins, it was found that there were no statistically significant differences in DC (％) between BAPO [44.2(6.5)-51.2(4.3)] and CQ/EDAB [42.4(4.4)-47.5(3.7)] (p<0.05). It was concluded that APO and BAPO photoinitiators exhibited reactivity comparable to that of CQ/tertiary amine system.

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“…1), which is frequently used in organophosphorus chemistry 14) . Two reaction schemes were used in this study for synthesis.…”

Section: Discussionmentioning

confidence: 99%

UV-VIS spectra and photoinitiation behaviors of acylphosphine oxide and bisacylphosphine oxide derivatives in unfilled, light-cured dental resins

Ikemura¹,

Ichizawa²,

Yoshida³

et al. 2008

Dent. Mater. J.

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“…1A (b)]. The latter is the reaction of trialkylphosphite with alkyl-alkylcarboxylate halides and is still frequently used in organophosphorus chemistry 31) . During the transformation, a tervalent phosphorus [P(III)] is converted into a pentavalent phosphorus [P(V)], which involves the conversion of >P-O-C linkage into >P(=O)-C linkage 30) .…”

Section: Discussionmentioning

confidence: 99%

Multi-purpose Bonding Performance of Newly Synthesized Phosphonic Acid Monomers

et al. 2007

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Multi-purpose bonding performance of three kinds of newly synthesized phosphonic acid monomers was investigated. Methacryloxyalkyl or acryloxyalkyl phosphonoacetates of 6-MHPA, 6-AHPA, 10-MDPA were synthesized in 42.8-51.9％ yields with a light yellow viscous liquid, and identified as new compounds by 1 H NMR, IR, and elemental analysis. Conventional adhesive monomers, namely VBPA, 4-META, and 4-AETA, and CEBA-p-TSMo-t-BPMA initiator were also used. Seven experimental composite-type adhesive resins comprising these six kinds of adhesive monomers and None (control) with the initiator were prepared. Tensile bond strengths of adhesive resins to unetched ground enamel and dentin, ground porcelain, and sandblasted Ni-Cr alloy were measured at a crosshead speed of 1.0 mm/min. Results showed that except with VBPA, there were no significant differences among 6-MHPA, 6-AHPA, 10-MDPA, 4-AETA, and 4-META in bonding performance to the adherends (p<0.01). It was found that the new phosphonic acid monomers provided good multipurpose adhesion to all adherends tested.

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“…After obtaining CQ-APO through the Michaelis-Arbuzov reaction 9,10) at Step 3, the νC=O absorption band (1776.44 cm -1 ) of CQ-COCl disappeared but the νC=O absorption band (1749.44 cm -1 ) of acylphosphine oxide group was recorded in the FT-IR spectrum, thus, the pale yellow crystal obtained could be identified as CQ-APO. Figure 6 shows a schematic illustration of the mechanism of Michaelis-Arbuzov reaction 9,10) , which is frequently used in organophoshorus chemistry 10,13) , between methoxydiphenylphosphine (MDPP) [CH3O-P(Ph)2] and CQ-COCl to yield CQ-APO and methyl chloride.…”

Section: Synthesis Of Cq-apo a Photoinitiator Having Both α-Diketone mentioning

confidence: 99%

Synthesis of a novel camphorquinone derivative having acylphosphine oxide group, characterization by UV-VIS spectroscopy and evaluation of photopolymerization performance

et al. 2010

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Camphorquinone (CQ) derivatives having acylphosphine oxide (APO) group are unknown. This study synthesized such a novel 7,7-dimethyl-2,3-dioxobicyclo[2.2.1]heptane-1-carbonyldiphenyl phosphine oxide (DOHC-DPPO = CQ-APO). Ultraviolet and visible (UV-VIS) spectra of CQ-APO, CQ, and APO were measured. Photopolymerization performances of experimental light-cured resins comprising these photoinitiators were investigated. Newly synthesized CQ-APO showed as a pale yellow crystal (mp 365K). UV-VIS spectrum of CQ-APO showed two maximum absorption wavelengths (λmax) [372 nm (from APO group) and 475 nm (from CQ moiety)] within 350-500 nm. Unfilled resin containing CQ-APO exhibited good photopolymerization time (9.6 sec) and relaxed operation time (50 sec), as well as a pronouncedly lower b value (4.0) in the CIELab color specification system than that containing CQ (84.0). Resin composites containing CQ-APO, exhibited high flexural strength . It was concluded that CQ-APO possessed two λmax peaks within 350-500 nm, and that CQ-APO-containing resins exhibited excellent color tone, good photopolymerization reactivity, relaxed operation time, and high mechanical strength.

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Palladium-Catalyzed Hydrophosphorylation of Allenes Leading to Regio- and Stereoselective Formation of Allylphosphonates

Abstract: Palladium 1,1‘-bis(diphenylphosphino)ferrocene complex catalysts promote the addition of to terminal allenes to afford the corresponding 1,2-adducts regio- and stereoselectively in high yields.

Cited by 76 publications

References 19 publications

UV-VIS spectra and photoinitiation behaviors of acylphosphine oxide and bisacylphosphine oxide derivatives in unfilled, light-cured dental resins

UV-VIS spectra and photoinitiation behaviors of acylphosphine oxide and bisacylphosphine oxide derivatives in unfilled, light-cured dental resins

Multi-purpose Bonding Performance of Newly Synthesized Phosphonic Acid Monomers

Synthesis of a novel camphorquinone derivative having acylphosphine oxide group, characterization by UV-VIS spectroscopy and evaluation of photopolymerization performance

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