Chloroform, oxidation

Methanol Beryllium dihydride, chloroform, oxidants, potassium r rf-butoxide... 

Mesityl oxide Methanol Methylamine N- M et hy lformam i de Methyl isobutyl ketone 2-Aminoethanol, chlorosulfonic acid, nitric acid, ethylenediamine, sulfuric acid Beryllium dihydride, chloroform, oxidants, potassium fcrf-butoxidc Nitromethane Benzenesulfonyl chloride Potassium ferf-butoxide... 

Manganese(IV) oxide in dichloromethane or potassium permanganate in chloroform oxidizes 2,4-disubstituted 1,2-dihydroquinazoline 3-oxides 6 to 2,4-substituted quinazoline 3-oxides 7. Potassium hexacyanoferrate(III) or iron(lll) chloride in alcohol can also be used for this oxidation, but the yields are lower. Oxidation of 2,4-disubstituted 1,2-dihydroquinazoline 3-oxidcs to 2,4-disubstituted quinazoline 3-oxides with lead(IV) acetate apparently proceeds via the corresponding nitroxides." ... 

Krief et al. have shown that selenium ylides behave as their sulfur analogues and convert a variety of carbonyl compounds to oxiranes <89H(28)1203>. The latter compounds can be directly obtained by using R2Se=CHR /i-hydroxyalkylselenides (available from carbonyl compounds by addition of RSeCH2Li) may serve as suitable precursors as well, either in a two-step protocol, via the selenonium salt by alkylation with magic methyl (MeS03F), or directly by treatment with thallous ethoxide in chloroform. Oxidation of the /t-hydroxyalkylselenides with peracid, followed by treatment of the resulting selenone with base, results in oxirane formation (Scheme 60). 

Ferric chloride in chloroform oxidizes the metacyclophane (12) to the bis-dienone (13) in high yield. ... 

Oxidation [1, 391, after citation of ref. 9a], Ferric chloride (1 N) in a 1 1 two-phase system with chloroform oxidizes (1), the trifluoroacetate of methoxy-O-methylnorbelladine, to the dienone (2) in 12% yield. The product (2) on hydrolysis with 2 N Na.CO ,-CHCI l undergoes a second intramolecular condensation to give the ring system of the crinine alkaloids, (3). Jb... 

DL-Form, prisms from water or from aq Nal ISO, soln, dec 270-272. Soly in water 144 mg/40 ml. Readily so] in dil acids and alkalies slightly sol in benzene, carbon disulfide practically insol in abs alcohol, ether, glacial acetic acid, petr ether, chloroform. Oxidizes readily. 

Stibinobenzene darkens and sinters at about 160° C., finally yielding a black mass. It is insoluble in water, but dissolves in glacial acetic acid and may be recrystalHsed from chloroform. Oxidation readily takes place in air, fuming nitric acid oxidises the compound explosively, and hydrogen peroxide in acetic acid solution converts it into phenylstibinic acid. 

Tetrabutylammonium periodate in chloroform oxidatively decarboxylates a-hydroxy-acids to aldehydes. The reaction is cleaner and faster than oxidation... 

CCls CHO. A colourless oily liquid with a pungent odour b.p. 98°C. Manut actured by the action of chlorine on ethanol it is also made by the chlorination of ethanal. When allowed to stand, it changes slowly to a white solid. Addition compounds are formed with water see chloral hydrate), ammonia, sodium hydrogen sulphite, alcohols, and some amines and amides. Oxidized by nitric acid to tri-chloroethanoic acid. Decomposed by alkalis to chloroform and a methanoate a convenient method of obtaining pure CHCI3. It is used for the manufacture of DDT. It is also used as a hypnotic. 

CfiHi 05 0 C6H4 CH20H. Colourless, bitter crystals, m.p. 20 PC soluble in water and alcohol, insoluble in chloroform. It occurs in the leaves, bark and twigs of species of willow and poplar. On oxidation with dilute nitric acid it is converted into helicin, the glucoside of salicylaldehyde, which has been made the starting point of further syntheses. Gives populin with benzoyl chloride. 

C7H6O2 Oily liquid of aromatic odour b.p. 196°C. (t is prepared by the action of chloroform and caustic potash on phenol (the Reimer-Tiemann reaction) or by the oxidation of the glucoside salicin. It is easily reduced to salicyl alcohol or oxidized to salicylic acid. 

Chloroform was formerly used in medicine as an anaesthetic. One disadvantage for this purpose is the ready oxidation which chloroform undergoes on exposure to light and air, generating the poisonous phosgene, or carbonyl chloride, COCU- This is counteracted by storing the liquid in dark amber-... 

Reduction of Fehling s solution. Boil i ml. of chloroform gently with 3 ml. of Fehling s solution with constant shaking for 3-4 minutes. Reduction occurs and reddish cuprous oxide slowly separates. 

Chloroform undergoes oxidation to the very poisonous phosgene upon exposure to light and air. Commercial specimens are therefore stored in brown bottles and contain 1-2 per cent, of alcohol the latter converts the toxic phosgene into the harmless substance diethyl carbonate ... 

Ethylenic compounds when oxidised with perbenzoic acid or perphthalic acid in chloroform solution yield epoxides (or oxiranes). This Is sometimes known as the Prileschajew epoxidation reaction. Thus pyrene affords styrene oxide (or 2-plienyloxirane) ... 

The acylpalladium complex formed from acyl halides undergoes intramolecular alkene insertion. 2,5-Hexadienoyl chloride (894) is converted into phenol in its attempted Rosenmund reduction[759]. The reaction is explained by the oxidative addition, intramolecular alkene insertion to generate 895, and / -elimination. Chloroformate will be a useful compound for the preparation of a, /3-unsaturated esters if its oxidative addition and alkene insertion are possible. An intramolecular version is known, namely homoallylic chloroformates are converted into a-methylene-7-butyrolactones in moderate yields[760]. As another example, the homoallylic chloroformamide 896 is converted into the q-methylene- -butyrolactams 897 and 898[761]. An intermolecular version of alkene insertion into acyl chlorides is known only with bridgehead acid chlorides. Adamantanecarbonyl chloride (899) reacts with acrylonitrile to give the unsaturated ketone 900[762],... 

Alkali metals Moisture, acetylene, metal halides, ammonium salts, oxygen and oxidizing agents, halogens, carbon tetrachloride, carbon, carbon dioxide, carbon disul-flde, chloroform, chlorinated hydrocarbons, ethylene oxide, boric acid, sulfur, tellurium... 

Chloroform Aluminum, magnesium, potassium, sodium, aluminum chloride, ethylene, powerful oxidants... 

Nitric oxide Aluminum, BaO, boron, carbon disulflde, chromium, many chlorinated hydrocarbons, fluorine, hydrocarbons, ozone, phosphine, phosphorus, hydrazine, acetic anhydride, ammonia, chloroform, Fe, K, Mg, Mn, Na, sulfur... 

Compatibihty of acetone with other materials should be carefliUy considered, especially in disposal of wastes. It reacts with chlorinating substances to form toxic chloroketones, and potentially explosively with some peroxy compounds and a number of oxidizing mixtures. Mixed with chloroform, acetone will react violently in the presence of bases. Other incompatibilities ate Hsted in the Sax handbook (53). 

The synthesis of phenoxaphosphine-containing PODs by the cyclodehydration of polyhydra2ides obtained from 2,8-dichloroformyl-lO-phenylphenoxaphosphine-lO-oxide and aUphatic and aromatic dihydra2ides has been described (60). All polymers are soluble in formic acid, y -cresol, and cone H2SO4, but insoluble or partially soluble in ben2ene, chloroform, and hexamethylphosphoric triamide. 

Resorcinol carboxylation with carbon dioxide leads to a mixture of 2,4-dihydroxyben2oic acid [89-86-1] (26) and 2,6-dihydroxyben2oic acid [303-07-1] (27) (116). The condensation of resorcinol with chloroform under basic conditions, in the presence of cyclodextrins, leads exclusively to 2,4-dihydroxyben2aldehyde [95-01-2] (28) (117). Finally, the synthesis of l,3-bis(2-hydroxyethoxy)ben2ene [102-40-9] (29) has been described with ethylene glycol carbonate in basic medium (118), in the presence of phosphines (119). Ethylene oxide, instead of ethyl glycol carbonate, can also be used (120). 

Methylene iodide [75-11-6], CH2I2, also known as diio dome thane, mol wt 267.87, 94.76% I, mp 6.0°C, and bp 181°C, is a very heavy colorless Hquid. It has a density of 3.325 g/mL at 20°C and a refractive index of 1.7538 at 4°C. It darkens in contact with air, moisture, and light. Its solubiHty in water is 1.42 g/100 g H2O at 20°C it is soluble in alcohol, chloroform, ben2ene, and ether. Methylene iodide is prepared by reaction of sodium arsenite and iodoform with sodium hydroxide reaction of iodine, sodium ethoxide, and hydroiodic acid on iodoform the oxidation of iodoacetic acid with potassium persulfate and by reaction of potassium iodide and methylene chloride (124,125). Diiodoform is used for determining the density and refractive index of minerals. It is also used as a starting material in the manufacture of x-ray contrast media and other synthetic pharmaceuticals (qv). 

Tris(2,4-pentanedionato)iron(III) [14024-18-1], Fe(C H202)3 or Fe(acac)3, forms mby red rhombic crystals that melt at 184°C. This high spin complex is obtained by reaction of iron(III) hydroxide and excess ligand. It is only slightly soluble in water, but is soluble in alcohol, acetone, chloroform, or benzene. The stmcture has a near-octahedral arrangement of the six oxygen atoms. Related complexes can be formed with other P-diketones by either direct synthesis or exchange of the diketone into Fe(acac)3. The complex is used as a catalyst in oxidation and polymerization reactions. 

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