N-Propyl phosphate

The above is a general procedure for preparing trialkyl orthophosphates. Similar yields are obtained for trimethyl phosphate, b.p. 62°/5 mm. triethyl phosphate, b.p. 75-5°/5 mm. tri-n-propyl phosphate, b.p. 107-5°/5 mm. tri-Mo-propyl phosphate, b.p. 83-5°/5 mm. tri-wo-butyl phosphate, b.p. 117°/5-5 mm. and tri- -amyl phosphate, b.p. 167-5°/5 mm. The alkyl phosphates are excellent alkylating agents for primary aromatic amines (see Section IV,41) they can also be ua for alkylating phenols (compare Sections IV,104-105). Trimethyl phosphate also finds application as a methylating agent for aliphatie alcohols (compare Section 111,58). 

B = adenyl), bearing more stable C-P bonds, also inhibited DNA synthesis, although it was less active than the isosterically similar di(n-propyl) phosphate triester analogue [21]. The phosphinate is unable to degrade to the 5 -monophosphate, therefore its inhibitory properties have been attributed to the release of ara-A. In contrast, the higher activity of the phosphate triester can be accounted for by some metabolism to the 5 -monophosphate. 

A soln. of triethyl phosphite in dry ether added dropwise at —50° to a soln. of n-propanol and monobromocyanoacetamide (prepn. s. 582) in the same solvent, kept an additional hr. at room temp. diethyl n-propyl phosphate. Y 85%. F. e., also from phenols, and unsym. pyrophosphates from dialkyl hydrogen phosphates, s. T. Hata and T. Mukaiyama, Bull. Ghem. Soc. Japan 35, 1106 (1962) with dibromomalonamide s. J. Org. Ghem. 28, 481 (1963). 

Pyrophosphoric acid P P -diesters are activated by trichloroacetonitrile and become phosphorylation agents.—E A soln. of pyridinium di-p-chlorophenyl pyrophosphate in pyridine treated with n-propanoi and trichloroacetonitrile, kept 24 hrs. at 70 , and the product isolated as the cyclohexylammonium salt cyclohexylammonium p-chlorophenyl n-propyl phosphate. Y 92%. F. e. s. F. Gramer, K.-H. Scheit, and H.-J. Baldauf, B. 95, 1657 (1962). 

A soln. of ethyl bis(2,2,2-trichloroethyl) phosphate in isopropanol allowed to stand 20 hrs. at room temp, with 15 equivalents cesium fluoride ethyl isopropyl trichloroethyl phosphate. Y ca. 100%. - Similarly Ethyl n-propyl 2,2,2-trichloroethyl phosphate in n-octanol with 5 equivalents CsF at 80° during 6 days ethyl n-octyl n-propyl phosphate. Y 87%. F. e. s. K. K. Ogilvie et al.. Am. Soc. 99, 1277 (1977). 

Triphenyl phosphate dissolved in dry n-propanol containing 10 molar equivalents cesium fluoride, and the product isolated after 8 hrs. tri-n-propyl phosphate. Y ca. 100%. F. e., also nucleotide derivs., and with tetra-n-butylammonium fluoride, s. K. K. Ogilvie and S. L. Beaucage, Chem. Commun. 1976, 443. 

Thus good yields (> 60 per cent) are obtained with aniline and methyl, ethyl, n-propyl and n-butyl phosphates with a- and P-naphthylamine and methyl or ethyl phosphate nuclear substituted anilines and methyl or ethyl phosphate. 

Diethyl 0-(3-methyl-5-pyrazolyl) phosphate (722) and 0,0-diethyl 0-(3-methyl-5-pyrazolyl) phosphorothioate (723) were prepared in 1956 by Geigy and they act, as do all organophosphates in both insects and mammals, by irreversible inhibition of acetylcholinesterase in the cholinergic synapses. Interaction of acetylcholine with the postsyn-aptic receptor is therefore greatly potentiated. 0-Ethyl-5-n-propyl-0-(l-substituted pyrazol-4-yl)(thiono)thiolphosphoric acid esters have been patented as pesticides (82USP4315008). 

D-Xylulose 5-phosphate (ii-threo-2-pentulose 5-phosphate, XP) stands as an important metabolite of the pentose phosphate pathway, which plays a key fimction in the cell and provides intermediates for biosynthetic pathways. The starting compound of the pathway is glucose 6-phosphate, but XP can also be formed by direct phosphorylation of D-xylulose with li-xylulokinase. Tritsch et al. [114] developed a radiometric test system for the measurement of D-xylulose kinase (XK) activity in crude cell extracts. Aliquots were spotted onto silica plates and developed in n-propyl alcohol-ethyl acetate-water (6 1 3 (v/v) to separate o-xylose/o-xylulose from XP. Silica was scraped off and determined by liquid scintillation. The conversion rate of [ " C]o-xylose into [ " C]o-xylulose 5-phosphate was calculated. Some of the works devoted to the separation of components necessary while analyzing enzyme activity are presented in Table 9.8. 

The use of a lipophilic zinc(II) macrocycle complex, 1-hexadecyl-1,4,7,10-tetraazacyclododecane, to catalyze hydrolysis of lipophilic esters, both phosphate and carboxy (425), links this Section to the previous Section. Here, and in studies of the catalysis of hydrolysis of 4-nitrophenyl acetate by the Zn2+ and Co2+ complexes of tris(4,5-di-n-propyl-2 -imidazolyl)phosphine (426) and of a phosphate triester, a phos-phonate diester, and O-isopropyl methylfluorophosphonate (Sarin) by [Cu(A(A(A/,-trimethyl-A/,-tetradecylethylenediamine)l (427), various micellar effects have been brought into play. Catalysis of carboxylic ester hydrolysis is more effectively catalyzed by A"-methylimidazole-functionalized gold nanoparticles than by micellar catalysis (428). Other reports on mechanisms of metal-assisted carboxy ester hydrolyses deal with copper(II) (429), zinc(II) (430,431), and palladium(II) (432). 

Gold, M. D., Blum, A., and Ames, B. N. Another Flame Retardant Tris-(1,3-Dichloro-2-Propyl) Phosphate and Its Expected Metabolites are Mutagens , Science (1978) 200, 785. 

Lynn, R.K., Wong, K., Dickinson, R.G., Gerber, N, Kennish, J.M. (1980) Diester metabolites of the flame retardant chemicals, tris(l,3-dichloro-2-propyl) phosphate and tris(2,3-dibromopropyPphosphate in the rat identification and quantification. Res. Commun. chem. Path. Pharmacol.. 28, 351-360... 

Morales, N.M. Matthews, H.B. (1980) In vivo binding of the flame retardants /rz.s(2,3-dibromo-propyl) phosphate and Zr/.s ( 1,3-dichloro-2-propyl) phosphate to macromolecules of mouse liver, kidney and muscle. Pull, environ. Contam. Toxicol.. 25, 34-38... 

Fig. 30. Effects of alkyl isocyanides (n-series) on the 600-MHz ring-current-shifted proton resonances of isolated a and p chains of Hb A, Hb A, and sperm whale myoglobin (Mb) in 0.2 M phosphate in D20 at pH 6.6 and 21°C CO, carbon monoxide MNC, methyl isocyanide ENC, ethyl isocyanide nPNC, n-propyl isocyanide nBNC, n-butyl isocyanide. [Adapted from Mims el al. (1983a)].

Dimethyl disulphide n-Propyl disulphide (Allium cepa) Glucose-6-phosphate dehydrogenase (G-6-PD) ... 

GABA, yaminobutyric acid BPE, bicyclic phosphorus ester DHP, a-dihydropicrotoxinin TBPS, 4-t-butyl-2,6,7-trioxa-l-phosphabicyclo-[2.2.2]octane 1-sulfide Pr-BP, 4-n-propyl-2,6,7-trioxa-l-phospha-bicyclo[2.2.2]octane 1-oxide BP, bicyclic phosphate pb, piperonyl butoxide EDTA, ethylenediaminetetraacetic acid disodium salt BH, bicuculline methiodide... 

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