Recall from Section 9-7 how acetylide ions are alkylated

Give the IUPAC names of the following alcohols.

Give both the \(\text { IUPAC }\) name and the common name for each alcohol. Equation Transcription: Text Transcription: IUPAC CH3CH2CH(OH)CH3 OH OH (CH3)2CHCH2CH2OH

For each molecular formula, draw all the possible constitutional isomers of alcohols with that formula. Give the IUPAC name for each alcohol. (a) \(\mathrm{C}_{3} \mathrm{H}_{8} \mathrm{O}\) (b) \(\mathrm{C}_{4} \mathrm{H}_{10} \mathrm{O}\) (c) \(\mathrm{C}_{3} \mathrm{H}_{6} \mathrm{O}\) (d) \(\mathrm{C}_{3} \mathrm{H}_{4} \mathrm{O}\) Equation Transcription: Text Transcription: C_3H_8O C_4H_10O C_3H_6O C_3H_4O

Give a systematic (IUPAC) name for each diol. Equation Transcription: Text Transcription: (IUPAC) CH_3CH(OH)(CH_2)_4CH(OH)C(CH_3)_3 HO-(CH_2)_8-OH HO OH OH OH HO OH

Predict which member of each pair will be more soluble in water. Explain the reasons for your answers. (a) hexan-1-ol or cyclohexanol (b) heptan-1-ol or 4-methylphenol (c) 3-ethylhexan-3-ol or octan-2-ol (d) hexan-2-ol or cyclooctane-1,4-diol

Dimethylamine, \(\left(\mathrm{CH}_{3}\right)_{2} \mathrm{NH}\), has a molecular weight of 45 and a boiling point of \(7.4^{\circ} C\) Trimethylamine, \(\left(\mathrm{CH}_{3}\right)_{3} \mathrm{~N}\), has a higher molecular weight (59) but a lower boiling point \(\left(3.5^{\circ} \mathrm{C}\right)\). Explain this apparent discrepancy. Equation Transcription: Text Transcription: (CH3) 2NH 7.4°C (CH3) 3N (3.5°C)

Predict which member of each pair will be more acidic. Explain your answers. (a) methanol or tert-butyl alcohol (b) 2-chloropropan-1-ol or 3-chloropropan-1-ol (c) 2-chloroethanol or 2,2-dichloroethanol (d) 2,2-dichloropropan-1-ol or 2,2-difluoropropan-1-ol

Problem 8P Without looking them up, rank the following compounds in decreasing order of acidity. These examples represent large classes of compounds that differ widely in acidity. water, ethanol, 2-chloroethanol, tert-butyl alcohol, ammonia, sulfuric acid, hexane, hex-1-yne, acetic acid

A nitro group effectively stabilizes a negative charge on an adjacent carbon atom through resonance: Two of the following nitrophenols are much more acidic than phenol itself. The third compound is only slightly more acidic than phenol. Use resonance structures of the appropriate phenoxide ions to show why two of these anions should be unusually stable.

The following compounds are only slightly soluble in water, but one of them is very soluble in a dilute aqueous solution of sodium hydroxide. The other is still only slightly soluble. (a) Explain the difference in solubility of these compounds in dilute sodium hydroxide. (b) Show how this difference might be exploited to separate a mixture of these two compounds using a separatory funnel. Equation Transcription: Text Transcription: OH OH

Which of the following compounds are suitable solvents for Grignard reactions? Equation Transcription: Text Transcription: n-hexane CH_3-O-CH_3 CHCI_3 CH_3OCH_2CH_2OCH_3

Show how you would synthesize the following primary alcohols by adding an appropriate Grignard reagent to formaldehyde. Equation Transcription: Text Transcription: CH_2OH OH CH_2OH

Show two ways you could synthesize each of the following secondary alcohols by adding an appropriate Grignard reagent to an aldehyde. Equation Transcription: Text Transcription: OH OH H C OH

Problem 15P Show how you would synthesize each tertiary alcohol by adding an appropriate Grignard reagent to a ketone. (a) 3-phenylhexan-3-ol (3 ways) (b) Ph 3 COH (c) 1-ethylcyclopentanol (d) 2-cyclopentylpentan-2-ol

Propose a mechanism for the reaction of acetyl chloride with phenylmagnesium bromide to give 1,1-diphenylethanol.

Problem 17P Show how you would add Grignard reagents to acid chlorides or esters to synthesize the following alcohols. (a) Ph3C-OH (b) 3-ethyl-2-methylpentan-3-ol (c) dicyclohexylphenylmethanol

A formate ester, such as ethyl formate, reacts with an excess of a Grignard reagent to give (after protonation) secondary alcohols with two identical alkyl groups. (a) Propose a mechanism to show how the reaction of ethyl formate with an excess of allyl- magnesium bromide gives, after protonation, hepta-1,6-dien-4-ol. (b) Show how you would use reactions of Grignard reagents with ethyl formate to synthe- size the following secondary alcohols. (i) pentan-3-ol (ii) diphenylmethanol (iii) trans,trans-nona-2,7-dien-5-ol

Show how you would synthesize the following alcohols by adding Grignard reagents to ethylene oxide.

In Section 9-7B, we saw how acetylide ions add to carbonyl groups in much the same way as Grignard and organolithium reagents. Acetylide ions also add to ethylene oxide much like Grignard and organolithium reagents. Predict the products obtained by adding the following acetylide ions to ethylene oxide, followed by a dilute acid workup. (a) \(H C \equiv C:^{-}\) (b) \(\mathrm{CH}_{3} \mathrm{CH}_{2}-\mathrm{C} \equiv \mathrm{C}:^{-}\) Equation Transcription: Text Transcription: HC \equiv C:- CH_3CH_2-C \equiv C:-

Recall from Section 9-7 how acetylide ions are alkylated by displacing unhindered alkyl halides. Like acetylide ions, Grignard and organolithium reagents are strong bases and strong nucleophiles. Fortunately, they do not displace halides as easily as acetylide ions do. If they did displace alkyl halides, it would be impossible to form the reagents from alkyl halides because whenever a molecule of reagent formed, it would react with a molecule of the halide starting material. All that would be formed is a coupling product. In fact, coupling is a side reaction that hurts the yield of many Grignard reactions. Equation Transcription: Text Transcription: H-CC:- R-CH2-Br H-CC-CH2-R + Br-

Predict the products of the following reactions.

Point out the flaws in the following incorrect Grignard syntheses.

Predict the products you would expect from the reaction of \(\mathrm{NaBH}_{4}\) with the following compounds. You may assume that these reactions take place in methanol as the solvent. Equation Transcription: Ph-COOH Text Transcription: NaBHa CH3-(CH2)8-CHO CH3CH2-C-OCH3 Ph-COOH

Repeat Problem 10-24 using \(\mathrm{LiA} 1 \mathrm{H}_{4}\) (followed by hydrolysis) as the reagent. Equation Transcription: Text Transcription: LiA1H_4

Show how you would synthesize the following alcohols by reducing appropriate carbonyl compounds.

Arrange the following compounds in order of decreasing acidity. \(\mathrm{CH}_{3} \mathrm{COOH} \quad \mathrm{CH}_{3} \mathrm{OH} \quad \mathrm{CH}_{3} \mathrm{CH}_{3} \quad \mathrm{CH}_{3} \mathrm{SO}_{3} \mathrm{H} \quad \mathrm{CH}_{3} \mathrm{NH}_{2} \quad \mathrm{CH}_{3} \mathrm{SH} \quad \mathrm{CH}_{3} \mathrm{C} \equiv \mathrm{CH}\) Equation Transcription: Text Transcription: CH3COOH CH3OH CH3CH3 CH3SO3H CH3NH2 CH3SH CH3CCH

Problem 29P Authentic skunk spray has become valuable for use in scent-masking products. Show how you would synthesize the two major components of skunk spray (3-methylbutane-1-thiol and but-2-ene-1-thiol) from any of the readily available butenes or from buta-1,3-diene.

Give IUPAC names for the following compounds.

Problem 30SP Starting from bromobenzene and any other reagents and solvents you need, show how you would synthesize the following compounds. Any of these products may be used as starting materials in subsequent parts of this problem. (a) 1-phenylpropan-1-ol (b) 1-phenylpropene (c) 1-phenylpropan-2-ol (d) 3-phenylprop-2-en-1-ol (e) 2-phenylbutan-2-ol (f) 2-phenylbut-2-ene

Give a systematic \(\text { (IUPAC) }\) name for each alcohol. Classify each as primary, secondary, or tertiary. Equation Transcription: Text Transcription: (IUPAC) OH Br-CHCH3 CH2OH

Give systematic \(\text { (IUPAC) }\) names for the following diols and phenols. Equation Transcription: Text Transcription: OH OH OH OH NO_2 OH CI Br

Problem 33SP Draw the structures of the following compounds. (Includes both new and old names.) (a) triphenylmethanol (b) 4-(chloromethyl)heptan-3-ol (c) 2-cyclohexen-1-ol (d) 3-cyclopentylhexan-3-ol (e) meso-2,4-pentanediol (f) cyclopentene glycol (g) 3-(iodomethyl)phenol (h) (2R,3R)-2,3-hexanediol (i) cyclopent-3-ene-1-thiol (j) dimethyl disulfide (k) 3-methylhex-4-yn-2-ol

Problem 34SP Predict which member of each pair has the higher boiling point, and explain the reasons for your predictions. (a) hexan-1-ol or 3,3-dimethylbutan-1-ol (b) hexan-2-one or hexan-2-ol (c) hexan-2-ol or hexane-1,5-diol (d) pentan-2-ol or hexan-2-ol

Problem 35SP Predict which member of each pair is more acidic, and explain the reasons for your predictions. (a) cyclopentanol or 3-chlorophenol (b) cyclohexanol or cyclohexanethiol (c) cyclohexanol or cyclohexanecarboxylic acid (d) butan-1-ol or 2,2-dichlorobutan-1-ol

Problem 36SP Predict which member of each group is most soluble in water, and explain the reasons for your predictions. (a) butan-1-ol, pentan-1-ol, or propan-2-ol (b) chlorocyclohexane, cyclohexanol, or cyclohexane-1,2-diol (c) phenol, cyclohexanol, or 4-methylcyclohexanol

Show how you would synthesize the following alcohols from appropriate alkenes. Equation Transcription: Text Transcription: OH CH_3 OH OH OH

Draw the organic products you would expect to isolate from the following reactions (after hydrolysis).

Show how you would use Grignard syntheses to prepare the following alcohols from the indicated starting materials and any other necessary reagents. (a) octan-3-ol from hexanal, \(\mathrm{CH}_{3}\left(\mathrm{CH}_{2}\right)_{4} \mathrm{CHO}\) (b) octan-1-ol from 1-bromoheptane (c) 1-cyclohexylethanol from acetaldehyde, \(\mathrm{CH}_{3} \mathrm{CHO}\) (d) 2-cyclohexylethanol from bromocyclohexane (e) benzyl alcohol \(\left(\mathrm{Ph}-\mathrm{CH}_{2}-\mathrm{OH}\right)\) from bromobenzene \(\text { (Ph - Br) }\) (g) cyclopentylphenylmethanol from benzaldehyde \((\mathrm{Ph}-\mathrm{CHO})\) Equation Transcription: Text Transcription: CH3(CH2)4CHO CH_3CHO (Ph-CH2-OH) (Ph-Br) OH CH_3 CH_3 OCH_2CH_3 (Ph-CHO)

Show how you would accomplish the following transformations. You may use any additional reagents you need.

Problem 41SP Show how you would synthesize: (a) 2-phenylethanol by the addition of formaldehyde to a suitable Grignard reagent (b) 2-phenylethanol from a suitable alkene (c) cyclohexylmethanol from an alkyl halide using an SN2 reaction (d) 3-cyclohexylpropan-1-ol by the addition of ethylene oxide to a suitable Grignard reagent (e) cis-pent-2-en-1-thiol from a suitable alkenyl halide (f) 2,5-dimethylhexane from a four-carbon alkyl halide

Complete the following acid–base reactions. In each case, indicate whether the equilibrium favors the reactants or the products, and explain your reasoning.

Suggest carbonyl compounds and reducing agents that might be used to form the following alcohols. (a) octan-1-ol (b) 1-cyclohexylpropan-1-ol (c) 1-phenylbutan-1-ol Equation Transcription: Text Transcription: OH HO CH_2OH HO OCH_3

Show how you would synthesize the following compounds from any starting materials containing no more than six carbon atoms. Equation Transcription: Text Transcription: OCH_2CH_3 CH_3

Geminal diols, or \(\text { 1, 1-diols }\) are usually unstable, spontaneously losing water to give carbonyl compounds. Therefore, geminal diols are regarded as hydrated forms of ketones and aldehydes. Propose a mechanism for the acid-catalyzed loss of water from \(\text { propane-2,2-diol }\) to give acetone. Equation Transcription: Text Transcription: 1,1-diols propane-2,2-diol CH_3 HO OH CH_3 C propane-2,2-diol H+ CH_3 C CH_3 H2O

Vinyl alcohols are generally unstable, quickly isomerizing to carbonyl compounds. Propose mechanisms for the following isomerizations. Equation Transcription: Text Transcription: OH H+ OH H+ OH -OH

Problem 47SP Compound A (C7H11Br) is treated with magnesium in ether to give B( C7H11MgBr) which reacts violently with D2O to give 1-methylcyclohexene with a deuterium atom on the methyl group (C). Reaction of B with acetone (CH3COCH3) followed by hydrolysis gives D ( C10H18O). Heating D with concentrated H2SO4 gives E( C10H16), which decolorizes two equivalents of Br2 to give F( C10H16Br4). E undergoes hydrogenation with excess H2 and a Pt catalyst to give isobutylcyclohexane. Determine the structures of compounds A through F, and show your reasoning throughout.

Grignard reagents react slowly with oxetane to produce primary alcohols. Propose a mechanism for this reaction, and suggest why oxetane reacts with Grignard reagents even though most ethers do not. Equation Transcription: Text Transcription: R-Mg-X R-CH2CH2CH2-O- +MgX salt of 1°alcohol

Determine the structures of compounds A through G, including stereochemistry where appropriate.

Problem 50SP Many hunting dogs enjoy standing nose-to-nose with a skunk while barking furiously, oblivious to the skunk spray directed toward them. One moderately effective way of lessening the amount of odor is to wash the dog in a bath containing dilute hydrogen peroxide, sodium bicarbonate, and some mild dish detergent. Use chemical reactions to describe how this mixture helps to remove the skunk spray from the dog. The two major components of skunk oil are 3-methylbutane-1-thiol and but-2-ene-1-thiol.

Propose structures for intermediates and products (A) through (K).

Problem 52SP Devise a synthesis for each compound, starting with methylenecyclohexane and any other reagents you need. (a) 1-methylcyclohexanol (b) cyclohexylmethanol (c) 1-(hydroxymethyl)cyclohexanol (d) trans-2-methylcyclohexanol (e) 2-chloro-1-methylcyclohexanol (f) 1-(phenylmethyl)cyclohexanol

Compare the properties of propan-2-ol (I) and the hexafluoro analog (II). (a) Compound II has almost triple the molecular weight of I, but II has a lower boiling point. Explain. (b) Explain why the dipole moment of Compound II is much lower than the dipole moment of I, despite the presence of the six electronegative fluorine atoms. (c) Why is II a stronger acid than I?

Predict the products of the following reactions. (a) \(\mathrm {CH_3CH_2Br}\) + \(\mathrm {Mg}\) (b) isobutyl iodide + \(2\ \mathrm{Li}\) (c) 1-bromo-4-fluorocyclohexane + \(\mathrm {Mg}\) (d) \(\mathrm {CH_2=CCl-CH_2CH_3}\) + \(2\ \mathrm{Li}\) Equation Transcription: Text Transcription: CH_{3}CH_{2}Br Mg 2 Li Mg THF CH_{2}=CCl-CH_{2}CH_{3} 2 Li