Chem301 Final Ch9,10,12[II] USD

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Chem301 Final Ch9,10,12[II] USD
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2012-12-16 17:54:37
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Daley reaction quick notes second set Ch9 ch10 ch12 Organic Chem 301 USD chapters parts
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general terms and definitions text book "Organic Chemistry" University of San Diego/ Klein: copyright 2012 John Wiley & Sons, Inc. arrow pushing, carbocations,addition reactions, alkynes, radical reactions.
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  1. SN1 Reaction
    • S: Substitution
    • N: Nucleophilic
    • 1: Unimolecular
    • Use polar protic solvent.
    • Substrate:     Tertiary
    • Nucleophile:  Weak nucleophile
    • L.G.:              Excellent leaving group
    • Solvent:          Polar protic
    • more info:
    • Complete SN1 reaction:
  2. SN1Regiochemistry
    • Intermediate C+ forms. Look out for rearrangements.
    • Most stable C+ species will be one Nuc attacks.
  3. SN1 Stereochemistry
    • Racemization - equal preferance for Nuc attack C+ atom above or below (planar carbon).
    • May have slight preference for inversion if ion-pair (C+ and LG-) difficult to separate (not big concern here).
  4. SN1 Curved arrow Mechanism
    • Yes, need to know including rate equation and reaction coordinate diagram.
    • rate = k [Sub]
  5. SN2 Reaction
    • S: Substitution
    • N: Nucleophilic
    • 2: bimolecular: the step involves 2 chemical entities.
    • Use polar aprotic solvent.
    • Substrate:       Methyl or primary
    • Nucleophile:  Strong nucleophile
    • L.G.:              Good leaving group
    • Solvent:          Polar Aprotic
    • more info:
  6. SN2 Regiochemistry
    Attack occures at LG-Carbon.
  7. SN2 Stereochemistry
    Stereochemical Inversion - backside attack. Remember, it does not necessaryily mean (R)-configurated substrate would become (S)-configurated product (R and S based on priority system).
  8. SN2 Curved arrow Mechanism
    • Yes, need to know.
    • Rate = k [Sub] [Nuc]
    • more info:
  9. Conversion of alcohol (bad LG) to tosylate (very good LG). Reaction
    Using TsCl, py (py=prymidine, base only reagent)
  10. Conversion of alcohol (bad LG) to tosylate (very good LG). Regiochemistry
    • Converts C-O-H to C-O-SO2C6H5Me group.
    • Can also do with triflate and mesitylate (know them).
  11. onversion of alcohol (bad LG) to tosylate (very good LG). Stereochemistry
    Retention of configuration - there is no attack at the Carbon atoms - it is the O atom of C-O-H that acts as a nucleophile attacking S atom of Cl-SO2C6H5Me, with eventual loss of Cl- nd formation of C-O-Ts group.
  12. Conversion of alcohol (bad LG) to tosylate (very good LG). Curved arrow Mechanism
    • Yes, need to know how to form tosylate.
  13. E1 Reaction
    • Need to know the conditions reactions (i.e. reagents, solvents, temperatures=higher).
    • Need to know when it can /may occur.
  14. E1 Regiochemistry
    • Intermediate C+ ion forms - must lookout for rearrangements.
    • Most stable C+ species will be one where beta-H is attacked from.
    • Will form most stable alkene (always a Zaitsev and trans over cis when possable) as major product.
  15. E1 Stereochemistry
    Will form most stable alkene (always Zaitsev and trans over cis when possable) as a major product.
  16. E1 Curved Arrow Mechanism
    • Yes, need to know including rate equation and reaction coordinate diagram.
    • Rate = k [Sub]
  17. E1
    • E: elimination,
    • 1: unimoleculare
    • Rate = k [substrate]
    • Much like the SN1 reaction, the rate is linearly dependent on the concentration of only one compound (the substrate). This observation is consistent with the stepwise mechanism (loss of the leaving group), just as we saw in SN1 reaction. The base does not participate in this step, and therefore, the concentration does not affect the rate.
  18. E2
    • E: elimination, 2: bimoleculare
    • Rate = k [substrate] [base]
    • Tertiary substrates react readily in E2 reactions: in fact, they react even more rapidly then primary substrates.
    •  
    • Much like the SN2 reaction, the rate is linearly dependent on the concentrations of two different compounds (the substrate and the base). The observation suggests that the mechanism must exhibit a step in which the substrate and the nucleophile collide with each other. This is consistant with a conserted mechanism in which there is only one mechanistic step involving both the substrate and the base.
  19. E2 Reaction
    Need to know conditions for reactions (i.e. reagents, solvents, temperatures). Need to know when it can/may occur.
  20. E2 Regiochemistry
    Attack occurs at beta-H that must be anti-periplanar (about 180o) orientation to LG (i.e. H-C-C-LG must be anti-periplanar). If above is met, small bases will yield Zaitsev product and bulky bases will yeild Hofmann product as major products.
  21. E2 Stereochemistry
    Stereochemical outcome (cis-/trans-) is determaned from attack at the beta-H being in anti-periplanar orientation to LG (i.e. H-C-C-LG must be anti-periplanar.
  22. E2 Curved Arrow Mechanism
    • Yes, need to know including rate equation and reaction coordinate diagram.
    • rate = k [Sub] [Nuc]
  23. Hydrohalogenation reaction
    Addition to alkene using HX (X=Cl, Br, or I) at room or low temperature.
  24. Hydrohalogenation Regiochemistry
    R.D.S. is alkene Nuc attack on electrophile H of HX, forming C+ intermediate. Look out for rearrangements. Most stable C+ species will be one Nuc (X-) attacks - which is most substituted carbon: Markovnikov addition. 
  25. Hydrohalogenation Stereochemistry
    Racemization - equal preferance for Nuc to attack C+ atom above or below (planar carbon).
  26. Hydrohalogenation Curved Arrow Mechanism
    • Yes, need to know including rate equation and reaction coordinat diagram.
    • (?)Rate = k [Sub] [Nuc](?)
    • more:
  27. Hydrohalogenation Reaction wih peroxide
    Addition to alkene using HX with catalytic peroxide (ROOR) at room or low temp reaction.
  28. Hydrohalogenation Regiochemistry with peroxide
    Anti-Markovnikov addition: Nuc (X- will go to least substituted C atom of alkene).
  29. Hydrohalogenation Stereochemistry with peroxide
    Racemization.
  30. Hydrohalogenation Curved Arrow Mechanism
    No, do not need to know, just that it is a radical mechanism and what the result is.
  31. Acid-Catalyzed Hydration Reaction
    • Addition to alkene using catalytic acid in water.
    • Know why catalytic acid (i.e. dilute) and room or low temp reaction.
  32. Acid-Catalyzed Hydration Regiochemistry
    R.D.S. is alkene Nuc attack on electrophilic H of H3O+ (or acid), forming C+ intermediate. Look out for rearrangements. Most stable C+ species will be one Nuc (H2O) attacks-which is most substituted carbon: Markovnikov addition.
  33. Acid-Catalyzed Hydration Stereochemistry
    Racemization - equal preference for water to attack C+ atom above or below (planar carbon).
  34. Acid-Catalyzed Hydration Curved Arrow Mechanism
    • Yes, need to know including rate equation and reaction coordinate diagram. Remember, the steps are really equalibrium steps and proton transfers are required to complete transformation.
    • (?)Rate = k [Sub] [Nuc](?)
  35. Oxymercuration - Decmercuration Reaction
    Addition of H-nucleophile (usually water or alcohol) to alkene using (1) Hg(OAc)2, (2) NaBH4.
  36. Oxymercuration - Decmercuration Regiochemistry
    R.D.S. is alkene Nuc attack on Hg(OAc)+ to yeild mercurinium ion. This intermediate stabilizes compound thus eliminating possible C+ rearrangements. Result is Markovnikov product.
  37. Oxymercuration - Decmercuration Stereochemistry
    Racemization - equal preference for mercurinium ion to form on either face of alkene thus even though anti-addition of Nuc (SN2-like), result is you get both enantiomers if product is chiral.
  38. Oxymercuration - Decmercuration Curved Arrow Mechanism
    Yes and No, need to know mercurinium ion formation and why Markovnikov product forms but not how to arrow push the C-Hg bond to C-Hbond.
  39. Hydroboration - Oxidation Reaction
    • Addition of H-BR2 to alkene using
    • 1) BH3, THF
    • 2) H2O2, NaOH
  40. Hydroboration - Oxidation Regiochemistry
    Attack from alkene to B-H bond attack (essentually hydride attack) to more substituted carbon center. Then oxidation with perioxide in base yeilds alcohol group with net anti-Markovnikov addition of H-OH (OH will go to least substituted C atom of alkene)
  41. Hydroboration - Oxidation Stereochemistry
    Racemization - equal preference for HBR2 to be attacked from either face of alkene. Note as is concerted mechanism, addition of H and BR2 units are syn. Final oxidation to alcohols does not change stereochemistry of C atom with BRattched (i.e. retention of configuration on oxidation). Thus net addition of H-OH is syn-additon but can occure from either side of alkene - would get racemic mixture if chiral products form.
  42. Hydroboration - Oxidation Curved Arrow Mechanism
    Yes and No, Need to know concerted attack to yeild syn-H and BR2 addition to alkene. While you should know mechanism of oxidation of C-BR2 group to C-OH, I am not requiring you to know it (other than conditions required to do it).
  43. Catalytic Hydrogenation Reaction
    Addition of H2 to alkene using M, H2 where M = Pd, Pt, or Ni.
  44. Catalytic Hydrogenation Regiochemistry
    Double bond is reduced to single bond.
  45. Catalytic Hydrogenation Stereochemistry
    Racemization - equal preference of H2 to add to either face of alkene. Note: addition of H atoms occurs in syn fashion.
  46. Catalytic Hydrogenation Curved Arrow Mechanism
    No, do not need to know - just that it occurs on metal surface and produces syn-addition of H2.
  47. Halogenation Reaction
    Addition of X2 to alkene, where X = Cl or Br, in NON-Nucleophilic solvent (e.g. CHCl3, CCl4)
  48. Halogenation Reaction Regiochemistry
    R.D.S. is alkene Nuc attack on X2 to yeild halonium ion (bromonium of chloronium). This Intermediate stabalizes compound thus eliminating possible C+ rearrangements.
  49. Halogenation Reaction Stereochemistry
    Racemization - equal preference for halonium ion to form on either face of alkene even though anti-addition of X- (SN2-like), result is you get both enantiomers if the product is chiral.
  50. Halogenation Reaction Curved Arrow Mechanism
    Yes, need to know halonium ion formation and anti-addition.
  51. Halohydrin Formation Reaction
    Addition of X and OH to alkene using X2 in water, where X = Cl or Br. Presence of nucleophilic solvent in halogenations reaction results in compitition with halogen for nucleophilic attack and as solvent is in swaping excess, halohydrin product dominates. Can be other solvents, like alcohol, to produce X-C-C-OR products (where R is alcohol group).
  52. Halohydrin Formation Regiochemistry
    R.D.S. is alkene Nuc attack on X2 to yield halonium ion (bromonium of chloronium). This intermediate stabalizes compound thus eliminating possible C+ rearrangements. Note: water attack occurs in anti-fashion and, in general, attack is at the more substituted carbon of the halonium ion.
  53. Halohydrin Formation Stereochemistry
    Racemization - equal preference for halonium ion to form on either face of alkene thus even though anti-addition of water (SN2-like), result is you get both enantiomers if the product is chiral.
  54. Halohydrin Formation Curved Arrow Mechanism
    Yes, need to know halonium ion formation and anti-addition of water. Also note you have a couple of proton Transfer steps: e.g. intermediate to final C-OH product.
  55. Dihydroxylation Reaction
    • Anti -addition of OH groups to alkene using
    • 1) Poeroxy acid (MCPBA or peroxyacetyl acid common),
    • 2)H3O+.
    • Ex:
  56. Dihydroxylation Regiochemistry
    Formation of epoxide intermediate (can think of epoxide forming from syn-addition). Epoxide  is converted to diol via acid-catalyst opening of epoxide ring from water SN2 (anti-) attack on the more substituted C atom of original alkene.
  57. Dihydroxylation Stereochemistry
    Racemization - equal preference for epoxide to form on either face of alkene thus even though anti-addition of water (SN2), result is you get both enantiomers if product is chiral.
  58. Dihydroxylation Curved Arrow Mechanism
    Yes, need to know epoxide formation and then acid catalyzed opening via protonation (proton transfer) of epoxide followed by SN2 anti-attack on C atom (followed by another proton transfer to yield alcohol group).
  59. Dihydroxylation Syn-addition Reaction
    • the syn-addition of OH groups to alkene using
    • 1) OsO4 (preferably in catalytic amount with added tBuOOH or NMO as oxidant to regenerate it)
    • 2) Na2SO3 or NaHSO3.
  60. Dihydroxylation Syn-addition Regiochemistry
    Formation of osmate ester (syn-addition to alkene). Osmate ester is then cleaved with NaSO3 or NaHSO3 to yield syn-diol product.
  61. Dihydroxylation Syn-addition Stereochemistry
    Racemization - equal preference for osmate ester to form on either face of alkene in syn- fashion, result is you get both enantiomers if product is chiral.
  62. Dihydroxylation Syn-addition Curved Arrow Mechanism
    Yes and No, need to know how permanganate ester is formed but not how it is cleaved (just need to know conditions for latter).
  63. Dihydroxylation Syn-addition Reaction
    • Syn-addition of OH groups to alkene using
    • 1) KMnO4
    • 2) NaOH
  64. Dihydroxylation Syn-addition Regiochemistry
    Formation of permanganate ester (not isolated) which reacts with NaOH to produce syn- diol product.
  65. Dihydroxylation Syn-addition Stereochemistry
    Racemization - equal preference for permanganate ester to form on either face of alkene in syn-fashion, result is you get both enantiomers if product is chiral.
  66. Dihydroxylation Syn-addition Curved Arrow Mechanism
    Yes and No, need to know how permanganate ester is formed but not how it is cleaved (just need to know conditions for latter).
  67. Oxidative Cleavage (Ozonolysis) Reaction
    • Splitting of alkene into two C=O species using
    • 1) O3
    • 2) DMS or Zn / H2O
    • Note: DMS = Me2S;
    • book/WileyPlus claims it is something else in some places - it is always Me2S. The result is it gets oxidized to DMS --> Me2S=O.
  68. Oxidative Cleavage (Ozonolysis) Regiochemistry
    First step is formation of an ozonide, which gets converted to more stable ozonide. From there, mild reducing agent cleaves it to two terminal C=O products (ketones or aldahydes or mixture).
  69. Oxidative Cleavage (Ozonolysis) Stereochemistry
    No stereochemistry - ketone and aldehydes are achiral.
  70. Oxidative Cleavage (Ozonolysis) Curved Arrow Mechanism
    No, do not need to know - just know what the result is.
  71. Formation of alkyne Reaction
    • from double elimination of a dihalide substrate using
    • 1) excess strong base (e.g. NaNH2, NH3(l))
    • 2) H2O
    • The two halogen atoms can be on the same C atom (germinal) as long as there are two beta-H atoms on adjacent C atom. They can also be 1,2-dihalogens (vicinyl, halides attached on adjacent C-atoms) as long as each C atom that contains the halogen also has an H atom.
  72. Formation of alkyne Regiochemistry
    Only one product possible - alkyne. Excess base yields alynide ion which is reprotonated to alkyne with water or other suitable proton sources (i.e. those more acidic than alkyne).
  73. Formation of alkyne Stereochemistry
    Only one product possible - alkyne.
  74. Formation of alkyne Curved Arrow Mechanism
    • Yes,
    • 1)step is just E2 (from way above on chart).
    • 2)step is E2 on a haloalkene that has an H atom trans to the halogen.
  75. Catalytic Hydrogenation Reaction
    syn-additions of 2 equivalents H2 to alkyne to form alkane using M, H2 - where M = Pt, Pd, Ni.
  76. Catalytic Hydrogenation Regiochemistry
    Triple bond is reduced to single bond.
  77. Catalytic Hydrogenation Stereochemistry
    None - product is not chiral.
  78. Catalytic Hydrogenation Curved Arrow Mechanism
    No, do not need to know - just that it occurs on metal surface and produces syn-additions of H2.
  79. Catalytic Hydrogenation Reaction
    syn-addition of 1 equivalent of H2 to alyne to form alkene using poisoned catalyst: Lindlar's (need to know reagents) or Ni2B.
  80. Catalytic Hydrogenation Regiochemistry
    Triple bond is reduced to cis-double bond.
  81. Catalytic Hydrogenation Stereochemistry
    Cis-double bond is formed owing to syn-addition.
  82. Catalytic Hydrogenation Curved Arrow Mechanism
    No, do not need to know - just that it occurs on metal surface and produces syn-addition of H2.
  83. Dissolving Metal Reduction Reaction
    anti-addition of two H atoms to alkyne forming trans-alkene using Na(s), NH3(l).
  84. Dissolving Metal Reduction Regiochemistry
    Triple bond is reduced to trans-double bond.
  85. Dissolving Metal Reduction Stereochemistry
    Trans-double bond is formed owing to anti-addition.
  86. Dissolving Metal Reduction Curved Arrow Mechanism
    No, do not need to know - just that it occurs via radical process and produces trans-alkene.
  87. Hydrohalogenation of Alkynes Reaction
    addition of 2 equivalents of HX to alkyne to produce germinal dihalide.
  88. Hydrohalogenation of Alkynes Regiochemistry
    Formation of germinal dihalide. Two halides on the same C-atom of original alkyne, more substituted one, in Markovnikov fashion.
  89. Hydrohalogenation of Alkynes Stereochemistry
    None - product is not chiral.
  90. Hydrohalogenation of Alkynes Curved Arrow Mechanism
    No, do not need to know - very complicated. Just know what it produces - germinal dihalide.
  91. Hydrohalogenation of Alkynes Reaction
    radical addition of HBr to alkyne to produce anti-Markovnikov alkene halide product uding HBr, HOOH conditions.
  92. Hydrohalogenation of Alkynes Regiochemistry
    Anti-Markovnikov addition of H-Br.
  93. Hydrohalogenation of Alkynes Stereochemistry
    Get mixture of E- and Z- haloalkenes with thermodynamically favored one being major product (i.e. one with larger groups on adjacent C atoms of alkene being trans to each other).
  94. Hydrohalogenation of Alkynes Curved Arrow Mechanism
    No, do not need to know - just that it is radical process and produces mixture of E- and Z- haloalkenes and which of those would be major product.
  95. Hydration of Alkynes Reaction
    addition of H-OH to an alkyne using acid catalyzed hydration conditions of H2SO4 (catalytic), H2O and added HgSO4. Result is not enol (C=C-OH) but quickly converted to ketone via Tautomerization.
  96. Hydration of Alkynes Regiochemistry
    Markovnikov addition of H-OH which is then converted to ketone. Not useful for disubstituted acetylene as get mixture of ketones, so only useful for terminal alkynes giving methyl ketones.
  97. Hydration of Alkynes Stereochemistry
    No stereochemical considerations.
  98. Hydration of Alkynes Curved Arrow Mechanism
    No and Yes, No you do not need to know how the H and OH add to the alkyne to yield the enol but you do need to know how to convert the enol to the ketone (acid catalyzed) via the tautomerization
  99. Hydroboration - Oxidation Reaction
    addition of H-BR2 to alkyne and further conversion of BR2 group to OH and then tautomerization to aldehyde using H2O2 and NaOH. Be sure to use H-BR2 (R = bulky group) to eliminate possibility second hydroboration of alkene formed on first hydroboration (result would be diborane-alkane product).
  100. Hydroboration - Oxidation Regiochemistry
    Anti-Markovnikov addition of H-BR2 (remember -really same reaction where alkyne acts as Nuc to attack electrophilic B, which later is converted to alcohol group - looking like anti-Markovnikov addition of H-OH). Only useful for terminal alkynes giving aldehydes.
  101. Hydroboration - Oxidation Stereochemistry
    No stereochemistry consideration.
  102. Hydroboration - Oxidation Curved Arrow Mechanism
    Yes and No, you need to know mechanism (same as with alkene) of hydroboration. You do not need to know how borane is converted to alcohol (only what reagents are required to do it). You then need to know how the enol undergoes base catalyzed tautomerization to the aldehyde.
  103. Halogenation of Alkynes Reaction
    addition of excess X2, where X= Cl or Br only, to alkynes in non-nuclophilic solvents (e.g. CHCl3, CCl4). Result is formation of tetrasubstituted haloalkane (R-C(X2)-C(X2)-R).
  104. Halogenation of Alkynes Regiochemistry
    Result is tetrahalogen substituted alkane formation (dihalide addition to each carbon of original alkyne). Only useful for excess equivalents of X2, single X2 addition results in both cis- and trans- dihalide alkenes.
  105. Halogenation of Alkynes Stereochemistry
    No stereochemistry consideration as get 1,1,2,2-tetrasubstitution of halogens on alkyne - product is not chiral.
  106. Halogenation of Alkynes Curved Arrow Mechanism
    No, mechanism is not well understood, unlike halogenations of alkenes, so you do not need to know curved arrow mechanism. You just need to know the conditions and results. 
  107. Ozonolysis of Alkynes Reaction
    • reaction of disubstituted alkyne using
    • 1) O3
    • 2) H2O to split triple bond between C's into 2 compounds where the C atoms of alkyne become carboxylic acid end groups (-CO2H). If monosubstituted alkyne is reacted, result is carboxylic acid for substituted side of alkyne and CO2 for other.
  108. Ozonolysis of Alkynes Regiochemistry
    Mechanism not well understood - just need to know alkyne splits into 2 products where each C atom of alkyne becomes -CO2H group, except if  terminal alkyne where the terminal C atom becomes CO2.
  109. Ozonolysis of Alkynes Stereochemistry
    No stereochemical considerations.
  110. Ozonolysis of Alkynes Curved Arrow Mechanism
    No - not required to know mechanism just conditions and results.
  111. Alkylation of Terminal Alkynes Reaction
    formation of C-C bond by nucleophilic attack of deprotonated terminal alkyne (with strong base; e.g. NaNH2, NH3) on 1o alkylhalide to give SN2 product.
  112. Alkylation of Terminal Alkynes Regiochemistry
    All the same considerations as any SN2 reaction. Only works with 1o alkylhalides, where substituted is favored over elimination E2. 2o alkylhalide will favor E2 and 3o alkylhalide will favor E2 and 3o alkylhalide will only react via E2.
  113. Alkylation of Terminal Alkynes Stereochemistry
    While it is stereochemical inversion at the carbon, as the substrate is 1o alkylhalide, there is no chirality and thus no real stereochemical considerations.
  114. Alkylation of Terminal Alkynes Curved Arrow Mechanism
    Yes, it is simply an SN2 reaction where you must first prepare the nucleophile by reacting the terminal alkyne with strong base.
  115. What reagents/solvents would you use?
    • 1) Br2
    • 2) xs NaNH2
    • 3) H2O
    • 4) NaNH2
    • 5) EtI
    • 6) H2, Lindlar's catalyst
  116. What reagents/solvents would you use?
    • 1) Br2
    • 2) xs NaNH2
    • 3) H2O
    • 4) 9-BBN
    • 5) H2O2, NaOH
  117. What reagents/solvents would you use?
    • 1) H2, Lindlar's catalyst
    • 2) dilute H2SO4
  118. What reagents/solvents would you use?
    • 1) H2, Lindlar's catalyst
    • 2) BH3 - THF
    • 3) H2O2, NaOH
  119. What reagents/solvents would you use?
    • 1) NaNH2
    • 2) EtI
    • 3) Na, NH3 (l)
    • 4) Br2
  120. What reagents/solvents would you use?
    • 1) H2, Lindlar's catalyst
    • 2) BH3 - THF
    • 3) H2O2, NaOH
  121. What reagents/solvents would you use?
    • 1) NaNH2
    • 2) EtI
    • 3) H2, Lindlar's catalyst
    • 4) Br2
  122. What reagents/solvents would you use?
    • 1) t-BuOK
    • 2) Br2
    • 3) xs NaNH2
    • 4) H2O
    • 5) O3
    • 6) H2O
  123. What reagents/solvents would you use?
    • 1) NaOEt
    • 2) Br2
    • 3) xs NaNH2
    • 4) H2O
    • 5) NaNH2
    • 6) MeI
    • 7) O3
    • 8) H2O
  124. Using ethylene (H2C=CH2) as your only source of carbon atoms, outline a synthesis for 3-hexanone.
  125. The pka of CH3NH2 is 40, while the pka of HCN is 9. Can the cyanide anion (the conjugate base of HCN) be used to deprotonate a terminal alkyne? Explain.
    The pka of HCN is lower than the pka of a terminal alkyne. Therefore, cyanide cannot be used as a base to deprotonate a terminal alkyne, as it would involve the formation of a stronger acid.
  126. What reagents/solvents would you use?
    • 1) xs NaNH2
    • 2) H2O
    • 3) 9-BBN or disiamylborane
    • 4) H2O2, NaOH
  127. What reagents/solvents would you use?
    • 1) xs NaNH2
    • 2) H2O
    • 3) H2SO4, H2O, HgSO4
  128. What reagents/solvents would you use?
    • 1) Br2
    • 2) xs NaNH2
    • 3) H2O
    • 4) H2SO4, H2O, HgSO4
  129. A terminal alkyne was treated with NaNH2 followed by propyl iodide. The resulting internal alkyne was treated with ozone followed by water, giving only one type of carboxylic acid. Provide a systematic. IUPAC name for the internal alkyne.
    4-octyne
  130. Using acetylene as your only source of carbon atoms, outline a synthesis for 3-hexyne.
  131. Using ethylene as your only source of carbon atoms, outline a synthesis for 3-hexanone.
  132. Using acetylene and methyl bromide as your only sources of carbon atoms, propose a synthesis for the following compound:
    • Step 1:
    • 1) H2, Lindlar's catalyst
    • 2) HBr
    • Step 2:
    • 1) NaNH2
    • 2) EtBr
    • 3) NaNH2
    • 4) MeBr
    • Step 3:
    • 1) H2, Lindlar's catalyst
    • 2) MCPBA
    • step1:
    • step 2:
    • step 3:
    • step 4:
    • Step 1:
    • Step 2:
    • Step 3:
    • Step 4:
    • AND
  133. 9-BBN
  134. Disiamylborane
  135. What do you get when you have an alkyne reacting with aqueous acid in the presence of mercuric sulfate (HgSO4)?
    You will always get ketone(s), 2 possible with an internal alkyne however could possibly the same compound with bith ketones (same name for both products).
  136. What will you get when having an alkyne react with:
    1)9-BBN
    2) H2O2, NaOH
    You will always ger an aldehyde EXCEPT when there is a cyclo-, then you get a ketone.

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