1-Butyl hydroperoxide

Flash point, 27°C. Extinguish fire with water spray, dry chemical, carbon dioxide, or vaporizing liquids.2 

Slightly soluble in water3 very soluble in esters and alcohols.4 

The liquid irritates the eyes and skin. Poisonous if swallowed. Avoid contact with skin, eyes, and clothing.3 

Wear eye protection, laboratory coat, and nitrile rubber gloves. Work from behind body shield. Cover spill with a 1 1 1 mixture by weight of sodium carbonate or calcium carbonate, clay cat litter (bentonite), and sand. Carefully transfer to a beaker using a plastic scoop. Follow waste disposal procedure.7 Wash the spill area thoroughly with soap and water. 

Wear nitrile rubber gloves, eye protection, and laboratory coat. Work from behind heavy body shield in the fume hood. Cautiously add peroxide to 10% aqueous sodium bisulfite 

DOT Label Organic Peroxide UN2093 for 72% and UN 2094 for 72 to 90% solutions in water Forbidden above 90% Formula C4H10O2 MW 90.12 CAS [75-91-2] 

It is used to initiate polymerization reactions and in organic syntheses to introduce peroxy groups into the molecule. 

It is moderately toxic the effects are somewhat similar to those of MEK peroxide. Symptoms from oral administration in rats were weakness, shivering, and prostration. 

LD50 value, intraperitoneal (rats) 87 mg/kg LD50 value, oral (rats) 406 mg/kg 

Inhalation of its vapors in high concentrations may be injnrions to the lungs. Toxicity in humans shonld generally be low. This compound is known to exhibit mutagenicity. Any carcinogenic effect on animals or humans has not been observed. 

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The first practical method for asymmetric epoxidation of primary and secondary allylic alcohols was developed by K.B. Sharpless in 1980 (T. Katsuki, 1980 K.B. Sharpless, 1983 A, B, 1986 see also D. Hoppe, 1982). Tartaric esters, e.g., DET and DIPT" ( = diethyl and diisopropyl ( + )- or (— )-tartrates), are applied as chiral auxiliaries, titanium tetrakis(2-pro-panolate) as a catalyst and tert-butyl hydroperoxide (= TBHP, Bu OOH) as the oxidant. If the reaction mixture is kept absolutely dry, catalytic amounts of the dialkyl tartrate-titanium(IV) complex are suflicient, which largely facilitates work-up procedures (Y. Gao, 1987). Depending on the tartrate enantiomer used, either one of the 2,3-epoxy alcohols may be obtained with high enantioselectivity. The titanium probably binds to the diol grouping of one tartrate molecule and to the hydroxy groups of the bulky hydroperoxide and of the allylic alcohol... 

Osmate esters are fairly stable but are readily cleaved m the presence of an 0x1 dizing agent such as tert butyl hydroperoxide... 

Because osmium tetraoxide is regenerated m this step alkenes can be converted to vie mal diols using only catalytic amounts of osmium tetraoxide which is both toxic and expensive The entire process is performed m a single operation by simply allowing a solution of the alkene and tert butyl hydroperoxide m tert butyl alcohol containing a small amount of osmium tetraoxide and base to stand for several hours... 

PEROXIDES AND PEROXIDE COMPOUNDS - ORGANIC PEROXIDES] (Vol 18) sec-Butyl hydroperoxide [13020-06-9]... 

CINNAMICACID,CINNAMALDEHYDEANDCINNAMYLALCOHOL] (Void) tert-Butyl hydroperoxide... 

Isobutane. Isobutane can be oxidized noncatalyticaHy to give predominantly /-butyl hydroperoxide [75-91-2] (TBHP) (reactions 2 and 3). The... 

With mercuric acetate (Hg(OOCCH2)2), olefins and / fZ-butyl hydroperoxide form organomercury-containing peroxides (66,100). The organomercury compound can be treated with bromine or a mild reducing agent, such as sodium borohydride, to remove the mercury. 

Table 4. Solvents for Purification of Propylene Oxide From Epoxidation Using fe/t-Butyl Hydroperoxide...

Limonene (15) can be isomerized to terpiaolene (39) usiag Hquid SO2 and a hydroperoxide catalyst (/-butyl hydroperoxide (TBHP)) (76). Another method uses a specially prepared orthotitanic acid catalyst with a buffer such as sodium acetate (77). A selectivity of about 70% is claimed at about 50% conversion when mn at 150°C for four hours. 

Peroxide Titanate Complexes. Titanates may influence reactions of organic peroxides (see Peroxides, organic). For example, /-butyl hydroperoxide epoxidizes olefins ... 

Another butadiene oxidation process to produce butanediol is based on the 1,4-addition of /-butyl hydroperoxide to butadiene (108). Cobalt on siHca catalyzes the first step. This is followed by hydrogenation of the resulting olefinic diperoxide to produce butanediol and /-butyl alcohol. 

The process can be modified to give predominandy or solely /-butyl alcohol. Thus, /-butyl hydroperoxide (and /-butyl alcohol) produced by oxidation of isobutane in the first step of the process can be decomposed under controlled, catalytic conditions to give gasoline grade /-butyl alcohol (GTBA) in high selectivity (19—22). 

Physical and Chemical Properties. The (F)- and (Z)-isomers of cinnamaldehyde are both known. (F)-Cinnamaldehyde [14371-10-9] is generally produced commercially and its properties are given in Table 2. Cinnamaldehyde undergoes reactions that are typical of an a,P-unsaturated aromatic aldehyde. Slow oxidation to cinnamic acid is observed upon exposure to air. This process can be accelerated in the presence of transition-metal catalysts such as cobalt acetate (28). Under more vigorous conditions with either nitric or chromic acid, cleavage at the double bond occurs to afford benzoic acid. Epoxidation of cinnamaldehyde via a conjugate addition mechanism is observed upon treatment with a salt of /-butyl hydroperoxide (29). 

When heated in the presence of a carboxyHc acid, cinnamyl alcohol is converted to the corresponding ester. Oxidation to cinnamaldehyde is readily accompHshed under Oppenauer conditions with furfural as a hydrogen acceptor in the presence of aluminum isopropoxide (44). Cinnamic acid is produced directly with strong oxidants such as chromic acid and nickel peroxide. The use of t-butyl hydroperoxide with vanadium pentoxide catalysis offers a selective method for epoxidation of the olefinic double bond of cinnamyl alcohol (45). 

Transition metal-catalyzed epoxidations, by peracids or peroxides, are complex and diverse in their reaction mechanisms (Section 5.05.4.2.2) (77MI50300). However, most advantageous conversions are possible using metal complexes. The use of t-butyl hydroperoxide with titanium tetraisopropoxide in the presence of tartrates gave asymmetric epoxides of 90-95% optical purity (80JA5974). 

Recently (79MI50500) Sharpless and coworkers have shown that r-butyl hydroperoxide (TBHP) epoxidations, catalyzed by molybdenum or vanadium compounds, offer advantages over peroxy acids with regard to safety, cost and, sometimes, selectivity, e.g. Scheme 73, although this is not always the case (Scheme 74). The oxidation of propene by 1-phenylethyl hydroperoxide is an important industrial route to methyloxirane (propylene oxide) (79MI5501). 

The molybdenum-catalyzed oxidation of alkynes by /-butyl hydroperoxide has been investigated 73JCS(P1)2851) (the epoxidation of alkenes by this system has become an important reaction Section 5.05.4.2.2(i)) but the formation of oxirenes was excluded. 

Treatment of 2-methylthiirane with t-butyl hydroperoxide at 150 °C in a sealed vessel gave very low yields of allyl disulfide, 2-propenethiol and thioacetone. The allyl derivatives may be derived from abstraction of a hydrogen atom from the methyl group followed by ring opening to the allylthio radical. Percarbonate derivatives of 2-hydroxymethylthiirane decompose via a free radical pathway to tar. Acrylate esters of 2-hydroxymethylthiirane undergo free radical polymerization through the double bond. 

Oxidation catalysts are either metals that chemisorb oxygen readily, such as platinum or silver, or transition metal oxides that are able to give and take oxygen by reason of their having several possible oxidation states. Ethylene oxide is formed with silver, ammonia is oxidized with platinum, and silver or copper in the form of metal screens catalyze the oxidation of methanol to formaldehyde. Cobalt catalysis is used in the following oxidations butane to acetic acid and to butyl-hydroperoxide, cyclohexane to cyclohexylperoxide, acetaldehyde to acetic acid and toluene to benzoic acid. PdCh-CuCb is used for many liquid-phase oxidations and V9O5 combinations for many vapor-phase oxidations. 

SHARPLESS Asymmetne Epoxidation EnanlioselectK/e epoxidation of altyl alcohois by means of Irtanlum a5(oxide, (+) or () diethyl tartarate (OET) and t butyl hydroperoxide (TBHP)... 

Di-tert-butyl peroxide (tert-butyl peroxide) [110-05-4] M 146.2, d 0.794, n 1.389. Washed with aqueous AgN03 to remove olefinic impurities, water and dried (MgS04). Freed from /cr/-butyl hydroperoxide by passage through an alumina column [Jackson et al. J Am Chem Soc 107 208 1985], and if necessary two high vacuum distns from room temp to a liquid-air trap [Offenbach and Tobolsky J Am Chem Soc 79 278 1957]. The necessary protection from EXPLOSION should be used. 

Alkyl hydroperoxides give alkoxy radicals and the hydroxyl radical. r-Butyl hydroperoxide is often used as a radical source. Detailed studies on the mechanism of the decomposition indicate that it is a more complicated process than simple unimolecular decomposition. The alkyl hydroperoxides are also sometimes used in conjunction with a transition-metal salt. Under these conditions, an alkoxy radical is produced, but the hydroxyl portion appears as hydroxide ion as the result of one-electron reduction by the metal ion. ... 

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