Exam 1 - Ochem Ii

Front 1

NaNH2

Back 1

Deprotonates - makes acetylide anion

Front 2

1) xs NaNH2 plus heat / 2) H20

Back 2

Removes two subs to make terminal alkyne

Front 3

1) MCPBA / 2)H30+

Back 3

OH double anti-addition via a epoxide intermediate - TRANS product

Front 4

OsO4 / H2O2

Back 4

Syn OH double addition - CIS product

Front 5

H2/Pd/C

Back 5

Syn H addition to completely eliminate double or triple bonds - CIS product

- Reduces ALL db's EXCEPT amides, esters & acids

Front 6

H2 / Lindlars

Back 6

Syn H addition to reduce an alkyne to alkene

Front 7

Na/NH3(liquid)

Back 7

Anti-addition of H to reduce alkyne to alkene

Front 8

HgSO4 * H2O / H2SO2

Back 8

alkyne to ketone

Front 9

1) Sia2 BH*THF / 2) H2O2 OH

Back 9

Terminal alkyne to aldehyde

Front 10

Cl2 or Br2

Back 10

Alkyne to alkene via cis OR trans chlorination/bromination.

Completely eliminates alkyne in excess or adequate amount.

Front 11

Ts

Back 11

Replaces H in OH to make excellent Sn2 LG

Include LG when using as a reagent (ie - TsCl)

Front 12

NaBH4 / EtOH

Back 12

Converts ketones & aldehydes to OH

Front 13

1) LiAlH4 / 2) H3O+

Back 13

Converts ketones, alde's & esters to OH. In esters, chain is cut in front of the O-C & O=C becomes OH.

Front 14

Na2Cr2O7 / H2SO4 * H2O

Back 14

1Y OH to carboxylic acid
2Y OH to ketone

Front 15

SOCl2

Back 15

Replaces OH with Cl. **NO RXN on 3Y alcohols...use HCl instead.

Front 16

PBr3

Back 16

Replaces OH with Br. **NO RXN on 3Y alcohols...use HBr instead.

Front 17

PCC

Back 17

1Y to aldehyde
2Y alcohol to a ketone


**NO RXN on 3Y alcohols

Front 18

Grignard

Back 18

* Replaces db or epoxide with OH & new adjoining C-C

* No C=O, then it just adds H

* Ester - OH, O-R removed & double addition
Ester in a ring - OH, double
addition & ring opens with
2nd OH at opposite end

Front 19

Acid / H2O or Base (like MeOH)

Back 19

Creates O=C instead of C=C like conc H2SO4 during dehyration of an diol ** ALKYL SHIFT to stabilize cation after H2O LG detaches

Front 20

* 1Y OH with PCC = aldehyde
1Y OH with Na2 = carb acid

* Both convert 2Y to ketone

* Neither reacts with 3Y

Back 20

Na2Cr2O7 / H2SO4 * H2O versus PCC

Front 21

Epoxide + HCl/ROH

Back 21

H joins to O, then OH from epox goes to least substituted end, OR goes to most

Front 22

Epoxide + ROH/HCl

Back 22

Epoxide opens, OR joins to least substituted end, H from acid bonds to O of epoxide

Front 23

Ester + Grignard

Back 23

carbonyl reduced to OH, ether portion is removed and double R group addition

* If a ring, ring splits & O becomes OH at opposite end, everything else above still applies

Front 24

Homolytic - the more s character, the more E needed. So sp3-sp3 is low and sp-s is high

Back 24

BDE trend

Front 25

Substituent Effect

Back 25

The more substituents, the lest stable the cation is & the faster it reacts with the base

Front 26

The farther away the charge will be from the electron neg element, the less stabilized it is & the less acidic the molecule is.

Inductive stabilizes anions & destabilizes cations

Back 26

Inductive Effect

Front 27

Donating Groups, like NH2 / NMe2 / OCH3,...

Back 27

destabilize negative charges by trying to put electrons into the ring/chain

Front 28

Withdrawing groups, like NO2 or R4N,...

Back 28

help stabilize negative charges (which increases acidity)

on dienophile - increase rxn rate
on diene - decrease rxn rate

Front 29

Csp-O most acidic < alkyne < alkene < alkane

Back 29

Acidity trend based on C-C bonds

Front 30

cation & radical stabilization trends

Back 30

3Y < 2Y < 1Y < primary being least

but most stable when adjacent to C=C bond

Front 31

anion stabilization trends

Back 31

primary< 1Y < 2Y < 3< least stable

stabilized by withdrawing groups

but most stable when adjacent to C=C bond

Front 32

1) O3 / 2) MeS

Back 32

Splits db in a ring - reduction reaction - ketone on both ends & H at one

Front 33

1) Hg(OAc)2 CH3OH
2) NaBH4

Back 33

Mark addition of OCH across a alkene

Front 34

(1st) aldehyde < ketone < OH < ene < yne < X < oxy (last)

Back 34

Nomenclature Numbering Priority Order

Front 35

Acid Halide + Grignard + H3O

Back 35

carbonyl to OH - halide eliminated - double R group addition

Front 36

C-N alkyne + Grignard

Back 36

drops N, puts C=O on the C & adds R group

NOTICE - C=O, not OH!!

Front 37

Na+ -H

Back 37

OH to O-