ChemInform Abstract: IMPROVED, REPRODUCIBLE PROCEDURES FOR THE PREPARATION OF DIETHYL METHYLPHOSPHONITE

Miles, J. A. L.; Balthazor, T. M.; Nufer, H.; Beeny, M. T.

doi:10.1002/chin.197931311

Cited by 4 publications

(4 citation statements)

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“…6b: 88.3% as a light yellow solid; mp 148-153 °C; NMR (CDC13) 1.32 (t, 3, c/hh = 7 Hz, CH2CH3), 4.13 (p, 2, s/hh = e/pH = 7 Hz, OCH2), 7.36-8.07 (m, 8), 8.18 (br s, 1, NH), 12.66 (br s, I, enol OH); mass spectrum (El, 100 eV), m/e 397 (M+•).…”

Section: Methodsmentioning

confidence: 99%

Phosphindolin-3-one. A useful intermediate for phosphindole synthesis

Balthazor¹

1980

J. Org. Chem.

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Section: Methodsmentioning

confidence: 99%

Phosphindolin-3-one. A useful intermediate for phosphindole synthesis

Balthazor¹

1980

J. Org. Chem.

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“…However, the two step reaction is complex, and the first step is to produce more by-products, which will affect the final yield. The second way to produce DEMP is by using CH3PCl2 as starting material and replacing reaction to get DEMP [10][11][12][13][14][15]. But this requires strict experimental conditions, And the adsorption of hydrochloric acid will produce a large amount of hydrochloride.…”

Section: Figure 1: Synthesis Of Dempmentioning

confidence: 99%

Study on the Synthesis of Diethyl Methyl-Phosphonite

Jiang¹,

Yan²,

Dai³

et al. 2018

Topics in Chemical &Amp; Material Engineering

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[Aims] Glyphosate is one of the most widely used herbicide in the world, Diethyl methyl-phosphonite(DEMP) is the key intermediate for glyphosate production. Various processes are known for the manufacture of DEMP. However, the substitution reaction has many disadvantages such as low product yield and purity. [Methods] In order to diminish the cost of production of its relevant products, we determine using methylphosphonous dichloride (CH3PCl2), alcohol(CH3CH2OH) and sodium hydride(NaH) to give DEMP. [Results] The acts of raw materials ratio,reaction temperature, and other factors on the yield were tested. The results showed that the yield was 43.7% and purity was 86.6%. Its structure was characterized by GC-7980. [Conclusions] CH3PCl2, CH3CH2OH and NaH were used as raw materials to prepare DEMP by a simple and economical operation. The reaction condition is gentle, and cut down the cost of treating by-product.

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“…The phosphinic acid and methylphosphinic acid groups Classical routes to the esters of alkylmethylphosphinic acids are: 1) alkylation of dialkyl alkylphosphonites (the Michaelis-Arbuzov reaction), 10,[25][26][27] 2) alcoholysis of dialkylchlorophosphines, [28][29][30][31][32][33] 3) reaction of alkylphosphonohalides with Grignard reagents, 34-40 and 4) cleavage of dialkylphenylphosphine oxides with NaOH. [41][42][43] Newer routes include: 5) stepwise silylation and alkylation of phosphinates (the silyl-Arbuzov reaction), 6,7,44-46 6) Michael addition of alkyl methylphosphinates to a,b-unsaturated substrates, 2,44,47,48 7) radical addition of alkyl alkylphosphinates to alkenes, and 8) alkylation of the anion of alkyl alkylphosphinates (the Michaelis-Becker reaction).…”

Section: Figurementioning

confidence: 99%

A Convenient Preparation of Difficultly Accessible sec-Alkylmethylphosphinates Using Sequential Pudovik/Abramov - Barton/McCombie Reactions

Hansen¹,

Kehler²

1999

Synthesis

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A one-pot procedure for the syntheses of (1-hydroxysec-alkyl)methylphosphinates from ketones, hexamethyldisilazane and ethyl methylphosphinate was developed. The hydroxy group could be removed by a modified Barton/McCombie radical deoxygenation procedure. The sec-alkylmethylphosphinates can be dealkylated/hydrolyzed by treatment with trimethylsilyl bromide or refluxing in hydrochloric acid. This is a convenient route to a variety of sec-alkylmethylphosphinates, which are difficult to prepare by other methods.The phosphinic acid group and methylphosphinic acid group ( Figure 1) continue to attract considerable interest as bioisosteric replacements for carboxylic acid groups, 1,2 being potential regulators, mediators or inhibitors of metabolic processes. 3 Several methylphosphinic acids act as potent agonists or antagonists at carboxylic acid receptors, e.g. the cholecystokinin receptor, 4 the b-adrenergic receptor, 5 and their analogs act at the receptors for the inhibitory neurotransmitter γ-aminobutyric acid (GABA) 6-8 and the excitatory neurotransmitter glutamate. 9,10 Furthermore, many phosphinic and methylphosphinic acids are inhibitors of metabolic enzymes, e.g. inhibitors of aminoacyl-t-RNA synthetase, 3 creatine kinase, 11 ornithine decarboxylase, 12 nitric oxide synthase, 13 matrix metalloproteinases, 14,15 and glutamine synthetase [16][17][18][19] including many herbicides like the widely used phosphinothricin. 20 A large number of phosphinic acids have also been prepared as transition state mimics for studies or inhibition of enzymes which have carboxylic acid derivatives as substrates. [21][22][23][24] Although the phosphinic acids often show similar biological profiles as methylphosphinic acids, recent animal experiments indicate that the methylphosphinic acid moiety is considerably more metabolically stable than the phosphinic acid moiety. 7 Figure 1 The phosphinic acid and methylphosphinic acid groups Classical routes to the esters of alkylmethylphosphinic acids are: 1) alkylation of dialkyl alkylphosphonites (the Michaelis-Arbuzov reaction), 10,25-27 2) alcoholysis of dialkylchlorophosphines, 28-33 3) reaction of alkylphosphonohalides with Grignard reagents, 34-40 and 4) cleavage of dialkylphenylphosphine oxides with NaOH. 41-43 Newer routes include: 5) stepwise silylation and alkylation of phosphinates (the silyl-Arbuzov reaction), 6,7,44-46 6) Michael addition of alkyl methylphosphinates to a,b-unsaturated substrates, 2,44,47,48 7) radical addition of alkyl alkylphosphinates to alkenes, and 8) alkylation of the anion of alkyl alkylphosphinates (the Michaelis-Becker reaction). 6,49,50 These routes all have some drawbacks involving either reactive trivalent phosphorus compounds or poisonous compounds as intermediates, or rather harsh conditions. Furthermore, the most popular routes (the Arbuzov and Michaelis-Becker reactions) generally give very low or no yield when alkylation with non-activated halides or with sec-alkyl halides are required. 26,45,49 As a consequence of these difficulties, only ve...

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ChemInform Abstract: IMPROVED, REPRODUCIBLE PROCEDURES FOR THE PREPARATION OF DIETHYL METHYLPHOSPHONITE

Abstract: Die in größeren Mengen benötigte Verbindung (II) wird auf den beiden angegebenen Wegen synthetisiert.

Cited by 4 publications

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Phosphindolin-3-one. A useful intermediate for phosphindole synthesis

Phosphindolin-3-one. A useful intermediate for phosphindole synthesis

Study on the Synthesis of Diethyl Methyl-Phosphonite

A Convenient Preparation of Difficultly Accessible sec-Alkylmethylphosphinates Using Sequential Pudovik/Abramov - Barton/McCombie Reactions

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