Organic Chemistry 2 Flashcards
alkene –> markovnikov alkyl halide
H-X
alkene –> anti-markovnikov alkyl halide
H-Br, peroxides
alkene –> markovnikov alcohol
H20, H+
alkene —> anti-markovnikov alcohol
1) BH3*THF, 2) H2O2, OH-
alkene —> syn addition alkane
H2 and Pt, Pd, or Ni
alkene –> anti addition alkyl dihalide
X2
alkene —> anti addition markovnikov halohydrin
X2, H20
alkene –> epoxide
peroxyacid, example: MCPBA
epoxide –> anti gycol
H+, H2O
alkene –> anti glycol
1) peroxyacid, 2) H+ H2O
alkene —> syn glycol
KMnO4 (cold, dilute), OH-, H2O
alkene –> syn glycol
OsO4 , H2O2
Alkene –>ozonide
O3
ozonide –> ketones and aldehydes
(CH3)2S
alkene —> ketones and aldehydes
1) O3, 2) (CH3)2S
alkene –> ketones and acids
KMnO4 (warm)
acetylide —> acetylide anion
NaNH2
acetylide anion —>alkyne
R-X
acetylide anion —> alcohol
carbonyl group containing compound (formaldehyde, aldehyde, or ketone)
alkyne —> alkane
2H2, Pt, Pd, or Ni
alkyne –> cis alkene
H2, Pd/BaSO4, quinoline (lindlar’s catalyst)
alkyne –> trans alkene
Na, NH3
alkyne –> haloalkane (4 X)
2X2
alkyne —> geminal haloalkane (markovnikov)
2 H-X
alkyne —> (vinyl alcohol ketone), markovnikov
HgSO4, H2SO4
alkyne —> (vinyl alcohol aldehyde), anti-markovnikov
1)SiaBH*THF, 2) H2O2, NaOH
alkyne –> alpha-diketone
KMnO4, H2O, Neutral
alkyne —> carboxylic acids
O3, H2O
alkene + H-X
markovnikov alkyl halide
alkene + H-Br –peroxides->
anti-markovnikov alkyl halide
alkene + water –H+->
markovnikov alcohol
alkene + 1)BH3*THF, 2)H2O2, OH-
anti-markovnikov alcohol
alkene +H2 –Pt,Pd, or Ni->
syn addition alkane
alkene + X2
anti addition alkyl dihalide
alkene + peroxyacid
syn addition epoxide + carboxylic acid
epoxide —H+, H2O->
anti glycol
alkene —1)peroxyacid, 2)H+, H2O->
anti glycol
alkene + KMnO4 (cold, dilute) —OH-, H2O->
syn glycol
alkene + OsO4 —H2O2 ->
syn glycol
alkene + O3
ozonide
ozonide –(CH3)2S
ketones and aldehydes
alkene + KMnO4(warm)
ketones and acids
acetylide + NaNH2
acetylide anion + Na+ + NH3
acetylide anion + R-X
alkyne molecule with desired R group
acetylide anion + R2C=O
alcohol
alkyne + 2H2 –Pt, Pd, or Ni ->
alkane
alkyne + H2 —Pd/BaSO4, quinoline (lindlar’s catalyst) –>
cis alkene
alkyne – Na, NH3 –>
trans alkene
alkyne + 2X2
haloalkane, 4 halogens
alkyne + 2H-X
geminal haloalkane, Markovnikov
alkyne – HgSO4, H2SO4–>
vinyl alcohol ketone , markovnikov
alkyne –1) SiaBH*THF, 2) H2O2, NaOH –>
vinyl alcohol aldehyde, anti-markovnikov
alkyne + KMnO4 —H2O, Neutral ->
alpha-diketone
alykne –1) KMnO4, OH-, 2) H+ –>
carboxyilic acids
alkyne –O3, H2O –>
carboxylic acids
What happens when you have a carboxylic acids with a salt?
No REACTION because it already has a negative charge
List, in order of decreasing basicity, the charged nucleophiles that are on the table in the blue sheet.
CH3-, NH2-, OH-, OR-, SH-/SR-, -OAc, Cl- (X-)
How would you remember the order of the charged nucleophiles?
Come Now Oliver Over Shore Over Clapping
What is capable of reacting with a carboxyllic acid? (Which charged nucleophile(s)?
CH3-, NH2-, OH, SH, -OAc
What would the LG be in the above case?
The H would bond with the nucleophiles, leaving the carboxylic O with a negative charge
How do you know when you can have a reaction with a charged nucleophile?
As long as the LG is MORE stable than the Nucleophile, the reaction WILL happen
Is the same true for salts, though?
Yes
What is the product of an acyl halides (carboxyllic with a Cl instead of an O at the far right) with a charged nucleophile?
Carboxyllic acid
What are the charged nucleophiles that are capable of carrying out this reaction? What is the LG of this reaction?
All of them “Cl”
What first happens to the acyl chloride before the reaction takes place (Before it is attacked with the nucleophile?)
It forms a resonance form with a positive charge on the Carbon and negative on oxygen
What is the name of the reaction of acyl chlorides with nucleophiles?
Acyl addition elimination (for biochem)
What does the reaction of anhydrides and nucleopiles yeild? What is the LG?
Carboxylic acids, LG = “RCOO-“
What are the charged nucleophiles that can react with the ESTER? What is the LG??
CH3- and the NH2- LG is the OR-
What are the charged nucleophiles that can react with a primary amide? What is the LG?
CH3- LG is NH2
What does the reduction of aldehydes and ketones yeild?
Alcohols
What are the reagents required for the carbonyls (aldehydes and ketone) reaction?
NaBH4–Sodium boronhydride and LiALH4, LithiumAluminum Hydride
What is the first steop of the carbonyl reaction?
The reagent gives a hydride to the central carbon atom, giving the oxygen a negative charge
What is the second stop of the carbonyl reaction?
dilute acid gives the negatively charged oxygen an H to stabalize the charge
What is the only functional group capable of reacting with a carboxyllic acid to form a salt?
strong base neutral nucleophiles can react to form a salt (O of carb. acid has a negative charge
What is fisher esterfication?
It is when a carb. acid reacts with a weak base to form water and an ester or anhydride
FE is to what and Salts are to what?
FE is to weak base and salts are to strong base
What is the order of reactivity of addition elimination reactions? IN DECREASING REACTIVITY
Acyl halides, anhydrides, esters and amides
What do all derivatives yield upon hydrolysis?
Carboxylic acids
What is hydrolysis:
Acid/water or base/water followed by acidification
PREPARATION SECTION OF TEST
PREPARATION SECTION OF TEST
What is needed for the oxidation of aromatic side chains at the benzyl position?
Strong oxidizing agents like hot HNO3 or KMnO4
What solvents are needed for oxidation of primary alcohols?
KMnO4 or CrO3, H2SO Chromic Acid
Solvent needed for oxidation of aldehydes?
KMnO4
How do you know what the product of the preparation of acids is?
It is usually the main compuund, like a benzene ring minus its attachments, but instead of its old attachments, it has the COOH
What are the solvents needed for carbonation of grignard reagents?
Make grignard reagent by MG metal, add CO2, then acidify with H+
Nitrile hydrolysis requires what?
Nitrile is first formed by Sn2 reaction on an alkyl bromide( from alcohols and HBr combination)
Second step?
KCN adds
Third step?
Water, dilute acid, or water and OH-
What’s the product?
R COOH
What is needed for the hydrolysis of acyl derivatives?
Hydrolysis with water (plus acid or base)
Acid chlorides and water give what products?
carb. acid and HCl
Anhydrides and water yeild what?
2 equivalents of carb. acid
What do esters need to form carb. acid and alcohol?
Water/acid
What is this hydrolysis reaction called in a base?
Saponification
What is the last step of saponification?
Forming NEUTRAL acid by acid an acidification step
Amides will form RCOOH and an amine with what solvent?
WATER
PREPARATION OF CARB ACID DERIVATIVES
PREPARATION OF CARB ACID DERIVATIVES
How do you form acid chlorides? What solvents are needed, I mean.
Carb. Acids and Thionyl chloride (SOCL2) and Phosphorus trichloride (PCl3)
What solvents are needed to form anhydrides?
Pyridine (with acid chlorides and carb. acids or RCOOH salt) or Heat (with carb. acids and loss of water)
What solvents are needed to form esters?
Fisher esterfication (Conc. H+, RCOOH, Alcohol), Acid chlorides and an alcohol, Anhydrides an analcohol
How will amides form?
Acid chlorides and an amine
How will amides and alcohols form?
Esters and an amine
How will salts and amides form?
Anhydrides and an amine
REDUCTION OF RCOOH AND DERIVATIVES
REDUCTION OF RCOOH AND DERIVATIVES
Esters will be reduced, how?
LAH (LiAlH4), followed by acidification yields two equivalents of alcohol
How will amides will be reduced
LAH, neutralization with acid yields an amine
Nitriles are also known as what?
Cyanides
How will nitriles be reduced
LAH, neutrilization with acid forms an amine
How else can amines form by reduction?
reduction with H2 and Pt or Pd
How will RCOOH be reduced?
LAH, acidification yeilds a primary alcohol
How will all reactions with neutral nucleophiles (Except for what) work?
Except for with amides, all other functional groups, the LG will be the larger group, it will look like a grignard reaction, the LG will be the largest molecules connected together
What will the amide reaction with netural nucleophile Water look like?
You will get an NH4 and salt because it’s an acid-base reaction
A reaction of an amide with another amide will give?
a fifty-fifty mixture
FACTORS AFFECTING BASICITY AND ACIDITY
FACTORS AFFECTING BASICITY AND ACIDITY
What are the three factors that impact the acid and base properties?
Hybridization, inductance, resonance
What type of hybridization makes a strong base?
SP3, less s character
What type of inductance makes a strong base?
lower left hand compounds, less electronegative groups, but additing electron donating group
What are electron donating groups?
CH3- and other alkyl groups
What affect does resonance have on amines?
Aromatic amines have resonance forms and their resonance forms spread electrons around ring, amking e- less available to react=weaker base
why are amides even worse bases than aromatic amine?
first order equal to second order
To have an amide, you need…
a c double bond O must be directy attached to nitrogen
What is the acidity of an amid?
very very acidic. PKA 0
What are the steps of saponification?
First, get resonance intermediate by moving double bond, then have nucleophile attack, then get rid of negative charge on O and have leaving group leave, then have the LG grab the H on the molecule….the last step is getting rid of the negative charge
Aldehydes are prepared by the oxidation of a
primary alcohol
an organic group containing one or more -CHO groups
aldehyde
What is the functional group for the aldehydes?
carbonyl group (-CHO)
general formula for the aldehydes
R-CHO
where is the functional group located on the carbon chain for the aldehydes?
at the end of the carbon chain
methyl alcohol oxidizes to form
formaldehyde
the molecular formula for formaldehyde
HCHO
another name for formaldehyde
methanal
a three-carbon chain aldehyde would be called
propanal
formaldehyde in water is known as
formalin
formalin is what percentage aqueous solution of formaldehyde by weight?
37%
formalin is what percentage aqueous solution of formaldehyde by volume?
40%
formed by the oxidation of ethanol, a two carbon chain aldehyde
acetaldehyde
another name for acetaldehyde
ethanal
a benzene derivative in which one of the hydrogens in the ring is replaced with an aldehyde group
benzaldehyde
benzaldehyde is known as an
aromatic aldehyde
an aldehyde with two aldehyde group (having a carbonyl group at each end of the carbon chain)
dialdehydes
the simplest dialdehyde is
glyoxal
two examples of dialdehydes
glyoxal and glutaraldehyde
the oxidation of a secondary alcohol yields a
ketone
the general formula for a ketone is
RCOR
a ketone has two ____ groups attached to a ___ group
two alkyl groups attached to a carbonyl group
the simplest ketone is
propanone
propanone is also known as (2)
acetone, dimethyl ketone
the general formula for carboxylic acids
R-COOH
the functional group in a carboxylic acid is known as a
carboxyl group
two examples of carboxylic acids
methanoic acid, ethanoic acid
another name for methanoic acid
formic acid
another name for ethanoic acid
acetic acid
_____ oxidize for form organic acids
aldehydes
_____ oxidizes to form formic acid (also means _____ oxidizes to form ____ acid)
formaldehyde (methanal, methanoic)
_____ oxidizes to form acetic acid (also means ____ oxidizes to form ____ acid)
acetaldehyde (ethanal, ethanoic)
general formula for esters
R-COO-R
two examples of esters
ethyl acetate, methyl salicylate
a colorless liquid that has a characteristic smell like certain glues or nail polish removers
ethyl acetate
ethyl acetate is derived from ____ and _____
ethanol and acetic acid
known as oil of wintergreen, a natural product of many species of plants
methyl salicylate
methyl salicylate is derived from _____ and _____
methanol and salicylic acid
derived from an alcohol and an organic acid
esters
What are two methods of making R-Hals?
1.Alkene + H-Hal ——-> R-Hal 2.R-OH + H-Hal ———–> R-Hal + H2O
How do you make Alkenes from R-Hals?
R-Hal + Na/KOH ———> Alkenes + salt + H2O Dissolved In ethanol at high temperatures with High conc of the Na/KOH 2ary or 3ary R-Hals are preferred.
How do you make Alcohols from R-Hals?
R-Hal + Na/KOH ———> Alcohol + salt Dissolved in water at low temperatures with low concentrations of Na/KOH. 1ary or 2ary R-Hal prefered.
How do you make amines from R-Hals?
R-Hal + NH3 ——–> R-NH2?
How can you test for which Hal is on your R-Hal?
R-Hal + Ag+ –> 1.Agcl - Wht ppt(sol In NH3) Very Slow 2.AgBr - Pale Cream ppt(Semi-sol) Slow 3.AgI - Yellow ppt(insoluble) Fast
How can you manufacture Grignards Reagent?
R-Hal + Mg ————> Grignards Reagents: Magnisium metal with trace of iodine. Usually requires cooling. In the presence of ethoxyethane
How can you make pure Alkanes with Grignards reagent?
R-MgHal + H2O —–> R + Mg(OH)Hal
How can you produce a carbonyl From Grignards reagent?
R-MgHal + CO2 ——> RCOMgHal + H2O -> RCOOH
How can you produce Alcohols from Grignards Reagents?
R-MgHal 1.+ methanal -> R-OMgHal + HCl -> R-OH 2.+ ethanal -> 2ary R-OH 3.+ Ketone -> 3ary R-OH
How Is ethanol Produced Industrially?
Ethene + H20(g) —> Ethanol (At 300 C, 60-70 atm and with a phosphurous (v) acid catalyst)
What are the conditions at which LDPE is produced? What are its uses?
T: 200 C, P 2000Atm O2 Impurity Uses: for plastic bags
What are the conditions at which HDPE is produced? What are its uses?
T: 60 C P: A 2-5Atm Cat: Ziegler-Natta. Uses: milk bottles, plastic pipes and so on.
What are the 3 orientations of PP and their uses?
Isotactic: Plastic Crates Atactic: Sealents, Adhesives and Roofing felt SyndioTactic: Medical tubing/bags ect.
PCE - uses and full name
Poly(chloroethane) Guttering, plastic windows, cable insulation, sheet meterials footwear, clothing ect.
PTFE - uses and full name
Poly(tetrafloroethane) - uses for wrapping foods and chemicals and have a non stick property used in the kitchen.
What are the manufacturing conditions of Epoxyethane?
T: 250 C P:15atm Catalyst: Ag
What are the Uses of Epoxyethane?
It is used to make long chain alcohols which can be used as: Anti-freeze materials, plasticizers non-ionic surfactants (detergants) and in the manufacture of polyesters.
How can you produce Carboxilic acids?
R-COMgHal + H2O —-> R-COOH + Mg(OH)Hal (under acidic conditions)
How can you produce Nitriles From R-Hals?
R-hal + KCN -> R-CN + KHal Reagents: Potatsium Cyanide dissolved in aquous ethanol. Conditions: heat under reflux. Doesn’t work with 3ary alkanes
How can you produce amines from R-Hals?
R-Hal + 2NH3 -> R-NH2 + NH4Hal Reagents ammonia in ethanolic solution
What is the equation for Fischer esterification?
R-OH + R-COO —-> Ester Catalyst: H2SO4
What are acid anhydrides?
Two carboxlyic acids joint by the same oxygen.
What is the Friedal-crafts reaction?
Electrophillic addition of aromatic rings.
E.N of the Halogen UP: Strength of the H-hal Bond?
Strength of the H-hal bond UP
Examples of nucloephiles
O:Water, Hydroxide, N:Azides Cyanide and Ammonia, Metal Halides,S: Sulfer Thiols.
Examples of electrophiles
H+, NO+, HCl, aklyl halides, acyl halides, Carbonyl compounds.
What is the Friedal-crafts reaction?
Electrophillic addition of aromatic rings.
E.N of the Halogen UP: Strength of the H-hal Bond?
Strength of the H-hal bond UP
Examples of nucloephiles
O:Water, Hydroxide, N:Azides Cyanide and Ammonia, Metal Halides,S: Sulfer Thiols.
Examples of electrophiles
H+, NO+, HCl, aklyl halides, acyl halides, Carbonyl compounds.
General formula for alkynes
CnH2n-2
General formula for alkenes
CnH2n
General formula for alkanes
CnH2n+2
CaC2 + 2H2O ->
->Ca(OH)2 + C2H2 (ethyne/acetylene)
Preparing ethyne
Water added to calcium carbide.
Preparing ethene in lab
Dehydrate ethanol with concentrated H2SO4 (gives poor yield)
Preparing ethene by cracking
Cracking saturated hydrocarbons via steam cracking naptha compounds (C4-C12)
Properties alkenes /alkynes
Non polar, insoluble in water, low M.p/B.p but increase with size
Sustitution
Alkanes with halogens, halogen atoms swap with hydrogen, hydrogen halide gas as a product, requires UV light
C2H6 + Br2 -(UV)>
->C2H5Br + HBr
Complete combustion of alkanes
CO2+H2O produced
Incomplete combustion
Produce CO and/ or C (soot) instead of CO2
Properties of alkanes
Single covalent bonds, Undergo combustion and substituion reactions, nonpolar(insoluble in water) Low MP/BP (increases with size), Less dense than water(float)
Isomer
Different form of same molecular formula with a different structural formula
Meth-
1 carbon
Eth-
2 carbons
Prop-
3 carbons
But-
4 carbons
CH2=CH2 + H2O -(dil. H2SO4/H3PO4)->
->CH3-CH2-OH
Functional group
The specific arrangement of atoms and/or bonds responsible for the main physical +chemical properties
Homologous series
Family of hydrocarbons with same functional group. Similar chemical + physical properties
Hydration
Adding water to alkene, forms alcohols
Halogenation
Adding a halogen to alkene, forms halogenoalkanes
Testing for unsaturation
Bromine water, decolourises from orange/brown to colourless
Hydrogenation
Adding hydrogen to an alkene, forms an alkane
CH2=CH2 + H2 -(nickel/platinum)->
->CH3-CH3
CH2=CH2 + Br2 ->
CH2BrCH2Br
