Ethyl dimethyl acetic acid

Acid moieties include formic acid itself, formates and orthoesters, formamide, DMF dimethyl acetal and ethyl diethoxyacetate, acids, acid chlorides and anhydrides, the last including a rare [3,4-oxalate esters, 2-acyl or 2-ethoxycar-bonyl derivatives e.g. 180) are formed. 

The mercaptals obtained by the acid catalyzed reaction of J3-ketoesters, e.g., ethyl acetoacetate, with methyl thioglycolate (73) undergo the Dieckmann cyclization with alcoholic potassium hydroxide at lower temperatures to give ethyl 3-hydroxy-5-methyl-2-thiophenecarboxylate (74) in 75% yield. ° Besides ethyl acetoacetate, ethyl a-ethylacetoacetate, ethyl benzoyl acetate, and ethyl cyclopentanonecarboxylate were also used in this reaction/ It is claimed that /8-diketones, hydroxy- or alkoxy-methyleneketones, or /8-ketoaldehyde acetals also can be used in this reaction. From acetylacetone and thioglycolic acid, 3,5-dimethyl-2-thiophenecarboxyl-ic acid is obtained. ... 

The A-substituted derivatives of 4-oxo-4//-pyrido[l,2-n]pyrimidine-3-carboxamides and -3-acetamides and l,6-dimethyl-4-oxo-1,6,7,8-tetrahy-dro-4//-pyrido[l,2-n]pyrimidine-3-carboxamide were prepared by treatment of the appropriate 3-carboxylic acids and acetic acid, first with an alkyl chloroformate in the presence ofNEt3 in CHCI3 below — 10°C, then with an amine (98ACH515). A-Phenethyl and A-[2-(3,4-dimethoxyphenyl)ethyl] derivatives of 6-methyl-6,7,8,9-tetrahydro-4//-pyrido[l, 2-n]pyrimidine-3-acetamide were obtained in the reaction of 6-methyl-6,7,8,9-tetrahydro-4//-pyrido[l,2-n]pyrimidine-3-acetic acid and phenethylamines in boiling xylene under a H2O separator. Hydrazides of 4-oxo-4//- and 4-oxo-6,7,8,9-tetrahydro-4//-pyrido[l, 2-n]pyrimidine-3-acetic acid were prepared from the appropriate ester with H2NNH2 H2O in EtOH. Heating 4-oxo-4//- and 6-methyl-4-oxo-6,7,8,9-tetrahydro-4//-pyrido[l, 2-n]pyrimidine-3-acetic hydrazides in EtOH in the presence of excess Raney Ni afforded fhe appropriafe 4-oxo-6,7,8,9-fefrahydro-4//-pyrido[l,2-n]pyrimidine-3-acefa-mide. In the case of the 4-oxo-4// derivative, in addition to N-N bond... 

Ethyl 9a-hydroxy-11a,15a-bis(2-tetrahydropyranyloxy)-16,16-dimethyl-prosta-trans-2,trans-l3-dienoate Potassium hydroxide Manganese sulfate Acetic acid... 

Synthesis of 16,16-dimethyl-trans-A -PGEi 2.35 g of the bis-tetrahydropyranyl ether were dissolved in 6 ml of tetrahydrofuran and 60 ml of 65%-acetic acid aqueous solution and the solution stirred at 60°C to 70°C for 20 minutes. The reaction mixture was extracted with ethyl acetate, and the organic layer was washed with water, dried and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel using ethyl acetate-cyclohexane (2 3) as eluent to yield 270 mg of the title compound. 

A solution of 1.18 g (7 mmol) 4-acetoxy-5,5-dimethyl-2-eyclopcnlonone and 1.13 g (7.1 mmol) of diethyl 1,3-propanedioate in 0.8 mL of ethanol is added to a solution of 40 mg (1.7 mmol) of sodium in 4 mL of ethanol and stirred for 0.5 h at 25 JC. The mixture is acidified with 1 mL of acetic acid and poured into 10 mL of water. The resulting mixture is extracted three times with 10 mL of diethyl ether. The combined ether layers are washed with 10 mL of 5% aq NaHC03,10 mL of brine and dried Over Na,S04. Evaporation of the solvent followed by chromatography (silica gel, henzene/ethyl acetate 30 1) affords the crude product which was recrystallized from hexane yield 478 mg (21 %) mp 65-66°C. 

The reaction of potassium 3-amino-4-oxo-3,4-dihydroquinazoline-2-thiolate 62 with a-bromophenylacetic acid 63 resulted in the formation of (3-amino-4-oxo-3,4-dihydroquinazolin-2-ylsulfanyl)-phenyl-acetic acid methyl ester 64 which on alkali treatment and subsequent acidification resulted in the synthesis of 2-phenyl- 1-thia-4,4a,9-triaza-anthracene-3,10-dione 65 <1999JCR(S)86>. Similarly, the reaction of potassium 3-amino-5,6-dimethyl-4-oxo-3,4,4a,7a-tetrahydrothieno[2,3- pyrimidine-2-thiolate 66 with a-bromo-ester 67 resulted in the formation of 2-(3-amino-5,6-dimethyl-4-oxo-3,4,4a,7a-tetrahydrothieno[2,3- / pyrimidin-2-ylsulfanyl)-propionic acid ethyl ester 68. Subsequent treatment with alkali followed by acidification resulted in the formation of 2,3,7-trimethyl-3a,9a-dihydro-l,8-dithia-4a,5,9-triazacyclopenta[ ]naphthalene-4,6-dione 69 <2000JHC1161>... 

For the Cu(OTf)2-promoted reaction between ethyl diazoacetate and cinnam-aldehyde dimethyl acetal, products 143-145 account for only 35% the total yield. C/C and C/H insertion products 151 and 152 are obtained additionally in 49 and 14% yield, respectively154). It was assumed that the copper compound acts through Lewis-acid catalysis here, just as it is believed to do when orthoesters are used as substrates 160). According to this, catalyst-induced formation of a methoxy-... 

Figure 11.11 Pyrogram of a paint sample collected from a decorative frame of the Universal Judgement by Bonamico Buffalmacco (fourteenth century, Monumental Cemetery of Pisa, Italy). Pyrolysis was performed with a microfurnace pyrolyser, at 600°C, in the presence of HMDS. 1, Benzene 2, ethyl acrylate 3, methyl methacrylate 4, acetic acid, trimethyl silyl ester 5, pyrrole 6, toluene 7, 2 methylpyrrole 8, 3 methylpyrrole 9, crotonic acid 10, ben zaldehyde 11, phenol 12, 2 methylphenol 13, 4 methylphenol 14, 2,4 dimethyl phenol 15, benzyl nitrile 16, 3 phenylpropionitrile 17, indole 18, phthalate 19, phthalate 20, ben zyl benzoate HMDS pyrolysis products [27]...

Acetic acid, methyl ester Acetic acid, ethyl ester Pentanoic acid, methylethyl ester Acetic acid, methylethyl ester Acetic acid, 3-propenyl ester Acetic acid, benzyl ester Oxalic acid, dimethyl ester Oxalic acid, diethyl ester Oxalic acid, fe(l-methylethyl) ester... 

Initially, a reaction of A-acetoxy-A-butoxybenzamide 25c with A-methyl aniline 61 in butyl benzoate 63(R = Bu) and acetic acid. Close examination of these highly coloured reaction mixtures indicated the presence of crystals of A,A-dimethyl-A,A-diphenyltetrazene 65 (Scheme 11, R = Bu). The reaction is promoted by polar solvents as reactants are unchanged in pure acetonitrile. A crossover experiment using a mixture of /V- a ce t o x y - A-- b u t o x y - to 1 u a m i d e 26d and A-acetoxy-A-ethoxybenz-amide 25a afforded clean yields of butyl /Moluatc and ethyl benzoate thus pointing to an intramolecular rearrangement.41... 

Cholest-3-ene- 5- acetamide, 2V,i7-dimethyl, 54, 77 5f3-Cholest-3-ene-5-acetic acid, ethyl ester, 54, 74... 

B. (4R,5S)-3-(1-Methoxyethyl)-4,5-diphenyl-2-oxazolidinone. A 2-L, threenecked, round-bottomed flask equipped with a magnetic stirrer, thermometer, and a reflux condenser is charged with (4R,5S)-4,5-diphenyl-2-oxazolidinone (20.0 g, 84 mmol), ( )-10-camphorsulfonic acid (9.7 g, 42 mmol) (Note 7), and acetaldehyde dimethyl acetal (700 mL) (Note 8). The mixture is heated at gentle reflux in an oil bath (bath temperature 80°C) for 5 hr (Note 9). The mixture is allowed to cool to ambient temperature, then concentrated under reduced pressure on a rotary evaporator (Note 10). Ethyl acetate (100 mL) is added to the residue, and the ethyl acetate solution is transferred to a beaker. The solution is neutralized with saturated sodium bicarbonate solution (100 mL) (Note 11), and transferred into a separatory funnel. The two layers are separated, and the lower aqueous layer is extracted with ethyl acetate (100 mL). 

Figure 18. Correlations between the solubility of cmchonidme and the reported empirical polarity (A) and dielectric constants (B) of 48 solvents [66]. Those solvents are indicated by the numbers in the figures 1 cyclohexane 2 n-pentane 3 n-hexane 4 triethylamine 5 carbon tetrachloride 6 carbon disulfide 7 toluene 8 benzene 9 ethyl ether 10 trichloroethylene 11 1,4-dioxane 12 chlorobenzene 13 tetrahydrofuran 14 ethyl acetate 15 chloroform 16 cyclohexanone 17 dichloromethane 18 ethyl formate 19 nitrobenzene 20 acetone 21 N,N-drmethyl formamide 22 dimethyl sulfoxide 23 acetonitrile 24 propylene carbonate 25 dioxane (90 wt%)-water 26 2-butanol 27 2-propanol 28 acetone (90 wt%)-water 29 1-butanol 30 dioxane (70 wt%)-water 31 ethyl lactate 32 acetic acid 33 ethanol 34 acetone (70 wt%)-water 35 dioxane (50 wt%)-water 36 N-methylformamide 37 acetone (50 wt%)-water 38 ethanol (50 wt%)-water 39 methanol 40 ethanol (40 wt%-water) 41 formamide 42 dioxane (30 wt%)-water 43 ethanol (30 wt%)-water 44 acetone (30 wt%)-water 45 methanol (50 wt%)-water 46 ethanol (20 wt%)-water 47 ethanol (10 wt%)-water 48 water. [Reproduced by permission of the American Chemical Society from Ma, Z. Zaera, F. J. Phys. Chem. B 2005, 109, 406-414.]...

The ozonolysis reaction, followed by reductive workup with sulfur dioxide, as described in Part A of the present procedure, illustrates a general method which has been developed for the preparation of acetals. Application of the procedure is illustrated by conversion of the following olefins in alcoholic solution to the corresponding acetals (1) l-chloro-4-(o-nitrophenyl)-2-butene to o-nitrophenylacetaldehyde dimethyl acetal in 84% yield (2) l,4-dibromo-2-butene tobromoacetaldehyde dimethyl acetal in 67% yield (3) 3-butenoic acid to malonaldehydic acid diethyl acetal ethyl ester in 61% yield (4) cyclopentadiene to malonaldehyde bis(diethyl acetal) in 48% yield and (5)... 

Catalytic hydrogenation transforms keto esters to hydroxy esters under very gentle conditions. In cyclic ketones products of different configuration may result. Ethyl 3,3-dimethylcyclohexanone-2-carboxylatC on hydrogenation over platinum oxide in acetic acid gave 96.3% yield of cis, and over Raney nickel in methanol gave 97% yield of trans ethyl 3,3-dimethyl-cyclohexanol-2-carboxylate, both at room temperature and atmospheric pressure [847]. 

Table 9.2 summarizes the uses of acetic acid. Vinyl acetate is another top 50 chemical. Acetic anhydride is used to make cellulose acetate and at times has been in the top 50 chemicals itself. Cellulose acetate is a polymer used mainly as a fiber in clothing and cigarette filters. Ethyl acetate is a common organic solvent. Acetic acid is used as a solvent in the manufacture of terephthalic acid (TA) and dimethyl terephthalate (DMT), which are monomers for the synthesis of poly(ethylene terephthalate), the polyester of the textile industry. A minor household use of acetic acid is as a 3-5% aqueous solution, which is called vinegar. 

Racemic methadone (MET) is administered to heroin addicts as a substitution therapy. However, methadone enantiomers possess different pharmacological effects, and the drug has been demonstrated to be enantioselectively metabolized to its two major metabolites, 2-ethylidene-l,5-dimethyl-3,3-diphenylpyrrolidine (EDDP) and 2-ethyl-5-methyl-3,3-diphenyl-l-pyrroline (EMDP). Stereoselective separation of MET, EDDP, and EMDP using an alpha-glycoprotein stationary phase and MS-MS detection was proposed by Kelly et al. [34]. Optimal separation conditions were 20 mM acetic acid isopropanol (93 7, pH 7.4), with a flow rate of 0.9mL/min. 

Carbonylation and homologation of ethers - The carbonylation and homologation of dimethyl ether to methyl and ethyl acetate (eqs. 4 and 5) in methyl acetate-acetic acid solution are considerably affected by the acidity of the reaction medium and by the nature of the iodide promoter which determines the concentration of HRu(CO)3l3. 

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