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[Session 7]
Carboxylic acids
[PHA2103] ndash [Organic Chemistry II]
apt Nurul Fajry Maulida MLifeSc
Learning objectives
In this session the students are able to describe the properties of carboxylic acids their general synthesis and reactivity and the example of carboxylic acid drugs
Contents Carboxylic Acids
1 Naming
2 Properties
3 General Synthesis
4 Different reactions involving carboxylic acid
5 Drugs containing carboxylic acid
1 Naming
Simple carboxylic acids derived from open-chain alkanes are systematically named by replacing the terminal -e of the corresponding alkane name with -oic acid The CO2H carbon atom is numbered C1
Compounds that have a -CO2H group bonded to a ring are named using the suffix -carboxylic acid The CO2H carbon is attached to C1 in this system and is not itself numberedAs a substituent the CO2H group is called a carboxyl group
Systematic Name
The names of acylgroups R-C=O derived from the parent acids
Common Name1 Naming
2 Properties
Sp2 hybridized plannar with C-C=O and O=C-O bond angles of approximately 120o
Strong H bonding has effect on boiling points carboxylic acids boil less easily than their corresponding alcoholsAcetic acid 1170oCEthanol 783oC
Carboxylic acids with more than six carbons are only slightly soluble in water The alkali metal salts of carboxylic acids are often highly water-soluble
Carboxylic acids dissociate slightly in dilute aqueous solution to give H3O+ and carboxylate anions RCO2
-
The extent of dissociation is given by an acidity constant Ka
Carboxylic acid is much weaker than mineral acids much stronger acids than alcohols and phenols
Why are carboxylic acids so much more acidic than alcohols even though both contain OH groups
the negative charge is delocalized over two equivalent oxygen atoms
the negative charge is localized on a single electronegative atom
2 Properties
The dissociation of a carboxylic acid is an equilibrium process any factor that stabilizes the carboxylate anionrelative to undissociated carboxylic acid will drive the equilibrium toward increased dissociation and result in increased acidity
the electron-withdrawing effect of the electronegative oxygen atom
three electron-withdrawing fluorine atoms delocalize the negative charge in the trifluoroacetate anion stabilizing the ion and increasing the acidity of CF3CO2H
Substituent effects on the acidity of p-substituted Benzoic Acids
2 Properties
Electron-donating (activating) group such as methoxy decreases acidity by destabilizing the carboxylate anionElectron-withdrawing (deactivating) group such as nitro increases acidity by stabilizing the carboxylate anion
2 Properties
3 General Synthesis
Oxidation of a substituted alkylbenzene with KMnO4 or Na2Cr2O7 gives a substituted benzoic acid
Both primary and secondary alkyl groups can be oxidized but tertiary groups are not affected
Oxidation of a primary alcohol or an aldehyde yields a carboxylic acidPrimary alcohols amp aldehyde are often oxidized with CrO3 in aqueous acid
bull SN2 reaction of alkyl halides rarr Nitrilesrarr hydrolysis of nitrile
the product acid has one more carbon than the starting alkyl halide
3 General Synthesis
bull Caboxylation of Grignard Reagents
bull Reaction of a Grignard reagent with CO2 (steam of dry CO2 gas) to yield a metal carboxylate followed by protonation to give a carboxylic acid
The organomagnesium halide adds to a C=O bond of carbon dioxide
3 General Synthesis
LiAlH4
4 Different reactions involving carboxylic acid
4 Different reactions involving carboxylic acid
5 Drugs containing carboxylic acid
bull Ciprofloxacin is a second generationfluoroquinolonederivative antibiotics
CinoxacinSynthetic antimicrobial related to oxolinic acid and nalidixic acid and used in urinary tract infections
Fluciclovine is indicated as a detection agent for positron emission tomography (PET) in men with suspected prostate cancer recurrence based on elevated blood prostate specific antigen (PSA) levels
L-Proline is extremely important for the proper functioning of joints and tendons and also helps maintain and strengthen heart muscles
Contents Nitriles
1 Naming
2 Properties
3 General Synthesis
4 Different reactions involving nitriles
5 Drugs containing nitriles
1 Naming
bull Compounds containing the CN functional group are called nitriles and can undergo some chemistry similar to carboxylic acids
bull Simple open- chain nitriles are named by adding -nitrile as a suffix to the alkane name
bull The nitrile carbon numbered C1
bull Nitriles can also be named as derivatives of carboxylic acids by replacing the -ic acid or -oic acid ending with -onitrile or by replacing the -carboxylic acid ending with -carbonitrile
bull The nitrile carbon atom is attached to C1 but is not itself numbered
bull If another carboxylic acid derivative is present in the same molecule the prefix cyano- is used for the CN group
bull Nitriles are analogous to carboxylic acids in that both have a carbon atom with three bonds to an electronegative atom and both contain pi bond
bull Some reactions of nitriles and carboxylic acids are similar
bull Both are electrophiles and undergo nucleophilic addition reactions
2 Properties
bull Cyanocycline A has been isolated from the bacterium Streptomyceslavendulae and was found to have antimicrobial and antitumor activity
bull More than 1000 cyanogenic glycosides are derived primarily from plants cyanogenic glycosides contain a sugar with an acetal carbon one oxygen of which is bonded to a nitrile-bearing carbon (sugar -1113148 O-1113148 C-1113148 CN)
On hydrolysis with aqueous acid the acetal is cleaved generating a cyanohydrin (HO1113148 -C-1113148 CN) which releases hydrogen cyanide
2 Properties
3 General Synthesis
(a) SN2 reaction of CN- with primary or secondary alkyl halide (already discussed)
(b) Dehydration of a primary amides (RCONH2)
bull The dehydration occurs by initial reaction of SOCl2 on the nucleophilic amide oxygen atom followed by deprotonation and a subsequent E2-like elimination reaction
4 Different reactions involving nitriles
bull Like a carbonyl group a nitrile group is strongly polarized and has an electrophiliccarbon atom
bull Nitriles react with nucleophiles to yield sp2-hybridized imine anions in a reaction analogous to the formation of an sp3-hybridized alkoxide ion by nucleophilicaddition to a carbonyl group
bull Some general reactions
4 Different reactions involving nitriles
(a) Hydrolysis to yield carboxylic acids
The reaction occurs in either basic or acidic aqueous solution
4 Different reactions involving nitriles
bull Nucleophilic addition of hydroxide ion to the amide carbonyl group yields a tetrahedral alkoxide ion Expulsion of amide ion NH21113148 as leaving group gives the carboxylate ion thereby driving the reaction toward the products Subsequent acidification in a separate step yields the carboxylic acid
4 Different reactions involving nitriles
(b) Reduction to yield primary amines (RNH2)
4 Different reactions involving nitriles
(c) Reaction with Grignard reagents to yield ketones
4 Different reactions involving nitriles
5 Drugs containing nitriles
Febuxostat is a xanathine oxidase(XO) inhibitor indicated in patients with gout suffering from hyperuricemia and is used in its chronic management
MilrinoneIndicated for the treatment of congestive heart failure
Ruxolitinibindicated to treat bone marrow cancer specifically intermediate or high-risk myelofibrosis
Saxagliptinorally active hypoglycemic (anti-diabetic drug) of the new dipeptidyl peptidase-4 inhibitor class of drugs
References
httpswwwamazoncomOrganic-Chemistry-Paula-Yurkanis-Bruice-ebookdpB01B7OIMJS
McMurry J E 2012 Organic Chemistry 8th Edition Brooks Cole Pub USA (ISBN 978-0495118374)
Klein DR 2012 Organic Chemistry as a Second Language Book 1 and 2
Fessenden RJ and Fessenden JS 1982 Organic Chemistry PWS Publisher
httpsdrivegooglecomfiled1sAZjTk9eMMzveBMea3QxNAwBLrhKpvNfviewusp=sharing
Learning objectives
In this session the students are able to describe the properties of carboxylic acids their general synthesis and reactivity and the example of carboxylic acid drugs
Contents Carboxylic Acids
1 Naming
2 Properties
3 General Synthesis
4 Different reactions involving carboxylic acid
5 Drugs containing carboxylic acid
1 Naming
Simple carboxylic acids derived from open-chain alkanes are systematically named by replacing the terminal -e of the corresponding alkane name with -oic acid The CO2H carbon atom is numbered C1
Compounds that have a -CO2H group bonded to a ring are named using the suffix -carboxylic acid The CO2H carbon is attached to C1 in this system and is not itself numberedAs a substituent the CO2H group is called a carboxyl group
Systematic Name
The names of acylgroups R-C=O derived from the parent acids
Common Name1 Naming
2 Properties
Sp2 hybridized plannar with C-C=O and O=C-O bond angles of approximately 120o
Strong H bonding has effect on boiling points carboxylic acids boil less easily than their corresponding alcoholsAcetic acid 1170oCEthanol 783oC
Carboxylic acids with more than six carbons are only slightly soluble in water The alkali metal salts of carboxylic acids are often highly water-soluble
Carboxylic acids dissociate slightly in dilute aqueous solution to give H3O+ and carboxylate anions RCO2
-
The extent of dissociation is given by an acidity constant Ka
Carboxylic acid is much weaker than mineral acids much stronger acids than alcohols and phenols
Why are carboxylic acids so much more acidic than alcohols even though both contain OH groups
the negative charge is delocalized over two equivalent oxygen atoms
the negative charge is localized on a single electronegative atom
2 Properties
The dissociation of a carboxylic acid is an equilibrium process any factor that stabilizes the carboxylate anionrelative to undissociated carboxylic acid will drive the equilibrium toward increased dissociation and result in increased acidity
the electron-withdrawing effect of the electronegative oxygen atom
three electron-withdrawing fluorine atoms delocalize the negative charge in the trifluoroacetate anion stabilizing the ion and increasing the acidity of CF3CO2H
Substituent effects on the acidity of p-substituted Benzoic Acids
2 Properties
Electron-donating (activating) group such as methoxy decreases acidity by destabilizing the carboxylate anionElectron-withdrawing (deactivating) group such as nitro increases acidity by stabilizing the carboxylate anion
2 Properties
3 General Synthesis
Oxidation of a substituted alkylbenzene with KMnO4 or Na2Cr2O7 gives a substituted benzoic acid
Both primary and secondary alkyl groups can be oxidized but tertiary groups are not affected
Oxidation of a primary alcohol or an aldehyde yields a carboxylic acidPrimary alcohols amp aldehyde are often oxidized with CrO3 in aqueous acid
bull SN2 reaction of alkyl halides rarr Nitrilesrarr hydrolysis of nitrile
the product acid has one more carbon than the starting alkyl halide
3 General Synthesis
bull Caboxylation of Grignard Reagents
bull Reaction of a Grignard reagent with CO2 (steam of dry CO2 gas) to yield a metal carboxylate followed by protonation to give a carboxylic acid
The organomagnesium halide adds to a C=O bond of carbon dioxide
3 General Synthesis
LiAlH4
4 Different reactions involving carboxylic acid
4 Different reactions involving carboxylic acid
5 Drugs containing carboxylic acid
bull Ciprofloxacin is a second generationfluoroquinolonederivative antibiotics
CinoxacinSynthetic antimicrobial related to oxolinic acid and nalidixic acid and used in urinary tract infections
Fluciclovine is indicated as a detection agent for positron emission tomography (PET) in men with suspected prostate cancer recurrence based on elevated blood prostate specific antigen (PSA) levels
L-Proline is extremely important for the proper functioning of joints and tendons and also helps maintain and strengthen heart muscles
Contents Nitriles
1 Naming
2 Properties
3 General Synthesis
4 Different reactions involving nitriles
5 Drugs containing nitriles
1 Naming
bull Compounds containing the CN functional group are called nitriles and can undergo some chemistry similar to carboxylic acids
bull Simple open- chain nitriles are named by adding -nitrile as a suffix to the alkane name
bull The nitrile carbon numbered C1
bull Nitriles can also be named as derivatives of carboxylic acids by replacing the -ic acid or -oic acid ending with -onitrile or by replacing the -carboxylic acid ending with -carbonitrile
bull The nitrile carbon atom is attached to C1 but is not itself numbered
bull If another carboxylic acid derivative is present in the same molecule the prefix cyano- is used for the CN group
bull Nitriles are analogous to carboxylic acids in that both have a carbon atom with three bonds to an electronegative atom and both contain pi bond
bull Some reactions of nitriles and carboxylic acids are similar
bull Both are electrophiles and undergo nucleophilic addition reactions
2 Properties
bull Cyanocycline A has been isolated from the bacterium Streptomyceslavendulae and was found to have antimicrobial and antitumor activity
bull More than 1000 cyanogenic glycosides are derived primarily from plants cyanogenic glycosides contain a sugar with an acetal carbon one oxygen of which is bonded to a nitrile-bearing carbon (sugar -1113148 O-1113148 C-1113148 CN)
On hydrolysis with aqueous acid the acetal is cleaved generating a cyanohydrin (HO1113148 -C-1113148 CN) which releases hydrogen cyanide
2 Properties
3 General Synthesis
(a) SN2 reaction of CN- with primary or secondary alkyl halide (already discussed)
(b) Dehydration of a primary amides (RCONH2)
bull The dehydration occurs by initial reaction of SOCl2 on the nucleophilic amide oxygen atom followed by deprotonation and a subsequent E2-like elimination reaction
4 Different reactions involving nitriles
bull Like a carbonyl group a nitrile group is strongly polarized and has an electrophiliccarbon atom
bull Nitriles react with nucleophiles to yield sp2-hybridized imine anions in a reaction analogous to the formation of an sp3-hybridized alkoxide ion by nucleophilicaddition to a carbonyl group
bull Some general reactions
4 Different reactions involving nitriles
(a) Hydrolysis to yield carboxylic acids
The reaction occurs in either basic or acidic aqueous solution
4 Different reactions involving nitriles
bull Nucleophilic addition of hydroxide ion to the amide carbonyl group yields a tetrahedral alkoxide ion Expulsion of amide ion NH21113148 as leaving group gives the carboxylate ion thereby driving the reaction toward the products Subsequent acidification in a separate step yields the carboxylic acid
4 Different reactions involving nitriles
(b) Reduction to yield primary amines (RNH2)
4 Different reactions involving nitriles
(c) Reaction with Grignard reagents to yield ketones
4 Different reactions involving nitriles
5 Drugs containing nitriles
Febuxostat is a xanathine oxidase(XO) inhibitor indicated in patients with gout suffering from hyperuricemia and is used in its chronic management
MilrinoneIndicated for the treatment of congestive heart failure
Ruxolitinibindicated to treat bone marrow cancer specifically intermediate or high-risk myelofibrosis
Saxagliptinorally active hypoglycemic (anti-diabetic drug) of the new dipeptidyl peptidase-4 inhibitor class of drugs
References
httpswwwamazoncomOrganic-Chemistry-Paula-Yurkanis-Bruice-ebookdpB01B7OIMJS
McMurry J E 2012 Organic Chemistry 8th Edition Brooks Cole Pub USA (ISBN 978-0495118374)
Klein DR 2012 Organic Chemistry as a Second Language Book 1 and 2
Fessenden RJ and Fessenden JS 1982 Organic Chemistry PWS Publisher
httpsdrivegooglecomfiled1sAZjTk9eMMzveBMea3QxNAwBLrhKpvNfviewusp=sharing
Contents Carboxylic Acids
1 Naming
2 Properties
3 General Synthesis
4 Different reactions involving carboxylic acid
5 Drugs containing carboxylic acid
1 Naming
Simple carboxylic acids derived from open-chain alkanes are systematically named by replacing the terminal -e of the corresponding alkane name with -oic acid The CO2H carbon atom is numbered C1
Compounds that have a -CO2H group bonded to a ring are named using the suffix -carboxylic acid The CO2H carbon is attached to C1 in this system and is not itself numberedAs a substituent the CO2H group is called a carboxyl group
Systematic Name
The names of acylgroups R-C=O derived from the parent acids
Common Name1 Naming
2 Properties
Sp2 hybridized plannar with C-C=O and O=C-O bond angles of approximately 120o
Strong H bonding has effect on boiling points carboxylic acids boil less easily than their corresponding alcoholsAcetic acid 1170oCEthanol 783oC
Carboxylic acids with more than six carbons are only slightly soluble in water The alkali metal salts of carboxylic acids are often highly water-soluble
Carboxylic acids dissociate slightly in dilute aqueous solution to give H3O+ and carboxylate anions RCO2
-
The extent of dissociation is given by an acidity constant Ka
Carboxylic acid is much weaker than mineral acids much stronger acids than alcohols and phenols
Why are carboxylic acids so much more acidic than alcohols even though both contain OH groups
the negative charge is delocalized over two equivalent oxygen atoms
the negative charge is localized on a single electronegative atom
2 Properties
The dissociation of a carboxylic acid is an equilibrium process any factor that stabilizes the carboxylate anionrelative to undissociated carboxylic acid will drive the equilibrium toward increased dissociation and result in increased acidity
the electron-withdrawing effect of the electronegative oxygen atom
three electron-withdrawing fluorine atoms delocalize the negative charge in the trifluoroacetate anion stabilizing the ion and increasing the acidity of CF3CO2H
Substituent effects on the acidity of p-substituted Benzoic Acids
2 Properties
Electron-donating (activating) group such as methoxy decreases acidity by destabilizing the carboxylate anionElectron-withdrawing (deactivating) group such as nitro increases acidity by stabilizing the carboxylate anion
2 Properties
3 General Synthesis
Oxidation of a substituted alkylbenzene with KMnO4 or Na2Cr2O7 gives a substituted benzoic acid
Both primary and secondary alkyl groups can be oxidized but tertiary groups are not affected
Oxidation of a primary alcohol or an aldehyde yields a carboxylic acidPrimary alcohols amp aldehyde are often oxidized with CrO3 in aqueous acid
bull SN2 reaction of alkyl halides rarr Nitrilesrarr hydrolysis of nitrile
the product acid has one more carbon than the starting alkyl halide
3 General Synthesis
bull Caboxylation of Grignard Reagents
bull Reaction of a Grignard reagent with CO2 (steam of dry CO2 gas) to yield a metal carboxylate followed by protonation to give a carboxylic acid
The organomagnesium halide adds to a C=O bond of carbon dioxide
3 General Synthesis
LiAlH4
4 Different reactions involving carboxylic acid
4 Different reactions involving carboxylic acid
5 Drugs containing carboxylic acid
bull Ciprofloxacin is a second generationfluoroquinolonederivative antibiotics
CinoxacinSynthetic antimicrobial related to oxolinic acid and nalidixic acid and used in urinary tract infections
Fluciclovine is indicated as a detection agent for positron emission tomography (PET) in men with suspected prostate cancer recurrence based on elevated blood prostate specific antigen (PSA) levels
L-Proline is extremely important for the proper functioning of joints and tendons and also helps maintain and strengthen heart muscles
Contents Nitriles
1 Naming
2 Properties
3 General Synthesis
4 Different reactions involving nitriles
5 Drugs containing nitriles
1 Naming
bull Compounds containing the CN functional group are called nitriles and can undergo some chemistry similar to carboxylic acids
bull Simple open- chain nitriles are named by adding -nitrile as a suffix to the alkane name
bull The nitrile carbon numbered C1
bull Nitriles can also be named as derivatives of carboxylic acids by replacing the -ic acid or -oic acid ending with -onitrile or by replacing the -carboxylic acid ending with -carbonitrile
bull The nitrile carbon atom is attached to C1 but is not itself numbered
bull If another carboxylic acid derivative is present in the same molecule the prefix cyano- is used for the CN group
bull Nitriles are analogous to carboxylic acids in that both have a carbon atom with three bonds to an electronegative atom and both contain pi bond
bull Some reactions of nitriles and carboxylic acids are similar
bull Both are electrophiles and undergo nucleophilic addition reactions
2 Properties
bull Cyanocycline A has been isolated from the bacterium Streptomyceslavendulae and was found to have antimicrobial and antitumor activity
bull More than 1000 cyanogenic glycosides are derived primarily from plants cyanogenic glycosides contain a sugar with an acetal carbon one oxygen of which is bonded to a nitrile-bearing carbon (sugar -1113148 O-1113148 C-1113148 CN)
On hydrolysis with aqueous acid the acetal is cleaved generating a cyanohydrin (HO1113148 -C-1113148 CN) which releases hydrogen cyanide
2 Properties
3 General Synthesis
(a) SN2 reaction of CN- with primary or secondary alkyl halide (already discussed)
(b) Dehydration of a primary amides (RCONH2)
bull The dehydration occurs by initial reaction of SOCl2 on the nucleophilic amide oxygen atom followed by deprotonation and a subsequent E2-like elimination reaction
4 Different reactions involving nitriles
bull Like a carbonyl group a nitrile group is strongly polarized and has an electrophiliccarbon atom
bull Nitriles react with nucleophiles to yield sp2-hybridized imine anions in a reaction analogous to the formation of an sp3-hybridized alkoxide ion by nucleophilicaddition to a carbonyl group
bull Some general reactions
4 Different reactions involving nitriles
(a) Hydrolysis to yield carboxylic acids
The reaction occurs in either basic or acidic aqueous solution
4 Different reactions involving nitriles
bull Nucleophilic addition of hydroxide ion to the amide carbonyl group yields a tetrahedral alkoxide ion Expulsion of amide ion NH21113148 as leaving group gives the carboxylate ion thereby driving the reaction toward the products Subsequent acidification in a separate step yields the carboxylic acid
4 Different reactions involving nitriles
(b) Reduction to yield primary amines (RNH2)
4 Different reactions involving nitriles
(c) Reaction with Grignard reagents to yield ketones
4 Different reactions involving nitriles
5 Drugs containing nitriles
Febuxostat is a xanathine oxidase(XO) inhibitor indicated in patients with gout suffering from hyperuricemia and is used in its chronic management
MilrinoneIndicated for the treatment of congestive heart failure
Ruxolitinibindicated to treat bone marrow cancer specifically intermediate or high-risk myelofibrosis
Saxagliptinorally active hypoglycemic (anti-diabetic drug) of the new dipeptidyl peptidase-4 inhibitor class of drugs
References
httpswwwamazoncomOrganic-Chemistry-Paula-Yurkanis-Bruice-ebookdpB01B7OIMJS
McMurry J E 2012 Organic Chemistry 8th Edition Brooks Cole Pub USA (ISBN 978-0495118374)
Klein DR 2012 Organic Chemistry as a Second Language Book 1 and 2
Fessenden RJ and Fessenden JS 1982 Organic Chemistry PWS Publisher
httpsdrivegooglecomfiled1sAZjTk9eMMzveBMea3QxNAwBLrhKpvNfviewusp=sharing
1 Naming
Simple carboxylic acids derived from open-chain alkanes are systematically named by replacing the terminal -e of the corresponding alkane name with -oic acid The CO2H carbon atom is numbered C1
Compounds that have a -CO2H group bonded to a ring are named using the suffix -carboxylic acid The CO2H carbon is attached to C1 in this system and is not itself numberedAs a substituent the CO2H group is called a carboxyl group
Systematic Name
The names of acylgroups R-C=O derived from the parent acids
Common Name1 Naming
2 Properties
Sp2 hybridized plannar with C-C=O and O=C-O bond angles of approximately 120o
Strong H bonding has effect on boiling points carboxylic acids boil less easily than their corresponding alcoholsAcetic acid 1170oCEthanol 783oC
Carboxylic acids with more than six carbons are only slightly soluble in water The alkali metal salts of carboxylic acids are often highly water-soluble
Carboxylic acids dissociate slightly in dilute aqueous solution to give H3O+ and carboxylate anions RCO2
-
The extent of dissociation is given by an acidity constant Ka
Carboxylic acid is much weaker than mineral acids much stronger acids than alcohols and phenols
Why are carboxylic acids so much more acidic than alcohols even though both contain OH groups
the negative charge is delocalized over two equivalent oxygen atoms
the negative charge is localized on a single electronegative atom
2 Properties
The dissociation of a carboxylic acid is an equilibrium process any factor that stabilizes the carboxylate anionrelative to undissociated carboxylic acid will drive the equilibrium toward increased dissociation and result in increased acidity
the electron-withdrawing effect of the electronegative oxygen atom
three electron-withdrawing fluorine atoms delocalize the negative charge in the trifluoroacetate anion stabilizing the ion and increasing the acidity of CF3CO2H
Substituent effects on the acidity of p-substituted Benzoic Acids
2 Properties
Electron-donating (activating) group such as methoxy decreases acidity by destabilizing the carboxylate anionElectron-withdrawing (deactivating) group such as nitro increases acidity by stabilizing the carboxylate anion
2 Properties
3 General Synthesis
Oxidation of a substituted alkylbenzene with KMnO4 or Na2Cr2O7 gives a substituted benzoic acid
Both primary and secondary alkyl groups can be oxidized but tertiary groups are not affected
Oxidation of a primary alcohol or an aldehyde yields a carboxylic acidPrimary alcohols amp aldehyde are often oxidized with CrO3 in aqueous acid
bull SN2 reaction of alkyl halides rarr Nitrilesrarr hydrolysis of nitrile
the product acid has one more carbon than the starting alkyl halide
3 General Synthesis
bull Caboxylation of Grignard Reagents
bull Reaction of a Grignard reagent with CO2 (steam of dry CO2 gas) to yield a metal carboxylate followed by protonation to give a carboxylic acid
The organomagnesium halide adds to a C=O bond of carbon dioxide
3 General Synthesis
LiAlH4
4 Different reactions involving carboxylic acid
4 Different reactions involving carboxylic acid
5 Drugs containing carboxylic acid
bull Ciprofloxacin is a second generationfluoroquinolonederivative antibiotics
CinoxacinSynthetic antimicrobial related to oxolinic acid and nalidixic acid and used in urinary tract infections
Fluciclovine is indicated as a detection agent for positron emission tomography (PET) in men with suspected prostate cancer recurrence based on elevated blood prostate specific antigen (PSA) levels
L-Proline is extremely important for the proper functioning of joints and tendons and also helps maintain and strengthen heart muscles
Contents Nitriles
1 Naming
2 Properties
3 General Synthesis
4 Different reactions involving nitriles
5 Drugs containing nitriles
1 Naming
bull Compounds containing the CN functional group are called nitriles and can undergo some chemistry similar to carboxylic acids
bull Simple open- chain nitriles are named by adding -nitrile as a suffix to the alkane name
bull The nitrile carbon numbered C1
bull Nitriles can also be named as derivatives of carboxylic acids by replacing the -ic acid or -oic acid ending with -onitrile or by replacing the -carboxylic acid ending with -carbonitrile
bull The nitrile carbon atom is attached to C1 but is not itself numbered
bull If another carboxylic acid derivative is present in the same molecule the prefix cyano- is used for the CN group
bull Nitriles are analogous to carboxylic acids in that both have a carbon atom with three bonds to an electronegative atom and both contain pi bond
bull Some reactions of nitriles and carboxylic acids are similar
bull Both are electrophiles and undergo nucleophilic addition reactions
2 Properties
bull Cyanocycline A has been isolated from the bacterium Streptomyceslavendulae and was found to have antimicrobial and antitumor activity
bull More than 1000 cyanogenic glycosides are derived primarily from plants cyanogenic glycosides contain a sugar with an acetal carbon one oxygen of which is bonded to a nitrile-bearing carbon (sugar -1113148 O-1113148 C-1113148 CN)
On hydrolysis with aqueous acid the acetal is cleaved generating a cyanohydrin (HO1113148 -C-1113148 CN) which releases hydrogen cyanide
2 Properties
3 General Synthesis
(a) SN2 reaction of CN- with primary or secondary alkyl halide (already discussed)
(b) Dehydration of a primary amides (RCONH2)
bull The dehydration occurs by initial reaction of SOCl2 on the nucleophilic amide oxygen atom followed by deprotonation and a subsequent E2-like elimination reaction
4 Different reactions involving nitriles
bull Like a carbonyl group a nitrile group is strongly polarized and has an electrophiliccarbon atom
bull Nitriles react with nucleophiles to yield sp2-hybridized imine anions in a reaction analogous to the formation of an sp3-hybridized alkoxide ion by nucleophilicaddition to a carbonyl group
bull Some general reactions
4 Different reactions involving nitriles
(a) Hydrolysis to yield carboxylic acids
The reaction occurs in either basic or acidic aqueous solution
4 Different reactions involving nitriles
bull Nucleophilic addition of hydroxide ion to the amide carbonyl group yields a tetrahedral alkoxide ion Expulsion of amide ion NH21113148 as leaving group gives the carboxylate ion thereby driving the reaction toward the products Subsequent acidification in a separate step yields the carboxylic acid
4 Different reactions involving nitriles
(b) Reduction to yield primary amines (RNH2)
4 Different reactions involving nitriles
(c) Reaction with Grignard reagents to yield ketones
4 Different reactions involving nitriles
5 Drugs containing nitriles
Febuxostat is a xanathine oxidase(XO) inhibitor indicated in patients with gout suffering from hyperuricemia and is used in its chronic management
MilrinoneIndicated for the treatment of congestive heart failure
Ruxolitinibindicated to treat bone marrow cancer specifically intermediate or high-risk myelofibrosis
Saxagliptinorally active hypoglycemic (anti-diabetic drug) of the new dipeptidyl peptidase-4 inhibitor class of drugs
References
httpswwwamazoncomOrganic-Chemistry-Paula-Yurkanis-Bruice-ebookdpB01B7OIMJS
McMurry J E 2012 Organic Chemistry 8th Edition Brooks Cole Pub USA (ISBN 978-0495118374)
Klein DR 2012 Organic Chemistry as a Second Language Book 1 and 2
Fessenden RJ and Fessenden JS 1982 Organic Chemistry PWS Publisher
httpsdrivegooglecomfiled1sAZjTk9eMMzveBMea3QxNAwBLrhKpvNfviewusp=sharing
The names of acylgroups R-C=O derived from the parent acids
Common Name1 Naming
2 Properties
Sp2 hybridized plannar with C-C=O and O=C-O bond angles of approximately 120o
Strong H bonding has effect on boiling points carboxylic acids boil less easily than their corresponding alcoholsAcetic acid 1170oCEthanol 783oC
Carboxylic acids with more than six carbons are only slightly soluble in water The alkali metal salts of carboxylic acids are often highly water-soluble
Carboxylic acids dissociate slightly in dilute aqueous solution to give H3O+ and carboxylate anions RCO2
-
The extent of dissociation is given by an acidity constant Ka
Carboxylic acid is much weaker than mineral acids much stronger acids than alcohols and phenols
Why are carboxylic acids so much more acidic than alcohols even though both contain OH groups
the negative charge is delocalized over two equivalent oxygen atoms
the negative charge is localized on a single electronegative atom
2 Properties
The dissociation of a carboxylic acid is an equilibrium process any factor that stabilizes the carboxylate anionrelative to undissociated carboxylic acid will drive the equilibrium toward increased dissociation and result in increased acidity
the electron-withdrawing effect of the electronegative oxygen atom
three electron-withdrawing fluorine atoms delocalize the negative charge in the trifluoroacetate anion stabilizing the ion and increasing the acidity of CF3CO2H
Substituent effects on the acidity of p-substituted Benzoic Acids
2 Properties
Electron-donating (activating) group such as methoxy decreases acidity by destabilizing the carboxylate anionElectron-withdrawing (deactivating) group such as nitro increases acidity by stabilizing the carboxylate anion
2 Properties
3 General Synthesis
Oxidation of a substituted alkylbenzene with KMnO4 or Na2Cr2O7 gives a substituted benzoic acid
Both primary and secondary alkyl groups can be oxidized but tertiary groups are not affected
Oxidation of a primary alcohol or an aldehyde yields a carboxylic acidPrimary alcohols amp aldehyde are often oxidized with CrO3 in aqueous acid
bull SN2 reaction of alkyl halides rarr Nitrilesrarr hydrolysis of nitrile
the product acid has one more carbon than the starting alkyl halide
3 General Synthesis
bull Caboxylation of Grignard Reagents
bull Reaction of a Grignard reagent with CO2 (steam of dry CO2 gas) to yield a metal carboxylate followed by protonation to give a carboxylic acid
The organomagnesium halide adds to a C=O bond of carbon dioxide
3 General Synthesis
LiAlH4
4 Different reactions involving carboxylic acid
4 Different reactions involving carboxylic acid
5 Drugs containing carboxylic acid
bull Ciprofloxacin is a second generationfluoroquinolonederivative antibiotics
CinoxacinSynthetic antimicrobial related to oxolinic acid and nalidixic acid and used in urinary tract infections
Fluciclovine is indicated as a detection agent for positron emission tomography (PET) in men with suspected prostate cancer recurrence based on elevated blood prostate specific antigen (PSA) levels
L-Proline is extremely important for the proper functioning of joints and tendons and also helps maintain and strengthen heart muscles
Contents Nitriles
1 Naming
2 Properties
3 General Synthesis
4 Different reactions involving nitriles
5 Drugs containing nitriles
1 Naming
bull Compounds containing the CN functional group are called nitriles and can undergo some chemistry similar to carboxylic acids
bull Simple open- chain nitriles are named by adding -nitrile as a suffix to the alkane name
bull The nitrile carbon numbered C1
bull Nitriles can also be named as derivatives of carboxylic acids by replacing the -ic acid or -oic acid ending with -onitrile or by replacing the -carboxylic acid ending with -carbonitrile
bull The nitrile carbon atom is attached to C1 but is not itself numbered
bull If another carboxylic acid derivative is present in the same molecule the prefix cyano- is used for the CN group
bull Nitriles are analogous to carboxylic acids in that both have a carbon atom with three bonds to an electronegative atom and both contain pi bond
bull Some reactions of nitriles and carboxylic acids are similar
bull Both are electrophiles and undergo nucleophilic addition reactions
2 Properties
bull Cyanocycline A has been isolated from the bacterium Streptomyceslavendulae and was found to have antimicrobial and antitumor activity
bull More than 1000 cyanogenic glycosides are derived primarily from plants cyanogenic glycosides contain a sugar with an acetal carbon one oxygen of which is bonded to a nitrile-bearing carbon (sugar -1113148 O-1113148 C-1113148 CN)
On hydrolysis with aqueous acid the acetal is cleaved generating a cyanohydrin (HO1113148 -C-1113148 CN) which releases hydrogen cyanide
2 Properties
3 General Synthesis
(a) SN2 reaction of CN- with primary or secondary alkyl halide (already discussed)
(b) Dehydration of a primary amides (RCONH2)
bull The dehydration occurs by initial reaction of SOCl2 on the nucleophilic amide oxygen atom followed by deprotonation and a subsequent E2-like elimination reaction
4 Different reactions involving nitriles
bull Like a carbonyl group a nitrile group is strongly polarized and has an electrophiliccarbon atom
bull Nitriles react with nucleophiles to yield sp2-hybridized imine anions in a reaction analogous to the formation of an sp3-hybridized alkoxide ion by nucleophilicaddition to a carbonyl group
bull Some general reactions
4 Different reactions involving nitriles
(a) Hydrolysis to yield carboxylic acids
The reaction occurs in either basic or acidic aqueous solution
4 Different reactions involving nitriles
bull Nucleophilic addition of hydroxide ion to the amide carbonyl group yields a tetrahedral alkoxide ion Expulsion of amide ion NH21113148 as leaving group gives the carboxylate ion thereby driving the reaction toward the products Subsequent acidification in a separate step yields the carboxylic acid
4 Different reactions involving nitriles
(b) Reduction to yield primary amines (RNH2)
4 Different reactions involving nitriles
(c) Reaction with Grignard reagents to yield ketones
4 Different reactions involving nitriles
5 Drugs containing nitriles
Febuxostat is a xanathine oxidase(XO) inhibitor indicated in patients with gout suffering from hyperuricemia and is used in its chronic management
MilrinoneIndicated for the treatment of congestive heart failure
Ruxolitinibindicated to treat bone marrow cancer specifically intermediate or high-risk myelofibrosis
Saxagliptinorally active hypoglycemic (anti-diabetic drug) of the new dipeptidyl peptidase-4 inhibitor class of drugs
References
httpswwwamazoncomOrganic-Chemistry-Paula-Yurkanis-Bruice-ebookdpB01B7OIMJS
McMurry J E 2012 Organic Chemistry 8th Edition Brooks Cole Pub USA (ISBN 978-0495118374)
Klein DR 2012 Organic Chemistry as a Second Language Book 1 and 2
Fessenden RJ and Fessenden JS 1982 Organic Chemistry PWS Publisher
httpsdrivegooglecomfiled1sAZjTk9eMMzveBMea3QxNAwBLrhKpvNfviewusp=sharing
2 Properties
Sp2 hybridized plannar with C-C=O and O=C-O bond angles of approximately 120o
Strong H bonding has effect on boiling points carboxylic acids boil less easily than their corresponding alcoholsAcetic acid 1170oCEthanol 783oC
Carboxylic acids with more than six carbons are only slightly soluble in water The alkali metal salts of carboxylic acids are often highly water-soluble
Carboxylic acids dissociate slightly in dilute aqueous solution to give H3O+ and carboxylate anions RCO2
-
The extent of dissociation is given by an acidity constant Ka
Carboxylic acid is much weaker than mineral acids much stronger acids than alcohols and phenols
Why are carboxylic acids so much more acidic than alcohols even though both contain OH groups
the negative charge is delocalized over two equivalent oxygen atoms
the negative charge is localized on a single electronegative atom
2 Properties
The dissociation of a carboxylic acid is an equilibrium process any factor that stabilizes the carboxylate anionrelative to undissociated carboxylic acid will drive the equilibrium toward increased dissociation and result in increased acidity
the electron-withdrawing effect of the electronegative oxygen atom
three electron-withdrawing fluorine atoms delocalize the negative charge in the trifluoroacetate anion stabilizing the ion and increasing the acidity of CF3CO2H
Substituent effects on the acidity of p-substituted Benzoic Acids
2 Properties
Electron-donating (activating) group such as methoxy decreases acidity by destabilizing the carboxylate anionElectron-withdrawing (deactivating) group such as nitro increases acidity by stabilizing the carboxylate anion
2 Properties
3 General Synthesis
Oxidation of a substituted alkylbenzene with KMnO4 or Na2Cr2O7 gives a substituted benzoic acid
Both primary and secondary alkyl groups can be oxidized but tertiary groups are not affected
Oxidation of a primary alcohol or an aldehyde yields a carboxylic acidPrimary alcohols amp aldehyde are often oxidized with CrO3 in aqueous acid
bull SN2 reaction of alkyl halides rarr Nitrilesrarr hydrolysis of nitrile
the product acid has one more carbon than the starting alkyl halide
3 General Synthesis
bull Caboxylation of Grignard Reagents
bull Reaction of a Grignard reagent with CO2 (steam of dry CO2 gas) to yield a metal carboxylate followed by protonation to give a carboxylic acid
The organomagnesium halide adds to a C=O bond of carbon dioxide
3 General Synthesis
LiAlH4
4 Different reactions involving carboxylic acid
4 Different reactions involving carboxylic acid
5 Drugs containing carboxylic acid
bull Ciprofloxacin is a second generationfluoroquinolonederivative antibiotics
CinoxacinSynthetic antimicrobial related to oxolinic acid and nalidixic acid and used in urinary tract infections
Fluciclovine is indicated as a detection agent for positron emission tomography (PET) in men with suspected prostate cancer recurrence based on elevated blood prostate specific antigen (PSA) levels
L-Proline is extremely important for the proper functioning of joints and tendons and also helps maintain and strengthen heart muscles
Contents Nitriles
1 Naming
2 Properties
3 General Synthesis
4 Different reactions involving nitriles
5 Drugs containing nitriles
1 Naming
bull Compounds containing the CN functional group are called nitriles and can undergo some chemistry similar to carboxylic acids
bull Simple open- chain nitriles are named by adding -nitrile as a suffix to the alkane name
bull The nitrile carbon numbered C1
bull Nitriles can also be named as derivatives of carboxylic acids by replacing the -ic acid or -oic acid ending with -onitrile or by replacing the -carboxylic acid ending with -carbonitrile
bull The nitrile carbon atom is attached to C1 but is not itself numbered
bull If another carboxylic acid derivative is present in the same molecule the prefix cyano- is used for the CN group
bull Nitriles are analogous to carboxylic acids in that both have a carbon atom with three bonds to an electronegative atom and both contain pi bond
bull Some reactions of nitriles and carboxylic acids are similar
bull Both are electrophiles and undergo nucleophilic addition reactions
2 Properties
bull Cyanocycline A has been isolated from the bacterium Streptomyceslavendulae and was found to have antimicrobial and antitumor activity
bull More than 1000 cyanogenic glycosides are derived primarily from plants cyanogenic glycosides contain a sugar with an acetal carbon one oxygen of which is bonded to a nitrile-bearing carbon (sugar -1113148 O-1113148 C-1113148 CN)
On hydrolysis with aqueous acid the acetal is cleaved generating a cyanohydrin (HO1113148 -C-1113148 CN) which releases hydrogen cyanide
2 Properties
3 General Synthesis
(a) SN2 reaction of CN- with primary or secondary alkyl halide (already discussed)
(b) Dehydration of a primary amides (RCONH2)
bull The dehydration occurs by initial reaction of SOCl2 on the nucleophilic amide oxygen atom followed by deprotonation and a subsequent E2-like elimination reaction
4 Different reactions involving nitriles
bull Like a carbonyl group a nitrile group is strongly polarized and has an electrophiliccarbon atom
bull Nitriles react with nucleophiles to yield sp2-hybridized imine anions in a reaction analogous to the formation of an sp3-hybridized alkoxide ion by nucleophilicaddition to a carbonyl group
bull Some general reactions
4 Different reactions involving nitriles
(a) Hydrolysis to yield carboxylic acids
The reaction occurs in either basic or acidic aqueous solution
4 Different reactions involving nitriles
bull Nucleophilic addition of hydroxide ion to the amide carbonyl group yields a tetrahedral alkoxide ion Expulsion of amide ion NH21113148 as leaving group gives the carboxylate ion thereby driving the reaction toward the products Subsequent acidification in a separate step yields the carboxylic acid
4 Different reactions involving nitriles
(b) Reduction to yield primary amines (RNH2)
4 Different reactions involving nitriles
(c) Reaction with Grignard reagents to yield ketones
4 Different reactions involving nitriles
5 Drugs containing nitriles
Febuxostat is a xanathine oxidase(XO) inhibitor indicated in patients with gout suffering from hyperuricemia and is used in its chronic management
MilrinoneIndicated for the treatment of congestive heart failure
Ruxolitinibindicated to treat bone marrow cancer specifically intermediate or high-risk myelofibrosis
Saxagliptinorally active hypoglycemic (anti-diabetic drug) of the new dipeptidyl peptidase-4 inhibitor class of drugs
References
httpswwwamazoncomOrganic-Chemistry-Paula-Yurkanis-Bruice-ebookdpB01B7OIMJS
McMurry J E 2012 Organic Chemistry 8th Edition Brooks Cole Pub USA (ISBN 978-0495118374)
Klein DR 2012 Organic Chemistry as a Second Language Book 1 and 2
Fessenden RJ and Fessenden JS 1982 Organic Chemistry PWS Publisher
httpsdrivegooglecomfiled1sAZjTk9eMMzveBMea3QxNAwBLrhKpvNfviewusp=sharing
Carboxylic acid is much weaker than mineral acids much stronger acids than alcohols and phenols
Why are carboxylic acids so much more acidic than alcohols even though both contain OH groups
the negative charge is delocalized over two equivalent oxygen atoms
the negative charge is localized on a single electronegative atom
2 Properties
The dissociation of a carboxylic acid is an equilibrium process any factor that stabilizes the carboxylate anionrelative to undissociated carboxylic acid will drive the equilibrium toward increased dissociation and result in increased acidity
the electron-withdrawing effect of the electronegative oxygen atom
three electron-withdrawing fluorine atoms delocalize the negative charge in the trifluoroacetate anion stabilizing the ion and increasing the acidity of CF3CO2H
Substituent effects on the acidity of p-substituted Benzoic Acids
2 Properties
Electron-donating (activating) group such as methoxy decreases acidity by destabilizing the carboxylate anionElectron-withdrawing (deactivating) group such as nitro increases acidity by stabilizing the carboxylate anion
2 Properties
3 General Synthesis
Oxidation of a substituted alkylbenzene with KMnO4 or Na2Cr2O7 gives a substituted benzoic acid
Both primary and secondary alkyl groups can be oxidized but tertiary groups are not affected
Oxidation of a primary alcohol or an aldehyde yields a carboxylic acidPrimary alcohols amp aldehyde are often oxidized with CrO3 in aqueous acid
bull SN2 reaction of alkyl halides rarr Nitrilesrarr hydrolysis of nitrile
the product acid has one more carbon than the starting alkyl halide
3 General Synthesis
bull Caboxylation of Grignard Reagents
bull Reaction of a Grignard reagent with CO2 (steam of dry CO2 gas) to yield a metal carboxylate followed by protonation to give a carboxylic acid
The organomagnesium halide adds to a C=O bond of carbon dioxide
3 General Synthesis
LiAlH4
4 Different reactions involving carboxylic acid
4 Different reactions involving carboxylic acid
5 Drugs containing carboxylic acid
bull Ciprofloxacin is a second generationfluoroquinolonederivative antibiotics
CinoxacinSynthetic antimicrobial related to oxolinic acid and nalidixic acid and used in urinary tract infections
Fluciclovine is indicated as a detection agent for positron emission tomography (PET) in men with suspected prostate cancer recurrence based on elevated blood prostate specific antigen (PSA) levels
L-Proline is extremely important for the proper functioning of joints and tendons and also helps maintain and strengthen heart muscles
Contents Nitriles
1 Naming
2 Properties
3 General Synthesis
4 Different reactions involving nitriles
5 Drugs containing nitriles
1 Naming
bull Compounds containing the CN functional group are called nitriles and can undergo some chemistry similar to carboxylic acids
bull Simple open- chain nitriles are named by adding -nitrile as a suffix to the alkane name
bull The nitrile carbon numbered C1
bull Nitriles can also be named as derivatives of carboxylic acids by replacing the -ic acid or -oic acid ending with -onitrile or by replacing the -carboxylic acid ending with -carbonitrile
bull The nitrile carbon atom is attached to C1 but is not itself numbered
bull If another carboxylic acid derivative is present in the same molecule the prefix cyano- is used for the CN group
bull Nitriles are analogous to carboxylic acids in that both have a carbon atom with three bonds to an electronegative atom and both contain pi bond
bull Some reactions of nitriles and carboxylic acids are similar
bull Both are electrophiles and undergo nucleophilic addition reactions
2 Properties
bull Cyanocycline A has been isolated from the bacterium Streptomyceslavendulae and was found to have antimicrobial and antitumor activity
bull More than 1000 cyanogenic glycosides are derived primarily from plants cyanogenic glycosides contain a sugar with an acetal carbon one oxygen of which is bonded to a nitrile-bearing carbon (sugar -1113148 O-1113148 C-1113148 CN)
On hydrolysis with aqueous acid the acetal is cleaved generating a cyanohydrin (HO1113148 -C-1113148 CN) which releases hydrogen cyanide
2 Properties
3 General Synthesis
(a) SN2 reaction of CN- with primary or secondary alkyl halide (already discussed)
(b) Dehydration of a primary amides (RCONH2)
bull The dehydration occurs by initial reaction of SOCl2 on the nucleophilic amide oxygen atom followed by deprotonation and a subsequent E2-like elimination reaction
4 Different reactions involving nitriles
bull Like a carbonyl group a nitrile group is strongly polarized and has an electrophiliccarbon atom
bull Nitriles react with nucleophiles to yield sp2-hybridized imine anions in a reaction analogous to the formation of an sp3-hybridized alkoxide ion by nucleophilicaddition to a carbonyl group
bull Some general reactions
4 Different reactions involving nitriles
(a) Hydrolysis to yield carboxylic acids
The reaction occurs in either basic or acidic aqueous solution
4 Different reactions involving nitriles
bull Nucleophilic addition of hydroxide ion to the amide carbonyl group yields a tetrahedral alkoxide ion Expulsion of amide ion NH21113148 as leaving group gives the carboxylate ion thereby driving the reaction toward the products Subsequent acidification in a separate step yields the carboxylic acid
4 Different reactions involving nitriles
(b) Reduction to yield primary amines (RNH2)
4 Different reactions involving nitriles
(c) Reaction with Grignard reagents to yield ketones
4 Different reactions involving nitriles
5 Drugs containing nitriles
Febuxostat is a xanathine oxidase(XO) inhibitor indicated in patients with gout suffering from hyperuricemia and is used in its chronic management
MilrinoneIndicated for the treatment of congestive heart failure
Ruxolitinibindicated to treat bone marrow cancer specifically intermediate or high-risk myelofibrosis
Saxagliptinorally active hypoglycemic (anti-diabetic drug) of the new dipeptidyl peptidase-4 inhibitor class of drugs
References
httpswwwamazoncomOrganic-Chemistry-Paula-Yurkanis-Bruice-ebookdpB01B7OIMJS
McMurry J E 2012 Organic Chemistry 8th Edition Brooks Cole Pub USA (ISBN 978-0495118374)
Klein DR 2012 Organic Chemistry as a Second Language Book 1 and 2
Fessenden RJ and Fessenden JS 1982 Organic Chemistry PWS Publisher
httpsdrivegooglecomfiled1sAZjTk9eMMzveBMea3QxNAwBLrhKpvNfviewusp=sharing
The dissociation of a carboxylic acid is an equilibrium process any factor that stabilizes the carboxylate anionrelative to undissociated carboxylic acid will drive the equilibrium toward increased dissociation and result in increased acidity
the electron-withdrawing effect of the electronegative oxygen atom
three electron-withdrawing fluorine atoms delocalize the negative charge in the trifluoroacetate anion stabilizing the ion and increasing the acidity of CF3CO2H
Substituent effects on the acidity of p-substituted Benzoic Acids
2 Properties
Electron-donating (activating) group such as methoxy decreases acidity by destabilizing the carboxylate anionElectron-withdrawing (deactivating) group such as nitro increases acidity by stabilizing the carboxylate anion
2 Properties
3 General Synthesis
Oxidation of a substituted alkylbenzene with KMnO4 or Na2Cr2O7 gives a substituted benzoic acid
Both primary and secondary alkyl groups can be oxidized but tertiary groups are not affected
Oxidation of a primary alcohol or an aldehyde yields a carboxylic acidPrimary alcohols amp aldehyde are often oxidized with CrO3 in aqueous acid
bull SN2 reaction of alkyl halides rarr Nitrilesrarr hydrolysis of nitrile
the product acid has one more carbon than the starting alkyl halide
3 General Synthesis
bull Caboxylation of Grignard Reagents
bull Reaction of a Grignard reagent with CO2 (steam of dry CO2 gas) to yield a metal carboxylate followed by protonation to give a carboxylic acid
The organomagnesium halide adds to a C=O bond of carbon dioxide
3 General Synthesis
LiAlH4
4 Different reactions involving carboxylic acid
4 Different reactions involving carboxylic acid
5 Drugs containing carboxylic acid
bull Ciprofloxacin is a second generationfluoroquinolonederivative antibiotics
CinoxacinSynthetic antimicrobial related to oxolinic acid and nalidixic acid and used in urinary tract infections
Fluciclovine is indicated as a detection agent for positron emission tomography (PET) in men with suspected prostate cancer recurrence based on elevated blood prostate specific antigen (PSA) levels
L-Proline is extremely important for the proper functioning of joints and tendons and also helps maintain and strengthen heart muscles
Contents Nitriles
1 Naming
2 Properties
3 General Synthesis
4 Different reactions involving nitriles
5 Drugs containing nitriles
1 Naming
bull Compounds containing the CN functional group are called nitriles and can undergo some chemistry similar to carboxylic acids
bull Simple open- chain nitriles are named by adding -nitrile as a suffix to the alkane name
bull The nitrile carbon numbered C1
bull Nitriles can also be named as derivatives of carboxylic acids by replacing the -ic acid or -oic acid ending with -onitrile or by replacing the -carboxylic acid ending with -carbonitrile
bull The nitrile carbon atom is attached to C1 but is not itself numbered
bull If another carboxylic acid derivative is present in the same molecule the prefix cyano- is used for the CN group
bull Nitriles are analogous to carboxylic acids in that both have a carbon atom with three bonds to an electronegative atom and both contain pi bond
bull Some reactions of nitriles and carboxylic acids are similar
bull Both are electrophiles and undergo nucleophilic addition reactions
2 Properties
bull Cyanocycline A has been isolated from the bacterium Streptomyceslavendulae and was found to have antimicrobial and antitumor activity
bull More than 1000 cyanogenic glycosides are derived primarily from plants cyanogenic glycosides contain a sugar with an acetal carbon one oxygen of which is bonded to a nitrile-bearing carbon (sugar -1113148 O-1113148 C-1113148 CN)
On hydrolysis with aqueous acid the acetal is cleaved generating a cyanohydrin (HO1113148 -C-1113148 CN) which releases hydrogen cyanide
2 Properties
3 General Synthesis
(a) SN2 reaction of CN- with primary or secondary alkyl halide (already discussed)
(b) Dehydration of a primary amides (RCONH2)
bull The dehydration occurs by initial reaction of SOCl2 on the nucleophilic amide oxygen atom followed by deprotonation and a subsequent E2-like elimination reaction
4 Different reactions involving nitriles
bull Like a carbonyl group a nitrile group is strongly polarized and has an electrophiliccarbon atom
bull Nitriles react with nucleophiles to yield sp2-hybridized imine anions in a reaction analogous to the formation of an sp3-hybridized alkoxide ion by nucleophilicaddition to a carbonyl group
bull Some general reactions
4 Different reactions involving nitriles
(a) Hydrolysis to yield carboxylic acids
The reaction occurs in either basic or acidic aqueous solution
4 Different reactions involving nitriles
bull Nucleophilic addition of hydroxide ion to the amide carbonyl group yields a tetrahedral alkoxide ion Expulsion of amide ion NH21113148 as leaving group gives the carboxylate ion thereby driving the reaction toward the products Subsequent acidification in a separate step yields the carboxylic acid
4 Different reactions involving nitriles
(b) Reduction to yield primary amines (RNH2)
4 Different reactions involving nitriles
(c) Reaction with Grignard reagents to yield ketones
4 Different reactions involving nitriles
5 Drugs containing nitriles
Febuxostat is a xanathine oxidase(XO) inhibitor indicated in patients with gout suffering from hyperuricemia and is used in its chronic management
MilrinoneIndicated for the treatment of congestive heart failure
Ruxolitinibindicated to treat bone marrow cancer specifically intermediate or high-risk myelofibrosis
Saxagliptinorally active hypoglycemic (anti-diabetic drug) of the new dipeptidyl peptidase-4 inhibitor class of drugs
References
httpswwwamazoncomOrganic-Chemistry-Paula-Yurkanis-Bruice-ebookdpB01B7OIMJS
McMurry J E 2012 Organic Chemistry 8th Edition Brooks Cole Pub USA (ISBN 978-0495118374)
Klein DR 2012 Organic Chemistry as a Second Language Book 1 and 2
Fessenden RJ and Fessenden JS 1982 Organic Chemistry PWS Publisher
httpsdrivegooglecomfiled1sAZjTk9eMMzveBMea3QxNAwBLrhKpvNfviewusp=sharing
Electron-donating (activating) group such as methoxy decreases acidity by destabilizing the carboxylate anionElectron-withdrawing (deactivating) group such as nitro increases acidity by stabilizing the carboxylate anion
2 Properties
3 General Synthesis
Oxidation of a substituted alkylbenzene with KMnO4 or Na2Cr2O7 gives a substituted benzoic acid
Both primary and secondary alkyl groups can be oxidized but tertiary groups are not affected
Oxidation of a primary alcohol or an aldehyde yields a carboxylic acidPrimary alcohols amp aldehyde are often oxidized with CrO3 in aqueous acid
bull SN2 reaction of alkyl halides rarr Nitrilesrarr hydrolysis of nitrile
the product acid has one more carbon than the starting alkyl halide
3 General Synthesis
bull Caboxylation of Grignard Reagents
bull Reaction of a Grignard reagent with CO2 (steam of dry CO2 gas) to yield a metal carboxylate followed by protonation to give a carboxylic acid
The organomagnesium halide adds to a C=O bond of carbon dioxide
3 General Synthesis
LiAlH4
4 Different reactions involving carboxylic acid
4 Different reactions involving carboxylic acid
5 Drugs containing carboxylic acid
bull Ciprofloxacin is a second generationfluoroquinolonederivative antibiotics
CinoxacinSynthetic antimicrobial related to oxolinic acid and nalidixic acid and used in urinary tract infections
Fluciclovine is indicated as a detection agent for positron emission tomography (PET) in men with suspected prostate cancer recurrence based on elevated blood prostate specific antigen (PSA) levels
L-Proline is extremely important for the proper functioning of joints and tendons and also helps maintain and strengthen heart muscles
Contents Nitriles
1 Naming
2 Properties
3 General Synthesis
4 Different reactions involving nitriles
5 Drugs containing nitriles
1 Naming
bull Compounds containing the CN functional group are called nitriles and can undergo some chemistry similar to carboxylic acids
bull Simple open- chain nitriles are named by adding -nitrile as a suffix to the alkane name
bull The nitrile carbon numbered C1
bull Nitriles can also be named as derivatives of carboxylic acids by replacing the -ic acid or -oic acid ending with -onitrile or by replacing the -carboxylic acid ending with -carbonitrile
bull The nitrile carbon atom is attached to C1 but is not itself numbered
bull If another carboxylic acid derivative is present in the same molecule the prefix cyano- is used for the CN group
bull Nitriles are analogous to carboxylic acids in that both have a carbon atom with three bonds to an electronegative atom and both contain pi bond
bull Some reactions of nitriles and carboxylic acids are similar
bull Both are electrophiles and undergo nucleophilic addition reactions
2 Properties
bull Cyanocycline A has been isolated from the bacterium Streptomyceslavendulae and was found to have antimicrobial and antitumor activity
bull More than 1000 cyanogenic glycosides are derived primarily from plants cyanogenic glycosides contain a sugar with an acetal carbon one oxygen of which is bonded to a nitrile-bearing carbon (sugar -1113148 O-1113148 C-1113148 CN)
On hydrolysis with aqueous acid the acetal is cleaved generating a cyanohydrin (HO1113148 -C-1113148 CN) which releases hydrogen cyanide
2 Properties
3 General Synthesis
(a) SN2 reaction of CN- with primary or secondary alkyl halide (already discussed)
(b) Dehydration of a primary amides (RCONH2)
bull The dehydration occurs by initial reaction of SOCl2 on the nucleophilic amide oxygen atom followed by deprotonation and a subsequent E2-like elimination reaction
4 Different reactions involving nitriles
bull Like a carbonyl group a nitrile group is strongly polarized and has an electrophiliccarbon atom
bull Nitriles react with nucleophiles to yield sp2-hybridized imine anions in a reaction analogous to the formation of an sp3-hybridized alkoxide ion by nucleophilicaddition to a carbonyl group
bull Some general reactions
4 Different reactions involving nitriles
(a) Hydrolysis to yield carboxylic acids
The reaction occurs in either basic or acidic aqueous solution
4 Different reactions involving nitriles
bull Nucleophilic addition of hydroxide ion to the amide carbonyl group yields a tetrahedral alkoxide ion Expulsion of amide ion NH21113148 as leaving group gives the carboxylate ion thereby driving the reaction toward the products Subsequent acidification in a separate step yields the carboxylic acid
4 Different reactions involving nitriles
(b) Reduction to yield primary amines (RNH2)
4 Different reactions involving nitriles
(c) Reaction with Grignard reagents to yield ketones
4 Different reactions involving nitriles
5 Drugs containing nitriles
Febuxostat is a xanathine oxidase(XO) inhibitor indicated in patients with gout suffering from hyperuricemia and is used in its chronic management
MilrinoneIndicated for the treatment of congestive heart failure
Ruxolitinibindicated to treat bone marrow cancer specifically intermediate or high-risk myelofibrosis
Saxagliptinorally active hypoglycemic (anti-diabetic drug) of the new dipeptidyl peptidase-4 inhibitor class of drugs
References
httpswwwamazoncomOrganic-Chemistry-Paula-Yurkanis-Bruice-ebookdpB01B7OIMJS
McMurry J E 2012 Organic Chemistry 8th Edition Brooks Cole Pub USA (ISBN 978-0495118374)
Klein DR 2012 Organic Chemistry as a Second Language Book 1 and 2
Fessenden RJ and Fessenden JS 1982 Organic Chemistry PWS Publisher
httpsdrivegooglecomfiled1sAZjTk9eMMzveBMea3QxNAwBLrhKpvNfviewusp=sharing
3 General Synthesis
Oxidation of a substituted alkylbenzene with KMnO4 or Na2Cr2O7 gives a substituted benzoic acid
Both primary and secondary alkyl groups can be oxidized but tertiary groups are not affected
Oxidation of a primary alcohol or an aldehyde yields a carboxylic acidPrimary alcohols amp aldehyde are often oxidized with CrO3 in aqueous acid
bull SN2 reaction of alkyl halides rarr Nitrilesrarr hydrolysis of nitrile
the product acid has one more carbon than the starting alkyl halide
3 General Synthesis
bull Caboxylation of Grignard Reagents
bull Reaction of a Grignard reagent with CO2 (steam of dry CO2 gas) to yield a metal carboxylate followed by protonation to give a carboxylic acid
The organomagnesium halide adds to a C=O bond of carbon dioxide
3 General Synthesis
LiAlH4
4 Different reactions involving carboxylic acid
4 Different reactions involving carboxylic acid
5 Drugs containing carboxylic acid
bull Ciprofloxacin is a second generationfluoroquinolonederivative antibiotics
CinoxacinSynthetic antimicrobial related to oxolinic acid and nalidixic acid and used in urinary tract infections
Fluciclovine is indicated as a detection agent for positron emission tomography (PET) in men with suspected prostate cancer recurrence based on elevated blood prostate specific antigen (PSA) levels
L-Proline is extremely important for the proper functioning of joints and tendons and also helps maintain and strengthen heart muscles
Contents Nitriles
1 Naming
2 Properties
3 General Synthesis
4 Different reactions involving nitriles
5 Drugs containing nitriles
1 Naming
bull Compounds containing the CN functional group are called nitriles and can undergo some chemistry similar to carboxylic acids
bull Simple open- chain nitriles are named by adding -nitrile as a suffix to the alkane name
bull The nitrile carbon numbered C1
bull Nitriles can also be named as derivatives of carboxylic acids by replacing the -ic acid or -oic acid ending with -onitrile or by replacing the -carboxylic acid ending with -carbonitrile
bull The nitrile carbon atom is attached to C1 but is not itself numbered
bull If another carboxylic acid derivative is present in the same molecule the prefix cyano- is used for the CN group
bull Nitriles are analogous to carboxylic acids in that both have a carbon atom with three bonds to an electronegative atom and both contain pi bond
bull Some reactions of nitriles and carboxylic acids are similar
bull Both are electrophiles and undergo nucleophilic addition reactions
2 Properties
bull Cyanocycline A has been isolated from the bacterium Streptomyceslavendulae and was found to have antimicrobial and antitumor activity
bull More than 1000 cyanogenic glycosides are derived primarily from plants cyanogenic glycosides contain a sugar with an acetal carbon one oxygen of which is bonded to a nitrile-bearing carbon (sugar -1113148 O-1113148 C-1113148 CN)
On hydrolysis with aqueous acid the acetal is cleaved generating a cyanohydrin (HO1113148 -C-1113148 CN) which releases hydrogen cyanide
2 Properties
3 General Synthesis
(a) SN2 reaction of CN- with primary or secondary alkyl halide (already discussed)
(b) Dehydration of a primary amides (RCONH2)
bull The dehydration occurs by initial reaction of SOCl2 on the nucleophilic amide oxygen atom followed by deprotonation and a subsequent E2-like elimination reaction
4 Different reactions involving nitriles
bull Like a carbonyl group a nitrile group is strongly polarized and has an electrophiliccarbon atom
bull Nitriles react with nucleophiles to yield sp2-hybridized imine anions in a reaction analogous to the formation of an sp3-hybridized alkoxide ion by nucleophilicaddition to a carbonyl group
bull Some general reactions
4 Different reactions involving nitriles
(a) Hydrolysis to yield carboxylic acids
The reaction occurs in either basic or acidic aqueous solution
4 Different reactions involving nitriles
bull Nucleophilic addition of hydroxide ion to the amide carbonyl group yields a tetrahedral alkoxide ion Expulsion of amide ion NH21113148 as leaving group gives the carboxylate ion thereby driving the reaction toward the products Subsequent acidification in a separate step yields the carboxylic acid
4 Different reactions involving nitriles
(b) Reduction to yield primary amines (RNH2)
4 Different reactions involving nitriles
(c) Reaction with Grignard reagents to yield ketones
4 Different reactions involving nitriles
5 Drugs containing nitriles
Febuxostat is a xanathine oxidase(XO) inhibitor indicated in patients with gout suffering from hyperuricemia and is used in its chronic management
MilrinoneIndicated for the treatment of congestive heart failure
Ruxolitinibindicated to treat bone marrow cancer specifically intermediate or high-risk myelofibrosis
Saxagliptinorally active hypoglycemic (anti-diabetic drug) of the new dipeptidyl peptidase-4 inhibitor class of drugs
References
httpswwwamazoncomOrganic-Chemistry-Paula-Yurkanis-Bruice-ebookdpB01B7OIMJS
McMurry J E 2012 Organic Chemistry 8th Edition Brooks Cole Pub USA (ISBN 978-0495118374)
Klein DR 2012 Organic Chemistry as a Second Language Book 1 and 2
Fessenden RJ and Fessenden JS 1982 Organic Chemistry PWS Publisher
httpsdrivegooglecomfiled1sAZjTk9eMMzveBMea3QxNAwBLrhKpvNfviewusp=sharing
bull SN2 reaction of alkyl halides rarr Nitrilesrarr hydrolysis of nitrile
the product acid has one more carbon than the starting alkyl halide
3 General Synthesis
bull Caboxylation of Grignard Reagents
bull Reaction of a Grignard reagent with CO2 (steam of dry CO2 gas) to yield a metal carboxylate followed by protonation to give a carboxylic acid
The organomagnesium halide adds to a C=O bond of carbon dioxide
3 General Synthesis
LiAlH4
4 Different reactions involving carboxylic acid
4 Different reactions involving carboxylic acid
5 Drugs containing carboxylic acid
bull Ciprofloxacin is a second generationfluoroquinolonederivative antibiotics
CinoxacinSynthetic antimicrobial related to oxolinic acid and nalidixic acid and used in urinary tract infections
Fluciclovine is indicated as a detection agent for positron emission tomography (PET) in men with suspected prostate cancer recurrence based on elevated blood prostate specific antigen (PSA) levels
L-Proline is extremely important for the proper functioning of joints and tendons and also helps maintain and strengthen heart muscles
Contents Nitriles
1 Naming
2 Properties
3 General Synthesis
4 Different reactions involving nitriles
5 Drugs containing nitriles
1 Naming
bull Compounds containing the CN functional group are called nitriles and can undergo some chemistry similar to carboxylic acids
bull Simple open- chain nitriles are named by adding -nitrile as a suffix to the alkane name
bull The nitrile carbon numbered C1
bull Nitriles can also be named as derivatives of carboxylic acids by replacing the -ic acid or -oic acid ending with -onitrile or by replacing the -carboxylic acid ending with -carbonitrile
bull The nitrile carbon atom is attached to C1 but is not itself numbered
bull If another carboxylic acid derivative is present in the same molecule the prefix cyano- is used for the CN group
bull Nitriles are analogous to carboxylic acids in that both have a carbon atom with three bonds to an electronegative atom and both contain pi bond
bull Some reactions of nitriles and carboxylic acids are similar
bull Both are electrophiles and undergo nucleophilic addition reactions
2 Properties
bull Cyanocycline A has been isolated from the bacterium Streptomyceslavendulae and was found to have antimicrobial and antitumor activity
bull More than 1000 cyanogenic glycosides are derived primarily from plants cyanogenic glycosides contain a sugar with an acetal carbon one oxygen of which is bonded to a nitrile-bearing carbon (sugar -1113148 O-1113148 C-1113148 CN)
On hydrolysis with aqueous acid the acetal is cleaved generating a cyanohydrin (HO1113148 -C-1113148 CN) which releases hydrogen cyanide
2 Properties
3 General Synthesis
(a) SN2 reaction of CN- with primary or secondary alkyl halide (already discussed)
(b) Dehydration of a primary amides (RCONH2)
bull The dehydration occurs by initial reaction of SOCl2 on the nucleophilic amide oxygen atom followed by deprotonation and a subsequent E2-like elimination reaction
4 Different reactions involving nitriles
bull Like a carbonyl group a nitrile group is strongly polarized and has an electrophiliccarbon atom
bull Nitriles react with nucleophiles to yield sp2-hybridized imine anions in a reaction analogous to the formation of an sp3-hybridized alkoxide ion by nucleophilicaddition to a carbonyl group
bull Some general reactions
4 Different reactions involving nitriles
(a) Hydrolysis to yield carboxylic acids
The reaction occurs in either basic or acidic aqueous solution
4 Different reactions involving nitriles
bull Nucleophilic addition of hydroxide ion to the amide carbonyl group yields a tetrahedral alkoxide ion Expulsion of amide ion NH21113148 as leaving group gives the carboxylate ion thereby driving the reaction toward the products Subsequent acidification in a separate step yields the carboxylic acid
4 Different reactions involving nitriles
(b) Reduction to yield primary amines (RNH2)
4 Different reactions involving nitriles
(c) Reaction with Grignard reagents to yield ketones
4 Different reactions involving nitriles
5 Drugs containing nitriles
Febuxostat is a xanathine oxidase(XO) inhibitor indicated in patients with gout suffering from hyperuricemia and is used in its chronic management
MilrinoneIndicated for the treatment of congestive heart failure
Ruxolitinibindicated to treat bone marrow cancer specifically intermediate or high-risk myelofibrosis
Saxagliptinorally active hypoglycemic (anti-diabetic drug) of the new dipeptidyl peptidase-4 inhibitor class of drugs
References
httpswwwamazoncomOrganic-Chemistry-Paula-Yurkanis-Bruice-ebookdpB01B7OIMJS
McMurry J E 2012 Organic Chemistry 8th Edition Brooks Cole Pub USA (ISBN 978-0495118374)
Klein DR 2012 Organic Chemistry as a Second Language Book 1 and 2
Fessenden RJ and Fessenden JS 1982 Organic Chemistry PWS Publisher
httpsdrivegooglecomfiled1sAZjTk9eMMzveBMea3QxNAwBLrhKpvNfviewusp=sharing
bull Caboxylation of Grignard Reagents
bull Reaction of a Grignard reagent with CO2 (steam of dry CO2 gas) to yield a metal carboxylate followed by protonation to give a carboxylic acid
The organomagnesium halide adds to a C=O bond of carbon dioxide
3 General Synthesis
LiAlH4
4 Different reactions involving carboxylic acid
4 Different reactions involving carboxylic acid
5 Drugs containing carboxylic acid
bull Ciprofloxacin is a second generationfluoroquinolonederivative antibiotics
CinoxacinSynthetic antimicrobial related to oxolinic acid and nalidixic acid and used in urinary tract infections
Fluciclovine is indicated as a detection agent for positron emission tomography (PET) in men with suspected prostate cancer recurrence based on elevated blood prostate specific antigen (PSA) levels
L-Proline is extremely important for the proper functioning of joints and tendons and also helps maintain and strengthen heart muscles
Contents Nitriles
1 Naming
2 Properties
3 General Synthesis
4 Different reactions involving nitriles
5 Drugs containing nitriles
1 Naming
bull Compounds containing the CN functional group are called nitriles and can undergo some chemistry similar to carboxylic acids
bull Simple open- chain nitriles are named by adding -nitrile as a suffix to the alkane name
bull The nitrile carbon numbered C1
bull Nitriles can also be named as derivatives of carboxylic acids by replacing the -ic acid or -oic acid ending with -onitrile or by replacing the -carboxylic acid ending with -carbonitrile
bull The nitrile carbon atom is attached to C1 but is not itself numbered
bull If another carboxylic acid derivative is present in the same molecule the prefix cyano- is used for the CN group
bull Nitriles are analogous to carboxylic acids in that both have a carbon atom with three bonds to an electronegative atom and both contain pi bond
bull Some reactions of nitriles and carboxylic acids are similar
bull Both are electrophiles and undergo nucleophilic addition reactions
2 Properties
bull Cyanocycline A has been isolated from the bacterium Streptomyceslavendulae and was found to have antimicrobial and antitumor activity
bull More than 1000 cyanogenic glycosides are derived primarily from plants cyanogenic glycosides contain a sugar with an acetal carbon one oxygen of which is bonded to a nitrile-bearing carbon (sugar -1113148 O-1113148 C-1113148 CN)
On hydrolysis with aqueous acid the acetal is cleaved generating a cyanohydrin (HO1113148 -C-1113148 CN) which releases hydrogen cyanide
2 Properties
3 General Synthesis
(a) SN2 reaction of CN- with primary or secondary alkyl halide (already discussed)
(b) Dehydration of a primary amides (RCONH2)
bull The dehydration occurs by initial reaction of SOCl2 on the nucleophilic amide oxygen atom followed by deprotonation and a subsequent E2-like elimination reaction
4 Different reactions involving nitriles
bull Like a carbonyl group a nitrile group is strongly polarized and has an electrophiliccarbon atom
bull Nitriles react with nucleophiles to yield sp2-hybridized imine anions in a reaction analogous to the formation of an sp3-hybridized alkoxide ion by nucleophilicaddition to a carbonyl group
bull Some general reactions
4 Different reactions involving nitriles
(a) Hydrolysis to yield carboxylic acids
The reaction occurs in either basic or acidic aqueous solution
4 Different reactions involving nitriles
bull Nucleophilic addition of hydroxide ion to the amide carbonyl group yields a tetrahedral alkoxide ion Expulsion of amide ion NH21113148 as leaving group gives the carboxylate ion thereby driving the reaction toward the products Subsequent acidification in a separate step yields the carboxylic acid
4 Different reactions involving nitriles
(b) Reduction to yield primary amines (RNH2)
4 Different reactions involving nitriles
(c) Reaction with Grignard reagents to yield ketones
4 Different reactions involving nitriles
5 Drugs containing nitriles
Febuxostat is a xanathine oxidase(XO) inhibitor indicated in patients with gout suffering from hyperuricemia and is used in its chronic management
MilrinoneIndicated for the treatment of congestive heart failure
Ruxolitinibindicated to treat bone marrow cancer specifically intermediate or high-risk myelofibrosis
Saxagliptinorally active hypoglycemic (anti-diabetic drug) of the new dipeptidyl peptidase-4 inhibitor class of drugs
References
httpswwwamazoncomOrganic-Chemistry-Paula-Yurkanis-Bruice-ebookdpB01B7OIMJS
McMurry J E 2012 Organic Chemistry 8th Edition Brooks Cole Pub USA (ISBN 978-0495118374)
Klein DR 2012 Organic Chemistry as a Second Language Book 1 and 2
Fessenden RJ and Fessenden JS 1982 Organic Chemistry PWS Publisher
httpsdrivegooglecomfiled1sAZjTk9eMMzveBMea3QxNAwBLrhKpvNfviewusp=sharing
LiAlH4
4 Different reactions involving carboxylic acid
4 Different reactions involving carboxylic acid
5 Drugs containing carboxylic acid
bull Ciprofloxacin is a second generationfluoroquinolonederivative antibiotics
CinoxacinSynthetic antimicrobial related to oxolinic acid and nalidixic acid and used in urinary tract infections
Fluciclovine is indicated as a detection agent for positron emission tomography (PET) in men with suspected prostate cancer recurrence based on elevated blood prostate specific antigen (PSA) levels
L-Proline is extremely important for the proper functioning of joints and tendons and also helps maintain and strengthen heart muscles
Contents Nitriles
1 Naming
2 Properties
3 General Synthesis
4 Different reactions involving nitriles
5 Drugs containing nitriles
1 Naming
bull Compounds containing the CN functional group are called nitriles and can undergo some chemistry similar to carboxylic acids
bull Simple open- chain nitriles are named by adding -nitrile as a suffix to the alkane name
bull The nitrile carbon numbered C1
bull Nitriles can also be named as derivatives of carboxylic acids by replacing the -ic acid or -oic acid ending with -onitrile or by replacing the -carboxylic acid ending with -carbonitrile
bull The nitrile carbon atom is attached to C1 but is not itself numbered
bull If another carboxylic acid derivative is present in the same molecule the prefix cyano- is used for the CN group
bull Nitriles are analogous to carboxylic acids in that both have a carbon atom with three bonds to an electronegative atom and both contain pi bond
bull Some reactions of nitriles and carboxylic acids are similar
bull Both are electrophiles and undergo nucleophilic addition reactions
2 Properties
bull Cyanocycline A has been isolated from the bacterium Streptomyceslavendulae and was found to have antimicrobial and antitumor activity
bull More than 1000 cyanogenic glycosides are derived primarily from plants cyanogenic glycosides contain a sugar with an acetal carbon one oxygen of which is bonded to a nitrile-bearing carbon (sugar -1113148 O-1113148 C-1113148 CN)
On hydrolysis with aqueous acid the acetal is cleaved generating a cyanohydrin (HO1113148 -C-1113148 CN) which releases hydrogen cyanide
2 Properties
3 General Synthesis
(a) SN2 reaction of CN- with primary or secondary alkyl halide (already discussed)
(b) Dehydration of a primary amides (RCONH2)
bull The dehydration occurs by initial reaction of SOCl2 on the nucleophilic amide oxygen atom followed by deprotonation and a subsequent E2-like elimination reaction
4 Different reactions involving nitriles
bull Like a carbonyl group a nitrile group is strongly polarized and has an electrophiliccarbon atom
bull Nitriles react with nucleophiles to yield sp2-hybridized imine anions in a reaction analogous to the formation of an sp3-hybridized alkoxide ion by nucleophilicaddition to a carbonyl group
bull Some general reactions
4 Different reactions involving nitriles
(a) Hydrolysis to yield carboxylic acids
The reaction occurs in either basic or acidic aqueous solution
4 Different reactions involving nitriles
bull Nucleophilic addition of hydroxide ion to the amide carbonyl group yields a tetrahedral alkoxide ion Expulsion of amide ion NH21113148 as leaving group gives the carboxylate ion thereby driving the reaction toward the products Subsequent acidification in a separate step yields the carboxylic acid
4 Different reactions involving nitriles
(b) Reduction to yield primary amines (RNH2)
4 Different reactions involving nitriles
(c) Reaction with Grignard reagents to yield ketones
4 Different reactions involving nitriles
5 Drugs containing nitriles
Febuxostat is a xanathine oxidase(XO) inhibitor indicated in patients with gout suffering from hyperuricemia and is used in its chronic management
MilrinoneIndicated for the treatment of congestive heart failure
Ruxolitinibindicated to treat bone marrow cancer specifically intermediate or high-risk myelofibrosis
Saxagliptinorally active hypoglycemic (anti-diabetic drug) of the new dipeptidyl peptidase-4 inhibitor class of drugs
References
httpswwwamazoncomOrganic-Chemistry-Paula-Yurkanis-Bruice-ebookdpB01B7OIMJS
McMurry J E 2012 Organic Chemistry 8th Edition Brooks Cole Pub USA (ISBN 978-0495118374)
Klein DR 2012 Organic Chemistry as a Second Language Book 1 and 2
Fessenden RJ and Fessenden JS 1982 Organic Chemistry PWS Publisher
httpsdrivegooglecomfiled1sAZjTk9eMMzveBMea3QxNAwBLrhKpvNfviewusp=sharing
4 Different reactions involving carboxylic acid
5 Drugs containing carboxylic acid
bull Ciprofloxacin is a second generationfluoroquinolonederivative antibiotics
CinoxacinSynthetic antimicrobial related to oxolinic acid and nalidixic acid and used in urinary tract infections
Fluciclovine is indicated as a detection agent for positron emission tomography (PET) in men with suspected prostate cancer recurrence based on elevated blood prostate specific antigen (PSA) levels
L-Proline is extremely important for the proper functioning of joints and tendons and also helps maintain and strengthen heart muscles
Contents Nitriles
1 Naming
2 Properties
3 General Synthesis
4 Different reactions involving nitriles
5 Drugs containing nitriles
1 Naming
bull Compounds containing the CN functional group are called nitriles and can undergo some chemistry similar to carboxylic acids
bull Simple open- chain nitriles are named by adding -nitrile as a suffix to the alkane name
bull The nitrile carbon numbered C1
bull Nitriles can also be named as derivatives of carboxylic acids by replacing the -ic acid or -oic acid ending with -onitrile or by replacing the -carboxylic acid ending with -carbonitrile
bull The nitrile carbon atom is attached to C1 but is not itself numbered
bull If another carboxylic acid derivative is present in the same molecule the prefix cyano- is used for the CN group
bull Nitriles are analogous to carboxylic acids in that both have a carbon atom with three bonds to an electronegative atom and both contain pi bond
bull Some reactions of nitriles and carboxylic acids are similar
bull Both are electrophiles and undergo nucleophilic addition reactions
2 Properties
bull Cyanocycline A has been isolated from the bacterium Streptomyceslavendulae and was found to have antimicrobial and antitumor activity
bull More than 1000 cyanogenic glycosides are derived primarily from plants cyanogenic glycosides contain a sugar with an acetal carbon one oxygen of which is bonded to a nitrile-bearing carbon (sugar -1113148 O-1113148 C-1113148 CN)
On hydrolysis with aqueous acid the acetal is cleaved generating a cyanohydrin (HO1113148 -C-1113148 CN) which releases hydrogen cyanide
2 Properties
3 General Synthesis
(a) SN2 reaction of CN- with primary or secondary alkyl halide (already discussed)
(b) Dehydration of a primary amides (RCONH2)
bull The dehydration occurs by initial reaction of SOCl2 on the nucleophilic amide oxygen atom followed by deprotonation and a subsequent E2-like elimination reaction
4 Different reactions involving nitriles
bull Like a carbonyl group a nitrile group is strongly polarized and has an electrophiliccarbon atom
bull Nitriles react with nucleophiles to yield sp2-hybridized imine anions in a reaction analogous to the formation of an sp3-hybridized alkoxide ion by nucleophilicaddition to a carbonyl group
bull Some general reactions
4 Different reactions involving nitriles
(a) Hydrolysis to yield carboxylic acids
The reaction occurs in either basic or acidic aqueous solution
4 Different reactions involving nitriles
bull Nucleophilic addition of hydroxide ion to the amide carbonyl group yields a tetrahedral alkoxide ion Expulsion of amide ion NH21113148 as leaving group gives the carboxylate ion thereby driving the reaction toward the products Subsequent acidification in a separate step yields the carboxylic acid
4 Different reactions involving nitriles
(b) Reduction to yield primary amines (RNH2)
4 Different reactions involving nitriles
(c) Reaction with Grignard reagents to yield ketones
4 Different reactions involving nitriles
5 Drugs containing nitriles
Febuxostat is a xanathine oxidase(XO) inhibitor indicated in patients with gout suffering from hyperuricemia and is used in its chronic management
MilrinoneIndicated for the treatment of congestive heart failure
Ruxolitinibindicated to treat bone marrow cancer specifically intermediate or high-risk myelofibrosis
Saxagliptinorally active hypoglycemic (anti-diabetic drug) of the new dipeptidyl peptidase-4 inhibitor class of drugs
References
httpswwwamazoncomOrganic-Chemistry-Paula-Yurkanis-Bruice-ebookdpB01B7OIMJS
McMurry J E 2012 Organic Chemistry 8th Edition Brooks Cole Pub USA (ISBN 978-0495118374)
Klein DR 2012 Organic Chemistry as a Second Language Book 1 and 2
Fessenden RJ and Fessenden JS 1982 Organic Chemistry PWS Publisher
httpsdrivegooglecomfiled1sAZjTk9eMMzveBMea3QxNAwBLrhKpvNfviewusp=sharing
5 Drugs containing carboxylic acid
bull Ciprofloxacin is a second generationfluoroquinolonederivative antibiotics
CinoxacinSynthetic antimicrobial related to oxolinic acid and nalidixic acid and used in urinary tract infections
Fluciclovine is indicated as a detection agent for positron emission tomography (PET) in men with suspected prostate cancer recurrence based on elevated blood prostate specific antigen (PSA) levels
L-Proline is extremely important for the proper functioning of joints and tendons and also helps maintain and strengthen heart muscles
Contents Nitriles
1 Naming
2 Properties
3 General Synthesis
4 Different reactions involving nitriles
5 Drugs containing nitriles
1 Naming
bull Compounds containing the CN functional group are called nitriles and can undergo some chemistry similar to carboxylic acids
bull Simple open- chain nitriles are named by adding -nitrile as a suffix to the alkane name
bull The nitrile carbon numbered C1
bull Nitriles can also be named as derivatives of carboxylic acids by replacing the -ic acid or -oic acid ending with -onitrile or by replacing the -carboxylic acid ending with -carbonitrile
bull The nitrile carbon atom is attached to C1 but is not itself numbered
bull If another carboxylic acid derivative is present in the same molecule the prefix cyano- is used for the CN group
bull Nitriles are analogous to carboxylic acids in that both have a carbon atom with three bonds to an electronegative atom and both contain pi bond
bull Some reactions of nitriles and carboxylic acids are similar
bull Both are electrophiles and undergo nucleophilic addition reactions
2 Properties
bull Cyanocycline A has been isolated from the bacterium Streptomyceslavendulae and was found to have antimicrobial and antitumor activity
bull More than 1000 cyanogenic glycosides are derived primarily from plants cyanogenic glycosides contain a sugar with an acetal carbon one oxygen of which is bonded to a nitrile-bearing carbon (sugar -1113148 O-1113148 C-1113148 CN)
On hydrolysis with aqueous acid the acetal is cleaved generating a cyanohydrin (HO1113148 -C-1113148 CN) which releases hydrogen cyanide
2 Properties
3 General Synthesis
(a) SN2 reaction of CN- with primary or secondary alkyl halide (already discussed)
(b) Dehydration of a primary amides (RCONH2)
bull The dehydration occurs by initial reaction of SOCl2 on the nucleophilic amide oxygen atom followed by deprotonation and a subsequent E2-like elimination reaction
4 Different reactions involving nitriles
bull Like a carbonyl group a nitrile group is strongly polarized and has an electrophiliccarbon atom
bull Nitriles react with nucleophiles to yield sp2-hybridized imine anions in a reaction analogous to the formation of an sp3-hybridized alkoxide ion by nucleophilicaddition to a carbonyl group
bull Some general reactions
4 Different reactions involving nitriles
(a) Hydrolysis to yield carboxylic acids
The reaction occurs in either basic or acidic aqueous solution
4 Different reactions involving nitriles
bull Nucleophilic addition of hydroxide ion to the amide carbonyl group yields a tetrahedral alkoxide ion Expulsion of amide ion NH21113148 as leaving group gives the carboxylate ion thereby driving the reaction toward the products Subsequent acidification in a separate step yields the carboxylic acid
4 Different reactions involving nitriles
(b) Reduction to yield primary amines (RNH2)
4 Different reactions involving nitriles
(c) Reaction with Grignard reagents to yield ketones
4 Different reactions involving nitriles
5 Drugs containing nitriles
Febuxostat is a xanathine oxidase(XO) inhibitor indicated in patients with gout suffering from hyperuricemia and is used in its chronic management
MilrinoneIndicated for the treatment of congestive heart failure
Ruxolitinibindicated to treat bone marrow cancer specifically intermediate or high-risk myelofibrosis
Saxagliptinorally active hypoglycemic (anti-diabetic drug) of the new dipeptidyl peptidase-4 inhibitor class of drugs
References
httpswwwamazoncomOrganic-Chemistry-Paula-Yurkanis-Bruice-ebookdpB01B7OIMJS
McMurry J E 2012 Organic Chemistry 8th Edition Brooks Cole Pub USA (ISBN 978-0495118374)
Klein DR 2012 Organic Chemistry as a Second Language Book 1 and 2
Fessenden RJ and Fessenden JS 1982 Organic Chemistry PWS Publisher
httpsdrivegooglecomfiled1sAZjTk9eMMzveBMea3QxNAwBLrhKpvNfviewusp=sharing
Contents Nitriles
1 Naming
2 Properties
3 General Synthesis
4 Different reactions involving nitriles
5 Drugs containing nitriles
1 Naming
bull Compounds containing the CN functional group are called nitriles and can undergo some chemistry similar to carboxylic acids
bull Simple open- chain nitriles are named by adding -nitrile as a suffix to the alkane name
bull The nitrile carbon numbered C1
bull Nitriles can also be named as derivatives of carboxylic acids by replacing the -ic acid or -oic acid ending with -onitrile or by replacing the -carboxylic acid ending with -carbonitrile
bull The nitrile carbon atom is attached to C1 but is not itself numbered
bull If another carboxylic acid derivative is present in the same molecule the prefix cyano- is used for the CN group
bull Nitriles are analogous to carboxylic acids in that both have a carbon atom with three bonds to an electronegative atom and both contain pi bond
bull Some reactions of nitriles and carboxylic acids are similar
bull Both are electrophiles and undergo nucleophilic addition reactions
2 Properties
bull Cyanocycline A has been isolated from the bacterium Streptomyceslavendulae and was found to have antimicrobial and antitumor activity
bull More than 1000 cyanogenic glycosides are derived primarily from plants cyanogenic glycosides contain a sugar with an acetal carbon one oxygen of which is bonded to a nitrile-bearing carbon (sugar -1113148 O-1113148 C-1113148 CN)
On hydrolysis with aqueous acid the acetal is cleaved generating a cyanohydrin (HO1113148 -C-1113148 CN) which releases hydrogen cyanide
2 Properties
3 General Synthesis
(a) SN2 reaction of CN- with primary or secondary alkyl halide (already discussed)
(b) Dehydration of a primary amides (RCONH2)
bull The dehydration occurs by initial reaction of SOCl2 on the nucleophilic amide oxygen atom followed by deprotonation and a subsequent E2-like elimination reaction
4 Different reactions involving nitriles
bull Like a carbonyl group a nitrile group is strongly polarized and has an electrophiliccarbon atom
bull Nitriles react with nucleophiles to yield sp2-hybridized imine anions in a reaction analogous to the formation of an sp3-hybridized alkoxide ion by nucleophilicaddition to a carbonyl group
bull Some general reactions
4 Different reactions involving nitriles
(a) Hydrolysis to yield carboxylic acids
The reaction occurs in either basic or acidic aqueous solution
4 Different reactions involving nitriles
bull Nucleophilic addition of hydroxide ion to the amide carbonyl group yields a tetrahedral alkoxide ion Expulsion of amide ion NH21113148 as leaving group gives the carboxylate ion thereby driving the reaction toward the products Subsequent acidification in a separate step yields the carboxylic acid
4 Different reactions involving nitriles
(b) Reduction to yield primary amines (RNH2)
4 Different reactions involving nitriles
(c) Reaction with Grignard reagents to yield ketones
4 Different reactions involving nitriles
5 Drugs containing nitriles
Febuxostat is a xanathine oxidase(XO) inhibitor indicated in patients with gout suffering from hyperuricemia and is used in its chronic management
MilrinoneIndicated for the treatment of congestive heart failure
Ruxolitinibindicated to treat bone marrow cancer specifically intermediate or high-risk myelofibrosis
Saxagliptinorally active hypoglycemic (anti-diabetic drug) of the new dipeptidyl peptidase-4 inhibitor class of drugs
References
httpswwwamazoncomOrganic-Chemistry-Paula-Yurkanis-Bruice-ebookdpB01B7OIMJS
McMurry J E 2012 Organic Chemistry 8th Edition Brooks Cole Pub USA (ISBN 978-0495118374)
Klein DR 2012 Organic Chemistry as a Second Language Book 1 and 2
Fessenden RJ and Fessenden JS 1982 Organic Chemistry PWS Publisher
httpsdrivegooglecomfiled1sAZjTk9eMMzveBMea3QxNAwBLrhKpvNfviewusp=sharing
1 Naming
bull Compounds containing the CN functional group are called nitriles and can undergo some chemistry similar to carboxylic acids
bull Simple open- chain nitriles are named by adding -nitrile as a suffix to the alkane name
bull The nitrile carbon numbered C1
bull Nitriles can also be named as derivatives of carboxylic acids by replacing the -ic acid or -oic acid ending with -onitrile or by replacing the -carboxylic acid ending with -carbonitrile
bull The nitrile carbon atom is attached to C1 but is not itself numbered
bull If another carboxylic acid derivative is present in the same molecule the prefix cyano- is used for the CN group
bull Nitriles are analogous to carboxylic acids in that both have a carbon atom with three bonds to an electronegative atom and both contain pi bond
bull Some reactions of nitriles and carboxylic acids are similar
bull Both are electrophiles and undergo nucleophilic addition reactions
2 Properties
bull Cyanocycline A has been isolated from the bacterium Streptomyceslavendulae and was found to have antimicrobial and antitumor activity
bull More than 1000 cyanogenic glycosides are derived primarily from plants cyanogenic glycosides contain a sugar with an acetal carbon one oxygen of which is bonded to a nitrile-bearing carbon (sugar -1113148 O-1113148 C-1113148 CN)
On hydrolysis with aqueous acid the acetal is cleaved generating a cyanohydrin (HO1113148 -C-1113148 CN) which releases hydrogen cyanide
2 Properties
3 General Synthesis
(a) SN2 reaction of CN- with primary or secondary alkyl halide (already discussed)
(b) Dehydration of a primary amides (RCONH2)
bull The dehydration occurs by initial reaction of SOCl2 on the nucleophilic amide oxygen atom followed by deprotonation and a subsequent E2-like elimination reaction
4 Different reactions involving nitriles
bull Like a carbonyl group a nitrile group is strongly polarized and has an electrophiliccarbon atom
bull Nitriles react with nucleophiles to yield sp2-hybridized imine anions in a reaction analogous to the formation of an sp3-hybridized alkoxide ion by nucleophilicaddition to a carbonyl group
bull Some general reactions
4 Different reactions involving nitriles
(a) Hydrolysis to yield carboxylic acids
The reaction occurs in either basic or acidic aqueous solution
4 Different reactions involving nitriles
bull Nucleophilic addition of hydroxide ion to the amide carbonyl group yields a tetrahedral alkoxide ion Expulsion of amide ion NH21113148 as leaving group gives the carboxylate ion thereby driving the reaction toward the products Subsequent acidification in a separate step yields the carboxylic acid
4 Different reactions involving nitriles
(b) Reduction to yield primary amines (RNH2)
4 Different reactions involving nitriles
(c) Reaction with Grignard reagents to yield ketones
4 Different reactions involving nitriles
5 Drugs containing nitriles
Febuxostat is a xanathine oxidase(XO) inhibitor indicated in patients with gout suffering from hyperuricemia and is used in its chronic management
MilrinoneIndicated for the treatment of congestive heart failure
Ruxolitinibindicated to treat bone marrow cancer specifically intermediate or high-risk myelofibrosis
Saxagliptinorally active hypoglycemic (anti-diabetic drug) of the new dipeptidyl peptidase-4 inhibitor class of drugs
References
httpswwwamazoncomOrganic-Chemistry-Paula-Yurkanis-Bruice-ebookdpB01B7OIMJS
McMurry J E 2012 Organic Chemistry 8th Edition Brooks Cole Pub USA (ISBN 978-0495118374)
Klein DR 2012 Organic Chemistry as a Second Language Book 1 and 2
Fessenden RJ and Fessenden JS 1982 Organic Chemistry PWS Publisher
httpsdrivegooglecomfiled1sAZjTk9eMMzveBMea3QxNAwBLrhKpvNfviewusp=sharing
bull Nitriles are analogous to carboxylic acids in that both have a carbon atom with three bonds to an electronegative atom and both contain pi bond
bull Some reactions of nitriles and carboxylic acids are similar
bull Both are electrophiles and undergo nucleophilic addition reactions
2 Properties
bull Cyanocycline A has been isolated from the bacterium Streptomyceslavendulae and was found to have antimicrobial and antitumor activity
bull More than 1000 cyanogenic glycosides are derived primarily from plants cyanogenic glycosides contain a sugar with an acetal carbon one oxygen of which is bonded to a nitrile-bearing carbon (sugar -1113148 O-1113148 C-1113148 CN)
On hydrolysis with aqueous acid the acetal is cleaved generating a cyanohydrin (HO1113148 -C-1113148 CN) which releases hydrogen cyanide
2 Properties
3 General Synthesis
(a) SN2 reaction of CN- with primary or secondary alkyl halide (already discussed)
(b) Dehydration of a primary amides (RCONH2)
bull The dehydration occurs by initial reaction of SOCl2 on the nucleophilic amide oxygen atom followed by deprotonation and a subsequent E2-like elimination reaction
4 Different reactions involving nitriles
bull Like a carbonyl group a nitrile group is strongly polarized and has an electrophiliccarbon atom
bull Nitriles react with nucleophiles to yield sp2-hybridized imine anions in a reaction analogous to the formation of an sp3-hybridized alkoxide ion by nucleophilicaddition to a carbonyl group
bull Some general reactions
4 Different reactions involving nitriles
(a) Hydrolysis to yield carboxylic acids
The reaction occurs in either basic or acidic aqueous solution
4 Different reactions involving nitriles
bull Nucleophilic addition of hydroxide ion to the amide carbonyl group yields a tetrahedral alkoxide ion Expulsion of amide ion NH21113148 as leaving group gives the carboxylate ion thereby driving the reaction toward the products Subsequent acidification in a separate step yields the carboxylic acid
4 Different reactions involving nitriles
(b) Reduction to yield primary amines (RNH2)
4 Different reactions involving nitriles
(c) Reaction with Grignard reagents to yield ketones
4 Different reactions involving nitriles
5 Drugs containing nitriles
Febuxostat is a xanathine oxidase(XO) inhibitor indicated in patients with gout suffering from hyperuricemia and is used in its chronic management
MilrinoneIndicated for the treatment of congestive heart failure
Ruxolitinibindicated to treat bone marrow cancer specifically intermediate or high-risk myelofibrosis
Saxagliptinorally active hypoglycemic (anti-diabetic drug) of the new dipeptidyl peptidase-4 inhibitor class of drugs
References
httpswwwamazoncomOrganic-Chemistry-Paula-Yurkanis-Bruice-ebookdpB01B7OIMJS
McMurry J E 2012 Organic Chemistry 8th Edition Brooks Cole Pub USA (ISBN 978-0495118374)
Klein DR 2012 Organic Chemistry as a Second Language Book 1 and 2
Fessenden RJ and Fessenden JS 1982 Organic Chemistry PWS Publisher
httpsdrivegooglecomfiled1sAZjTk9eMMzveBMea3QxNAwBLrhKpvNfviewusp=sharing
bull Cyanocycline A has been isolated from the bacterium Streptomyceslavendulae and was found to have antimicrobial and antitumor activity
bull More than 1000 cyanogenic glycosides are derived primarily from plants cyanogenic glycosides contain a sugar with an acetal carbon one oxygen of which is bonded to a nitrile-bearing carbon (sugar -1113148 O-1113148 C-1113148 CN)
On hydrolysis with aqueous acid the acetal is cleaved generating a cyanohydrin (HO1113148 -C-1113148 CN) which releases hydrogen cyanide
2 Properties
3 General Synthesis
(a) SN2 reaction of CN- with primary or secondary alkyl halide (already discussed)
(b) Dehydration of a primary amides (RCONH2)
bull The dehydration occurs by initial reaction of SOCl2 on the nucleophilic amide oxygen atom followed by deprotonation and a subsequent E2-like elimination reaction
4 Different reactions involving nitriles
bull Like a carbonyl group a nitrile group is strongly polarized and has an electrophiliccarbon atom
bull Nitriles react with nucleophiles to yield sp2-hybridized imine anions in a reaction analogous to the formation of an sp3-hybridized alkoxide ion by nucleophilicaddition to a carbonyl group
bull Some general reactions
4 Different reactions involving nitriles
(a) Hydrolysis to yield carboxylic acids
The reaction occurs in either basic or acidic aqueous solution
4 Different reactions involving nitriles
bull Nucleophilic addition of hydroxide ion to the amide carbonyl group yields a tetrahedral alkoxide ion Expulsion of amide ion NH21113148 as leaving group gives the carboxylate ion thereby driving the reaction toward the products Subsequent acidification in a separate step yields the carboxylic acid
4 Different reactions involving nitriles
(b) Reduction to yield primary amines (RNH2)
4 Different reactions involving nitriles
(c) Reaction with Grignard reagents to yield ketones
4 Different reactions involving nitriles
5 Drugs containing nitriles
Febuxostat is a xanathine oxidase(XO) inhibitor indicated in patients with gout suffering from hyperuricemia and is used in its chronic management
MilrinoneIndicated for the treatment of congestive heart failure
Ruxolitinibindicated to treat bone marrow cancer specifically intermediate or high-risk myelofibrosis
Saxagliptinorally active hypoglycemic (anti-diabetic drug) of the new dipeptidyl peptidase-4 inhibitor class of drugs
References
httpswwwamazoncomOrganic-Chemistry-Paula-Yurkanis-Bruice-ebookdpB01B7OIMJS
McMurry J E 2012 Organic Chemistry 8th Edition Brooks Cole Pub USA (ISBN 978-0495118374)
Klein DR 2012 Organic Chemistry as a Second Language Book 1 and 2
Fessenden RJ and Fessenden JS 1982 Organic Chemistry PWS Publisher
httpsdrivegooglecomfiled1sAZjTk9eMMzveBMea3QxNAwBLrhKpvNfviewusp=sharing
3 General Synthesis
(a) SN2 reaction of CN- with primary or secondary alkyl halide (already discussed)
(b) Dehydration of a primary amides (RCONH2)
bull The dehydration occurs by initial reaction of SOCl2 on the nucleophilic amide oxygen atom followed by deprotonation and a subsequent E2-like elimination reaction
4 Different reactions involving nitriles
bull Like a carbonyl group a nitrile group is strongly polarized and has an electrophiliccarbon atom
bull Nitriles react with nucleophiles to yield sp2-hybridized imine anions in a reaction analogous to the formation of an sp3-hybridized alkoxide ion by nucleophilicaddition to a carbonyl group
bull Some general reactions
4 Different reactions involving nitriles
(a) Hydrolysis to yield carboxylic acids
The reaction occurs in either basic or acidic aqueous solution
4 Different reactions involving nitriles
bull Nucleophilic addition of hydroxide ion to the amide carbonyl group yields a tetrahedral alkoxide ion Expulsion of amide ion NH21113148 as leaving group gives the carboxylate ion thereby driving the reaction toward the products Subsequent acidification in a separate step yields the carboxylic acid
4 Different reactions involving nitriles
(b) Reduction to yield primary amines (RNH2)
4 Different reactions involving nitriles
(c) Reaction with Grignard reagents to yield ketones
4 Different reactions involving nitriles
5 Drugs containing nitriles
Febuxostat is a xanathine oxidase(XO) inhibitor indicated in patients with gout suffering from hyperuricemia and is used in its chronic management
MilrinoneIndicated for the treatment of congestive heart failure
Ruxolitinibindicated to treat bone marrow cancer specifically intermediate or high-risk myelofibrosis
Saxagliptinorally active hypoglycemic (anti-diabetic drug) of the new dipeptidyl peptidase-4 inhibitor class of drugs
References
httpswwwamazoncomOrganic-Chemistry-Paula-Yurkanis-Bruice-ebookdpB01B7OIMJS
McMurry J E 2012 Organic Chemistry 8th Edition Brooks Cole Pub USA (ISBN 978-0495118374)
Klein DR 2012 Organic Chemistry as a Second Language Book 1 and 2
Fessenden RJ and Fessenden JS 1982 Organic Chemistry PWS Publisher
httpsdrivegooglecomfiled1sAZjTk9eMMzveBMea3QxNAwBLrhKpvNfviewusp=sharing
4 Different reactions involving nitriles
bull Like a carbonyl group a nitrile group is strongly polarized and has an electrophiliccarbon atom
bull Nitriles react with nucleophiles to yield sp2-hybridized imine anions in a reaction analogous to the formation of an sp3-hybridized alkoxide ion by nucleophilicaddition to a carbonyl group
bull Some general reactions
4 Different reactions involving nitriles
(a) Hydrolysis to yield carboxylic acids
The reaction occurs in either basic or acidic aqueous solution
4 Different reactions involving nitriles
bull Nucleophilic addition of hydroxide ion to the amide carbonyl group yields a tetrahedral alkoxide ion Expulsion of amide ion NH21113148 as leaving group gives the carboxylate ion thereby driving the reaction toward the products Subsequent acidification in a separate step yields the carboxylic acid
4 Different reactions involving nitriles
(b) Reduction to yield primary amines (RNH2)
4 Different reactions involving nitriles
(c) Reaction with Grignard reagents to yield ketones
4 Different reactions involving nitriles
5 Drugs containing nitriles
Febuxostat is a xanathine oxidase(XO) inhibitor indicated in patients with gout suffering from hyperuricemia and is used in its chronic management
MilrinoneIndicated for the treatment of congestive heart failure
Ruxolitinibindicated to treat bone marrow cancer specifically intermediate or high-risk myelofibrosis
Saxagliptinorally active hypoglycemic (anti-diabetic drug) of the new dipeptidyl peptidase-4 inhibitor class of drugs
References
httpswwwamazoncomOrganic-Chemistry-Paula-Yurkanis-Bruice-ebookdpB01B7OIMJS
McMurry J E 2012 Organic Chemistry 8th Edition Brooks Cole Pub USA (ISBN 978-0495118374)
Klein DR 2012 Organic Chemistry as a Second Language Book 1 and 2
Fessenden RJ and Fessenden JS 1982 Organic Chemistry PWS Publisher
httpsdrivegooglecomfiled1sAZjTk9eMMzveBMea3QxNAwBLrhKpvNfviewusp=sharing
bull Some general reactions
4 Different reactions involving nitriles
(a) Hydrolysis to yield carboxylic acids
The reaction occurs in either basic or acidic aqueous solution
4 Different reactions involving nitriles
bull Nucleophilic addition of hydroxide ion to the amide carbonyl group yields a tetrahedral alkoxide ion Expulsion of amide ion NH21113148 as leaving group gives the carboxylate ion thereby driving the reaction toward the products Subsequent acidification in a separate step yields the carboxylic acid
4 Different reactions involving nitriles
(b) Reduction to yield primary amines (RNH2)
4 Different reactions involving nitriles
(c) Reaction with Grignard reagents to yield ketones
4 Different reactions involving nitriles
5 Drugs containing nitriles
Febuxostat is a xanathine oxidase(XO) inhibitor indicated in patients with gout suffering from hyperuricemia and is used in its chronic management
MilrinoneIndicated for the treatment of congestive heart failure
Ruxolitinibindicated to treat bone marrow cancer specifically intermediate or high-risk myelofibrosis
Saxagliptinorally active hypoglycemic (anti-diabetic drug) of the new dipeptidyl peptidase-4 inhibitor class of drugs
References
httpswwwamazoncomOrganic-Chemistry-Paula-Yurkanis-Bruice-ebookdpB01B7OIMJS
McMurry J E 2012 Organic Chemistry 8th Edition Brooks Cole Pub USA (ISBN 978-0495118374)
Klein DR 2012 Organic Chemistry as a Second Language Book 1 and 2
Fessenden RJ and Fessenden JS 1982 Organic Chemistry PWS Publisher
httpsdrivegooglecomfiled1sAZjTk9eMMzveBMea3QxNAwBLrhKpvNfviewusp=sharing
(a) Hydrolysis to yield carboxylic acids
The reaction occurs in either basic or acidic aqueous solution
4 Different reactions involving nitriles
bull Nucleophilic addition of hydroxide ion to the amide carbonyl group yields a tetrahedral alkoxide ion Expulsion of amide ion NH21113148 as leaving group gives the carboxylate ion thereby driving the reaction toward the products Subsequent acidification in a separate step yields the carboxylic acid
4 Different reactions involving nitriles
(b) Reduction to yield primary amines (RNH2)
4 Different reactions involving nitriles
(c) Reaction with Grignard reagents to yield ketones
4 Different reactions involving nitriles
5 Drugs containing nitriles
Febuxostat is a xanathine oxidase(XO) inhibitor indicated in patients with gout suffering from hyperuricemia and is used in its chronic management
MilrinoneIndicated for the treatment of congestive heart failure
Ruxolitinibindicated to treat bone marrow cancer specifically intermediate or high-risk myelofibrosis
Saxagliptinorally active hypoglycemic (anti-diabetic drug) of the new dipeptidyl peptidase-4 inhibitor class of drugs
References
httpswwwamazoncomOrganic-Chemistry-Paula-Yurkanis-Bruice-ebookdpB01B7OIMJS
McMurry J E 2012 Organic Chemistry 8th Edition Brooks Cole Pub USA (ISBN 978-0495118374)
Klein DR 2012 Organic Chemistry as a Second Language Book 1 and 2
Fessenden RJ and Fessenden JS 1982 Organic Chemistry PWS Publisher
httpsdrivegooglecomfiled1sAZjTk9eMMzveBMea3QxNAwBLrhKpvNfviewusp=sharing
bull Nucleophilic addition of hydroxide ion to the amide carbonyl group yields a tetrahedral alkoxide ion Expulsion of amide ion NH21113148 as leaving group gives the carboxylate ion thereby driving the reaction toward the products Subsequent acidification in a separate step yields the carboxylic acid
4 Different reactions involving nitriles
(b) Reduction to yield primary amines (RNH2)
4 Different reactions involving nitriles
(c) Reaction with Grignard reagents to yield ketones
4 Different reactions involving nitriles
5 Drugs containing nitriles
Febuxostat is a xanathine oxidase(XO) inhibitor indicated in patients with gout suffering from hyperuricemia and is used in its chronic management
MilrinoneIndicated for the treatment of congestive heart failure
Ruxolitinibindicated to treat bone marrow cancer specifically intermediate or high-risk myelofibrosis
Saxagliptinorally active hypoglycemic (anti-diabetic drug) of the new dipeptidyl peptidase-4 inhibitor class of drugs
References
httpswwwamazoncomOrganic-Chemistry-Paula-Yurkanis-Bruice-ebookdpB01B7OIMJS
McMurry J E 2012 Organic Chemistry 8th Edition Brooks Cole Pub USA (ISBN 978-0495118374)
Klein DR 2012 Organic Chemistry as a Second Language Book 1 and 2
Fessenden RJ and Fessenden JS 1982 Organic Chemistry PWS Publisher
httpsdrivegooglecomfiled1sAZjTk9eMMzveBMea3QxNAwBLrhKpvNfviewusp=sharing
(b) Reduction to yield primary amines (RNH2)
4 Different reactions involving nitriles
(c) Reaction with Grignard reagents to yield ketones
4 Different reactions involving nitriles
5 Drugs containing nitriles
Febuxostat is a xanathine oxidase(XO) inhibitor indicated in patients with gout suffering from hyperuricemia and is used in its chronic management
MilrinoneIndicated for the treatment of congestive heart failure
Ruxolitinibindicated to treat bone marrow cancer specifically intermediate or high-risk myelofibrosis
Saxagliptinorally active hypoglycemic (anti-diabetic drug) of the new dipeptidyl peptidase-4 inhibitor class of drugs
References
httpswwwamazoncomOrganic-Chemistry-Paula-Yurkanis-Bruice-ebookdpB01B7OIMJS
McMurry J E 2012 Organic Chemistry 8th Edition Brooks Cole Pub USA (ISBN 978-0495118374)
Klein DR 2012 Organic Chemistry as a Second Language Book 1 and 2
Fessenden RJ and Fessenden JS 1982 Organic Chemistry PWS Publisher
httpsdrivegooglecomfiled1sAZjTk9eMMzveBMea3QxNAwBLrhKpvNfviewusp=sharing
(c) Reaction with Grignard reagents to yield ketones
4 Different reactions involving nitriles
5 Drugs containing nitriles
Febuxostat is a xanathine oxidase(XO) inhibitor indicated in patients with gout suffering from hyperuricemia and is used in its chronic management
MilrinoneIndicated for the treatment of congestive heart failure
Ruxolitinibindicated to treat bone marrow cancer specifically intermediate or high-risk myelofibrosis
Saxagliptinorally active hypoglycemic (anti-diabetic drug) of the new dipeptidyl peptidase-4 inhibitor class of drugs
References
httpswwwamazoncomOrganic-Chemistry-Paula-Yurkanis-Bruice-ebookdpB01B7OIMJS
McMurry J E 2012 Organic Chemistry 8th Edition Brooks Cole Pub USA (ISBN 978-0495118374)
Klein DR 2012 Organic Chemistry as a Second Language Book 1 and 2
Fessenden RJ and Fessenden JS 1982 Organic Chemistry PWS Publisher
httpsdrivegooglecomfiled1sAZjTk9eMMzveBMea3QxNAwBLrhKpvNfviewusp=sharing
5 Drugs containing nitriles
Febuxostat is a xanathine oxidase(XO) inhibitor indicated in patients with gout suffering from hyperuricemia and is used in its chronic management
MilrinoneIndicated for the treatment of congestive heart failure
Ruxolitinibindicated to treat bone marrow cancer specifically intermediate or high-risk myelofibrosis
Saxagliptinorally active hypoglycemic (anti-diabetic drug) of the new dipeptidyl peptidase-4 inhibitor class of drugs
References
httpswwwamazoncomOrganic-Chemistry-Paula-Yurkanis-Bruice-ebookdpB01B7OIMJS
McMurry J E 2012 Organic Chemistry 8th Edition Brooks Cole Pub USA (ISBN 978-0495118374)
Klein DR 2012 Organic Chemistry as a Second Language Book 1 and 2
Fessenden RJ and Fessenden JS 1982 Organic Chemistry PWS Publisher
httpsdrivegooglecomfiled1sAZjTk9eMMzveBMea3QxNAwBLrhKpvNfviewusp=sharing
References
httpswwwamazoncomOrganic-Chemistry-Paula-Yurkanis-Bruice-ebookdpB01B7OIMJS
McMurry J E 2012 Organic Chemistry 8th Edition Brooks Cole Pub USA (ISBN 978-0495118374)
Klein DR 2012 Organic Chemistry as a Second Language Book 1 and 2
Fessenden RJ and Fessenden JS 1982 Organic Chemistry PWS Publisher
httpsdrivegooglecomfiled1sAZjTk9eMMzveBMea3QxNAwBLrhKpvNfviewusp=sharing
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