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Organic Chemistry 2 > Chapter 21 - Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution Reactions > Flashcards

Chapter 21 - Carboxylic Acid Derivatives: Nucleophilic Acyl Substitution Reactions Flashcards

1
Q

An aldehyde or ketone undergoes _____ _____ and does not have any leaving groups.

A

nucleophilic addition

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2
Q

Carboxylic acid derivatives undergo _____ _____ _____ and does have a leaving group.

A

nucleophilic acyl substitution

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3
Q

Nucleophiles react more readily with _____ carbonyl groups.

A

unhindered

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4
Q 
Order in increasing reactivity:
thioester
ester
acid anhydride
acid chloride
amide
A 
amide
ester
thioester
acid anhydride
acid chloride
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5
Q

A _____ reactive derivative can be converted into a _____ one.

A

more; less

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6
Q

Acid halides and acid anhydrides react rapidly with _____.

A

water

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7
Q

Acid chloride and water yield _____ _____.

A

carboxylic acid

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8
Q

Acid anhydride and water yield _____ _____.

A

2 carboxylic acids

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9
Q

In hydrolysis, _____ is used as a reagent to make _____ _____.

A

water; carboxylic acids

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10
Q

In alcoholysis, _____ is used as a reagent to make _____.

A

alcohol; esters

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11
Q

In aminolysis, _____ or a(n) _____ is used to make an _____.

A

ammonia; amine; amide

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12
Q

In a reduction reaction, a(n) _____ _____ is used to make a(n) _____ or _____.

A

hydride source; aldehyde; alcohol

NaBH4, LiAlH4, H-

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13
Q

In a Grignard reaction, a(n) _____ reagent is used to make a(n) _____ or _____.

A

organometallic; ketone; alcohol

R’MgX

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14
Q

What reagent would you use to convert a carboxylic acid to an acid chloride? Acid bromide?

A

SOCl2

PBr3

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15
Q

With SOCl2, carboxylic acid is converted into a _____ _____ which then reacts with _____.

A

chlorosulfite intermediate; chloride

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16
Q

Acid anhydrides can be derived from two molecules of _____ _____ by heating to remove _____.

A

carboxylic acid; water

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17
Q

Conversion of carboxylic acid into esters occur through a reaction of a _____ _____ with a primary _____ _____.

A 
carboxylate anion (RO-); alkyl halide (CH3–I)
(RO- produced from reacting a carboxylic acid with NaOH or NaHCO3)
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18
Q

Fischer esterification reaction involves the synthesis of esters by an _____ _____ nucleophilic acyl substitution reaction of a carboxylic acid with an _____.

A

acid-catalyzed (H–Cl); alcohol

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19
Q

The conversion of carboxylic acids into amides is difficult with a direct reaction. It is prepared by activating the carboxylic acid with _____ followed by the addition of the amine.

A

DCC

amine = R–:NH2

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20
Q

Carboxylic acids are reduced by _____ to give _____ _____.

A

LiAlH4; primary alcohols

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21
Q

Acid chloride reacts with NH3 to yield _____.

A

an amide (–Cl ==> –NH2)

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22
Q

Acid chloride reacts with H20 to yield _____.

A

a carboxylic acid (–Cl ==> –OH)

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23
Q

Acid chloride reacts with R’–OH to yield _____.

A

an ester (–Cl ==> –OR’)

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24
Q

Acid chloride reacts with R’–COO- to yield _____.

A

an acid anhydride

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25
Q

Acid chloride reacts with R’2–CuLi to yield _____.

A

a ketone (–Cl ==> –R’)

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26
Q

A carboxylate ion is formed from reacting a carboxylic acid with _____ or _____.

A

NaOH; NaHCO3

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27
Q

Esters are produced in the reaction of acid chlorides with _____ in the presence of _____ or _____

A

alcohols; pyridine; NaOH

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28
Q

When converting acid halides into esters, the _____ _____ alcohol attacks the _____ _____.

A

less hindered; carbonyl carbon

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29
Q

In the conversion of acid halides into amides, _____ _____ cannot be used.

A

trisubstituted amines (R3N)

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30
Q

LiAlH4 reduces acid chlorides to yield _____ and then _____ _____.

A

aldehydes; primary alcohols

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31
Q

What mechanism does reduction occur?

A

nucleophilic acyl substitution

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32
Q

Grignard reagents react with acid chlorides to yield _____ _____ with two identical substituents.

A

tertiary alcohols

CH3MgBr/ether and then CH3MgBr/H3O+

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33
Q

Grignard reagents react with acid chlorides to yield tertiary alcohols with _____ _____ _____.

A

two identical substituents

34
Q

The diorganocopper reaction (Gilman reagent) converts an acid chloride into a(n) _____.

A

ketone

35
Q

The diorganocopper reaction (Gilman reagent) converts an acid chloride into a ketone. There is an _____ _____ intermediate.

A

acyl diorganocopper

36
Q

In the preparation of an acid anhydride, there is a nucleophilic acyl substitution of a(n) _____ with a(n) _____.

A

carboxylate; acid chloride

37
Q

In the conversion of acid anhydrides to esters, acetic anhydride forms _____ _____ from alcohols. This occurs in basic conditions = _____ / _____.

A

acetate esters; NaOH / H2O

38
Q

In the conversion of acid anhydrides to amides, acetic anhydride is used to prepare N-substituted _____ from amines. This occurs in basic conditions = _____ / _____.

A

acetamides; NaOH / H2O

39
Q

Esters are usually prepared from _____ _____.

A

carboxylic acids

40
Q

Acid chlorides are converted into esters by treatment with a(n) _____ in the presence of a(n) _____.

A

alcohol; base (pyridine or NaOH)

41
Q

What is the limitation when R–COOH is treated with 1. NaOH / 2. R’X to form R–COOR’?

A

–R’ can only come from a PRIMARY alkyl halide

42
Q

Go step by step to form an ester from a carboxylic acid.

A

R–COOH treated w/ SOCl2 ==> acid chloride

acid chloride treated w/ R’–OH / pyridine ==> R–COOR’

43
Q

Esters are less reactive toward nucleophiles as compared to _____ _____ or _____.

A

acid chlorides; anhydrides

44
Q

Cyclic esters are called _____ and react similarly to _____ _____.

A

lactones; acyclic esters

45
Q

Hydrolysis of esters forms _____ _____.

A

carboxylic acids

46
Q

An ester is hydrolyzed by aqueous _____ or a aqueous _____ to yield a carboxylic acid and an alcohol.

A

base; acid

47
Q

What is saponification?

A

ester hydrolysis in basic solution

48
Q

Nucleophilic addition of -OH to the ester carbonyl group gives the usual _____ _____ intermediate which is then deprotonated to form a(n) _____ ion.

A

tetrahedral alkoxide; carboxylate

49
Q

Fischer esterification is a(n) _____-catalyzed ester hydrolysis reaction. It involves a _____ intermediate and the transfer of a proton to OR’ to make it a better _____ _____.

A

acid; tetrahedral; leaving group

50
Q

Ammonia reacts with esters to form _____ because esters are _____ reactive.

A

amides; more

51
Q

A reduction (LiAlH4) of esters yields _____ _____.

A

primary alcohols

52
Q

A reduction (LiAlH4) of lactones yields a _____.

A

diol

53
Q

Esters react with 2 equivalents of a Grignard reagent (followed by H3O+) to yield a _____ alcohol

A

tertiary

54
Q

The aldehyde intermediate of ester reduction can be isolated if 1 equivalent of _____ is used as the reducing agent.

A

DIBAH (DIBAL-H)

55
Q

Amides are the _____ reactive of the common acid derivative.

A

least

56
Q

A cyclic amide is called a _____.

A

lactam

57
Q

You need at least _____ hydrogen(s) attached to nitrogen to make an amide.

A

one

58
Q

A tertiary amine (will / won’t) react with acid chloride.

A

won’t

59
Q

The conversion of amides into carboxylic acids is _____.

A

hydrolysis

60
Q

An amide in basic condition results in the addition of _____ and loss of the _____ ion.

A

hydroxide; amide

61
Q

After the loss of the amide ion, a _____ ion is produced when hydrolysis occurs in basic conditions.

A

carboxylate

62
Q

The conversion of amides into amines is _____.

A

reduction

63
Q

Amides are reduced with _____ to an _____ rather than an alcohol. (converts C=O ==> CH2)

A

LiAlH4; amine

64
Q

_____ cannot reduce an amide.

A

NaBH4

65
Q

LiAlH4 is effective with both acyclic and cyclic amides.

A

again, C=O ==> CH2 in lactams

66
Q

Nucleophilic carboxyl substitution in nature often involves a(n) _____ or _____ _____.

A

thioester; acyl phosphate

67
Q

Reaction of a(n) _____ and a(n) _____ _____ gives an ongoing cycle that produces a polyamide (nylon).

A

diamine; diacid chloride

68
Q

Reaction of a(n) _____ and a(n) _____ produces a polyester.

A

diol; diacid

69
Q

Step-growth polymers are formed on _____ side(s) of the reaction.

A

both

70
Q

Chain-growth polymers are formed on _____ side(s) of the reaction.

A

one

71
Q

Main classes of synthetic polymers are _____-growth polymers and _____-growth polymers.

A

chain; step

72
Q

Transesterification means a(n) _____ forms from an ester.

A

ester

73
Q

Glycolic acid, lactic acid, and 3-hydroxybutyric acid react with _____ in the presence of _____. They form polymers.

A

themselves; heat

74
Q

In the presence of _____, polylactic acid is hydrolyzed into _____ _____.

A

water; lactic acid

75
Q

In IR spectroscopy, carbonyl groups absorb around _____-_____ 1/cm.

A

1700; 1800

76
Q

In IR spectroscopy, acid chlorides absorb around _____ 1/cm.

A

1810

77
Q

In IR spectroscopy, acid anhydrides absorb around _____ 1/cm and also around _____ 1/cm.

A

1820; 1760

78
Q

In IR spectroscopy, esters absorb around _____ 1/cm. This is higher than _____ or _____.

A

1735; aldehydes; ketones

79
Q

Hydrogens on the carbon next to a C=O are near _____ δ in the H NMR spectrum.

A

2

80
Q

_____ _____ absorb in the same range so NMR does not distinguish them from each other.

A

Acid derivatives

81
Q

In C NMR, carbonyl carbon atoms of the various acid derivatives absorb from _____ δ to _____ δ.

A

170; 220

Organic Chemistry 2 (4 decks)

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