Dialkyl α-Hydroxyphosphonates Derived from Chloral<sup>1</sup>

Barthel, W. F.; Giang, P. A.; Hall, S. A.

doi:10.1021/ja01645a046

Cited by 50 publications

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“…Synthesis of 0,0-Dialkyl 2,2,2-Trichloro-l-acyloxy ethyl Phosphonates and Related Compounds. The dialkyl -hydroxyethyl phosphonates shown in Table I w'ere prepared by the addition of chloral to equimolar dialkyl hydrogen phosphites (5,79). Carboxylic esters were synthesized by esterification of the -hydroxyethyl phosphonates with equimolar acid anhydrides or acyl chlorides (2,5).…”

Section: Methodsmentioning

confidence: 99%

“…The dialkyl -hydroxyethyl phosphonates shown in Table I w'ere prepared by the addition of chloral to equimolar dialkyl hydrogen phosphites (5,79). Carboxylic esters were synthesized by esterification of the -hydroxyethyl phosphonates with equimolar acid anhydrides or acyl chlorides (2,5). A single acyloxy derivative, butonate, was also prepared in very low yields by coupling a-chloro-/3-trichloroethyl n-butyrate (70) with equimolar dimethyl phosphite and by the addition of methanol and phosphorus trichloride to the a-chloro-/3-trichloroethyl n-butyrate intermediate in a 3 to 1 to 1 molar ratio.…”

Section: Methodsmentioning

confidence: 99%

“…per second) was distilled at 120°to 125°C. and 760 mm., and then reacted with equimolar chloral to form Dipterex in 83% yield (5,79). Chromatography of the chloroform-soluble ma-terials of the reaction mixture on silica gel with «-hexane, followed by chloroform elutrients, yielded more than 99% of the total radioactivity7 in the chloroform fraction.…”

Section: Characterization Of Other Derivativesmentioning

confidence: 99%

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Pesticide Toxicity, Biological Activity of Several O,O-Dialkyl Alpha-Acyloxyethyl Phosphonates

Arthur¹,

Casida²

1958

J. Agric. Food Chem.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Characterization Of Other Derivativesmentioning

confidence: 99%

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Pesticide Toxicity, Biological Activity of Several O,O-Dialkyl Alpha-Acyloxyethyl Phosphonates

Arthur¹,

Casida²

1958

J. Agric. Food Chem.

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“…A number of dialkyl a-hydroxyphosphonates derived from chloral and dialkyl hydrogen phos-phite have been described in previous papers. 1 In our extension of this study of dialkyl hydroxyphosphonates as possible insecticidal agents, dimethyl 2,3,4,5,6-D-gZwco-pentaacetoxy-l-hydroxy-ithexylphosphonate (I) was synthesized from dglucose in four steps. Although I proved to be of little value as an insecticide, it may be of interest to the carbohydrate chemist for the preparation of new derivatives.…”

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confidence: 99%

Notes - Cyanamide Derivatives. LIV. Cyanoformamidine and Its Reactions

Shirai¹,

Odo²,

Sugino³

1958

J. Org. Chem.

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“…hydroxyethyl Insecticides Phosphonate (designated as the hydroxyethyl phosphonate or LI3/59 based on the Bayer code number). Red phosphorus-32 was chlorinated to yield phosphorus-32 trichloride (19), which was slowly added to 3 equivalents of anhydrous methanol to yield dimethyl hydrogen phosphite-32 (6,30). The addition of equimolar chloral to the dimethyl hydrogen phosphite-32 yielded , -dimethyl 2,2,2-trichloro-l-hydroxyethyl phosphonate (6,28) in 34% yield with a specific activity of approximately 1 me.…”

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confidence: 99%

Mode of Action of Insecticides, Metabolism and Selectivity of O,O-Dimethyl 2,2,2-Trichloro-1-hydroxyethyl Phosphonate and Its Acetyl and Vinyl Derivatives

Arthur¹,

Casida²

1957

J. Agric. Food Chem.

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0,O-dimethyl 2,2,2-trichloro-l -hydroxyethyl phosphonate (L13/59) and its acetyl derivative (0,O-dimethyl 2,2,2-trichloro-l -acetoxyethyl phosphonate), and vinyl derivative formed on dehydrochlorination (0,O-dimethyl 2,2-dichlorovinyl phosphate) were investigated with phosphorus-32-tagged materials in relation to their metabolism and selective toxicity. A marked variation in species susceptibility was demonstrated; the vinyl phosphate was generally more toxic but less selectively toxic than the two phosphonates. Antiesterase activity of the three compounds appeared to be due to dimethyl phosphorylation of the enzymatically active sites. Acetyl L13/59 may be enzymatically deacetylated in vivo to form the more active antiesterase, L13/59. The greater activity with the free a-hydroxyl may be due to hydrogen bonding between the L13/59 and the esterase. Although several different types of experimental approaches were utilized, no evidence was obtained for in vivo L13/59 dehydrochlorination and rearrangement to the more toxic vinyl phosphate. The low mammalian toxicity of L13/59 appears to be due to phosphonate hydrolysis b y serum esterases and elimination of the trichloro-portion of the molecule in the urine as trichloroethyl glucuronide. Studies are reported on the rate and products of acid and alkaline hydrolysis of the three derivatives, as are observations on their phytotoxicity, volatility, and in vivo distribution in certain insects and plants.A 2 , 2 , 2 -tric hloro-1 -hydroxyethyl phosphonate (L13/59) has attracted considerable interest for housefly control and for potential use as a systemic in the treatment of animals infested with endo-and ectoparasitic arthropods (7, 7, 27, 37). In the presence of dilute alkali, this trichlorohydroxyethyl phosphonate undergoes a dehydrochlorination and rearrangement reaction, yielding the highly insecticidal vinyl derivative. 0,O-dimethyl 2,2-dichlorovinyl phosphate (DDVP) (5, 29, 37). The formation of an acetyl derivative, 0,O-dimethyl 2,2,2-trichloro -1-acetoxyethyl phosphonate, involves blocking the active hydrogen taking part in dehydrochlorination and possibly in hydrogen bonding reactions.Mammals poisoned with L13/59 display a rapid recovery of cholinesterase activity of serum and brain compared with the phosphate and phosphorothioate insecticides now being used (24). DuBois and Cotter (76) postulated that this rapid in vivo reactivation of the cholinesterase and possibly the low toxicity to mammals may be due to the ease of metabolic degradation and a rapid dissociation of the enzyme-inhibitor combination.This investigation concerns the metabolism and selective toxicity of L13/59 and its acetyl phosphonate and vinyl phosphate derivatives.Radio-phosphorus-labeled insecticides were used to investigate the in vivo and in vitro metabolism of thrse materials. Materials and Methods 0,O-Dimethyl 2,-Synthesis of 2,Z-Tr ic hlor o-lRadiophosphorus h y d r o x y e t h y lPhosphonate (desInsecticides ignated as the hydroxyethyl phosphonate or L13/59 based on the Bayer code num...

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Dialkyl α-Hydroxyphosphonates Derived from Chloral¹

Cited by 50 publications

References 0 publications

Pesticide Toxicity, Biological Activity of Several O,O-Dialkyl Alpha-Acyloxyethyl Phosphonates

Pesticide Toxicity, Biological Activity of Several O,O-Dialkyl Alpha-Acyloxyethyl Phosphonates

Notes - Cyanamide Derivatives. LIV. Cyanoformamidine and Its Reactions

Mode of Action of Insecticides, Metabolism and Selectivity of O,O-Dimethyl 2,2,2-Trichloro-1-hydroxyethyl Phosphonate and Its Acetyl and Vinyl Derivatives

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Dialkyl α-Hydroxyphosphonates Derived from Chloral1

Cited by 50 publications

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Pesticide Toxicity, Biological Activity of Several O,O-Dialkyl Alpha-Acyloxyethyl Phosphonates

Pesticide Toxicity, Biological Activity of Several O,O-Dialkyl Alpha-Acyloxyethyl Phosphonates

Notes - Cyanamide Derivatives. LIV. Cyanoformamidine and Its Reactions

Mode of Action of Insecticides, Metabolism and Selectivity of O,O-Dimethyl 2,2,2-Trichloro-1-hydroxyethyl Phosphonate and Its Acetyl and Vinyl Derivatives

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Dialkyl α-Hydroxyphosphonates Derived from Chloral¹