118b mt1 Study Guide 2

Nasiri CHE118B Midterm 1 Study Guide
Spring 2019 || S. Ly sdly@ucdavis.edu
CH 11: Alkenes
→ NAMING

● E-Z system: View each vinyl carbon separately. Determine which of the two groups has priority.
○ High priority groups are on the…
■ Same side >> (Z)
■ Opposite sides >> (E)
○ No E/Z needed for cyclic alkenes
● Always number substituents with lowest possible numbers
● Alkenes as substituents: alkenyls or a
lkylidenes

● Alcohols have higher priority than alkenes
○ A chain with both = alkenol
○ Parent chain priority: alcohols > cycloalkanes > longest C chain
■ Cycloalkanes have higher priority over alkanes, no matter the # Cs
■ Alkanes with more carbons have priority over alkenes with less.

* PRACTICE
Give the proper IUPAC names of the following molecules.
1.

2.
3.
4.

→ PROPERTIES
● C=C bond disallows free bond rotation

● Boiling point: cis > trans
○ Cis molecules have a dipole moment
● Melting point: cis < trans
○ Shape of a trans molecule stacks/packs together better than cis
● More substituted alkenes are more stable because of hyperconjugation
○ Trans more stable than cis because cis has more steric hindrance

● Cyclic alkenes (3-7 C) only has cis configuration because p orbitals must be parallel

→ SYNTHESIS
I. Dehydrohalogenation (E2)

** Fill in mechanism:

● The base you use can change what product you get!
○ Hindered/bulky base (LDA, KOC(CH3)3) >> HOFMANN PRODUCT (less substituted)
○ Unhindered base (NaOC2H5) >> ZAITSEV PRODUCT (more substituted)

● E2 requires antiperiplanar geometry (LG and H opposite to each other)
○ This affects whether the resulting alkene is E/Z (check your stereochemistry!)
○ If starting reagent is cyclic >> no bond rotations >> H and LG MUST be trans!

II. Dehydration (E1)

● Unless you’re dealing with a primary alcohol, ALWAYS check for carbocation rearrangement

* PRACTICE
Fill in appropriate blanks.
5.

6.

7.

8.

9.

CH 12: Reactions of Alkenes

→ HYDROGENATION

● Syn addition
● Hydrogens add to less hindered side
● Will hydrogenate ALL double bonds on a compound

→ MARKOVNIKOV ADDITION

● Electrophile bonds to less subbed vinyl carbon
● Nucleophile bonds to more substituted vinyl carbon.
● Rearrangement is possible!
● In the case where a compound has multiple double bonds and you only have 1 eq. of reagent, the
reaction will occur with the more substituted alkene.
○ EXCEPTION: boron compounds - BH3, BR2H, etc.. (hydroboration-oxidation)

→ ADDITION OF WATER

** Fill in mechanism for acid-catalyzed H2O addition:

** Fill in mechanism for oxymercuration-demercuration:

** Fill in mechanism for hydroboration-oxidation:

→ CARBENE ADDITION
I. Using diazomethane

** Fill in the mechanism. Include the resonance structures for diazomethane.

II. Simmon-Smith method

III. Using dichlorocarbene

** Fill in the mechanism, including the formation of CCl2 from CHCl3.

→ HALOGENATION

● Will form enantiomers
● Anti addition
● Reacting with X2 and a nucleophile will result in anti addition of X and Nu

→ EPOXIDE SYNTHESIS
I. Halogenation method

** Fill in the mechanism:

II. Using peroxycarboxylic acid


→ EPOXIDE OPENING

● Always anti
● Can use alcohol instead of water
● In acidic mediums, a carbocation is formed on the more substituted carbon, and the water/alcohol
adds there.
● In basic mediums, SN2 occurs, the base (water/alcohol) attacks/adds on the less substituted
carbon (less steric hindrance).

** Fill in the mechanism for acidic medium:

** Fill in the mechanism for basic medium:

→ SYNTHESIS OF SYN VICINAL DIOLS

● KMnO4 and H2O will overoxidize the compound into a carboxylic acid.

→ OZONOLYSIS

● Always count your carbons! The numbers on the product and reactant sides should match.


→ ANTIMARKOVNIKOV ADDITION OF HBr

● ONLY for HBr
○ HCl and HI will react normally (Markovnikov), even in the presence of ROOR

* PRACTICE
Fill in the appropriate blanks.
1.

2.
3.
4.
5.
6.
7.

8.
9.
10.
11.
12.

CH 13: Alkynes
→ NAMING

● Alkenynes = contains double and triple bond -- number the C’s starting from end closer to first pi
bond. If they have the same distance, alkene takes priority (en > yn, alphabetically)
● Remember, alcohol has a higher priority still
● As a substituent - alkynyl

* PRACTICE
Give the proper IUPAC names.
1.
2.
3.

→ SYNTHESIS
Dehydrohalogenation of dihaloalkanes
I. Internal alkyne


II. Terminal alkyne

● The terminal H on an alkyne is weakly acidic >> can form organometallics
○ Can be deprotonated by NH2- but NOT RO- … the RO- anion is more stable than the
alkynide anion, so deprotonation would not be favorable

→ HYDROGENATION
● H2 + cat. completely turns alkyne into alkane
● What if we want to stop the reaction at the alkene? >> use a less reactive reagent: Lindlar’s
catalyst -- it does not reduce alkenes
● Syn addition only (produces CIS alkenes)
● What if we want to make a trans alkene? >> metallic reduction using Na and NH3

** Fill in mechanism for metallic reduction of an alkyne:

→ HALOGENATION/HYDROHALOGENATION
I. Adding X2 and HX to internal alkynes

● X and X or H and X add anti/trans to each other, first forming an alkene
○ Alkene can further react with more X2/HX and undergoes Markovnikov addition
● If your starting alkyne is asymmetrical, you will get a product mixture
II. Adding HX to terminal alkynes

● Markovnikov addition

III. Adding HBr to terminal alkynes, anti-Markovnikov

→ ADDITION OF H2O
I. Internal alkyne

** Fill in the mechanism and include the tautomerization steps:

II. Terminal alkyne

** Fill in the mechanism for anti-Markovnikov addition of H2O and include tautomerization steps.
Hint: The mechanism parallels the one for alkenes.

** What’s the difference between the tautomerization steps for Markovnikov and anti-Markovnikov addition
of water?

* PRACTICE
Fill in the appropriate blanks.
4.
5.

6.
7.
8.
9.
10.

* KEY
Refer to lecture notes for mechanisms. If you need help or have found any mistakes, e-mail me or come to my office
hours (MON: 9 - 10:45 AM CHEM159 // TUES: 4:30 - 6:00 PM CHEM163K)
CH 11
1. (S,Z)-3-bromo-4-methoxy-3-buten-2-ol
2. (E)-1-ethylidene-2-methylcyclohexane
3. 5-bromo-1-methylcyclopentene
4. (2S)-1-(2-propenylcyclohexyl)-2-propanol
5. Any bulky base (LDA, KOC(CH3)3…)
6.
7.
8.
9.

CH 12
1.
2.

3.
4.
5.
6.
7. 1) any base to form alkene 2) H2O, non-nuc acid (H shift occurs)
8.
9.

10.
11. 1) OsO4 2) SH2
a. Note that the presence of a stereocenter initially leads to a pair of diastereomers NOT enantiomers
12. 1) H2O, H2SO4, heat 2) H2SO4, heat 3) HBr 4) LDA 5) Br2, ROOR

CH 13
1. (E)-1-chloro-1-fluoro-2-methylhex-1-en-5-yne
2. (2E,6E)-2-ethylideneoct-6-en-4-yn-1-ol
3. (1-methyl-2-butynyl)cyclopropane
4.
5.
6.
7. H2, Lindlars
8.
9. 1) H2, Lindlars or Na, NH3 2) O3 3) SH2
10.

118b mt1 Study Guide 2

Diunggah oleh

Informasi Dokumen

Judul Asli

Hak Cipta

Format Tersedia

Bagikan dokumen Ini

Bagikan atau Tanam Dokumen

Opsi Berbagi

Apakah menurut Anda dokumen ini bermanfaat?

Apakah konten ini tidak pantas?

Hak Cipta:

Format Tersedia

118b mt1 Study Guide 2

Diunggah oleh

Hak Cipta:

Format Tersedia

Nasiri CHE118B Midterm 1 Study Guide

Spring 2019 || S. Ly sdly@ucdavis.edu

CH 12: Reactions of Alkenes

** Fill in mechanism for acid-catalyzed H2O addition:

** Fill in the mechanism for acidic medium:

** Fill in the mechanism:

** Fill in mechanism for metallic reduction of an alkyne:

III. Adding HBr to terminal alkynes, anti-Markovnikov

II. Terminal alkyne

Anda mungkin juga menyukai

118b mt1 Study Guide 2

Diunggah oleh

Informasi Dokumen

Judul Asli

Hak Cipta

Format Tersedia

Bagikan dokumen Ini

Bagikan atau Tanam Dokumen

Opsi Berbagi

Apakah menurut Anda dokumen ini bermanfaat?

Apakah konten ini tidak pantas?

Hak Cipta:

Format Tersedia

118b mt1 Study Guide 2

Diunggah oleh

Hak Cipta:

Format Tersedia

Nasiri CHE118B Midterm 1 Study Guide

Spring 2019 || S. Ly ​sdly@ucdavis.edu

CH 12: Reactions of Alkenes

** Fill in mechanism for acid-catalyzed H2O addition:

** Fill in the mechanism for acidic medium:

** Fill in the mechanism:

** Fill in mechanism for metallic reduction of an alkyne:

III. Adding HBr to terminal alkynes, anti-Markovnikov

II. Terminal alkyne

Anda mungkin juga menyukai

Spring 2019 || S. Ly sdly@ucdavis.edu