Exam 2 Quinn

oxid of 2^o ROH: what reagents?

Na₂Cr₂O₇, H₂SO₄, H₂O or CrO₃, H₂SO₄, H₂O, (What key intermediate do these form?)

oxid of 2^o ROH: what product?

ketone

oxid of 2^o ROH: what mechanism?

Oxidation of 1^o ROH: what reagents?

H₂CrO₄, H₂O to get carboxylic acid (how do we make H₂CrO₄?), PCC/Dess-Martin and CH₂Cl₂ to stop at aldehyde

Oxidation of 1^o ROH: draw PCC

Oxidation of 1^o ROH: draw Dess-Martin

what is —OAc?

Oxid 1^o ROH: What Product?

carboxylic acid or aldehyde

Oxid 1^o ROH to carbox acid: mechanism?

Oxid 1^o ROH to aldehyde: mechanism with PCC?

Oxid 1^o ROH to aldehyde: mechanism with D-M?

Oxid 2^o ROH: do these reagents also work on Oxid 1^o ROH?

H₂CrO₄ will —> 1^o to carbox acid, but need PCC or D-M to stop at aldehyde.

what does PCC or D-M do to 2^o ROH

—> ketone

Tosylate Formation: what are the reagents?

TsCl and Pyridine

Tosylate Formation: what are the products?

Tosylate Formation: mech?

Esterification rxn: reactants?

Esterification reaction: products?

Intramolecular Esterification mechanism

Esterification mechanism

Williamson Ether reactants

1) NaH or Na+ 2) R-LG

What does second step williamson ether reactant have to be?

1^o or 2^o ROH, unhindered (mostly 1^o since 2^o will give a major E2 product)

Williamson Ether mechanism

Williamson Ether mechanism

product

ROH rxn with H-X reactants?

just H-X!

ROH rxn with H-X products?

-X where -OH was (stereochem?) BUT also possible elimination

ROH rxn with H-X mechanism?

2 possible! Sn1 for 3^o OH, Sn2 for 1^o, 2^o can be either (don't forget C⁺ rearrangement)

What reagents can you use for ROH rxns with PX₃? (what can PX₃ be)

PCl₃, PCl₅, PBr₃, P/I₂

ROH rxn with PX₃ products?

inverted -X where -OH was

which ROHs does PX₃ react with and why?

1^o and 2^o because Sn2, no C⁺ rearrangement, 3^o has too much steric hindrance

What can you use to switch out a 1^o -OH for an -X? by what type of rxn(s)?

H-X or PX₃ by Sn2

What can you use to switch out a 2^o -OH for an -X? by what kind of rxn(s)?

PX₃ preferred since no C⁺ rearr (Sn2), but can use H-X if okay to risk Sn1

What can you use to switch out a 3^o -OH for an -X? by what kind of rxn(s)?

Can't use PX₃, have to use H-X and has to be Sn1 (risk C⁺ rearr)

ROH rxn with PX₃ Mech

what does the drawing of the Px₃ for I look like if you wanna use it with ROH

if you see PCl₅ what do you do to react with ROH

PCl₅ —> PCl₃

what is thionyl chloride?

Cl₂-S=O

what do you call Cl₂-S=O

thionyl chloride

which rxn(s) can you use to get inverted -X in place of -OH

1^o ROH can use HX or PX₃, 2^o ROH can use PX₃, 3^o ROH can do sn1 with HX but that yields racemic mixture so no way to predict stereochem

which rxn(s) can you use to get conserved configuration -X in place of -OH (and what _ary) ROHs does this work on?

rxn with SOCl₂, thionyl chloride, works on 1^o and 2^o ROHs

reactants in ROH with thionyl chloride rxn?

products in thionyl chloride rxn?

ROH w/ SOCl₂ mech

give 4 acids with non-nuc cbs

H₂SO₄, HF, H₃PO₄, HNO₃

ROH dehydration reactants

H₂SO₄, HF, H₃PO₄, or HNO₃ with H₂O and heat

ROH dehydration products

alkene and water

what 3 things keep in mind for ROH dehydration?

1) 3^o > 2^o > 1^o because of C⁺ 2) C⁺ can rearrange 3) = will form between C⁺ and most substituted adjacent C

ROH dehydration mechanism

pinacol rearrangement reactants

H₂SO₄, HF, H₃PO₄, or HNO₃ with H₂O

pinacol rearrangement product

ketone with alkyl shift in mech

pinacol rearrangement mech

What two rxns from last unit do we know to form ketones and aldehydes?

Friedel-Crafts Acylation and Ozonolysis of Alkenes

Hg-cat hydration reagents

HgCl₂, H₂SO₄, H₂O, then HCl for the acid-cat tautomerization

Does hg-cat hydration form mark or anti-mark enol?

mark

Hg-cat hydration products

mark enol —> ketone

Acid-cat taut mech for hg-cat hydration (of alkynes)

Hydroboronation/Oxidation of alkynes reagents

1) Sia₂BH 2) H₂O₂, ^-OH, then ^-OH and H₂O for base-cat taut

Hydroboronation/Oxidation of alkynes products

anti-mark enol —> aldehyde

Does hydroboronation/oxidation make mark or anti-mark enol?

anti-mark

base-cat taut for hydroboronation-oxidation mech

synthesis of ketones from carboxylic acids reagents

1) R-Li (xs) 2) H₃O⁺

carboxylic acid and R-Li mechanism (what reagent missing)

synthesis of ketones from nitriles reagents

1) R’—MgX, 2) H₃O⁺, then more H₃O⁺ to hydrolyze

synthesis of ketones from nitriles mech

2 ways to make acyl chlorides

1) adding SOCl₂ and pyr to R-OH and 2) adding SOCl₂ and pyr to carbox acid

reduction of acyl chloride to aldehyde reagent

LiAl(OtBu)₃H

reaction of acyl chloride to aldehyde mechanism

Rxn of acyl chloride to ketone reagent

R—Cu^-—R ⁺Li

rxn acyl chloride to ketone mechanism

what does hydride reduction do

ketone —> alcohol

hydride reduction reagents

2 options: 1) LiAlH₄ 2) H₃O⁺ or 1)NaBH₄ 2) ROH

hydride reduction mechanism

what does organometallic addn do

aldehyde—>alcohol (replacing -H with -R)

organometallic addn reagents

2 options: 1) R-Li 2)H₃O⁺ or 1) R—Mgx 2)H₃O⁺

organometallic addn example mech

hydration reagents each way

ketone —> H20 and H2SO4 —> 2 Rs and 2 OHs attached to central C

2 Rs and 2 OHs attached to central C —> H2SO4 and H20

hydration mech