Ethyl camphorate

In 1965, Denney et al. (98) reported the reaction of a number of alkenes with ferf-butyl hydroperoxide (TBHP) and cupric salts of chiral acids. The use of ethyl camphorate copper complex 144 in the allylic oxidation of cyclopentene provides, upon reduction of the camphorate ester, the allylic alcohol in low yield and low selectivity, Eq. 82. The initial publication only provided the observed rotation of cyclopentenol, but comparison to subsequent literature values (99) reveals that this reaction proceeds in 12% ee and 43% yield (based on the metal complex). 

This mechanism suggests that the reaction can be performed in an enantiose-lective manner, if the copper ion is appropriately modified by chiral ligand(s). In 1965, the Cu(II)-a-ethyl camphorate complex was found to promote the asymmetric Kharash-Sosnovsky reaction, although the enantioselectivity was only modest [18]. Thirty years later, this chemistry was followed by three highly enan-... 

In 1965, Denny et al. for the first time reported a catalytic asymmetric Kharasch-Sosnovsky reaction by using Cu(II)-(a)-ethyl camphorate as a catalyst, though enantioselectivity was low (Scheme 9) [21]. A quarter of a century later, natural or synthetic amino acids were introduced as chiral auxiliaries and much improved enantioselectivity (up to 65% ee) was achieved (Scheme 10) [22]. Although no detailed information on the structures of these copper complexes has been obtained, the observed non-linear relationship between the ee of the chiral auxiliary and the ee of the product suggests that the copper-amino acid complex is not monomeric but instead is oligomeric (at least dimeric) species [22e]. 

Bismuth Ethyl Camphorate. d-Camphoric acid ethyl ester bismuth salt bismuth(IH) salt of d-camphoric acid monoethyl ester. C H BiOu) mol wt 890.82. C 48.54%, H 6,45%, Bi 23.46%, O 21.55%, Prepd from sodium ethyl camphorale and bismuth nitrate W. M. Lauter, H. A. Braun, J. Am. Pharm. Assoc. 25, 394 (1936). 

Gupric a-ethyl camphorate dissolved in cyclopentene containing ferf-butyl hydroperoxide, and stirred 40hrs. -> ( + )-a-ethyl ) -J -cyclopentenyl camphorate (Y 78%) treated with LiAlH4 in dry ether (—)-zl -cyclopentenol (Y 43%). 

Comparison of Table 5.4 and 5.7 allows the prediction that aromatic oils will be plasticisers for natural rubber, that dibutyl phthalate will plasticise poly(methyl methacrylate), that tritolyl phosphate will plasticise nitrile rubbers, that dibenzyl ether will plasticise poly(vinylidene chloride) and that dimethyl phthalate will plasticise cellulose diacetate. These predictions are found to be correct. What is not predictable is that camphor should be an effective plasticiser for cellulose nitrate. It would seem that this crystalline material, which has to be dispersed into the polymer with the aid of liquids such as ethyl alcohol, is only compatible with the polymer because of some specific interaction between the carbonyl group present in the camphor with some group in the cellulose nitrate. 

Ethyl Cinnamate.—The cinnamic ester of ethyl alcohol is a natural constituent of a few essential oils, including camphor oil and storax. It is formed synthetically by condensing cinnamic acid and ethyl alcohol by dry hydrochloric acid gas. It has a soft and sweet odour, and is particularly suitable for blending in soap perfumes. It is an oil at ordinary temperatures, melting at 12°, and boiling at 271°. Its specific gravity is 1 0546, and its refractive index 1 5590. 

A rich family of 2-alkoxycarbonyl-l,3,2-oxazaphospholidine-2-oxides 179-181 was prepared from the reaction of camphor derived aminoalcohols 177 and 178 with either methoxycarbonyl phosphonic dichloride or ethyl dichlorophosphite followed by the reaction with methyl bromoacetate. The reaction with aminoalcohol 177a afforded the phosphorus epimers 179 and 180, in ratios from 1/1 to 12/1 depending on the iV-substituent which could be separated easily by column chromatography. The reaction with aminoalcohols 178a-c, however, gave a single epimer 181a-c in each case (Scheme 50) [81]. 

Knochel and coworkers synthesized a series of camphor-derived pyridine and quinoline P,N ligands. The catalysts 30 (Fig. 29.17) were used to hydrogenate substrates 1 and 2 in up to 95% and 96% ee, respectively [33]. The selectivities were moderate for other unfunctionalized alkenes however, a high enantioselec-tivity was reported for the hydrogenation of ethyl acetamidocinnamate 10 [34]. 

Tolman and co-workers (67) investigated a series of pyrazolyl-derived ligands for this reaction. Initial investigations centered on the use of tris(pyrazolyl) phosphine oxide (95) as a ligand with chirality derived from camphor. Diastereoselectivities with ethyl diazoacetate are poor, slightly favoring the cis isomer, and enantioselectivities are modest, Eq. 50. The BHT esters greatly increase the diastereoselectivity of this process (96 4) at the expense of enantioselectivity (10% ee for trans isomer). 

Uses Plasticizer plastic manufacturing and processing denaturant for ethyl alcohol ingredient in insecticidal sprays and explosives (propellant) dye application agent wetting agent perfumery as fixative and solvent solvent for nitrocellulose and cellulose acetate camphor substitute. 

BRN 1912585, see Hexachlorobenzene BRN 1912384, see 2,4-Dinitrotoluene BRN 1913355, seep,p -DDE BRN 1914064, see Di-fl-butyl phthalate BRN 1914072, see p,p -DDD BRN 1915474, see Chlordane BRN 1915994, see Di-fl-octyl phthalate BRN 2049930, see Naled BRN 2051258, see Pindone BRN 2052046, see 2,6-Dinitrotoluene BRN 2054389, see 4,6-Dinitro-o-cresol BRN 2055620, see 2,4,5-T BRN 2057367, see Methoxychlor BRN 2059093, see Parathion BRN 2062204, see Benzyl butyl phthalate BRN 2215168, see Diuron BRN 2542580, see EPN BRN 2807677, see 2-Acetylaminofluorene BRN 3195880, see a-BHC BRN 3196099, see Camphor BRN 3910347, see cis-Chlordane, frans-Chlordane Brocide, see 1,2-Dichloroethane Brodan, see Chlorpyrifos Bromchlophos, see Naled Bromex, see Naled Bromic ether, see Ethyl bromide Bromobenzol, see bromobenzene 4-Bromobiphenyl ether, see 4-Bromophenyl phenyl ether 4-Bromodiphenyl ether, see 4-Bromophenyl phenyl ether p-Bromodiphenyl ether, see 4-Bromophenyl phenyl ether Bromoethane, see Ethyl bromide Bromofluoroform, see Bromotrifluoromethane Bromofume, see Ethylene dibromide Brom-o-gaz, see Methyl bromide Bromomethane, see Methyl bromide Bromomethyl chloride, see Bromochloromethane... 

Fluorotrichloromethane, see Trichlorofluoromethane Fly-die, see Dichlorvos Fly fighter, see Dichlorvos FMC 5462, see a-Endosulfan, p-Endosulfan FMC 10242, see Carbofuran Foliclol, see Parathion Folidol, see Parathion Folidol E 605, see Parathion Folidol E E 605, see Parathion Folidol oil, see Parathion Forane, see 1,1,2-Trichlorotrifluoroethane Foredex 75, see 2,4-D Forlin, see Lindane Formal, see Malathion, Methylal Formaldehyde bis(p-chloroethylacetal), see Bis(2-chloroethoxy) methane Formaldehyde dimethylacetal, see Methylal Formalin, see Formaldehyde Formalin 40, see Formaldehyde Formalith, see Formaldehyde Formic acid, ethyl ester, see Ethyl formate Formic acid, methyl ester, see Methyl formate Formic aldehyde, see Formaldehyde Formic ether, see Ethyl formate Formira, see Formic acid Formisoton, see Formic acid Formol, see Formaldehyde Formosa camphor, see Camphor Formula 40, see 2,4-D... 

Also the use of moisture stable ionic liquids as solvents in the Diels-Alder reaction has been carried out, and in all examples an enhanced reaction rate was observed [182,183]. The application of pyridinium-based ionic liquids allowed the utilization of isoprene as diene [184]. The chiral ionic liquid [bmim][L-lactate] was used as a solvent and accelerated the reaction of cyclopentadiene and ethyl acrylate, however, no enantiomeric excess was observed [183]. In addition several amino acid based ionic liquids have been recently tested in the Diels-Alder reaction. Similar exo. endo ratios were found but the product was obtained as racemate. The ionic liquids were prepared by the addition of equimolar amounts of HNO3 to the amino acids [185]. Furthermore, an enantiopure imidazolium salt incorporating a camphor motive was tested in the Diels-Alder reaction. No enantiomeric excess was found [186]. 

First, the effects of aerobic and anaerobic culture conditions on toxaphene degradation were studied with washed P. putida cells grown on camphor and incubated with no readily usable carbon source. The radioactivities remaining in water after extraction with n-hexane were used as an indicator of metabolic activity. This was further extracted with ethyl acetate after acidification to divide this "total polar metabolites" fraction into aqueous buffer phase and ethyl acetate phase, i.e., the total polar metabolites reported refer to summation of the aqueous buffer and ethyl acetate soluble phases (Table 4). All radioactivities have been corrected by zero time controls and autoclaved 8 hr controls are included in each experiment. 

Figure 27. Epoxide hydrolase catalyzed kinetic resolution of c/.v-2-ethyl-3-methyloxirane and formation of 2i ,3f -2,3-pentanediol as monitored by complexation gas chromatography on 0.08 M nickel(II) bis[3-(heptafluorobutanoyl)-(1 / )-camphorate] in methylpolysiloxane [25 m x 0.25 mm (i.d.) glass capillary column. 95CC, 1.1 bar nitrogen]191 2,3-pentanediol as acetonides 0.14 M nickel(ll) bis[3-(heptafluo-robutanoyl)-(l /t,2S)-pinan-4-onatc]151 in SE-30. Note that there is a change in the numbering of the chiral carbon atoms of the oxiranc vs. the diol due to nomenclature requirements.

Ketones Acetone Camphor Oil Cyclohexanone Diisobutyl Ketone Isophorone Mesityl Oxide Methyl Ethyl Ketone Methyl Isobutyl Ketone... 

Kaempferia galanga L. Shan Na (Galanga) (rhizome) Bomeol, camphor, cineol, ethyl alcohol.49 Stomachic, carminative, stimulant. 

Phenol Antimicrobial preservative disinfectant (not oral) Camphor, menthol, thymol, acetaminophen, phenacetin, chloral hydrate, phenazone, ethyl aminobenzoate, methenamine, phenyl salicylate, resorcinol, terpin hydrate, sodium phosphate, or other eutectic formers. Phenol also softens cocoa butter in suppository mixtures... 

Polymers based on COCs that have been described for photoresists are schematically shown in Figure 2.3. In addition, to the formulation a photoacid generator, di-(4-fcrf-butylphenyl)iodonium-10-camphor sulfonate is added. Other optional additives include anti-striation agents, plasticizers, speed enhancers, etc. Ethyl lactate acts as a solvent (61). Several other types of photoacid generators have been described (62). 

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