Diethyl chloroacetal

Ethyl vinyl ether was the first to be prepared, in 1878, by treatment of diethyl chloroacetal with sodium (216). Methyl vinyl ether was first Hsted in Reppe patents on vinylation in 1929 and 1930 (210,211). 

Ethoxyacetylene has been prepared from /3-bromovinyl ethyl ether and potassium hydroxide in 50-55% yield 6 from a,/3-di-bromoethyl ethyl ether and potassium hydroxide 6 and from diethyl chloroacetal, diethyl bromoacetal, a,/3-dichloroethyl ethyl ether, or a,/3-dibromoethyl ethyl ether and sodium amide.10... 

Diethyl chloroacetal refluxed with an equimolar amount of neopentyl glycol in the presence of 1 mole-% p-toluenesulfonic acid under a fractionating column with distillation of the resulting ethanol, benzene added when most of the ethanol has been removed after ca. 2 hrs., the remaining ethanol removed as benzene azeotrope, the catalyst destroyed with solid K-carbonate, and the product distilled 2-chloromethyl-5,6-dimethyl-m-dioxane. Y 95%. Numerous e., mostly m-dioxanes and other cyclic acetals, also direct acetalation of 0x0 compounds, e. g. acrolein, s. C. S. Rondestvedt, Jr., J. Org. Chem. 26, 2247 (1961) transaeetalation s. a. S. J. Angyal and R. M. Hoskinson, Soc. 1962, 2985 N. B.Lorette and W. L. Howard, Org. Synth. A2, 1 (1962). 

Malonic acid may be prepared from chloroacetic acid by the following series of reactions (compare Diethyl Malonate, Section 111,153) —... 

The physical properties of cyanoacetic acid [372-09-8] and two of its ester derivatives are Hsted ia Table 11 (82). The parent acid is a strong organic acid with a dissociation constant at 25°C of 3.36 x 10. It is prepared by the reaction of chloroacetic acid with sodium cyanide. It is hygroscopic and highly soluble ia alcohols and diethyl ether but iasoluble ia both aromatic and aUphatic hydrocarbons. It undergoes typical nitrile and acid reactions but the presence of the nitrile and the carboxyUc acid on the same carbon cause the hydrogens on C-2 to be readily replaced. The resulting malonic acid derivative decarboxylates to a substituted acrylonitrile ... 

Hydrochloric acid [7647-01-0], which is formed as by-product from unreacted chloroacetic acid, is fed into an absorption column. After the addition of acid and alcohol is complete, the mixture is heated at reflux for 6—8 h, whereby the intermediate malonic acid ester monoamide is hydroly2ed to a dialkyl malonate. The pure ester is obtained from the mixture of cmde esters by extraction with ben2ene [71-43-2], toluene [108-88-3], or xylene [1330-20-7]. The organic phase is washed with dilute sodium hydroxide [1310-73-2] to remove small amounts of the monoester. The diester is then separated from solvent by distillation at atmospheric pressure, and the malonic ester obtained by redistillation under vacuum as a colorless Hquid with a minimum assay of 99%. The aqueous phase contains considerable amounts of mineral acid and salts and must be treated before being fed to the waste treatment plant. The process is suitable for both the dimethyl and diethyl esters. The yield based on sodium chloroacetate is 75—85%. Various low molecular mass hydrocarbons, some of them partially chlorinated, are formed as by-products. Although a relatively simple plant is sufficient for the reaction itself, a si2eable investment is required for treatment of the wastewater and exhaust gas. 

Carbon Monoxide Process. This process involves the insertion of carbon monoxide [630-08-0] into a chloroacetate. According to the hterature (34) in the first step ethyl chloroacetate [105-39-5] reacts with carbon monoxide in ethanol [64-17-5] in the presence of dicobalt octacarbonyl [15226-74-1], Co2(CO)g, at typical temperature of 100°C under a pressure of 1800 kPa (18 bars) and at pH 5.7. Upon completion of the reaction the sodium chloride formed is separated along with the catalyst. The ethanol, as well as the low boiling point components, is distilled and the nonconverted ethyl chloroacetate recovered through distillation in a further column. The cmde diethyl malonate obtained is further purified by redistillation. This process also apphes for dimethyl malonate and diisopropyl malonate. 

Sodium azide, reaction with l butyl chloroacetate, 46, 47 reaction with diazomum salt from o amino-f> -ni trobiphcny L, 46, 86 Sodium chlorodifluoroacetate, 47, SO reaction with tnphenylphosphme and benzaldehyde, 47, SO Sodium ethoxide, 46, 2S reaction with diethyl succinate, 46,2S Sodium formate as reducing agent in preparation of palladium catalyst, 46, 90... 

Major photoproducts reported in soil treated with alachlor were 2, 6 -diethylacetanilide, 1-chloro-2, 6 -diethylacetanilide, 2,6-diethylaniline, chloroacetic acid, 2, 6 -diethyl-A -methoxy-methylaniline, and l-chloroacetyl-2,3-dihydro-7-ethylindole. Organic matter in soil enhanced the rate of photolysis (Chesters et al, 1989). 

A. Triethyl a-phtkalimidoethane-a,a, -tricarboxylate. Three hundred and twenty-seven grams (1.0 mole) of diethyl sodium phthalimidomalonate and 735 g. (6.0 moles) of ethyl chloro-acetate (b.p. 144-145°) are placed in a 2-1. Claisen flask fitted with a reflux condenser and rubber stoppers. The mixture is heated under reflux in an oil bath at 150-160° for 2.25 hours. The excess ethyl chloroacetate is removed by distillation at 30 mm. until the heating bath temperature reaches 150° and no more distillate is obtained (Note 1). The brown residual mass is... 

Compound Name Ethylhexaldehyde N-Propyl Alcohol Diethyl Carbonate Ethyl Chloracetate Ethyl Chloride Ethyl Chloroacetate Ethyl Chloroformate Ethyl Chloroacetate Ethyl Chloroacetate Ethyl Phosphorodichloridate Ethyldichlorosilane Ethylene... 

Condensation, of paraldehyde with diethyl malonate, 32, 54 of a-phene thyl chloride with diphenylacetonitrile, 39, 74 of phenylacetylene with ethyl orthoformate, 39, 59 of 1-phenylbiguanide with ethyl chloroacetate, 38,1 of potassium diphenylacetonitrile with benzyl chloride, 39, 73 of potassium trithiocarbonate with potassium chloroacetate, 39, 77 of sodium acetylacetonate to tetraacetylethane, 39, 61 of sodium formylacetone with cyano-acetamide, 32, 32 of tetracyanoethylene with N,N-dimethylaniline, 39, 68 of thiophene, paraldehyde, and hydrogen chloride, 38, 86 of thiourea with furfuryl alcohol, 36,66... 

Diethyl malonate may be prepared from chloroacetic acid by a similar method. 

Chloro-6-mercaptopyridazine Chloroacetic acid diethyl amide Caustic soda... 

Hydrazones are useful intermediates in the preparation of pyrazoles. 3-Oxo-3-(pyrrol-2-yl)-propanenitrile 9 was coupled with aromatic diazonium salts to yield the corresponding 2-arylhydrazones 10, which then reacted with chloroacetonitrile and ethyl chloroacetate to yield 4-aminopyrazole derivatives 11 <07SC3579>. The cyclization of hydrazone dianions of 12 with diethyl oxalate 13 afforded pyrazole-5-carboxylates 14 <07TL3591>. 

Cyclic acetals have been prepared in 75-90% yields by an alcohol exchange between dimethyl or diethyl acetals and a glycol. Thus, anhydrous glycerol and chloroacetal, on heating under a fractionating column to remove the liberated alcohol, give chloroethylidene glycerol (88%). The reaction, catalyzed by a small amount of concentrated sulfuric acid, has been extended to the formation of numerous halo cyclic acetals and mixed acetals. ... 

Diethyl chloroaoetanllidomalonate, prepared by the reaction of amiidomalonic ester with chloroacetic anhydride or with the acid -in the presence of phosphorus trichloride, W ae treated with triethyl auiiuv in benxece solution at room temperature to give an 88% yield of... 

Dimethylethylenediamine with ethyl a-benzoyl-a-chloroacetate afforded 2-ethoxycarbonyl-l,4-dimethyl-3-phenyl-l,4,5,6-tetrahydropyrazine (60) (1594), and jV,jV -diethyl-A -(r,r-dimethylpropynyl)ethylenediamine (61) refluxed with mercuric oxide in aqueous methanolic sulfuric acid is reported to give 4-ethyl-2,3,3-trimethyI-2,3,4,5-tetrahydropyrazine ( ) (1595). 

Nylen successfully used the Michaelis-Becker reaction for the preparation of phosphonoacetic esters. 56 Thus, diethyl l-(ethoxycarbonyl)methylphosphonate can be obtained in satisfactory yield (50%) by the reaction of sodium diethyl phosphite with ethyl chloroacetate in refluxing Et20 (Scheme The choice of the reaction solvent is crucial to the success of the reaction.For... 

The Michaelis-Becker reaction has been investigated with a-chloro-, a-bromo-, and a-iodoac-etates. In contrast to a-chloroacetates, on treatment with sodium diethyl phosphite, a-bromo- and a-iodoacetates undergo reduction to the corresponding acetates. Low yields (18-30%) of unsubstituted and a-alkyl substituted / w(2,2,2-trilluorocthyl) l-(ethoxycarbonyl)methylphosphonates, prepared from sodium bE(2,2,2-trifluoroethyl) phosphite and the corresponding a-bromo esters, have recently been reported. ... 

This simple procedure constitutes a very convenient, low-cost, and efficient synthesis of cinnamic acids. For example, reaction of a 25% MeONa in MeOH solution containing dimethyl phosphite with chloroacetic acid and then with aryl aldehydes affords (/ )-cinnamic acids in the range of 54-89%. This procedure is also apphcable to the carboxyvinylation of aldehydes or ketones with 2-bromoalkanoic acids and diethyl phosphite using NaH in DME as the base/solvent system. One of the major advantages of the overall procedure is that it avoids the need lo synthesize precursor reagents. 

Ethoxyacetic acid was first prepared by Heintz by the reaction of chloroacetic acid with sodium ethylate. The procedme described above is essentially that of Sommelet. Ethoxyacetic acid has also been prepared by hydrolysis of ethoxyacetonitrile with concentrated hydrochloric acid and by the action of excess sodium ethylate on 1,1,1,2-tetrachlorethane and on a,/3-dichloro-vinyl ethyl ether. A recent patent reports a synthesis from diethyl ether and carbon dioxide at high pressure. 

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