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Chapter 24: Problem 618

Show how you would synthesize the following compounds from the indicated starting materials and any desired inorganic reagents. (a) di-n-octyl sodium sulfosuccinate, \(\mathrm{CH}_{3}\left(\mathrm{CH}_{2}\right)_{7} \mathrm{O}_{2} \mathrm{CCH}_{2} \mathrm{CH}\left(\mathrm{SO}_{3} \mathrm{Na}\right)-\mathrm{CO}_{2} \cdot\left(\mathrm{CH}_{2}\right)_{7} \mathrm{CH}_{3}\) ("Aerosol" detergent) from maleic anhydride and n-octyl alcohol. (b) \(\left(\mathrm{CH}_{2}\right)_{3}\left(\mathrm{SO}_{3} \mathrm{H}\right)_{2}\) from \(\left(\mathrm{CH}_{2}\right)_{3} \mathrm{Br}_{2}\) (c) methyl 1 -butanesulfinate from \(\mathrm{n}\) -butyl bromide (a) from C=Cc1ccccc1 (e) optically active ethyl benzenesulfinate from optically active 2-octyl- benzenesulfinate.

Short Answer

Expert verified
(a) Synthesis of di-n-octyl sodium sulfosuccinate: 1. Heat maleic anhydride and n-octyl alcohol with an acid catalyst to form di-n-octyl maleate. 2. Add aqueous sodium bisulfite to the di-n-octyl maleate to form di-n-octyl sodium sulfosuccinate. (b) Synthesis of \(\left(\mathrm{CH}_{2}\right)_{3}\left(\mathrm{SO}_{3}\mathrm{H}\right)_{2}\): 1. React \(\left(\mathrm{CH}_{2}\right)_{3} \mathrm{Br}_{2}\) with sodium sulfite to form \(\left(\mathrm{CH}_{2}\right)_{3}\left(\mathrm{SO}_{3}\mathrm{H}\right)_{2}\). (c) Synthesis of methyl 1-butanesulfinate: 1. Perform a nucleophilic substitution (SN2) reaction of n-butyl bromide with methyl sulfonate anion to form methyl 1-butanesulfinate. (d) Synthesis of a compound from C=Cc1ccccc1: 1. Perform electrophilic addition of bromine to the alkene in C=Cc1ccccc1 to form BrCH-CHBr-c1ccccc1. (e) Synthesis of optically active ethyl benzenesulfinate: 1. Oxidize optically active 2-octyl benzenesulfinate with H2O2/OH- to form optically active benzenesulfinic acid. 2. Esterify the resulting benzenesulfinic acid with ethyl alcohol to obtain optically active ethyl benzenesulfinate.

Step by step solution

01

Reaction with maleic anhydride and n-octyl alcohol

\ Heat maleic anhydride and n-octyl alcohol together in the presence of a catalyst (e.g. acidic catalyst) to form di-n-octyl maleate. \[ \ce{C4H2O3 + 2(CH3(CH2)7OH) -> (CH3(CH2)7O2CCH=CHCO2(CH2)7CH3)} \]
02

Hydrolyze the resulting ester to form di-n-octyl sodium sulfosuccinate

\ React the di-n-octyl maleate obtained in Step 1 with aqueous sodium bisulfite to perform a nucleophilic addition reaction and hydrolyze the ester, forming di-n-octyl sodium sulfosuccinate: \[ \ce{(CH3(CH2)7O2CCH=CHCO2(CH2)7CH3) + 2 NaHSO3 -> CH3(CH2)7O2CCH2CH(SO3Na)CO2(CH2)7CH3}\] (b) \(\left(\mathrm{CH}_{2}\right)_{3}\left(\mathrm{SO}_{3}\mathrm{H}\right)_{2}\) from \(\left(\mathrm{CH}_{2}\right)_{3} \mathrm{Br}_{2}\)
03

Reaction with sodium sulfite

\ Perform a nucleophilic substitution reaction by reacting \(\left(\mathrm{CH}_{2}\right)_{3} \mathrm{Br}_{2}\) with sodium sulfite: \[ \ce{(CH2)3Br2 + 2 Na2SO3 -> (CH2)3(SO3H)2 + 2 NaBr}\] (c) methyl 1-butanesulfinate from n-butyl bromide
04

Reaction with sodium sulfite

\ Nucleophilic substitution (SN2) of n-butyl bromide by methyl sulfonate anion: \[ \ce{CH3(CH2)3Br + CH3OSO2Na -> CH3(CH2)3OSO2CH3 + NaBr}\] (d) a compound from C=Cc1ccccc1
05

Reaction with bromine

\ Perform electrophilic addition of bromine to the alkene in C=Cc1ccccc1: \[ \ce{C=Cc1ccccc1 + Br2 -> BrCH-CHBr-c1ccccc1}\] (e) optically active ethyl benzenesulfinate from optically active 2-octyl benzenesulfinate
06

Oxidation of 2-octyl benzenesulfinate

\ Oxidize optically active 2-octyl benzenesulfinate to an optically active benzenesulfinic acid: \[ \ce{ 2-Octyl-Benzenesulfinate ->[H2O2/OH^-] Benzenesulfinic Acid}\]
07

Esterification with ethyl alcohol

\ Perform an esterification reaction with ethyl alcohol: \[ \ce{ Benzenesulfinic Acid + CH3-CH2-OH ->[H^+] Optically Active Ethyl Benzenesulfinate + H2O}\]

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Most popular questions from this chapter

The sulfhydryl group of coenzyme A plays an important role in the biosynthesis of fatty acids from units of acetic acid. The key steps are suggested to be carboxylation with carbon dioxide of acetyl coenzyme \(\mathrm{A}\) (which is a thioester abbreviated as O=CSC(=O)O to give malonyl coenzyme \(\mathrm{A}\) followed by condensation of the malonyl coenzyme A with acetyl coenzyme \(\mathrm{A}\), or a molecule of an acyl coenzyme \(\mathrm{A}\), to produce an acyl malonyl coenzyme \(\mathrm{A}\) This is followed by decarboxylation and reduction to an acyl coenzyme \(A\) with two more carbon atoms than the starting acyl coenzyme \(\mathrm{A}\). Each repetition of the process gives a fatty acid (or thioester of a fatty acid) with an additional two carbons. All the steps are of course controlled by specific enzymes. \(5^{\prime}-\) (adenosine 3' -phosphate) \(-\mathrm{OP}(\mathrm{O})(\mathrm{OH}) \mathrm{OP}(\mathrm{O})(\mathrm{OH}) \mathrm{OCH}_{2} \mathrm{C}\left(\mathrm{CH}_{3}\right)_{2}\) \(\mathrm{CH}(\mathrm{OH})-\mathrm{CONH}\left(\mathrm{CH}_{2}\right)_{2} \mathrm{CONH}\left(\mathrm{CH}_{2}\right)_{2} \mathrm{SH}\) coenzyme \(\mathrm{A}(\mathrm{CoA}\) SH ) (a) Write out the complete structure of coenzyme A as corresponds to the above condensed formula; what products would you expect coenzyme \(\mathrm{A}\) to give on vigorous hydrolysis? (b) Work out the steps for synthesis of hexanoic acid from acetic acid with the acid of coenzyme \(A\), using the abbreviation CoA-SH and indicating the general nature of each step in terms of the kind of reagents that might be used to achieve it in ordinary laboratory operations. What advantages would you expect to accrue from CoA-SH as compared to CoA-OH as the acyl carrier? (c) Suppose the enzymic synthesis of hexanoic acid to be carried on in the presence of radioactive carbon dioxide; would the postulated course of the reaction be precluded if the hexanoic acid produced were completely devoid of radioactivity? Explain in detail.

Methionine is the active agent for many biological methylations, particularly of nitrogen. Transmethylation involving methionine is activated by ATP. Suggest a mechanism for the transfer of a methyl group from methionine to an amine in which ATP would combine with methionine in such a way as to make the methyl group of the methionine readily reactive toward nucleophilic agents.

(a) Methyl chloromethyl sulfone reacts with strong alkali to yield ethylene and sodium sulfite. Write a mechanism for this reaction which is in accord with the reagents and the products. (b) Butadiene when heated with sulfur dioxide undergoes 1,4 -addition with formation of an unsaturated cyclic sulfone. How might this sulfone (in conjunction with the reaction which gives an alkene from an a-halosulfone) be used in a synthesis of cyclobutadiene?

Write the structural formulas for the following substances: (a) di-t-butyl thioketone (b) ethylene sulfide (c) methyl thioacetate (d) \(\beta, \beta^{\prime}\) - dichloroethyl sulfide (mustard gas) (e) tris-(methylsulfony1)-methane (f) cis-1,4-dithiacyclohexane dioxide (g) trimethylene disulfide (h) 5 -thia-1,3-cyclopentadiene (thiophene)

Give each of the following pairs of compounds a chemical test, preferably a test-tube reaction, which would serve to distinguish one from the other. (a) \(\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{SH}\) and \(\mathrm{CH}_{3} \mathrm{SCH}_{3}\) (b) \(\left(\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{~S}\right)_{2}\) and \(\left(\mathrm{CH}_{3} \mathrm{CH}_{2}\right)_{2} \mathrm{~S}\) (c) \(\mathrm{CH}_{3} \mathrm{~S}(\mathrm{O}) \mathrm{OCH}_{3}\) and \(\mathrm{CH}_{3} \mathrm{CH}_{2} \mathrm{SO}_{3} \mathrm{H}\) (d) \(\mathrm{CH}_{3} \mathrm{~S}(\mathrm{O}) \mathrm{OCH}_{3}\) and \(\mathrm{CH}_{3} \mathrm{~S}(\mathrm{O})_{2} \mathrm{CH}_{3}\) (e) \(\mathrm{CH}_{3} \mathrm{SCH}_{2} \mathrm{CH}_{2} \mathrm{OH}\) and \(\mathrm{CH}_{3} \mathrm{OCH}_{2} \mathrm{CH}_{2} \mathrm{SH}\)
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