Organophosphorus compounds. V. Dialkyl alkylphosphonates from alkyl halides and sodium dialkyl phosphonates in liquid ammonia

1965 ◽  
Vol 18 (2) ◽  
pp. 163 ◽  
Author(s):  
A Meisters ◽  
JM Swan
Keyword(s):  
Carbon Tetrachloride ◽  
Good Yield ◽  
Benzyl Chloride ◽  
Liquid Ammonia ◽  
Organophosphorus Compounds ◽  
Alkyl Halides ◽  
Ethyl Bromide ◽  
Equivalent Quantity ◽  
Dialkyl Phosphonates

Liquid ammonia is a useful solvent for the reaction of various alkyl halides with sodium dialkyl phosphonates. In this medium ethyl bromide, amyl bromide, octyl bromide, ally1 chloride, and benzyl chloride give the corresponding dialkyl alkylphosphonates in good yield. In other cases, alternative products are formed. Thus sodium diethyl phosphonate reacts with carbon tetrachloride or chloroform in liquid ammonia to give diethyl phosphoramidate; dibromomethane gives diethyl methylphosphonate and an equivalent quantity of diethyl phosphoramidate. p-Nitrobenzyl bromide gives mainly 1,2-di(p-nitrophenyl)ethane, 1-bromooct-1-yne is reduced to oct-1-yne, and 3-bromoprop-1-yne gives mainly propyne together with some diethyl prop-l- ynylphosphonate.

Reactions of aliphatic halides with solutions of alkali metals in liquid ammonia: I. Experiments with alkyl halides

2010 ◽  
Vol 81 (12) ◽  
pp. 1033-1052 ◽  
Author(s):  
A. Beverloo ◽  
M. C. Dieleman ◽  
P. E. Verkade ◽  
K. S. de Vries ◽  
B. M. Wepster
Keyword(s):  
Alkali Metals ◽  
Liquid Ammonia ◽  
Alkyl Halides

Reduction by Dissolving Metals

1955 ◽  
Vol 8 (4) ◽  
pp. 512 ◽  
Author(s):  
AJ Birch ◽  
J Cymerman-Craig ◽  
M Slaytor
Keyword(s):  
Acid Hydrolysis ◽  
Good Yield ◽  
Liquid Ammonia ◽  
The Right

The reduction by sodium and ethanol, with or without liquid ammonia as solvent, of various amidines followed by acid hydrolysis, leads in many cases to a good yield of the corresponding aldehyde. Further reduction in liquid ammonia of several 2-aryl-imidazolines or imidazolidines followed by acid hydrolysis leads to the 2,5-dihydro-benzaldehyde derivative. The reduction of some acid amides by sodium and proton sources in liquid ammonia has been examined. Under the right conditions this process is of preparative value for aldehydes.

Synthesis of Double Alkyl EO/PO Random Copolyethers with KOH Catalyst

2012 ◽  
Vol 472-475 ◽  
pp. 2681-2685
Author(s):  
Jian Guo Guo ◽  
Su Qin He ◽  
Jian Ming Jiang
Keyword(s):  
Molecular Weight ◽  
Ethylene Oxide ◽  
Propylene Oxide ◽  
Potassium Hydroxide ◽  
Random Copolymer ◽  
Alkyl Halides ◽  
Ethyl Bromide ◽  
Hydroxyl Group ◽  
Molar Ratio ◽  
End Capping

Ethylene oxide (EO) and propylene oxide (PO) random copolymer was synthesized with 1,2-propanediol as initiator, then the end-capping process was carried out by adding various alkyl halides and potassium hydroxide (KOH) to produce the double alkyl EO/PO random copolyethers. The factors effecting alkyl-capping rate were discussed. The results showed that when the molar ratio of hydroxyl group/KOH/1-bromobutane was 1/1.9/1.9, reacting time 6.5 hr and reacting temperature 50°C, the alkyl-capping rate could reach over 80%. The end-capping rate would also increase with the increasing content of ethylene oxide in the random polyether, and the end-capping rate of the EO/PO/EO block-polyether was high than that of the random polyether with same molecular weight. Instead of 1-bromobutane, ethyl bromide promised a higher whereas chloralkane gave a lower end-capping rate respectively.

ORGANIC DEUTERIUM COMPOUNDS: XV. SYNTHESIS OF SOME DEUTERATED ALKANES

1956 ◽  
Vol 34 (3) ◽  
pp. 354-358 ◽  
Author(s):  
Mary Elaine Leblanc ◽  
A. T. Morse ◽  
L. C. Leitch
Keyword(s):  
Carbon Tetrachloride ◽  
Methyl Iodide ◽  
Zinc Dust ◽  
Deuterium Oxide ◽  
Alkyl Halides ◽  
Ethyl Iodide ◽  
Improved Method

An improved method of preparing deuterated alkanes from the halides has been developed. Dehalogenation of ethyl iodide, 1,1-dibromoethane, and 1,1,1-trichloroethane with zinc dust in deuterium oxide – dioxane solutions, or even with deuterium oxide alone, gave excellent yields of ethane-d1, ethane-1,1-d2, and ethane-1,1,1-d3. Methane-d1, -d2, -d3, and -d4 were prepared similarly from methyl iodide, dibromomethane, chloroform, and carbon tetrachloride respectively. The isotopic purity of the products was over 90 mol.%. The reaction is also applicable to higher alkyl halides.

Organophosphorus compounds. P-Arylated perhydro-1,2-azaphosphorines

1977 ◽  
Vol 30 (3) ◽  
pp. 579 ◽  
Author(s):  
DG Hewitt ◽  
GL Newland
Keyword(s):  
Thionyl Chloride ◽  
Good Yield ◽  
Aqueous Ammonia ◽  
Organophosphorus Compounds ◽  
Phosphinic Acid ◽  
Sodium Hydride ◽  
Hydrolysis Of ◽  
Phenylmagnesium Bromide

Treatment of ethyl 4-bromobutylphosphonochloridate with phenylmagnesium bromide, followed by acid-catalysed hydrolysis of the product, gave 4- bromobutyl(phenyl)phosphinic acid. This was converted into the corresponding phosphinamide by treatment with thionyl chloride and then with aqueous ammonia. Cyclodehydrobromination with sodium hydride in warm xylene then gave a good yield of 2-phenylperhydro-1,2- azaphosphorine 2-oxide. Some other routes to this compound were investigated.

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