- Preparation method of bis(2,2,2-trifluoroethyl)methyl phosphate
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The invention discloses a synthesis method of bis(2,2,2-trifluoroethyl)methyl phosphate, wherein the method comprises the following steps: step 1, preparing methyl dichlorophosphate by using phosphorus oxychloride and methanol as raw materials; and step 2, preparing bis(2,2,2-trifluoroethyl)methyl phosphate by taking the methyl dichlorophosphate prepared in the step 1, trifluoroethanol, methylbenzene, a second catalyst and an acid-binding agent as raw materials. The method has the advantages of few side reactions and high product purity and yield.
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Paragraph 0017-0019; 0021-0023; 0025-0026; 0028-0029
(2021/01/29)
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- The chlorination reaction of O-alkyl S-alkyl(aryl) thiophosphoric(-nic) acid derivatives with phosphorus oxychloride
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It is reported that a variety of O-alkyl S-alkyl(aryl) thiophosphoric(-nic) acid derivatives 4 can be readily chlorinated with phosphorus oxychloride giving S-alkyl(aryl) thiophosphoro(-no)chloridates 2 and O-alkyl phosphorodichloridates 3.
- He, Zheng-Jie,Chen, Wen-Bing,Ma, Fu-Peng,Zhou, Zheng-Hong,Tang, Chu-Chi
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- THE ISOMERIZATION/CHLORINATION OF O,O-DIALKYL PHENYLTHIOPHOSPHONATES WITH PHOSPHORUS OXYCHLORIDE - A NEW CONVENIENT SYNTHESIS OF S-ALKYL PHENYLTHIOPHOSPHONIC ACID DERIVATIVES
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A new method for the synthesis of S-alkyl phenylthiophosphonic acid derivatives is reported.The chlorination of O,O-dialkyl phenylthiophosphonates with phosphorus oxychloride proceeds with isomerization to give S-alkyl phenylthiophosphonochloridates, which react further with various nucleophiles in the presence of triethylamine to give the title compounds.Key words: Phosphonothionate; phosphonothiolate; phosphonodithiolate; phosphonamidethiolate; isomerization; chlorination.
- Tang, Chu Chi,Wu, Gui Ping,Huang, Guang Yan,Li, Zhen,Jin, Gui Yu
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p. 159 - 164
(2007/10/02)
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- ORGANOSILICON AND ORGANOPHOSPHORUS COMPOUNDS WITH PSEUDOHALIDE GROUPS 3. REACTIONS OF ALKOXYDIMETHYLSILYL CYANIDES WITH TETRACOORDINATED PHOSPHORUS HALIDES
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The reactions of alkoxydimethylsilyl cyanides with some tetracoordinated phosphorus chlorides and fluorides were investigated.It was shown that the investigated reactions are realized primarily with the replacement of two halogen atoms by functional groups.The transformations of the phosphorus acid cyanides obtained with metal fluorides were studied. Keywords: silyl cyanides, phosphorus(IV) halides, substitution reactions, metal fluorides.
- Krolevets, A. A.,Antipova, V. V.,Petrovskii, P. V.,Martynov,I. V.
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p. 153 - 157
(2007/10/02)
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- A convenient synthesis of S-alkyl O-aryl thiophosphoric acid derivatives
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A new convenient synthesis of S-alkyl O-aryl thiophosphoric acid derivatives is reported. The chlorination of O-aryl O,O-dialkyl thiophosphates with phosphorus oxychloride proceeds with isomerization to give S-alkyl O-aryl thiophosphorochloridates, which react further with various nucleophiles in the presence of base to give the title compounds.
- Tang,Wu,Zhang
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p. 454 - 456
(2007/10/02)
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- Exocyclic Cleavage in the Alkaline Hydrolysis of Methyl Ethylene Phosphate: Evidence Against the Significance of Stereoelectronic Acceleration in Reactions of Cyclic Phosphates
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The hydrolysis of methyl ethylene phosphate serves as a mechanistic probe of phosphate reactivity and as a model for enzyme catalysis.Early reports, based on proton NMR and GC analysis, indicated that observable amounts of exocyclic cleavage products are obtained in the alkaline hydrolysis reaction .However, later reports based on phosphorus NMR analysis of reactions in 5 M sodium hydroxide by advocates of a stereoelectronic theory indicated that, consistent with the theory, ring cleavage is the exclusive initial process .In the present study, the products of the reaction of methyl ethylene phosphate with hydroxide under a variety of conditions were determined by proton NMR and by phosphorus NMR with and without rapid quenching.Reactions of the products were also analyzed.The products of exocyclic cleavage, methanol and ethylene phosphate, are produced in the initial reaction to the extent that was reported in 1969.Subsequent reaction of the ring-cleaved products is too slow to account for the initial production of methanol.These data suggest that ring strain and apicophilicities of substituents, rather, than orbital interactions, account for the substantial differences in the reactivity of phosphate esters.
- Kluger, Ronald,Thatcher, Gregory R. J.
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p. 6006 - 6011
(2007/10/02)
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- Phosphorodiamidates, III: Synthesis of Akyl Phosphorodiamidates
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In previous papers we described procedures to synthesize phenyl and 4-nitrophenyl phosphorodiamidates.In this paper a procedure is described to synthesize N,N'-disubstituted phosphorodiamidates from alkyl phosphorodichloridates and primary amines.
- Roth, Hermann J.,Lenig, Arthur R.
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p. 581 - 584
(2007/10/02)
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- Three-membered Heterocycles,10. - Phosphonohydrazidic Esters by Alkoxide-induced Rearrangement of N-Chlorophosphonic Diamides
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Phosphoric and phosphonic amides 8 are formed from phosphoric and phosphonic chlorides 6 and primary amines 7 in high yields. 2,5-Dimethyl-2,5-hexanediamine (7e) reacts with phenylphosphonic dichloride (6c) to give the perhydro-1,3,2-diazaphosphepine 8h.The amides 8 are converted almost quantitatively into the N-chlorophosphoric and N-chlorophosphonic amides 9 by means of tert-butyl hypochlorite.The N,N'-di-tert-alkyl-N-chlorophosphonic diamides 9 derived from methyl-, tert-butyl-, or phenylphosphonic acid react with methoxide or tertiary alkoxides to afford the phosphonohydrazidic esters 10-13.The methyl ester 10d is also formed from 1,2,3-tri-tert-butyldiazaphosphiridine 3-oxide (14) and methanol. 1H-, 13C-, and 31P-NMR spectra prove that the sharply melting phosphonohydrazidic esters 10-13 exist in solution as two diastereomers with ratios ranging from 9:1 to 6:4.The hydrazidic methyl ester 10d which was investigated as a representative example exhibits a temperature dependent 1H-NMR spectrum.Due to the presence of the tert-alkyl groups, inversion at the tertiary nitrogen atom is slow on each NMR time scale. The independence of the IR spectrum on the concentration shows that the predominant diastereomer of 10d is stabilized by an intramolecular hydrogen bond.The electron impact induced decomposition of the amides 8, N-chloroamides 9, and phosphonohydrazidic esters 10-13 ultimately produces cations which are derived from monomeric metaphosphoric or metaphosphonic acid. 6 N hydrochloric acid first splits off the P-N-tert-butyl group of the methyl ester 10d to give the intermediate 15 which can be isolated or which undergoes further hydrolysis to tert-butylphosphonic acid (17) and tert-butylhydrazine(19).The tert-butyl ester 11d yields the same final products in hot hydrochloric acid.At low temperatures and short reaction times, however, di-tert-butylhydrazine (18) is formed.
- Quast, Helmut,Heuschmann, Manfred,Abdel-Rahman, Mohamed O.
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p. 943 - 966
(2007/10/02)
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- Preparation of 3-substituted cephalosporins
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There is described a process for preparing an enamine of formula (IX): STR1 where R2 is a carboxylic acid protecting group and R3 is the residue of a carboxylic acid derived acyl group and where R5 and R6 are the same or different C1-4 alkyl or C7-10 aralkyl groups; or taken together with the adjacent nitrogen atom form a heterocyclic ring containing from 4 to 8 carbon atoms and optionally a further heteroatom selected from oxygen and nitrogen; by reacting a compound of formula (XII): STR2 with an amine of formula HNR5 R6, the reactant of formula (XII) being prepared by reaction of an appropriate enol derivative with a phosphorus reagent. The enamines of formula (IX) are useful in the preparation of 3-hydroxycephalosporins.
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