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10-1 Alcohols & Thiols & Ethers Sources Structure, Nomenclature, Properties Acidity and Basicity Rx with active metals Conversion to R-X, inorganic acid halides Rxs with HX S N 1/S N 2, sulfonates Dehydration of alcohols Oxidation of 1 o and 2 o alcohols Oxidation of glycols [Pinacol & Thiols/Sulfur chemistry - skip] CH 2 OH 6, 31, ss34 Chapter 10 Chapter 11

10-1 Alcohols & Thiols & Ethers Sources Structure, Nomenclature, Properties Acidity and Basicity Rx with active metals Conversion to R-X, inorganic acid

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Text of 10-1 Alcohols & Thiols & Ethers Sources Structure, Nomenclature, Properties Acidity and Basicity Rx...

  • Slide 1
  • 10-1 Alcohols & Thiols & Ethers Sources Structure, Nomenclature, Properties Acidity and Basicity Rx with active metals Conversion to R-X, inorganic acid halides Rxs with HX S N 1/S N 2, sulfonates Dehydration of alcohols Oxidation of 1 o and 2 o alcohols Oxidation of glycols [Pinacol & Thiols/Sulfur chemistry - skip] 6, 31, ss34 Chapter 10 Chapter 11
  • Slide 2
  • 10-2 Chapter 10 reactions acid base active metal substitution oxidation sources nomenclature (alcohol & ethers) properties
  • Slide 3
  • 10-3 Preparation of alcohols - (review)
  • Slide 4
  • 10-4 Chapter 10 sources nomenclature (alcohol & ethers) properties reactions acid base active metal substitution oxidation
  • Slide 5
  • 10-5 Nomenclature alcohols & ethers IUPAC names alcohol sp 3 C-OH -longest chain that contains the -OH = root -OH gp lowest number - suffix -e to -ol ether R-O-R sp 3 C, sp 2 C, spC in R & R bonded to O -always subsituent - #-prefix, alkoxy (special ethers #,#-epoxy) 1-ethoxy-2-butanol
  • Slide 6
  • 10-6 Epoxides - 11 - special ethers Nomenclature - #,#-epoxy (substituent) or oxirane #,#-epoxy-#-pentyn-#-ol (4S)-4,5-epoxy-2-pentyn-1-ol ether acetylene alcohol
  • Slide 7
  • 10-7 Nomenclature-Alcohols IUPAC names Longest chain that contains the -OH = root Give -OH group lowest number Change suffix -e to -ol (S)-2-methyl-1-butanol
  • Slide 8
  • 10-8 oxygen sp 3 Structure - Alcohols Alcohol functional group: -OH group bonded to an sp 3 hybridized carbon bond angles ~ 109.5 CO H H H 3 C H
  • Slide 9
  • 10-9 Physical Properties Hydrogen bonding: H bonded to an electronegative atom (F, O, or N) etc. R O H O H R O H R O H R Hydrogen bond weak (~ 5 kcal/mol)
  • Slide 10
  • 10-10 Physical Properties ethanol & dimethyl ether - constitutional isomers but weak hydrogen bonds have dramatic effects: hydrogen bonds no hydrogen bonds
  • Slide 11
  • 10-11 Quiz Name:___________________________ seat:_____ Write a reaction equation that represents one of the source of alcohols.
  • Slide 12
  • 10-12 Reactions alcohols: acid base indirect substitution indirect -elimination active metals oxidation ethers: base indirect substitution indirect -elimination epoxides: substitution, indirect & direct
  • Slide 13
  • 10-13 Acidity of Alcohols weak acids conjugate bases strong
  • Slide 14
  • 10-14 Acidity of Alcohols RSH 8.5
  • Slide 15
  • 10-15 Acidity of Alcohols Acidity on: stabilization and solvation electron donation destabilize alkoxides decreases solvation
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  • 10-16 Alcohols + Li, Na, K (active metals) form metal alkoxides metal alkoxide sodium methoxide alcohols rx with metals
  • Slide 17
  • 10-17 rx with metals sodium cyclohexoxide
  • Slide 18
  • 10-18 basicity of alcohols/ethers weak Lewis base (water-like) R = H or alkyl oxonium ion
  • Slide 19
  • 10-19 3 alcohols (ethers) react very rapidly with HCl, HBr, HI. Alcohols/Ethers indirect Substitution ( with HX) 1alcohols/ethers are unreactive under these conditions R = H or alkyl
  • Slide 20
  • 10-20 2 alcohols + HBr (or HI ) racemization, rearrangement, olefins indirect Substitution ( with HX)
  • Slide 21
  • 10-21 2 o or 3 o ROH/ROR with HX - S N 1 -H + +X - [-HOR] good leaving group racemization, rearrangement, olefins R = H or alkyl
  • Slide 22
  • 10-22 1 o ROH/ROR with HI or HBr - S N 2 X (-) displace R = H or alkyl
  • Slide 23
  • 10-23 indirect Substitution (with SOCl 2 )
  • Slide 24
  • 10-24 indirect Substitution (with PBr 3 ) 2 nd ROH to RBr 3 rd ROH to RBr
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  • 10-25 indirect Substitution R= H, alkyl R= H, alkyl; X= Br, I
  • Slide 26
  • 10-26 alcohols - alkyl sulfonates, good Lgp
  • Slide 27
  • 10-27 alkyl sulfonates (sulfonate ester) S S S R good leaving group for Sn2 rx DMF
  • Slide 28
  • 10-28 rx: alkyl sulfonates prep:
  • Slide 29
  • 10-29 rx: alkyl sulfonates prep:
  • Slide 30
  • 10-30 1 alcohols (ethers) with H 2 SO 4 or H 3 PO 4 dehydration of ROH/[-HOR] of ROR 2 alcohols (ethers) 3 alcohols (ethers) R = H or alkyl
  • Slide 31
  • 10-31 Dehydration of ROH (-OR of ethers) Mechanism - same forward or reverse. alkene addition and -elimination compete
  • Slide 32
  • 10-32 Pinacol Rearrangement This section out [rearrangement under dehydration conditions]
  • Slide 33
  • 10-33 Chapter 10 sources nomenclature properties reactions acid base active metal substitution oxidation
  • Slide 34
  • 10-34 Oxidation
  • Slide 35
  • 10-35 Oxidation: 1 ROH Pyridinium chlorochromate (PCC): pyridine + CrO 3 [Cr(VI)] + HCl PCC converts 1 alcohols to aldehydes and 2 o alcohols to ketones
  • Slide 36
  • 10-36 Oxidation aldehyde acid ketone NR (no reaction)
  • Slide 37
  • 10-37 -elimination of H and chromate +
  • Slide 38
  • 10-38 Oxidation: 1 ROH hydrate
  • Slide 39
  • 10-39 Oxidation 1 o and 2 o ROH K 2 Cr 2 O 7 and many other reagents
  • Slide 40
  • 10-40 Oxidation of Glycols with H 5 IO 6 (or HIO 4 2H 2 O) acyclic or cis-1,2 cyclic diols
  • Slide 41
  • 10-41 Oxidation of Glycols with H 5 IO 6 (or HIO 4 2H 2 O) 11
  • Slide 42
  • 10-42 OsO 4 / HIO 4 equivalent to O 3 /red. source of diols
  • Slide 43
  • 10-43 mechanism Oxidation of Glycols with H 5 IO 6 (or HIO 4 2H 2 O)
  • Slide 44
  • 10-44 Oxidation of Glycols with H 5 IO 6 (or HIO 4 2H 2 O) 10
  • Slide 45
  • 10-45 Oxidation of Glycols with H 5 IO 6 (or HIO 4 2H 2 O) 10
  • Slide 46
  • 10-46 How does one make butanal from 1-bromobutane?
  • Slide 47
  • 10-47 What else can be made using the chemistry of chapters 3, 6, 7, 8, 9, 10, 11 & 15?
  • Slide 48
  • 10-48 Chapter 15 future chapter chemistry
  • Slide 49
  • 10-49 Chapter 10 sources nomenclature properties reactions acid base active metal substitution oxidation Chapter 11/15