18933-98-7

Upstream product

• 64-17-5 ethanol 
• 63581-66-8 benzylphosphonic acid monomethyl ester 
• 1080-32-6 O,O-diethyl benzylphosphonate 
• 100-39-0 benzyl bromide 
• 308795-35-9 (C₆H₅CH₂POC₂H₅O₂BClC₆H₁₁)2 
• 100-44-7 benzyl chloride 
• 6881-57-8 benzylphosphonic acid 
• 78-39-7 Triethyl orthoacetate 
• 945933-82-4 benzylphosphonic acid benzyl ethyl ester 
• 122-52-1 triethyl phosphite 
• 155801-93-7 2,4-dinitrophenyl ethyl benzyl phosphonate 

Downstream Products

• 72448-73-8 ethyl hydrogen [(4-nitrophenyl)methyl]phosphonate 
• 945933-82-4 benzylphosphonic acid benzyl ethyl ester 
• 945933-84-6 benzylphosphonic acid ethyl isopropyl ester 
• 41760-95-6 monoethyl P-benzylphosphonochloridate 
• 27272-09-9 O-ethyl N,N-diethyl-P-benzylphosphonamidate 

Relevant academic research and scientific papers

Selective hydrolysis of phosphorus(v) compounds to form organophosphorus monoacids

An azide and transition metal-free method for the synthesis of elusive phosphonic, phosphinic, and phosphoric monoacids has been developed. Inert pentavalent P(v)-compounds (phosphonate, phosphinate, and phosphate) are activated by triflate anhydride (Tf2O)/pyridine system to form a highly reactive phosphoryl pyridinium intermediate that undergoes nucleophilic substitution with H2O to selectively deprotect one alkoxy group and form organophosphorus monoacids.

Selective esterification of phosphonic acids

Here, we report straightforward and selective synthetic procedures for mono-and diesteri-fication of phosphonic acids. A series of alkoxy group donors were studied and triethyl orthoacetate was found to be the best reagent as well as a solvent for the performed transformations. An important temperature effect on the reaction course was discovered. Depending on the reaction temperature, mono-or diethyl esters of phosphonic acid were obtained exclusively with decent yields. The sub-strate scope of the proposed methodology was verified on aromatic as well as aliphatic phosphonic acids. The designed method can be successfully applied for small-and large-scale experiments without significant loss of selectivity or reaction yield. Several devoted experiments were performed to give insight into the reaction mechanism. At 30?C, monoesters are formed via an intermediate (1,1-diethoxyethyl ester of phosphonic acid). At higher temperatures, similar intermediate forms give diesters or stable and detectable pyrophosphonates which were also consumed to give diesters.31P NMR spectroscopy was used to assign the structure of pyrophosphonate as well as to monitor the reaction course. No need for additional reagents and good accessibility and straightforward purification are the important aspects of the developed protocols.

Optimization and a Kinetic Study on the Acidic Hydrolysis of Dialkyl α-Hydroxybenzylphosphonates

The two-step acidic hydrolysis of α-hydroxybenzylphosphonates and a few related derivatives was monitored in order to determine the kinetics and to map the reactivity of the differently substituted phosphonates in hydrolysis. Electron-withdrawing substituents increased the rate, while electron-releasing ones slowed down the reaction. Both hydrolysis steps were characterized by pseudo-first-order rate constants. The fission of the second P-O-C bond was found to be the rate-determining step.

Transition metal-free access to 3,4-dihydro-1,2-oxaphosphinine-2-oxides from phosphonochloridates and chalcones through tandem Michael addition and nucleophilic substitution

A novel and transition metal-free synthesis of 3,4-dihydro-1,2-oxaphosphinine 2-oxides was developed. LiHMDS-mediated tandem Michael addition and nucleophilic substitution of readily available phosphonochloridates and chalcones afforded a variety of valuable 3,4-dihydro-1,2-oxaphosphinine 2-oxides bearing diverse functionalities in excellent yields and satisfactory to good diastereoselectivity (up to 99% yield and up to 99?:?1 dr).

Investigation of reactive intermediates and reaction pathways in the coupling agent mediated phosphonamidation reaction

The preparation of carboxamides through the coupling agent mediated reaction of carboxylic acids and amines is one of the most frequently employed reaction types of modern organic synthesis and has largely replaced older methods of amide formation based on reactive acyl chloride intermediates. However, the preparations of analogous phosphonamidates still rely on the use of phosphonochloridate intermediates - a method that is incompatible with sensitive functional groups. Herein, we present a comprehensive study in which different coupling agents are tested in the phosphonamidation reaction. The procedures, parallel to those typically applied to the preparation of carboxamides, were generally unsuccessful with regard to the coupling reactions of monoesters of phosphonic acids and amines, with the exception of those mediated by (benzotriazol-1-yloxy)tripyrrolidinophosphonium hexafluorophosphate (PyBOP). The implementation of a preactivation period in the absence of the amine coupling partner allowed for efficient phosphonamidate formation with coupling agents such as (1-cyano-2-ethyoxy-2-oxoethylideneaminooxy)dimethylamino-morpholino-carbenium hexafluorophosphate (COMU), [ethyl cyano(hydroxyimino)acetato-O2]tri-1-pyrrolidinylphosphonium hexafluorophosphate (PyOxim), dicyclohexyl carbodiimide (DCC), N,N′-diisopropylcarbodiimide (DIC), and N,N,N′,N′-tetramethyl-O-(1H-benzotriazol-1-yl)uronium hexafluorophosphate (HBTU). The reactive intermediates observed by 31P NMR analysis were individually synthesized and examined to understand their influence on the reaction. A phosphonamidation reaction that uses (1-cyano-2-ethyoxy-2-oxoethylideneaminooxy)dimethylamino-morpholino-carbenium hexafluorophosphate (COMU) to mediate the coupling of monoalkyl esters of phosphonic acids and amines was developed. A preactivation period without the amine was needed to obtain the product. Using this step allowed for other coupling agents to be successfully used in the reaction.

HIV-1 non-nucleoside reverse transcriptase inhibitors: Incorporation of benzylphosphonate moiety for solubility improvement

Benzylphosphonates of 5'-norcarbocyclic analogue of 2',3'-dideoxy-2',3'-didehydrouridine and its N3-benzyl derivatives with different substituents at the phosphorus atom were designed and synthesized in attempt to improve solubility of potentia

Synthetic Strategy and Performances of a UV-Curable Poly Acryloyl Phosphinate Flame Retardant by Carbene Polymerization

A route to synthesize poly ethyl (4-acrylamidebenzyl) phosphinate (PPAC) was discussed and the optimal route was determined. Diethyl benzylphosphonate was synthesized by Arbuzov reaction, then, a nitryl was introduced onto the aromatic ring by the nitration reaction of ethyl benzylphosphonate. Subsequently the carbene polymerization of the product was carried out. Finally, the nitryls were reduced and amidated to introduce the acryloyl group into the prepolymer to obtain the target product (PPAC). PPAC can rapidly photopolymerize under UV light irradiation. The addition of PPAC decreased the smoke production rate (SPR), CO2 production (CO2P), and CO production (COP) of the UV-cured resin.

Phosphonic acid analogs of GABA through reductive dealkylation of phosphonic diesters with lithium trialkylborohydrides

Lithium trialkylborohydrides were found to effect rapid monodealkylation of phosphonic diesters, and this reaction was applied to the synthesis of alkylphosphonic acid 2-aminoethyl esters [H2N(CH2)2OP(OH)R, 4], a little-ex

Ionic-liquid-promoted Michaelis-Arbuzov rearrangement

Room-temperature imidazolium ionic liquids, [Rmim][X], proved to be environmentally benign recyclable solvents promoting the Michaelis-Arbuzov rearrangement, which can be performed even at room temperature in a short period of time. The best ionic liquid of choice depended on the starting phosphorus(III) ester, namely, for triethyl phosphite [bmim][NTf2] demonstrated better results while for ethyl diphenylphosphinite it was [hmim][Br].

Inhibitors of protein isoprenyl transferases

Compounds having the formula or a pharmaceutically acceptable salt thereof wherein R1 is (a) hydrogen, (b) loweralkyl, (c) alkenyl, (d) alkoxy, (e) thioalkoxy, (f) halo, (g) haloalkyl, (h) aryl-L2—, and (i) heterocyclic-L2—; R2 is selected from(a) (b) —C(O)NH—CH(R14)—C(O)OR15, (d) —C(O)NH—CH(R14)—C(O)NHSO2R16,(e) —C(O)NH—CH(R14)-tetrazolyl, (f) —C(O)NH-heterocyclic, and(g) —C(O)NH—CH(R14)—C(O)NR17R18; R3 is substituted or unsubstituted heterocyclic or aryl, substituted or unsubstituted cycloalkyl or cycloalkenyl, ?and —P(W)RR3RR3′; R4 is hydrogen, lower alkyl, haloalkyl, halogen, aryl, arylakyl, heterocyclic, or (heterocyclic)alkyl; L1 is absent or is selected from (a) —L4—N(R5)—L5—, (b) —L4—O—L5—, (c) —L4—S(O)n—L5—(d) —L4—L6—C(W)—N(R5)—L5—, (e) —L4—L6—S(O)m—N(R5)—L5—, (f) —L4—N(R5)—C(W)—L7—L5—, (g) —L4—N(R5)—S(O)p—L7—L5—, (h) optionally substituted alkylene, (i) optionally substituted alkenylene, (j) optionally substituted alkynylene (k) a covalent bond, (l) and (m) are inhibitors of protein isoprenyl transferases. Also disclosed are protein isoprenyl transferase inhibiting compositions and a method of inhibiting protein isoprenyl transferases.