chem241 - ketones & aldehydes

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48 Terms

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ketone

knowt flashcard image
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aldehyde

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aldehyde nomenclature

suffix “—al” (-anal)

  • higher priority > ketone


<p>suffix “—al” (-anal)</p><ul><li><p>higher priority &gt; ketone</p></li></ul><p></p>
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ketone nomenclature

suffix “—one”

<p>suffix “—one” </p>
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naming priorities

carbox acid > aldehyde > ketone > alcohol > amine > thiols

<p>carbox acid &gt; aldehyde &gt; ketone &gt; alcohol &gt; amine &gt; thiols </p>
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physical properties

  • strong dipole

  • ↑ BP


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Nu acyl substitution

add Nu & protonate C=O → OH

  • SNu

  • Wnu


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SNu acyl substitution

reagents

  • 1. SNu

  • 2. dil H+


<p>reagents </p><ul><li><p>1. SNu</p></li><li><p>2. dil H+ </p></li></ul><p></p>
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WNu acyl substitution

reagents

  • 1. H3O+

  • WNu (H2O, MeOH, EtOH)


<p>reagents </p><ul><li><p>1. H<sub>3</sub>O+</p></li><li><p>WNu (H<sub>2</sub>O, MeOH, EtOH) </p></li></ul><p></p>
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chirality

rxm defined by Nu type

  • re-face

  • si-face

    • mostly attack both sides (racemic)

      • show both products

      • distinguish between faces


<p>rxm defined by Nu type</p><ul><li><p><strong>re-face</strong></p></li><li><p><strong>si-face</strong> </p><ul><li><p>mostly attack <u>both</u> sides (racemic) </p><ul><li><p>show both products</p></li><li><p>distinguish between faces </p></li></ul></li></ul></li></ul><p></p>
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re-face

R config (CW)

<p>R config (CW) </p>
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si-face

S config (CCW)

<p>S config (CCW)</p>
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carbon Nu addition

make OH group + other group

  • grignard

  • organolithium

  • alkyne

  • cyanonuclleophile (cyanohydrin)

  • corey-seebach

  • wittig rxn


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grignard Nu addition

SN2

  • reagents: RMgBr, RMgCl, RMgI

  • limitation → no acidic proton


<p>SN2</p><ul><li><p>reagents: RMgBr, RMgCl, RMgI</p></li><li><p>limitation → no acidic proton </p></li></ul><p></p>
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organolithium Nu addition

violent reaction, prefer grignard

  • reagents:

    • 1. RLi

    • H+


<p>violent reaction, prefer grignard </p><ul><li><p>reagents: </p><ul><li><p>1. RLi</p></li><li><p>H+ </p></li></ul></li></ul><p></p>
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alkyne Nu addition

reagents

  • 1. SNu

  • ketone

  • dil H+


<p>reagents</p><ul><li><p>1. SNu</p></li><li><p>ketone</p></li><li><p>dil H+ </p></li></ul><p></p>
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cyanonucleophile addition

cyanohydrin

  • reagents

    • HCN, NaCN, sodium salt catalyst (+C≡N)

  • sterics

  • cabonyl of aldehye not stabilized by hyperconjugation


<p>cyanohydrin </p><ul><li><p>reagents</p><ul><li><p>HCN, NaCN, sodium salt catalyst (+C≡N)</p></li></ul></li><li><p>sterics</p></li><li><p>cabonyl of aldehye not stabilized by hyperconjugation </p></li></ul><p></p>
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corey-seebach

replace “H” in aldehyde only w/ E+

  • reagents

    • 1. C3H2S2, AlCl3

    • 2. BuLi, THF, 0°C

    • E+ (RX)

    • MgO, H2O


<p>replace “H” in aldehyde only w/ E+ </p><ul><li><p>reagents </p><ul><li><p>1. C<sub>3</sub>H<sub>2</sub>S<sub>2</sub>, AlCl<sub>3</sub></p></li><li><p>2. BuLi, THF, 0°C</p></li><li><p>E+ (RX) </p></li><li><p>MgO, H<sub>2</sub>O </p></li></ul></li></ul><p></p>
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wittig reaction

add P(Ph)3 to RX group

  • reagents:

    • 1. PPh3

    • BuLi or NaH


<p>add P(Ph)<sub>3</sub> to RX group </p><ul><li><p>reagents: </p><ul><li><p>1. PPh<sub>3</sub></p></li><li><p>BuLi or NaH</p></li></ul></li></ul><p></p>
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wittig mechanism

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oxygen Nu addition

react w/ keton to get hydrate geminal diol

  • reagents: ketone, H2O, acid/base


<p>react w/ keton to get <strong>hydrate geminal diol </strong></p><ul><li><p>reagents: ketone, H<sub>2</sub>O, acid/base </p></li></ul><p></p>
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hydrate geminal diol

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hydrate formation

make hydrate geminal diol from ketone

  • basic

  • acidic


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basic hydrate formation

reagents:

  • ketone

  • OH—

  • H2O


<p>reagents: </p><ul><li><p>ketone</p></li><li><p>OH<sup>—</sup></p></li><li><p>H<sub>2</sub>O</p></li></ul><p></p>
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acidic hydrate formation

reagents

  • ketone

  • H3O+

  • excess H2O


<p>reagents</p><ul><li><p>ketone</p></li><li><p>H<sub>3</sub>O+</p></li><li><p>excess H<sub>2</sub>O </p></li></ul><p></p>
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hemiacetal formation

when Nu is ROH → hemiacetal

  • basic

  • acidic


<p>when Nu is <strong>ROH</strong> → hemiacetal </p><ul><li><p>basic</p></li><li><p>acidic</p></li></ul><p></p>
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basic hemiacetal formation

reagents

  • ketone

  • excess EtOH


<p>reagents </p><ul><li><p>ketone</p></li><li><p>excess EtOH</p></li></ul><p></p>
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acidic hemiacetal formation

reagents

  • ketone

  • excess EtOH2+


<p>reagents</p><ul><li><p>ketone</p></li><li><p>excess EtOH<sub>2</sub>+ </p></li></ul><p></p>
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EtOH2 formation

  • under acidic condition

    • if excess ROH → rxn go forward → acetal


<ul><li><p>under <strong>acidic </strong>condition</p><ul><li><p>if excess ROH → rxn go forward → <strong>acetal </strong></p></li></ul></li></ul><p></p>
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acetal formation

add geminal OMe groups

  • acetals are protecting groups for ketones & aldehydes


<p>add geminal OMe groups </p><ul><li><p>acetals are protecting groups for ketones &amp; aldehydes </p></li></ul><p></p>
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acetal example

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nitrogen Nu

react w/ ketones & aldehydes to give imine/enamine

  • 1° amine → imine

  • 2° amine → enamine


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imine formation

1° amines

  • reagents: R-NH2, H+

    • need alpha-H


<p>1° amines </p><ul><li><p>reagents: R-NH<sub>2</sub>, H+ </p><ul><li><p><strong>need alpha-H</strong></p></li></ul></li></ul><p></p>
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imine mechanism

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enamine formation

2° amines

  • reagents: R-NH, H+

    • E/Z often reverse this rxn


<p>2° amines </p><ul><li><p>reagents: R-NH, H+ </p><ul><li><p>E/Z often reverse this rxn </p></li></ul></li></ul><p></p>
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enamine mechanism

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stork enamine reaction

reagents

  • 1. R-NH, RX

  • 2. H2O, H+


<p>reagents</p><ul><li><p>1. R-NH, RX</p></li><li><p>2. H<sub>2</sub>O, H+ </p></li></ul><p></p>
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redox reactions

reduce C=O → OH

  • carbonyl reduction

    • aldehyde & ketone reduction

  • catalytic reduction

  • clemmenson reaction

  • wolf kishen

  • mozingo rxn

  • reductive amination


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carbonyl reduction

reduce C=O → OH

  • reagents: NaBH4, EtOH

    • NaBH4 - reducing agent for ketones & aldehydes


<p>reduce C=O → OH </p><ul><li><p>reagents: NaBH<sub>4</sub>, EtOH</p><ul><li><p>NaBH<sub>4</sub> - reducing agent for ketones &amp; aldehydes </p></li></ul></li></ul><p></p>
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carbonyl aldehyde reduction

reagents:

  1. NaBH4

  2. dil H+


<p>reagents: </p><ol><li><p>NaBH<sub>4</sub></p></li><li><p>dil H+ </p></li></ol><p></p>
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carbonyl ketone reduction

reagents:

  1. LiAlH4

  2. dil H+


<p>reagents: </p><ol><li><p>LiAlH<sub>4</sub></p></li><li><p>dil H+ </p></li></ol><p></p>
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carbonyl reagent differences

  • important for labeling


<ul><li><p>important for labeling </p></li></ul><p></p>
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catalytic reduction

reagents:

  • H2, Pt or H2, Pd


<p>reagents: </p><ul><li><p>H<sub>2</sub>, Pt or H<sub>2</sub>, Pd</p></li></ul><p></p>
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clemmensan reaction

not benzylic position → reduce to CH2 (ketone/aldehyde) ONLY

  • under acidic cond.

  • reagents

    • Zn(Hg), HCl


<p>not benzylic position → reduce to CH<sub>2</sub> (ketone/aldehyde) ONLY </p><ul><li><p>under <strong>acidic</strong> cond. </p></li><li><p>reagents</p><ul><li><p>Zn(Hg), HCl</p></li></ul></li></ul><p></p>
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wolf kishen

reagents

  • H2N—NH2, KOH, â–ł


<p>reagents</p><ul><li><p>H<sub>2</sub>N—NH<sub>2</sub>, KOH, △</p></li></ul><p></p>
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reductive amination

reagents:

  1. R-NH2, H+

  2. H2, Ni


<p>reagents: </p><ol><li><p>R-NH<sub>2</sub>, H+</p></li><li><p>H<sub>2</sub>, Ni</p></li></ol><p></p>
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1 step reductive amination

reagents:

  • R-NH2, H+, NaBH3CN or NaBH(OAc)3


<p>reagents: </p><ul><li><p>R-NH<sub>2</sub>, H+, NaBH<sub>3</sub>CN or NaBH(OAc)<sub>3</sub></p></li></ul><p></p>