ORGANIC CHEMISTRY
5th Edition
ISBN: 9781259977596
Author: SMITH
Publisher: MCG
expand_more
expand_more
format_list_bulleted
Concept explainers
Question
Chapter 22, Problem 22.82P
Interpretation Introduction
Interpretation: An explanation, with reference to the accepted mechanism of nucleophilic acyl substitution, for the evidence of a tetrahedral intermediate is to be stated.
Concept introduction: The replacement or substitution of one
Expert Solution & Answer
Want to see the full answer?
Check out a sample textbook solutionStudents have asked these similar questions
Propose a mechanism for the conjugate addition of a nucleophile ( Nuc:" ) to acrylonitrile (
CH,=CHCN ). Use resonance forms to show how the cyano group activates the double
bond for conjugate addition.
Compelling evidence for the existence of a tetrahedral intermediate in nucleophilic acyl substitution was obtained in a series
of elegant experiments carried out by Myron Bender in 1951. The key experiment was the reaction of aqueous "OH with ethyl
benzoate (CeHgCoOCH,CH3) labeled at the carbonyl oxygen with 190. Bender did not allow the hydrolysis to go to completion,
and then examined the presence of a label in the recovered starting material. He found that some of the recovered ethyl
benzoate no longer contained a label at the carbonyl oxygen. With reference to the accepted mechanism of nucleophilic acyl
substitution, explain how this provides evidence for a tetrahedral intermediate.
The starting materiai contains a
label on the carbonyl oxygen.
CeH5 OCH,CH,
CH5 OCH,CH,
ethyl benzoate
Unlabeled starting
material was recovered.
The following reaction involves two sequential Heck reactions. Draw structural formu-
las for each organopalladium intermediate formed in the sequence and show how the
final product is formed. Note from the molecular formula given under each structural
formula that this conversion corresponds to a loss of H and I from the starting material.
Acetonitrile, CH,CN, is the solvent.
1% mol Pd(OAc),
4% mol Ph,P
CH,CN
C4H171
C4H16
Chapter 22 Solutions
ORGANIC CHEMISTRY
Ch. 22 - Prob. 22.1PCh. 22 - Draw the three possible resonance structures for...Ch. 22 - Prob. 22.3PCh. 22 - Give an IUPAC or common name for each compound. a....Ch. 22 - Problem 22.5 Draw the structure corresponding to...Ch. 22 - Problem 22.6 Explain why the boiling point of is...Ch. 22 - Problem 22.7 How would the compounds in each pair...Ch. 22 - Problem 22.8 Deduce the structures of compounds ...Ch. 22 - Problem 22.9 Without reading ahead in Chapter 22,...Ch. 22 - Rank the compounds in each group in order of...
Ch. 22 - Prob. 22.11PCh. 22 - Prob. 22.12PCh. 22 - Prob. 22.13PCh. 22 - Prob. 22.14PCh. 22 - Problem 22.15 Draw the products of each...Ch. 22 - Problem 22.16 Draw the products of each reaction.
...Ch. 22 - Prob. 22.17PCh. 22 - Problem 22.18 Draw a stepwise mechanism for the...Ch. 22 - Prob. 22.19PCh. 22 - Problem 22.20 Fenofibrate is a...Ch. 22 - Problem 22.21 What product is formed when the...Ch. 22 - How would you synthesize olestra from sucrose?
Ch. 22 - Problem 22.23 What is the composition of the soap...Ch. 22 - Problem 22.24 Draw a stepwise mechanism for the...Ch. 22 - Prob. 22.25PCh. 22 - Problem 22.26 Some penicillins cannot be...Ch. 22 - Prob. 22.27PCh. 22 - Prob. 22.28PCh. 22 - Prob. 22.29PCh. 22 - Problem 22.30 Glucosamine is a dietry supplement...Ch. 22 - Draw the products of each reaction. a. c. b.Ch. 22 - Draw a tautomer of each compound.
a. b. c.
Ch. 22 - Draw the product of each reaction. a. b.Ch. 22 - Draw the product of each reaction. a. b.Ch. 22 - Prob. 22.35PCh. 22 - Problem 22.36 Outline two different ways that can...Ch. 22 - 22.37 Rank the following compounds in order of...Ch. 22 - Prob. 22.38PCh. 22 - Prob. 22.39PCh. 22 - 22.40 Give the IUPAC or common name for each...Ch. 22 - 22.41 Give the structure corresponding to each...Ch. 22 - Prob. 22.42PCh. 22 - 22.43 Explain why is a stronger acid and a weaker...Ch. 22 - (a) Propose an explanation for the difference in...Ch. 22 - Draw the product formed when phenylacetic acid is...Ch. 22 - Draw the product formed when phenylacetonitrile ...Ch. 22 - 22.47 Draw the organic products formed in each...Ch. 22 - Prob. 22.48PCh. 22 - Prob. 22.49PCh. 22 - Prob. 22.50PCh. 22 - Prob. 22.51PCh. 22 - Prob. 22.52PCh. 22 - Prob. 22.53PCh. 22 - 22.54 Draw a stepwise mechanism f or the following...Ch. 22 - 22.55 When acetic acid () is treated with a trace...Ch. 22 - Prob. 22.56PCh. 22 - Prob. 22.57PCh. 22 - Draw a stepwise mechanism for the following...Ch. 22 - Prob. 22.59PCh. 22 - Prob. 22.60PCh. 22 - Prob. 22.61PCh. 22 - Draw a stepwise mechanism for the following...Ch. 22 - 22.63 Acid-catalyzed hydrolysis of forms compound...Ch. 22 - 22.64 What carboxylic acid and alcohol are needed...Ch. 22 - Problem 22.65 Devise a synthesis of each compound...Ch. 22 - Prob. 22.66PCh. 22 - Prob. 22.67PCh. 22 - Prob. 22.68PCh. 22 - Prob. 22.69PCh. 22 - 22.70 What polyester or poly amide can be prepared...Ch. 22 - 22.71 What two monomers are needed to prepare each...Ch. 22 - Prob. 22.72PCh. 22 - 22.73 How can IR spectroscopy be used to...Ch. 22 - 22.74 Rank the following compounds in order of...Ch. 22 - 22.75 Identify the structures of each compound...Ch. 22 - 22.76 Identify the structures of A and B, isomers...Ch. 22 - Prob. 22.77PCh. 22 - 22.78 Identify the structure of compound C...Ch. 22 - 22.79 Identify the structures of D and E, isomers...Ch. 22 - 22.80 With reference to amides A and B, the...Ch. 22 - Prob. 22.81PCh. 22 - Prob. 22.82PCh. 22 - Prob. 22.83PCh. 22 - Draw a stepwise mechanism for the following...Ch. 22 - Draw a stepwise mechanism for the following...
Knowledge Booster
Learn more about
Need a deep-dive on the concept behind this application? Look no further. Learn more about this topic, chemistry and related others by exploring similar questions and additional content below.Similar questions
- The following reactivity order has been found for the saponification of alkyl acetates by aqueous NaOH. Explain. CH3CO2CH3 > CH3CO2CH2CH3 > CH3CO2CH(CH3)2 > CH3CO2C(CH3)3arrow_forwardAcid-catalyzed hydrolysis of the following epoxide gives a trans diol. Of the two possible trans diols, only one is formed. How do you account for this stereoselectivity?arrow_forwardA step in a synthesis of PGE1 (prostaglandin E1, alprostadil) is the reaction of a trisubstituted cyclohexene with bromine to form a bromolactone. Propose a mechanism for formation of this bromolactone and account for the observed stereochemistry of each substituent on the cyclohexane ring. Alprostadil is used as a temporary therapy for infants born with congenital heart defects that restrict pulmonary blood flow. It brings about dilation of the ductus arteriosus, which in turn increases blood flow in the lungs and blood oxygenation.arrow_forward
- Following is a synthesis for toremifene, a nonsteroidal estrogen antagonist whose structure is closely related to that of tamoxifen. (a) This synthesis makes use of two blocking groups, the benzyl (Bn) group and the tetrahydropyranyl (THP) group. Draw a structural formula of each group and describe the experimental conditions under which it is attached and removed. (b) Discuss the chemical logic behind the use of each blocking group in this synthesis. (c) Propose a mechanism for the conversion of D to E. (d) Propose a mechanism for the conversion of F to toremifene. (e) Is toremifene chiral? If so, which of the possible stereoisomers are formed in this synthesis?arrow_forwardTreatment of 1-aminoadamantane, C10H17N, with methyl 2,4-dibromobutanoate in the presence of a nonnucleophilic base, R3N, involves two successive SN2 reactions and gives compound A. Propose a structural formula for compound A.arrow_forwardSolvolysis of the following bicyclic compound in acetic acid gives a mixture of products, two of which are shown. The leaving group is the anion of a sulfonic acid, ArSO3H. A sulfonic acid is a strong acid, and its anion, ArSO3, is a weak base and a good leaving group. Propose a mechanism for this reaction.arrow_forward
- -Hydroxyketones and -hydroxyaldehydes are also oxidized by treatment with periodic acid. It is not the -hydroxyketone or aldehyde, however, that undergoes reaction with periodic acid, but the hydrate formed by addition of water to the carbonyl group of the -hydroxyketone or aldehyde. Write a mechanism for the oxidation of this -hydroxyaldehyde by HIO4.arrow_forwardPh3P-CHCH3 H₂C H3C Aldehydes and ketones are converted into alkenes by means of a direct nucleophilic addition called the Wittig reaction. In the reaction, a triphenylphosphorine ylide, also called a phosphorane, adds to an aldehyde/ketone to give a four-membered cyclic intermediate called an oxaphosphetane. The oxaphosphetane is not isolated but instead spontaneously decomposes to release triphenylphosphine oxide and an alkene. CH3 00 + The ylide is formed by reaction of triphenylphosphine, a good nucleophile, with a primary alkyl halide in an SN2 reaction, followed by deprotonation of the carbon with a strong base, such as butyllithium. The carbonyl carbon and the carbon originally bonded to the halogen become the two carbons with the double bond in the product alkene X m CH3 The real value of the Wittig reaction lies in its ability to yield an alkene of predictable structure, as the C=C bond is precisely where the C=O bond was in the reactant and no isomers (other than E/Z isomers)…arrow_forwardCH3 Ph3P-CHCH3 H3C H3C Aldehydes and ketones are converted into alkenes by means of a direct nucleophilic addition called the Wittig reaction. In the reaction, a triphenylphosphorine ylide, also called a phosphorane, adds to an aldehyde/ketone to give a four-membered cyclic intermediate called an oxaphosphetane. The oxaphosphetane is not isolated but instead spontaneously decomposes to release triphenylphosphine oxide and an alkene. Ph3P-CHCH3 H3C The ylide is formed by reaction of triphenylphosphine, a good nucleophile, with a primary alkyl halide in an S 2 reaction, followed by deprotonation of the carbon with a strong base, such as butyllithium. The carbonyl carbon and the carbon originally bonded to the halogen become the two carbons with the double bond in the product alkene :0: CH3 Com The real value of the Wittig reaction lies in its ability to yield an alkene of predictable structure, as the C-C bond is precisely where the C=O bond was in the reactant and no isomers (other than…arrow_forward
- Br Brz CH3 CH3 H3C CH2CI2 H3C Br Electrophilic addition of bromine, Br2; to alkenes yields a 1,2-dibromoalkane. The reaction proceeds through a cyclic intermediate known as a bromonium ion. The reaction occurs in an anhydrous solvent such as CH,Cl). In the second step of the reaction, bromide is the nucleophile and attacks at one of the carbons of the bromonium ion to yield the product. Due to steric clashes, the bromide ion always attacks the carbon from the opposite face of the bromonium ion so that a product with anti stereochemistry is formed. Draw curved arrows to show the movement of electrons in this step of the mechanism. Arrow-pushing Instructions Br: :Br: .CH3 H3C H3C CH3 Br:arrow_forwardRank the attached compounds in order of increasing reactivity in asubstitution reaction with −CN as nucleophile.arrow_forwardH₂C=CHCCH3 then H3O+ The Michael reaction is a conjugate addition process wherein a nucleophilic enolate anion (the donor) reacts with an a,ß-unsaturated carbonyl compound (the acceptor). The best Michael reactions are those that take place when a particularly stable enolate anion is formed via treatment of the donor with a strong base. Alternatively, milder conditions can be used if an enamine is chosen as the donor, this variant is termed the Stork reaction. In the second step, the donor adds to the ẞ-carbon of the acceptor in a conjugate addition, generating a new enolate. The enolate abstracts a proton from solvent or from a new donor molecule to give the conjugate addition product. Draw curved arrows to show the movement of electrons in this step of the mechanism. Arrow-pushing Instructions N 9aarrow_forward
arrow_back_ios
SEE MORE QUESTIONS
arrow_forward_ios
Recommended textbooks for you
- Organic ChemistryChemistryISBN:9781305580350Author:William H. Brown, Brent L. Iverson, Eric Anslyn, Christopher S. FootePublisher:Cengage Learning
- EBK A SMALL SCALE APPROACH TO ORGANIC LChemistryISBN:9781305446021Author:LampmanPublisher:CENGAGE LEARNING - CONSIGNMENT
Organic Chemistry
Chemistry
ISBN:9781305580350
Author:William H. Brown, Brent L. Iverson, Eric Anslyn, Christopher S. Foote
Publisher:Cengage Learning
EBK A SMALL SCALE APPROACH TO ORGANIC L
Chemistry
ISBN:9781305446021
Author:Lampman
Publisher:CENGAGE LEARNING - CONSIGNMENT