Benzyl-propyl

A number of substrates having a benzylic ether moiety were reacted with 51 to afford the corresponding benzylic esters in good yields (equation 84). For evaluating the effects of p-substiments on the oxidation of a series of benzylic ethers, a competitive oxidation of p-substimted benzylic propyl ethers with 51 was carried out. The Hammett correlation plot for the oxidation reaction gave a better correlation of the relative ratio factors with the a rather than with the a+ substituent constants and afforded a reaction constant p+ = —0.57 (r = 0.99). This p+ value shows that 51 is an electrophilic species and appears to be comparable to the p+ value of —0.65 for benzylic hydrogen abstraction from dibenzyl ethers by the benzoyloxy radicaP . 

N-Monosubstituierte Carbonsaure-ester-imide (z. B. Benzoesaure-ethylester-propylimid) lassen sich, nach Protonierung (bei pH = 6), auch mittels Lithium-cyanoboranat zu se-kundaren Aminen (z. B. zu Benzyl-propyl-amirr, 74%) reduzieren1. 

Table 9.1 summarizes the effects of N-substitution and counterions on the photochromic behavior of viologens. The rate of electron transfer decreased withN-substitution as follows dibenzyl > benzyl, propyl > dipropyl and with the counteranion, Cl > Br-> I-> BF4T The order is consistent with the first dark redox... 

Cbz Cp DABCO DBU DDQ (DHQD)2CLB (DHQD)2PYR DMF DME DMPU DMSO Et Fmoc HMPA ia KHMDS LDA LiHMDS Me MEM Ms NaHMDS Ph Piv PMB Pr Py (saltmen)Mn(N) benzyloxy carbonyl p 5 -cyclopentadienyl l,4-diazabicyclo[2.2.2]octane l,8-diazabicyclo[5.4.0]undec-7-ene 2,3 -dichloro-5,6-dicyanobenzoquinone dihydroquinidinyl p-chlorobenzoale (see Chart 1) dihydroquinidinyl pyrimidine (see Chart 1) dimethylformamide dimethoxyethane l,3-dimethyl-3,4,5,6-tetrahydro-2(l//)-pyrimidinone dimethylsulfoxide ethyl 9-fluorenylmethoxy carbonyl hexamethylphosphoric triamide inverse addition potassium hexamethyldisilazide lithium diisopropylamide lithium hexamethyldisilazide methyl (2-methoxy ethoxy )methyl methanesulfonyl sodium hexamethyldisilazide phenyl pivaloyl p -methoxy benzyl propyl pyridine nitrido[A,A/-(l,l,2,2-tetramethyl) bis(salicylideneaminato)]manganese (see Chart 1)... 

Benzyl propyl acetate. See Dimethyl benzyl carbinyl acetate... 

Synonyms Benzyl dimethyl carbinyl acetate Benzyl propyl acetate Dimethyl benzyl carbinoacetate a,a-Dimethylphenethyl acetate a,a-Dimethylphenethyl alcohol acetate 1,1-Dimethyl-2-phenyl acetate DMBCA Definition Obtained by acetylation of dimethylbenzyl carbinol Empirical C12H16O2 Formula C6HgCH2C(CH3)200CCH3... 

Draw the structure of benzyl propyl ketone and then give the lUPAC name using normal rules for naming an aliphatic ketone (Chapter 16, Section 16.2.1). 

Esters. Methyl, ethyl, n-propyl, n butyl, benzyl, cyclohexyl... 

Methyl, ethyl, n-propyl, isopropyl, n-hutyl, benzyl, cyclohexyl esters of formic, acetic, oxalic, succinic, tartaric, citric, benzoic, salicylic (and other substituted benzoic acids), phthalic and cinnamic acids phenyl esters of acetic, benzoic and salicylic acids. 

The following liquids may be used (boiling points are given in parentheses) — chlorobenzene (132-3°) bromobenzene (155°) p cymene (176°) o-dichloro-benzene (180°) aniline (184°) methyl benzoate (200°) teti-alin (207°) ethyl benzoate (212°) 1 2 4-trichlorobenzene (213°) iaopropyl benzoate (218°) methyl salicylate (223°) n-propyl benzoate (231°) diethyleneglycol (244°) n-butyl benzoate (250°) diphenyl (255°) diphenyl ether (259°) dimethyl phth ate (282°) diethyl phthalate (296°) diphenylamine (302°) benzophenone (305)° benzyl benzoate (316°). 

The following melting points have been recorded —methyl cellosolve, 152° cellosolve, 128° wo-propyl cellosolve, 80° butyl cellosolve, 85° phenyl cellosolve, 145° benzyl cellosolve, 104° methyl carbitol. 82° ethyl carbitol, 76° . butyl carbitol, 54°. 

Successful results have been obtained (Renfrew and Chaney, 1946) with ethyl formate methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec.-butyl and iso-amyl acetat ethyleneglycol diacetate ethyl monochloro- and trichloro-acetates methyl, n-propyl, n-octyl and n-dodecyl propionates ethyl butyrate n-butyl and n-amyl valerates ethyl laurate ethyl lactate ethyl acetoacetate diethyl carbonate dimethyl and diethyl oxalates diethyl malonate diethyl adipate di-n-butyl tartrate ethyl phenylacetate methyl and ethyl benzoates methyl and ethyl salicylates diethyl and di-n-butyl phthalates. The method fails for vinyl acetate, ieri.-butyl acetate, n-octadecyl propionate, ethyl and >i-butyl stearate, phenyl, benzyl- and guaicol-acetate, methyl and ethyl cinnamate, diethyl sulphate and ethyl p-aminobenzoate. 

The ketones are readily prepared, for example, acetophenone from benzene, acetyl chloride (or acetic anhydride) and aluminium chloride by the Friedel and Crafts reaction ethyl benzyl ketones by passing a mixture of phenylacetic acid and propionic acid over thoria at 450° and n-propyl- p-phenylethylketone by circulating a mixture of hydrocinnamic acid and n-butyric acid over thoria (for further details, see under Aromatic Ketones, Sections IV,136, IV,137 and IV,141). 

The dibenzyl ketone has a very high b.p. (ca. 200°/21 mm.) and this remains in the flask when the unsymmetrical ketone has been removed by distillation. The dialkyl ketone has a comparatively low b.p. and is therefore easily removed by fractionation under normal pressure acetone is most simply separated by washing with water. In this way methyl benzyl ketone (R = CHj), ethyl benzyl ketone (R = CHgCH,) and n-propyl benzyl ketone (R = CHjCHjCH,) are prepared. By using hydrocinnamic acid in place of phenylacetic acid ... 

The formation of alkylbenzenes, largely free from unaaturated compounds, provides another interesting application of organosodium compounds. Thus pure M-butylbenzene is readily obtained in good yield from benzyl sodium and n-propyl bromide. Benzyl-sodium is conveniently prepared by first forming phenyl-sodium by reaction between sodium and chlorobenzene in a toluene medium, followed by heating the toluene suspension of the phenyl-sodium at 105° for about 35 minutes ... 

It is worth noting here that the results of some other studies of aromatie substitutions, sueh as the Friedel-Crafts benzylation and iso-propylation of alkylbenzenes, and the bromination of alkylbenzenes with bromine, eatalysed by ferrie ehloride, are under suspicion as depending upon slow mixing. As regards halogenation eatalysed by Lewis aeids, positive evidenee to support this eritieism has been obtained. ... 

The N,N-disubstituted thioureas (135) condensed with a-halocarbonyl compounds give 2-disubstituted aminothiazoies (136) but in lower yields (30 to 70%) (Scheme 65 and Table 11-20) (518). For example, N,N-dialkylthioureas condensed with chloroacetaldehyde or dibromoether lead to Ar,At-dialkyl-2-aminothiazoles in 136, Ri=R2 = methyl (342, 404, 436, 637), ethyl (343, 436), n-propyl (518), n-butyl (518), ally] (518), and benzyl (26, 29). When chloroacetone and dichloroacetone are the carbonyl reactants the corresponding 4-methyl (518) and 4-chloromethyl derivatives (572) were obtained. 

Property Methyl Ethyl / -Propyl Butyl Benzyl... 

When exposed to ait, the sodium salts tend to take up moisture and form dihydrates. The alkah metal xanthates are soluble ia water, alcohols, the lower ketones, pyridine, and acetonitrile. They are not particularly soluble ia nonpolar solvents, eg, ether or ligroin. The solubiUties of a number of these salts are Hsted ia Table 4. Potassium isopropyl xanthate is soluble ia acetone to ca 6 wt %, whereas the corresponding methyl, ethyl, / -propyl, n-huty isobutyl, isoamyl, and benzyl [2720-79-8] xanthates are soluble to more than 10 wt % (12). The solubiUties of the commercially available xanthates ia water are plotted versus temperature ia Figure 1 (14). 

Catalyst Cation. The logarithms of extraction constants for symmetrical tetra- -alkylammonium salts (log rise by ca 0.54 per added C atom. Although absolute numerical values for extraction coefficients are vastly different in various solvents and for various anions, this relation holds as a first approximation for most solvent—water combinations tested and for many anions. It is important to note, however, that the lipophilicity of phenyl and benzyl groups carrying ammonium salts is much lower than the number of C atoms might suggest. Benzyl is extracted between / -propyl and -butyl. The extraction constants of tetra- -butylammonium salts are about 140 times larger than the constants for tetra- -propylammonium salts of the same anion in the same solvent—water system. 

Esters of low volatility are accesible via several types of esterification. In the case of esters of butyl and amyl alcohols, water is removed as a binary azeotropic mixture with the alcohol. To produce esters of the lower alcohols (methyl, ethyl, propyl), it may be necessary to add a hydrocarbon such as benzene or toluene to increase the amount of distilled water. With high boiling alcohols, ie, benzyl, furfuryl, and P-phenylethyl, an accessory azeotroping Hquid is useful to eliminate the water by distillation. 

Alcohols.—It may be a liquid alcohol (methyl, ethyl, propyl, etc., glycerol, benzyl) or a solution of it in nater. In the former case its boiling-point will have already been determined. Itttiay be fiirthei identified (1) by converting it into the benzoic... 

Condensation of the TV-substituted p-aminocrotonic acid ester 15 with p-benzoquinone (4) has been successfully carried out to furnish the 5-hydroxyindole 29 when the substituent R on the nitrogen of the aminocrotonic acid ester was methyl, ethyl, -propyl, isopropyl, or -butyl, -hexyl, p-cyanoethyl, p-hydroxyethyl, carbethoxymethyl, benzyl, phenyl, o-tolyl, dimethylaminopropyl, y-hydroxypropyl etc ... 

Benzyl or n-propyl)-5-methyl-3W-pyrazole-3,4-dione 4-oximes 31a,b were prepared by two routes. Thus, efliyl 3-oxobutanoate 27 was eiflier heated wifli... 

A -benzyl or W-propyl-/V-nitrosohydrazir es 28a,b at 50 C for 6 days ot nitrosated to ethyl 2-(hydroxyimino)-3-oxobutanoate 29 which was then heated with benzyl-hydrazine 30a OT n-propylhydrazine 30b in ethanol (87JOU1773) (Scheme 8). 

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