Alcohols reactions with styrene oxid

Catalytic amounts of tin(II) chloride have been found to give good yields (72-86%) of the trans-amino alcohols when oxiranes have been treated with aromatic amines in acetonitrile at room temperature.27 Only the reaction with styrene oxide was regiospe-ciflc with the amine adding to the benzylic carbon of the epoxide ring. 

The unusual reactivity of selenoboranes towards epoxides gives new selective routes to /3-hydroxy-selenides and allyl alcohols.Thus, 1,2-epoxyoctane with B(SeMe)3 at 0°C for 0.7 h, followed by aqueous NaHCOa, gave (164) (81%) whereas the same reaction with styrene oxide gave (165) (63%) as the major product. For trisubstituted oxirans, however, the products were allylic alcohols, e.g. (167) (76%) from (166) on treatment with B(SePh)3 at 20 °C for 1.5 h. 

Sulfinic esters, aromatic, by oxidation of disulfides in alcohols, 46, 64 Sulfonation ot d,l camphor to d,l-10-camphorsulfomc acid, 45,12 Sulfoxides, table of examples of preparation from sulfides with sodium metapenodate, 46,79 Sulfur dioxide, reaction with styrene phosphorus pentachlonde to give styrylphosphomc diclilonde, 46,... 

Reaction of styrene oxide with tetraallyltin in the presence of Bi(OTf)3 (2 mol%) affords the corresponding l-phenyl-4-penten-2-ol (Fig. 5). In a similar fashion, various aryl substituted epoxides react smoothly with tetraallyltin to give the corresponding homoallylic alcohols. This method give generality as cycloalkyl oxiranes and sterically hindered ones give the corresponding homoallylic alcohols. 

Various epoxides and aziridines undergo smooth ring opening with water in presence of bismuth triflate (10 mol%) to provide the corresponding v/c-diols and p-amino alcohols with excellent regioselectivity [35]. Reaction of styrene oxide with water in the presence of Bi(OTf)3 affords styrene 1,2-diols (Fig. 7). Similarly,... 

PHENYL-l, 2-EPOXYETHANE (96-09-3) CgHjO Combustible polymerizable liquid (flash point 165°F/74°C 175°F/79°Ct Fire Rating 2). Violent reaction with strong oxidizers, nitric acid, sulfuric acid. Reacts with acids, alcohols, alkalis, bases, amines, amides, and inorganic hydroxides some salts, possibly causing explosive polymerization. Reacts with 4-(4 -nitrobenzyl)pyridine. On small fires, use dry chemical powder (such as Purple-K-Powder), Halon , or COj extinguishers. See also styrene. 

Six-membered cyclic nitronic esters, the 4//-5,6-dihydrooxazine-jV-oxides (35), exhibit much the same reactivity as their five-membered analogs. Reactions with styrene, methyl acrylate, and allyl alcohol give isoxazolidines of type 1.133... 

Last isochormanic system drawn, l,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclo-penta-( )-2-benzopyran, which was developed in the middle 1960 (3) by Beets and Heer-inga from IFF is know also commercially as, e.g., Galaxolide, Abbalide. This molecule is S5mthesized as follows there is a condensation-cyclization stage of tert-smy alcohol and a-methyl styrene in acidic conditions to obtain the indane system, followed by a Friedel-Crafts reaction with propylene oxide to get the side chain. The side chain is finally closed to the isochromanic system using formaldehyde ... 

Dehydrogenation processes in particular have been studied, with conversions in most cases well beyond thermodynamic equihbrium Ethane to ethylene, propane to propylene, water-gas shirt reaction CO -I- H9O CO9 + H9, ethylbenzene to styrene, cyclohexane to benzene, and others. Some hydrogenations and oxidations also show improvement in yields in the presence of catalytic membranes, although it is not obvious why the yields should be better since no separation is involved hydrogenation of nitrobenzene to aniline, of cyclopentadiene to cyclopentene, of furfural to furfuryl alcohol, and so on oxidation of ethylene to acetaldehyde, of methanol to formaldehyde, and so on. 

A mixture containing 186 g (0.20 mol) of 2-aminopyridine, 0.55 g of lithium amide and 75 cc of anhydrous toluene was refluxed for 1.5 hours. Styrene oxide (12.0 g = 0.10 mol) was then added to the reaction mixture with stirring over a period of ten minutes. The reaction mixture was stirred and refluxed for an additional 3.5 hours. A crystalline precipitate was formed during the reaction which was removed by filtration, MP 170°C to 171°C, 1.5 g. The filtrate was concentrated to dryness and a dark residue remained which was crystallized from anhydrous ether yield 6.0 g. Upon recrystallization of the crude solid from 30 cc of isopropyl alcohol, 2.0 g of a light yellow solid was isolated MP 170°C to 171°C. 

Sulphated zirconia catalysts can be acidic or superacidic depending on the method of treatment. A variety of acid-catalysed reactions, referred to earlier in this section, can be carried out with sulphated zirconia. Yadav and Nair (1999) have given a state-of-the art review on this subject. Examples of benzylation of benzene with benzyl chloride / benzyl alcohol, alkylation of o-xylene with. styrene, alkylation of diphenyl oxide with 1-dodecene, isomerization of epoxides to aldehydes, acylation of benzene / chlorobenzene with p-chloro benzoylchloride, etc. are covered in the review. 

Heteropoly acids can be synergistically combined with phase-transfer catalysis in the so-called Ishii-Venturello chemistry for oxidation reactions such as oxidation of alcohols, allyl alcohols, alkenes, alkynes, P-unsaturated acids, vic-diols, phenol, and amines with hydrogen peroxide (Mizuno et al., 1994). Recent examples include the epoxidations of alkyl undecylenates (Yadav and Satoskar, 1997) and. styrene (Yadav and Pujari, 2000). 

Graft copolymers of nylon, protein, cellulose, starch, copolymers, or vinyl alcohol have been prepared by the reaction of ethylene oxide with these polymers. Graft copolymers are also produced when styrene is polymerized by Lewis acids in the presence of poly-p-methoxystyrene. The Merrifield synthesis of polypeptides is also based on graft copolymers formed from chloromethaylated PS. Thus, the variety of graft copolymers is great. 

Under optimized conditions regarding the choice of Br0nsted acid (mandelic acid 20), stoichiometry (1 1 ratio 9 and mandelic acid 20), solvent (the respective alcohol neat conditions), temperature (rt or 50°C), and catalyst loading (lmol% 9 and lmol% mandelic acid 20) electron-rich and electron-deficient styrene oxides underwent alcoholysis with simple aliphatic, stericaUy demanding as well as unsaturated and acid-labile alcohols. The completely regioselective (>99%) alcoholysis was reported to produce the corresponding P-aUcoxy alcohols 1-10 in moderate (41%) to good (89%) yields without noticeable decomposition or polymerization reactions of acid-labile substrates (Scheme 6.27). Notably, aU uncatalyzed reference experiments showed no conversion even after two weeks under otherwise identical conditions. 

Scheme 1.64). The Ag(I)-mediated cyclization afforded dipole 306 for 1,3-dipolar cycloaddition with methyl vinyl ketone to yield adducts 307 and the C(2) epimer as a 1 1 mixture (48%). Hydrogenolytic N—O cleavage and simultaneous intramolecular reductive amination of the pendant ketone of the former dipolarophile afforded a mixture of alcohol 308 and the C(6) epimer. Oxidation to a single ketone was followed by carbonyl removal by conversion to the dithiolane and desulfurization with Raney nickel to afford the target compound 305 (299). By this methodology, a seven-membered nitrone (309) was prepared for a dipolar cycloaddition reaction with Al-methyl maleimide or styrene (301). 

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