Propose a mechanism for the aluminum chloride-catalyzed reaction of benzene with chlorine.

Explain why each compound or ion should be aromatic, antiaromatic, or nonaromatic. (a) The cyclonona-tetraene cation (b) The cyclononatetraene anion (c) The [16]annulene dianion (d) The [18]annulene...

Name the following compounds: (a) (b) (c) (d) (e) (f) (g) (h) CH,CH,C CH OH CH CH CH NO COOH Br OCH(CH)2 OH NO NO CH,OCH,CH,

Name the following compounds: (a) (b) (c) (d) (e) (f) (g) (h) CI Cl NO, OCH COOH CH,( OCH COOH Cl OH CI CI Cl CH CHCH,CH, CHO BFi

Predict the major products when the following compounds are irradiated by light and treated with (1) 1 equivalent of Br2 and (2) excess Br2. (a) Isopropylbenzene (b) (tetralin)

How would you convert the following compounds to aromatic compounds? (a) (b) (c) (d) (e) (f) Cl

Classify the following compounds as aromatic, antiaromatic, or nonaromatic. (a) (b) (c) (d)

Predict the major products formed when benzene reacts (just once) with the following reagents. (a) Tert-butyl bromide, AlC3 (b) 1-chlorobutane, AlC3 (c) Isobutyl alcohol + BF3 (d) Bromine + a nail...

(a) Outline the syntheses indicated in Solved Problem 18-2, beginning with aldehydes and alkyl halides. (b) Both of these syntheses of 1-phenylbuta-1, 3-diene form the central double bond. Show how...

Depending on the reaction conditions, two different imines of formula C8H9N might be formed by the reaction of benzaldehyde with methylamine. Explain, and give the structures of the two imines.

(a) Propose a mechanism for the acid-catalyzed reaction of cyclohexanone with ethylene glycol to give cyclohexanone ethylene acetal. (b) Propose a mechanism for the acid-catalyzed hydrolysis of...

Both Nabh4 and are commercially available, and D2O is common and inexpensive. Show how you would synthesize the following labeled compounds, starting with butan-2-one. (a) (b) (c) CH CH,-CH OD OD...

Show how you would synthesize each compound from starting materials containing no more than six carbon atoms. (a) (b) (c) CH2CH CHC CH

(a) Simple aminoacetals hydrolyze quickly and easily in dilute acid. Propose a mechanism for hydrolysis of the following aminoacetal: (b) The nucleosides that make up DNA have heterocyclic rings...

(a) Why do most long-chain fatty acids show a large peak in the mass spectrum at m z60? (b) Use equations to explain the prominent peaks at m/z 74 and m/z 87 in the mass spectrum of 2-methylpentanoic...

(a) The solution given for Solved Problem 20-1 was missing some important resonance forms of the intermediates shown in brackets. Complete this mechanism by drawing all the resonance forms of these...

Propose a mechanism for conversion of the dianion to the ketone under mildly acidic conditions.

(a) The Key Mechanism for Fischer esterification omitted some important resonance forms of the intermediates shown in brackets. Complete the mechanism by drawing all the resonance forms of these two...

Show how to synthesize the following compounds, using appropriate carboxylic acids and amines. (a) (b) (c) CH C N CH CH32 N,N-diethyl-meta-toluamide (DEET insect repellent) NHC -CH acetanilide NCH3)2...

Show how you would use extractions with a separatory funnel to separate a mixture of the following compounds: benzoic acid, phenol, benzyl alcohol, aniline.

Arrange each group of compounds in order of increasing basicity. (a) CH3COO-, ClCH2COO-, PhO- (b) Sodium acetylide, sodium amide, and sodium acetate (c) Sodium benzoate, sodium ethoxide, and sodium...

Predict the products (if any) of the following acid-base reactions. (a) acetic acid + ammonia (b) phthalic acid + excess NaOH (c) p-toluic acid + potassium trifluoroacetate (d) -bromopropionic acid +...

Give both IUPAC names and common names for the following compounds. (a) PhCH2CH2COOH (b) PhCO2K (c) (CH3)2CHCHBrCOOH (d) HOOCCH2CH(CH3)CO2H (e) (CH3)2CHCH2COONa (f) CH3CH(NH2)CH2COOH (g) (h) (i) COOH...

Arrange each group of compounds in order of increasing acidity. (a) Phenol, ethanol, acetic acid (b) P-toluenesulfonic acid, acetic acid, chloroacetic acid (c) Benzoic acid, o-nitrobenzoic acid,...

(a) Show how you would use acetic anhydride and an appropriate alcohol or amine to synthesize (i) benzyl acetate, (ii) N,N-diethylacetamide. (b) Propose a mechanism for each synthesis in part (a).

Propose a mechanism for the following ring-opening transesterification. Use the mechanism in Problem 21-13 as a model. H+ CH3OH HO OCH,

Predict the products, if any, of the following reactions. (a) (b) (c) (d) (e) (f) (g) (h) (i) (j) (1) LiAIH (2) HO COOH (1) NaCN (2) H,0, heat CH,Br (1) SoCh 2) AIC COOH KMnO,. Hho (warm, concd.)...

Propose a mechanism for the hydrolysis of N,N-dimethylacetamide (a) Under basic conditions. (b) Under acidic conditions.

Propose a mechanism for the basic hydrolysis of benzonitrile to the benzoate ion and ammonia.

Show how you would add a Grignard reagent to an ester or a nitrile to synthesize (a) 4-phenylheptan-4-ol (b) heptan-4-ol (c) pentan-2-one

Aldehydes, ketones, carboxylic acids, and esters all give strong carbonyl stretching absorptions in the IR spectrum. How can you use other peaks in their IR spectra to distinguish among these four...

Propose a mechanism for the formation of 9-hydroxynonanoic acid lactone, as shown in the preceding figure.

Draw structures to correspond with the following common and systematic names: (a) Phenyl formate (b) Cyclohexyl benzoate (c) Cyclopentyl phenylacetate (d) N-butylacetamide (e) N,N-dimethylformamide...

Predict the major products formed when benzoyl chloride (PhCOCl) reacts with the following reagents. (a) Ethanol (b) Sodium acetate (c) Aniline (d) Anisole and aluminum chloride (e) Excess...

Acid-catalyzed transesterification and Fischer esterification take place by nearly identical mechanisms. Transesterification can also take place by a base-catalyzed mechanism, but all attempts at...

An ether extraction of nutmeg gives large quantities of trimyristin, a waxy crystalline solid of melting point 57 C. The IR spectrum of trimyristin shows a very strong absorption at 1733 cm-1. Basic...

An enolate is a very strong nucleophile. Bromine is a strong electrophile, so it can react with much weaker nucleophiles. Give mechanisms for the reactions of bromine with cyclopentene and with...

Acid-catalyzed halogenation is synthetically useful for converting ketones to α, β-unsaturated ketones, which are useful in Michael reactions (Section 22-18). Propose a...

Show how you would accomplish the following multistep syntheses, using the indicated starting material and any necessary reagents. (a) hept-6-en-1-ol e-caprolactone (b) methoxybenzene...

Give the expected products for the aldol condensations of (a) Propanal (b) Phenylacetaldehyde (c) Pentan-3-one

(a) Show each step in the mechanism of the acid-catalyzed interconversion of (R)- and (S)-3-methylpentan-2-one. (b) When cis-2,4-dimethylcyclohexanone is dissolved in aqueous ethanol containing a...

A student wanted to dry some diacetone alcohol and allowed it to stand over anhydrous potassium carbonate for a week. At the end of the week, the sample was found to contain nearly pure acetone....

An unknown compound gives the NMR, IR, and mass spectra shown next. Propose a structure, and show how it is consistent with the observed absorptions. Show fragmentations that account for the...

The IR spectrum, 13C NMR spectrum, and 1HNMR spectrum of an unknown compound (C6H8O3) appear next. Determine the structure, and show how it is consistent with the spectra. wavelength (um) 5 5.5 6 710...

Propose a complete mechanism for the acid-catalyzed aldol condensation of acetone.

Cinnamaldehyde is used as a flavoring agent in cinnamon candies. Show how cinnamaldehyde is synthesized by a crossed aldol condensation followed by dehydration. cinnamaldehyde-C

A student intends to carry out the following synthesis: CH2 Ph (1) base (2) PhCH, Br

Predict the products from crossed Claisen condensation of the following pairs of esters. Indicate which combinations are poor choices for crossed Claisen condensations. (a) (b) (c) (d) Ph -CH2 C-OCH,...

Show the resonance forms for the enolate ions that result when the following compounds are treated with a strong base. (a) Ethyl acetoacetate (b) Pentane-2,4-dione (c) Ethyl a-cyanoacetate (d)...

Show how cyclohexanone might be converted to the following δ-diketone

Show how Claisen condensations could be used to make the following compounds. (a) (b) (c) (d) C Ph CHCHC-CH-CH --,, C-ocH,CH,

(a) Explain why the following substituted acetic acid cannot be formed by the malonic ester synthesis. (b) Sections 22-2B and 22-3 showed the use of lithium diisopropylamide (LDA) to deprotonate a...

Show the ketones that would result from hydrolysis and decarboxylation of the following β-keto esters. (a) (b) (c) PhCH,-CH-C-CH COOC,H C-C-CH COOCH,CH OCH,CH3

Predict the major products of the following reactions. (a) (b) (c) (1) LDA (2) CH2=CHCH-Br acetone LDA (2) CH,CHI (1) LDA ()CHI

Show how an acetoacetic ester synthesis might be used to form a -sikeone such as heptane- 2,6-dione.

Propose a mechanism for the conjugate addition of a nucleophile (Nuc) to acrylonitrile (H2C=CHCN) and to nitroethylene. Use resonance forms to show how the cyano and nitro groups activate the double...

Propose a mechanism for the following reaction. CH o H,CCH CH,CH,

Show how the following ketones might be synthesized by using the acetoacetic ester synthesis. (a) (b) (c) PhCH,CH-C CH CH H,C-CHCH,CH-CCH

(a) Although the following compound is a substituted acetone derivative, it cannot be made by the acetoacetic ester synthesis. Explain why (two reasons). (b) The use of LDA to make enolate ions...

Pentane-2,4-dione (acetylacetone) exists as a tautomeric mixture of 8% keto and 92% enol forms. Draw the stable enol tautomer, and explain its unusual stability. acetylacetone

Write equations showing the expected products of the following enamine alkylation and acylation reactions. Then give the final products expected after hydrolysis of the iminium salts. (a) Pyrrolidine...

Predict the products of the following Claisen condensations. (a) (b) (c) (d) (e) CH OCH3 CH3OH CH3 COOCH3 CH3OH OCH CH,CH,-C-CHCHCHCH C-0CH, CH,OHDieckmann) - - - NaOCH 3 CH,OH + CHO-C-C OCH CH2 C...

Allose is the C3 epimer of glucose. Draw the cyclic hemiacetal form of D-allose, first in the chair conformation and then in the Haworth projection.

Show how you would use an aldol, Claisen, or another type of condensation to make each compound. (a) (b) (c) (d) (e) (f) CHO COOEt ,, Ph

Show reaction sequences (not detailed mechanisms) that explain these transformations: (a) (b) CH,O 2 (1) NaOEt OEt 2) H COOH + CH2(COOEt)2 (1) NaOEt (2) HO+

(a) There is only one ketotriose, called dihydroxyacetone. Draw its structure. (b) There is only one aldotriose, called glyceraldehyde. Draw the two enantiomers of glyceraldehyde.

(a) Show that D-glucose, D-mannose, and D-fructose all give the same osazone. Show the structure and stereochemistry of this osazone. (b) D-Talose is an aldohexose that gives the same osazone as...

(a) Show the product that results when fructose is treated with an excess of methyl iodide and silver oxide. (b) Show what happens when the product of part (a) is hydrolyzed using dilute acid. (c)...

Classify the following monosaccharides. (Examples: D-aldohexose, L-ketotetrose.) (a) (+)-glucose (b) (-)-arabinose (c) L-fructose (d) (e) (f) (g) CHO HO HO OH HO CH,OH +)-gulose CH,OH HOH CH,OH...

(a) Give the products expected when (+)-glyceraldehyde reacts with HCN. (b) What is the relationship between the products? How might they be separated? (c) Are the products optically active? Explain.

Draw the following sugar derivatives. (a) Methyl -D-glucopyranoside (b) 2, 3, 4, 6-tetra-O-methyl-D-mannopyranose (c) 1, 3, 6-tri-O-methyl-D-fructofuranose (d) Methyl 2, 3, 4,...

The relative configurations of the stereoisomers of tartaric acid were established by the following syntheses: (1) D-(+)-glyceraldehyde HCN diastereomers A and B (separated) (2) Hydrolysis of A and...

Draw the structures (using chair conformations of pyranoses) of the following disaccharides. (a) 4-O-(-D-glucopyranosyl)-D-galactopyranose (b) -D-fructofuranosyl--D-mannopyranoside (c)...

Give the complete systematic name for each structure. (a) (b) (c) (d) HOCH, O OCH CH2OH OH H OCH CHO HO OH OH CH OH.O OH CH,OHo NH CH3

(a) Show how you would use a Strecker synthesis to make phenylalanine. (b) Propose a mechanism for each step in the synthesis in part (a).

Using Table 1.3, determine which is the more electropositive element: sodium or aluminum, carbon or nitrogen, carbon or silicon. Table 1.3 Table 1.3 Valence Electrons of the First 18 Elements Group I...

Write the structural formulas for all isomers of each of the following compounds, and name each isomer by the IUPAC system. (The number of isomers is indicated in parentheses.) a. C4H10 (2) b. C4H9Cl...

Examine the relationships of isomers as described in Figure 2.8 (p. 56). Then classify the following pairs of structures as structural isomers, conformers, configurational (cis-trans) isomers, or...

Write a structural formula for each of the following compounds: a. 1-bromo-3-heptene b. 3-methylcyclopentene c. Vinyl bromide d. vinylcyclohexane e. 1,3-difluoro-2-butene f. 4,5-dimethyl-2-heptyne g....

Devise a synthesis for each of the following, starting with benzene: a. M-bromobenzenesulfonic acid b. P-nitrotoluene

Name the following compounds: a. b. C. CI C Br d. Cl e. f. CH3 NO2 CH3 Cl g- h. CH CH, Br Br

The explosive TNT (2,4,6-trinitrotoluene) can be made by nitrating toluene with a mixture of nitric and sulfuric acids, but the reaction conditions must gradually be made more severe as the nitration...

Place the members of the following groups in order of decreasing priority according to the R-S convention: a. CH3-, H-, C6H5-, CH3CH2- b. CH3CH2-, CH3CH2CH2-, CH2=CH-, O=CH- c. CH3CH2-, HS-, H-, Br-...

Assume that the four groups in each part of Problem 5.34 are attached to one carbon atom. a. Draw a three-dimensional formula for the R configuration of the molecule in 5.34a and 5.34b. b. Draw a...

Rank the following five compounds in order of increasing acid strength: 2-chloroethanol, p-chlorophenol, p-methylphenol, ethanol, and phenol.

Arrange the compounds in each of the following groups in order of increasing solubility in water, and briefly explain your answers: a. 1-octanol; ethanol; ethyl chloride b. HOCH2(CHOH)3CH2OH;...

Name each of the following compounds: a. CH3CH2CH2OCH2CH(CH3)2 b. CH3OCH2CH(CH3)2 c. d. e. CH3CH2CH(OCH3)CH2CH2CH2OH f. g. h. CH3OCH2CH2C¡¡CH CH.CH-CH

Using eq. 10.42 as a model, write an equation for the hydrolysis of acetamide. R-C-NH.+H-C-OH +NH,(10.42) H+ or HOT amide acid

Complete the equation for each of the following reactions: a. CH3CH2CH2CO2H + PCl5 b. CH3(CH2)6CO2H + SOCl2 c. d. e. CH3(CH2)5CONH2 + LiAlH4 f. CH +KMnO4 CH3 co2NH+ heat CO,CH,CH, + LiAlH4

Place aniline, p-toluidine, and p-nitroaniline in order of increasing basicity. X=H X=CH, X= No, p-nitroaniline aniline p-toluidine NH,

Place the following compounds (a) in order of increasing basicity and (b) in order of increasing acidity. NHCCH3 NH2 NH2 acetanilide cyclohexylamine aniline

Give a synthesis of from aniline. NHCH2CHs

Give a synthesis for from toluene. H2N CH3 NH2

A sample of methylcyclohexane is suspected of being contaminated with toluene, from which it had been prepared by hydrogenation. At 261 nm, toluene has a molar absorptivity = 224, whereas...

Describe the bonding in methylsilane (H3CSiH3), assuming that it is analogous to that of ethane. What is the principal quantum number of the orbitals of silicon that are hybridized?

Keeping the same atomic connections and moving only electrons, write a more stable Lewis structure for each of the following. Be sure to specify formal charges, if any, in the new structure. (a) (b)...

Write structural formulas for all the constitutional isomers of molecular formula C3H6O that contain (a) Only single bonds (b) One double bond

Of the orbital overlaps shown in the illustration, one is bonding, one is anti bonding, and the third is nonbonding (neither bonding nor anti bonding). Which orbital overlap corresponds to which...

Give the IUPAC name for each of the following compounds: (a) CH3(CH2)25CH3 (b) (CH3)2CHCH2(CH2)14CH3 (c) (CH3CH2)3CCH(CH2CH3)2 (d) (e) (f) (g)

Identify the more stable stereoisomer in each of the following pairs, and give the reason for your choice: (a) cis- or trans-1-Isopropyl-2-methylcyclohexane (b) cis- or...