Butanoic acid reactions

C. Manufactured from butyrolactone and ammonia. Easily hydrolysed to 4-amino-butanoic acid, its most important use is for the formation of N-vinylpyrrolidone by reaction with elhyne. 

Draw the structure of the principal product formed from each of the following condensation reactions (a) butanoic acid... 

The reactions are assumed to take place under isothermal conditions at 130°C at 10 bar. The liquid feed of BA is 0.0133 kmol-s 1 and the gaseous feed of chlorine is 0.1 kmol-s-1. The objective is to maximize the fractional yield of a-monochlorobutanoic acid with respect to butanoic acid. Specialized software is required to perform the calculations, in this case, using simulated annealing. 

Example 14.1 Consider again the chlorination reaction in Example 7.3. This was examined as a continuous process. Now assume it is carried out in batch or semibatch mode. The same reactor model will be used as in Example 7.3. The liquid feed of butanoic acid is 13.3 kmol. The butanoic acid and chlorine addition rates and the temperature profile need to be optimized simultaneously through the batch, and the batch time optimized. The reaction takes place isobarically at 10 bar. The upper and lower temperature bounds are 50°C and 150°C respectively. Assume the reactor vessel to be perfectly mixed and assume that the batch operation can be modeled as a series of mixed-flow reactors. The objective is to maximize the fractional yield of a-monochlorobutanoic acid with respect to butanoic acid. Specialized software is required to perform the calculations, in this case using simulated annealing3. 

The elimination of the original CHj group from ionized n-butanoic acid, 38, was shown to proceed also mainly via a two-step process. The reaction is initiated by a hydrogen migration via a four-membered transition state 38->39, which... 

Hydralazine 219 is a good precursor for that ring system. Its reactions with pyruvic acid (75JOC2901), arylidene pyruvic acids (81AP1030), and 4-aryl-2-oxo-butanoic acids (87JHC63) gave the respective hydrazones... 

Valine (Val or V) ((5)-2-amino-3-methyl-butanoic acid) is a nonpolar, neutral, aliphatic amino acid with the formula HOOCCH(NH2)CH(CH3)2. Along with Leu and He, Val is a branched-chain amino acid and is found in high concentrations in the muscles. Val is needed for muscle metabolism and coordination, tissue repair, and for the maintenance of proper nitrogen balance in the body. ° The steric hindrance present in Val and He (caused by branching) lowers the rate of coupling reactions, resulting in an increase in side reactions. ... 

Kolbe noted also the formation of traces of methyl acetate and butyl valerate from electrolysis of acetate and valerate respectively. Careful analysis of reaction products by Petersen (1900) identified compounds which are today formulated as being derived from carbocations formed by loss of one electron from the alkyl radical [50]. Propanoic acid gives mostly ethene while butanoic acid and 2-methyl-propanoic acid give mostly propene. Acetate and long chain alkylcarboxylates give mostly the Kolbe type dimer hydrocarbon on electrolysis of their potassium salts in concentrated solution at a platinum electrode, using high current density and low temperatures [51]. 

Benzofuranyl)butanoic acid readily forms the acid chloride, and this undergoes intramolecular Friedel-Crafts acylation on treatment with tin(IV) chloride in carbon disulfide at room temperature, providing 1,2,3,4-tetra-hydro-l-dibenzofuranone (54%). " This intermediate has been converted to dibenzofuran by lithium aluminum hydride reduction and subsequent dehydrogenation, to 1-methyldibenzofuran by Grignard reaction and dehydrogenation, and to 1-dibenzofuranol by reaction with iV-bromosuccinimide and subsequent dehydrobromination with pyridine. 

A reaction by Clough et al. comes close to the direct synthesis shown in Scheme 1 (89TL7469). Here amides (62) react in a radical mechanism to 4-methylene compounds (63) that with 03/PPh3 are converted to tetramic acids (64). (See Fig. 29.) Several authors, however, prepared esters of 4-amino-3-oxo-butanoic acid, which served as precursors for intramolecular cyclization to tetramic acids (82JHC883). Koehler and Gerlach in an initial stage of a synthesis of dysidine, contained in marine sponge... 

Problem 16.48 (a) Write a formula for a fat (found in butter) of butanoic acid. (6) Alkaline hydrolysis of a fat of a high-molecular-weight acid gives a carboxylate salt (a soap). Write the equation for the reactions of the fat of palmitic acid, n-C,3H, COOH, with aqueous NaOH. ... 

Esters are rarely used as electrophiles in Reformatsky reactions. An example was reported by Atkins and coworkers the quinohne ester 89 failed to react with butanoic acid esters in classical Claisen condensation conditions, but was found to smoothly react with f-butyl ester 90 in the presence of zinc in good yield (equation 54)138. 

An interesting oxidative decarboxylation process was reported for a /(-hydroxy acid. Reaction of 2-ethyl-2-(l -hydroxycyclobutyl)butanoic acid with vanadium(III) chloride in the presence of 1 equivalent of l,8-bis(dimethylamino)naphthalcne (Proton Sponge) gave 3-cyclobutylidene-pentane (20).181... 

Another interesting example of resolution through formation of diastereo-mers is the isolation of four stereoisomers of 3-amino-2-methyl-3-trifluoro-methyl butanoic acid [55]. In this process, the chemical-enzymatic method by the combination of chemical and enzymatic reaction is a very convenient. At first, -phenylacetyl derivatives 61a and 61b were prepared in excellent isolated yields via the Schotten-Baumann procedure. After these materials were hydrolysed with penicillin acylase (EC 3.5.1.11) from Escherichia coli until attainment of 50% conversion, enzymatically unconverted -phenylacetyl derivatives 62 a and 62 b (organic layer) and amino acids 63 b and 63 d (aqueous layer) were separated. Acidic hydrolysis of unconverted materials produced other stereoisomers 63 a and 63 c in high optical pure form. 

Cognate preparations sulphuric acid catalyst. Ethyl butanoate. Use a mixture of 88 g (92 ml, 1 mol) of butanoic acid, 23 g (29 ml, 0.5 mol) of ethanol and 9g (5 ml) of concentrated sulphuric acid. Reflux for 14 hours. Pour into excess of water, wash several times with water, followed by saturated sodium hydrogen carbonate solution until all the acid is removed, and finally with water. Dry with anhydrous sodium sulphate, and distil. The ethyl butanoate passes over at 119.5-120.5 °C. Yield 40g (69%). An improved yield can be obtained by distilling the reaction mixture through an efficient fractionating column until the temperature rises to 125 °C, and purifying the crude ester as detailed above under methyl acetate. 

Reaction of 4-(hydroxyl methylphosphinyl)butanoic acid (154) with thionyl chloride followed by successive treatment with copper powder, potassium iodide, and potassium carbonate affords l-methyl-2-oxophospholane 1-oxide (155) in 65% yield. 3-Bromo-, 3-amino-, 3-acethylamino-l-methyl-2-oxophospholanes (156-158) are prepared by substitution of the 3-methylene position (Scheme 51) [64]. 

Consider the reactor design for the production chlorination of butanoic acid as an example to illustrate the technology developments. A full study is given in Ref. 34, and only a brief summary of the results is presented here. The chlorination of butanoic acid (BA) involves two reactions in the liquid phase ... 

Yinylogous enamine dyes are obtained by reaction of aromatic amines with mucochloric acid (2,3-dichloro-4-oxo-2-butanoic acid), followed by condensation with quaternary quinaldine. After methylation of the enamine nitrogen atom with dimethyl sulfate, the dye 5 is obtained, which dyes bleached sulfite pulp red [15]. 

Recently, we [67] have described the reduction of the methyl ester of 4-chloro-3-oxobutanoic acid (39) to the methyl ester of S-( )-4-chloro-3-hydroxy-butanoic acid (40) (Fig. 13) by cell suspensions of Geotrichum candidum SC 5469., S ( )-(40) is a key chiral intermediate in the total chemical synthesis of a cholesterol antagonist (SQ 33600), which acts by inhibiting hydroxymethylglu-taryl CoA (HMG CoA) reductase. In the biotransformation process, a reaction... 

The mixture of (2S,3S,5S)-2-(2,6-dimethylphenoxyacetyl)amino-3-hydroxy-5-amino-l,6-diphenylhexane (100 g, 0.22 mol), 2S-(l-tetrahydro-pyrimid-2-onyl)-3-methyl butanoic acid methyl ester (44.8 g, 0.22 mol) and 750 ml DMF was cooled in an ice/water bath. N-Hydroxybenzotriazole (90.9 g, 0.67 mol), l-ethyl-3-[3-dimethylaminopropyl]carbodiimide (86 g, 0.45 mol) and triethylamine (62.5 ml, 0.45 mol) were added and the ice bath was removed, allowing the reaction mixture to stir with warming to room temperature for 5 hours. The mixture was diluted with 1000 ml of IPAC and quenched with 1000 ml of water. The mixture was shaken and separated, the aq. layer was extracted IPAC, the organics were washed with 10% HCI, solution of NaHC03 with 100 ml hexanes, then washed 500 ml water, and brine, dried over MgS04, filtered and concentrated to provide. (2S,3S,5S)-2-(2,6-dimethylphenoxyacetyl)amino-3-hydroxy-5-(2S-(l-tetrahydro-pyrimid-2-onyl)-3-methylbutanoyl)amino-l,6-diphenylhexane as a white foam. 

Amination,1 The reaction of the dioxanone 2, derived from (R)-3-hydroxy-butanoic acid, with di-r-butyl azodicarboxylate (14,115-116) provides the derivative 3 in high diastereomeric excess. The same amination of an alkyl (R)-3-hydroxy-... 

Cyclodehydration of arylpropionic and -butanoic acids. This cyclization to 1-indanones and 1-tetralones can be effected in a one-pot reaction via the mixed anhydride formed with triflic acid (4, 533—534). 

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