- Cleavage of Aromatic C-O Bonds via Intramolecular SNAr Reaction and Preparation of P, C, Axial-Stereogenic Menthyl Phosphine Derivatives
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Phosphine ligands with up to six chiral sites were prepared, starting from 2-phenylphenol, via O- and P-alkylation, cyclization, and coupling. The chirality was transferred from (L)-menthyl to phosphorus, α-carbon, and axis, to achieve excellent diastereoselectivities. During an intramolecular SNAr reaction with alkoxyl as the leaving groups, the C-O bond was converted to a C-C bond. Both phosphine boranes and oxides could be used for the conversions, affording a series of cyclic phosphines.
- Li, Qiang,Wang, Xiao-Ning,Yan, Bing-Xia,Ye, Jing-Jing,Zhang, Yu,Zhao, Chang-Qiu,Zheng, Hong-Xing
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- Multinuclear NMR Studies and Spin System Analyses on Dibenzo[c.e][1,2]Oxaphosphorine 2-Oxides
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2H-Dibenzo[c.e][1,2]oxaphosphorine 2-oxide (HDOPO), 2-(N,N-diethylamino)-dibenzo[c.e][1,2]oxaphosphorine 2-oxide (DEADOPO), and 2-ethoxy-dibenzo[c.e][1,2]oxaphosphorine 2-oxide (EtODOPO) are fully characterized in CDCl3 by 1H, 13C, 31P, and 15N NMR spectroscopy on 800- and 500-MHz instruments. A strategy enabling their unambiguous signal assignment is presented, with special emphasis on 2D 1H,13C HMBC spectra. Additional line-shape iterations of the aromatic 1H multiplets (ABCDX and ABCDEX spin systems) provided all long-range nJH,H and nJP,H coupling constants with utmost precision. The experimental results augmented with those of the model compound phenylphosphonous acid clearly demonstrate that nJH,H couplings of the PH proton as well as the nJP,C values do not decrease in a monotonic manner with the number of intervening bonds from the phosphorus atom. This fact may potentially lead signal misassignments, if the analysis starts out from the coupling constants, as it occurred for HDOPO in the recent publication by Wagner et al. (Phosphorus, Sulfur and Silicon, 187, 2012, 781-798). The corrected assignment will be given in the present paper. Finally, the A2M3X or ABM3X type 1H spectral patterns of ethyl groups are also analyzed and explicit equations are derived to evaluate the strongly coupled ABM3X multiplets in EtODOPO.
- Szakács, Zoltán,H?gele, Gerhard,Dékány, Miklós,ábrányi-Balogh, Péter,Keglevich, Gy?rgy
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- Practical synthesis of 6-chloro-dibenzo[c.e][1,2]oxaphosphorine
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The title P-heterocycle 3, a versatile intermediate in synthesis, was prepared by two independent methods. The first involves an environmentally friendly version of an old protocol starting from 2-phenylphenol (1) and phosphorus trichloride. Their interaction could be accomplished at 50C under solventless conditions. Cyclization of the intermediate (2) so obtained could be realized best under microwave conditions at 150C in the presence of ZnCl2. This method offers advantages over the traditional ones. According to another approach, the chloro-dibenzooxaphosphorine (3) was obtained by the novel reaction of 6H-dibenzo[c.e][1,2]oxaphosphorine-6-oxide (4) with phosphorus trichloride in boiling chloroform. Efficiency of the syntheses was demonstrated by converting the crude product 3 to a more stable phosphonic amide (6) that was stable enough to be isolated.
- Abranyi-Balogh, Peter,Keglevich, Gyoergy
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- Preparation method of DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) and intermediate of DOPO
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The invention relates to a preparation method of DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) and an intermediate of DOPO and belongs to the field of chemistry. Aiming at solving the technical problems, the invention provides the preparation method of the DOPO intermediate CDOP; the method comprises the following steps: raising the temperature of a mixture of o-phenylphenol, zinc chloride and phosphorus trichloride to 60 DEG C to 140 DEG C and carrying out esterification reaction; continually raising the temperature to 160 DEG C to 220 DEG C and reacting to obtain the product. Byadopting the preparation method provided by the invention, the phosphorus trichloride can be added in one step in a material feeding process and the excessive phosphorus trichloride and reaction byproducts do not need to be removed by decompressing and distilling after the reaction is finished, so that the production operation is greatly simplified; compared with an existing technology, the preparation method has remarkable advantages.
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Paragraph 0039; 0046; 0047; 0051; 0052; 0057-0074
(2018/04/01)
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- One-pot synthesis of new 6-(alkylamine)dibenzo[c,e][1,2]oxaphosphinine-6-oxides
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Several new 6-(alkylamine)-6H-dibenz[c,e][1,2]oxaphosphinine-6-oxides were prepared through a one-pot reaction, starting with 2-phenylphenol, phosphorus trichloride, and a Zn catalyst, to form 6-chloro-6H-dibenz[c,e][1,2]oxaphosphine. The alkylamine derivatives were subsequently prepared through a nucleophilic substitution reaction involving aliphatic amines and H2O2oxidation under soft conditions. This method has the advantages that it is a one-pot synthesis, does not require an inert atmosphere, and involves in situ catalyst formation.
- ávila-Zárraga, José Gustavo,Pérez, Ignacio,Beristain, Erick,Gavilan, Irma,Romero, Moises
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p. 364 - 367
(2017/02/10)
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- Preparation method of DiDOPO compound
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The invention discloses a preparation method of a DiDOPO compound. The preparation method is characterized by comprising the step of reacting by virtue of a ketone compound II and a chlorinated organic phosphine compound III in the presence of an oxygen-containing compound, so as to obtain a compound I. Compared with an existing synthetic method for preparing DiDOPO through reaction of DOPO and aromatic alkyl ketone under the catalysis of phosphorus oxychloride and the like, the preparation method has the advantages that reaction steps are shortened, the cost is effectively lowered, the operability and safety of a process are improved, a product is relatively easily purified, and the yield of the product is relatively high.
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Paragraph 0088; 0089; 0090
(2017/12/05)
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- Method for synthesizing 9, 10-dihydro-9-oxygen-10-phosphaphenanthrene-10-oxide
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The invention discloses a method for synthesizing 9, 10-dihydro-9-oxygen-10-phosphaphenanthrene-10-oxide. The method includes adding phosphorus trichloride into excessive o-phenylphenol drop by drop and carrying out esterification reaction to obtain phosphorous acid tri-orthophthalic phenyl ester; adding ZnCl2 catalysts into the phosphorous acid tri-orthophthalic phenyl ester, adding phosphorus trichloride into the phosphorous acid tri-orthophthalic phenyl ester drop by drop and carrying out acylation reaction to obtain 6-chlorine-(6 hydrogen)-dibenzo-(c, e)-oxygen phosphorus heterocyclic hexa-rings; sequentially carrying out hydrolysis reaction and cyclization reaction on the 6-chlorine-(6 hydrogen)-dibenzo-(c, e)-oxygen phosphorus heterocyclic hexa-rings to obtain the 9, 10-dihydro-9-oxygen-10-phosphaphenanthrene-10-oxide. The method has the advantages that the o-phenylphenol can be prevented from being volatilized or oxidized at high temperatures, the method is high in reaction speed and suitable for industrial production, and target products are high in yield and purity.
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Paragraph 0015; 0029; 0038; 0047; 0052; 0055-0056
(2018/02/04)
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- HALOGEN-FREE ACTIVE ESTER CURING AGENT COMPOUND FOR EPOXY RESINS, FLAME RETARDANT COMPOSITION COMPRISING SAME, ARTICLES MADE THEREFROM AND METHOD OF MAKING SAID COMPOUND
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There is provided herein a curing agent compound for curing thermosetting resins, e.g., epoxy resins, a composition comprising a thermoplastic and/or thermosetting resin, e.g., an epoxy resin and the curing agent, an article comprising the curing agent, and a method of making the curing agent.
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Paragraph 0109; 0110; 0111; 0112
(2017/02/09)
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- Superacid-catalyzed Friedel–Crafts phosphination of 2-hydroxybiphenyls with phosphorus trichloride
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Cyclic phosphorus compounds, 6H-dibenz[c,e][1,2]oxaphosphorin-6-oxide derivatives, were efficiently synthesized by the Friedel–Crafts reaction of 2-hydroxybiphenyls with phosphorus trichloride in the presence of superacids, especially trifluoromethanesulfonic acid (TfOH) as a catalyst. TfOH was investigated for the first time as an effective catalyst for the aromatic phosphination of 2-hydroxybiphenyls.
- Ito, Takatoshi,Iwai, Toshiyuki,Nakai, Takeo,Mihara, Masatoshi,Mizuno, Takumi,Ohno, Toshinobu,Ishikawa, Akira,Kobayashi, Jun-ichi
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p. 336 - 342
(2016/10/11)
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- TETRAMERISATION OF ETHYLENE
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A process for the tetramerisation of ethylene includes contacting ethylene with a catalyst under ethylene oligomerisation conditions. The catalyst comprises a source of chromium, a ligating compound, and an activator. The ligating compound includes a phosphine that forms part of a cyclic structure.
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Page/Page column 34
(2014/12/09)
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- Convenient synthesis of tropos phosphine-oxazoline ligands
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Tropos phosphine-oxazoline ligands have shown interesting coordination behavior and excellent chiral inducing ability in asymmetry catalysis. Here we present a convenient and economic route for the synthesis of this type of ligands. According to this new route, the ligands with different electronic and steric properties have been prepared successfully.
- Liu, Yuanyuan,Yang, Guoqiang,Yao, Dongmei,Tian, Fengtao,Zhang, Wanbin
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experimental part
p. 87 - 94
(2011/12/15)
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- A novel selective aza-Morita-Baylis-Hillman (aza-MBH) domino reaction and aza-MBH reaction of N-sulfonated imines with acrolein catalyzed by a bifunctional phosphine organocatalyst
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An efficient, bifunctional phosphine organocatalyst catalyzed aza-MBH reaction and aza-MBH domino reaction was developed between N-sulfonated imines and acrolein under mild conditions in moderate to excellent yields. Acrolein was added to a solution of N-(2-chlorobenzylidene)-4-methylhenzenesulfonamide and catalyst LBBA in CHCl3. The stirring was maintained at room temperature until completion of the reaction. The residue was purified by a flash column chromatography to yield 3a as a colorless solid. The OH group is utilized to stabilize the intermediate A through hydrogen bonding. The Michael addition of A with N-sulfonated imine gives intermediate B, when THF is used as the solvent. The aza-MBH/Michael/aldol/dehydrate domino reaction also provides an efficient method to synthesize tetrahydropyridine derivatives, which can be used as building blocks in organic synthesis.
- Meng, Xiangtai,Huang, You,Chen, Ruyu
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supporting information; experimental part
p. 6852 - 6856
(2009/07/18)
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- Bisbiphenylacylphosphine oxide and preparation method therefore
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A bisbiphenylacylphosphine oxide of formula (I) and its preparation method are provided. The formula of —Ar— is First, 10-chloro-9,10-dihydro-9-oxa-10-phosphaphenanthrene (CDOP) is prepared by using 2-phenylphenol, and then is esterified to synthesize 6-methoxy-(6H)-dibenz[c,e][1,2]oxa-phosphorin (MDOP). Next, acid chloride compounds are added for performing the Arbuzov reaction to synthesize bisbiphenylacylphosphine oxide. CDOP is hydrolyzed to be derived into 9,10-dihydro-9-oxa-10-phosphaphen-anthrene-10-oxide (DOPO), and then DOPO reacts with arylaldehyde to form secondary alcohol. Therefore, bisbiphenylacylphosphine oxide is prepared by using secondary alcohol under oxidation. Also, under a coupling reaction, DOPO reacts with the acid chloride compounds by using a Lewis acid as a catalyst to prepare bisbiphenylacylphosphine oxide.
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Page/Page column 4
(2008/06/13)
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- Method for preparing arylphosphonite antioxidant
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A method for preparing an arylphosphonite antioxidant of the formula (I) below is disclosed, wherein Ar is First, the reactants 2-phenylphenol and phosphorus trichloride are heated under the existence of a zinc chloride catalyst for producing 6-chloro-6H-dibenz[c,e][1,2]oxaphosphorin (CDOP) of the formula (II) below: Next, the excess phosphorus trichloride is removed. Finally, an organic solution of a di-hydroxylphenol compound of the formula (III), [in-line-formulae]Ar—(OH)2??(III)[/in-line-formulae] wherein Ar is defined as the above, is heated with the CDOP of formula (II) to form the product of the formula (I).
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Page/Page column 5-6
(2008/06/13)
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- Method for preparing a biphenylphosphonate compound
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A method for preparing a biphenylphosphonate compound of the following formula (I): wherein n is 2 or 3; Ar is a C6-C16 aromatic group; which comprising (a) reacting an o-phenylphenol with a phosphorus trichloride in the presence of a zinc chloride catalyst to form a 6-chloro-6H-dibenz [c,e][1,2] oxaphosphorin of the following formula (II); (b) reacting a polyhydroxybenzene compound of the formula (III) [in-line-formulae](HO)n—Ar ??(III) [/in-line-formulae] wherein n and Ar are defined the same as the above, with the compound of formula (II) to form a compound of the following formula (IV) wherein n and Ar are defined the same as the above; and (c) oxidizing the compound of formula (IV) in the presence of water and ozone to form the compound of formula (I).
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Page/Page column 3; 4
(2008/06/13)
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- Catalyst comprising a complex of a metal of subgroup VIII, on the basis of a phosphonite ligand and method for hydroformylation
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The catalyst comprises at least one bi- or more highly dentate phosphonite ligand of the general formula I or salts and mixtures thereof and is useful in a process for hydroformylating compounds containing at least one ethylenically unsaturated double bond by reaction with carbon monoxide and hydrogen.
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- Organophosphorous composition, method of producing organophosphorous compound, polyester composition and method of producing the same
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A polyester having a good color tone can be obtained by using, as an ester-forming component, a compound derived from an organophosphorous composition comprising an organophosphorous compound represented by the general formula (1): wherein R1and R2represent an organic group or a halogen atom, and m and n represent an integer of 0 to 4, provided that R1and R2may be the same or different when m or n is an integer of 2 to 4, and a divalent metallic compound in an amount more than 30 ppm and not more than 2300 ppm in terms of a divalent metal based on the organophosphorous compound.
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- Catalyst comprising at least one phosphonite ligand based nickel (O) complex and method for the production of nitriles
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A catalyst comprising at least one nickel(0) complex which comprises at least one mono-, bi- or multidentate phosphonite ligand of the formula I or salts and mixtures thereof, is prepared as described, and the catalysts are used to prepare mixtures of monoolefinic C5mononitriles with nonconjugated C═C and C≡N bonds by catalytic hydrocyanation of butadiene or of a 1,3-butadiene-containing hydrocarbon mixture in the presence of a catalyst of this type.
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- Process for preparing 6-oxo-(6H)-dibenz-[c,e][1,2]-oxaphosphorins (ODOPs)
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Optionally substituted ODOP is obtained by reaction of optionally substituted o-phenylphenol with PCl3 in the presence of Lewis acids at elevated temperature in a first stage, with according to the invention an excess of at least 0.05 mol of PCl3 per mol of o-phenylphenol being maintained during the entire reaction time, and, after removal of the PCl3, by hydrolysis in a second stage using 1-2 mol of H2 O per chlorine equivalent of the product of the first stage at 50°-150° C. and with removal of HCl and residual H2 O.
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- New class of bicyclic oxyphosphoranes with an oxaphosphorinane ring: Molecular structures and activation energies for ligand exchange
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Members of a new class of bicyclic oxyphosphorane compounds containing a six-membered oxaphosphorinane ring, Me2C(CH2O)2P(OC12H 8)(OXyl) (1), CH2(MeCHO)2P(OC12H8)(OXyl) (2), and C6H4(CH2O)2P(OC12H 8)-(OXyl) (3), were synthesized in 85-90% yield by the oxidative addition reaction of a diol to the cyclic phosphine precursors. X-ray analysis revealed trigonal bipyramidal (TBP) geometries with the rings spanning axial-equatorial positions. 31P NMR spectral data showed that pentacoordination was retained in solution. Variable-temperature 1H NMR spectra recorded over the range of-90 to 85°C supported intramolecular ligand exchange processes (pseudorotation) where each of the rings was required to be located in diequatorial positions in exchange intermediates. Application of a well-parametrized model treatment, including element effect and ring strain terms, resulted in excellent agreement between calculated and experimental activation energies for ligand exchange in 1-3. Strain energies for diequatorial placement of rings in 1-3 follow the order dibenzo-fused oxaphosphorinane > dioxaphosphorinane > benzo-fused dioxaphosphepane. The results of this study have application to nucleophilic displacement reactions of cyclic phosphorus compounds involving oxyphosphorane intermediates, e.g., cAMP. 1 crystallizes in the triclinic space group P1 with a = 8.607(1) A?, b = 16.817(2) A?, c = 17.153(2) A?, α = 115.15(1)°, β = 90.78(1)°, γ = 91.46(1)°, and Z = 4. 2 crystallizes in the monoclinic space group P21/n with a = 9.315(2) A?, b = 17.422(3) A?, c = 14.096(2) A?, β = 102.04(1)°, and Z = 4. 3 crystallizes in the monoclinic space group P21/c with a = 9.734(1) A?, b = 27.769(4) A?, c = 9.263(1) A?, β = 113.17(1)°, and Z = 4. The final conventional unweighted residuals are 0.037 (1), 0.040 (2), and 0.035 (3).
- Prakasha,Day, Roberta O.,Holmes, Robert R.
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p. 8095 - 8104
(2007/10/02)
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- 6H-DIBENZOXAPHOSPHORINS: SYNTHESIS AND CHEMISTRY
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The reaction of 1-phenylphenol with phosphorus trichloride at elevated temperature using zinc chloride as a catalyst gave the 6H-dibenzoxaphosphorin 1.The reaction of 1 with the phenols 3a-e gave the corresponding 6-phenoxy derivatives 4a-e.In the case of the sterically hindered phenol 3e, an improved procedure involved the reaction of the sodium phenolate of 3e with 1.The reaction of the benzenethiols 5a-b with 1 using triethylamine as an acid acceptor gave the corresponding derivatives 6a-b.
- Pastor, Stephen D.,Spivack, John D.,Steinhuebel, Leander P.
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