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Schaum's Outline of Organic Chemistry

George Hademenos, George Hademenos

Chapter 15

CARBONYL COMPOUNDS: ALDEHYDES AND KETONES - all with Video Answers

Educators


Chapter Questions

01:47

Problem 1

Give the common and IUPAC names for (a) $\mathrm{CH}_3 \mathrm{CHO}$, (b) $\left(\mathrm{CH}_3\right)_2 \mathrm{CHCH}_2 \mathrm{CHO},($ c) $\mathrm{CH}_3 \mathrm{CH}_2 \mathrm{CH}_2 \mathrm{CHClCHO}$, (e) $\left(\mathrm{CH}_3\right)_2 \mathrm{CHCOCH}_3,(e) \mathrm{CH}_3 \mathrm{CH}_2 \mathrm{COC}_6 \mathrm{H}_5,(f) \mathrm{H}_2 \mathrm{C}=\mathrm{CHCOCH}_3$.
(a) Acetaldehyde (from acetic acid), ethanal;
(b)
<smiles>C[C](C)CC=O</smiles>
$\beta$-methylbutyraldehyde, 3-methylbutanal;
(c) $\alpha$-chlorovaleraldehyde, 2 -chloropentanal;
(d) methyl isopropyl ketone, 3-methyl-2-butanone;
(e) ethyl phenyl ketone, 1-phenyl-1-propanone (propiophenone);
$(f)$ methyl vinyl ketone, 3-buten-2-one.
The $\mathrm{C}=\mathrm{O}$ group has numbering priority over the $\mathrm{C}=\mathrm{C}$ group.

Sima Sarker
Sima Sarker
Numerade Educator
01:01

Problem 1

What products are formed in the following reactions? (a) $\mathrm{CH}_3 \mathrm{CH}_2 \mathrm{OH}, \mathrm{Cr}_2 \mathrm{O}_7^{2-}, \mathrm{H}^{+} ;($b) $\mathrm{CH}_3 \mathrm{CHOHCH}_3, \mathrm{Cr}_2 \mathrm{O}_7^{2-}, \mathrm{H}^{+}\left(60^{\circ} \mathrm{C}\right) ;($ c $) \mathrm{CH}_3 \mathrm{COCl}, \mathrm{LiAl}\left(\mathrm{O}-t-\mathrm{C}_4 \mathrm{H}_9\right){ }_3 \mathrm{H} ;($ d $) \mathrm{CH}_3 \mathrm{COCl}_2 \mathrm{C}_6 \mathrm{H}_6, \mathrm{AlCl}_3 ;(e)$ $\mathrm{CH}_3 \mathrm{COCl}, \mathrm{C}_6 \mathrm{H}_5 \mathrm{NO}_2, \mathrm{AlCl}_3$
(a) $\mathrm{CH}_3 \mathrm{CHO}$ (some oxidation to $\mathrm{CH}_3 \mathrm{COOH}$ occurs).
(b)
<smiles>CC(C)=O</smiles>
(c)
<smiles>CC=O</smiles>
(d) $\mathrm{C}_6 \mathrm{H}_5 \mathrm{COCH}_3$.
(e) No reaction; acylation like alkylation does not occur because $\mathrm{NO}_2$ deactivates the ring.

Narayan Hari
Narayan Hari
Numerade Educator
01:08

Problem 2

Give structural formulas for (a) methyl isobutyl ketone, (b) phenylacetaldehyde, (c) 2-methyl-3pentanone, $(d)$ 3-hexenal, $(e) \beta$-chloropropionaldehyde.
(a)
<smiles>CC(=O)CC(C)C</smiles>
(b)
<smiles>O=CCc1ccccc1</smiles>
(c)
<smiles>CCC(=O)C(C)C</smiles>
(d)
<smiles>CCC=CCC=O</smiles>
(e)
<smiles>O=CCCCl</smiles>

Emily Himsel
Emily Himsel
Numerade Educator

Problem 2

Give mechanisms for (a) acid-catalyzed acetal formation,
(a)
<smiles>[R]C=[O+][R]O</smiles>
hemiacetal
<smiles>[R]OC([R])O[R]</smiles>
$$
+\mathrm{H}_2 \mathrm{O}
$$
acetal
(b) base induced hemiacetal formation with $\mathrm{OR}^{-}$in $\mathrm{ROH}$.

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01:36

Problem 3

Name the following compounds: (a) $\mathrm{OHCCH}_2 \mathrm{CH}_2 \mathrm{CH}_2 \mathrm{CH}\left(\mathrm{CH}_3\right) \mathrm{CHO}$, (b) $p-\mathrm{OHCC}_6 \mathrm{H}_4 \mathrm{SO}_3 \mathrm{H}$, (c) $\mathrm{H}_3 \mathrm{C} \stackrel{\Delta}{\mathrm{CHO}}$, (d) $o-\mathrm{BrC}_6 \mathrm{H}_4 \mathrm{CHO}$.
(a) 2-Methyl-1,6-hexanedial. (b) $-\mathrm{SO}_3 \mathrm{H}$ takes priority over $-\mathrm{CHO}$; thus $p$-formylbenzenesulfonic acid. (c) The corresponding acid is a cyclopropanecarboxylic acid, and -oxylic acid is replaced by -aldehyde: 2-methylcyclopropanecarbaldehyde. (d) The -oic acid in benzoic acid is replaced by -aldehyde: o-bromo-benzaldehyde (also called 2-bromobenzenecarbaldehyde).

Lottie Adams
Lottie Adams
Numerade Educator
06:55

Problem 4

(a) Draw (i) an atomic orbital representation of the carbonyl group and (ii) resonance structures. (b) What is the major difference between the $\mathrm{C}=\mathrm{O}$ and $\mathrm{C}=\mathrm{C}$ groups?

Kathleen Pankow
Kathleen Pankow
Numerade Educator

Problem 5

Isopropyl chloride is treated with triphenylphosphine $\left(\mathrm{Ph}_3 \mathrm{P}\right)$ and then with $\mathrm{NaOEt}$. $\mathrm{CH}_3 \mathrm{CHO}$ is added to the reaction product to give a compound, $\mathrm{C}_5 \mathrm{H}_{10}$. When $\mathrm{C}_5 \mathrm{H}_{10}$ is treated with diborane and then $\mathrm{CrO}_3$, a ketone is obtained. Give the structural formula for $\mathrm{C}_5 \mathrm{H}_{10}$ and the name of the ketone.
The series of reactions is:
$$
\begin{gathered}
\text { Formation of Ylide } \\
\left(\mathrm{CH}_3\right)_2 \mathrm{CHCl}+\mathrm{Ph}_3 \mathrm{P} \longrightarrow\left[\left(\mathrm{CH}_3\right)_2 \mathrm{CH}-\stackrel{+}{\mathrm{PPh}} \mathrm{Ph}_3\right] \stackrel{\mathrm{NaOEt}}{\longrightarrow}\left(\mathrm{CH}_3\right)_2 \mathrm{C}=\mathrm{PPh}_3+\mathrm{EtOH}+\mathrm{Na}^{+} \mathrm{Cl}^{-}
\end{gathered}
$$

Wittig Reaction
<smiles></smiles>
Anti-Markovnikov Hydroboration-Oxidation
<smiles>CC=C(C)C</smiles>
<smiles>CC(=O)CCC(C)C(C)(C)C</smiles>
3-Methyl-2-butanone

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04:17

Problem 5

Account for the following: (a) $n$-butyl alcohol boils at $118^{\circ} \mathrm{C}$ and $n$-butyraldehyde boils at $76^{\circ} \mathrm{C}$, yet their molecular weights are close, 74 and 72 , respectively; $(b)$ the $\mathrm{C}=\mathrm{O}$ bond $(0.122 \mathrm{~nm})$ is shorter than the $\mathrm{C}-\mathrm{O}$ $(0.141 \mathrm{~nm})$ bond; $(c)$ the dipole moment of propanal $(2.52 \mathrm{D})$ is greater than that of 1-butene $(0.3 \mathrm{D}) ;(d)$ carbonyl compounds are more soluble in water than the corresponding alkanes.
(a) H-bonding between alcohol molecules is responsible for the higher boiling point.
(b) The sharing of two pairs of electrons in $\mathrm{C}=\mathrm{O}$ causes the double bond to be shorter and stronger.
(c) The polar contributing structure [Problem 15.4(a)(ii)] induces the large dipole moment of the aldehyde.
(d) H-bonding between carbonyl oxygen and water renders carbonyl compounds more water-soluble than hydrocarbons.

Shahina -
Shahina -
Numerade Educator
01:49

Problem 6

Compare aldehydes and ketones as to stability and reactivity.
As was the case for alkenes, alkyl substituents lower the enthalpy of the unsaturated molecule. Hence, ketones with two R's have lower enthalpies than aldehydes with one R. The electron-releasing R's diminish the electrophilicity of the carbonyl C, lessening the chemical reactivity of ketones. Furthermore, the R's, especially large bulky ones, make approach of reactants to the $\mathrm{C}$ more difficult.

Shahina -
Shahina -
Numerade Educator
02:27

Problem 7

Draw up a table of corresponding sequential oxidation levels of hydrocarbons and organic $\mathrm{Cl}, \mathrm{O}$, and $\mathrm{N}$ compounds.
See Table 15-1.

Niamat Khuda
Niamat Khuda
Numerade Educator
05:59

Problem 8

Suggest a mechanism for the reaction of $\mathrm{RCH}_2 \mathrm{Cl}$ with DMSO.
A C-O bond is formed and the $\mathrm{Cl}^{-}$is displaced in Step I by an $\mathrm{S}_{\mathrm{N}} 2$ attack. The $\mathrm{C}=\mathrm{O}$ bond results from an $\mathrm{E} 2$ $\beta$-elimination of $\mathrm{H}^{+}$and $\mathrm{Me}_2 \mathrm{~S}$, a good leaving group as indicated in Step 2.
Step 1
an alkoxysulfonium salt
Step 2
<smiles>[R]CO[AsH3]</smiles>
$\frac{\text { base }}{-\mathrm{H}^{+}}-\mathrm{O}=\mathrm{CHR}+\mathrm{Me}_2 \mathrm{~S}$

Prashant Singh
Prashant Singh
Numerade Educator
03:55

Problem 9

Which is the only aldehyde that can be prepared by $\mathrm{HgSO}_4$-catalyzed hydration of an alkyne? Since the addition of $\mathrm{H}_2 \mathrm{O}$ to $\mathrm{C}=\mathrm{C}$ is Markovnikov regiospecific, $\mathrm{RC} \equiv \mathrm{CH}$ or $\mathrm{RC} \equiv \mathrm{CR}$ must give ketones. Only $\mathrm{HC}=\mathrm{CH}$ is hydrated to give an aldehyde, $\mathrm{CH}_3 \mathrm{CHO}$.

Ian Kaigh
Ian Kaigh
Numerade Educator
01:35

Problem 10

Suggest a mechanism for acylation of $\mathrm{ArH}$ with $\mathrm{RCOC}$ The mechanism is similar to that of alkylation:

Grigoriy Sereda
Grigoriy Sereda
Numerade Educator
03:11

Problem 11

Can formylation of an arene, ArH, with an acid chloride be employed to prepare ArCHO?
No. The needed acid chloride is the hypothetical "formyl chloride," $\mathrm{HCOCl}$. But this compound cannot be realized; attempts to prepare it from formic acid $\left(\mathrm{HCOOH}+\mathrm{SOCl}_2\right)$ yield only mixtures of $\mathrm{HCl}$ and carbon monoxide, $: \mathrm{C} \equiv \mathrm{O}$ :

Arenes can be formylated by generating the active intermediate, $: 0 \mathrm{O}=\dot{\mathrm{C}}-\mathrm{H}$, from reagents other than $\mathrm{HCOCl}$. The Gatterman-Koch reaction uses a high-pressure gaseous mixture of $\mathrm{CO}$ and $\mathrm{HCl}$.
$$
\mathrm{CO}+\mathrm{HCl} \frac{\mathrm{AKC}_1 \cdot \mathrm{CuCl}^{-}}{-\mathrm{Cl}^{-}} \mathrm{O}=\stackrel{+}{\mathrm{C}}-\mathrm{H} \frac{\mathrm{ArH}}{-\mathrm{H}^{+}}-\mathrm{ArCHO}
$$

Niamat Khuda
Niamat Khuda
Numerade Educator
10:14

Problem 12

(a) Why doesn't reaction of $\mathrm{RMgX}$ with $\mathrm{R}^{\prime} \mathrm{COCl}$ give a ketone? (b) Account for the different behaviors of $\mathrm{RMgX}$ and $\mathrm{R}_2 \mathrm{CuLi}$. (c) What is the relationship between the reactivity of an organometallic and the activity of the metal?
(a) The ketone $\mathrm{RCOR}^{\prime}$ is formed initially, but once formed, since it is more reactive than $\mathrm{RCOCl}$, it reacts further with $\mathrm{RMgX}$ to give the $3^{\prime}$ alcohol $\mathrm{R}^{\prime} \mathrm{R}_2 \mathrm{COH}$. (b) The C-to- $\mathrm{Mg}$ bond has much more ionic character than has the $\mathrm{C}$-to$\mathrm{Cu}$ bond. Therefore, the $\mathrm{R}$ group in $\mathrm{RMgX}$ is more like $\mathrm{R}^{--}$and is much more reactive. $(c)$ The more active the metal, the more apt it is to carry a + charge and the more apt is the C to carry a - charge.

Bobby Barnes
Bobby Barnes
University of North Texas
02:56

Problem 13

Synthesize: $(a)$ p-methoxybenzaldehyde from benzene; $(b)$ cyclohexylethanal by hydroboration and oxidation; $(c)$ phenylacetaldehyde, using 1,3-dithiane; $(d)$ phenyl $n$-propyl ketone from a dithiane; $(e)$ cyclohexyl phenyl ketone from $\mathrm{PhCOOH}$ and $\mathrm{RLi} ;(f)$ 2-heptanone, using a cuprate.

Lottie Adams
Lottie Adams
Numerade Educator

Problem 15

Show the substances needed to prepare the following compounds by the indicated reactions:
(a)
<smiles>CCC(=O)CCc1ccccc1</smiles>
(Grignard)
(b)
<smiles>O=C(C=CCc1ccccc1)Cc1ccccc1</smiles>
(Acylation of an alkene)
(c) 2, 4- $\mathrm{Cl}_2 \mathrm{C}_6 \mathrm{H}_3 \mathrm{COC}_6 \mathrm{H}_5$ Friedel-Crafts acylation)
(a) $\mathrm{R}^{\prime} \mathrm{C} \equiv \mathrm{N}+\mathrm{RMgX}$. The carbonyl $\mathrm{C}$ in $\mathrm{RCOR}^{\prime}$ and one alkyl group ( $\left.\mathrm{R}^{\prime}\right)$ come from $\mathrm{R}^{\prime}-\mathrm{C} \equiv \mathrm{N}$; the other $\mathrm{R}$ from $\mathrm{RMgX}$. The two possible combinations are:
$$
\mathrm{CH}_3 \mathrm{CH}_2 \mathrm{C} \equiv \mathrm{N}+\mathrm{ClMgCH}_2 \mathrm{CH}_2 \mathrm{C}_6 \mathrm{H}_5 \text { or } \mathrm{CH}_3 \mathrm{CH}_2 \mathrm{MgBr}+\mathrm{N} \equiv \mathrm{CCH}_2 \mathrm{CH}_2 \mathrm{C}_6 \mathrm{H}_5
$$
(b) The $\mathrm{R}$ attached to $\mathrm{C}=\mathrm{C}$ is part of the alkene. $\mathrm{O}={ }^{\mathrm{C}} \mathrm{R}^{\prime}$ comes from $\mathrm{R}^{\prime} \mathrm{COCl}$.
$$
\mathrm{C}_6 \mathrm{H}_5 \mathrm{CH}_2 \mathrm{CH}=\mathrm{CH}_2+\mathrm{ClCOCH}_2 \mathrm{C}_6 \mathrm{H}_5 \stackrel{\mathrm{BF}_3}{\longrightarrow} \text { product }
$$
(c) 2,4- $\mathrm{Cl}_2 \mathrm{C}_6 \mathrm{H}_3 \mathrm{COCl}+\mathrm{C}_6 \mathrm{H}_6 \stackrel{\mathrm{AlCl}_3}{\longrightarrow}$ product $\mathrm{C}_6 \mathrm{H}_5 \mathrm{COCl}$ and 1,3- $\mathrm{C}_6 \mathrm{H}_4 \mathrm{Cl}_2$ cannot react with $\mathrm{AlCl}_3$ because the two aryl Cl's deactivate the ring.

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Problem 16

Prepare the following compounds from benzene, toluene, and alcohols of four or fewer C's: $(a)$ 2-methylpropanal (isobutyraldehyde), (b) p-chlorobenzaldehyde, (c) p-nitrobenzophenone ( $p$ - $\mathrm{NO}_2 \mathrm{C}_6 \mathrm{H}_4 \mathrm{COC}_6 \mathrm{H}_5$ ), $(d)$ benzyl methyl ketone, (e) $p$-methylbenzaldehyde.
(a) $\left(\mathrm{CH}_3\right)_2 \mathrm{CHCH}_2 \mathrm{OH} \frac{\mathrm{Cu}}{250 \cdot \mathrm{C}}\left(\mathrm{CH}_3\right)_2 \mathrm{CHCHO}$ (RCHO is not oxidized further.)
(c) $\mathrm{C}_6 \mathrm{H}_5 \mathrm{CH}_3 \frac{\mathrm{HNO}_3}{\mathrm{H}_2 \mathrm{SO}_4}-p-\mathrm{O}_2 \mathrm{NC}_6 \mathrm{H}_4 \mathrm{CH}_3 \stackrel{\mathrm{KMnO}_4}{\mathrm{H}^{+}}$
$$
p-\mathrm{O}_2 \mathrm{NC}_6 \mathrm{H}_4 \mathrm{COOH} \stackrel{\mathrm{SOCl}_2}{\longrightarrow} p-\mathrm{O}_2 \mathrm{C}_6 \mathrm{H}_4 \mathrm{COCl} \underset{\mathrm{AlCl}_3}{\longrightarrow} p-\mathrm{C}_2 \mathrm{NC}_6 \mathrm{H}_4 \mathrm{COC}_6 \mathrm{H}_5
$$

We cannot acylate $\mathrm{C}_6 \mathrm{H}_5 \mathrm{NO}_2$ with $\mathrm{C}_6 \mathrm{H}_5 \mathrm{COCl}$ because $\mathrm{NO}_2$ deactivates the ring.
(d)
(e) $\mathrm{C}_6 \mathrm{H}_5 \mathrm{CH}_3+\mathrm{CO}, \mathrm{HCl} \underset{\mathrm{CuCl}}{\stackrel{\mathrm{AlCl}_3}{\longrightarrow}} p-\mathrm{CH}_3 \mathrm{C}_6 \mathrm{H}_4 \mathrm{CHO}$

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06:06

Problem 17

Give the products of reaction for $(a)$ benzaldehyde + Tollens' reagent; $(b)$ cyclohexanone + $\mathrm{HNO}_3$, heat; (c) acetaldehyde + dilute $\mathrm{KMnO}_4 ;(d)$ phenylacetaldehyde $+\mathrm{LiAlH}_4 ;(e)$ methyl vinyl ketone $+\mathrm{H}_2 / \mathrm{Ni} ;$ $(f)$ methyl vinyl ketone $+\mathrm{NaBH}_4 ;(g)$ cyclohexanone $+\mathrm{C}_6 \mathrm{H}_5 \mathrm{MgBr}$ and then $\mathrm{H}_3 \mathrm{O}^{+} ;(h)$ methyl ethyl ketone + strong oxidant; (i) methyl ethyl ketone $+\mathrm{Ag}\left(\mathrm{NH}_3\right)_2^{+}$.
(a) $\mathrm{C}_6 \mathrm{H}_5 \mathrm{COO}^{-} \mathrm{NH}_4^{+}, \mathrm{Ag}^{\circ}$
(b) $\mathrm{HOOC}\left(\mathrm{CH}_2\right)_4 \mathrm{COOH}$,
(c) $\mathrm{CH}_3 \mathrm{COOH}$,
(d) $\mathrm{C}_6 \mathrm{H}_5 \mathrm{CH}_2 \mathrm{CH}_2 \mathrm{OH}$,
(e) $\mathrm{CH}_3-\mathrm{CH}(\mathrm{OH}) \mathrm{CH}_2 \mathrm{CH}_3(\mathrm{C}=\mathrm{O}$ and $\mathrm{C}=\mathrm{C}$ are reduced),
(f) $\mathrm{CH}_3-\mathrm{CH}(\mathrm{OH}) \mathrm{CH}=\mathrm{CH}_2$ (only $\mathrm{C}=\mathrm{O}$ is reduced, not $-\mathrm{C}=\mathrm{C}-$ ).

Benjamin Angeles
Benjamin Angeles
Numerade Educator
03:37

Problem 18

Devise a mechanism for the Cannizzaro reaction from the reactions
$$
2 \mathrm{ArCDO} \underset{\mathrm{H}_2 \mathrm{O}}{\stackrel{\mathrm{OH}^{-}}{\longrightarrow}} \mathrm{ArCOO}^{-}+\mathrm{ArCD}_2 \mathrm{OH} \quad 2 \mathrm{ArCHO} \underset{\mathrm{D}_2 \mathrm{O}}{\stackrel{\mathrm{OD}^{-}}{\longrightarrow}} \mathrm{ArCOO}^{-}+\mathrm{ArCH}_2 \mathrm{OH}
$$

The D's from $\mathrm{OD}^{-}$and $\mathrm{D}_2 \mathrm{O}$ (solvent) are not found in the products. The molecule of ArCDO that is oxidized must transfer its D to the molecule that is reduced. A role must also be assigned to $\mathrm{OH}^{-}$.

Rashmi Sinha
Rashmi Sinha
Numerade Educator
08:56

Problem 19

For the Cannizzaro reaction, indicate $(a)$ why the reaction cannot be used with aldehydes having an $\alpha \mathrm{H},-\mathrm{CHCHO} ;(b)$ the role of $\mathrm{OH}^{-}$and $\mathrm{OD}^{-}$(Problem 15.18); (c) the reaction product with ethanedial, $\mathrm{O}=\mathrm{CH}-\mathrm{CH}=\mathrm{O}$; (d) the reaction products of a crossed-Cannizzaro reaction between (i) formaldehyde and benzaldehyde, (ii) benzaldehyde and $p$-chlorobenzaldehyde.
(a) An $\alpha \mathrm{H}$ is acidic and is removed by $\mathrm{OH}^{-}$, leaving a carbanion that undergoes other reactions.
(b) They are strong nucleophiles that attack the electrophilic $\mathrm{C}$ of $\mathrm{C}=\mathrm{O}$ to give a tetrahedral intermediate. This intermediate reestablishes the resonance-stabilized $\mathrm{C}=\mathrm{O}$ group by transferring an $: \mathrm{H}^{-}$to the $\mathrm{C}=\mathrm{O}$ of another aldehyde molecule.
(c) An internal Cannizzaro yields hydroxyacetic acid, $\mathrm{HOCH}_2 \mathrm{COOH}$.
(d) (i) $\mathrm{H}_2 \mathrm{CO}$ is mainly attacked by $\mathrm{OH}^{-}$because it is more electrophilic than $\mathrm{PhCHO}$, whose $\mathrm{Ph}$ group delocalizes the electron deficiency of the $\mathrm{C}$ of $\mathrm{C}=\mathrm{O}$. (ii) There is little difference in the reactivities of the two aldehydes, and both sets of products are found $\mathrm{PhCOOH}$ and $\mathrm{PhCH}_2 \mathrm{OH}$ mixed with $p-\mathrm{ClC}_6 \mathrm{H}_4 \mathrm{COOH}$ and $p-\mathrm{ClC}_6 \mathrm{H}_4 \mathrm{CH}_2 \mathrm{OH}$.

Zubair Abdulla
Zubair Abdulla
Numerade Educator
01:01

Problem 20

The order of reactivity in nucleophilic addition is

Account for this order in terms of steric and electronic factors.
A change from a trigonal $s p^2$ to a tetrahedral $s p^3 \mathrm{C}$ in the transition state is accompanied by crowding of the four groups on $\mathrm{C}$. Crowding and destabilization of the transition state is in the order
$$
\mathrm{CH}_2=\mathrm{O}<\mathrm{RCH}=\mathrm{O}<\mathrm{R}_2 \mathrm{C}=\mathrm{O}
$$

Also, the electron-releasing R's intensify the - charge developing on $\mathrm{O}$, which destabilizes the transition state and decreases reactivity.
lowers the enthalpy of the ground state, raises $\Delta H^{\ddagger}$ and decreases the reactivity of $\mathrm{C}=\mathrm{O}$ toward nucleophilic attack. Hence, acid derivatives RCOY, in which
$$
\mathrm{Y}=-\ddot{\mathrm{X}}:-\mathrm{NH}_2,-\ddot{\mathrm{O}} \mathrm{R},-\underset{\mathrm{O}}{\mathrm{O}}-\underset{\mathrm{O}}{\mathrm{C}}-\mathrm{R}
$$
are less reactive than $\mathrm{RCHO}$ or $\mathrm{R}_2 \mathrm{CO}$.

Narayan Hari
Narayan Hari
Numerade Educator
02:59

Problem 21

Explain the order of reactivity $\mathrm{ArCH}_2 \mathrm{COR}>\mathrm{R}_2 \mathrm{C}=\mathrm{O}>\mathrm{ArCOR}>\mathrm{Ar}_2 \mathrm{CO}$ in nucleophilic addition.

When attached to $\mathrm{C}=\mathrm{O}$, Ar's, like $-\mathrm{Y}$ : (Problem 15.20), are electron-releasing by extended $\pi$ bonding (resonance) and deactivate $\mathrm{C}=\mathrm{O}$. Two Ar's are more deactivating than one $\mathrm{Ar}$. In $\mathrm{ArCH}_2 \mathrm{COR}$ only the electronwithdrawing inductive effect of $\mathrm{Ar}$ prevails; consequently, $\mathrm{ArCH}_2$ increases the reactivity of $\mathrm{C}=\mathrm{O}$.

Kaitlynn Wade
Kaitlynn Wade
Numerade Educator
01:11

Problem 22

Why is cyanohydrin formation useful in synthesis?
The cyanohydrin not only adds an additional $\mathrm{C}$ at the site of the $\mathrm{C}=\mathrm{O}$ but also introduces two new functional groups, $\mathrm{OH}$ and $\mathrm{CN}$, which can be used to introduce other functional groups. The $\mathrm{OH}$ can be used to form an alkene $(\mathrm{C}=\mathrm{C})$, an ether $(-\mathrm{RO})$, or a halogen compound $(\mathrm{C}-\mathrm{X})$; the $\mathrm{C} \equiv \mathrm{N}$ can be reduced to an amine $\left(\mathrm{CH}_2 \mathrm{NH}_2\right)$, be hydrolyzed to a carboxyl $(\mathrm{COOH})$ group, or react with Grignard reagents if the $\mathrm{OH}$ is protected.

Narayan Hari
Narayan Hari
Numerade Educator
06:32

Problem 23

$\mathrm{NaHSO}_3$ reacts with $\mathrm{RCHO}$ in $\mathrm{EtOH}$ to give a solid adduct. (a) Write an equation for the reaction. (b) Explain why only $\mathrm{RCHO}$, methyl ketones $\left(\mathrm{RCOCH}_3\right)$ and cyclic ketones react. (c) If the carbonyl compound can be regenerated on treating the adduct with acid or base, explain how this reaction with $\mathrm{NaHSO}_3$ can be used to separate $\mathrm{RCHO}$ from noncarbonyl compounds such as $\mathrm{RCH}_2 \mathrm{OH}$.
(a) $\mathrm{HSO}_3^{-}$can protonate $\mathrm{RCHO}$.
Sodium bisulfite adduct (solid)
A $\mathrm{C}-\mathrm{S}$ bond is formed because $\mathrm{S}$ is a more nucleophilic site than $\mathrm{O}$.
(b) $\mathrm{SO}_3^{2-}$ is a large ion and reacts only if $\mathrm{C}=\mathrm{O}$ is not sterically hindered, as is the case for $\mathrm{RCHO}^{\mathrm{RCOCH}}$, and cyclic ketones.

Tom Rutherford
Tom Rutherford
Numerade Educator
05:13

Problem 24

Write the formula for the solid derivative formed when an aldehyde or ketone reacts with each of the following ammonia derivatives:
(a)
<smiles>NO</smiles>
(b)
<smiles>c1ccccc1</smiles>
(c)
<smiles>[NH]NC(N)=O</smiles>
Hydroxylamine
Phenylhydrazine
Semicarbazide

Carina Carlos
Carina Carlos
Numerade Educator

Problem 25

Why do carbonyl compounds having an $\alpha \mathrm{H}$ react with $\mathrm{R}_2 \mathrm{NH}\left(2^{\circ}\right)$ to yield enamines,
<smiles></smiles>
but give imines,
<smiles>[R20]=C(C)C(C)(C)C</smiles>
with $\mathrm{RNH}_2\left(1^{\circ}\right)$ ?

After protonation of the $\mathrm{O}$, the nucleophilic $\mathrm{RNH}_2$ adds to the $\mathrm{C}$ and the adduct loses $\mathrm{H}^{+}$, to give the carbinolamine. Dehydration proceeds by protonation of the $\mathrm{O}$ of $\mathrm{OH}$, loss of $\mathrm{H}_2 \mathrm{O}$, and then loss of $\mathrm{H}^{+}$, to give the imine.

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10:46

Problem 26

Reaction of 1 mole of semicarbazide with a mixture of 1 mol each of cyclohexanone and benzaldehyde precipitates cyclohexanone semicarbazone, but after a few hours the precipitate is benzaldehyde semicarbazone. Explain.

The $\mathrm{C}=\mathrm{O}$ of cyclohexanone is not deactivated by the electron-releasing $\mathrm{C}_6 \mathrm{H}_5$ and does not suffer from steric hindrance. The semicarbazone of cyclohexanone is the kinetically controlled product. Conjugation makes $\mathrm{PhCH}=\mathrm{NNHCONH}_2$ more stable, and its formation is thermodynamically controlled. In such reversible reactions the equilibrium shifts to the more stable product (Fig. 15-1).

Jennifer Hudspeth
Jennifer Hudspeth
Numerade Educator
01:30

Problem 27

Symmetrical ketones, $\mathrm{R}_2 \mathrm{C}=\mathrm{O}$, form a single oxime, but aldehydes and unsymmetrical ketones may form two isomeric oximes. Explain.

Aadit Sharma
Aadit Sharma
Numerade Educator
03:27

Problem 29

Show how a $\mathrm{C}=\mathrm{O}$ group can be protected by acetal formation in the conversion of $\mathrm{OHCCH}_2 \mathrm{C}=\mathrm{CH}$ to $\mathrm{OHCCH}_2 \mathrm{C}=\mathrm{CCH}_3$.

The introduction of $\mathrm{CH}_3$ requires that the terminal alkyne $\mathrm{C}$ first become a carbanion and then be methylated. Such a carbanion, acting like the $\mathrm{R}$ group of $\mathrm{RMgX}$, would react with the $\mathrm{C}=\mathrm{O}$ group of another molecule before it could be methylated. To prevent this, $\mathrm{C}=\mathrm{O}$ is protected by acetal fornation before the carbanion is formed. The acetal is stable under the basic conditions of the methylation reactions. The aldehyde is later unmasked by acidcatalyzed hydrolysis.

Mikayla Stephens
Mikayla Stephens
Numerade Educator
28:26

Problem 30

In acid, most aldehydes form nonisolable hydrates (gem-diols). Two exceptions are the stable chloral hydrate, $\mathrm{Cl}_3 \mathrm{CCH}(\mathrm{OH})_2$, and ninhydrin,
<smiles>O=C1c2ccccc2C(=O)C1(O)O</smiles>
(a) Given the bond energies 749,464 and $360 \mathrm{~kJ} / \mathrm{mol}$ for $\mathrm{C}=\mathrm{O}, \mathrm{O}-\mathrm{H}$ and $\mathrm{C}-\mathrm{O}$, respectively, show why the equilibrium typically lies toward the carbonyl compound. (b) Account for the exceptions.
(a) Calculating $\Delta H$ for
<smiles>CC#CO[PH+]=C(C)C</smiles>
we obtain
$$
\begin{aligned}
& {[749+2(464)]+[2(-360)+2(-464)]=\Delta H} \\
& (\mathrm{C}=\mathrm{O}) \quad(\mathrm{O}-\mathrm{H}) \quad(\mathrm{C}-\mathrm{O}) \quad(\mathrm{O}-\mathrm{H}) \\
& \text { cleavages } \\
& \text { formations } \\
& \text { endothermic } \\
& \text { exothermic } \\
&
\end{aligned}
$$
or $\Delta H=+29 \mathrm{~kJ} / \mathrm{mol}$. Hydrate formation is endothermic and not favored. The carbonyl side is also favored by entropy because two molecules,
are more random than 1 gem-diol molecule.
(b) Strong electron-withdrawing groups on an $\alpha \mathrm{C}$ destabilize an adjacent carbonyl group because of repulsion of adjacent + charges. Hydrate formation overcomes the forces of repulsion.

Susan Hallstrom
Susan Hallstrom
Numerade Educator
11:54

Problem 31

Show steps in the synthesis of cyclooctyne, the smallest ring with a triple bond, fron $\mathrm{C}_2 \mathrm{H}_5 \mathrm{OOC}\left(\mathrm{CH}_2\right)_6 \mathrm{COOC}_2 \mathrm{H}_5$.
The 1,8-diester is converted to an eight-membered ring acyloin, which is then changed to the alkyne.

Ian Kaigh
Ian Kaigh
Numerade Educator
02:49

Problem 32

Which alkenes are formed from the following ylide-carbonyl compound pairs? (a) 2-butanone and $\mathrm{CH}_3 \mathrm{CH}_2 \mathrm{CH}_2 \mathrm{CH}=\mathrm{P}\left(\mathrm{C}_6 \mathrm{H}_5\right)_3,($ b $)$ acetophenone and $\left(\mathrm{C}_6 \mathrm{H}_5\right)_3 \mathrm{P}=\mathrm{CH}_2,(c)$ benzaldehyde and $\mathrm{C}_6 \mathrm{H}_5-\mathrm{CH}=\mathrm{P}\left(\mathrm{C}_6 \mathrm{H}_5\right)_3$, (d) cyclohexanone and $\left(\mathrm{C}_6 \mathrm{H}_5\right)_3 \mathrm{P}=\mathrm{C}\left(\mathrm{CH}_3\right)_2$. (Disregard stereochemistry.)
The boxed portions below come from the ylide.
(a)
<smiles>CCCCCC</smiles>
(b)
<smiles>CC(C)(C)c1ccccc1</smiles>
(c) $\mathrm{C}_6 \mathrm{H}_5-\mathrm{CH}=\mathrm{CH}-\mathrm{C}_6 \mathrm{H}_5$
(d)
<smiles>CC(C)=C1CCCCC1</smiles>

Vasu Makani
Vasu Makani
Numerade Educator
02:25

Problem 33

$$
\text { Give structures of the ylide and carbonyl compound needed to prepare: }
$$

Ian Kaigh
Ian Kaigh
Numerade Educator

Problem 34

Use the Reformatsky reaction to prepare

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02:41

Problem 35

Propanal reacts with 1-butene in the presence of uv or free-radical initiators (peroxides, sources of RO-) to give $\mathrm{CH}_3 \mathrm{CH}_2 \mathrm{COCH}_2 \mathrm{CH}_2 \mathrm{CH}_2 \mathrm{CH}_3$. Give steps for a likely mechanism.

Niamat Khuda
Niamat Khuda
Numerade Educator
09:14

Problem 36

(a) What properties identify a carbonyl group of aldehydes and ketones? $(b)$ How can aldehydes and ketones be distinguished?
(a) A carbonyl group (1) forms derivatives with substituted ammonia compounds such as $\mathrm{H}_2 \mathrm{NOH}$, (2) forms sodium bisulfite adduct with $\mathrm{NaHSO}_3$, (3) shows strong ir absorption at $1690-1760 \mathrm{~cm}^{-1}(\mathrm{C}=\mathrm{O}$ stretching frequency), (4) shows weak $n-\pi^*$ absorption in uv at $289 \mathrm{~nm}$. (b) The $\mathrm{H}-\mathrm{C}$ bond in RCHO has a unique ir absorption at $2720 \mathrm{~cm}^{-1}$. In nmr the $\mathrm{H}$ of $\mathrm{CHO}$ has a very downfield peak at $\delta=9-10 \mathrm{ppm}$. RCHO gives a positive Tollens' test.

Ronald Prasad
Ronald Prasad
Numerade Educator
03:26

Problem 37

What are the similarities and differences between $\mathrm{C}=\mathrm{O}$ and $\mathrm{C}=\mathrm{C}$ bonds?
Both undergo addition reactions. They differ in that the $\mathrm{C}$ of $\mathrm{C}=\mathrm{O}$ is more electrophilic than a $\mathrm{C}$ of $\mathrm{C}=\mathrm{C}$, because $\mathrm{O}$ is more electronegative than $\mathrm{C}$. Consequently, the $\mathrm{C}$ of $\mathrm{C}=\mathrm{O}$ reacts with nucleophiles. The $\mathrm{C}=\mathrm{C}$ is nucleophilic and adds mainly electrophiles.

Nima Gharibi
Nima Gharibi
Numerade Educator
08:29

Problem 38

Give another acceptable name for each of the following: (a) dimethyl ketone, (b) 1-phenyl-2butanone, $(c)$ ethyl isopropyl ketone, $(d)$ dibenzyl ketone, $(e)$ vinyl ethyl ketone.
(a) acetone or propanone, (b) benzyl ethyl ketone, (c) 2-methyl-3-pentanone, (d) 1,3-diphenyl-2-propanone, (e) 1-penten-3-one.

Lottie Adams
Lottie Adams
Numerade Educator
01:36

Problem 39

Identify the substances (I) through (V).
(a) $\left(\right.$ I) $+\mathrm{H}_2 \stackrel{\mathrm{Pd}\left(\mathrm{BaSO}_4\right)}{\longrightarrow}\left(\mathrm{CH}_3\right)_2 \mathrm{CH}-\mathrm{CHO}$
(b)
<smiles>CC(=O)C(C)(C)C</smiles>
(c) (IV) $+\mathrm{H}_2 \mathrm{O} \stackrel{\mathrm{HgSO}_4 \mathrm{H}_2 \mathrm{SO}_4}{\longrightarrow}-\mathrm{CH}_3 \mathrm{CH}_2-\underset{\mathrm{O}}{\mathrm{C}}-\mathrm{CH}_3$
(d) (V) $\underset{-\mathrm{H}_2 \mathrm{O}}{\stackrel{\mathrm{H}_2 \mathrm{SO}_4}{\longrightarrow}}$
<smiles>CCC(=O)C(CC)(CC)CC</smiles>
(a)
<smiles>CC(C)C(=O)Cl</smiles>
(I) (b)
<smiles>CC(C)(C)C(=O)O[Na]</smiles>
(II), $\mathrm{CHI}_3$ (III)
(c) $\mathrm{H}-\mathrm{C} \equiv \mathrm{C}-\mathrm{CH}_2 \mathrm{CH}_3$ or $\mathrm{CH}_3-\mathrm{C} \equiv \mathrm{C}-\mathrm{CH}_3$ (IV)
(d)
<smiles>CCCCCCC(O)(CCC)C(O)CC</smiles>

Deepanshu Kumar
Deepanshu Kumar
Numerade Educator
01:02

Problem 40

By rapid test-tube reactions distinguish between (a) pentanal and diethyl ketone, $(b)$ diethyl keton and methyl n-propyl ketone, (c) pentanal and 2,2-dimethylpropanal, (d) 2-pentanol and 2-pentanone.
(a) Pentanal, an aldehyde, gives a positive Tollens' test (Ag mirror). (b) Only the methyl ketone gives CHI (yellow precipitate) on treatment with $\mathrm{NaOI}$ (iodoform test). (c) Unlike pentanal, 2,2-dimethylpropanal has no $\alpha \mathrm{H}$ an so does not undergo an aldol condensation. Pentanal in base gives a colored solution. $(d)$ Only the ketone 2-pentanon gives a solid oxime with $\mathrm{H}_2 \mathrm{NOH}$. Additionally, 2-pentanol is oxidized by $\mathrm{CrO}_3$ (color change is from orange-red t green). Both give a positive iodoform test.

Narayan Hari
Narayan Hari
Numerade Educator
04:07

Problem 41

Use benzene and any aliphatic and inorganic compounds to prepare (a) 1,1-diphenylethanol, ( 4,4-diphenyl-3-hexanone.
(a) The desired $3^{\circ}$ alcohol is made by reaction of a Grignard with a ketone by two possible combinations:
$$
\left(\mathrm{C}_6 \mathrm{H}_5\right)_2 \mathrm{CO}+\mathrm{CH}_3 \mathrm{MgBr} \text { or } \mathrm{C}_6 \mathrm{H}_5 \mathrm{COCH}_3+\mathrm{C}_6 \mathrm{H}_5 \mathrm{MgBr}
$$

Since it is easier to make $\mathrm{C}_6 \mathrm{H}_5 \mathrm{COCH}_3$ than $\left(\mathrm{C}_6 \mathrm{H}_5\right)_2 \mathrm{CO}$ from $\mathrm{C}_6 \mathrm{H}_6$, the latter pair is used. Benzene is used t prepare both intermediate products.
$$
\left.\begin{array}{c}
\mathrm{C}_6 \mathrm{H}_6+\mathrm{CH}_3 \mathrm{COCl} \stackrel{\mathrm{AlCl}_3}{\longrightarrow} \mathrm{C}_6 \mathrm{H}_5 \mathrm{COCH}_3 \\
+ \\
\mathrm{C}_6 \mathrm{H}_6 \stackrel{\mathrm{Br}_2}{\mathrm{Fe}} \mathrm{C}_6 \mathrm{H}_5 \mathrm{Br} \stackrel{\mathrm{Mg}}{\mathrm{Et}_2 \mathrm{O}}-\mathrm{C}_6 \mathrm{H}_5 \mathrm{MgBr}
\end{array}\right\} \stackrel{\text { 1. reaction }}{2 \cdot \mathrm{H}_2 \mathrm{O}}\left(\mathrm{C}_6 \mathrm{H}_5\right)_2 \mathrm{C}(\mathrm{OH}) \mathrm{CH}_3
$$
(b) The $4^{\circ} \mathrm{C}$ of $\mathrm{CH}_3 \mathrm{CH}_2 \mathrm{CO}^{\circ}{ }^{\circ} \mathrm{C} \mathrm{Ph}_2 \mathrm{CH}_2 \mathrm{CH}_3$ is adjacent to $\mathrm{C}=\mathrm{O}$, and this suggests a pinacol rearrangement of
<smiles>CCC(O)C(O)(O)CC</smiles>
which is made from $\mathrm{CH}_3 \mathrm{CH}_2 \mathrm{COPh}$ as follows:

Vasu Makani
Vasu Makani
Numerade Educator
09:21

Problem 42

Use butyl alcohols and any inorganic materials to prepare 2-methyl-4-heptanone.
The indicated bond
<smiles>CCC(=O)[14CH2][14CH](C)[14CH2]C</smiles>
is formed from 2 four-carbon compounds by a Grignard reaction.
2-Methyl-4-heptanol

Katie Miller
Katie Miller
Numerade Educator
01:29

Problem 43

Compound (A), $\mathrm{C}_3 \mathrm{H}_{10} \mathrm{O}$, forms a phenylhydrazone, gives negative Tollens' and iodoform tests and is reduced to pentane. What is the compound?

Phenylhydrazone formation indicates a carbonyl compound. Since the negative Tollens' test rules out an aldehyde, (A) must be a ketone. A negative iodoform test rules out the $\mathrm{CH}_3 \mathrm{C}=\mathrm{O}$ group, and the reduction product, pentane, establishes the C's to be in a continuous chain. The compound is $\mathrm{CH}_3 \mathrm{CH}_2 \mathrm{COCH}_2 \mathrm{CH}_3$.

Raghvendra Singh
Raghvendra Singh
Numerade Educator

Problem 44

A compound $\left(\mathrm{C}_5 \mathrm{H}_8 \mathrm{O}_2\right)$ is reduced to pentane. With $\mathrm{H}_2 \mathrm{NOH}$ it forms a dioxime and also gives positive iodoform and Tollens' tests. Deduce its structure.

Reduction to pentane indicates $5 \mathrm{C}$ 's in a continuous chain. The dioxime shows two carbonyl groups. The positive $\mathrm{CHI}_3$ test points to
<smiles>CC(C)=O</smiles>
while the positive Tollens' test establishes a $-\mathrm{CH}=\mathrm{O}$. The compound is
<smiles>CC(=O)CCC=O</smiles>

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01:01

Problem 45

The Grignard reagent of $\mathrm{RBr}(\mathrm{I})$ with $\mathrm{CH}_3 \mathrm{CH}_2 \mathrm{CHO}$ gives a $2^{\circ}$ alcohol (II), which is converted to $\mathrm{R}^{\prime} \mathrm{Br}$ (III), whose Grignard reagent is hydrolyzed to an alkane (IV). (IV) is also produced by coupling (I). What are the compounds (I), (II), (III), and (IV)?

Since $\mathrm{CH}_3 \mathrm{CH}_2 \mathrm{CHO}$ reacts with the Grignard of (I) to give (II) after hydrolysis, (II) must be an alkyl ethyl carbinol
<smiles>[R]C(O)CC</smiles>
Grignard of (I)
(II)

The conversion of (II) to (IV) is
<smiles>[R]C(O)CC</smiles>
<smiles>[R]C(Br)CC[C@H](C)Br</smiles>
<smiles>[R]C(Br)CCCCCC</smiles>
(II)
(III)
(IV)
(IV) must be symmetrical, since it is formed by coupling (I). $\mathrm{R}$ is therefore $-\mathrm{CH}_2 \mathrm{CH}_2 \mathrm{CH}_3$. (I) is $\mathrm{CH}_3 \mathrm{CH}_2 \mathrm{CH}_2 \mathrm{Br}$.
(IV) is $n$-hexane. (II) is $\mathrm{CH}_3 \mathrm{CH}_2 \mathrm{CH}(\mathrm{OH}) \mathrm{CH}_2 \mathrm{CH}_2 \mathrm{CH}_3$. (III) is $\mathrm{CH}_3 \mathrm{CH}_2 \mathrm{CHBrCH}_2 \mathrm{CH}_2 \mathrm{CH}_3$.

Narayan Hari
Narayan Hari
Numerade Educator
07:08

Problem 46

Translate the following description into a chemical equation: Friedel-Crafts acylation of resorcinol(1,3-dihydroxybenzene) with $\mathrm{CH}_3\left(\mathrm{CH}_2\right)_4 \mathrm{COCl}$ produces a compound which on Clemmensen reduction yields the important antiseptic, hexylresorcinol.

Anupa Sharad Medhekar
Anupa Sharad Medhekar
Numerade Educator
08:56

Problem 47

Treatment of benzaldehyde with HCN produces a mixture of two isomers that cannot be separated by very careful fractional distillation. Explain.
Formation of benzaldehyde cyanohydrin creates a chiral $\mathrm{C}$ and produces a racemic mixture, which cannot be separated by fractional distillation.

Ian Kaigh
Ian Kaigh
Numerade Educator
01:01

Problem 48

Prepare 1-phenyl-1-(p-bromophenyl)-1-propanol from benzoic acid, bromobenzene and ethanol.
The compound is a $3^{\circ}$ alcohol, conveniently made from a ketone and a Grignard reagent as shown.
<smiles>O=C(CCCCCC(=O)c1ccccc1)OC(=O)c1ccccc1</smiles>
<smiles>CCC(O)(c1ccccc1)c1ccccc1</smiles>

Narayan Hari
Narayan Hari
Numerade Educator
00:59

Problem 49

Convert cinnamaldehyde, $\mathrm{C}_6 \mathrm{H}_5-\mathrm{CH}=\mathrm{CH}-\mathrm{CH}=\mathrm{O}$, to 1-phenyl-1,2-dibromo-3-chloropropane, $\mathrm{C}_6 \mathrm{H}_5 \mathrm{CHBrCHBrCH}_2 \mathrm{Cl}$.

We must add $\mathrm{Br}_2$ to $\mathrm{C}=\mathrm{C}$ and convert $-\mathrm{CHO}$ to $-\mathrm{CH}_2 \mathrm{Cl}$. Since $\mathrm{Br}_2$ oxidizes $-\mathrm{CHO}$ to $-\mathrm{COOH},-\mathrm{CHO}$ must be converted to $\mathrm{CH}_2 \mathrm{Cl}$ before adding $\mathrm{Br}_2$.
$$
\mathrm{C}_6 \mathrm{H}_5-\mathrm{CH}=\mathrm{CH}-\mathrm{CH}=\mathrm{O} \stackrel{\text { I. } \mathrm{NaBH}_4}{2 . \mathrm{H}_2 \mathrm{O}}-\mathrm{C}_6 \mathrm{H}_5-\mathrm{CH}=\mathrm{CH}-\mathrm{CH}_2 \mathrm{OH} \stackrel{\mathrm{PCl}_3}{\longrightarrow}
$$

Narayan Hari
Narayan Hari
Numerade Educator

Problem 50

Compounds "labeled" at various positions by isotopes such as ${ }^{14} \mathrm{C}$ (radioactive), $\mathrm{D}$ (deuterium) and ${ }^{18} \mathrm{O}$ are used in studying reaction mechanisms. Suggest a possible synthesis of each of the labeled compounds below, using ${ }^{14} \mathrm{CH}_3 \mathrm{OH}$ as the source of ${ }^{14} \mathrm{C}, \mathrm{D}_2 \mathrm{O}$ as the source of $\mathrm{D}$, and $\mathrm{H}_2{ }^{18} \mathrm{O}$ as the source of ${ }^{18} \mathrm{O}$. Once a ${ }^{14} \mathrm{C}$ labeled compound is made, it can be used in ensuring syntheses. Use any other unlabeled compounds. (a) $\mathrm{CH}_3{ }^{14} \mathrm{CH}_2 \mathrm{OH}$, (b) ${ }^{14} \mathrm{CH}_3 \mathrm{CH}_2 \mathrm{OH}$, (c) ${ }^{14} \mathrm{CH}_3 \mathrm{CH}_2 \mathrm{CHO}$, (d $) \mathrm{C}_6 \mathrm{H}_5{ }^{14} \mathrm{CHO}$, (e) ${ }^{14} \mathrm{CH}_3 \mathrm{CHDOH},(f) \mathrm{CH}_3 \mathrm{CH}^{18} \mathrm{O}$.
(a) The $1^{\circ}$ alcohol with a labeled carbinol $\mathrm{C}$ suggests a Grignard reaction with $\mathrm{H}_2{ }^{14} \mathrm{C}=\mathrm{O}$.
(b) Now the Grignard reagent is labeled instead of $\mathrm{H}_2 \mathrm{CO}$.
$$
{ }^{14} \mathrm{CH}_3 \mathrm{OH} \stackrel{\mathrm{HBr}}{\longrightarrow}{ }^{14} \mathrm{CH}_3 \mathrm{Br} \underset{\mathrm{Et}_2 \mathrm{O}}{\stackrel{\mathrm{Mg}}{\longrightarrow}}{ }^{14} \mathrm{CH}_3 \mathrm{MgBr} \frac{1 . \mathrm{CH}_2 \mathrm{O}}{2 \cdot \mathrm{H}_2 \mathrm{O}^{-}}-{ }^{14} \mathrm{CH}_3 \mathrm{CH}_2 \mathrm{OH}
$$
(c)(e) D on carbinol $\mathrm{C}$ is best introduced by reduction of a $-\mathrm{CHO}$ group with a D-labeled reductant. ${ }^{14} \mathrm{CH}_3 \mathrm{CH}_2 \mathrm{OH}^{-}$ from $(b) \underset{\text { heat }}{\stackrel{\mathrm{Cu}}{ }}{ }^{14} \mathrm{CH}_3 \mathrm{CHO}$ then $\mathrm{D}_2 / \mathrm{Pt}$ or $\mathrm{LiAlD}_4 \longrightarrow{ }^{14} \mathrm{CH}_3 \mathrm{CHDOD} \stackrel{\mathrm{H}_2 \mathrm{O}}{\longrightarrow}{ }^{14} \mathrm{CH}_3 \mathrm{CHDOH}$. D of OD is easily exchanged with excess $\mathrm{H}_2 \mathrm{O}$.
(f) Add $\mathrm{CH}_3 \mathrm{CHO}$ to excess $\mathrm{H}_2{ }^{18} \mathrm{O}$ with a trace of $\mathrm{HCl}$.
$$
\mathrm{H}_2{ }^{18} \mathrm{O}+\mathrm{CH}_3 \mathrm{CHO} \stackrel{\mathrm{H}^{+}}{\rightleftharpoons}=\left[\begin{array}{c}
\mathrm{CH}_3 \mathrm{CH}^{18} \mathrm{OH} \\
\mathrm{OH}
\end{array}\right] \stackrel{\mathrm{H}^*}{=} \mathrm{CH}_3 \mathrm{CH}^{18} \mathrm{O}+\mathrm{H}_2 \mathrm{O}
$$
hydrate

The unstable half-labeled hydrate can lose $\mathrm{H}_2 \mathrm{O}$ to give $\mathrm{CH}_3 \mathrm{CH}^{18} \mathrm{O}$.

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Problem 52

Deduce the structure of a compound, $\mathrm{C}_4 \mathrm{H}_6 \mathrm{O}$, with the following spectral data: (a) Electronic absorption at $\lambda_{\max }=213 \mathrm{~nm}, \varepsilon_{\max }=7100$ and $\lambda_{\max }=320 \mathrm{~nm}, \varepsilon_{\max }=27$. (b) Infrared bands, among others, at 3000 , 2900,1675 (most intense) and $1602 \mathrm{~cm}^{-1}$. (c) $\mathrm{Nmr}$ singlet at $\delta=2.1 \mathrm{ppm}(3 \mathrm{H}$ s), three multiplets each integrating for $1 \mathrm{H}$ at $\delta=5.0-6.0 \mathrm{ppm}$.

The formula $\mathrm{C}_4 \mathrm{H}_6 \mathrm{O}$ indicates two degrees of unsaturation and may represent an alkyne or some combination of two rings, $\mathrm{C}=\mathrm{C}$ and $\mathrm{C}=\mathrm{O}$ groups.
(a) $\lambda_{\max }$ at $213 \mathrm{~nm}$ comes from the $\pi \rightarrow \pi^*$ transition. It is more intense than the $\lambda_{\max }$ at $320 \mathrm{~nm}$ from the $\mathrm{n} \rightarrow \pi^*$ transition. Both peaks are shifted to higher wavelengths than normal (190 and $280 \mathrm{~nm}$, respectively), thus indicating an $\alpha, \beta$-unsaturated carbonyl compound. The 2 degrees of unsaturation are a $\mathrm{C}=\mathrm{C}$ and a $\mathrm{C}=\mathrm{O}$.
(b) The given peaks and their bonds are $3000 \mathrm{~cm}^{-1}, s p^2 \mathrm{C}-\mathrm{H} ; 2900 \mathrm{~cm}^{-1}, s p^3 \mathrm{C}-\mathrm{H} ; 1675 \mathrm{~cm}^{-1}, \mathrm{C}=\mathrm{O}$ (probably conjugated to $\mathrm{C}=\mathrm{C}$ ); $1602 \mathrm{~cm}^{-1}, \mathrm{C}=\mathrm{C}$. All are stretching vibrations. Absence of a band at $2720 \mathrm{~cm}^{-1}$ means no aldehyde $\mathrm{H}$. The compound is probably a ketone.
(c) The singlet at $\delta=2.1 \mathrm{ppm}$ is from a
<smiles>CC(C)=O</smiles> There are also three nonequivalent vinylic H's $(\delta=5.0-6.0 \mathrm{ppm})$ which intercouple. The compound is
<smiles>C=CC(C)=O</smiles>
shown with nonequivalent H's.

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Problem 53

A compound, $\mathrm{C}_5 \mathrm{H}_{10} \mathrm{O}$, has a strong ir band at about $1700 \mathrm{~cm}^{-1}$. The nmr shows no peak at $\delta=9-10 \mathrm{ppm}$. The mass spectrum shows the base peak (most intense) at $m / e=57$ and nothing at $m / e=43$ or $m / e=71$. What is the compound?

The strong ir band at $1700 \mathrm{~cm}^{-1}$ indicates a $\mathrm{C}=\mathrm{O}$, accounting for the one degree of unsaturation. The absence of a signal at $\delta=9-10 \mathrm{ppm}$ means no
<smiles>CC=O</smiles>
proton. The compound is a ketone, not an aldehyde. Nmr is the best way to differentiate between a ketone and an aldehyde.
Carbonyl compounds undergo fragmentation to give stable acylium ions:
<smiles>[R]C[O+]=C([R])[R]</smiles>
The possible ketones are
<smiles>CCC(=O)CC</smiles>
(A)
<smiles>CCCC(C)=O</smiles>
(B)
<smiles>CC(=O)C(C)C</smiles>
(C)

Compounds (B) and $(\mathrm{C})$ would both give some $\mathrm{CH}_3 \mathrm{C} \equiv \mathrm{O}^{+}(m / e=43)$ and $\mathrm{C}_3 \mathrm{H}_7 \mathrm{C} \equiv \mathrm{O}^{+}(m / e=71)$. These peaks were absent; therefore (A), which fragments to $\mathrm{CH}_3 \mathrm{CH}_2 \mathrm{C} \equiv \mathrm{O}^{+}(m / e=57)$, is the compound.

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01:07

Problem 54

Give the steps in the preparation of DDT, $\left(p-\mathrm{ClC}_6 \mathrm{H}_4\right)_2 \mathrm{CHCCl}_3$, from choral (trichloroacetaldehyde) and chlorobenzene in the presence of $\mathrm{H}_2 \mathrm{SO}_4$.

Narayan Hari
Narayan Hari
Numerade Educator