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Halo Alkanes Naming
- Don't have their own name ending- No Respect
- 1-Chloro-Propane, etc.
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Alky Halides
- BP increases 20-30 degrees fro every carbon added
- Density is greater than water- Sinks
- Weigh alot
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Boiling Point is Directly related to
- Shape
- Hydrogen Bonding
- Polarity
- Molecular Weight
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Hydrogen bonded to FON
Able to form hydrogen bonds with self and has inordinatel high BP
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Synthesis of Alkyl Halides
- SHEA
- Substitution
- Halogenation
- Exchange
- Addition
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Substitution
- Synthesis
- Someone steps up, someone steps down
- R-OH------> (HX)--------> R-X + H2O
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Cleavage of PCl3 in substitution
PCl2+ and Cl-
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Cleavage of Iodine in Substitution
I+ and I-
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nI2x
- No I2 with X
- Iodine is always a problem because it is so large
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*** Remember- the reaction of 1 family is synthesis of another family
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Exchange of Halide
- Synthesis
- R-X + Na+ I- -----> (Acetone) -------> R-I + Na+X-
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**** Remember- Carbons w/ Halogen is partially positive and Halogen is partially negative
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Halogenation of Halo Alkanes
- Synthesis
- Sayetzef- Poor get poorer (Major), Rich get poorer (Minor)
- Major will create 2o Carbocation/ Free Radical
- Minor will create 1o Carbocation/ Free Radical
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Addition of Hydrogen Halides to Alkenes
- Synthesis
- nI2x
- -C=C- -------> C-C with X on the C-C
- Alkene to Alkane
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Reactions of Alkyl Halides
North South G-R-i -D
- Grignard Reagent
- Reduction of Metal by an Acid
- Dehydrohalogenation
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Nucleophile
- Negatively charged atom/ molecule
- I am negative, I love positive
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Grignard Reagent
- Reaction
- Provides an R- group
- R-X + Mg ---------> (Dry Ether) ---------> RMgX
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Reduction by a Metal and Acid
- Reaction
- R-X + Zn + HX ------> R-H + ZnX
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Dehydrohalogenation of Alkyl Halides
- Reaction
- Sayetzef- Poor get Poorer (Major), Rich get Poorer (Minor)
- -C-C- (with one X on one C) -------> (Base) ---------> -C=C-
- Alkane to Alkene
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Oxidation
- Gain of Oxygen
- Loss of Hydrogen
- Loss of Electron
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Reduction
- Loss of Oxygen
- Gain of Hydrogen
- Gain of Electron
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Nucleophiles are...
- 1) Groups with Negative Charges
- OH-, O-R-, -C(triple bond)C-R, I-, C(triple bond)N-, -SH, -S-R
- 2) Lone Pairs/ unshared pair of electrons (i.e, :NH3)
- 3) Groups so polarized as to almost be with a negative charge
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Nucleophilic Subsitution
Sn1 an Sn2
-
Sn1
- 1) First order kinetics
- 2) Racemization
- 3) Rearrangement (Carbocation Mediated)
- 4) Has 3o Alkyl Halides Reaction
* 2 Steps
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Sn2
- 1) Second order Kinetics
- 2) Complete Stereochemical Inversion
- 3) Absense of Rearragement (NOT carbocation mediated
- 4) 1o alkly halides react fastest
*One Step
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Alcohols
- BP increases by 20-30 degrees for each carbon added
- Density is less than 1
- Most alchols float
- Aromatic Rings, Diols and Triols Don't float- greater than 1
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Benzen Rings Side Group
Phenyl
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Solubility
g/ 100g of H2O
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Dipel Moment
The greater the #, the more polar the molecule
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Synthesis of Alcohols (8 kinds)
- Oxymercuration-Demurcuration
- Hydroboration-Oxidation
- Grignard Synthesis
- Hydrolysis of Alkyl Halides
- Aldol Condensation
- Reduction of Carbonyl Compounds
- Reduction of Acids and Esters
- Hydroxylation of Alkenes
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Reactions of Alcohols (6 kinds)
- Reaction of Hydrogen Halides
- Reaction with phosphorus Trihalides
- Dehydration
- Reaction as acids: reaction with active metals
- Ester Formation
- Oxidation
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Oxymercuration- demurcuration of OH
- Synthesis
- Markovnikov- Major only, Rich get Richer
- -C=C- + Hg(OAc)2 + H2O ------> CH2(OH)CH2(HgOAc) ------> (NaBH4) -------> CH2(OH)-CH3Alkene to Alkane
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Hydration of Alcohols
- Synthesis
- Markovnikov- Major (2o)/ Minor (1o)
- Alkene to Alkane
- -C=C- + H2O ------> -C-C-OH
- Alkene to Alkane
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Hydroboration-Oxidation of Alcohol
- Synthesis
- Minor Only- Rich still gets Richer
- No carbocation rearrangement
- -C=C- + (BH3)2 ------> CH3CH2(B) ------> (H2O2 OH-) -------> CH3CH2(OH) + B(OH)3
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Benzylic Carbon
- Carbon NEXT TO the carbon participating in the benzene ring
- Easiest to remove
- C-Benzene Ring
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Alpha Carbon
- Carbon nexty to carbonyl carbon
- Easiest to remove
- C-C-C(O)
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Allylic Carbon
- Carbon next to carbon participating in double bond
- Easiest to remove
- C-C=C
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Formaldehyde in Grignard Synthesis
-
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Higher Aldehydes in Grignard Synthesis
2o Alcohol
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Apoxide/ Ethylene Oxide in Grignard Synthesis
1o Alcoho with 2 carbons added
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Ester in Grignard Synthesis
3o alcohol
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Hydrolysis of Alkyl Halides
R-X + OH (or H2O) --------> R-OH + X (or HX)
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Hydroxy
Naming for alcohol when alcohol is not determined to be the functional group
-
Aldol
Alcholy and Aldahide
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Aldol Condensation
- Aldehyde + Aldehyde + Base = Aldol
- Base removes an alpha H
- Electrons in second aldehyde hanging out looking for a home
- second aldehyde attachs carbonyl carbon
- Creates an Aldol (alcohol and aldeyde)
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Reduction of Carbonyl Compounds
- Creation of alcohol by reduction (GAIN OF H)
- R-C(O)(OH) + 2Li+ AlH4- + 2H+Cl-------> R-CH2(OH) + H20
- Oxygen attaches to a H and creates OH
- Original OH attaches to H and creates H20
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Carbocylic Acids
R-C(O)(OH)
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Hydroxylation of Alkenes
- KMnO4, Cold, Dil
- Major and Minor creates Diol
- -C=C- -----> -C-C- Diol
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Reactions of Alcohols (6 Kinds)
- Reaction with hydrogen halides
- REaction with phosporus trihalides
- Dehydration
- Reaction as acids: Reaction iwth active metals
- Ester Formation
- Oxidation
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Reaction with Hydrogen Halides
- R-OH + HX --------> R-X + H2O
- Double check for Hydride shift in the R group
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Reactivity of ROH
Allyl, Benzyl > 3o > 2o > 1o
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Reaction with phosporus trihalides
3R- OH + PX3 ------> 3R-X + H3PO3
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Dehydration
- Syetzef- Poor get Poorer (Major), Rich get Poorer (Minor)
- Hydride shift may occur
- -CH2-CH2(OH)- --------> (Acid) -------> -Ch2=CH2- + H2O
- Alkane to Alkene
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Reactions as Acids: Reaction with Active Metals
- Basis of Breathalizer
- RO-H + M --------> RO-M+ + H
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Esther Drinks Coors
R-C(O)(O)R
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Ethanol + Butanoic Acid
Ethyl Butanoate
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Carbonyl Carbon
Partially positive carbon
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Ester Formation
Hidden in the thame of ester, you will find the reagent.
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Oxidation of Alcohol- 1o alcohol
- Has Major/ Minor
- Major creates an aldehyde
- Minor creates a carboxylic Acid (Reacting with KMnO4)
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Oxidation of Alcohol- 2o Alcohol
- Creates a Ketone
- Reacting with K2Cr2O3 or CrO3
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Carboxylic Acid
R-C(O)(OH)
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Oxidation of Alchol- 3o Alcohol
NO REACTION
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ID of Alcohols
- CLIP
- Chromic Anhydride in Sulfuric Acid- Jone's Reagent
- Lucas Test
- Iodoform Test
- Periodic Acid Test
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Chromic Anhydride in Sulfuric Acid- Jone's Reagent
1o alcohol in CrO3 + H2SO4 ------> Aldehyde (Blue Green)
2o alcohol in CrO3 + H2SO4 -------> Ketone (Blue Green)
3o alcohol in CrO3 + H2SO4 --------> NO REACTION
When a primary or secondary alcohol is added to clear orange chromic in anhydride the solution becomes opque and Blue-Green
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Lucas Test
R-OH + HCl + ZnCl2 -------> Cloudiness R-Cl + H2O
3o reacts instantly
2o reacts within 5 minutes
1o WILL NOT REACT
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Iodoform Test
- Reacts with METHYL ALCOHOLS
- Tests for Iodine
- R-CH(OH)-CH3 + 3NaOI -------> R-CH(O) + CH(I3)
- Creates Yellow Precipitate
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Periodic Acid Test
- Tests for Vicinal Diols
- Non Vicinal = NO REACTION
- R-CH(OH)-CH(OH)-R + HIO4 -------> R-C(O)-H + R-C(O)-H + HIO3
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