- Reaction of Phosphites with Unsaturated Acid Chlorides: Synthesis and Reactions of Dimethyl But-2-enoylphosphonate
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Dimethyl trans-but-2-enoylphosphonate has been prepared in moderate yield from the reaction of trimethyl phosphite with excess of trans-but-2-enoyl chloride.When the reaction is carried out using equimolar quantities of reactants the major product is the trans-but-2-enoyl ester (5).This ester is formed by the facile reaction of the trans-but-2-enoyl phosphonate with trimethyl phosphite to give the pentacovalent oxaphospholen (6) which is then attacked by trans-but-2-enoyl chloride.The reactions of trialkyl phosphites with 2-methylpropenoyl and propenoyl chlorides follow similar pathways but at different relative rates.
- Szpala, Anthony,Tebby, John C.,Griffiths, D. Vaughan
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Read Online
- METHOD FOR PRODUCING ORGANOPHOSPHORUS COMPOUND
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PROBLEM TO BE SOLVED: To provide a method for producing an organophosphorus compound which has excellent energy efficiency without containing a halogenated alkyl or a by-product derived from a halogenated alkyl. SOLUTION: There is provided a method for producing an organophosphorus compound by reacting a trivalent organophosphorus compound represented by the following general formula (1) in the presence of a super strong acid and/or at least one acid catalyst containing a solid superstrong acid catalyst to generate a pentavalent organophosphorus compound represented by the following general formula. (where Z1 represents OR2 or R2; Z2 represents OR3 or R3; R1, R2 and R3 represent an alkyl group, an alkenyl group or the like; when R2 and R3 are an alkyl group or the like, R2 and R3 may be bonded to each other to form a cyclic structure; and R1 may be a hydrogen atom.) SELECTED DRAWING: None COPYRIGHT: (C)2020,JPOandINPIT
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Paragraph 0083; 0094
(2020/05/02)
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- Phosphate compound and synthetic method thereof, and non-aqueous electrolyte
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The invention relates to a phosphate compound, a method for synthesizing the phosphate compound, and a non-aqueous electrolyte; the main means for suppressing side reactions on the surface of an electrode comprises coating an electrode active material and adding an effective film-forming additive to an electrolyte to form a passivation film having sufficient thickness and density on the surface ofthe electrode; the two means are undoubtedly used for preventing the electrolyte from contacting the surface of the electrode to obtain and lose electrons and preventing the surface of the electrodefrom being corroded by decomposition byproducts of the electrolyte. The phosphate compound disclosed by the invention has the beneficial effects that the phosphate compound is easy to prepare and purify, high in thermal stability, convenient to store, strong in compatibility with other components of an electrolyte and other components in a battery, moderate in viscosity, high in dielectric constant, capable of dissolving a lithium salt, has certain wetting capacity, and has flame-retardant and positive and negative electrode surface film-forming functions.
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Paragraph 0009; 0027; 0031; 0065-0068
(2020/12/31)
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- Water determines the products: An unexpected Br?nsted acid-catalyzed PO-R cleavage of P(iii) esters selectively producing P(O)-H and P(O)-R compounds
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Water is found able to determine the selectivity of Br?nsted acid-catalyzed C-O cleavage reactions of trialkyl phosphites: with water, the reaction quickly takes place at room temperature to afford quantitative yields of H-phosphonates; without water, the reaction selectively affords alkylphosphonates in high yields, providing a novel halide-free alternative to the famous Michaelis-Arbuzov reaction. This method is general as it can be readily extended to phosphonites and phosphinites and a large scale reaction with much lower loading of the catalyst, enabling a simple, efficient, and practical preparation of the corresponding organophosphorus compounds. Experimental findings in control reactions and substrate extension as well as preliminary theoretical calculation of the possible transition states all suggest that the monomolecular mechanism is preferred.
- Li, Chunya,Wang, Qi,Zhang, Jian-Qiu,Ye, Jingjing,Xie, Ju,Xu, Qing,Han, Li-Biao
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supporting information
p. 2916 - 2922
(2019/06/18)
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- Catalytic Phosphite Hydrolysis under Neutral Reaction Conditions
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Cationic phosphametallocene-based platinum(II) aqua complexes were used as efficient precatalysts for the hydrolysis of aromatic and aliphatic tertiary phosphites under neutral reaction conditions at room temperature, leading to the selective cleavage of one P-O bond of the phosphite. NMR labeling experiments combined with stoichiometric model reactions and theoretical density functional theory calculations, performed with the appropriate model compounds, shed light on the operative catalytic cycle, which comprises intramolecular water molecule transfer to the cis-coordinated phosphite molecule.
- Oberhauser, Werner,Manca, Gabriele
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supporting information
p. 4824 - 4827
(2018/05/17)
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- Synthesis and herbicidal activity of α-[(substituted phenoxybutyryloxy or valeryoxy)]alkylphosphonates and 2-(substituted phenoxybutyryloxy)alkyl-5,5-dimethyl-1,3,2-dioxaphosphinan-2-one containing fluorine
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Based on our previous work on the structural modification of the lead compound I, three series of novel fluorine-containing phosphonates derivatives (II, III and IV) were designed and synthesized. Their post-emergence herbicidal activities against some species of weeds were evaluated in a green house. The compounds II were synthesized by introducing of two methylene into the structure I. Compared with the commercial herbicidal clacyfos, compounds II showed moderate herbicidal activity with 60–85% inhibition effect against chingma abutilon (Abutilon theophrasti), common amaranth (Amaranthus retroflexus) and white eclipta (Eclipta prostrate) at a rate of 150 g ai/ha. The compounds III were designed by introducing open-chain phosphonates, which displayed notable herbicidal activity. Especially, the compounds III-1–III-4, III-6, III-8, III-11 and III-12 exhibited significant herbicidal activity (80–100%) comparing to the clacyfos against all tested broadleaf weeds, while compounds IV with five carbon atoms in the carboxylic acid chain were inactive against all of the tested weeds. Structure-activity relationship analyses indicated that the length of the carbon chain had a great effect on the herbicidal activity. Furthermore, a broad spectrum test confirmed that compounds III-4 and III-8 were comparable with glyphosate against all of the tested weeds at a rate of 75 g ai/ha.
- Wang, Wei,Zhou, Yuan,Peng, Hao,He, Hong-Wu,Lu, Xing-Tao
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- Total Synthesis and Structural Revision of Chaetoviridins A
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The first synthesis of the proposed structures of chaetoviridins A 1-4 has been achieved in 10 steps by controlling the syn- or anti-aldol side chain. The angular lactone has been regioselectively introduced by condensation of a chiral dioxin-4-one to cazisochromene. Comparison of the NMR and circular dichroism data of the synthesized and reported natural products led to the complete reassignment and renaming of the chaetoviridins.
- Makrerougras, Mehdi,Coffinier, Romain,Oger, Samuel,Chevalier, Arnaud,Sabot, Cyrille,Franck, Xavier
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supporting information
p. 4146 - 4149
(2017/08/14)
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- The formation of dimethyl amino(pyrene-1-yl)methylphosphonates in the Kabachnik-Fields reaction with dibenzyl phosphite, pyrene-1-carboxaldehyde and a non-aromatic amine in methanol
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The Kabachnik-Fields reaction of pyrene-1-carboxaldehyde with dibenzyl phosphite and aliphatic amines in methanol led to the formation of dimethyl amino(pyren-1-yl)methyl-phosphonates, in some cases accompanied by dimethyl hydroxy(pyren-1-yl)methyl-phosphonate. These results are exclusive for the above compounds, in all other studied cases (aromatic aldehydes, aromatic amines) the mixtures of several aminophosphonates were obtained.
- Lewkowski, Jaros?aw,Rodriguez Moya, Maria
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p. 713 - 718
(2017/06/05)
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- Synthesis and Herbicidal Activity of α-(Substituted Phenoxybutyryloxy or Valeryloxy)alkylphosphonates and 2-(Substituted Phenoxybutyryloxy)alkyl-5,5-dimethyl-1,3,2-dioxaphosphinan-2-one
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On the basis of our work on the modification of alkylphosphonates 1, a series of α-(substituted phenoxybutyryloxy or valeryloxy)alkylphosphonates (4-5) and 2-(substituted phenoxybutyryloxy)alkyl-5,5-dimethyl-1,3,2-dioxaphosphinan-2-one (6) were designed and synthesized. The bioassay results indicated that 14 of title compounds 4 exhibited significant postemergence herbicidal activity against velvetleaf, common amaranth, and false daisy at 150 g ai/ha. Compounds 5 were inactive against all tested weeds. Compounds 6 exhibited moderate to good inhibitory effect against the tested dicotyledonous weeds. Structure-activity relationship (SAR) analyses showed that the length of the carbon chain as linking bridge had a great effect on the herbicidal activity. Broad-spectrum tests of compounds 4-1, 4-2, 4-9, 4-30, and 4-36 were carried out at 75 g ai/ha. Especially, 4-1 exhibited 100% inhibition activity against the tested dicotyledonous weeds, which was higher than that of glyphosate.
- Wang, Wei,Zhang, Sha-Sha,Zhou, Yuan,Peng, Hao,He, Hong-Wu,Lu, Xing-Tao
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p. 6911 - 6915
(2016/10/03)
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- Synthesis and biological activity of 1-(Substituted phenoxyacetoxy)- 1-(pyridin-2-yl or thien-2-yl)methylphosphonates
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A series of novel O,O-dimethyl 1-(substituted phenoxyacetoxy)-1-(pyridin-2-yl or thien-2-yl)methylphosphonates 6a-n and 7a-d were synthesized. Their structures were confirmed by IR, 1H NMR, mass spectroscopy, and elemental analyses. The results of preliminary bioassays show that some of the title compounds exhibit moderate to good herbicidal and fungicidal activities. For example, the title compounds 6a, 6c, 6l, 6m, and 7d possess 90-100% inhibition against most of the tested plants at the dosage of 1500 g ai/ha, whereas the title compounds 6b, 6g-h and 6n possess 92-100% inhibition against Fusarium oxysporum, Phyricularia grisea, Botrytis cinereapers, Gibberella zeae, Sclerotinia sclerotiorum, and Cercospora beticola at the concentration of 50mg/L.
- Wang, Tao,Wang, Wei,Peng, Hao,He, Hongwu
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p. 173 - 179
(2015/01/30)
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- Stability of phosphite coordinated to ruthenium(II) in aqueous media
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Changes in the reactivity of phosphorus(III) esters, which are promoted by coordination to the ruthenium(II) metal centre, were the focus of this study. Nuclear magnetic resonance data, which were acquired as a function of time, suggest that the phosphite coordination to the ruthenium(II) centre stabilises these molecules in terms of hydrolysis. This stabilisation is greater when the coordination occurs to the trans-[Ru(H2O)(NH3) 4]2+ rather than to the trans-[Ru(NO)(NH3) 4]3+ fragment, and these results are interpreted considering the 4dπ(RuII) → 3dπ(P(III)) back-bonding interactions. The correlation between the data on alkyl phosphite hydrolysis constants in trans-[Ru(NO)(NH3)4P(III)]n + (P(III) = P(OEt)3, P(O)(OEt)2, P(O iPr)3 and P(OBu)3) complexes and the δ13C data show that the hydrolysis of phosphites that are coordinated to Ru(II) preferably occurs via the Michaelis-Arbuzov mechanism. Only the nitrosyl complex, where P(III) = P(OMe)3, did not exhibit this correlation, which suggests that the hydrolysis likely occurs via the Aksnes mechanism in this case.
- Truzzi, Daniela R.,Franco, Douglas W.
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p. 238 - 244
(2014/07/21)
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- Catalytic enantioselective hydrophosphonylation of aldehydes using the iron complex of a camphor-based tridentate Schiff base [FeCl(SBAIB-d)]2
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An iron(III)-Schiff base-catalyzed, highly enantioselective hydrophosphonylation of various aldehydes is described. Under the optimized reaction conditions, 5 mol% of the iron/camphor-based tridentate Schiff base complex [FeCl(SBAIB-d)]2 produces high yields (up to 99%) of α-hydroxy phosphonates in excellent enantioselectivities (up to 99%). The merits of this catalytic system are an easily synthesizable catalyst, inexpensive starting materials, practically simple aerobic reaction conditions, and low catalyst loading (5 mol%). Copyright
- Boobalan, Ramalingam,Chen, Chinpiao
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supporting information
p. 3443 - 3450
(2013/12/04)
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- Method for the esterification of P-O components
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The present invention is directed to a new method for esterification of P-O components. More specifically, the present invention relates to a new method for esterification of P-O components containing at least one P-O-H functional group, whereby the P-O-H functional group(s) is converted into P-O-R functional group(s). The method according to the invention may find particular use in the manufacture of diesters of phosphorous acid.
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Paragraph 0038; 0039; 0043
(2013/04/25)
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- METHOD FOR THE ESTERIFICATION OF P-O COMPONENTS
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The present invention is directed to a new method for esterification of P-O components. More specifically, the present invention relates to a new method for esterification of P-O components containing at least one P-O-H functional group, whereby the P-O-H functional group(s) is converted into P-O-R functional group(s). The method according tothe invention may find particular use in the manufacture of diesters of phosphorous acid.
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Paragraph 0038-0042
(2013/04/25)
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- Synthesis and herbicidal activity of O,O-dimethyl-(3-phenacryloyloxy) alkyl phosphonates
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In an attempt to discover novel compounds with high biological activity and low toxicity, a series of new O,O-dimethyl-(3-phenacryloyloxy) alkyl phosphonates 4a-m have been designed and synthesized by the reaction of 3-phenacryloyl chloride with α-hydroxyalkyl phosphonate. All new compounds were characterized by elemental analysis, IR, and 1H NMR spectroscopy as well as by mass spectrometry. The results of preliminary bioassay indicate that some of the target compounds have excellent inhibitory activities on Triticum aestivum (wheat) and Brassica napus L. (rape). Copyright Taylor and Francis Group, LLC.
- Wang, Tao,Huang, Hai Jin,Luo, Jin,Yu, Dan Hong
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scheme or table
p. 135 - 141
(2012/05/04)
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- PROCESS FOR THE MANUFACTURE OF DIALKYLPHOSPHITES
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A process for the manufacture of dialkyl phosphites is disclosed. In detail, dialkyl phosphites are prepared starting from P4O6, or partially hydrated species thereof cumulatively P-O, by reacting specific molar ratios of alcohol and P-O, containing from 1 to 6 P-O-P bonds in the molecule, in the presence of trialkylphospite (TAP) to thus yield high purity and high yield of dialkyl phosphites. The P-O reactant is preferably represented by liquid P4O6.
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Page/Page column 8
(2010/12/26)
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- Synthesis and biological activity of O,O-Dimethyl-2,6-Pyridinyl diformyloxy alkyl phosphonates
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In an attempt to discover novel compounds with high activity and low toxicity, a series of new O,O-dimethyl-2,6-pyridinyl diformyloxy alkyl phosphonates 4a-4p has been designed and synthesized by the reaction of 2,6-pyridinyl diformyloxy chloride with α-hydroxyalkyl phosphonate. The structures of all new compounds were characterized by elementary analysis, IR, 1H NMR, and MS spectroscopies. The results of a preliminary bioassay indicate that some of the target compounds have obviously promotive action for plant growth against the stalk of barnyard grass.
- Wang, Tao,Lei, Da You,Huang, Ying,Ao, Li Hua
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scheme or table
p. 2777 - 2785
(2010/04/03)
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- Phosphorus halides complexes with 4-dimethylaminopyridine and N-methylimidazole
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Formation of complexes between phosphorus halides and 4- dimethylaminopyridine or N-methylimidazole was studied. The following phosphorus halides: trichloride, oxychloride, and sulfochloride, were found to form equilibrium mixtures of the complexes containing different numbers of the ligand molecules. Among the studied phosphorus halides only pentachloride and tribromide form stable complexes with a constant composition.
- Bezgubenko,Pipko,Sinitsa
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scheme or table
p. 911 - 918
(2011/04/15)
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- Reduction of dichlorvos and omethoate residues by O2 plasma treatment
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A practical, inexpensive, and green chemical process is greatly needed for degrading pesticides in food and environmental water. In this work, the impact of O2 plasma treatment on reduction of dichlorvos (DDVP) and omethoate in maize was determ
- Bai, Yanhong,Chen, Jierong,Mu, Hui,Zhang, Chunhong,Li, Baoping
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experimental part
p. 6238 - 6245
(2010/07/06)
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- Synthesis of O,O-dialkyl 2-oxo-2-(4-(selenomorpho-linosulfonyl)phenylamino) ethylphosphonate
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A series of O,O-dialkyl 2-oxo-2-(4-(seleomorpholinosulfonyl)phenylamino) ethy lphosphonate were synthesized by reactions of 2-chloro-N-(4- (seleomorpholino sulfonyl)phenyl)acetamide with dialkylphosphite in the presence of sodium hydride. The structure of all new compounds has been confirmed by 1H NMR,31P NMR, IR, Mass spectroscopy and elemental analyses. Copyright Taylor & Francis Group, LLC.
- Wang, Fang,Hu, Liming,Li, Xiaopeng,Xu, Xuemei,Du, Hongguang
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scheme or table
p. 610 - 616
(2009/04/11)
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- An efficient synthesis of O,O- di propyl (E)-2-[1-methyl 2-oxopropylidene]phosphorohydrazidothiolate (E) oxime and its analogues: A potential marine toxin
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An efficient method for the synthesis of Ptychodiscus brevis toxin O,O- di n-propyl (E)-2-[1-methyl 2-oxopropylidene]phosphorohydrazidothiolate (E) oxime (TG-1) and its analogues has been developed using thermally stable and recyclable silica gel and Na2SO4 as a condensing agent and water scavenger, respectively. The compounds were evaluated against fish Rasbora daniconius by determining the LC50 and LC90 values. The results of biological evaluation showed that these compounds have high degree of toxicity. Copyright Taylor & Francis Group, LLC.
- Gupta, Arvind K.,Dubey,Parashar,Kaushik
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scheme or table
p. 1892 - 1910
(2009/08/07)
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- Synthesis and herbicidal activity of O,O-dialkyl phenoxyacetoxyalkylphosphonates containing fluorine
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A series of substituted phenoxyacetoxyalkylphosphonates bearing fluorine were designed and synthesized. All the new compounds were identified by elemental analysis, IR, 1H NMR and MS and were tested for herbicidal activity in greenhouse at a rate of 1.5 kg/ha. The results of preliminary bioassay showed that fluorine moiety introduced to the core structure could help to improve the herbicidal activity, and compounds with a 3-trifluoromethyl in benzene ring exhibited higher inhibitory activity.
- Chen, Ting,Shen, Ping,Li, Yanjun,He, Hongwu
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p. 291 - 295
(2007/10/03)
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- Electrocatalytic eco-efficient functionalization of white phosphorus
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The novel eco-efficient methods to transform white phosphorus into the esters of phosphoric, phosphorous and phosphonic acids, tertiary phosphines and other organophosphorus compounds under conditions of electrochemical catalysis were elaborated. The mechanism of these processes was investigated using the method of cyclic voltammetry and preparative electrolysis.
- Budnikova, Yulia H.,Yakhvarov, Dmitry G.,Sinyashin, Oleg G.
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p. 2416 - 2425
(2007/10/03)
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- Catalytic vapour-phase hydrolysis and photocatalytic oxidation of dimethyl methylphosphonate on a TiO2 surface
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The products of dimethyl methylphosphonate (DMMP) hydrolysis and photocatalytic oxidation on TiO2 were identified and quantified by a FTIR technique at different relative air humidities and concentrations of DMMP.
- Trubitsyn, Dmitry A.,Vorontsov, Alexander V.
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p. 197 - 199
(2007/10/03)
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- Reconsideration of the base-free batch-wise esterification of phosphorus trichloride with alcohols
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Batch-wise esterification of phosphorus trichloride with different alcohols in the absence of base and cleavage of the reaction products by the HCl released in course of the reaction were reinvestigated. The role of the kind of alcohol, mixing order of reagents, temperature, time of reaction, and excursion of gaseous HCl in the proportional composition of the reaction products were studied. Considering the mechanism of esterification and cleavage of the products, the optimized conditions to retain the cleavage process and high-yield production of dialkyl hydrogen phosphonates were determined.
- Fakhraian,Mirzaei
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p. 401 - 404
(2013/09/05)
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- Preparation of phosphinodipeptide analogs as building blocks for pseudopeptides synthesis
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A simple and effective preparation of phosphinodipeptides, in good overall yields, has been developed. This one pot procedure, allowing the variation of the substituents in α and/or β position to the phosphorus atom and also in α position to the nitrogen atom, consists in the addition of alkyl hypophosphites to imines, followed by Michael-addition on acrylates. To show the value of phosphinodipeptides analogs 1 as synthetic intermediates, selective deprotections of the three functional groups are described.
- Cristau, Henri-Jean,Coulombeau, Agnès,Genevois-Borella, Arielle,Sanchez, Frédéric,Pirat, Jean-Luc
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p. 381 - 391
(2007/10/03)
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- Inhibitors of phosphatidyl myo-inositol cycle
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The present invention relates to the preparation and biological activity of 3-deoxy-D-myo-inositol ether lipid analogs as inhibitors of phosphatidylinositol-3-kinase signaling and cancer cell growth. The compounds of the present invention are useful as anti-tumor agents which effectively inhibit the growth of mammalian cells.
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- Oxidation in organophosphorus chemistry: Potassium peroxymonosulphate
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Potassium peroxymonosulphate (Oxone) is used as an efficient, chemoselective and stereoselective oxidizing agent for a wide variety of phosphorous, phosphothio- and phosphoseleno-compounds.
- Wozniak, Lucyna A.,Stec, Wojciech J.
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p. 2637 - 2640
(2007/10/03)
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- Novel α-hydroxyphosphonates - Enol phosphates rearrangement
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CsF was found to be a very efficient basic catalyst for the rearrangement of α-hydroxy-β,γ-epoxy(aziridino)phosphonates to enol phosphates. DBU and potassium fluorides (anhydrous or dihydrate) appeared less active in promoting this rearrangement, but strong enough to execute the retro-Abramov reaction. Because of the competition from the retro-Abramov reaction, stereochemistry of the rearrangement cannot be unequivocally assigned, but it seems reasonable that intermediates having the dimethoxy-phosphoryl group and O-epoxide or N-aziridine atoms as leaving groups in the antiperiplanar positions are involved.
- Wroblewski,Karolczak
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p. 1191 - 1202
(2007/10/03)
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- Synthesis of organophosphorus compounds in terms of elemental phosphorus, sulfur and their derivatives
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We have developed new facile methods for synthesizing various organophosphorus compouds on the basis of elemental phosphorus and sulfur, phosphorus sulfides and esters of thiophosphorous acids.
- Batyeva, Elvira S.,Nizamov, Il'yas S.,Kursheva, Lidiya I.,Frolova, Liliya V.
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- CYCLOPENTANE(ENE) HEPATANOIC OR CYCLOPENTANE(ENE) HEPTENOIC ACID, 2-HYDROCARBYL PHOSPHINYLOXYALKYL OR PHOSPHONAMIDOALKYL AS THERAPEUTIC AGENTS
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The present invention relates to cyclopentane (or cyclopentane) heptanoic or cyclopentane (or cyclopentene) heptenoic acid, 2-hydrocarbyl phosphinyloxyalkyl or phosphonamidoalkyl, 1-esters, and derivatives thereof, useful as therapeutic agents. In particular, the therapeutic agents of this invention are useful as ocular hypotensives.
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- Electrosynthesis of aliphatic esters of phosphorus acids from white phosphorus in alcohol solutions, involving radical cations of phenothiazine and triarylamine
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Aliphatic esters of phosphorus acids can be prepared from white phosphorus by electrolysis of emulsified white phosphorus in alcohol solutions of phenothiazine or triarylamine.
- Budnikova, Yu. G.,Kargin, Yu. M.
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p. 504 - 507
(2007/10/03)
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- Thermal Retro-Trimerization of Some 1,3,5,2,4,6-Trioxatriphosphorinanes to Phosphenites
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Pyrolysis in a packed tube of the vapor from three 2,4,6-tris(aryloxy)-1,3,5,2,4,6-trioxatriphosphorinanes was performed at 300-350 deg C and 1E-6 mm; the product was collected on a cold finger chilled by liquid nitrogen.The cracking of the trimer was complete, and the product at -195 deg C appeared to consist only of the monomeric aryl phosphenite, ArOP=O.On warming, dimerization occured, later followed by trimer formation.The weak 31P NMR signal for the phosphenite (about δ 238 for three O-aryl derivatives) persisted in the solution for several weeks if water was rigorously excluded.Treatment of the phosphenite with water or alcohols at -195 deg C gave a mixture of products; the major product (ArO-PH(O)OH) came from addition of the nucleophile to the P=O bond, but significant amounts (10-20percent) of dialkyl H-phosphonates (HP(O)(OR)2) were present, apparently from displacement of the O-aryl substituent of the phosphenite, followed by addition to the double bond.
- Quin, Louis D.,Ionkin, Alexey S.
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p. 5186 - 5189
(2007/10/02)
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- ALKYLATING PROPERTIES OF DIALKYL PHOSPHITES
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When the mixture of amines and dialkyl phosphites is used in the reaction, as for example in the Kabachnik-Fields reaction, all possible N-alkylated products are formed.N-ethylation by diethyl phosphite is much slower than N-methylation by dimethyl phosphite and the latter can be easily formed via transesterification when the methanol is present in the mixture.Key words: Amine alkylation, dialkyl phosphites, Kabachnik-Fields synthesis.
- Gancarz, Roman
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p. 193 - 200
(2007/10/02)
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- A FACILE SYNTHESIS OF TRIALKYLSILYLPHOSPHITES AND PHOSPHATES
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Trialkylsilylphosphites (1a-1d) and trialkylsilylphosphates (2a-2d) were synthesized in good yield by a facile method.The method could be easily used to prepare P-O-Si bond and P-Si bond compounds from dialkylphosphites and trialkylchlorosilanes.Key words: Phosphates; trialkylsilylphosphites; trialkylchlorosilanes.
- Li, Zhonghua,Zhu, Chuanfang,Zhao, Yongzhen
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p. 229 - 232
(2007/10/02)
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- Failure of aminophosphonate synthesis due to facile hydroxyphosphonate-phosphate rearrangement
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In a Kabachnik-Fields synthesis of aminophosphonates amines can catalyse the formation of hydroxyphosphonates, and their further rearrangement to phosphates, unabling the formation of aminophosphonates.
- Gancarz,Gancarz
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p. 145 - 148
(2007/10/02)
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- ELECTROCHEMICALLY INDUCED PROCESSES IN THE FORMATION OF PHOSPHORUS ACID DERIVATIVES. 1. SYNTHESIS OF TRIALKYL PHOSPHATES FROM WHITE PHOSPHORUS
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An electrochemical method, based on the joint action of nucleophilic and electrophilic reagents on P4, is proposed in order to utilize white phosphorus in the formation of the esters of phosphorus acids.The action of alkoxide ions on white phosphorus in an alcohol medium in the presence of iodine generated at the anode leads to the formation of phosphate esters.A scheme in which the intermediate products are dialkyl and trialkyl phosphites and the side product is dialkyl alkylphosphonate is proposed for the process.Key words: Phosphate esters, white phosphorus, electrosynthesis.
- Romakhin, A. S.,Budnikova, Yu. G.,Zaripov, I. M.,Kargin, Yu. M.,Nikitin, E. V.,et al.
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p. 1031 - 1035
(2007/10/02)
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- 2-azabicyclo(2.2.1)hept-5-ene-2-acetic acid, derivatives thereof and related compounds, process for the preparation of said compounds and the use of said compounds for the manufacture of N-phosphonomethylglycine
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The present invention describes a novel compound, 2-azabicyclo[2.2.1]hept-5-ene-2-acetic acid, its preparation and the preparation of related compounds, and the use of said compounds as intermediates for the preparation of N-phosphonomethylglycine.
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- Prodrugs of Phosphonoformate: Products, Kinetics and Mechanisms of Hydrolysis of Dibenzyl (Methoxycarbonyl)phosphonate
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Dibenzyl (methoxycarbonyl)phosphonate (1) has been prepared by the reaction of benzyl alcohol with (methoxycarbonyl)phosphonic dichloride.The hydrolysis of 1 proceeded rapidly, with a half-life of 60 min at 36.4 deg C and pH 7.4, by two main pathways.The dominant pathway (k1, 6.56 * 10-3 min-1) yielded the diester, benzyl (methoxycarbonyl)phosphonate (2) and benzyl alcohol (3), with P-O cleavage.The second (k2, 3.55 * 10-3 min-1) gave dibenzyl phosphite (4), possibly arising from the hydrolysis of the carboxyl ester followed by decarboxylation.Benzyl phosphite (5) was also observed, which arises from the hydrolysis of 4 with P-O cleavage (k5, 9.04 * 10-4 min-1).Other products formed in small amounts were, benzyl (benzyloxycarbonyl)phosphonate (6) (k3, 3.59 * 10-4 min-1) and dibenzyl phosphate (7) (k4, 4.24 * 10-4 min-1).The rapid and complicated hydrolysis of 1, involving four competitive reactions, two of which involve C-P bond cleavage, suggests that triesters of phosphonoformate are unlikely to be suitable prodrug forms.
- Mitchell, Antony G.,Nicholls, Dave,Walker, Ian,Irwin, William J.,Freeman, Sally
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p. 1297 - 1304
(2007/10/02)
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- Trimethyl Phosphite Adsorbed on Silica: An NMR and Infrared Study
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Infrared spectroscopy and phosphorus-31 magic angle spinning nuclear magnetic resonance spectroscopy have been used to study the adsorption of trimethyl phosphite (TMP) on silica.At 23 deg C TMP reacts rapidly with surface silanol groups to give SiOCH3 as a chemisorbed product and liquid dimethyl phosphite (DMP).However, formation of DMP ceases when about half of the SiOH groups have been consumed because DMP strongly hydrogen bonds to the remaining silanols thereby inhibiting further reaction between TMP and SiOH.TMP also undergoes isomerization to dimethyl methylphosphonate (DMMP) which is catalyzed by SiOH.As the number of initial silanol groups is decreased (by using higher temperatures of vacuum activation) the quantity of DMP produced decreases whereas that of DMMP increases.A mechanism for formation of DMP and DMMP has been suggested.At 100 deg C isomerization does not occur, all SiOH groups are consumed, and the major product is DMP/SiOCH3 accompanied by a small quantity of a chemisorbed phosphorus-containing species having the proposed structure (SiO)2P-H(=O).The latter is stable up to 400 deg C.If TMP is heated with silica from 100 to 400 deg C, in addition to SiOCH3, the major new chemisorbed product of the reaction which can be identified by IR and NMR is (SiO)2P-Me(=O) (Me = CH3).The advantages of a combined IR-NMR approach are discussed.
- Gay, Ian D.,McFarlan, A. J.,Morrow, B. A.
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p. 1360 - 1368
(2007/10/02)
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- EVALUATION OF THE N-PHTHALOYL MOIETY AS PROTECTING GROUP IN AMINOACYLPHOSPHONIC DERIVATIVES
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Reaction of dimethyl benzoylphosphonate with hydrazine hydrate gave exclusively benzhydrazide.Reaction of methyl lithium benzoylphosphonate with hydrazine hydrate gave the corresponding hydrazone (3) as a 65:35 mixture of E and Z isomers.Reaction of hydrazine hydrate with diisopropyl 4-phthalimidobutanoylphosphonate gave mainly products resulting from nucleopholic attack of hydrazine on the carbonyl of the acylphosphonate and only a small percentage of phthalhydrazide.From our results it appears that the N-phthaloyl protecting group is not suitable for the transient protection of amino groups during attempts to synthesize aminoacylphosphonates.
- Breuer, Eli,Safadi, Muhammad,Chorev, Michael,Gibson, Dan
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p. 239 - 246
(2007/10/02)
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- DISPLACEMENT RATE OF ARYLOXY SUBSTITUENTS IN CYCLIC AND ACYCLIC TRIPHOSPHITES BY METHOXIDE IONS, AND WATER
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The displacement rate of aryloxy substituents by methoxide ions in the following triphosphites: 2-phenoxy-1,3,2-dioxaphospholane (I), 2-methoxy-benz-1,3,2-dioxaphospholene (II), and dimethyl phenylphosphite (III), is for each phosphite higher in methanol than in dichloromethane.On the other hand, dichloromethane discriminates much more strongly between five-membered cyclic and acyclic phosphites than methanol, as shown by the following rate ratios cyclic/acyclic in CH3OH: I/III = 13, II/III = 2; and in CH2Cl2: I/III = 1.8 x 103, II/III = 1.1 x 103. Water, as nucleophile towards the same phosphites in deuteroacetone, appears to exhibit somewhat similar magnitude of discrimination as methoxide in methanol. Key Words: Cyclic and acyclic triphosphites; displacement rate of aryloxy substituents.
- Aksnes, Gunnar,Froeyen, Paul
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- Nucleoside 3'-N,N-dialkylphosphonamidates: Novel building blocks for oligonucleotide synthesis
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Nucleoside 3'-N,N-diisopropylphosphonamidates reacted with tris(2,4,6-tribromophenoxy)dichlorophosphorane (BDCP) to generate the corresponding aminophosphorochloridites without cleavage of the P-N bond. The reaction was applied to internucleotidic bond formation.
- Wada,Ishikawa,Hata
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p. 6363 - 6366
(2007/10/02)
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- 2-azabicyclo[2.2.1.]hept-5-ene-2-acetic acid, derivatives thereof and related compounds, process for the preparation of said compounds, and the use of said compounds for the manufacture of N-phosphonomethylglycine
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The present invention describes a novel compound, 2-azabicyclo[2.2.1]hept-5-ene-2-acetic acid, its preparation and the preparation of related compounds and the use of said compounds as intermediates for the preparation of N-phosphonomethylglycine.
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- The Behaviour of 3-Aryliminoxindoles toward Alkyl Phosphites
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3-Aryliminoxindoles (6a-c) react with trialkyl phosphites (TAP, 2a-c) only in presence of a protonating agent (H2O or CH3COOH) to give the respective dialkyl 3-(arylamino-2-oxo-1H-indol-3-yl)-phosphonates (9a-i).Compounds 9 are equally obtained by reacting 6a-c with the appropriate dialkyl phosphite (DAP, 4a-c) in absence of solvent.The role displayed by the arylimine-moiety on the reaction courses is discussed.A mechanism that accounts for formation of 9 from the reaction of anils 6 with TAP, is presented.Structural assignment are based upon analytical, chemical and spectroscopic (i.r., 1H-n.m.r., 31P-n.m.r. and m.s.) results.
- Abdou, Wafaa M.,Abd El-Rahman, Naglaa M.,Mahran, Mohamed R. H.
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p. 906 - 912
(2007/10/02)
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- ORGANOPHOSPHORUS CHEMISTRY. 2. THE REDUCTION OF QUINQUEVALENT PHOSPHORUS TO THE TRIVALENT STATE
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Phosphoryl and phosphonyl chlorides are reduced conveniently to the monobasic acid forms of the corresponding phosphorous and phosphonous acids by the use of sodium borohydride dispersed in dioxane.
- Engel, Robert,Chakraborty, Subir
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p. 665 - 670
(2007/10/02)
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- THE REACTION BETWEEN THIOPHOSGENE AND TRIALKYL PHOSPHITES
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The reaction between trialkyl phosphites and thiophosgene, even at low temperature, does not lead to esters of thiocarbonyl bisphosphonic acid as had previously been reported.The initial products appear to be stabilised phosphorus ylids formed by two carbophilic and one thiophilic reactions between thiophosgene and the trialkyl phosphite with no desulfuration.Following thermal or acidic treatment, the ylids undergo protonation-dealkylation reactions to give phosphorothio-substituted methane bisphosphonates.Key words: carbophilic addition; methane bisphosphonates; thiophilic addition; thiophosgene; trialkyl phosphites; ylids.
- Masson, S.,Sene, A.,Hutchinson, D. W.,Thornton, D. M.
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