358-63-4Relevant articles and documents
Fluorinated phosphorus compounds - Part 7. The reactions of bis(fluoroalkyl) phosphorochloridates with nitrogen nucleophiles
Timperley, Christopher M.,Marriott, Stephen N.,Waters, Matthew J.
, p. 111 - 122 (2002)
Forty bis(fluoroalkyl) phosphoramidates (RFO)2P(O)R were prepared in 10-91% yield by treating phosphorochloridates (RFO)2P(O)Cl where RF was HCF2CH2, HCF2CF2/sub
Phosphoranimines containing cationic N-imidazolinium moieties
Klaehn, John R.,Rollins, Harry W.,McNally, Joshua S.,Arulsamy, Navamoney,Dufek, Eric J.
, p. 254 - 265 (2017)
Three new monomeric phosphoranimines (PAs; R′[sbnd]N[dbnd]PR3) were synthesized by the Staudinger route using 2-azido-1,3-dimethylimidazolinium hexafluorophosphate [ADMImPF] and various phosphines to form their respective PA salts of triphenylphosphine (1), tri(n-octyl)phosphine (2), and tris(2,2,2-trifluoroethoxy)phosphite (3). These PA salts have a cationic imidazolinium moiety attached to nitrogen. Interestingly, 2 is a room temperature ionic liquid (RTIL) with a melting point around ?5?°C and a viscosity of 740cP at 25.5?°C. 1 and 2 show stability to moisture exposure and atmosphere for weeks whereas 3 is not stable toward atmospheric moisture undergoing decomposition to form 2-amino-1,3-dimethylimidazolinium phosphate (4). Thermal analyses reveal that 1 and 2 are stable to 90?°C under nitrogen, but 3 undergoes degradation by exposure to moisture and/or elevated temperature. All compounds exhibit similar multinuclear NMR chemical shifts as compared to their corresponding phosphine oxide counterparts. However, their respective X-ray structure determinations indicate that 2 has an open structure with the octyl groups that avoid the ionic charges, whereas 1 and 3 have tighter structural packing of the hexafluorophosphate to their pendant groups.
Synthesis method of tris(2,2,2-trifluoroethyl)phosphate
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Paragraph 0023-0042, (2021/06/06)
The invention provides a synthesis method of tris(2,2,2-trifluoroethyl)phosphate, and belongs to the technical field of battery electrolytic solution additives. The method comprises the following steps: under the protection of nitrogen, adding trifluoroethanol as a raw material and an acid-binding agent into a solvent, then adding phosphorus oxychloride for reaction, carrying out suction filtration on the obtained reaction liquid, washing, drying, decolorizing, and concentrating to obtain tris(2,2,2-trifluoroethyl)phosphate. The key point is that the reaction temperature is controlled to be less than -5 DEG C when the phosphorus oxychloride is dropwise added, the dropwise adding time is 3.5-5 hours, the temperature is naturally returned to 0 DEG C after dropwise adding, the temperature is kept for 1.5-2 hours, and the reaction is stopped; and during concentration, the vacuum degree is controlled to be 0.093 MPa, concentration is conducted for 1-1.5 h at a temperature of 40-55 DEG C, then concentration is conducted for 1-2 h at a temperature of 60-63 DEG C, and the tris(2,2,2-trifluoroethyl)phosphate is obtained. The synthesis method is simple, and the synthesized product is high in yield and high in purity.
Preparation method of cefprozil
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Paragraph 0017, (2019/04/14)
The invention relates to a preparation method of cefprozil. A synthesis method comprises the following steps: taking 7-ACA (7-aminocephalosporanic acid) as a starting raw material; after carrying outsilylation protection, carrying out a series of reactions including iodination and the like to generate a compound 2; taking the compound 2 to react with methyl D-(-)-4-hydroxy-phenylglycinate under the catalysis of immobilized penicillin acylase to generate a compound 1, so as to obtain a target product cefprozil. The preparation method provided by the invention has the advantages of moderate reaction conditions, environmental friendliness, high conversion ratio, simple technology and high cis-isomer content.
Preparation method of fluorine-containing phosphate
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Paragraph 0032; 0033, (2017/05/30)
The invention provides a preparation method of fluorine-containing phosphate. In the presence of an organic solvent, under the action of an acid binding agent, fluorine-containing alcohol reacts with phosphorus oxychloride, so that the corresponding fluorine-containing phosphate is obtained. The method provided by the invention has the characteristics of being novel, high in product yield, high in purity, safe to operate and the like.
Trialkyl phosphites and diaryliodonium salts as co-initiators in a system for radical-promoted visible-light-induced cationic polymerization(1)
Nalli, Thomas W.,Stanek, Lee G.,Molenaar, Rebekka H.,Weidell, Krysia L.,Meyer, Justin P.,Johnson, Brandon R.,Steckler, Timothy T.,Wackerly, Jay Wm.,Studler, Missy Jo,Vickerman, Kevin L.,Klankowski, Stephen A.
, p. 3561 - 3569 (2013/06/04)
Trialkyl phosphites ((RO)3P) can act as co-initiators for the diaryliodonium-induced cationic polymerization of cyclohexene oxide (CHO) or THF. A radical initiation step is also required, consistent with the essential role of a radical chain reaction of the phosphite with the iodonium salt to form polymerization-starting aryltrialkoxyphosphonium salts (ArP+(OR) 3). We used the visible photolysis of phenylazoisobutyronitrile (PAIBN) as the radical initiation step. The presence of multiple fluorine substituents on the phosphite, as in tris(2,2,2-trifluoroethyl) phosphite (TFP), allows polymerization to proceed with a minimal amount of chain transfer from nucleophilic attack by the phosphite. In a typical experiment, a CHO solution of bis(4-tert-butylphenyl)iodonium hexafluorophosphate (0.05 M), TFP (0.1 M), and PAIBN (0.02 M) was illuminated with a 65-W compact fluorescent bulb for 1 h, resulting in a 78% conversion to poly(cyclohexene oxide) with an average molecular weight (MW) of 25000. We also used competition experiments to determine approximate rate constants for reactions of phenyl radicals with CHO (k = 2 × 106 M-1 s-1) and with TFP (k = 2 × 108 M-1 s-1).
Fluorinated phosphorus compounds part 8. The reactions of bis(fluoroalkyl) phosphorochloridates with sulfur nucleophiles
Timperley, Christopher M.,Saunders, Sally A.,Szpalek, Josef,Waters, Matthew J.
, p. 161 - 171 (2007/10/03)
The reactivity of bis (fluoroalkyl)phosphorochloridates to nucleophiles is summarised. Previous data and the results described here indicate that reactivities decrease in the order: amines > alcohols > thiols. The synthesis of CF3CH2OP(O)(SEt)2 in 30% yield was accomplished by treating CF3CHOP(O)Cl2 with two molar equivalents of EtSH and Et3N in ether. The chloridates (CF3CH2O)2P(O)Cl and (C2F5CH2O)2-P(O)Cl did not react with MeSH in ether at -78 °C or when heated with Pb(SMe)2 in benzene. Ethanethiol and propanethiol reacted with fluorinated chloridates in the presence of triethylamine to give thiolates (RFO)2P(O)SR in 13-41% yield where RF was CF3CH2, C2F5CH2, C3F7CH2 or (CF3)2CH and R was Et or n-Pr. Similarly, reaction of phosphorobromidates (RFCH2O)2P(O)Br, made by brominating the corresponding bis(fluoroalkyl) H-phosphonates, with benzenethiol gave derivatives (RFCH2O)2P(O)SPh in 43 and 46% yield where RF was CF3 and C2F5, respectively. Treatment of the chloridothiolate Cl(EtO)P(O)SMe, prepared in two steps from triethyl phosphite, with flouroalcohols and triethylamine in ether gave species RFO(EtO)P(O)SMe in 62-74% yield where RF was CF3CH2, C2F5CH2, C3F7CH2 or (CF3)2CH. The reactions of bis(trifluoroethyl) phosphorochloridate with 2-mercaptoethanol, 3-mercaptopropanol and ethane-1,2-dithiol gave several unexpected products whose structures were tentatively assigned.
Fluorinated phosphorus compounds - Part 6. The synthesis of bis(fluoroalkyl) phosphites and bis(fluoroalkyl) phosphorohalidates
Timperley, Christopher M.,Arbon, Robert E.,Saunders, Sally A.,Waters, Matthew J.
, p. 65 - 78 (2007/10/03)
Reaction of phosphorus trichloride with tert-butanol and fluoroalcohols gave bis(fluoroalkyl) phosphites (RFO)2P(O)H in 42-89% yield, where RF = HCF2CH2, H(CF2)2CH2, H(CF2)4CH2, CF3CH2, C2F5CH2, C3F7CH2, (CF3)2CH, (FCH2)2CH, CF3(CH3)2C, (CF3)2CH3C, CF3CH2CH2, C4F9CH2CH2 and C6F13CH2CH2. Treatment of these with chlorine in dichloromethane gave the bis(fluoroalkyl) phosphorochloridates (RFO)2P(O)Cl in 49-96% yield. The chloridate (CF3CH2O)2P(O)Cl was isolated in much lower yield from the interaction of thionyl chloride with bis(trifluoroethyl) phosphite. Heating the latter in dichloromethane with potassium fluoride and a catalytic amount of trifluoroacetic acid gave the corresponding fluoridate (CF3CH2O)2P(O)F in 84% yield. Treatment of bis(trifluoroethyl) phosphite with bromine or iodine gave the bromidate (CF3CH2O)2P(O)Br and iodidate (CF3CH2O)2P(O)I in 51 and 46% yield, respectively. The iodidate is the first dialkyl phosphoroiodidate to have been isolated and characterised properly - its discovery lags behind the first isolation of a dialkyl phosphorochloridate by over 130 years. The fluoroalkyl phosphoryl compounds are generally more stable than known unfluorinated counterparts.
Fluorinated phosphorus compounds: Part 3. the synthesis of symmetrical and unsymmetrical fluoroalkyl phosphates
Timperley, Christopher M.,Holden, Ian,Morton, Ian J.,Waters, Matthew J.
, p. 153 - 161 (2007/10/03)
Treatment of phosphorus pentachloride with four molar equivalents of fluoroalcohol gave symmetrical phosphates (RFO)3P=O in isolated yields between 10-92% [RF=CF3CH2, C2F5CH2, HCF2CF2CH2, C3F7CH2, (FCH2)2CH, (CF3)2CH, C2F5(CH3)CH]. The reaction proceeded best for fluoroalcohols having many fluorine atoms. 2,2-Difluoroethanol HCF2CH2OH and 1,3-difluoroisopropanol (FCH2)2CHOH did not react cleanly and gave product mixtures. Hexafluoroisopropanol produced a 3:7 mixture of symmetrical phosphate [(CF3)2CHO]3P=O and chlorophosphorane [(CF3)2CHO]4PCl. The latter reacted readily with water and alcohols. Heating the chloridates CF3CH2OP(O)Cl2, (CF3CH2O)2P(O)Cl and (C2F5CH2O)2P(O)Cl with various fluoroalcohols in the presence of calcium chloride catalyst gave unsymmetrical phosphates in isolated yields between 46-83%. The mixed phosphate (CF3CH2O)2P(O)OCH2C 2F5 did not react with butanol or propylamine in dichloromethane at room temperature.
Fluorinated phosphorus compounds: Part 1. The synthesis and reactions of some fluoroalkyl phosphoryl compounds
Timperley, Christopher M.,Bird, Michael,Broderick, John F.,Holden, Ian,Morton, Ian J.,Waters, Matthew J.
, p. 215 - 223 (2007/10/03)
Fluoroalkyl phosphorochloridates CF3CH2OP(O)Cl2 and (RFCH2O)2P(O)Cl (RF=CF3, C2F5) were prepared from phosphorus oxychloride, fluoroalcohols and triethylamine, but selective substitution was difficult. Phosphates (RFCH2O)2P(O)OR (RF=CF3, C2F5 and R=Me, Et, n-Pr, i-Pr) were isolated in yields of 38-84% from the reactions of the phosphorochloridates with alcohols and triethylamine. Success of the inverse reaction, i.e. ROP(O)Cl2 and RFCH2OH, depended on the R group (Me, Et) and the RF group (CF3, C2F5). The phosphates did not react with bromotrimethylsilane in chloroform. Addition of amines to CF3CH2OP(O)Cl2 or (CF3CH2O)2P(O)Cl gave phosphoramidates (RR′N)2P(O)OCH2CF3 or (CF3CH2O)2P(O)NRR′ (R and R′=H, Me, Et) in yields of 58-75%. The inverse reactions of Me2NP(O)Cl2 and (Me2N)2P(O)Cl with trifluoroethanol were slow, but were catalysed by 4-dimethylaminopyridine. Anhydrous hydrogen chloride split one of the P-N bonds of (Me2N)2P(O)OCH2CF3 to give Me2NP(O)Cl(OCH2CF3), but was without action on (CF3CH2O)2P(O)NMe2.
