1066-50-8Relevant academic research and scientific papers
The mechanism of thionyl chloride reaction with dialkyl alkylphosphonothionate using 31P NMR
Purnanand,Shakya,Saxena, Shefali,Sharma,Lal, Basant
, p. 1093 - 1099 (2002)
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.
Clean synthesis of linear and star amphiphilic poly(?-caprolactone)-: Block -poly(ethyl ethylene phosphonate) block copolymers: Assessing self-assembly and surface activity
Baheti, Payal,Bouilhac, Cécile,Gimello, Olinda,Howdle, Steven M.,Lacroix-Desmazes, Patrick,Rheinberger, Timo,Wurm, Frederik R.
, p. 3248 - 3261 (2020)
Anionic ring-opening polymerization (AROP) of 2-ethyl-2-oxo-1,3,2-dioxaphospholane (EP) has been utilized to create alternative hydrophilic moieties for utilization in surfactants. The current "go-to" hydrophilic unit is poly(ethylene glycol) (PEG), but this is non-biodegradable and there is some evidence that its use can lead to accumulation of toxic by-products. We have created new approaches leading to water-dispersible, fully degradable amphiphilic block copolymers. Our approach utilized poly(?-caprolactone)-based macroinitiators in a solvent free process with organocatalyst DBU. We have prepared a comprehensive set of novel amphiphilic PCL-b-PEP block copolymers including linear diblock, triblock and star diblock copolymers characterized by SEC, 1H and 31P NMR and MALDI-TOF analyses. Supercritical carbon dioxide (scCO2) was exploited to efficiently extract the residual EP monomer leading to significantly increased gravimetric yields of purified product compared to conventional techniques such as dialysis. The self-assembly of the amphiphilic copolymers in water was investigated by DLS and cryo-TEM and their surface-activity as a function of concentration was investigated by tensiometry showing behavior that matches or exceeds commercially available surfactants.
A Library of Well-Defined and Water-Soluble Poly(alkyl phosphonate)s with Adjustable Hydrolysis
Wolf, Thomas,Steinbach, Tobias,Wurm, Frederik R.
, p. 3853 - 3863 (2015)
Poly(alkyl ethylene phosphonate)s with different alkyl side chains exhibit significant differences in their degradation behavior. Three novel 2-alkyl-2-oxo-1,3,2-dioxaphospholanes, cyclic monomers for the ring-opening polymerization (ROP) toward poly(alkyl alkylene phosphonate)s, were synthesized by robust two- or three-step protocols in reasonable yields and high purity. The polymerization was promoted by the organocatalysts 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) and proceeded with high control over molecular weight and narrow molecular weight distributions (A 1.2) up to full conversion. These polymers with methyl, ethyl, and isopropyl side chains are perfectly soluble in water (up to 25 mg mL-1) without a temperature-dependent phase separation. They showed no toxicity against HeLa cells after 24 h of incubation at any tested concentration. Polymers with butyl side chains exhibit decreased solubility and concentration-dependent cloud point temperatures and show toxicity against HeLa cells at concentrations above 25 mL-1. The polymers showed no acetylcholinesterase inhibition. All polymers exhibited significantly different degradation times under both neutral as well as basic conditions (variation of the alkyl side chain allowed stabilities from 8 h up to 6 days).
The mild preparation of synthetically useful phosphonic dichlorides: Application to the synthesis of cyclic phosphonic diesters and diamides
Stowel,Ueland,McClard
, p. 3261 - 3262 (1990)
A very mild method for the preparation of synthetically useful phosphonic dichlorides has been developed and its application toward the synthesis of 2-alkyl-2-oxo-1,3,2-dioxophosphorinanes and 1,3-dimethyl-2-alkyl-2-oxo-1,3,2-diazaphospholidines is reported.
Microsynthesis and electron ionization mass spectral studies of O(S)-alkyl N,N-dimethyl alkylphosphono(thiolo)thionoamidates for Chemical Weapons Convention verification
Saeidian, Hamdollah,Babri, Mehran,Abdoli, Morteza,Sarabadani, Mansour,Ashrafi, Davood,Naseri, Mohammad Taghi
, p. 2805 - 2814 (2013/01/15)
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
Reaction of Trichloro(o-phenylenedioxy)phosphorane with Four-Coordinate Phosphorus Esters
Khusainova,Reshetkova,Cherkasov
, p. 367 - 369 (2007/10/03)
Reactions of trialkyl phosphates and dialkyl alkenylphosphonates with trichloro(o-phenylenedioxy)phosphorane result in selective replacement of one alkoxy group on the phosphorus by a chlorine atom. Alkylphosphonates react with trichloro(o-phenylenedioxy)phosphorane to give alkyl alkylphosphonochloridates as the major products and small amounts of alkylphosphonic dichlorides.
The asymmetric synthesis of α-substituted α-methyl and α-phenyl phosphonic acids: Design, carbanion geometry, reactivity and preparative aspects of chiral alkyl bicyclic phosphonamides
Bennani, Youssef L.,Hanessian, Stephen
, p. 13837 - 13866 (2007/10/03)
The design, preparation, structural and spectroscopic analyses of topologically unique and enantiomerically pure alkyl phosphonamides are described. In the case of α-ethyl and α-benzyl phosphonamides, the geometry of both the secondary and tertiary carbanions was determined to be planar through deprotonation/deuteration/alkylation experiments. Stereoselective alkylations of such systems proceeded in good yields and with high diastereoselectivities. The resulting α,α-alkylated phosphonamides were hydrolyzed to give the corresponding α,α-alkyl phosphonic acids with high degrees of enantiomeric purity.
Easy preparation of alkylphosphonyl dichlorides
Patois, C.,Berte-Verrando, S.,Savignac, P.
, p. 485 - 487 (2007/10/02)
Phosphonic acid esters bearing an alkyl, halogen or carboxylate substituent on the α-carbon are readily converted into the parent phosphonic dichlorides when treated with a mixture of 2.5 eq of phosphorus pentachloride and 1.3 eq of phosphorus oxychloride.Keywords - phosphonates / chlorination / phosphorus pentachloride / phosphorus oxychloride / phosphonyl dichloride
ORGANIC PHOSPHORUS COMPOUNDS 90. A CONVENIENT, ONE-STEP SYNTHESIS OF ALKYL- AND ARYLPHOSPHONYL DICHLORIDES
Maier, Ludwig
, p. 465 - 470 (2007/10/02)
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.
Process for making phosphonic acid ester chlorides
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, (2008/06/13)
The disclosure relates to a process for making phosphonic acid ester chlorides of the general formula (I) in which R stands for an alkyl group with 1 to 6 carbon atoms or an aryl group and R' stands for an alkyl group with 1 to 20 carbon atoms or an aryl group. More particularly, a compound of general formula (II) is reacted with a sulfuric acid monoester of general formula (III) R and R' in formulae (II) and (III) having the meanings given above; the reactants are used in about equimolar proportions and the reaction is effected at a temperature of from -20° C. to 50° C. After termination of the reaction, the phosphonic acid ester chloride is separated from the reaction mixture by subjecting this latter to distillation under vacuum.
