Cumyl amines

To a stirred solution of 120 ml of methylene chloride, 18 ml of dry pyridine, and 5 ml of iodine pentafluoride maintained at —10°C to —20°C in a Dry Ice-carbon tetrachloride slurry is added a solution of 13.5 gm (0.1 mole) of cumyl-amine in 10 ml of methylene chloride over a 1 hr period. The reaction mixture is stirred for another hour at —10°C, and then for 1 hr at 0°. After this time, water is added to the reaction mixture and stirring is continued until the yellow solid which had formed is dissolved. The lower organic layer is separated and washed in turn with water, 1 N hydrochloric acid, a saturated sodium thiosulfate solution, and again with water. After drying with anhydrous magnesium sulfate and filtration, the product solution is partially evaporated by means of a rotary evaporator at a temperature below 30°C. The brown solid obtained on cooling is separated and recrystallized twice from methylene chloride yield 4.75 gm (17.9%), m.p. 86.9°-88.7°C. 

AMINES - LOWERALIPHATIC AMINES] (Vol 2) tert-Butyl tert-cumyl peroxide [3457-61-2]... 

Clearly, the tertiaiy nature of the chloride would make an Sn2 mechanism highly unlikely. Furthermore, the nitro substituent is essential to the success of these reactions. Cumyl chloride itself undergoes elimination of HCl on reaction with amines. 

The chemistry of the di-/-butyl and cumyl peroxides is relatively uncomplicated by induced or ionic decomposition mechanisms. However, induced decomposition of di-/-butyl peroxide has been observed in primary or secondary alcohols31" "14 (Scheme 3.37) and primary or secondary amines.312 The reaction... 

Hydroperoxides oxidize aromatic amines more readily than analogous phenols. Thus, at 368 K cumyl hydroperoxide oxidizes a-naphthylamine and a-naphthol with ku = 1.4 x 10 4 and 1.7 x 10 5L mol-1 s 1, respectively [115,118], The oxidation of amines with hydroperoxides occurs apparently by chain mechanism, since the step of free radical generation proceeds much more slowly. This was proved in experiments on amines oxidation by cumyl hydroperoxide in the presence of /V,/V -diphcnyl-l, 4-phcnylcnediamine (QH2) as a radical acceptor [125]. The following reactions were supposed to occur in solution (80% decane and 20% chlorobenzene) ... 

The oxidation of primary and secondary alcohols in the presence of 1-naphthylamine, 2-naphthylamine, or phenyl-1-naphthylamine is characterized by the high values of the inhibition coefficient / > 10 [1-7], Alkylperoxyl, a-ketoperoxyl radicals, and (3-hydroxyperoxyl radicals, like the peroxyl radicals derived from tertiary alcohols, appeared to be incapable of reducing the aminyl radicals formed from aromatic amines. For example, when the oxidation of tert-butanol is inhibited by 1-naphthylamine, the coefficient /is equal to 2, which coincides with the value found in the inhibited oxidation of alkanes [3], However, the addition of hydrogen peroxide to the tert-butanol getting oxidized helps to perform the cyclic chain termination mechanism (1-naphthylamine as the inhibitor, T = 393 K, cumyl peroxide as initiator, p02 = 98 kPa [8]). This is due to the participation of the formed hydroperoxyl radical in the chain termination ... 

Hydroperoxides oxidize aromatic amines more readily than analogous phenols. Thus, at 368 cumyl hydroperoxide oxidizes a-naphthylamine and a-naphthol with ku = 1.4 x 10 4... 

The Birch reduction has been applied to electron-deficient pyrroles substituted with a chiral auxiliary at the C(2)-position <1999TL435>. Using either (—)-8-phenylmenthol or (- -)-/ra /-2-(ot-cumyl)cyclohexanol as auxiliaries, high levels of stereoselectivity were obtained. Pyrrole 911, prepared from the l/7-pyrrole-2-carboxylic acid 910 in 90% yield, was reduced under modified Birch conditions (Scheme 176). The best conditions involved lithium metal (3 equiv), liquid ammonia and THE at —78°C. The addition of A, A -bis(2-methoxyethyl)amine (10 equiv) helped to reduce side reactions caused by the lithium amide formed in the reaction <1998TL3075>. After 15 min, the Birch reductions were quenched with a range of electrophiles and in each case 3,4-dehydroproline derivatives 912 were formed in excellent yields and with good diastereoselectivities. 

Nitrones, C=N" (R)=0, are generated by the oxidation of N-hydroxyl secondary amines with 5% aq. NaOCl. ° Secondary amines, such as dibenzylamine, can be converted to the corresponding nitrone by heating with cumyl hydroperoxide in the presence of a titanium catalyst. Imines are oxidized to amides with mcpba and BF3 OEt2. ° ... 

A different approach is based on the Cj-symmetrical triol amines introduced by Nugent [30]. Together with titanium tetraisopropoxide they afford titanium species of type 17 which react further with cumyl hydroperoxide to give a rigid monomeric titanium peroxide 18 [31].Thelatter (withR=Ph) was characterized by NMR spectroscopy and ESI-MS studies [32]. 

Although the CRI reaction of diazo compounds 17a and 17b yielded the pentacyclic intermediates 20 and 28, further alkylation to form a C8 quaternary carbon center was unsuccessful under various conditions. This appears to be due to steric hindrance by the bulky benzyl and cumyl groups after protection of the free amine. To improve the CRI reaction. Dr. Jun Yang modified the diazonamide substrate by replacing the amide functionality (17) with an ester... 

Oxidation reactions of both acyclic and cyclic secondaiy amines to obtain nitrones catalysed by (trialkanolaminato)titanium(iv) complexes in the presence of cumyl hydroperoxide as oxidant occurred in high yields, even when 1 mol% of catalyst was used. ... 

It is obvious from Table 1 that the material balance for CHP is excellent. CHP is essentially quantitatively accounted for as cumyl alcohol and acetophenone. These results agree well with those from previous studies of hydroperoxide reduction by amines (2) alcohols are usually obtained in greater than 80% yield. Alkoxy radical products are also formed, consistent with our observation of acetophenone from /3-scission of the cumyloxy radical. 

When primary aromatic amines are used instead of tertiary amines the products of reaction are either azoxy compounds [186] or nitro compounds [187]. In the presence of soluble complexes of titanium, aniline, o- and p-toluidine and m-nitro aniline are oxidized by er -butyl hydroperoxide or cumyl hydroperoxide to the corresponding azoxy compounds in 92-99% yields [182], equation (129). 

Several amino-styrenic monomers are known for example see 19C—23C in Figure 38. The simplest of these, the primary amine species 4-vinylaniline (or 4-aminostyrene), 23C, is susceptible to polymerization imder conventional free radical conditions, as are 19C-22C. For example, the UV-induced graft polymerization of 23C from a Si surface was recently disclosed (218). These monomers tend to polymerize most effectively in aqueous media in their hydrochloride salt form. Given the reactive nature of the amine functionality in 23C it is also a suitable precursor for the synthesis of novel amide-based styrenics (219). The controlled polymerization of 19C, 20C, and 22C, under classical anionic conditions is also possible (220,221). For example, AB diblock copol5uners of22C with styrene can be prepared at -78°C, in THF using cumyl potassium as the initiator with 22C being polymerized first. Near-monodisperse w-butyl quats of 19C, 20C, and 22C have also been reported. These were prepared by the post-polymerization modification of polymers from 19C, 20C, and 22C with R-butyl bromide (220). 

Tertiary alcohols, dicumyl alcohol (The Goodyear Tire Rubber Company) and cumyl alcohol (Aldrich) were used to carry out the necessary conversion of excess isocyanate groups to amine groups as mentioned earlier Thus, these tertiary alcohols are not directly involved in the chain extension step The amount of excess MDI and tertiary alcohols... 

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