Organic Chemistry-Semester 1 – Flashcards
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Unlock answersAcid/Base
Electrophile/Nucleophile
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Neutralized Substance (frequently HOH)
A + :B → AB |
Sn2
Alkane w/ Leaving Group (1°) to Replaced Leaving Group
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Nucleophile
H H H C-C-L + :Nu →[ Nu-C-L ] → Nu-C-C + :L H CH H
Inversion |
Sn1
Alkane w/ Leaving Group (2/3°) to Alkane w/ New Substituent (has E1 by-product) |
Nu:
C C C C-C-L → C-C + + :Nu → C-C-Nu C C C
Racemate |
E2
Alkane w/ Leaving Group (1/2°) to Alkene |
Nu:
H H H H-C-C-L + :Nu → [Nu--H--C==C--L] → C=C H H H |
E1
Alkane w/ Leaving Group (3°) to Alkene |
Nu:
C C C H-C-C-L → H-C-C+ + :Nu → [ Nu--H--C==C ] → C C C C C=C C |
Dehydrohalogenation
Alkyl Halide to Alkene |
Nu:
By E2/1 |
Acid Catalysed Dehydration
Alcohol (3º>2º>1º) to Alkene |
Strong Acid
H adds to -OH
Proceeds as E1/2 |
Double Elimination
Vicinal Dihalide to Alkyne |
Nu: (2eq)
2 repeated E2 reactions |
Rearrangement
1º/2º Cation
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3º Cation
An entire subsituent moves over to the 1º/2º cation to make more stable |
Replacement
Terminal Alkyne to Terminal Alkynide
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NaNH2, NH3, Li...
R-CΞC-H → R-CΞC: |
Hydrogenation
Alkene to Alkane |
H2, Pd/Ni
Double bond attacks H in H2 |
Hydrogenation
Alkyne
Syn Alkene
OR
Anti Alkene |
Ni2B, H2 OR Li, EtNH2 (Radical)
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Addition
Alkene to Alkyl Halide |
HX
Double bond attacks H (adds to side w/ most H's), creates a Cation, X- attacks. ; ;REARRANGEMENT can happen. |
Acid Catalysed Hydration ; Alkene to Alcohol ; |
1)HA 2) OH- ; Double bond attacks H on Acid, then Conj. Base attacks cation.; OH- attacks C with sulfonate. |
Acid Catalysed Hydration ; Alkene to Alcohol (3;/2;) ; |
SA, H2O ; Double bond attacks H on acid, forms cation.; H2O attacks cation.; Conjugate base deprotonates the O+ formed. |
Oxymercuration/Demercuration ; Alkene to; Alcohol (no rearrangement) |
Hg(COOCH3)2 , THF (becomes Cation), H2O ; Double bond attacks Hg, forms bond from both C's. Hydrogenation occurs. NaBH4, OH- H- attacks C w/ Hg
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Hydroboration
Alkene to Alkyl Borane |
BH3
Double bond attacks B, kicks out an H
(occurs for each H) |
Oxidation and Hydrolysis
Alkylborane to Alcohol |
HOO-, NaOH
Peroxide Ion attacks B, R attacks 1st O, forms ether. Repeats 3 times.
OH- attacks B, kicks out -O-R, which attacks H on BOROH. |
Addition
Alkene to Vicinal Dihalide |
Cl2, CCl4
C=C forms ring with a Cl, Cl- attacks from other side
TRANS |
Addition
Alkene to Halohydrin |
X2, H2O
C=C forms ring with X, H2O goes through Hydration |
Carbene Formation
Diazomethane (:CH2-NΞN:) to Carbene |
hν
N-C bond breaks and :CH2 forms |
Cyclopropane formation
Alkene to Cyclopropane |
Carbene
Cyclic donation from double bond to carbene and vice versa. |
Oxidation
Alkene to Diol (Syn) |
1) OsO4, Pyradine 2)NaSO3/H2O OR KMnO4, OH-, H2O
Double Bond attacks an O, an O attacks the other Carbon, and the H's attack at O bonds. |
Oxidative Cleavage ; Alkene (alkyne) to Carboxylic Acid, CO2, or Ketone (carboxylic acid) |
1) KMnO4, OH-, H2O, heat 2)H3O+ ; Breaks double bond, adds a =O. |
Oxonolysis ; Alkene ; 1) O3, CH2Cl2 2);Zn, HOAc |
Aldehyde/Ketone ; Forms C-C;Ring ;; O-O-O Which changes to a C-O-C Ring ;;;;;;;;;;;;;;;;;;;; O; O Which breaks apart w/ Zn, HOAc |
Addition ; Alkyne to Dihaloalkene (trans) Tetrahaloalkane |
X2, CCl4 ; Adds 1/2 times depending on eq (like addition to Alkene). |
Addition ; Alkyne to Haloalkene |
HX (for Markovnikov) ; HX and ROOR (for Anti-Markovnikov) ; |
Addition ; Haloalkene to Geminal Dihalide |
HX ; Adds Markovnikov, so adds X to C with other X. |
Radical ; Alkane to Alkyl Halide |
X2, Light ; Cl; abstracts the H, leaving a radical.; Cl; attacks the radical. |
Anti-Markovnikovian Addition ; Alkene to Alkyl Halide |
HX, light, ROOR ; RO; abstracts H from HX, X; attacks double bond, the radical C abstract and H from HX. ; ; |
Substitution ; Alcohol to Alkyl Halide ; |
HX, PBr3, SOCl2 and pyradine ; OH attacks either P or H, making a good leaving group.; X- will then attack the C. |
Intermolecular Dehydration ; 1; Alcohol to Ether |
HA ; R-OH ; R-OH2 ; [ROH--R--OH2] → ROR → ROR H |
Williamson Synthesis
Alcohols to Ether |
K or NaH and R'-L
R-OH → R-ONa/K → R-O-R' (Na/K+ and L-) |
Alkoxymercuration/Demercuration
Alkene to Ether |
1) Hg(OOCCF3)2, HO-R' 2) NaBH2, OH-
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Protecting Groups
Alcohol to Protected Ether |
H2SO4, C=C(CH3)2 OR ClSi(CH3)2CH3, Imidiazole, DMF (Bu4NF, THF to remove)
Use to get a base to attack a C rather than an H |
Cleavage
Ether to Alkyl Halide and Alcohol |
H-X
H adds to O, stablest cation forms (or X attacks-Mark) H R-O-R' → R-OH + R'+ or R'X |
Formation of Epoxides
Alkene to Epoxide |
Peroxyacid
Forms cyclic bond with OH from ROOH, also forms a carboxylic acid |
Acid Catalysed Ring Opening
Epoxide to Akyl ____ |
Water or other Weak Acid
O attacks H from Acid, acid attacks C and OH breaks off to form an Alkyl whatever. |
Base Catalysed Ring Opening
Epoxide to Alkyl______ |
Strong Base and NH4Cl
Base attacks the C, O breaks off, attacks a Hydrogen. |
Reduction by Hydride Transfer
Carboxyl Group to Alcohol |
1) LiAlH4, Et2O 2) H2SO4/H2O or BH4, H2O
Donates an H, O- attacks an H (or pushes out an OH-) |
Oxidation
Alcohol to Aldehyde (1°), Carboxylic Acid (1°), or Ketone |
PCC, CH2Cl2 or KMnO4, OH-, H2O, heat, H3O+ or CrO3 (HCrO4, Acetone), H2O (JONES REAGENT) |
Organometal Formation
Alkyl Halide to Organometal |
Mg or Li (Et2O, THF)
Replaces X |
Acid/Base
(What can go WRONG)
Carboxyl group with an acidic H to Alkane |
Organometallic attacks the H rather than the C with the =O
(Works with -OH, and CΞCH notably) |
Grignard/Lithium Rxn
Carboxyl Group to Alcohol |
Grignard/Organolithium Reagent or C≡C:, H3O+
R group on Organometallic attacks C with =O. Also works in Epoxides with C-O
Esters will act as a leaving group |
Corey-Posner, Whiteside-House Synthesis
Alkyl Halide to Dialkyl cuprate |
Li in Et2O and CuI
Li replaces X, Cu takes place of Li to get CuLi compound with 2 alkyl groups |
Corey-Posner Whiteside-House Synthesis (part deux)
Alkyl Halide to Alkane |
Dialkyl Cuprate
Alkyl Group takes place of X |
Allylic Substitution
Alkene with ≥1 branch to Halo-alkene |
X2, Heat also: NBS, hv, CCl4
X· Forms, abstracting an H and leaving a radical on an allylic carbon. Through RESONANCE, many different placements of the X occur. |
Diels-Alder Reaction
Diene (best if with e- donating group) to Six-Membered Ring |
Alkene with e- withdrawing group (Electron Acceptor)
Resonance makes the donor/acceptor possible, number carbons along double bonds 1-4 and 5-6 to show bonds of ring.
***IN=UP, OUT=DOWN***
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