Chapter 10: QUIZ 1

Alkoxides: R-OH + NaH RO-Na+ Making Alcohols Alkyl Halides SN2 for 1; I > Br > Cl Inversion

Alkenes

Direct hydration using an acid (H2SO4): Markovnikov (Rich gets richer: C with H gets more H) Markovnikov

Indirect Hydration: Oxymercuratio n Indirect Hydration: Hydroboration

Anti-Markovnikov: Syn Addition

Diols from alkenes

Cis (2 OH groups in same plane): from OsO4

Trans (2 OH groups in opposite planes): from Performic Acid (HCO3H)

Grignard Reaction of Aldehydes &Ketones Grignard Reaction of Alkynes Grignard

Grignard + Formaldehyde 1 (R group from Grignard) Grignard + Other aldehyde 2 (1 R group from Grignard and aldehyde) Grignard + Ketone 3 (1 R group from Grignard and 2 from ketone) Acetylene protonates reagent s R group (1 product) Negative charged acetylene joins carbonyl Carbonyl Is protonated to give alcohol R-Mg-X + CH2CH2O R- CH2CH2OH

Reaction with Ethylene Oxide Grignard Reaction of Carboxylic Esters Reduction of Aldehydes & Ketones Reduction of Esters Catalytic Hydrogenation R-MgX + R-C-OOR RR2-C-OH
group from the ester) (2 groups come from Grignard and the non-O

Hydride ions from: NaBH4

like a hammer)

(+ ethanol, mild like a feather)

LiAlH4

(+water, strong

LiAlH4 generates two products (acts on esters, aldehydes, and ketones) R-C-OOR R-CH2-OH + R-OH (1, 2, 3) The OR group of ester just gets
an H added

Mild + Ni, Pt, or Pd: reactive in hydrogenation Moderate + Ni: Reactive with carbonyls NaBH4: reactive with carbonyl R-Mg-X + MgX2

Grignard Reagents: R-X + Mg Organolithium: R-X + Li

(dry environment with ether)

(dry environment with Ar or N2)

R-Li + Li-X

C has a partial negative charge

Chapter 11: QUIZ 2

Oxidation: introduction of oxygen (O) or halogens, removal of two hydrogens (H) Reduction: Removal of oxygen (O) or halogens, introduction of two hydrogens (H) Alkane Alcohol Aldehyde Carboxylic Acid Oxidation 1 Chromic Acid (sodium dichromate + sulfuric acid) Potassium Permanganate (KMnO4) PCC & Dess Martin stop reaction at aldehydes Chromic Acid Potassium Permanganate PCC (Reaction typically goes no further than ketone) NO REACTION Potassium Permanganate oxidizes double bond (MILD) H2O2, Br2 oxidize to disulfides (R-S-S-R) (STRONG) KMnO4 oxidizes to sulfonic acid

3 Alke ne Thiol s

1,2 Diols

Periodic acid, HIO4, cleaves adjacent carbons with OH groups to form double bonded oxygens

Alcohol Reactions SN1: carbocation intermediate Cleavage Cleavage of H Cleavage at O Esters Mesylate esters RO Tosylate ester O- acts as nucleophile and donates electrons Activate OH group to X-OH to make a good leaving group SN2: transition state

OR

OTs activates the alcohol and is a good leaving group When OTs is a leaving group inversion Reaction of R-OH with H-X 1/2 SN2 [transition states] PBr3 (avoids carbocations) PI3 made in situ SOCl2 (R-OH + SOCl2 R-Cl + HCl + SO2) w/o pyridine SNi & retention; w/ pyridine SN2 & inversion (NO HCl as product) SN1 (carbocation intermediate) HCl/ZnCl2 (rearrangement problems in 2 & 1) HBr (rearrangement problems in 2 & 1)

PBr3 (slow) HI Dehydration 1/2 3 E1 with rearrangements E1 makes it work best for tertiary R-OH + H2SO4 Alkene + H2O Alkene formation (E1 reaction) competes with ether (R-O-R) formation (SN2 reaction), which are favored at 140C

Esters Organi c Inorga nic Sulfonate Nitrate (R-O-N=O): Makes nitroglycerine O Nitrite (R-O-N=O) Phosphate (OH groups can be replaced by R-O) Borate

Chapters 12 and 13
1. IR: functional groups 2. MS: molecular weights, elements present, and empirical formula 3. NMR: carbon skeleton INFRARED SPECTRUM Wavelength and frequency inversely related X-rays. UV. Visible (Purple-Red). Near IR. High frequency, Short wavelength. IR. Microwave. Radio Low frequency, Long wavelength

c = frequency / wavelength E = h * frequency Interpretation 4. Location (on x-axis) 5. Intensity (how low the band dips based on dipole moment change) 6. Broadness (of top of band) Location Depends on Hooke's Law Wavelength = (1 / 2 pi * c)(sqrt (force / (mm / m + m))) Wavelength increases as bonds get stronger and as masses get larger 3500-2700 (N,O,C)-H, triple-C-H 2300-2100 (C,N) triple C 1800-1600 (C,O,N) = C (around 1660) 1400-600 (C,O,N)-C Alkane: C-C, C-H Alkene: 1642, cis bond is weaker than a more intense trans band Alkyne: 2119, hard to identify internal alkyne Aromatic: aryl stretch produces 3 bands at 1500-1600 Ketone: intensity at C=O at 1710 Aldehyde: intensity at C=O at 1725, overtone Ether: process of elimination Alcohol: broad OH stretch Carboxylic acid: CH stretch between broad OH stretch, intensity at C=O Ester of carboxylate acid: intensity at C=O at 1735, CH stretch, CO stretch MASS SPECTRA Splits molecules into ions and radicals Instrument only reads ions Br: M+ and M+2 are similar sizes Cl: Br: M+ one third of M+2 I: at 127 and a large gap N: odd M+ and some even fragments S: M+2 larger than usual A stable cation of 43 is a good cleavage, producing CH3-CH-CH3 NUCLEAR MAGNETIC RESONANCE Inactive nuclei produce no signal (same proton and neutron number) Interpretation 7. Number of signals: H's in same environment produce one signal (chemically nonequivalent

8. Location of signals: depends on shielding and de-shielding due to electrons density 9. Relative intensity of signal: measured by integration of curve 10.Splitting of signals due to coupling (NOT on Midterm 1) Graph shows: Peaks Low electrons density. Low shield. Axis High Hz. High electrons density High shield Low Hz