Ethers hydrocyanic

This type of alkynol ether hydrocyanation gives rise to a new stereospecific route to a-alkyli-dene y-lactones. Acidic hydrolysis and cyclization of some of the products obtained, as above, give a-alkylidene-y-lactones in 65-83% yield with the double-bond geometry predetermined via stereoselective hydrocyanation2T... 

Miscellaneous Reactions. Sodium bisulfite adds to acetaldehyde to form a white crystalline addition compound, insoluble in ethyl alcohol and ether. This bisulfite addition compound is frequendy used to isolate and purify acetaldehyde, which may be regenerated with dilute acid. Hydrocyanic acid adds to acetaldehyde in the presence of an alkaU catalyst to form cyanohydrin the cyanohydrin may also be prepared from sodium cyanide and the bisulfite addition compound. Acrylonittile [107-13-1] (qv) can be made from acetaldehyde and hydrocyanic acid by heating the cyanohydrin that is formed to 600—700°C (77). Alanine [302-72-7] can be prepared by the reaction of an ammonium salt and an alkaU metal cyanide with acetaldehyde this is a general method for the preparation of a-amino acids called the Strecker amino acids synthesis. Grignard reagents add readily to acetaldehyde, the final product being a secondary alcohol. Thioacetaldehyde [2765-04-0] is formed by reaction of acetaldehyde with hydrogen sulfide thioacetaldehyde polymerizes readily to the trimer. 

Substances that form carbanions, such as nitro compounds, hydrocyanic acid, malonic acid, or acetylacetone, react with vinyl ethers in the presence of water, replacing the alkyl group under mild conditions (245). 

Acrylics are chemically resistant at room temperature to dilute acids, except hydrofluoric and hydrocyanic, all alkalis and mineral oils. They are attacked by chlorinated solvents, aromatic hydrocarbons, ketones, alcohols, ethers and esters [60]. 

Hychoxyaldehydes hate been obttiined indirectly by the use of the crystalline compound HCl.HCN (which hychochloiic acid forms with hydrocyanic acid) acting upon a phenol ether,... 

A solution of (R)-oxynilrilase (F.C 4.1.2.10, 100 pi., 1000 unils/ml.) is dropped onto 1.5 g of Avicel cellulose (soaked in 0.02 M sodium acetate buffer. pH 4.5). 20 mL of diisopropyl ether are added, followed by 5 mmol of ketone and 200 pL of hydrocyanic acid, and the mixture is stirred (Table 3). The catalyst is filtered off. washed with diisopropyl ether, and the combined filtrates are concentrated. 

Hydrogen cyanide (Table 15.1) is a colorless, flammable liquid or gas that boils at 25.7°C and freezes at minus 13.2°C. The gas rarely occurs in nature, is lighter than air, and diffuses rapidly. It is usually prepared commercially from ammonia and methane at elevated temperatures with a platinum catalyst. It is miscible with water and alcohol, but is only slightly soluble in ether. In water, HCN is a weak acid with the ratio of HCN to CN about 100 at pH 7.2, 10 at pH 8.2, and 1 at pH 9.2. HCN can dissociate into H+ and CN. Cyanide ion, or free cyanide ion, refers to the anion CN derived from hydrocyanic acid in solution, in equilibrium with simple or complexed cyanide molecules. Cyanide ions resemble halide ions in several ways and are sometimes referred to as pseudohalide ions. For example, silver cyanide is almost insoluble in water, as are silver halides. Cyanide ions also form stable complexes with many metals. 

The potassium cyanide complex of 18-crown-6 in benzene or acetonitrile undergoes Michael addition to unsaturated carbonyl compounds (Liotta et al., 1977). In the presence of acetone cyanohydrin, the catalytic (i.e. catalytic in potassium cyanide and crown ether) cycle for hydrocyanation shown in (21)... 

Achillea alpina L. A. millefolium L. Shi Cao (Siberian yarrow) (aerial part) Alkaloids, essential oils, achillin, flavonoides, betonicine, achilleine, d-camphor, oxalic acids, ether oils, hydroxycinnamic acids, hydrocyanic acids, hydroxybenzoic acids, anthocyanidines, anthraquinones, phytosterines, carotene, coumarins, monoterpene, sesquiterpene glucosides, desacetylmatricarin.33-222-450 Antibacterial, treat menopause, abdominal pain, acute intestinal disorder, wound infection, snakebite. 

Polygonum bistorta L. Cao He Che (Snakeweed, bistort) (stem, root) Iodine, oxalic acids, coumarins, hydroxycinnamic acids, ether oil, hydroxybenzoic acids, hydrocyanic acids, anthocyanidines, carotenes, anthraquinones, phytosterines, monoterpene, sesquiterpene glucoside, caffeic acid, quercimeritrin, avicularin, gallic acid, protocatechuic acid 50.221.222,223,224 Diuretic, laxative, hemostatic, antifebrile. 

Taraxacum officinale G. H. Weber ex Wigg. Western Pu Gong Ying (Dandelion) (root) Inulin, essential oils, choline, hydroxycinnamic acids, carotenes, ether oils, monoterpene, oxalic acids, hydrocyanic acids, sesquiterpene glucosides, flavonoids, hydroxybenzoic acid, coumarins, anthocyanidines, anthraquinones, phytosterines, squalene, cerylic alcohol, arabinose, vitamins , , C.88-222-450 Sudorific, stomachic, tonic, a remedy for sores, boils, ulcers, abscesses, snakebites. 

The thiocyanates are generally soluble in water, the exceptions being those of lead, silver, mercury and copper. Most of them dissolve also in alcohol and ether. Aqueous solutions of the alkali thiocyanates undergo atmospheric oxidation under the influence of sunlight with solutions of medium concentration this change takes place rapidly, with separation of a yellow, amorphous precipitate consisting of pseudocyanogen sulphide, (CNS)3 (cf. p. 236). The concentration of thiocyanate most favourable to the separation of this sulphide is about 50 per cent, in summer and 10 per cent, in winter. In addition to this substance the products of the photochemical oxidation of potassium thiocyanate include hydrocyanic acid, sulphate, carbon dioxide, ammonia and ammonium salts ... 

It consists of small tabular crystals which readily sublime. It is only slightly soluble in water, alcohol and ether in chloroform and in carbon disulphide it is more soluble. It is decomposed by cold water into the triselenide, ammonium selenoeyanate and selenious and hydrocyanic acids. Hot water decomposes it into selenious and hydrocyanic acids.3... 

FORMAMIDE. Form amide (meibanamide), HCONHi. is the lirsi member of the primary amide series and is the only one liquid at room temperature. II is hygroscopic and has a faint odor of ammonia. Formamide is a colorless to pale yellowish liquid, freely miscible with water, lower alcohols and glycols, and lower esters and acetone. It is virtually immiscible in almost all aliphatic and aromatic hydrocarbons, chlorinated hydrocarbons, and ethers. By virtue of its high dielectric constant, close to that of water and unusual for an organic compound, formamide has a high solvent capacity lor many heavy-metal salts and for salts of alkali and alkalinc-carth metals. It is an important solvent, in particular for resins and plasticizers. As a chemical intermediate, formamide is especially useful in the synthesis of heterocyclic compounds, pharmaceuticals, crop protection agents, pesticides, and for the manufacture of hydrocyanic acid. 

The details of this preparation are practically the same as those given for p-tolu-nitrile (Preparation 82). A cuprous-potassium cyanide solution, prepared as therein described, is warmed to about 70°, and added in small portions to a solution of benzene-diazonium chloride prepared from 18-6 gms. (1 mol.) of aniline as described in Preparation 379. When the addition is complete, the liquid is warmed on a water bath for 15 minutes and distilled in steam the distillate is extracted with ether. The ethereal solution is washed repeatedly with dilute caustic soda and with dilute sulphuric acid, dried over anhydrous potassium carbonate, filtered, and the oil which remains on driving off the ether fractionated. Owing to the evolution of cyanogen and hydrocyanic acid, this preparation must be carried out in a good fume cupboard. 

Yield.—Theoretical. White rhombohedral crystals with greenish tinge infusible almost insoluble in water, solution being decomposed on boiling with evolution of hydrocyanic acid insoluble in alcohol or in ether. Many other aromatic organic bases yield similar compounds. (J. C. S., 121,1293.)... 

Hydrocyanic, HCN.—Colourless volatile liquid B.P. 26° burns with reddish-violet flame soluble in water, alcohol and ether. Aqueous solution does not redden blue litmus. 

Initial preparative work with oxynitrilases in neutral aqueous solution [517, 518] was hampered by the fact that under these reaction conditions the enzymatic addition has to compete with a spontaneous chemical reaction which limits enantioselectivity. Major improvements in optical purity of cyanohydrins were achieved by conducting the addition under acidic conditions to suppress the uncatalyzed side reaction [519], or by switching to a water immiscible organic solvent as the reaction medium [520], preferably diisopropyl ether. For the latter case, the enzymes are readily immobilized by physical adsorption onto cellulose. A continuous process has been developed for chiral cyanohydrin synthesis using an enzyme membrane reactor [61]. Acetone cyanhydrin can replace the highly toxic hydrocyanic acid as the cyanide source [521], Inexpensive defatted almond meal has been found to be a convenient substitute for the purified (R)-oxynitrilase without sacrificing enantioselectivity [522-524], Similarly, lyophilized and powered Sorghum bicolor shoots have been successfully tested as an alternative source for the purified (S)-oxynitrilase [525],... 

When a 1/2 to 2% solution of cocaine is injected into a mixed nerve or into the subdural canal, the selective action is very marked, so that there is complete anesthesia, without motor impairment. If the contact is prolonged, by stopping the circulation, or if stronger solutions are employed, the motor fibers become paralyzed, so that the difference is merely quantitative. A similar difference in the susceptibility of motor and sensory structures exists also for the alcohol group, aconitine, phenol, hydrocyanic acid, and for pressure, and even for the centrally acting narcotics, ether, etc. It is therefore a characteristic of nervous tissue rather than of cocaine. It is now generally... 

In 2000, Kagan and Holmes reported that the mono-lithium salt 10 of (R)- or (S)-BINOL catalyzes the addition of TMS-CN to aldehydes (Scheme 6.8) [52]. The mechanism of this reaction is believed to involve addition of the BI NO Late anion to TMS-CN to yield an activated hypervalent silicon intermediate. With aromatic aldehydes the corresponding cyanohydrin-TMS ethers were obtained with up to 59% ee at a loading of only 1 mol% of the remarkably simple and readily available catalyst. Among the aliphatic aldehydes tested cyclohexane carbaldehyde gave the best ee (30%). In a subsequent publication the same authors reported that the salen mono-lithium salt 11 catalyzes the same transformation with even higher enantioselectivity (up to 97% Scheme 6.8) [53], The only disadvantage of this remarkably simple and efficient system for asymmetric hydrocyanation of aromatic aldehydes seems to be the very pronounced (and hardly predictable) dependence of enantioselectivity on substitution pattern. Furthermore, aliphatic aldehydes seem not to be favorable substrates. 

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