Altius - covid 2 (507) Flashcards
fluorescent light emitted
will be lower energy than the source light- this is bc some energy is lost (vibrations) low energy equal longer wavelength
newtons third law
(ask Marc why and what causes them to accelerate then) - is it less mass?
every action has an equal and opposite force- even if its moving, static or accelerating. Partner forces are always equal!
normative social influence vs informational social influence
part of Ash experiments
- normative is when we alter out behaviour to fir in with those around us and informational social influence is when we doubt ourselves and believe others to be ore informed than us
first 5 layers of our skin is composed of
epidermis —> all epithelial cells
after the epidermis, 2 layers of
dermis –> CT (actin, elastin, laminin, collagen) hold things together
papillary dermis
thin, loose, blood vessels, nerve endings
reticular dermis
contains glands and hair follivles
thick, dense CT - what makes hiar stand on end
last layer of skin
hypodermis/ subcutaneous fat
how do we categorize burns
1, 2 , 3 degree- depends on what layer it gets to - epidermis, dermis, hypodermis
holocrine glands
HOLE cell breaks
- lubricate skin, releases sebum (oil)
- face chest back
apocrine
apex breaks off ( top) - emotional sweating- armpits and groin
merocrine
exocytosis - most of sweat everywhere in the body
DNA bases from largest to smallest
largest is Guanine ( 2 rings - purine), then Adenine
then thiamine ( 1 ring pyrimidine) then smallest is cytosine
smallest DN base
cytosine
largest DNA base
gaunine
retro-aldol
is the reverse of aldol reaction - here a bond is broken beteen the alpha and beta carbon- yeilding either 2 aldehydes, 2ketones or 1 of each
- to figure out what it yeilds- look at subs on the carbonyl carbon and the B carbon
- if there is an H bond to either = aldehyde
is the alpha hydrogen on aldehyde or ketone more acidic? why?
more acidic on aldehydes bc ketone and more elcron donating group - destabalize negative enolate form
pentanal or pentone a strong acid?
pentanal - bc aldehyde –> so expect a higher Ka, lower pka
are aldehydes or ketones more reactive? why?
aldehydes are more reactive bc ketones are more sterically hindered
how can you tell the thermo product from the kinetic product
the thermo- will have the double bond on the more susituited carbon, kinetic with less subsituted
keto, enol and enolate
keto- thermo
enol- tauntamor- kinetic- can be deprononated by strong base to form enolate (good nucleophine - neg charge seeks pos nucleus)
micheal addition
an enolat attacks an a,B-unsaturated carbonyl to create a bond
stong bases to deprotonate aldehydes or ketones to form enolate
OH, LDA, KH
enamines and imines
they are tauntamors
imine
contains C=N, like a carbonyl but with an N
how do imines form
ammonia (Nu) attacks aldehyde or ketone, water leaves, producing imine (condenstation rxn) and (nu subsitution)
- need acid to protonate the OH –> water to leve
enamines
so imine is a C=N-R and then thought tautomerization emanine is RHN-C=C (a hydrogen shifts to the N and double bond moves)
aldol condenstation
first strong base deprotonates the a hydrogen and enolate is formed, enolate than attacks carbonylcarbon on another keto/aldehyde species and an aldol is formed
in the next step the aldol is dehydrated, the OH is removed aas water
- for step 2 to happen: strong base and high temp bcstong base is neede to deprotonate the alpha (middle) hydrogen when this happens a double bond forms here and OH is kicked off - combines with H to make water
how can we push retro-aldol rxn?
need aqueous base and heat
how to produce aldehydes and ketones
oxidation of primary (aldehyde) and secondary (ketones) alcolols
PCC
used to synth an aldehyde, this is a weaker oxidizing agent, need to use this so the reaction will stop at aldehyde and not continue to CA
what oxidizing agents can you use to get a ketone from secondary alcohol?
any of the bc this is the most oxidized product (secondary acohol- wont break the c-c bond)
secondary alohol with oxidizing agent=
ketone
primary alcohol with PCC
aldyhyde
primary alcolo with Na2Cr2O7
CA
Nu attack to carbonyl
one of the most important rxn on MCAT
when this happens, c=o dissapears and o gets the extra electrons ( now ask can the carbonyl reform?), the only way it can is if there is a good leaving group - if not (aldyhydes and ketons) = alcohol
- CA and derivatives, have a good leaving group and so carbonyl reforms and leavig group gets kicked off- subsitution
if water is nu for aldehyde
nu addition, a geminal diol forms ( 2 OH)
if one alcholo equivalent attacks
nu addition, hemiacetal forms (OH and OR)
if 2 alcohol equivalents
nu addition, acetal forms (SN1 rxn) and acid
(SN1- unimolecular, depends only on the concentration od electrophile- how much leavig group leaves) carbocation forms
why is acid needed for formation of acetal?
bc the OH in the hemiacetal needs to get protonated by acid, so that is a good leaving group (SN1 so it leaves before getting attacked by second alcohol equivalent)
acetals and ketones are
inert and so good protcting groups
when ammonia is the Nu on an aldehyde or ketone
imine
NH3+ (Nu) attacks, NH3+- CRR-OH, then hydride shift - so a H moves from theN to the OH –> to create water which than leaves
- here, there is no hydroxy group left on- not a simple nu addition, this is a nu subsitution and condensation rxn
nu addition vs nu subsitution
addition is when the Nu is added, sub is when it displaces
carboxylic acid suffix
-oic acid
if carboxylic is a salt the suffix is
-oate
synth od CA
oxdation of alcohol
when a NU attacks a CA
nucliphilic subsitution bc the OH can get protonated and act as a good leaving group
whats an amide
a CA derivitive where the Oh is replaced with NHR
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how are amides made
CA + NH3 or another amine ( in either basic or acidic)
resonance of amides
double bond can go between the C=N or the C=O
- this stabalizes the bond and restricts motion
what are lactams?
amides that are cyclic- replace oic acid with lactam
requirment for ester formation? why?
Nu subsitution (OR for OH)
CA + alcohol ( usually primary) —> needs to be in acid bc the carboyl OH gets protonated - this pulls even more electrons from the carbon making it even more electrophilic, OH attackes- now 3 OH ‘ attached, one leaves as water
cyclic esters are called?
cyclic amided are called?
esters= lactones amides= lactams
lactone vs lactam
lactone- ester
lactam- amide
anhydrides are formed how?
condesation of 2 CA
CA reduced to?
primary alcohols - bc nucleophilic addition of hydrides
decarboxylation is
complete loss of carboxyl group as CO2
happens with 1,3- dicarboxylic acids and other B-keto acids
how does decarboxylation happen
1) sometimes spontanouesly with heat
this reaction is unique bc the electrophile and the nucleophile are in the same molecule !!! there is a six member transistion intermediate
saponification
when long chain CA react with sodium or potassium hydroxide, a salt is formed- this is saponification
this happens when FA are mixed with lye resulting in a salt that is known as SOAP!!
soap is just a CA salt !!
is water of an alcohol a better acid
water
acidity trend
generally bond strength decreases down the periodic table therfore acidity increases and more elctroneg, more acdic
nucleophilic trends
- more negative charge more nu
- don’t want electroneg (bc then it would hold electrons tight) so less electroneg better nu
- less steric hindrance better nu
- protic solvents ( CA, alcohol, water, amonia- anything that can hydrogen bond) could inhibit nu
amide vs imine
amide is CA derivative with NR2, imine is C=N in spot of a carboxyl group
sufflix for esters
oic acid is replaced with oate
ethyl ethanoate - the first word is whats attachced to the ester
how are anhydrides made?
condensation of two CA (OH on one is NU and attacks carbonyl on other)
reactivity of CA derivatives towards Nu attack
anhydrides are most reactive ( 3 electron withdrawing groups) so make for a very electrophilic carbon, then esers, CA and then amide ( amides have an electron donating group so less reacitve)
induction refers to
tug or war of electrons across sigma bonds- generatig a dipole, whereas resonance with atoms that have an unhybridized p-orbital - can delocalize pi electrons through resonance - electron clouds
which lactams/ lactones are more sensitive to hydrolysis?
the ones that have ring strain
- 4 ring (B-lactams) is way more reactive then g-lactam
- due to torsional and eclipsing strain
can all CA derivatives participate in Nu acyl substitutions
yes, at different rates ( depending on electrophilicity- anhydride most, ester, CA, amide)
Nucleophillic subsitutuion reaction: ammonia + annhydride
here the ammonia attacks the carbonyl carbon, and a carboxylic acid is a leaving group –> yield an amide + CA
Nucleophilic acyl substitution: alcohol + anhydride
alcohol is the Nu, attacks the carbonyl carbon–> yield an ester and a CA
how can we break apart an anhydride into its 2 CA
with water
what is transesterification
when an alcohol replaces another alcohol in an ester
how can amides be hydrolyzed
under highly acidic conditions via Nu substation
or under highly basic conditions (here OH- is a strong base and can attack)
- we need the acidic conditions bc we ned the carbonyl oxygen to be protonated, making the molecule more susceptible to Nu attack (this is bc amides are the lease reactive to Nu substitutions), here water can cacts as a Nu and yeild a CA and ammonia
L or D amino acids in our body
L —> which means that NH2 is on the left
L amino acids have R or S configuration?
all have S except for cysteine which is R bc of higher priority of sulfur
hydrolysis of a peptide bond with
strong acid or base
synth of amino acids
Sketcher synth ( aldehyde, NH4Cl, KCN) - last step needs acid
or Gabreil synthesis
breifly describe sketcher synth
oxygen on aldyhede is protonated, imine is formed then CN- attacks so we get a compund with both an amino and a nitrile (triple bond) group called an aminonitrile
next nitrile group is protonates and then water attacks, hydroxyl group now added, another water attacks and a carboonyl is formed, kicking of ammonia and creating a CA
the starting material of sketcher synth is ______ therfore the product mixture is ______
planar, racemic - bc the incoming Nu can attack from either side of the carbonyl thus L and D amino acids are formed
sketcher synth yeilds L or D amino acids
both- racemic mixture bc starting material is planar
Gabriel (malonic-ester) synth
in this methos potassium phthalimide is reacted with diethyyl bromomalonate in an SN2 reaction ( bc secondary carbon with good leaving group Br)
- the bulkiness of the Nu- makes sure that multiple reaction dont occur
does gabriel produce L or D amino acids
racemic mixture just like sketcher synth
if an acid is needed for a reaction is it considered a reactant?
NO
pyrophosphate
PPi ( this is released when a new nucleotide is added to a growing DNA strand)
- it is an acid anhydride
ATP, GTP and other nucleotides are considered
organic bc bound to a carbon
