Methylcyclopentane, reaction with

Methylcyclopentane-1,3,5-tnone, reaction with semicarbazide hydrochloride, 47, 84... 

Competition kinetics. Cyclization of the 1-hexenyl radical competes with the reaction with BihSnH to form methylcyclopentane. 

Cycloalkanes possessing a tertiary carbon atom may be alkylated under conditions similar to those applied for the alkylation of isoalkanes. Methylcyclopentane and methylcyclohexane were studied most.5 Methylcyclopentane reacts with propylene and isobutylene in the presence of HF (23-25°C), and methylcyclohexane can also be reacted with isobutylene and 2-butene under the same conditions.20 Methylcyclopentane is alkylated with propylene in the presence of HBr—AlBr3 (—42°C) to produce l-ethyl-2-methylcyclohexane.21 C12H22 bicyclic compounds are also formed under alkylation conditions.21 22 Cyclohexane, in contrast, requires elevated temperature, and only strong catalysts are effective. HC1—AICI3 catalyzes the cyclohexane-ethylene reaction at 50-60°C to yield mainly dimethyl- and tetra-methylcyclohexanes (rather than mono- and diethylcyclohexanes). The relatively weak boron trifluoride, in turn, is not active in the alkylation of cyclohexane.23... 

Cyclic 1,2-diketones, such as3-methylcyclopentane-l,2-dione, act as oxygen nucleophiles in palladium(0)-catalyzed reactions with a range of cyclic and acyclic allylic esters. The products of these reactions were subjected to a lanthanide-catalyzed Claisen rearrangement to access the C-alkylated products. 

The known vinyl ketone (11) has been prepared by the route (7)- (8)— (9). The last compound on heating gave (11). Whereas the reaction between (9) and 2-methylcyclopentane-l,3-dione gave (12), the corresponding reaction with (10) gave (13), evidently owing to the benzenesulphenic acid produced in the reaction. 

METHYLCYCLOPENTANE (96-37-7) Forms explosive mixture with air (flash point <20°F/<—7°C). Violent reaction with strong oxidizers. Incompatible with strong acids, caustics, aliphatic amines, isocyanates. Flow or agitation of substance may generate electrostatic charges due to low conductivity. 

D.1. Reactions with Nucleophiles. Previously, a jr-allylic palladium complex was generated by reaction of palladium reagents with allylic hydrocarbons prior to reaction with nucleophiles. In the catalytic version of this reaction, an allylic halide or an allylic acetate is used with a palladium(O) reagent. Why use a palladium complex when enolate alkylation is a well-known process (sec. 9.3.A) A typical enolate coupling reaction is the conversion of 2-methylcyclopentane-l,3-dione (373) to the enolate anion by reaction with NaOH, allowing reaction with allyl bromide. Under these conditions only 34% of 374 was obtained. When allyl acetate was used in place of allyl bromide in this reaction and tetra w(triphenylphosphino)palladium was used as a catalyst, a 94% yield of 374 was obtained.224 in this reaction, formation of the Jt-allyl palladium complex facilitated coupling with the nucleophilic enolate derived from 373, which exhibited poor reactivity in the normal enolate alkylation sequence. 

With a molecule such as chloromethane, however, there is no way to prove that attack by the nucleophile has involved inversion of configuration of the carbon atom because one form of methyl chloride is identical to its inverted form. With a molecule containing chirality centers such as f-Tchloro-3-methylcyclopentane, however, we can observe the results of an inversion of configuration by the change in stereochemistry that occurs. When r-l-chloro-3-methylcyclopentane reacts with hydroxide ion in an 5 2 reaction, the product is rw r-3-methylcyclopentanol. The hydroxyl group ends up bonded on the opposite side of the ring from the chlorine it replaces. ... 

The one-step coupling reaction with metallic halides such as Pb(II) [111], Ge(IV) and several others have found wide application in the synthesis of organometallic compounds. Although the in situ reaction of 1,3-bisbromo-methylcyclopentane, magnesium and dichlorosilanes gave satisfactory yields of 3-sila[l,2,3]bicyclooctanes [112], similar reactions with dichlorogermanes resulted in poor yields [113] ... 

Developed in the early 1970s, this reaction, also called the Hajos-Parrish reaction or Hajos-Parrish-Ender-Sauer-Wiechert reaction, is one of the earliest processes for the stereoselective synthesis of Wieland-Miescher ketone, an important building block for steroids and terpenoid synthesis. This reaction is a proline mediated asymmetric variation to the Robinson annulation. Hajos and Parrish of Hoffmann-La Roche Inc. in 1971 and 1974 published an asymmetric aldol cyclization of triketones such as that of structure 39, which affords optically active annulation products in the presence of catalytic amounts of (S)-proline (Z-proline). One of the early examples is the synthesis of 41 from the triketone 39 (a product of the Michael addition of MVK to the corresponding 2-methylcyclopentane-l,3-dione), the reaction is performed in two steps first by ring formation in the presence of 3 mol % of (iS)-proline in DMF to afford the ketol 40 in 100% yield after crystallization with 93% ee and then by reaction with toluenesulfonic acid to give the dehydrated adduct 41. The formation of the Wieland-Miescher Ketone 44 follows the same synthetic route, starting from the tri-ketone 42 to give the end product in 75% optical purity and 99.8% of optical yield. 

The values of the adsorption coefficient of hydrogen for both reactions were practically identical (1.9 and 2.1 atm-1). Here, the selectivity of the branched reactions depends on the partial pressure of methylcyclopentane. This difference may be accounted for by assuming that either the cleavage of the C—C bond of methylcyclopentane in the (3-position and in the 7-position with respect to the methyl group does not take place on the same sites of the surface of platinum (or on the sites of the same activity), or that the mechanism of hydrogenolysis is more complex than that ex-... 

Cyclohexane (C) and methylcyclopentane (M) are isomers with the chemical formula C6H12. The equilibrium constant for the rearrangement C M in solution is 0.140 at 25°C. (a) A solution of 0.0200 mol-L 1 cyclohexane and 0.100 mol-I. 1 methylcyclopentane is prepared. Is the system at equilibrium If not, will it will form more reactants or more products (b) What are the concentrations of cyclohexane and methylcyclohexane at equilibrium (c) If the temperature is raised to 50.°C, the concentration of cyclohexane becomes 0.100 mol-L 1 when equilibrium is reestablished. Calculate the new equilibrium constant, (d) Is the reaction exothermic or endothermic at 25°C Explain your conclusion. 

Bodner and Domin (2000) demonstrated the inability of many university students to interpret abbreviated structural portrayals with some atoms implied, rather than shown. The students were asked to predict the major products of the reaction of bromine with methylcyclopentane portrayed as in Fig. 1.2, and to estimate the ratio of the products if bromine radicals were just as likely to attack one hydrogen atom as another. Most of the 200 students predicted three products, with a relative abundance 3 2 2 (Fig. 1.4). 

A similar reaction occurs with 2-methylcyclopentane-l,3-dione,176 and can be done enantioselectively by using the amino acid L-proline to form an enamine intermediate. The (S)-enantiomer of the product is obtained in high enantiomeric excess.177... 

Reaction of the heterocycle with 2-methylcyclopentane-1,3-dione in the presence of pyridine leads directly to tetracyclic intermediate 20. 5 The first step in this transformation probably consists in formation of the olefin 18 by elimination of dimethylamine. 

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