Organic Chemistry (Kaplan MCAT 2019)

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nucleophilicity _______ with increasing electron density because ______

increases more negative charge

what is the least reactive carb acid derivative? most reactive?

least- amides most-anhydride

bulkier molecules are _____ nucleophilic

less

a compound that rotates plane polarized light to the left is called what?

levorotatory, -

electrophiles will almost always act as ______ ______ in reactions

lewis acids

axial vs equatorial

substituents attached perpenticular (straight up and down) are axial and those pointing outwards parallel are equatorial

structural isomers share only a _____ _______ and have _______ physical and chemical properties

molecular formula differing

When two atomic orbitals combine they form

molecular orbitals

non bonded strain (van der Waals repulsion) occurs when

nonadjacent atoms or groups compete for the same space

TLC mobile phase

nonpolar solvent, which climbs the carb through capillary action

____ and _____ amino acids tend to by hydrophobic and reside in the interior of proteins

nonpolar-nonromantic and aromatic

Gas Chromatography mobile phase

nonreactive gas

mess compounds are made up of two halves that are mirror images, thus they are _____ optically active

not

in TLC, the polar phase is nonpolar, so polar compounds will ________, and nonpolar samples will _________.

not move very far move pretty far

how can you synthesize a carboxylic acid?

oxidation of primary alcohols or aldehydes usually using Na2Cr2O7, K2Cr2O7, CrO3, or KMnO4

almost all organic reactions can be divided into two groups...

oxidation-reduction and electrophile-nucleophile

O2, CrO4-, and Cl2 are examples of good _______ agents

oxidizing

if an aldehyde is not the highest priority group, how will it be named?

oxo-

if a ketone isn't the highest priority group, how is it named?

oxo- or keto-

what are the 4 main reactants in the gabriel's synthesis?

potassium pthalimide diethyl bromomalonate alkyl halide water

B lactam have very high _____ strain because....

ring strain they are a 4 membered rings with both torsional and angle strain

aldehyde naming

replace -e with -al

carboxylic acid naming

replace -e with -oic acid

amide naming

replace -oic acid with -amide

lactam naming

replace -oic acid with -lactam

anhydride naming

replace the acid at the end of the name of the parent carboxylic acid with anhydride

at the end of filtration one is left with the solid, called the ________, and the liquid, called the _______

residue filtrate

what stabilizes the negative charge on a deprotonated carboxylic acid

resonance and Electron withdrawing oxygens

resonance of amides

resonance between the carbonyl and the lone pair on the nitrogen stabilizes the bond and restricts its motion

rotation is limited around the peptide bond becasue

resonance gives the C-N bond partial double bond character

covalent bonding

results from the sharing of electron pairs between two atoms

cleavage of anhydride using alcohols

results in the formation of an ester and carboxylic acid

why are ketones less likely to react with nucleophiles than aldehydes

the extra alkyl group destabilizes the carbanion and increases steric hinderance

gravity filtration is used when

the product of interest is in the filtrate

vacuum filtration is used when

the product of interest is in the solid

optical activity refers to

the rotation of plane polarized light by a chiral molcule

amides may or may not participate in hydrogen bonding so their boiling points are either _____________ or __________ than that of carboxylic acids

the same lower

aldehyde naming

usually are number 1 replace -e of the parent alkane with -al

why would esterification reactions not be carried out in water?

water molecules would hydrolyze the desired products back into the parent carboxylic acids

alcohols are poor leaving groups but they can by protonated or reacted to form goof leaving groups such as...

water, mesylates, or tosylates

strength of pi and sigma bonds

sigma bonds are stronger, so if a bond is broken it is usually a pi bond

methanoic acid common name

formic acid

what are the common names for: methanoic acid ethanoic acid propanoic acid

formic acid acetic acid propionic acid

a proton with 3 adjacent hydrogens will have how many peaks? what will the area ratios be?

4 1:2:2:1

the normal region of IR spectra are from

400-4000 cm-1

gamma-butyrolactone contains a ______ membered ring

5

cyclic carboxylic acid synthesis results in ______ and _______ membered rings and is driven forward by _________

5 and 6 membered rings ring stability and heat

how much s character does an sp bond have? sp2? sp3?

50 33 25

aromatic hydrogens appear in the ________ ppm range

6-8.5

quinones

-phenols treated with oxidizing agents -Named by indicating the position of the carbonyls numerically & adding quinone to the name of parent phenol -Serve as electron acceptors in e- transport chain

chemoselectivity

-preferential reaction of one functional group in the presence of other functional groups

What is the most common form of NMR

-proton NMR, which uses the 1H nucleus

protons on sp3 hybridized carbons are usually in the ________ ppm range protons on sp2 hybridized carbons are usually in the ________ ppm range protons on sp hybridized carbons are usually in the ________ ppm range

0-3 4.6-6 2-3

what is the Rf if the solvent traveled 10 cm and the compound traveled 5 cm

0.5

when looking at plane polarized light rotation, chemists use what standard conditions?

1 g/ml concentration 1 dm (10 cm) tube length

n possible values? l possible values? m(l) possible values? m(s) possible values?

1 to infinity 0 to (n-1) -l to l -1/2 or +1/2

If 1000 triacylglycerols undergo saponification, what will be the product?

3000 soap molecules and 1000 glycerols

most oxidizing agents will turn aldehydes into __________, PCC on the other hand will not because ________

carboxylic acids it is not strong enough to oxidize past the point of aldehyde

functional groups from more to less reactive

carboxylic acids and their derivatives, aldehydes, ketones, alcohols and amines

boiling points of carboxylic acids

carboxylic acids can form more than one hydrogen bond, so there is an even increased boiling point compared to alcohols also, increased molecular weights increase boiling point

esters are formed by the condensation reaction of

carboxylic acids or anhydrides with alcohols

aldehydes are ______ _______, meaning they appear at the end of a parent chain

chain terminating

the most stable conformation of cyclohexane is the ______ conformation, which minimizes all three types of strain

chair

cyclohexane exists mainly in what configurations?

chair, boat, or stint/skew-boat

aldehydic hydrogens appear in the ________ ppm range

9-10

nucleophilicity is determined by four major factors

charge, electronegativity, steric hinderance, solvent

tosylates

contain the functional group -SO3C6H4CH3, which is derived from toluenesulfonic acid

Retardation Factor (Rf)

A ratio used in thin-layer chromatography to identify a compound; calculated as how far the compound traveled relative to how far the solvent front traveled.

Arrhenius acid

Produces H+ ions when dissolved in water

Arrhenius base

Produces OH- ions when dissolved in water

characteristics of the conversion from a hemiacetal to an acetal

SN1, the -OH is lost as a molecule of water, forming a carbocation, the alcohol then attacks the carbocation

does backside attack occur in SN1 or SN2?

SN2

salts of carboxylic acid naming

begin with the cation, followed by the name of the acid with the ending -oate replacing -oic acid

saponification

The process of soap formation

The alkene is named ____ if the two highest-priority substituents on each carbon are on the same side of the double bond

Z zame zide

plane polarization rotatio reactions measured at different concentrations and tube lengths than the standard conditions can be convereted to a standardized specific rotation using this equation

[a]= a(obs)/(c x l) specific rotation in degrees= observed rotation in degrees divided by concentration (g/ml) times path length (dm)

carbonyl group

a chemical group consisting of a carbon atom linked by a double bond to an oxygen atom two examples are ketones and aldehydes

gauche conformation

a conformation with a 60 degree dihedral angle between the largest groups

coordinate covalent bonds

a covalent bond in which one atom contributes both bonding electrons

alkanes

a hydrocarbon containing only single covalent bonds

zwitterion

a molecule or ion having separate positively and negatively charged groups, such as an amino acid

when an aldehyde is mixed with a diol it forms an _______. when a ketone is mixed with a diol it forms a _______.

acetal ketal

ethanoic acid

acetic acid

ethanoic acid common name

acetic acid

functional groups that act as acids include

alcohols, aldehydes and ketones at the alpha carbons, carboxylic acids, and most carboxylic acid derivatives

what are the four reactant in strecker synthesis?

aldehyde NaH4Cl KCN H2O

aldol condensation basics

aldehyde or ketone acts as an electrophile (keto form) and a nucleophil (enolate form), the product is the formation of a carbon-carbon bond an enolate is formed, which attacks the cabonyl carbon, forming an aldol, then -OH is removed as water, forming a double bond

strecker synthesis reactant

aldehyde, ammonium chloride (NH4Cl), and potassium cyanide (KCN)

are aldehydes or alcohols higher priority groups when naming?

aldehydes

acidity of the alpha hydrogens on ketones compared to aldehydes

aldehydes are more acidic because the ketone has more EDGs

what is more reactive, ketones or aldehydes?

aldehydes because less sterics

NMR spectroscopy measures

alignment of nuclear spin with an applied magnetic field, which depeds on the magnetic environment of the nucleus itself.

sp2 hybridization are seen commonly in what?

alkenes

acyl derivatives examples?

all molecules with a carboxylic acid derived carbonyl carboxylic acids, amides, esters, anhydrides, and others

during NMR spec, nuclei may be in the ____ state or in the ____ state the ____ state is higher energy the _____ state is lower energy

alpha or beta state higher energy-Beta lower energy-alpha

during NMR spec, tadiofrequency pulses push the nucleus from the ___ to the ___ state, and these ______ can be measured

alpha to beta state frequencies

the carbon adjacent to the carbonyl is termed the _____ carbon, the carbon to away is termed the ______ carbon and so on

alpha, beta, gamma, delta

conjugation requires

alternating single and multiple bonds because this pattern aligns a number of unhybridized p orbitals down te backbond of the molecules

carboxylic acid derivate examples

amides esters and anhydrides

why do amides contain partial double bond character between the nitrogen atom and carbonyl carbon?

amides have two resonance structures so the true structure is a hybrid of the two

____ and _____ are the main functional groups that act as bases

amines and amides

amino acids contain

amino group, carboxyl group, R group, hydrogen

carboxylic acids can be converted to amides if the incoming nucleophile is ______ or a ______

ammonia (NH3) amine

cleavage of anhydride using ammonia

ammonia acts as a nucleophile and cleaves the anhydride bond results in a carboxylic acid and an amide

amino acids are amphoteric because they have both.....

an acidic carboxyl group and basic amino group

anhydrides can be cleaved by the addition of a nucleophile addition of ammonia or an amine results in ________ addition of alcohol results in ________ addition of water results in ________

an amide and a carboxylic acid ester and a carboxylic acid two carboxylic acids

Ring strain arises from three factors

angle strain, torsional strain, or non bonded strain (sterics)

symmetric anhydrides are named by replacing acid with

anhydride

carboxylic acid derivatives ranked by electrophilicity

anhydrides are the most reactive, followed by carboxylic acids and esters, then amides

Reactivity of carboxylic acid derivatives from most to least reactive

anhydrides, esters and carboxylic acids, amides

the most stable Newman projection for butane

anti

what is the conformation called when the two highest priority groups are 180 degrees apart?

anti

two times of staggered conformation

anti and gauche

If the signs of the wave functions are different, a higher-energy _____ orbital is produced

antibonding

alpha-racemization

any aldehyde or ketone with a chiral alpha carbon will rapidly become a racemic mixture as the keto and enol forms interconvert

alpha carbon

any carbon attached directly to a carbonyl carbon

primary alcohols are oxidized to carboxylic acids by

any oxidizing agent besides PCC

the polar layer during extraction is the ______ phase and the nonpolar layer is the _______ phase

aqueous organic

Deprotection of alcohols is done by

aqueous acid

what will convert a cyclic acetal to a carbonyl and a dialcohol

aqueous acid

to push a retro-aldol reaction ______ and ______ are adde

aqueous base heat

positively charged (basic) amino acids

arginine lysine histidine all side chains has positively charged nitrogen atoms

Chapter 4

Chapter 4

Chapter 5

Chapter 5

Chapter 6

Chapter 6

Chapter 8

Chapter 8

Chapter 9

Chapter 9

the form of phosphoric acid in strongly basic conditions

PO4

when two equivalents of alcohol are added to an aldehyde, what is the product

acetal

what is the most oxidized functional group that appears on the MCAT?

carboxylic acids

mesylates

contain functional group -SO3CH3, which is derived from methanesulfonic acid

kinetic is to thermodynamic as ______ is to _____

speed stability

a scientist takes a 0.5 g/ml solution of an unknown pure dextrorotary organic molecule and places it in a test tube with a diameter of 1 cm. he observed that a plane of polarized light rotates 12 degrees. what is the specific rotation of this molecule?

+240 degrees 12/(0.5 g/ml)(0.1 dm)=12/0.05=240 dextrorotary=+

Gabriel Synthesis

- An amino acid is generated from phthalimide (nucleophile) and diethyl bromomalonate, using two SN2 reactions, hydrolysis, and decarboxylation.

proton NMR is good for

- Determine the relative number of protons and their relative chemical environments - Showing how many adjacent protons there are by splitting patterns. - Inferring certain functional groups

Alcohols are named by replacing the suffix -e with _____ or by naming the alkyl group as a derivative followed by _____

-ol (2-propanol) alcohol (ethyl alcohol)

alpha hydrogens

- hydrogens connected to an alpha carbon - are acidic

enolate

- results from deprotonation that is stablized by resonance with the carbonyl - good nucleohpiles

Nonpolar, nonaromatic amino acids

- tend to have side chains that are saturated hydrocarbons alanine valine leucine isoleucine glycine proline methionine

Recrystallization

- the product is dissolved in a minimum amount of hot solvent - if the impurities are more soluble, the crystals will reform while the flask cools, excluding the impurities

acids with a pKa below ______ are considered strong acids

-2

weak organic acids often have pKa values between

-2 and 20

if an aldehyde is attached to a ring, the suffix _____ is used

-carbaldehyde

ketones are named by replacing the -e of the parent alkane with

-one commonly names by listing the alkyl groups in alphabetical order followed by ketone

in a hemiacetal the central carbon is bound to what?

-OH, -OR, -H, -R

nucleophilic substitution reaction

-SN1 and SN2 -nucleophile forms a bond with a carbon and a leaving group leaves

heterolytic reactions

-a bond is broken and both e- are given to one of the 2 products essentially is the opposite of coordinate covalent bonding

dicarboxylic acid naming

-dioic acid

geminal diols

-diols with hydroxyl groups on the same carbon

reducing agents

-elements in redox reactions that donates e- to another species it losses e- so it becomes oxidized

carboxylic acids are names by replacing the -e of the parents alkane with

-oic acid

pKa can be calculated by

-log(Ka)

leaving groups

-molecular fragments that retain e- after heterolysis

nucleophiles

-nucleus loving -negatively charged so they are attracted to the + nucleus -have lone pairs or π bonds that can be used to form covalent bonds to electrophiles

Jones oxidation

-uses CrO3 dissolved with H2SO4 in acetone -oxidizes primary alcohols to carboxylic acids or secondary alcohols to ketones

functional groups ordered from least to most oxidized

1-alkanes 2-alcohols, alkyl halides, amines 3-aldehydes, ketones, imines 4-carboxylic acids, anhydrides, esters, amides 5-carbon dioxide

alcohols are neamed by replacing the e at the end of the alkane with ol, so a terminal alcohol with all single bonds and 6 carbons would be called

1-hexanol

ststrecker synthesis steps

1. ammonia attacks the carbonyl carbon forming an imine 2.an aminonitrile is generated by KCN attacking the imine 3. an amino acid is generated from the aminonitrile

esterification steps

1. carbonyl oxygen is protonated 2. primary alcohol attacks carbonyl carbon 3. -OH on alpha carbon is protonated to H2O and then leaves as a leaving group 4. carbonyl is deprotonated

Steps in Problem Solving

1. know the nomenclature 2. ID the functional groups 3. ID the other reagents 4. ID the most reactive functional groups 5. ID the first step 6. consider stereoselectivity

nucleophilic acyl substitution steps

1. nucleophilic addition 2. elimination of a leaving group (H2O) and formation of the carbonyl

steps of michael addition

1. the base deprotonates the alpha carbon, making it a good nucleophile 2. the carbanion attacks the double bond of an ab-unsaturated carbonyl compound, resulting in michael addition

R and S forms

1. used the Cahn-Ingold Prelog priority rules to assign priority to the four substituents on the chiral center -only look at the atoms that are directly attached to the carbon -higher atomic number gets priority *if tie is there look at the combination of the atoms attached to the atom attached to the chiral center* -double bond, bonded to it twice 2. draw a circle connecting 1 to 2 to 3 clockwise --> R - RIGHT counterclockwise --> S - LEFT 3. If H is not going into the page (dashed lines or up/down) then opposite configuration

an electron is known to be in the n=4 shell and the l=2 subshell. how many possible combinations of quantum numbers could this electron have?

10

carboxylic acid hydrogens appear in the ________ ppm range

10.5-12

each orbital contains ______ electrons

2

two different ways to name an pentene with the double bond between the 2nd and 3rd carbon

2-pentene or pent-2-ene

isopropyl alcohol

2-propanol

What two peaks would you expect to see in the IR spectrum of a carboxylic acid?

3000 O-H 1750 C=o

meso compound

A compound with chirality centers and an internal plane of symmetry causing it to be an achiral molecule

fischer projection

A method of drawing organic molecules in which horizontal lines are coming out of the page (wedges) and vertical lines are going into the page (dashes)

chiral

A molecule or carbon atom bonded to four different groups and without a plane of symmetry; thus, it is not superimposable upon its mirror image and has an enantiomer.

achiral

A molecule that is superimposable on its mirror image

oxidation state

A positive or negative whole number that represents the "charge" an atom in a compound would have if all shared electrons were assigned to the atom with a greater attraction for those electrons.

solute

A substance that is dissolved in a solution.

NMR shifts for Alkyl groups, alkynes, alkenes, aromatics, aldehydes, and carboxylic acids

Alkyl groups 0-3 ppm alkynes 2-3 ppm alkenes 4.6-6 ppm aromatics 6-8.5 ppm aldehydes 9-10 ppm carboxylic acids 10.5-12 ppm

column chromatography stationary phase

Alumina or silica gel

the form of phosphoric acid in strongly acidic conditions

H3PO4

phosphoric acid

H3PO4 extremely important biochemically, forms the high energy bonds of ATP

nitriles

C triple bond N

most reduced form of carbon

CH4, where it has an oxidative charge of -4

most oxidized form of carbon

CO2, where it has an oxidative charge of +4

Chapter 3

Chapter 3

Chapter 1

Chapter 1

Chapter 10

Chapter 10

Chapter 11

Chapter 11

Chapter 2

Chapter 2

ionic bonding

Chemical bonding that results from the electrical attraction between cations and anions, electrons are transferred from one atom to another

Ubiquinone

Coenzyme Q vital electron carrier associates with Complexes 1, 2, and 3 of the ETC

aminonitrile

Compound containing an amino group and a nitrile group

Stereoisomers

Compounds with the same structural backbone, but a different arrangement in space (wedges and dashes)

aldol

Contains both aldehyde and alcohol functional groups.

Jones reactions require what?

CrO3, H2SO4, and acetate

tosylates are prepared using

alcohols with p-tosylsulfonyl chloride, forming esters of tosylsulfonic acid

When a new nucleotide is incorporated into a DNA strand by _______________, the following phosphate(s) of the incoming nucleotide is released:

DNA polymerase pyrophosphate (PPi) (P2O7)

Dextrorotary vs Levorotary

Dex is clockwise, Lev is Counter

the alkene is named _____ if the two highest-priority substituents on each carbon are on the opposite side of the double bond

E

how to remember what examines are?

ENEamines ene=double bond amine=nitrogen

electron withdrawing groups and electron donating groups effect on phenol acidity

EWGs increase acidity and EDGs decrease acidity

diols/glycols

alcohols with two hydroxyl groups

How are peptide bonds broken?

H+ or -OH hydrolysis

byproduct of anhydride synthesis

H2O

what is the leaving group of a nucleophilic acyl substitution?

H2O

which of the following are lewis bases? Ag+ H2O NH3

H2O and NH3

at physiological pH what two phosphoric acids are in the highest concentration

H2PO4 and HPO4

Before absorbing an ultraviolet photon, electron scan be found in: The HOMO only The LUMO only Both the HOMO and LUMO neither the HOMO nor the LUMO

HOMO only

what is the major historical distinction between HPLC and column chromotography?

HPLC at high pressure

what is the major current distinction between HPLC and column chromotography?

HPLC is computerized

phenols

Hydroxyl groups attached to aromatic rings -Two groups on adjacent carbons are called ortho- or o- -Two groups separated by a carbon is called meta- or m- -Two groups on opposite sides of the ring are called para- or p-

How are hydroxyquinones produced?

Hydroxyquinones are produced by the oxidation of quinones adding a variable of additional hydroxyl groups.

In a protic solvent, which halogen would be the best nucleophil

I-

some examples of good leaving groups

I-, Br-, Cl-

phylloquinone

Important for photosynthesis and reactions of clotting factors in blood

Solvent

In a solution, the substance in which the solute dissolves.

all amino acids are ___-isomers, and all have ____ configurations except for cysteine

L-isomers S

amides can be reduced to amines using

LiAlH4

carboxylic acids can be reduced by __________, but not by less reactive __________.

LiAlH4 NaBH4

what is stronger, NaBH4 or LiAlH4, and why?

LiAlH4 is a more powerful reducing agent that NaBH4, because the Al-H bond is weaker and thus less stable than B-H bond

Immiscible liquids

Liquids that repel each other and do not mix to form a solution

_______ is the medical application of NMR spec

MRI

naming of quinones

Numerically indicate carbonyls and add quinone to name of parent phenol

difference between NH and OH peaks in IR spec

OH is broad and NH is sharp

The release of ________ provides energy for the formation of a new phosphodiester bond on a DNA strand

PPi (pyrophosphate) (P2O7)

spin-spin coupling (splitting)

Occurs when we have 2 protons in close proximity to each other that are not magnetically identical

rotary evaporator (rotovap)

Once the desired product is extracted substance is placed in rotovap in order to evaporate the solvent Leaving solute extract behind

primary alcohols can be oxidized to aldehydes by

PCC

to oxidize a primary alcohol to an aldehyde you must use

PCC

primary alcohols can be oxidized by one level to become aldehydes by ______, otherwise they are oxidized all the way to carboxylic acids by _______

PCC CrO3, Na2Cr2O7, K2Cr2O7

secondary alcohols can be oxidized to form ketones by

PCC or any stronger oxidizing agent

condensation reactions

Result in the formation of a bond between two monomers with the release of a water molecule

relative configuration

The Spatial arrangement of groups in a chiral molecule compared to another chiral molecule.

decarboxylation

The complete loss of a carboxyl group as carbon dioxide

the coupling constant, J, is

The magnitude of splitting in NMR spectroscopy, measured in hertz.

retro-aldol reaction

The reverse of an aldol condensation reaction, in which a carbon-carbon bond is cleaved with heat and base, yielding two aldehydes, two ketones, or one of each.

For any molecule with n chiral centers...

There are 2^n possible stereoisomers.

When is fractional distillation used?

To separate two compunds with boiling points less than 25 degrees apart

isomers

Two different molecules that have the same chemical formula but different structures

what is a wash?

When you are using the extraction to remove impurities rather than separate out the desired product.

peaks that have more than 4 shifts will be referred to as

a multiplet

examines contain

a nitrogen and a double bond

LiAlH4 will reduce esters to

a pair of alcohols

amide synthesis is done by the reaction of a carboxylic acid derivative with _______

a primary or secondary amine or ammonia

SN1 reactions yield what product

a racemic mixture

both the strecker and gabriel synthesis result in

a racemic mixture of amino acids

oxidation reduction reactions

a reaction that involves the transfer of electrons between reactants

during ion exchange chromatography, after all other compounds have moved through the column, ____________ is used to elute the charged molecules that have stuck to the column

a salt gradient

what can cause the deprotonation of an alpha carbon, causing an enolate to form

a strong base, such as OH-, LDA, KH

what is the reverse of extraction?

a wash

what is the final product of an aldol condensation?

ab-unsaturated carbonyl

IN an IR spectrum, how does extended conjugation of double bonds affect the absorbance band of carbonyl (C=O) stretches compared with normal absorption? The absorbance band will occur at a lower wavenumber The absorbance band will occur at a higher wavenumber The absorbance band will occur at the same wavenumber The absorbance band will disappear.

absorbance will occur at a lower wavenumber

UV spectroscopy measures

absorption of UV light, which causes movement of electrons between molecular orbitals

oxidizing agents

accepts an electron from another species because it is gaining electrons it is itself reduced

what is the smaller possible ketone?

acetone

When benzaldehyde is reacted with acetone, which will act as the nucleophile? Benzaldehdye, after addition of strong acid Benzaldehyde after reaction with strong base Acetone, after addition of strong acid Acetone, after reaction with strong base

acetone after reactions with a strong base

what can be used to increase solubility during extraction?

acid base properties

the carboxyl group on an amino acid is ________ and the amino group is ______

acidic basic

How to separate a racemic mixture

add another enantiomer, this will create two diastereomers diastereomers have different physical properties and can be separated by common lab techniques such as crystallization, filtration, or distillation

symmetric anhydrides can be split into two carboxylic acids by

adding H2O

moelcular orbitals are obtained mathematically by ......

adding or subtracting the wave functions of the atomic orbitals

how do hydroxyquinones differ from quinones?

addition of one or more hydroxy groups

in order to separate a biological effector from solution, what chromatographic technique would be used

affinity chromatography using antibodies

if a molecule with two double bonds adjacent to each other and an alcohol, which functional group would take precidence in naming?

alcohol

given an alcohol, alkane, and aldehyde with equally long carbon chain, which will have the highest BP

alcohol because of Hydrogen bonding

aldehydes and ketones undergo reduction to form ______ by _____

alcohols hydrides such as NaBH4 or LiAlH4

what property or properties do structural isomers have in common?

atomic weight

would an acid or a base be most effective in extracting benzoic acid from diethyl ether?

base

good nucleophiles tend to be good _____

bases

saponification is the process where fats are hydrolyzed under ______ conditions

basic

ion exchange chromatography

beads are coated with charged substances to bind compounds with opposite charge

size exclusion chromatography

beads have small pores which trap smaller compounds and allow larger compounds to travel through faster

SN2

bimolecular nucleophilic substitution 1 step (concerted) -nucleophile attacks at the same time the leaving group leaves second order, the rate depends on the concentration of substrate and nucleophile

to appear on an IR spec, vibration of a bond must change the

bond dipole moment

if signs of the wave function are the same a ____ is produced

bonding orbital

nonpolar amino acids

both aromatic and nonaromatic hydophobic and tend to be on the interior of proteins Glycine, Alanine, Valine, Leucine, Isoleucine, Phenylalanine, Tryptophan, Methionine, Proline

priority of functional groups on MCAT from highest to lowest

carboxylic acid, anhydride, ester, amide, aldehyde, ketone, alcohol, alkene, alkyne, alkane

in protic solvents, nucleophilicity of halogens (I, Cl, F, Br) decreases in this order

bottom to top I>Br>Cl>F this is because the protons in solution will be attracted to the nucleophile. HF is the conjugate base of a weak acid and HI is the conjugate base of a strong acid. F will be bound to H and will be unable to attack, while I will be less effected by the protons in solution and will be able to easily attack the electrophile

configurational isomers can only change from one to another by

breaking and reforming covalent bonds

OH IR spec peak (not carboxylic acid)

broad peak at 3300 cm-1

what can slow down a chair flip?

bulky groups are attached (such as a test butyl group)

how are carboxylic acid derivates all formed?

by replacing the -OH on the carboxyl group with another leaving group (-NH2, -OR, and -OCOR)

amphoteric

can act as an acid or a base example: water

protecting groups

can be used to increase steric hindrance or otherwise decrease the reactivity of a particular portion of a molecule

if one diastereomer rotates light clockwise 10 degrees, the other diastereomer will rotate light in which magnitude/direction?

can't tell diastereomers have no relation to each other in terms of optical activity

NaBH4 cannot reduce ________

carboxylic acids

cis-trans isomers (geometric isomers)

carbons have covalent bonds to the same atoms, but these atoms differ in their spatial arrangements due to the inflexibility of double bonds

what is the most common electrophile seen on test day?

carbonyl carbon

hydration of a carbonyl steps

carbonyl is hydrated by water, then protonated, resulting in a geminal diol

why are alcohol boiling points greater than carbonyl boiling points?

carbonyls have no Hydrogen bonding

the primary product of a primary alcohol with a strong oxidant like dichromate will be

carboxylic acid

what is the product of amide hydrolysis?

carboxylic acid and ammonia

NMR spectra are standardized using __________ which is measured in parts per million

chemical shift

whenever you see a carbon with 4 different substituents, this about

chirality

if both groups on a ring are on the same size it is said to be ______ and if they are on opposite sides it is said to be ______

cis trans

R form if 1,2,3 goes ______, S form if 1,2,3 goes _____

clockwise counterclockwise

the system of labeling optical activity always uses + or d- to refer to _______ rotation and always uses - or l- to refer to ______ rotation

clockwise counterclockwise

mnemonic for an R chiral center

clockwise turning of the steering wheel turns the car to the right so it is R

the smaller the number of n the .....

closer the shell is to the nucleus and the lower its energy is

Gas Chromatography stationary phase

coil of crushed metal or a polymer

carboxylic acid derivative synthesis is an example of a _______ reaction that gives off _____

condensation H2O

imine formation is an example of a ________ reaction and also a _______ _________

condensation nucleophilic substitution

esterification is a ______ reaction with ______ as the byproduct

condensation water

anhydrides can be formed how?

condensation of two carboxylic acids

stereospecific reaction

configuration of the reactant determines the configuration of the products

the most similar of all isomers

conformational isomers

conformational vs configurational bonds

conformational= differ in rotation around a single bond configurational= can be interconverted only by breaking bonds

The more stable the ______ _______ is the more likely thatthe proton will leave, making the molecule more acidic

conjugate base

what chemical properties of ubiquinone allow it to carry out its biological functions

conjugated rings that stabilize the ring when accepting electrons, long alkyl tails that allow it to dissolve in the lipid bilayer

enones are a classic example of

conjugation

organic chemistry is deeply rooted in ______ bonding

covalent

HCN reactions with aldehydes and ketones form

cyanohydrins

many anhydrides are ______ because of an intramolecular dehydration of a _______

cyclic dicarboxylic acid

lactones are

cyclic esters

torsional strain results when

cyclic molecules must assume a conformation that has eclipsed or gauche interactions

all optically active amino acids are L/S, except

cysteine

phosphate bonds are high energy because

large negative charges in adjacent phosphate groups and resonance stabilization of phosphates

generally bond strength ____ down the periodic table and therefore acidity _____

decreases increases

nucleophilicity _____ as electronegativity increases because _____

decreases these atoms are more likely to share electron density

in basic solution, an amino acid can become fully _______ and in an acid solution, it can become fully _______

deprotonated- because the bases will take hydrogens protonated- because the acids will donate hydrogens

absolute configuration

describes the exact spatial arrangement of groups of atoms independent of other molecules.

Deshielding mneumonic

deshield, downfield

NMR: deshielding

deshielding of protons occurs when EWGs pull electron density away from the nucleus, allowing it to be more easily affected by the magnetic field

when looking at a fischer projection and the lowest group is on a vertical line (out of the page) you need to

determine the R/S order by numbering 1,2, and 3 and then the true R/S will be the opposite

a compound that rotates plane polarized light to the right is called what?

dextrorotary, +

cis-trans isomers are a subgroup of

diastereomers

are carboxylic acids more or less acidic than dicarboxylic acids?

dicarboxylic acids are more acidic than carboxylic acids because the carboxylic acids act as EWGs towards each other

what serves as the electrophile during gabriel synthesis

diethyl bromobalonate

diasteromers physical and chemical properties

different physical and chemical properties, though come chemical properties may be similar because they have the same functional groups diastereomers have no relation to each other in terms of plane-polarized light

carboxylic acids tend to form ________, pairs of molecules that are connected by two hydrogen bonds

dimers

_____ are often used as protecting groups for aldehyde or ketone carbonyls

diols

strong acids........

dissociate completely

in aqueous solution, PPi will likely

dissociate into 2 inorganic phosphates

during distillation, the liquid with the lowest bp vaporizes first and is collected as the

distillate

More basic molecules have ______ pKa

larger

UV spec is most useful for studying compounds containing

double bonds or heteroatom with lone pairs that create conjugated systems

an imine contains a nitrogen atom

double bound to a carbon atom

splitting patterns include

doublets triplets multiplets

in polar protic solvents, nucleophilicity increase _____ the periodic table

down

pKa decreases _____ the periodic table and increases with ______ electronegativity

down increased

Deshielding moves a peak further ______

downfield

NMR spec with higher chemical shifts are located ______ which is to the _______. Lower chemical shifts are located _____ which is to the _______.

downfield to the left upfield to the right

ketone naming

drop -e add -one

p orbital shape

dumbbell shaped, contain a node where the probability of finding the electron is zrritlsao

what is the conformation called when the two highest priority groups are 120 degrees apart?

eclipsed

spin quantum number (m sub s)

either +1/2 or -1/2, indicating the spin orientation of an electron

2 ways that you can prevent multiple products from forming during aldol condensation?

either use only one type of aldehyde or ketone OR if one molecule has no a-hydrogens then it cannot become an enolate and cannot act as a nucleophile

Electrophiles are

electron loving with a positive charge or positively polarized atom

lewis acid

electron pair acceptor, electrophiles usually

lewis base

electron pair donor, nucleophiles usually

substituents effect on anion stability and acidity

electron withdrawing groups stabilize the anions and make stronger acids, the closer the substituent groups are to the carboxyl group the greater the effect will be

carbonyl carbon is

electrophilic

Imines naturally tautomerize to form:

enamines

just as enols are tautomers of carbonyls, ______ are tautomers of imines

enamines

these stereoisomers are non-superimposable and have opposite configurations at every chiral center

enantiomers

the two categories of configurational isomers

enantiomers and diastereomers

physical and chemical properties of two enantiomers

enantiomers have nearly identical physical and chemical properties, but they rotate light in opposite directions and react differently in chiral environments

alkene and alkyne endings

ene, yne

the conversion between keto and enol is called what?

enolization or tautomerization

during size exclusion chromatography the ________ compounds will travel quicker

larger

cyclopentane exists mainly in what configuration?

envelope

large molecules in the chair conformation are more favorable in the axial or equatorial position?

equatorial

base strength is relative to _______ and is therefore a ________ property

equilibrium position of a reaction thermodynamic

triacyglycerols are what?

esters of long chain carboxylic acids (fatty acids) and glycerol (1,2,3-propanetriol)

carboxylic acids include

esters, amides, and anhydrides

acetaldehyde and acetic acid both refer to molecules with ______ as the parent alkane

ethane

ethyl alcohol

ethanol

what are the products of the transesterification reaction between isopropyl butanoate and ethanol?

ethyl butanoate and 2-propanol

extraction is carried out in a separator funnel, one phase collected and the solvent is then ________

evaporated

imines can undergo tautomerization to form

examines

when is the kinetic product favored?

favored reactions that are rapid, irreversible, at lower temperatures, with a strong, sterically hindered base

SN1 reactions are ______ order and the rate depends on what?

first only the concentration of the substrate

naming esters

first term is alkyl name of the esterifying group second term is the name of parent acid, with -oate replacing -oic acid the group the replaces the H of the alcohol in the carboxylic acid is names as a substituent

alkyl halides are indicates by a prefix:

fluoro, chloro, bromo, iodo

menaquinone

form of vitamin K produced by bacteria in the large intestine

the common names of aldehydes and carboxylic acids that contain only one Carbon is what?

form-

the same common name prefixes are used from both aldehydes and carboxylic acids; _________ for one carbon, _________ for two carbons, ________ for three carbons

form- acet- propion-

what are the common names for: Methanal Ethanal Propanal

formaldehyde acetaldehyde proprionaldehyde

rate determining step for SN1

formation of the carbocation

saponification occurs by

mixing fatty acids with lye (NaOH or KOH)

d orbital shape

four of the d orbitals are closer shaped and the fifth looks like a donut wwrapped around the center of a p orbital

if you were given solution with a BP of 308 K and a solution with BP of 313K, what distillation technique would work best?

fractional, these are close BPs

during affinity chromatography, after the protein is retained in the column, it can be eluted by washing the column with a __________ that does what?

free receptor (or target or antibody) that competes with the bead-bound receptor and ultimately frees up the protein

wavenumber is directly proportional to ______

frequency

NMR spectra are usually plotted as

frequency vs.

reduction

gain of electrons, decrease in oxidation number

what is the conformation called when the two highest priority groups are 60 degrees apart?

gauche

in the presence of water, aldehydes and ketones react to form

geminal diols

Geminal diols vs. Vicinal diols

geminal diols have hydroxyl groups on the same Carbon and vicinal diols have hydroxyl groups on adjacent carbons

________ diols have hydroxyl groups on the same Carbon and _______ diols have hydroxyl groups on adjacent carbons

geminal, vicinal Mneumonic- gemini twins are paired, vicinal are in the vicinity of eachother

what is the dominant strain during flagpole interactions

non bonded strain

all amino acids except _______ are optically active

glycine

diols are also called ?

glycols

weak bases are ____ leaving groups

good

molecules with more than one hydroxyl group show _______ degrees of Boiling Points and Melting Point increases

greater this is due to increased Hydrogen bonding

during a chair flip, the cyclohexane molecule briefly passes through a fourth conformation called what?

half chair

conformational isomers are the same molecule but are ________________.

in different points in their natural rotation

good oxidizing agents

have a high affinity for electrons or have a very high oxidation state. Examples O2, O3, Cl2, MnO4-, CrO4-, CrO2-7. and pyridinium chlorochromate. These contain a metal and a large number of oxygen atoms.

when an amino acid is placed in solution it will do what?

have a positive charge on the amino group and negative on the carboxyl group, making it a zwitterion

to appear on a UV spectrum, a molecule must

have a small enough energy difference between its HOMO and LUMO to permit an electron to move from one orbital to another

good reducing agents

have low electronegativities and ionization energies or contain a hydride ion (H-) Examples- Sodium, Magnesium, Aluminum, Zinc, NaH, CaH2, LiAlH4, NaBH4. These compounds contain a metal and a large number of hydrides.

sigma bonds are formed by ______ or _____ overlap of atomic orbitals

head to head tail to tail

B-dicarboxylic acids may spontaneously decarboxylate when _________

heated

certain cyclic anhydrides can be formed by simply __________

heating carboxylic acids

when one equivalent of alcohol is added to an aldehyde, what is the product?

hemiacetal

when one equivalent of alcohol is added to an ketone, what is the product?

hemiketal

Strong acids have ___ Ka values and _______ pKa values

high low

the more electronegative the atom, the _______ the acidity

higher

carbonyl BP and MPs are ______ than alkanes and _______ than alcohols

higher less

anhydride boiling points compared to carboxylic acids

higher based on much greater weight

boiling points of alcohols compared to analogous hydrocarbons

higher due to intermolecular hydrogen bonding

conjugation shifts the UV absorption spectrum to

higher maximum wavelengths (lower frequencies)

when is the thermodynamic product favored?

higher temperatures, slow reversible reactions, and with weaker and smaller bases

eclipsed conformation

highest energy no separation. or 120 separation.

hydrolysis of amide occurs under what conditions? why?

highly acidic or basic acidic- allow the carbonyl oxygen to become protonated, making the molecule more susceptible to nucleophilic attack by a water molecule

protic solvents can ____ nucleophilicity by _____

hinder protonating the nucleophile or through hydrogen bonding

what is used to maintain solubility during gravity filtration?

hot solvent

Gas Chromatography separates vaporizable compounds based on

how well they adhere to the absorbent in the column

reduction reactions often feature an increase in the number of bonds to ______ and reducing agents often contain ____ bonded to a large number of ______

hydrogen metals hydride ions

carboxylic acids have higher boiling points than their corresponding alcohols primarily because

hydrogen bonding is much stronger than in alcohols

Three intermolecular forces that affect solubility

hydrogen bonding, dipole-dipole interactions, van der waals forces

at physiological pH, inorganic phosphate includes molecules of both

hydrogen phosphate (HPO4) and dihydrogen phosphate (H2PO4)

pyrophosphate is unstable and is

hydrolyzed into two inorganic phosphates

when the alcohol is not the highest priority group it is named as a substituent with the prefix

hydroxy-

what is more acidic in a B-dicarboxylic acid, the alpha hydrogen or the hydroxyl hydrogen

hydroxyl hydrogen

common ammonia derivatives that react with aldehydes and ketones

hydroxylamine (which forms oximes), hydrazine (which forms hydrazones), and semicarbazide (forms semicarbazones)

the IR spec of two enantiomers will be

identical

Thin-Layer And Paper Chromatography is used to

identify a sample

IR spec is best for

identifying the presence of or the absence of functional groups

When is vacuum distillation used?

if boiling points are over 150 degrees C to prevent degradation of the product

when is simple distillation used

if boiling points are under 150 degrees C and are at least 25 degrees C apart

When is HPLC used?

if the sample size is small or if forms such as capillary action will affect the results

the reaction between ammonia and an aldehyde would yield

imine

what is more common, imine form of the examine form?

imine

would acid dissolve better in aqueous acid or aqueous base? why?

in base, like disolves like refers to polarity

esters that are cyclic are called

lactones

the ______ (area under the curve) of an NMR peak is proportional to the number of protons contained under the peak

integration

anytime 2 groups are switched on a chiral carbon, the stereochemistry is

inverted

rotating a Fischer diagram 90 degrees _____ the stereochemistry while rotating it 180 degrees _______ the stereochemistry

inverts retains

switching one pair of substituents in a fischer diagram _____ the stereochemistry of the chiral center. switching two pairs _____ the stereochemistry

inverts retains

gas chromatography/mass spectrometry

ionizes the fragments molecules and passes these fragments through a magnetic field to determine molecular weight or structure

What makes fractional distillation different from simple distillation?

it has more surface area and allows the vapor to condense at more areas, allowing for a more refined seperation of liquids

why is cysteine's configuration R?

it has sulfur in its R group so there is a change in priority

Phosphoric Acid (H3PO4) is an excellent buffer because

it has three hydrogens with pKa values that span nearly the entire pH scale

what makes glycine unique?

it is achiral

why is vacuum distillation useful?

it is good for high boiling points so as to not degrade the products, the increased pressure makes the solutions boil at lower temps

when two equivalents of alcohol are added to an ketone, what is the product

ketal

Due to the acidity of the a-hydrogen, aldehydes and ketones exist in solution as a mixture of two isomers

keto form and the enol form

secondary alcohols can be oxidized to

ketones

electrophilicity is a _____ property where acidity is a ______ property

kinetic thermodynamic

if a reaction is reversible, the _____ product can be converted to the ______ product

kinetic (less stable) thermodynamic (more stable)

azimuthal quantum number

l

lactones vs lactams mneumonic

lactAM is a cyclic AMide lactone is a cyclic ester

amides that are cyclic are called

lactams

sp hybrid shape

linear

cyclic carboxylic acids are named

list the cycloalkane with the suffix "carboxylic acid"

when naming amides, how are substituents on the nitrogen named?

listed as prefixes with the letter "N-"

soaps are basically _________ chain _________

long chain salts

during UV spec, the smaller the difference between HOMO and LUMO the ______ the the wavelengths a molecule can absorb

longer

the closer the HOMO and LUMO are, the

longer the wavelength

oxidation

loss of electrons, increase in oxidation number in organic chem it is easier to view oxidation as increasing the number of bonds to oxygen or other heteroatoms (atoms besides carbon and hydrogen)

injected compounds into gas chromatography must be volatile, meaning......

low melting point, subliminal solids or vaporizable liquids

the alpha state of the nuclei is the ________ energy stage

lower

alpha state= _____ energy beta state= _____ energy

lower higher

magnetic quantum number

m sub l

spin quantum number

m sub s

gas chromatography may be combined with

mass spectrometry

IR spectroscopy

measures absorption of infrared light, which causes molecular vibration (stretching, bending, twisting, and folding)

what does NMR spec measure and what is it good for?

measures alignment of a nucleus within a magnetic field, good at finding connectivity by looking at hydrogen

acid dissociation constant (Ka)

measures the strength of an acid in solution

formaldehyde and formic acid both refer to molecules with ______ as the parent chain

methane

alkanes with 1 Carbon to 12 Carbons

methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane

formic acid

methanoic acid

SN2 reactions favor ______ or ____ carbons are preferred over _______ carbons, and _______ carbons wont react

methyl or primary secondary tertiary

mesylates are prepared using

methylsulfonyl chloride and an alcohol in the presence of a base

hybrid orbitals are formed by

mixing different types of orbitals

enantiomers

molecules that are mirror images of each other EVERY chiral center in the molecule is opposite

bonding orbitals are ______ stable than anti bonding orbitals

more

multiple extractions with smaller volumes of fresh water is ______ effective than one large extraction

more

the more oxidized the functional group, the _____ reactive it will be in both oxidation-reduction and nucleophile-electrophile reactions

more

the Hydrogen of the phenol alcohol is ________ acidic than normal alcohols. why?

more the resonance of the aromatic ring causes increased stability of the conjugate base

anti conformation

most favorable of staggered conformations, two largest groups are 180 rotated from eachother

are there more keto or enol tautomers in solution?

much more keto

principal quantum number

n

a proton's peak is split into ______ sub peaks, where n is the number of protons that are three bonds away from the proton of interest

n+1

five categories of amino acids

non polar nonaromatic, aromatic, polar, negatively charged (acidic), positively charged (basic)

ester naming

name group off of the Oxygen as a substituent and then name the carboxylic acid with -oate ending Picture shown is ETHYL ETHANOATE

non symmetric anhydrides are named by

naming both carboxylic acids (minus "acid") and then adding anhydride

when anhydrides are asymmetrical, name them by

naming the two chains alphabetically followed but the word anhydride

tertiary alcohols can be oxidized by

never, they cannot be oxidized without breaking a carbon-carbon bond

are all quinones aromatic?

no

racemic mixtures have _______ optical activity

no

will Carbon-12 appear in NMR spec?

no

physical properties

no change in the composition of matter examples: MP, BP, solubility, odor, color, density

symmetric stretches do not appear on IR spectra because they involve _____

no net charge in dipole movement

staggered newman projection

no overlap of atoms along the line of sight

carboxylic acid derivatives of higher reactivity can form derivatives of lower reactivity but not vice versa. esters form anhydrides?

no, anhydrides are more reactive than esters

is conversion from an ester to an anhydride possible by a nucleophilic reaction?

no, that would be going from less to more reactive

During the Gabriel synthesis, phthalimide serves as the; Nucleophile Base Leaving group Electrophile

nucleophile

HCN is a class example of a _______

nucleophile

How do the definitions of nucleophile and electrophile differ from those of Lewis Acids and Lewis Base?

nucleophile and electrophile are kinetic Lewis Acids and Lewis Base are thermodynamic

describe the SN2 backside attack?

nucleophile attacks the carbon from the opposite side as the leaving group, inverting the configuration

briefly describe the mechanism of nucleophilic acyl substitution reactions

nucleophile attacks the carbonyl carbon and then the leaving group leaves(H2O)

How must the nucleophile and leaving group be related in order substitution reaction to proceed?

nucleophile must be a stronger base, LG must be more stable and less reactive,

_______ tend to have lone pairs of pi bonds that can be used to form ________ bonds to ________

nucleophiles covalent electrophiles

carbonyls can act as either _______ or ________

nucleophiles (condensation reactions) electrophiles (nucleophilic addition reactions)

many of the reactions in which carboxylic acids participate proceed via and single mechanism: ________.

nucleophilic acyl substitution

most notable examples of organic phosphates

nucleotide triphosphate (ATP or GTP) and DNA

nuclei with _______, ________, or both will have a magnetic moment when placed in a magnetic field

odd mass numbers, odd atomic numbers, or both

chair flip

one chair conformation is converted to the other briefly passes through the half chain conformation all axial groups become equatorial all equatorial groups become axial dashed lines remain dashed wedges remain wedges

how does enol get its name?

one from Carbon=Carbon double bond ol from the alcohol

two examples of cyclic anhydrides

ophthalmic and succinct anhydrides, which aris from intramolecular condensation or dehydration of diacids

within each subshell there may be multiple ______

orbitals

orbital hybridization

orbitals involved in covalent bonding in an atom are hybridized so that they are identical in properties, and those properties are intermediate to the properties of the original orbitals

the ______ layer is usually on the top and the _______ layer is usually on the bottom

organic layer on top aqueous on the bottom ****though it can be different, it all comes down to density

organic phosphates vs inorganic phosphates

organic phosphates are bound to Carbon

Ortho, Meta, Para

ortho (1,2) meta (1,3) para (1,4)

what is the name of the smallest dicarboxylic acid?

oxalic acid (ethandioic acid)

what are the first 6 straight chain dicarboxylic acids in order?

oxalic, masonic, succinic, glutamic, adipic, and pimelic acids

alpha hydrogen acidity

oxygen pulls some of the electron density out of the bond between the alpha carbon and alpha hydrogens, weakening them and making these hydrogens acidic

how is pka defined and what does low pka indicate

pKa=-logKa low pKa = increased acidity

amino acids undergo condensation reactions to form

peptide bonds

IR spectra are plotted as ___________________ versus _______ ______________

percent transmittance vs. wave number (1/wavelength)

stability of the conjugate base is determine why what factors?

periodic trends (electronegativity) size of the anion resonance

what trends increase electrophilicity?

positive charge, better LGs

what are the most acidic oxygens

phenols

how are quinones usually produced

phenols treated with oxidizing agents

aromatic amino acids

phenylalanine, tyrosine, tryptophan

phosphoric acid is sometimes referred to as

phosphate group or inorganic phosphate

phosphate is found in the ________ bonds that link the sugar moieties in DNA

phosphodiester

Vitamin k1 (________) and vitamin K2 (________) are examples of biochemically relevant quinones

phylloquinone menaquinones

boiling point and melting point are examples of ________ properties

physical

gabriel synthesis requires

potassium pthalimide diethyl bromomalonate basic conditions

if a solvent is not given, assume that the reaction occurs in a ______ solvent.

polar polar solvents are able to dissolve nucleophiles, which is necessary for these reactions to occur

the stationary phase or absorbent is usually a __________

polar solid

_____, ______, and ______ amino acids are all hydrophilic and form H bonds with water in aqueous solution

polar, acidic, and basic

column chromatography utilizes

polarity, size, or affinity to separate compounds based on physical and chemical characteristics

polypeptides

polymers of amino acids that make up proteins

acetone is significant as the smallest ketone, its IUPAC name is what?

popanone

esterification occurs most rapidly with ______ alcohols

primary

aldehydes will be reduced to ______ and ketones will be reduced to ______

primary alcohol secondary alcohol

LiAlH4 will reduce carboxylic acids to

primary alcohols

carboxylic acids can be reduced to _______________ by the use of LIAlH4

primary alcohols

what alcohols can be synthesized into carboxylic acids

primary alcohols only

only ______ and ______ amines will undergo condensation reactions to form amides because..........

primary and secondary the loss of a hydrogen from the nucleophile is necessary for this reaction to proceed

Cahn-Ingold-Prelog priority rules

priority is given by looking at the atoms connected to the chiral carbon or double-bonded carbons - whichever has the highest atomic number gets highers priority - if there is a tie, one moves outward from the chiral carbon or double bond until the tie is broken

propionic acid

propanoic acid

propanoic acid common name

propionic acid

in addition to making alcohols good leaving groups, tosyl and mesyl groups can also be used as

protecting groups when we do not want alcohols to react

Bronsted-Lowry base

proton acceptor

Bronsted-Lowry acid

proton donor

cyclobutane exists mainly in what configuration?

puckered V shape

treatment of phenols with oxidizing agents produces compounds called

quinones

when + and - enantiomers are present in equal proportion the mixture is said to be

racemic

the products of streaker synthesis are a ______ mixture

racemic L and D amino acids are created

what kind of mixtures/molecules are optically inactive?

racemic mixtures, miso compounds, chiral compounds

magnetic quantum number (m sub l)

ranges from -l to +l for a given subshell. determines the orbital in which the electron resides

azimuthal quantum number (l)

ranges from 0 to n-1. 0, 1, 2, and 3 correspond to s, p, d, and f subshells respectively energy also increase as the azimuthal number increases

kinetic produces form ________ and are _________ stable

rapid, less

Sn2 rate law

rate = k[substrate][nucleophile]

rate law for SN1

rate=k[alkyl group containing leaving group]

how can you synthesize esters?

reacting carboxylic acids with alcohols under acidic conditions

chemical properties

reactivity of molecule, resulting in a change in composition: generally attributable to functional groups in a molecule

Na+, LiAlH4, and Aluminum are examples of good ______ agents

reducing

The conversion of ubiquinone to ubiquinol requires what type of reaction?

reduction

TMS provides a

reference peak at chemical shift of 0

nucelophile strength is based on ________________ and is therefore a _____ property

relative rates of reaction with a common electrophile kinetic

conformational isomers differ by

rotation around a single (sigma) bond

Within one principal energy level, which sub shell has the least energy? s p d f

s

when long chain carboxylic acids react with NaOH or KOH, a ______ called _______ is formed

salt soap

C=O IR spec peak

sharp peak around 1750

carboxylic acid OH IR spec peak

sharp peak at 3000 cm-1

NH peak on IR spec

sharp peak at 3300 cm-1

n describes what organizational level? l describes what organizational level? m(l) describes what organizational level? m(s) describes what organizational level?

shell subshell orbital ------

TLC stationary phase is

silica gel, a polar solid

High Performance Liquid Chromatography (HPLC)

similar to column chromatography but uses sophisticated computer-mediated solvent and temperature gradients

amides are names

similar to esters except that a the suffix becomes "-amide" substiuents attached to the nitrogen are labeled with a capital N-

three types of distillation

simple, vacuum, fractional

why is a single bond stronger than a pi bond?

single bonds have more overlap

decarboxylation occurs through a ___________ in its transition state

six membered ring

Principle quantum number n is essentially a measure of

size

n describes ______ l describes ______ m(l) describes ______ m(s) describes ______

size shape orientation spin

what is the best chromatographic technique to seperate large molecules from small molecules?

size exclusion chromatography

thermodynamic products form ________ and are _____ stable

slow, more

hydration reactions generally proceed slowly but can be increased by adding

small amount of catalytic acid or base

during size exclusion, the _________ compounds move more slowly through the column

smaller

More acidic molecules will have a ____ pKA

smaller (or even negative)

filtration isolates a _____ (residue) from a ______ (filtrate)

solid from a liquid

the mobile phase runs through the stationary phase and is usually a ________ that elutes the sample through he sample phase

solid or gas

column chromatography mobile phase

solvent that travels by gravity

s orbitals are what shape?

spherical

good leaving groups are able to

stabilize the extra electrons

conjugation makes _____ compounds because of the presence of multiple _________

stable resonance structures

if an isomer has the same connectivity is a _________ and if it doesn't have the same connectivity it is a ________

stereoisomer structural/constitutional isomer

Diastereomers

stereoisomers that are not mirror images differ in some but not all chiral centers

Diastereomers

stereoisomers that are not mirror images, differ in some but not all chiral centers

two ways of synthesizing amino acids?

strecker and gabriel synthesis

strecker synthesis compared to gabriel

strecker is more elegant, more simple and efficient

Sn2 reactions require what?

strong nucleophiles and non-sterically hindered electrophiles

what are the least similar of all isomers?

structural/constitutional isomers

why is glycine not optically active?

the alpha carbon is not chiral due to having two Hydrogen atoms

enol and keto are

tautomers

polar amino acids

tend to have terminal groups containing oxygen, sulfur, and nitrogen serine, threonine, asparagine, glutamine, cysteine

negatively charged (acidic) amino acids

terminal carboxylate anions in their R groups aspartatic acid, glutamatic acid

Sn2 reactions won't occur with _______ substrates

tertiary

would an SN! reaction happen more quickly on a primary or a tertiary carbon?

tertiary the more substituted it is, the more stable the carbocation will be

SN1 reactions favor _____ or _____ carbons

tertiary or secondary tertiary and secondary carbons will be more stable carbocation

sp3 hybridization

tetrahedral

alcohols may be protected from reactions by the reversible reduction to ______________

text-butyl ethers

angle strain results when

the bond angles deviate from their ideal values by being stretched or compressed

what bond is broken during a retro-aldol reaction

the bond between the alpha and beta carbons of the carbonyl

resonance

the bonding in molecules or ions that cannot be correctly represented by a single Lewis structure

why is the kinetic formation of an enolate quicker than the thermodynamic product of an enolate

the carbon that is deprotonated to create the kinetic product is less hindered and therefore can be accessed by the base more easily

affinity chromatography

the column is made to have high affinity for a compound by coating the beads with a receptor or antibody to the compound

the amount of rotation when looking at plane-polarized light depends on what?

the concentration of the optically active compound and the length of the tube through which light passes

induction

the distribution of charge across sigma bonds

the principal quantum number n represents

the energy level of a given electron in an atom

when naming diols

the entire hydrocarbon name is preserved and diol is added to the end, name locations of all hydrocarbon groups i.e. ethane-1,2-diol

conjugation

the presence of alternating single and multiple bonds

where are the acidic hydrogens located on B-dicarboxylic acids

the hydrogen of the hydroxyl and on the alpha carbon

structural isomers (constitutional isomers)

the least similar of isomers, the only this the same between structural isomers is their chemical formula

nitrogen and nitrogen based functional groups act as good nucleophiles due to

the lone pair on the Nitrogen atom

EWG effect on NMR shifting

the more electronegative groups present, they pull electron density away from the protons. The more electron density that is pulled away from the proton, the more deshielded it will be and the further downfield the proton will appear

what does the conjugate base's stability have to do with deprotonation of acids

the more stable the conjugate base, the easier to the hydrogen can leave and the stronger the acid

when two possible enolates are possible, which is the the favored?

the most substituted

cyanohydrins gain their stability by

the newly formed C-C bond

oxidation reactions tend to fature and increase in _________ and oxidizing agents often contain ________ bonded to a large number of ________ atoms

the number of bonds to oxygen metals oxygen

the height of each peak in NMR is proportional to

the number of protons it contains

what is the key difference between nucleophilic addition to an aldehyde or ketone and nucleophilic acyl substitution?

the presence of a good leaving group in carboxylic acids

NMR spec is useful for determining

the structure of a compound, including functional groups

organic chemistry

the study of all chemicals containing carbon

distillation separates liquids based on

their boiling points

tertiary alcohols are oxidized with difficulty because

there is no hydrogen attached to the carbon with the hydroxyl group

what makes soaps special?

they are amphipathic, the polar head organizes itself on the outsdie of the micelle and the nonpolar tails are on the inside, nonpolar molecules such as grease and dirt can dissolve in the interior of the molecule, while the micelle as a whole can dissolve in water

adjacent phosphate groups on a nucleotide triphosphate experience a large amount of repulsion becasue

they are negatively charged

How can aldehydes or ketones be protected using alcohols?

they can be reacted with two equivalents of an alcohol or a diol to form acetals or ketals, which serve as protecting groups

how quickly do tertiary carbons react in an SN2 reaction

they don't react, too much steric hinderance

why would alkanes and hydrogen ions never serve as leaving groups?

they form very reactive, strongly basic anions

what makes phosphoric acids good buffers

they have 3 hydrogens all with different pKas

rotation of double and triple bonds

they hinder rotation, locking the atoms into position

Why do esters have lower boiling points than carboxylic acids?

they lack H bonding

why are carboxylic acids good acids?

they like to give away protons and when they do give away protons the negative charge is stable because it is by two oxygen atoms

what must be true about the two solvents used for an extraction to work?

they must be immiscible

carboxylic acids characteristics

they're good acids, they like to give away protons and when they do give away protons the negative charge is stable because it is by two oxygen atoms they also participate in hydrogen bonding, which results in high intermolecular forces and high boiling points

with _____ bonds to oxygen atoms, carboxylic acids are some of the most oxidized functional groups encountered in organic chemistry

three

saponification of one triacylglyceron results in what?

three soap (fatty acid) molecules and one glycerol

tosylates are derived from

toluenesulfonic acid

in aprotic solvents, nucleophilicity of halogens (I, Cl, F, Br) decreases in this order

top to bottom F>Cl>Br>I this is because there are no protons to get in the way of the attacking nucleophile. In aprotic solvents, nucleophilicity relates directly to basicity

highest total energy conformation

totally eclipsed

what is the conformation called when the two highest priority groups are 0 degrees apart?

totally eclipsed

reverse phase chromatography uses what?

uses a nonpolar card with a polar solvent

in what way is gas chromatography different from all other techniques discussed?

uses gases

many common oxidizing and reducing agents are _______ metals, this is because _________

transition they take many different oxidation states

UV spectra are plotted as

transmittance or absorbance vs. wavelength

what is the storage form of fat in the body

triglycerides

sp2 hybridzation shape

trigonal planar

size of single double and triple bonds

triple bonds are shorter than double, and double are shorter than single

Strength of single, double, and triple bonds

triple bonds are stronger than double, and double are stronger than single

rank the following orbitals decreasing order of strength: sigma bonds, pi bonds, double bonds, triple bonds

triple---> double---> sigma---> pi

butanoic anhydride can be formed by

two butanoic acid molecule coming together and giving off H2O

anhydrides are created via the condensation of

two carboxylic acids

anhydride formation

two carboxylic acids come together and give off H2O

a hydroquinone is a benzene ring with ______________. A hydroxyquinone contains ________

two hydroxyl groups two carbonyls and a variable number of hydroxyl groups

extraction combines

two immiscible liquids, one of which easily dissolves the compound of interest

Pi bonds are formed by which of the following orbitals? two s-orbitals two p-orbitals one s- and one p-orbital two sp2 hybridized orbitals

two p orbitals

pi bonds are formed when

two p orbitals lining up parallel (side to side) and their electron clouds overlapping, forming a bonding molecular orbital

all forms of chromatography use __________ to separate compounds based on physical or chemical properties

two phases (mobile and stationary)

ubiquinone can be reduced to form

ubiquinal

SN1

unimolecular nucleophilic substitution 2 steps -leaving group leaves forming a carbocation -nucleophile attacks carbocation first order so the rate only depends on the concentration of the substrate

in polar parotid solvents, nucleophilicity increases _____ the periodic table

up

what is the purpose of a mesylate or tosylate?

used to convert an alcohol into a better leaving group, also can be used as a protecting group

if we were given a solution with a BP of 156C and one with a BP of 204C, which distillation technique would be best

vacuum because of the high temps

carboxylic acid smell

very strong and unpleasant

what happens during an aldol reaction when there are multiple kinds of aldehydes or ketones?

we cannot control which will act as nucleophiles and electrophiles, so we get a mixture of products

_____ bases make good leaving groups

weak

what are the features of good leaving groups?

weak bases, resonance, can stabilize electrons

an acid-base reaction will only proceed if the products that will be formed are _____ than the original reactants

weaker

in Fischer projections the horizontal lines are ______ and the vertical lines are _____

wedges dashes

Transesterification

when alcohol acts as a nucleophile and displaces the esterifying group on an ester one ester is transformed into another

under what conditions will carboxylic acid spontaneously decarboxylate?

when heated

if the stability of various resonance forms differ, the true electron density

will favor the most stable form

NMR spectra are calibrated using TMS, which has a chemical shift of ______.

zero


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