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Give the order of increasing basicity
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RO- > HO- > RCO2- > ROH > H20
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T:F In protic solvents, large atoms tend to be better nucleophiles. What is the nucleophillic strength in protic solvents.
What is the nucleophillic strength in aprotic solvents: basicity is proportional to nucleophilicty
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CN- > I- > RO- > HO-> Br- > Cl- > F- > H20
F-> Cl- > Br- > I-
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What is the leaving group strength in substitution reactions.
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I- > Br- > Cl- > Fl-
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Describe the products of the following alkene reactions and if they are MK/AMK or syn/anti additions.
Alkene + H2
Alkene + HX
Alkene + X2
Alkene + H+/Water
Alkene + Free Radical X (Radical, HX)
Alkene + BH3/THF
Alkene + cold/dilute KMno4
Alkene + hot KmNo4 + H+
Alkene + O3/ZnC/H20
Alkene + O3/H2O2
Alkene + 1) 03 2) Zn/H20 3) NaBh4
Alkene + MCPBA
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1) Hydrogenation--> syn addition alkane
2) Hydrohalogenation--> alkyl Halid--> MK
3) Halogenation--> disubs alykl halide--> anti addition
4) Hydration-->Alcohol ---> MK
5) Hydrohalogenation--> AMK
6) Hydroboration--> Alcohol--> AMK--> syn addition
7) Alcohol--> 1, 2 diols --> syn addition--> MnO2 is the product
8) Cleave Double Bond--> (non terminal produce 2COOH and terminal produce Ketone + CO2)
9) Ozonolysis --> 2 Aldehyde or 2ketone (disubs)
10) Same has hot acidic KMno4
11) Reduce aldehyde/ketone with mild reducing agent to produce 2 alcohols
12) epoxides
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Synthesis of Alkynes:
Geminal Alkyl Halde --> 2 rounds of elimination will get you what?
How is a acetylide ion produced and how does is it used to make alkynes
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1) HBr and alkyne (requires a lot of heat )
2) It is produced by removing a proton from terminal alkyne which is very acidic. This now acts as a nucleophile and targets alkyl halides to add onto an alkyne.
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Reduction:
Alkyne + H2, Pd/BaS04 (Lindlar's catalyst)
Alkyne + Na, NH3
Addition:
Alkyne + Br2 or 2Br2
Free Radcal Addtion of X
Alkyne + B2H6/CH3COOH (non terminal)
Alkyne + R2BH/H2O2 OH- (terminal)
Alkyne + hot KMnO4, H
Alkyne + O3/H20 (terminal?)
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Cis- alkyne
trans alkyne
1) Halogenated Alkene 2) Alkyl Halide
2) Halogenated Alkene--AMK--trans isomer
3) 3 Alkenes = syn= cis-alkene
4) vinyl alcohol--> carbony compound (ketone)
5) 2COOH
6) 2 COOH (terminal--> CO2)
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Name all the activating/e donors groups
Name all the deactivating groups
where do the activating vs. deactivating groups direct? What is the exception? |
O-, NH2, OH, OR, R
CHO, COOR, COOH, COCl, CN, SO3H, NR3+, NO2
Activating: O/P Deactivating: meta |
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Electrophillic Aromatic Substitution Reactions:
What must be present for halogenation of aromatic compounds to occur? T:F: F is too reactive, I is too unreactive, Br is just right! Name the reagents of sulfonation of aromatic compounds and what does it produceName the reagents of nitration of aromatic compounds and what does this produce? Name the reagents of acylation of aromatic compounds? and what does this produce? What is the intermediate of acylation? Name the reagents of reduction of aromatic compounds and what does this produce? |
Lewis acid TSO3/H2SO4: sulfonic acidH2SO4/HNO3--> deprotonation--:> nitrocompound
lewis acid catalyst and acyl chloride: add c=o acyl group to aromatic compound + HCL + ALCl3 regenerated acyl group turned into carbocation by lewis acid (now a great electrophile to attack aromatic) H2/Rh/C + heat--> cyclohexane |
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T:F: Strong acids have high Ka's and low pKAs Why is phenol very acidic? What do e- withdrawing/donating groups do to acidity?What do alkyl groups do to carbocations vs. carbanions and how does this contribute to acidity?
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aromatic ring stabilizes -ive charged anion, more reactive e-withdrawing: increases acidity: more likely for proton to be pulled e- donating: decreases acidity: proton pulled towards e- donating groups alkyl groups donate e- density: they help stabilize positive charge and destabilize alkoxide negative anion (since charges like to be spread out) therefore: alkyl groups decrease acidity |
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What are the three ways alcohols can be synthesized?
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Nucleiphillic subsitution: Sn1, Sn2 electrophillic addition to double bond of alkenesNucleophillic addition to carbonyl: reduction reactions from aldehydes, ketones, COOH, esters
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How can phenols be synthesized?
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Arylsulfonic acids with hot NAOH
and hydrolysis of diazoniumm salts: 1) nitration of amino compound --> diazonium salt--> add H+ to form phenol |
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Alcohol Reactions: Elimination: Alcohol + H2SO4/Heat-->
Substitution: T:F: displacement of hydroxyl group is rare because hydroxide ion is a poor leaving groupwhat must be done to make hydroxyl a good leaving groupAlcohol + SOCL2--> Alcohol + HBr3 What is similar of the above two reactions? Why do phenols undergo electrophillic subsitution rxns readily? Is the OH group activator or deactivator? Oxidation: T:F: every oxidizing agent converts primary alcohols to COOH except PCC Alcohol + PCC--> Alcohol + Na2Cr2O7/H2SO4--> Jones Oxidation: Alcohol + CrO3H2So4---> Phenol + oxidizing reagents (CrO3, H2SO4)--> What is the strongest oxidizing agent of the above? T:F: PCC is a weak oxidizing agent |
E:major/minor alkene
S:Tmust be protonated for Sn1 reactions or even better converted to tosylate group which is an excellent leaving group for Sn2 rxns acyl chloride acyl bromide poor alcohol leaving group converted to a good leaving group lone pairs of OH group donate electron density to ring OH - strongly activating: O/P directing O: TPrimary: aldehydes Secondary: ketones Primary: COOH Secondary: ketones Primary: COOH Secondary: ketones Quinones: OH becomes ketone groups and one double bond is removed Jones Reagent T |
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ETHERS
T:F: smaller rings have more angle strain, making them less stable and more reactive Can ethers H-bond? T:F: boil at around same temp range as alkanes Synthesis: What are the reagents of the Williamson ether synthesis? Which reagents behave as electrophiles/nucleophiles? Describe the rxnT:F: this reaction is in competition with E2T:F: halide must be non-hindered Phenol + Alkyl halide (NaOH/H20)--> Alcohol + Base/ -H+ --> what kind of reaction?What is characteristic of the above reactionAlkene + mCPBA--> what kind of reaction? Ethers + oxygen--> Ethers + high temps/HBr or HI---> |
TNoT
metal alkoxides and primary alkyl halides or tosylates alkoxides: Nucleophiles halide or tosylate: electrophilesalkoxides displace halide or tosylate via Sn2 TT: alkoxides only attack non hindered halides ether thorugh williamson synthesis epoxide: Sn2intramolecular: nucleophile and LG are part of same molecule epoxide: oxidation (syn) peroxides alkyl halides and alchohols |
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Ether cleavage:Under what conditions do ether cleavages occur and what reagents? What is the first step?T:F: reaction then proceeds via an Sn1 or Sn2 mechanism depending on conditions and structure of etherWhat are the products of ether cleavage and do they undergo further reactions? When is the cleavage of epoxides acid/base catalyzed? T:F: base induced cleavage has Sn2 characterCan benzene undergo Sn2 reactions?
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Rigourous conditions: heat and with alkyl halide protonation of oxygen
True: if the substrate is hindered, it is Sn1, if it is unhindered, its Sn2 The products are alkyl halide and alchohol, the carbocation via Sn1 reactions makes an alkyl halide with further reaction with halide Acid catalyzed: Nucleophile attacks more substituted carbon ( Halide attacks C attached to most carbons and H adds on to less substituted) Base Catalyzed: nucleophile attacks least subsituted carbon of epoxide TNo |
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Is the dipole of C=0 greater than C--OH? Can carbonyl compounds H-Bond?T:F: aldehydes are more reactive than ketones
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Yes, carbonyl lacks a H which would cancel some of the C--0 dipole. Oxygen is more electronegative pulling electrons away from carbon making carbon electrophillic
No True |
