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Definition
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Definition
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Definition
| lipid soluble (lipophilic/hydrophobic); van der waals interaction between alkane molecules cannot be easily disrupted by polar water molecules |
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Definition
| stable - heat, air, light, etc - won't affect it |
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Definition
| has 4 attachments to carbon |
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Definition
stable, little reactivity, excreted from body unchanged
Exception: hydroxylation at end of chain or adjacent to the final carbon |
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Definition
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Term
| properties of Alkene bonds |
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Definition
| all C-C, C=C and C-H bonds are non-polar; only weak van der waals interactions are possible |
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Definition
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Definition
| multiple bonds give a reactive site (able to react with oxygen O=O); prone to oxidation -> peroxide formation; unstable and explosive |
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Definition
| metabolically stable; sometimes alkene fxnal group serves as reaction center |
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Term
| alkenes: cycloalkanes - alkene isomers |
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Definition
| have the same empirical formula - C(n)H(2n) |
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Term
| bonds of cycloalkanes (alkene isomers) |
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Definition
| all C-C and C-H bonds are non-polar; weak van der waals interactions only; do not show free rotation around bonds |
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Term
| conformational forms or isomers |
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Definition
1,2-dimethylcyclohexane
high energy - methyl groups in axial conformation
low energy - methyl groups in equatorial conformation
this is important in drug-receptor interactions |
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Definition
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Definition
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Term
| bonds of aromatic hydrocarbons |
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Definition
C-C bonds are not single or double bonds - they are conjugated - hybrids
electrons in C-C bonds are delocalized; they are planar "flat" molecules; non-polar; van der waals interxns |
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Term
| boiling and melting pt of aromatic hydrocarbons |
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Definition
| higher than alkanes, cycloalkanes, alkenes and cycloalkenes because of flatness of the molecules, tighter packing and stronger van der waals interxns |
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Term
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Definition
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Term
| aromatic hydrocarbon solubility |
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Definition
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Term
| aromatic hydrocarbons undergo _____ rxns |
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Definition
| hydroxylation - very important during metabolism (in vivo); does not occur in vitro; stable on shelf; flammable |
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Term
| _______ ________ play a significant role in the binding of a drug to biologic proteins |
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Definition
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Term
| metabolism of aromatic hydrocarbons |
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Definition
| prone to oxidation in vivo (aromatic hydroxylation); rapid removal of chemicals from body; cytochrome P450 isoforms; hydroxylation increase water solubility and may increase drug activity (carcinogenic prop.) |
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Term
| ________undergo conjugation via _______ or _________ yielding a glucuronide conjugate and sulfate conjugate, respectively. |
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Definition
| phenols; glucuronidation; sulfonation |
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Term
| bonding of halogenated hydrocarbons |
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Definition
monohaloalkanes have a permanent dipole, but doesn't guarantee dipole-dipole bonding;
weak intermolecular bonding
only van der waals bonding |
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Term
| bp of halogenated hydrocarbons |
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Definition
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Term
| solubility of halogenated hydrocarbons |
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Definition
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Term
| pH of halogenated hydrocarbons |
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Definition
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Term
| metabolism of halogenated hydrocarbons |
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Definition
not readily metabolized; increased potential for human toxicity; not readily excreted by kidneys;
prolonged biological half-life ->systemic toxicity;
potential carcinogenic properties |
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Term
| bond properties of alcohols |
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Definition
| polar bond; permanent dipole; H-bond acceptor and donor; van der waals interxns for hydrocarbon portion |
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Definition
| high bp (due to H-bonding) |
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Term
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Definition
| water soluble for 5-6 carbons; -OH group promotes water solubility |
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Term
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Definition
| neutral; acidity decreases as alkyl group increases; halogens increase the acidity. |
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Term
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Definition
relatively stable;
will oxidize in the presence of an oxidizing agent:
primary R-OH ->carboxylic acid
secondary R-OH ->Ketone
tertiary R-OH -> NO rxn |
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Term
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Definition
| relatively stable in vitro; readily metabolized in vivo by variety of enzymes; primary and secondary alcohols are prone to oxidation by oxidase enzymes; available for conjugation rxns (increased water solubility) |
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Term
| OH group of phenol: O is very ____ and the H is very ______ |
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Definition
| electronegative; electropositive |
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Term
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Definition
| have polar bond and permanent dipole; H bond acceptor and donor; intermolecular H bonding |
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Definition
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Definition
| hydrophilic: as lipophilic nature increases (methyl or halogen addition), water solubility decreases; addition of a second phenol increases water solubility |
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Term
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Definition
| weakly acidic (pKa ~10) - due to electron delocalization; phenolate ion is stabilized by resonance; has ability to make salt, which increases water solubility |
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Term
| chemical reactivity/stability of phenols |
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Definition
| easily oxidize to quinones (highly colored) in air; prevent oxidation by storing away from oxygen and light and/or adding antioxidants |
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Term
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Definition
can be oxidized or hydroxylated -> diphenolic compound
new -OH group either ortho or para to original -OH
undergo conjugation rxns (increases water solubility) |
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Definition
polar bond, permanent dipole
H-bond acceptor (can H-bond to water)
van der waal interxns (weak) |
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Definition
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Definition
| lipid soluble; very low water solubility |
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Definition
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Definition
relatively stable and non-reactive
EXCEPTION: can form peroxides (rxn with oxygen)
flammable |
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Term
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Definition
relatively stable; are excreted unchanged; undergoes metabolic dealkylation (CYP 450)-> R-OH (phenol);
subsequent conjugation |
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Term
| bonds of aldehydes and ketones |
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Definition
carbonyl group -> polar; permanent dipole
H bond acceptor and donor |
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Term
| bp of aldehydes and ketones |
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Definition
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Term
| _________exist in equilibrium with "enol" form |
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Definition
| ketones (aldehydes to a lesser extent) |
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Term
| solubility of aldehydes and ketones |
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Definition
water soluble, but less than alcohols
1 ketone can solubilize 5 to 6 carbons
solubility decreases as number of carbons increase |
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Term
| pH of aldehydes and ketones |
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Definition
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Definition
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Definition
| prone to oxidation to carboxylic acids and polymerization |
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Term
| stability of acetals, hemiacetals, ketals, and hemiketals |
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Definition
| stable at neutral and basic pH; unstable at acidic pH; conversion back to aldehyde |
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Term
| metabolism of aldehydes and ketones |
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Definition
| aldehydes are readily oxidized into carboxylic acids; ketones (sometimes aldehydes) undergo reduction to a secondary alcohol |
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Term
| why are amines extremely important fxnal groups in medicinal chemistry? |
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Definition
they promote water solubility (solubilizing of drugs as the free base of a water-soluble salt of the amine)
act as a binding site, holding the drug to a specific site in the body -> biological response |
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Term
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Definition
polar bond; permanent dipole
dipole-dipole interactions
H-bond donor (primary, secondary, aryl) and acceptor
dipole-ion interactions for salts |
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Term
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Definition
alkyl amine- moderate bp
aryl amine- high bp |
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Term
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Definition
primary>secondary>tertiary amines
primary amine can solubilize 6-7 carbons
salts>free base (not neutral)
quaternary ammonium salts are VERY water soluble |
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Term
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Definition
basic (weak base to neutral)
basicity:
2>3>1 for alkylamines
--alkyl groups are electron-donating and increase basicity (increase pKa)
--there is steric hindrance in tertiary amine |
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Term
| in amines, aryl groups are electron-_____ and _____ basicity (____pKa) |
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Definition
| electron-withdrawing and decrease basicity (decrease pKa)- may actually be considered weak acids |
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Term
| special case of amines - ammonium salts (quaternary) |
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Definition
| N is bonded to 4 carbons; salt formation is not reversible like primary, secondary, and tertiary amines; salts produce acidic solution in water; quaternaries can dissolve 20-30 carbons |
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Term
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Definition
secondary and tertiary amines undergo N-dealkylation
primary amines undergo deamination
minor: methylation rxn
primary and secondary (not 3) undergo conjugation rxns |
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Term
| bonds in carboxylic acids |
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Definition
polar bonds; permanent dipole
H-bond donor and acceptor |
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Term
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Definition
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Term
| solubility acid form of carboxylic acids |
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Definition
water soluble - up to 6 carbons
slightly water soluble - 6-10 carbons
water insoluble - >10 carbons |
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Term
| solubility of salt form of carboxylic acids |
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Definition
Na+, K+, and NH4+ salts are very water soluble
Ca2+, Mg2+, and Zn2+ salts are not soluble
Salts are produced in basic solution |
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Term
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Definition
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Term
| conjugate bases are stabilized by _____ in carboxylic acids |
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Definition
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Term
in carboxylic acids,
if R is electron-donating, _____ acidity and _____ pKa |
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Definition
| decreases acidity and increases pKa |
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Term
in carboxylic acids,
if R is electron-withdrawing, ______acidity and ______pKa |
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Definition
| increases acidity and decreases pKa |
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Term
in carboxylic acids,
if R is aromatic, Ortho substituents have ____ effect |
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Definition
| variable effect on acidity and pKa |
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Term
in carboxylic acids,
if there are meta or para substituents on an aromatic ring, electron donating substituent ______ acidity and ______ pKa |
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Definition
| decreases acidity and increases pKa |
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Term
in carboxylic acids,
if there are meta or para substituents on an aromatic ring, electron withdrawing substituent ______ acidity and ______ pKa |
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Definition
| increases acidity and decreases pKa |
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Term
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Definition
| carboxylic acid + alcohol |
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Term
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Definition
wear polar bonds; permanent dipole
H-bond acceptor (hydrogen bonds to water and alcohol) |
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Term
| physical-chemical properties of esters are similar to ______ |
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Definition
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Term
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Definition
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Definition
| low water solubility; decrease as hydrocarbon chain increases; better solubility in ethanol |
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Definition
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| reactivity/stability of esters |
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Definition
| easily hydrolyzed back to carboxylic acid and alcohol, especially in a basic medium |
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Definition
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Definition
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Definition
polar bond; permanent dipole
resonance strengthens polarity compared to esters
H-bond donor (except disubstituted amides) and H-bond acceptor |
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Definition
| higher than ethers because of resonance (except when disubstituted) |
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Definition
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Term
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Definition
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Term
| stability/reactivity of amides |
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Definition
| very stable to hydrolysis in vivo compared to esters |
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Term
| carbonates= _____ + _____ |
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Definition
| carbonic acid + 2 alcohols |
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Term
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Definition
polar bonds; permanent dipole
H-bond acceptor |
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Term
| physical and chemical props of carbonates are similar to _____ |
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Definition
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Term
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Definition
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Definition
low water solubility; decreases as hydrocarbon chain increases
better solubility in ethanol |
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Definition
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Term
| stability/reactivity of carbonates |
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Definition
| very unstable to hydrolysis in vivo like esters |
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Definition
polar bonds; permanent dipole
H-bond acceptor |
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Definition
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Term
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Definition
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Term
| stability/reactivity of carbamates |
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Definition
| unstable to acid or base hydrolysis |
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Definition
| carboxylic acid + 2 amines |
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Definition
polar bond; permanent dipole
H-bond acceptor and donor |
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Definition
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Term
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Definition
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Term
| reactivity/stability of urea |
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Definition
| stable to acid and base hydrolysis |
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Term
| amidine is a functional derivative of ____ |
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Definition
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Term
| guanidine is a functional derivative of ____ |
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Definition
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Term
| pH of amidines and guanidines |
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Definition
| highly basic (both have unshared pair of electrons); basicity is increased through resonance |
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Term
| ____ and ____ contain imide nitrogens |
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Definition
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