Ethers 3-diketones

Diisopropyiethane, see 2,3,4-Trimethyipentane Diisopropyimethane, see 2,4-Dimethyipentane Diisopropyi oxide, see Isopropyi ether Diketone alcohol, see Diacetone alcohol Dilantin DB, see 1,2-DichIorobenzene... 

Poly(arylene ether phthalazine)s were prepared by two different routes [47], As shown in Eq. (13), one route involved the preparation of precursor poly(arylene ether diketone)s and subsequent reaction with hydrazine while the other route concerned the reaction of difluorophthalazine monomers with various bisphen-ols. The poly(arylene ether phthalazine)s prepared by the two routes exhibited very similar Tgs. The synthetic route to the difluorophthalazine monomers is also shown in Eq. (13). A comparison of the properties of a representative series of poly (ary lene ether diketone)s and the corresponding poly(arylene ether... 

Table 19. Properties or poiy(arylene ether diketone)s and poly(arylene ether phthaiazine)s...

Decant the liquid layer into a 2 5 litre flask, and dissolve the sodium derivative of acetylacetone in 1600 ml. of ice water transfer the solution to the flask. Separate the impiue ethyl acetate layer as rapidly as possible extract the aqueous layer with two 200 ml. portions of ether and discard the ethereal extracts. Treat the aqueous layer with ice-cold dilute sulphimic acid (100 g. of concentrated sulphiu-ic acid and 270 g. of crushed ice) until it is just acid to htmus. Extract the diketone from the solution with four 200 ml. portions of ether. Leave the combined ether extracts standing over 40 g. of anhydrous sodium sulphate (or the equivalent quantity of anhydrous magnesium sulphate) for 24 hours in the ice chest. Decant the ether solution into a 1500 ml. round-bottomed flask, shake the desiccant with 100 ml. of sodium-dried ether and add the extract to the ether solution. Distil off the ether on a water bath. Transfer the residue from a Claisen flask with fractionating side arm (Figs. II, 24, 4r-5) collect the fraction boiling between 130° and 139°. Dry this over 5 g. of anhydrous potassium carbonate, remove the desiccant, and redistil from the same flask. Collect the pure acetji-acetone at 134r-136°. The yield is 85 g. 

Conjugate addition of vinyllithium or a vinyl Grignard reagent to enones and subsequent oxidation afford the 1.4-diketone 16[25]. 4-Oxopentanals are synthesized from allylic alcohols by [3,3]sigmatropic rearrangement of their vinyl ethers and subsequent oxidation of the terminal double bond. Dihydrojasmone (18) was synthesized from allyl 2-octenyl ether (17) based on Claisen rearrangement and oxidation[25] (page 26). 

As stated previously, 3-monoethyl enol ethers can be prepared from A" -3,17-diketones and A -3,20-diketones by warming with stoichiometric amount or a large excess of ethyl orthoformate at room temperature. With 2,2-dimethoxypropane, the 3-methyl enol ether is the only reaction product even at high temperatures. 

Selective hydroxylation with osmium tetroxide (one equivalent in ether-pyridine at 0 ) converts (27) to a solid mixture of stereoisomeric diols (28a) which can be converted to the corresponding secondary monotoluene-sulfonate (28b) by treatment with /7-toluenesulfonyl chloride in methylene dichloride-pyridine and then by pinacol rearrangement in tetrahydrofuran-lithium perchlorate -calcium carbonate into the unconjugated cyclohepte-none (29) in 41-48 % over-all yield from (27). Mild acid-catalyzed hydrolysis of the ketal-ketone (29) removes the ketal more drastic conditions by heating at 100° in 2 hydrochloric acid for 24 hr gives the conjugated diketone (30). 

Selective fluonnation in polar solvents has proved commercially successful in the synthesis of 5 fluorouracil and its pyrimidine relatives, an extensive subject that will be discussed in another section Selective fluonnation of enolates [47], enols [48], and silyl enol ethers [49] resulted in preparation of a/phn-fluoro ketones, fieto-diketones, heta-ketoesters, and aldehydes The reactions of fluorine with these functionalities is most probably an addition to the ene followed by elimination of fluonde ion or hydrogen fluoride rather than a simple substitution In a similar vein, selective fluonnation of pyridmes to give 2-fluoropyridines was shown to proceed through pyridine difluondes [50]... 

Terminally unsaturated fluonnated alkenoic acids can be obtained from poly-fluorocycloalkenes by reaction with potassium hydroxide m rert-butyl alcohol [24] (equation 26) The use of a tertiary alcohol is critical because primary and secondar y alcohols lead to ethers of the cycloalkenes The use of a polar aprotic solvent such as diglyme generates enols of diketones [26] (equation 27) The compound where... 

Enamines in which the vinyl nitrogen system is in conjugation with another functional group can be obtained from reactions of secondary amines with /8-ketoaldehydes and -diketones or their monoenol ether or vinyl halide derivatives (41-46). 

Boron trifluoride etherate, is also a good catalyst for this hydride transfer to chalcone. Unlike triphenylmethyl perchlorate, however, chalcone is able to enter Michael additions with the 1,5-diketone followed by eliminations leading to unexpected products, e.g., 3-benzyl-2,4,6-triphenylpyrylium from 2-carbethoxy-l,3,5-tri-phenylpentane-l,5-dione and chalcone the benzyl group originates from chalcone, the elimination product being ethyl benzoylacetate. ... 

Digitoxigenin, structure of, 1097 Digitoxin, structure of, 989 Dihalide, alkynes from, 261 Dihedral angle, 94 Diiodomelhane. Simmons-Smith reaction with, 228-229 Diisobutylaluminum hydride, reaction with esters, 812 structure of, 699 Diisopropylamine, pK.d of, 923 1,3-Diketone, pfCa of, 852 Dimethyl disulfide, bond angles in, 20 structure of, 20 Dimethyl ether, electrostatic... 

The mother liquor contains only 2-3 g. more of the diketone, which can be separated as the copper derivative by shaking an ethereal extract with a saturated aqueous solution of copper acetate,... 

A solution of 2-methyl-l-(trimethylsilyloxy)cyclohex-l-ene (10 mmol) in dichloromethane (8 ml) was added dropwise over 15 min with stirring to acetyl chloride (10 mmol) and TiCl4 (10 mmol) in dichloromethane (15 ml) at -78 °C. After 1 h at -78 °C, the reaction mixture was allowed to warm to ambient temperature over 2h. It was then diluted with ether (20ml), and poured into saturated sodium hydrogen carbonate solution (50 ml). Normal work-up, followed by chromatography on silica gel, gave the /1-diketone (9.1 mmol, 91%). 

Diketones can be converted to a-keto enol ethers by treatment with an alkoxytrimethylsilane (ROSiMe3). ... 

Carboxylic esters can be treated with ketones to give p-diketones in a reaction that is essentially the same as 10-118. The reaction is so similar that it is sometimes also called the Claisen condensation, though this usage is unfortunate. A fairly strong base, such as sodium amide or sodium hydride, is required. Yields can be increased by the catalytic addition of crown ethers. Esters of formic acid (R H) give P-keto aldehydes. Ethyl carbonate gives P-keto esters. 

Ordinary ketones are generally much more difficult to cleave than trihalo ketones or p-diketones, because the carbanion intermediates in these cases are more stable than simple carbanions. However, nonenolizable ketones can be cleaved by treatment with a 10 3 mixture of t-BuOK—H2O in an aprotic solvent such as ether, dimethyl sulfoxide, 1,2-dimethoxyethane (glyme), and so on, or with sohd t-BuOK in the absence of a solvent. When the reaction is applied to monosubstituted diaryl ketones, that aryl group preferentially cleaves that comes off as the more stable carbanion, except that aryl groups substituted in the ortho position are more readily cleaved than otherwise because of the steric effect (relief of stain). In certain cases, cyclic ketones can be cleaved by base treatment, even if they are enolizable. " OS VI, 625. See also OS VH, 297. 

Certain ketoximes can be converted to nitriles by the action of proton or Lewis acids. Among these are oximes of a-diketones (illustrated above), a-keto acids, a-dialkylamino ketones, a-hydroxy ketones, p-keto ethers, and similar compounds. These are fragmentation reactions, analogous to 17-25 and 17-26. For example, ot-dialkylamino ketoximes also give amines and aldehydes or ketones besides nitriles. 

Silyi enol ethers can be dimerized to symmetrical 1,4-diketones by treatment with Ag20 in DMSO or certain other polar aprotic solvents." The reaction has been performed with R , R = hydrogen or alkyl, though best yields are obtained when r = r = H. In certain cases, unsymmetrical 1,4-diketones have been prepared by using a mixture of two silyi enol ethers. Other reagents that have been used to achieve either symmetrical or cross-coupled products are iodosobenzene-Bp3-Et20," ceric ammonium nitrate," and lead tetraacetate." If R =0R (in which case the substrate is a ketene silyi acetal), dimerization with TiCU leads to a dialkyl succinate (34, r =0R)." ... 

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