- Poly(phosphonate)s via olefin metathesis: Adjusting hydrophobicity and morphology
-
Olefin metathesis step-growth (acyclic diene metathesis (ADMET)) and chain-growth (ring-opening metathesis) polymerization was used to prepare linear poly(phosphonate)s with variable hydrophilicity. The first phosphonate monomer, i.e., di(undec-10-en-1-yl) methylphosphonate, for ADMET polymerization was developed, and potentially degradable and biocompatible, unsaturated poly(phosphonate)s were prepared with molecular weights up to 23 000 g mol -1 with molecular weight dispersities D -1 (homopolymer) and 47 000 g mol-1 (copolymers). Poly(phosphonate)s are potentially hydrolytically degradable materials and therefore promising materials for biomedical applications.
- Steinbach, Tobias,Alexandrino, Evandro M.,Wahlen, Christian,Landfester, Katharina,Wurm, Frederik R.
-
-
Read Online
- Vibrational spectra and possible conformers of dimethylmethylphosphonate by normal mode analysis
-
A careful assignment of the i.r. and Raman spectra of CH3P(O)(OCH3)2, CD3P(O)(OCH3)2, CH3P(O)(OCD3)2 and CD3P(O)(OCD3)2 and a comparison with those of the parent molecules CH3OP(O)Cl2 and CD3OP(O)Cl2 suggest that only one conformer exists in the liquid state.This conformer is probably close to the most stable one calculated by CNDO/2 and ab initio STO-3G methods, with one CH3O group trans and the other cis to the P=O group.The characteristic modes of the CP(O)(OC)2 skeleton are analysed through a force field calculation.It is shown that the stretching vibrations of the single bonds PC and PO are strongly coupled.As already observed for carboxylic esters, it is shown that only mixed skeletal modes and mostly the bending modes are sensitive to the conformation of the methoxy groups around the P-O single bond.On the other hand the ν(P=O) mode does not vary for the different conformers, and the extra components appearing in its vicinity, as well as in that of the ν(P-C) main vibrational mode, are best understood as being due to Fermi resonances with harmonic or combination tones coupling with these modes.
- Moravie, R. M.,Froment, F.,Corset, J.
-
-
Read Online
- Solid-Phase Synthesis of a Special Phosphorylated Peptide as a Biomarker for LC-MS/MS Detection for OPNA Exposure
-
A synthesis of d5-VX adducted nonapeptide via solid-phase approach has been developed. The d5-VX peptide could be used as the isotope-labeled internal standard for LC-MS/MS detecting the BuChE-OPNA biomarkers. The Kaiser test was utilized to ensure the right connections of all of the amino acids. This method offers an access to the synthesis and detection of other phosphorylated nonapeptides.
- Li, Xinhai,Yuan, Ling,Wang, Qinggang,Liang, Longhui,Huang, Guilan,Liu, Shilei,Liu, Jingquan
-
-
Read Online
- Solid-phase synthesis for novel nerve agent adducted nonapeptides as biomarkers
-
An efficient synthesis of d5-VX adducted nonapeptide and d15-GD adducted nonapeptide via solid-phase approach has been developed. The deuterated peptides could be used as the isotope-labeled internal standard for LC-MS/MS detecting the BuChE-OPNA biomarkers. This method also offers an access to the synthesis and detection of other phosphorylated nonapeptides.
- Li, Xinhai,Yuan, Ling,Wang, Qinggang,Liang, Longhui,Huang, Guilan,Li, Xiaosen,Zhang, Chunhong,Liu, Shilei,Liu, Jingquan
-
-
Read Online
- Synthesis of the Tripeptides Tyr-Thr-Lys Phosphorylated with Isopropyl Methyl- and (Deuteromethyl)phosphonochloridates as Reference Standards for the Analysis of Biomedical Samples
-
A procedure for the phosphorylation of the tripeptide Tyr-Thr-Lys with isopropyl methyl- or (deuteromethyl)phosphonochloridate is developed. The phosphorylated tripeptides are intended for use as reference standards in the analysis of blood samples of people suspected to have been exposed to acetylcholinesterase inhibitors. Conditions of hromatographic separation and purification of the synthesized compounds are determined and optimized, which ensures the preparation of high-purity phosphorylated tripeptides.
- Rodin,Baygildiev,Krylov,Osipov,Krylov,Yashkir,Rybalchenko
-
p. 2103 - 2107
(2019/11/29)
-
- RESORCINOL DERIVATIVES FOR THEIR COSMETIC USE
-
The invention relates to resorcinol derivatives of formula (I) and also the salts thereof, the solvates thereof and the optical and/or geometrical isomers thereof, including enantiomers and diastereoisomers, and the racemic mixtures thereof, alone or as a mixture. The invention also relates to a cosmetic process for depigmenting, lightening and/or bleaching keratin materials, especially the skin, using these compounds (I).
- -
-
Page/Page column 22; 23
(2018/12/13)
-
- Method for synthesizing flame retardant intermediate methanephosphonic dichloride
-
The invention discloses a method for synthesizing flame retardant intermediate methanephosphonic dichloride. The method comprises the following steps: A, adding sulfonyl chloride into a sealed reactor, and cooling to 0 to 5 DEG C in low temperature bath; B, slowly dropwise adding methanephosphonic dichloride into a reaction system, keeping the reaction temperature at 15 to 20 DEG C, wherein the dripping time is 1 to 3 hours; C, after the material is added, continuously stirring and reacting for 0.5 to 1 hour at the temperature of 0 to 30 DEG C; D, after the reaction is completed, distilling abyproduct thionyl chloride by virtue of decompression distillation, and collecting fraction at 40 to 50 DEG C; and E, continuously increasing the distilling temperature, decompression distilling, andobtaining the methanephosphonic dichloride product, and collecting the fraction at 70 to 80 DEG C. The method is mild in reaction condition, simple in operation, low in cost, free from adding and generating gases, high in safety, and easy in industrialized production; and the purity of the methanephosphonic dichloride product and the byproduct thionyl chloride can reach up to 98 percent or more, and the reaction yield is 95 percent or more.
- -
-
Page/Page column 5-7
(2018/11/10)
-
- Methylphosphonic acid dimethyl heptyl esters synthetic method
-
The invention relates to a synthesis method of dimethylheptyl methylphosphonate, and aims to solve the difficulty in raw material measurement and the safety problem caused by the use of the high-pressure reaction kettle in the existing technique, thereby lowering the production cost. The invention has the advantages of simple operating procedure, high output and high yield, and is suitable for industrial production. The method comprises the following steps: adding an acyl-chlorination reagent into a reaction vessel, wherein the acyl-chlorination reagent is thionyl chloride, phosphorous pentachloride or triphosgene; dropwisely adding dimethyl methyl phosphonate (DMMP) into the acyl-chlorination reagent at room temperature and adding catalytic amount of catalyst, wherein the consumption of the acyl-chlorination reagent is 2-5 times of the DMMP (0.6-1.5 times for triphosgene) on mol basis, and the catalyst is N,N-di-substituted-formamide or N-containing aromatic heterocyclic ring or N-substituted N-containing aromatic heterocyclic ring or tertiary amine; and uniformly stirring at room temperature.
- -
-
Paragraph 0035; 0037
(2017/06/03)
-
- New method for synthesizing substituted phosphinate
-
The invention discloses a new method for synthesizing substituted phosphinate. The method comprises the step of generating the substituted phosphinate by reducing halogenated phosphonate under the effect of a reducing agent. The optimal preparation method for the substituted phosphinate is screened through a large number of experiments according to the invention; the whole process is reasonably designed; the technological operation is simple and efficient; especially, the optimal reaction conditions are screened, including reaction solvent, reaction temperature, reaction time and optimal reaction pH value; the reaction yield is obviously increased; the yield reaches up to 85-95%; the side reaction is less; the production cost is greatly lowered; the industrial production can be realized; and the method has a wide application prospect.
- -
-
Paragraph 0022-0024
(2017/12/27)
-
- A reaction in the preparation of glyphosate, the application of the phosphine type flame retardant (by machine translation)
-
The invention relates to an application of a new intramolecular heterogeneous reaction of phosphor in the preparation of products of glyphosate, phosphine fire retardants and chloromethyl phosphonic dichloride. The application which develops a new approach of a synthetic route of the products and improves disadvantages of high original synthetic technology cost and large wastewater discharge amounts of the products can reach industrial design standards of clear production.
- -
-
Paragraph 0073-0075
(2018/12/13)
-
- 4 - (hydroxy-(methyl) phosphinyl) - 2-oxo-butyric acid production process
-
The invention discloses a preparation method of 4-(hydroxy-(methyl)phosphinyl)-2-oxobutyric acid. The preparation method comprises following steps: synthesis of methylphosphoric dichloride; recovery of diethyl phthalate, synthesis of methyl chloro phosphinic propionyl chloride; synthesis of methoxyl methyl phosphinic methyl propionate; synthesis of 4-(hydroxy-(methyl)phosphinyl)-2-oxobutyric acid; and post treatment. Technology processes of the preparation method are simple; yield is high; production cost is low; and production technology is clean. In addition, when 4-(hydroxy-(methyl)phosphinyl)-2-oxobutyric acid obtained by the preparation method is used for synthesis of weed killer glufosinate-ammonium, levo glufosinate-ammonium with high weed killing function is obtained, so that weed killing effect of glufosinate-ammonium is improved greatly.
- -
-
Paragraph 0060-0068
(2017/02/24)
-
- Microsynthesis and electron ionization mass spectral studies of O(S)-alkyl N,N-dimethyl alkylphosphono(thiolo)thionoamidates for Chemical Weapons Convention verification
-
RATIONALE The availability of mass spectra and interpretation skills are essential for unambiguous identification of the Chemical Weapons Convention (CWC)-related chemicals. The O(S)-alkyl N,N-dimethyl alkylphosphono(thiolo) thionoamidates are included in the list of scheduled CWC-related compounds, but there are very few spectra from these compounds in the literature. This paper examines these spectra and their mass spectral fragmentation routes. METHODS The title chemicals were prepared through microsynthetic protocols and were analyzed using electron ionization mass spectrometry with gas chromatography as a MS-inlet system. Structures of fragments were confirmed using analysis of fragment ions of deuterated analogs, tandem mass spectrometry and density functional theory (DFT) calculations. RESULTS Mass spectrometric studies revealed some interesting fragmentation pathways during the ionization process, such as alkene and amine elimination and McLafferty-type rearrangements. The most important fragmentation route of the chemicals is the thiono-thiolo rearrangement. DFT calculations are used to support MS results and to reveal relative preference formation of fragment ions. The retention indices (RIs) of all the studied compounds are also reported. CONCLUSIONS Mass spectra of the synthesized compounds were investigated with the aim to enrich the Organization for the Prohibition of Chemical Weapons (OPCW) Central Analytical Database (OCAD) which may be used for detection and identification of CWC-related chemicals during on-site inspection and/or off-site analysis such as OPCW proficiency tests. Copyright
- Saeidian, Hamdollah,Babri, Mehran,Abdoli, Morteza,Sarabadani, Mansour,Ashrafi, Davood,Naseri, Mohammad Taghi
-
p. 2805 - 2814
(2013/01/15)
-
- Detoxification of O, S-diethyl methyl phosphonothiolate (OSDEMP), a simulant of VX, by N, N-dichlorourethane as an effective decontaminating agent
-
N, N-Dichlorourethane has been synthesized and characterized by FT-IR, NMR. Efficiency of this compound as decontaminant has been evaluated by the reaction of O, S-diethyl methyl phosphonothiolate (OSDEMP), a simulant of VX at RT. The decontamination reaction has been monitored by gas chromatography (GC) and the products have been identified by GC-MS.
- Singh, Ravindra,Gutch,Acharya,Prabha
-
experimental part
p. 1504 - 1509
(2011/12/02)
-
- α-haloenamines as reagents for the conversion of phosphorus oxyacids to their halogenated analogues
-
Phosphorus oxyacids are converted to their halogenated analogues under mild conditions. α-Haloenamines are shown to be effective halogen transfer reagents affording good to high yields of the desired products at reaction times, in some cases, less than one minute. Georg Thieme Verlag Stuttgart.
- Norlin, Rikard,Juhlin, Lars,Lind, Per,Trogen, Lars
-
p. 1765 - 1770
(2007/10/03)
-
- The mechanism of thionyl chloride reaction with dialkyl alkylphosphonothionate using 31P NMR
-
Based on 31P NMR studies of thionyl chloride reaction with dialkyl alkylphosphonothionates, a method for preparation of alkylphosphonic dichloride has been investigated. A mechanism via intermediacy of ester chloride is suggested.
- Purnanand,Shakya,Saxena, Shefali,Sharma,Lal, Basant
-
p. 1093 - 1099
(2007/10/03)
-
- Synthesis of chiral 2-oxo- and 2-thio-1,3,2-oxazaphospho-lidines via the asymmetric cyclization of l-serinoates with (thio)phosphoryl dichlorides
-
In this paper is described the asymmetric cyclization of L-serine derivatives with phosphoro(no-)dichloridates or their thio-analogues, and investigated the asymmetric induction effect of chiral carbon centre on the forming chiral phosphorus centre. Some cyclization products have been separated as a pure diastereomer and their configuration is preliminarily discussed.
- He, Zheng-Jie,Chen, Wen-Bin,Zhou, Zheng-Hong,Tang, Chu-Chi
-
p. 3473 - 3479
(2007/10/03)
-
- Inhibition of human gastric and pancreatic lipases by chiral alkylphosphonates. A kinetic study with 1,2-didecanoyl-sn-glycerol monolayer
-
Enantiomerically pure alkylphosphonate compounds RR'P(O)PNP (R=C(n)H(2n+1), R'=OY with Y=C(n')H(2n'+1) with n=n' or n≠n'; PNP=p-nitrophenoxy) noted (RY), mimicking the transition state occurring during the carboxyester hydrolysis were synthesized and investigated as potential inhibitors of human gastric lipase (HGL) and human pancreatic lipase (HPL). The inhibitory properties of each enantiomer have been tested with the monomolecular films technique in addition to an enyzme linked immunosorbent assay (ELISA) in order to estimate simultaneously the residual enzymatic activity as well as the interfacial lipase binding. With both lipases, no obvious correlation between the inhibitor molar fraction (α50) leading to half inhibition, and the chain length, R or Y was observed. (R11Y16)s were the best inhibitor of HPL and (R10Y11)s were the best inhibitors of HGL. We observed a highly enantioselective discrimination, both with the pure enantiomeric alkylphosphonate inhibitors as well as a scalemic mixture. We also showed, for the first time, that this enantioselective recognition can occur either during the catalytic step or during the initial interfacial adsorption step of the lipases. These experimental results were analyzed with two kinetic models of covalent as well as pseudo-competitive inhibition of lipolytic enzymes by two enantiomeric inhibitors. Copyright (C) 1999 Elsevier Science Ireland Ltd.
- Cavalier, Jean-Francois,Ransac, Stephane,Verger, Robert,Buono, Gerard
-
-
- Studies on chiral thiophosphoric acids and their derivatives 16. - The asymmetric cyclization of L-(+)-prolinol with (thio)phosphoro(-no)dichloridates
-
The cyclizations of L-(+)-prolinol 5 with (thio)phosphoro(-no)dichloridates 6 give 1,2,3-azaphosphaoxabicyclo[3.3.0]octanes 7 consisting of unequal amounts of diastereoisomers, eight pairs of which have been successfully resolved by silica gel column chromatography or recrystallization. The influences of reaction temperature, solvent and substrate concentration upon the asymmetric induction have also been investigated.
- He, Zheng-Jie,Wang, You-Ming,Tang, Chu-Chi
-
-
- 1,8-Diazabicyclo[5.4.0]undecene mediated transesterification of p-nitrophenyl phosphonates: A novel route to phosphono esters
-
DBU (1,8-diazabicyclo[5.4.0]undecene) was found to efficiently mediate the transesterification of p-nitrophenyl (PNP) phosphonates by various alcohols. The reactions of bis-PNP phosphonates in the presence of DBU, using both primary and secondary alcohols, phenols and amines, proceed rapidly and with high yield to afford the corresponding monoalkyl/aryl mono-PNP phosphonates as sole products (1, Scheme 2). The resulting monoalkyl/aryl mono-PNP phosphonates can be further reacted with a second alcohol to give the corresponding differently disubstituted phosphonates 3, or selectively hydrolysed to yield the monoalkyl/aryl phosphonic acids 2. We have applied this chemistry to the preparation of a series of phosphono ester transition state analogues 11a-e (Scheme 3) that were used as haptens for raising catalytic antibodies.
- Tawfik,Eshhar,Bentolila,Green
-
p. 968 - 972
(2007/10/02)
-
- CONVERSIONS OF THE ADDUCTS OF α-DICHLORONITROSOALKANES WITH DICHLOROPHOSPHINES
-
Structure, stability and some reactions of the obtained adducts of α-dichloronitrosoalkanes with dichlorophosphines are discussed.One-pot synthesis of O-(alkylchloroformoimino)phosphonic acid chlorides and esters is described.Key words: O-(alkylchloroformoimino)trichlorophosphoranes; O-(alkylchloroformoimino)chlorophosphonates; O-(alkylchloroformoimino)-O-alkylphosphonates; amides of O-(alkylchloroformoimino)phenylphosphonic acids.
- Lyashenko, Yu. E.,Sokolov, V. B.,Martynov, I. V.
-
-
- ORGANIC PHOSPHORUS COMPOUNDS 90. A CONVENIENT, ONE-STEP SYNTHESIS OF ALKYL- AND ARYLPHOSPHONYL DICHLORIDES
-
N,N-Disubstituted formamides such as dimethylformamide, N-formylpyrrolidine, N-formylpiperidine etc. and also pyridine and hexamethylphosphonic acid triamide catalyze the chlorination of phosphonates with thionyl chloride to give phosphonyl dichlorides in high yield.Thus RP(O)Cl2, R=CH3, C2H5, n-C12H25, C6H5, have been isolated in better than 90 per cent yield.The procedure is less satisfactory for the production of 2-chloroethylphosphonyl dichloride.Only a 34 per cent yield was realized.The chlorination proceeds very likely through the intermediate formation of the halfesters, RP(O)(OR)Cl since these could be isolated under favorable circumstances.
- Maier, Ludwig
-
p. 465 - 470
(2007/10/02)
-
- A MILD AND FACILE SYNTHESIS OF ALKYL- AND ARYLPHOSPHONYL DICHLORIDES UNDER NEUTRAL CONDITIONS. REACTION OF BIS(TRIMETHYLSILYL) PHOSPHONATES WITH PCl5
-
Bis(trimethylsilyl) phosphonates, which are prepared from the dialkyl esters with chlorotrimethylsilane/sodium iodide, are transformed in high yields into the corresponding phosphonyl dichlorides on the treatment with phosphorus pentachloride under mild and neutral conditions.
- Morita, Tsuyoshi,Okamoto, Yoshiki,Sakurai, Hiroshi
-
p. 435 - 438
(2007/10/02)
-
- Process for producing phosphonic acid halides
-
Phosphonic acid halides are prepared by reacting a dialkylphosponate with thionyl chloride or thionyl bromide in the presence of a nitrogen compound from the group comprising N,N-disubstituted formamides, tertiary amines and N,N-disubstituted phosphoric acid triamides. Phosphonic acid dihalides as well as phosphonic acid alkylester monohalides can be prepared by the new process.
- -
-
-