Ethyl phosphoramidate,

C8H9N02 4-(aminomethyl)benzoic acid 56-91-7 518.92 45.705 2 13838 C8H10CI2NO3 ethyl phosphoramidic acid 2,4-dichlorophenyl 36031-66-0 440.15 38.165 1,2... 

Synonyms Bay 68138 ENT 27572 Ethyl 3-methyl-4-(methylthio)phenyI (1-methyl-ethyl)phosphoramidate Ethyl-4-methylthio-w-tolyl isopropyl phosphoramidate Isopro-pylamino-(9-ethyl-(4-methylmercapto)-3-methylphenyl)phosphate l-(Methylethyl)ethyl 3-methyl-4-(methyltliio)phenyl phosphoramidate Phenamiphos. 

The present preparation illustrates a general and convenient irethod for ring contraction of cyclic ketones. The first step is the usual procedure for the preparation of enamines. The second step involves 1,3-dipolar cycloaddition of diphenyl phosphorazidate to an enamine followed by ring contraction with evolution of nitrogen. Ethyl acetate and tetrahydrofuran can be used as a solvent in place of toluene. Pyrrolidine enamines from various cyclic ketones smoothly undergo the reaction under similar reaction conditions. Diphenyl (cycloalkyl-1-pyrrolidinylmethylene)phosphoramidates with 5,6,7, and 15 members in the ring have been prepared in yields of 68-76%. 

Thus the reaction product of diethyl ether and diphosphorus pentoxide, a pale yellowish syrupy mass, was designated as ethyl metaphosphate (147), other ethoxy-containing compounds give the same product 102-103) it can be reprecipitated from chloroform/ether and reacts with aniline to give the phosphoramidate 148 104) which is conceivably a trapping product of ethyl metaphosphate 147, or a cleavage product of polymeric metaphosphates. 

Powerful evidence for the intermediacy of a metaphosphorimidate of type 189 nevertheless comes from the product spectrum obtained on reaction of 202 with KOH in ethanol or propanol. The principal products dimethyl sulfide and potassium O-ethyl (or propyl) phosphoramidate can be readily rationalized in terms of the reaction sequence presented in the Scheme 138). 

Several approaches to the 1,2,3-triazole core have been published in 2000. Iodobenzene diacetate-mediated oxidation of hydrazones 152 led to fused 1,2,3-triazoloheterocycles 153 <00SC417>. Treatment of oxazolone 154 with iso-pentyl nitrite in the presence of acetic acid gave 1,2,3-triazole 155, a precursor to 3-(W-l,2,3-triazolyl)-substituted a,P-unsaturated a amino acid derivatives <00SC2863>. Aroyl-substituted ketene aminals 156 reacted with aryl azides to provide polysubstituted 1,23-triazoles 157 <00HC387>. 2-Aryl-2T/,4/f-imidazo[43-d][l,2,3]triazoles 159 were prepared from the reaction of triethyl AM-ethyl-2-methyl-4-nitro-l//-imidazol-5-yl phosphoramidate (158) with aryl isocyanates <00TL9889>. 

An Arbuzov reaction of triethyl phosphite with A-chloroamines RNHC1 (R = i-Pr, cyclohexyl or PhCH2), prepared from the corresponding amines and aqueous sodium hypochlorite, leads to the phosphoramides 357 with the elimination of ethyl chloride395. 

In 2008, Yamamoto et al. disclosed an asymmetric 1,3-dipolar cycloaddition of diarylnitrones 156 with ethyl vinyl ether (157) (Scheme 66). Under the influence of the bulky chiral A-triflyl phosphoramide (5)-4s (5 mol%, R = 2,6- Prj-4-Ad-C Hj), the enrfo-products 158 were formed as the major diastereomers in good yields and enantioselectivities (66 to >99%, 7 1-32 1 endolexo, 70-93% ee(endo)) [86]. High asymmetric induction was achieved only with electron-deficient aryl groups on the nitrones. 

An asymmetric intermolecular carbonyl-ene reaction catalyzed by 1 mol% of chiral A-triflyl phosphoramide (/ )-4t (1 mol%, R = 4-MeO-CgH ) was developed by Rueping and coworkers (Scheme 69) [88], Various a-methyl styrene derivatives 163 underwent the desired reaction with ethyl a,a,a-trifluoropyruvate 164 to afford the corresponding a-hydroxy-a-trifluoromethyl esters 165 in good yields along with high enantioselectivities (55-96%, 92-97% ee). The presence of the trifluoromethyl group was crucial and the use of methyl pyruvate or glyoxylate instead of 164 resulted in lower reactivities or selectivities. 

Yamamoto also applied N-triflyl phosphoramide 13b to the 1,3 dipolar addition of various electron-deficient diaryl nitrones and ethyl vinyl ether (Scheme 5.33)... 

The incorporation of more inorganic appendages into TSIL cations has also been achieved through the use of l-(3-aminopropyl)imidazole. Phosphoramide groups are readily synthesized by treatment of phosphorous(V) oxyhahdes with primary or secondary amines. In just such an approach, l-(3-aminopropyl)imidazole was allowed to react with commerdaUy available (C H5)2POCl2 in dichloromethane. After isolation, the resulting phosphoramide was then quaternized at the imidazole N(3) position by treatment with ethyl iodide (Scheme 2.3-2). The viscous, oily product was found to mix readily with more conventional ionic Hquids such as [HMIM][PF ], yielding a more tractable material. This particular TSIL has been used to extract a number of actinide elements from water. Similarly, the thiourea-appended TSILs discussed earlier have been used for the extraction of Hg and Cd from IL-immiscible aqueous phases. 

The benzene is distilled from the filtrate under reduced pressure, and the N,N -diethylene-N"-ethyl-(N -(l,3,4-thiadiazo-2-yl)phosphoramide is recrystallized from hexane, melting point 95°-96°C. 

METHYLETHYL)PHOSPHORAMIDATE ETHYL-4-(METHYLTHIO)-m-TOLYL ISOPROPYL PHOSPHORAMIDATE ISOPROPYLAMINO-O-ETHYL-(4-METHYLMERCAPTO-3-... 

ETHYL-3-METHYL-4-(METHYLTHIO)PHENYL(l-METHYLETHYL)PHOSPHORAMIDATE see FAKOOO ETHYLMETHYLNITROSAxMINE see MKBOOO... 

C6H18N30P hexannethyl phosphoramide 680-31-9 in benzene 5.540 1 11729 C7H14 2-ethyl-1-pentene 3404-71-5 gas 0.000 2... 

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