Isomers of ketones

X = CF3COO) were formed but within minutes to hours, they underwent quantitative isomerization (recyclization) to 1,3,4-thiadiazolidin-2-iminium cations 89B. The same cations were formed from the open-chain aldehyde thiosemicarbazones in trifluoroacetic acid solution. Deprotonation of the salts 89B with C5D5N yielded the open-chain thiosemicarbazones 88A and not the cyclic isomers 88B. The open-chain isomers of ketone 2-methyl- or 2,4-dialkylthiosemicarbazones obtained in this way (89B —> 88A) are unstable and readily cyclize into 88C when their solutions are stored or when they undergo a recrystallization or thin-layer chromatography procedure. 

An improved version of the Carroll reaction, the ester enolate Carroll rearrangement, was reported in 1984 by Wilson and Ptice. Dianions of allylic acetoacetates, generated by treatment with 2 equiv. of LDA at -78 °C in THF, were rearranged at room temperature or 65 C to yield >keto acids in 40-80% yield (equation 12). In the course of a synthesis of the sesquiterpene isocomene, Snider and Beal used this method for the rearrangement of acetoacetate (73), prepared in 83% yield from reaction of cyclopen-tene (72) with diketene and a catalytic amount of DMAP (Scheme 11). The ( )-isomer of ketone (74) is obtained stereospecifically, since there is a severe steric interaction between the methyl groups in the Carroll rearrangement transition state leading to the (Z)-isomer. 

High-resolution mass spectra were obtained for unidentified compounds a, b, c, d, and f. The molecular formula of compounds a, b, c, and d is C12H22O. Proposed structures are isomers of ketones, e.g., a and b might be 2- or 4-isomers of ethylisopropyl cyclohexyl ketone and c and d might be cyclohex-4-ylhexan-2-one or cyclohex-4-yl-4-methylpentan-2-one, respectively. An unidentified compound (e) was found also for the quasi-molecular ion M + 1105. The only fragment was M - 18 in chemical ionisation mass spectroscopy. The molecular formula of unidentified compound f is C15H14O. The proposed structure is... 

High resolution mass spectra were obtained for unidentified compounds a, b, c, d (Tables 3.4 and 3.5). The molecular formula of compounds a, b, c is Proposed structures are isomers of ketones, for example, a and b might be 2- or 4-... 

Isomers of ketone (67) have also been obtained, opening up the route to the synthesis of isomers of cortisone. The oxidation of (67) yielded the anti-trans-diketone (71) and its reduction the corresponding diol (70). The anti-c is-diketone (72) was obtained from the diol (64) by acelyl protection of the 14-hydroxy group, oxidation at C, deacelylation to the ketol (68), and oxidation of the latter at 0 4. By isomerizing compound (72), the anti-trans-diketone (71) was obtained. By isomerization at Cg and oxidation, the ketol (68) gave a third isomer, the syn-trans-diketone (69) [659]. An unsuccessful attempt has been made to obtain the last of the theoretically possible isomers, the syn-cis compound, by means of a diene synthesis [660]. 

This starting material A (also 224A) is an isomer of the ketone we made in fi ame 328, and is easy to make using the intramolecular strategy of that fi ame ... 

Geranyl acetoacetate (685) is converted into geranylacetone (686). On the other hand, a mixture of E- and Z-isomers of 688 is obtained from neryl acetoacetate (687). The decarboxylation and allylation of the allyl malonate or cyanoacetate 689 affords the o-allylated acetate or nitriie[447]. The trifluoromethyl ketone 691 is prepared from cinnamyl 4.4,4-trifluoroacetoace-tate (690)[448],... 

Amin omethyl-3,5,5-trimethyl cyclohexyl amine (21), commonly called isophoronediamine (IPD) (51), is made by hydrocyanation of (17) (52), (53) followed by transformation of the ketone (19) to an imine (20) by dehydrative condensation of ammonia (54), then concomitant hydrogenation of the imine and nitrile functions at 15—16 MPa (- 2200 psi) system pressure and 120 °C using methanol diluent in addition to YL NH. Integrated imine formation and nitrile reduction by reductive amination of the ketone leads to alcohol by-product. There are two geometric isomers of IPD the major product is ds-(22) [71954-30-5] and the minor, tram-(25) [71954-29-5] (55). 

That the methyl group in the pyrrolidine enamine of 2-methylcyclo-hexanone (7) is in fact axial was demonstrated by Johnson and Whitehead (8). They found that careful hydrolysis of the pyrrolidine enamine of the conformationally more stable system, i.e., 2-methyI-4-t-butylcyclohexanone (13), led to a 1 4 mixture of cis and trans isomers of the ketone (14 and 15), showing that the methyl group in the enamine is largely in the axial orientation. 

This value is in excellent agreement with the calculated free energy value by the consideration of various nonbonded interactions in the epimers (69 and 70) [(2 X 1,3-diaxial Me—H interaction) — (1 x 1,3-diaxial Me—H interaction + 1 X l,2- < Me—H interaction) = (0.9 x 2) — (0.9 + 0.6) = 0.3 kcal/mole]. Hydrolysis of the enamine with dilute acetic acid gave a 3 2 mixture of cis and trans isomers of the ketone, thus confirming the assignments made to the enamine components. 

Interestingly, the reaction of tricyclenone (100) with morpholine also led to the exo isomer of the saturated ketone (101), involving the cleavage of the cyclopropane ring. 

Acylation with aromatic acid chlorides was believed to occur on carbon 91). The dibenzoylation of the enamine (113) with benzoyl chloride in the presence of triethylamine has, however, been shown to give a mixture of three products (92). The major components are the cis and Irons isomers of the O-acylated enamino ketone (Ola and b) and the minor isomer is the 2,6-diacylated enamine (132). 

The lithium aluminum hydride-aluminum chloride reduction of ketones is closely related mechanistically to the Meerwein-Ponndorf-Verley reduction in that the initially formed alkoxide complex is allowed to equilibrate between isomers in the... 

When the terpene a-fenchene (isopinene) is hydrated by means of acetic and sulphuric acids, it yields an isomer of fenchyl alcohol, which is known as isofenchyl alcohol (q.v.), and which on oxidation yields iso-fenchone, as fenchyl alcohol yields fenchone. The two ketones, fenchone and isofenchone, are sharply differentiated by isofenchone yielding iso-fenchocamphoric acid, Cj Hj O, on oxidation with potassium permanganate, which is not the case with fenchone. According to Aschan,i the hydrocarbon found in turpentine oil, and known as /9-pinolene (or cyclo-fenchene—as he now proposes to name it), when hydrated in the usual manner, yields both fenchyl and isofenchyl alcohols, which on oxidation yield the ketones fenchone and isofenchone. According to Aschan the relationships of these bodies are expressed by the following formulae —... 

Ketones react with alcohols to yield products called acetals. Why does the all-cis isomer of 4- cvf-butyl-l13-cyclohexanediol react readily with acetone and an acid cataty st to form an acetal while other stereoisomers do not react In formulating your answer, draw the more stable chair conformations of all four stereoisomers and the product acetal. Use molecular models for help. 

The use of hydrazone or enamine derivatives of ketones or aldehydes offers the advantage of stcreocontrol via chelated azaenolates. Extremely useful synthetic methodology, with consistently high anti selectivity, has been developed using azaenolates based on (S)- or (R)-l-amino-2-(methoxymethyl)pyrrolidine (SAMP or RAMP)51 58 (Enders method, see Section 1.5.2.4.2.2.3.). An example which illustrates the efficiency of this type of Michael addition is the addition of the lithium azaenolate of (5 )-l-amino-2-(methoxymethyl)pyrrolidine (SAMP) hydrazone of propanal (R = II) to methyl (E )-2-butenoate to give the nub-isomer (an 1 adduct) in 80% yield with a diastereomeric ratio > 98 2,... 

Dinitrophenyl-hydrazine has been successfully employed in the analysis of simple aldehydes, substituted aldehydes, glyoxal and gluteraldehyde (43-45), all the isomers of the C3 to C7 aliphatic ketones (44,45) and in the determination of formaldehyde in tobacco smoke (46). 

The study of optical isomers has shown a similar development. First it was shown that the reduction potentials of several meso and racemic isomers were different (Elving et al., 1965 Feokstistov, 1968 Zavada et al., 1963) and later, studies have been made of the ratio of dljmeso compound isolated from electrolyses which form products capable of showing optical activity. Thus the conformation of the products from the pinacolization of ketones, the reduction of double bonds, the reduction of onium ions and the oxidation of carboxylic acids have been reported by several workers (reviewed by Feokstistov, 1968). Unfortunately, in many of these studies the electrolysis conditions were not controlled and it is therefore too early to draw definite conclusions about the stereochemistry of electrode processes and the possibilities for asymmetric syntheses. 

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