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Alkynes
Pure hydrocarbon with at least one triple bond
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To make Alkynes
Take Alkenes and do it twice
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Double Dehydrohalogenation of Alkynes
- Synthesis
- Must have Vicinal Dihalide
- Sayetzef (Poor get Poorer, Rich get Poorer)
- alKENE to alKYNE
- Both Halogens Leave, 2 Hydrogens Leave
- Remember: Nitrogen likes 3 bonds (NH2)
- Start Point: Halogens attach to carbon double bond
- First Synthesis (Reaction in Alcohol): Alkene w/ 1 Halogen and 1 Hydrogen on double bond + H2O + K+X-
- Second Synthesis (Reaction in NaNH2): Alkyne- No X or H on triple bond + NH3 + NA+X-
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Synthesis of Alkynes General Rule
Do the synthesis and then do it again
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Metal Acetylides
- Synthesis
- Chain Lengthening
- Will have large side group
- Triple bond and X must be on 1o carbon
- Remember: Nitrogen likes 3 bonds (NH2)
- -C(triple bond)C-H (Reaction in LiNH2) -C(triple bond)C-Li + RX (Creates) -C(Triple Bond)C-R + LiX
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Addition of Hydrogen
- Reaction
- 2H2
- Markovnikov w/ Major & Minor
- Rich get Richer, Poor get Richer
- Add hydrogen twice
- Major: Na or Li (LiNH2 or Na+NH2), Creates Trans
- Minor: H2 (Lindlar Catalyst), Creates Cis
- alKYNE to alKENE in major/ minor
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Addition of Halogens
- Reaction
- 2X2 = Cl2, Br2
- No Major/ Minor
- Alkyne to Alkene to Haloalkane
- Add Halogens twice
- Alkyne (Reaction with X2) Vicinal Haloalkene (Reaction with X2) Gem-Dihalide
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Addition of Hydrogen Halides
- Reaction
- 2(HX)
- Markovnikov w/ Major & Minor
- Rich get Richer, Poor get Richer
- alKYNE to alKENE to alKANE
- ---------------------------------H X -------------------------------------------H X
- Alkyne (Reaction w/ HX) -C=C- (Reaction w/ HX) Gem-Dihalide -C-C-
- ----------------------------------------------------------------------------------H X
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Addition of water- Hydration
- Reaction
- Enol which is unstable
- Markovnikov, Major/ Minor
- Rich get Richer, Poor get poorer
- alKYNE to alKENE to alKANE
- Sulfuric acid provides H+, H2O provides OH-
- H2SO4 or HgSO4
- Major: Keto-enol
- Minor: Ado-enol
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Formation of Metal Acetylides
- Reaction
- No Major/ Minor
- Remains of Alkyne
- Hydrogen on triple bond carbon leaves
- Remember: N likes 3 bonds
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Tautomerism
Repetative Part
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Benzenes
- C6H6
- Bond length is between = and -
- Flat ring
- Looks like cyclohexane but isn't
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Kekule
Name of Benzene ring
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SEA
- Substitution
- by an
- Electrophile
- on an
- Aromatic Ring
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Electrophile
- Element/ compound that is positively charged and therefore, highly drawn towards negative elements/ compounds
- I love negative people, so I am positive
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When you see H2SO4 and HNO3
- Create NO2+HONO2 + H+ ------> NO2 + H2O
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Sulfonation
Benzene + 2H2SO in SO3 ------> H2SO4 (on ring) + H2O
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Halogenation of Benzene Ring
- Benzene Ring + Cl2 in FeCl3 --------> Cl+ (on Ring) + HCl-
- Cl- chills with the FeCl3 in the intermediate then jumps of to join H
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Freidal-Crafts Alklylation
- Benzene + R-Cl in AlCl3 -------> R (on ring) + HCl-Cl- chills with the AlCl3 in the intermediate then jumps of to join H
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Freidel- Crafts Acylation
- .................... O......................................O
- .....................ll........................................ll
- Benzene + R-C-Cl in AlCl3 -----------> C-R (on ring) + HCl-
- Cl- chills with AlCl3 before joining H
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If an element/ compound is on the benzene ring and has a lone pair
It will pump electrons into the ring and therefore, the electrophile will got to Ortho/ Para Positions.
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If an element/ compound is on the benzene ring and is taking electrons from the ring, the carbon is partially positive
And the electrophile will go to the Meta positions
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Double or Triple bonds on the benzene ring are electon withdrawals
and are deactivating Meta Directors
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When the benzene has an Ortho/Para Director as #1...
the Ortho/ Paras are negative
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When the benzene has a Meta Director as #1...
the Ortho/ Paras are positive
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What position is affected on the benzene ring?
- Ortho & Para are always affected.
- They are either negative or positive.
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If you are a group on a ring withdrawing electrons...
.... you are a deactivator meta.
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If you are a group on a ring giving electrons...
... you are an activator Ortho Para.
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The first group on the benzene ring goes
... anywhere it wants to.
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Creation Times of Benzene rings
- Activator on benzene- 3minutes
- Plain Benzene- 5minues
- Deactivator on benzene- 8minutes
- Halogen on Benzene- 10 minutes
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HOP
- Halogens Ortho Para
- Deactivator
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Lone Pairs+ Ortho Para =Activator
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Electron Withdrawing + Meta = Deactivator
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Steps to determine location of 2 groups on benzene ring
- Isolate groups to determine location.
- When Meta and Ortho/ Para options overlap, doesn't matter where it is located.
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In the event of a 'tie'/ no overlap of meta and ortho/para locations...
... activators defeate deactivators
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Aromaticity
- 1) Cyclic, plane
- 2) Conjugated
- 3) Huckel's Rule
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Huckel's Rule
- (4n+2) Pi electrons
- 2pi, 6pi, 10pi, 14pi, 18pi
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Aromatic is ______ stable than open counter part
MORE
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Anti-aromatic is ______ stable than open counterpart
LESS
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Aromatic > straight Chain Equivilent > Cyclo
comparative stability of aromatics
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CnH2n+2 (Alkanes)
CnH2n (Alkenes, clycloakanes, Cis/ Trans, E-Z)
CnH2n-2 (Alkynes, cycloalkenes)
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SP3
- All alkanes (single bonds) are SP3 orbitals
- 3 SP3 around carbon
- 109.5o
- Tetrahedral form around carbon
- 1 pi bond (1.54A length)
- 3 sigma bonds (1.10A length)
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Sigma Bonds
single ponds between carbons, carbons and hydrogens
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Pi Bond
The double (only 1) or triple (only 2) bond
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SP2
- Alkenes
- 1 pi bond (1.34A length)
- planar
- 120o
- 3 SP2 around the carbon
- * Aromatics are SP22 sigma bonds(1.09A length)
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SP1
- Alkyne
- 2 pi bonds
- Linear
- 180o
- 2 SP1 around carbon (1.24A length)
- 3 sigma bonds (1.08A Length)
- 50% spherical
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Bond Lengths
- Alkane:
- Pi: 1.54, Sigma: 1.10
- Alkene:
- Pi: -.2, Sigma: -.01
- Alkyne:
- Pi: - .1, Sigma: -.01
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3o> Allyl/ Benzyl/ 2o> 1o> Ch3+
Stability of Carbocation/ Carbon Free Radical Intermediate
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SNHFF
- Sulfonation
- Nitration
- Halogenation
- Freidel-Crafts Alklyation
- Freidel-Crafts Acylation
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Strongly Activating Ortho Para Groups
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Moderately Activating ORtho Para Groups
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Weakly Activating Ortho Para Groups
- R (i.e. CH2CH2CH3)
- Benzene Ring on Benzene Ring
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Deactivating Meta Directors
- NO3
- .......CH3
- CH3-N-CH3
- C(triple bond) N
- O=C-O-H
- O=C-O-R
- SO3H
- O=C-H
- O=C-R
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Deactivating, Ortho Para Directors
Halogens
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