Give the IUPAC names of the following alcohols. (a) HO CH3 C CH2CH3 (a) (b) (b) Br OH

Give the IUPAC names of the following alcohols. (a) HO CH3 C CH2CH3 (a) (b) (b) Br OH (c) CH3 (c) OH (d) (d) CH3 OH (e) C H3C CH2OH Cl C C (e) CH3 H2 (f) (f) H H CH2CH2CH3 CH3 OH Br

Give both the IUPAC name and the common name for each alcohol. (a) CH3CH2CH(OH)CH3 (b) (b) OH (c) (c) OH (d) (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) C3H8O (b) C4H10O (c) C3H6O (d) C3H4O

Give a systematic (IUPAC) name for each diol. (a) \(CH_3 CH(OH)(CH_2)_4 CH(OH)C(CH_3)_3\) (b) \(HO-(CH_2)_8-OH\)

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 (e) OH OH H H or OH OH H H

Dimethylamine, (CH3)2NH, has a molecular weight of 45 and a boiling point of 7.4 C. Trimethylamine, (CH3)3N, has a higher molecular weight (59) but a lower boiling point (3.5 C). Explain this apparent discrepancy.

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

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 \(\left(-\mathrm{NO}_{2}\right)\) 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.

Which of the following compounds are suitable solvents for Grignard reactions? (a) n-hexane (b) CH3OCH3 (c) CHCl3 (d) cyclohexane (e) benzene (f) CH3OCH2CH2OCH3 THF (tetrahydrofuran) (g) O O (h) O 1,4-dioxane

Predict the products of the following reactions. (a) CH3CH2Br + Mg ether T (b) isobutyl iodide + 2Li hexane T (c) 1-bromo-4-fluorocyclohexane + Mg THF T (d) CH2CClCH2CH3 + 2 Li ether T

Show how you would synthesize the following primary alcohols by adding an appropriate Grignard reagent to formaldehyde. (a) (a) CH2OH (b) (b) OH (c) (c) CH2OH

Show two ways you could synthesize each of the following secondary alcohols by adding an appropriate Grignard reagent to an aldehyde. C OH (a) (b) (c) OH H OH

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. (1) ether solvent CH3 (2) H3O+ O C Cl + 2 MgBr CH3 OH C 1,1-diphenylethanol acetyl chloride phenylmagnesium bromide

Show how you would add Grignard reagents to acid chlorides or esters to synthesize the following alcohols. (a) Ph3COH (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 allylmagnesium bromide gives, after protonation, hepta-1,6-dien-4-ol. (b) Show how you would use reactions of Grignard reagents with ethyl formate to synthesize 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. (a) 2-phenylethanol (b) 4-methylpentan-1-ol (c) CH3 (c) CH2CH2OH

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) HCC- (b) CH3CH2CC-

Show how you would synthesize the following compounds from alkyl halides, vinyl halides, and aryl halides containing no more than six carbon atoms. (a) octane (b) vinylcyclohexane (c) trans-oct-3-ene (d) cyclopentyl propyl ketone

Predict the products of the following reactions. (a) sec@butylmagnesium iodide + D2O (b) n@butyllithium + CH3CH2OH (c) isobutylmagnesium bromide + but@1@yne

Point out the flaws in the following incorrect Grignard syntheses.

Predict the products you would expect from the reaction of NaBH4 with the following compounds. You may assume that these reactions take place in methanol as the solvent. (a) CH3 (CH2)8 CHO (b) (b) CH3CH2 C OCH3 O (c) PhCOOH (d) (d) O (e) O H (e) C O C O OCH3 (f) (f ) H O C O O

Repeat Problem 10-24 using \(LiAlH_4\) (followed by hydrolysis) as the reagent.

Show how you would synthesize the following alcohols by reducing appropriate carbonyl compounds. (a) heptan-1-ol (b) heptan-2-ol (c) 2-methylhexan-3-ol (d) O OH (d) O

Arrange the following compounds in order of decreasing acidity. CH3COOH CH3OH CH3CH3 CH3SO3H CH3NH2 CH3SH CH3CCH

Give IUPAC names for the following compounds. (a) (a) CH3 SH CH3CHCH2CHCH3 (b) CH3 CH3CH2 CH3 CH2SH C C (b) (c) (c) SH

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.

Draw structures and assign names for alcohols, phenols, diols, and thiols.

Predict relative boiling points, acidities, and solubilities of alcohols.

Show how to convert alkenes, alkyl halides, and carbonyl compounds to alcohols. (Problems 10-37, 38, 40, 41, 43, 52, 56, 57, and 57)

Predict the alcohol products of the hydration, hydroboration, and dihydroxylation of alkenes.

Use Grignard and organolithium reagents to synthesize primary, secondary, and tertiary alcohols with the required carbon skeletons.

Propose syntheses and oxidation products for simple thiols. (Problems 10-37, 40, and 50)

Give a systematic (IUPAC) name for each alcohol. Classify each as primary, secondary, or tertiary. (a) (a) OH (b) (b) OH Br CHCH3 (c) (c) Cl OH (d) (d) O Br H (e) (e) OH Cl f) (f) OH (g) (g) CH2OH

Give systematic (IUPAC) names for the following diols and phenols. (a) (a) Cl OH OH (b) (b) H H OH OH (c) NO2 (c) OH (d) Cl Br (d) OH

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

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

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

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

Draw the organic products you would expect to isolate from the following reactions (after hydrolysis). (a) (a) MgBr + H2C O (b) (b) MgCl + O (c) (c) CH CH3 CH3 MgI + Ph CHO (d) (d) O OH CH3MgI + (e) CHO + NaBH4 (e) (f) (f ) Ph Ph Ph MgBr + O C (g) (g) 2 Ph MgBr + O O (h) (h) 2 MgCl + Ph O C Cl (i) MgBr O + (i) (j) ( j) CH2 O C OCH3 + NaBH4 O (k) CH2 O C OCH3 + LiAlH4 (k) O (l) (l) (1) Hg(OAc)2, H2O (2) NaBH4 (m) (m) (1) BH3 . THF (2) H2O2, OH (n) (n) H H3C CH2CH2CH3 H C C cold, dilute KMnO4 OH (o) H3O+ (o) H H3C CH2CH2CH3 H C C HCO3H (p) (CH2CH)2CuLi + CH3CH2CHCHCH2Br

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

Show how you would synthesize the following alcohols from appropriate alkenes.

Show 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, CH3(CH2)4CHO (b) octan-1-ol from 1-bromoheptane (c) 1-cyclohexylethanol from acetaldehyde, CH3CHO (d) 2-cyclohexylethanol from bromocyclohexane (e) benzyl alcohol (PhCH2 OH) from bromobenzene (PhBr)

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

Show how you would synthesize the following: (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 acidbase reactions. In each case, indicate whether the equilibrium favors the reactants or the products, and explain your reasoning. (a) (a) CH3CH2 O + OH (b) Cl (b) KOH + Cl OH (c) (c) OH + CH3O (d) OH KOH (d) + (e) (CH3)3CO- + CH3CH2OH H (f) (CH3)3CO- + H2O H (g) KOH + CH3CH2OH H

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 (d) (d) OH (e) (e) HO CH2OH (f) (f ) HO O OCH3

Show how you would synthesize the following compounds from any starting materials containing no more than six carbon atoms.

Geminal diols, or 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 propane-2,2-diol to give acetone.

Vinyl alcohols are generally unstable, quickly isomerizing to carbonyl compounds. Propose mechanisms for the following isomerizations. H H H OH C C (a) CH C H H H (b) O (c) O OH OH O vinyl alcohol acetaldehyde H+ H+ OH

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. R Mg X + O R CH2 22 CH CH O +MgX Grignard reagent oxetane salt of 1 alcohol

Determine the structures of compounds A through G, including stereochemistry where appropriate. O A C6H12O heat B C6H10 CH3 D C6H12O G C10H16 F C10H18O (2) O (3) E C5H9Br C C5H8O (1) CH3MgI (2) H3O+ (2) H3O+ H2SO4 H2, Pt H2SO4 heat H2SO4 heat KMnO4 warm, concd. (1) CH3MgI (1) Mg, ether HBr PhCO3H H3O

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). Mg, ether (2) H3O Br2 (1) CH3(CH2) 3CHO CH3CH2Br KOH, H2O (1) O3, 78 C (2) (CH3) 2S (1) NaNH2, 150 C NaNH2 (2) H2O H2SO4, heat (1) Sia2BH (2) H2O2, NaOH 2 HBr 1-bromobutane (A) Na (B) (C) (D) (E) (F) CH3(CH2)  3CHO CH3CH2CH2CHO (G) non-1-yne (H) (K) (J) (I) (1) CH3 (2) H3O O C CH2CH3

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?

Compounds containing deuterium (D = 2 H) are useful for kinetic studies and metabolic studies with new pharmaceuticals. One way to introduce deuterium is by using the reagent LiAlD4, equivalent in reactivity to LiAlH4. Show how to make these deuterium-labeled compounds, using LiAlD4 and D2O as your sources of deuterium, and any non-deuterated starting materials you wish. (a) CH3CHDOH (b) CH3CD2OH (c) CH3CD2OD

Show how to make these deuterium-labeled compounds, using CD3MgBr and D2O as your sources of deuterium, and any non-deuterated starting materials you wish. (a) CH3CH(OD)CD3 (b) CH3C(OH)(CD3)2 (c) CD3CH2CH2OH (d) Ph(CD3)2COD

Often, compounds can be synthesized by more than one method. Show how this 3 alcohol can be made from the following: (a) two different ketones OH (b) two different alkenes (c) an ester (d) a 3 alkyl bromide

Show how this 1 alcohol can be made from the following: OH H H (a) a 1 alkyl bromide (b) formaldehyde (c) a 7-carbon aldehyde (d) a carboxylic acid (e) an alkene (f) ethylene oxide

For each synthesis, start with bromocyclohexane and predict the products. Assume that an excess of each reactant is added so that all possible reactions that can happen will happen. (a) (a) Br KOH MgBr (1) O3, 78 C dilute H3O+ (2) Me EtOH, 2S ether A B C (b) (b) Br KOH KMnO4 LiAlH4 dilute H3O+ EtOH, NaOH, ether A E F (c) (c) Br KOH mCPBA PhMgBr dilute H3O+ H2SO4 EtOH, ether

Ever since the Grignard reaction was discovered to react with ethylene oxide, chemists have experimented with other epoxides to test the limits of this reaction (which chemists call the scope of the reaction). The conclusion is that the success of the Grignard reaction is limited by steric hindrance in the epoxide. One group published results of several Grignard reagents on one epoxide; one of their products is shown here. What Grignard reagent and what epoxide were used to make this compound? Comment on the steric requirements of the epoxide and the stereochemistry of the product. (Reference: Schomaker, J. M., et al., Org. Lett., 2003, 5(17), 3089.)

Problem 8-54 describes a new method to perform ozonolysis reactions that used pyridine (py) to generate the final aldehydes and ketones in a non-aqueous reaction medium. In a subsequent publication (J. Org. Chem., 2013, 78, 42), Professor Dussault (U. of Nebraska at Lincoln) described a “tandem” process in which two reactions are performed sequentially without having to isolate the intermediate aldehyde or ketone. Show the final product from each sequence. (Hint: The isolated products were from the larger part of the structure. Ignore stereochemistry.)