CHM 102
Quiz yourself by thinking what should be in
each of the black spaces below before clicking
on it to display the answer.
Help!
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| Carbocation is a___and___. | Electrophile lewis acid
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| Leaving group tendency-Strong bases are___. strong acids are___leaving group. | Poor leaving group
strong
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| Leaving group tendency-F-,OH-,NH2-,CH3- | (F-)>OH->NH2->CH3-
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| Leaving group tendency-RO-,PhO-,MeCOO-,CF3COO-,OH- | (CF3COO-)>(MeCOO-)>PhO->OH->RO-
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| Leaving group tendency-CH3COO-,CH3SO3-,CF3SO3- | [CF3SO3-]>(CH3SO3-)>(CH3COO-)
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| Leaving group tendency-N2 NH3 H2O | [N2]>[H2O]>NH3
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| Leaving group tendency-Halogens | (I-)>(Br-)>(Cl-)>(F-)
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| Leaving group tendency-Nosylate,brosylate,tosylate | (NsO-)>(BsO-)>(TsO-)
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| Diazotization reaction___. | RNH2->(NaNO2+HCl)R+ + N2
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| CR OF carbocation 1- | Combination of nucleophile
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| CR OF carbocation Comb degree order___elimin degree order___. | 1>2>3
3>2>1
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| CR OF carbocation Comb depends on temperature as___and elimn. as___. | Inversly
directly
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| CR OF carbocation Comb depends on nucleophilicity as___and basic strength as___. | Directly
Inversly
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| If during a reaction more than one alkene is produced then the most stable alkene is___. | Zaitsev rule
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| C+ + Halogen ->C + E C/E ratio is in order | F->Cl->Br->I-
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| Tert-butyl-C-C(+)(-C)-C | Hoffman product is major
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| Rearangement produces a___and if the step is RDS or shift is stabilised by backbonding then__. | More stable carbocation
Better electron donor
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| Cyclopentane-CH2+->(rearrangement)___ | Cyclohexane carbocation
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| Cyclopropane-CH2+->(rearrangement)___ | Not rearranges
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| RI CARBOCATION CH3CH2OH+Conc H2SO4 110 C 140 C 170 C | CH3CH2HSO4
Et-O-Et
CH2=CH2
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| In dehydration of alcohol after formation of carbocation-at low temperature___,at high temperature___. | Nucleophile attack
Base attack
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| E1 lg__first and then___takes proton. | Leaves base
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| E1 rate directly proportional to concentration of substrate and___. | Independent of base
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| E1 rate is___to lg tendency. | Directly proportional
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| E1 rate for different substrate___. | Benzyl>allylic>3>2>1
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| E1 mechanism is favored by___. | Good lg,polar solvent,poor base,poor nucleophile,high temperature
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| E1 C-C(-OH,-C)-C(-OH,-C)-C ->(conc H2SO4,heat)___. | Pinacolon Tert butyl-C(=O)-C
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| Cyclopentane(OH)-Cyclopentane-E1 | Decalin with bridge double bond
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| E1 reagents that take halogens | SbCl5,AlCl3,AlBr3,AgNO3
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| E1 C-C-NH2(NaNO2,HCl)->___. | C-C-ONO,C-C-Cl,C-C-O-C-C,major C-C-OH
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| Ae Classical carbocation mechanism | >C=C<->(RDS)E->C-C<+->E-C-C-Nu
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| Ae Classical carbocation mechanism Rate is__and proportional to___. | Second order
electrophilicity of electrophile
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| Ae Alenylation of alkene C=C->(Catalytic H2SO4)___. | Formation of carbocation,attack on alkene,deprotonation.
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| Ae Alkylation of alkene->(HF 0 C)___. | Formation of carbocation,attack on alkene,rearrangement
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| Ae Hyrohalogenation of alkene___. Rate for different halogen___. | RDS formation of carbocation,attack of nucleophile
I>Br>Cl>F
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| Anti-Markonikoff addition___. | ROOR->2RO'+HBr->ROH + Br'->formation of carbon radical
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| HF,HCL,HBr,HI__only shows Kharash-Peroxide effect. | HBr
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| Rate of Ae >=< >= \= = | >=< > >= > \= > =
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| Rate of Ae =-Ph__(para). OMe Me H CN NO2 | OMe>Me>H>CN>NO2
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| Rate of Ae =-Ph__ OMe(meta,para),NO2(meta,para),H | OMe(p)>H>OMe(m)>NO2(m)>NO2(p)
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| Rate of Ae Styrene and stillbene | Stillbene>styrene
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| Ae Triple bond___react when not in conjugation, but when it is in conjugation the triple bond___. | Will not
is first to react
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| In peroxide reaction the -ve part in following reagents CCl4 CBr4 CCl3Br CBr3-Cl H-CF3 I-CF3 H-CI3 EtSH is___. |
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| Prins reaction Alkene+___(dil. H2SO4)->___by___. | HCHO 1,3 diol alkene C attack HCHO then OH attacks positive charged carbon
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| Non classical carbocation mechanism___ | First Br attacks on double bond and then other Br attacks
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| Ae KCP__when___,___ | Ea,energy barrier is less low temperature
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| Ae C_=C-H+HCl(HgCl2) to get___only because___ | C=C-Cl it is attached to HgCl2 as it has lost its nucleophilicity
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| Ph-CH(OH)-C_=CH + H+ ->___. | Cinnamaldehyde Ph-CH=CH-CH=O
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| C_=C->(CH2N2 hv)___ C_=C->(CH2N2)___ | Cyclopropene
1,2 azacyclopentane
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| C=C-CN self polymer___. C=C-CN polymer with But-3-yne-1-ene | Orlon
Buna N
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| C2H2 +AsCl3,AlCl3___which counteracted by___. | Cadet bunsen
Lewsite(Cl-C=C-AsCl2) BAL
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| NCM Ae Rate is proportional to___. | Electrophilicity of electrophile
Nucleophilicity of nucleophile
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| NCM Ae Rate in halogens | F2>Cl2>Br2>I2
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| Cis on anti addition gives___. | Threo
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| NCM Ae In HOBr reaction the nucleophile is___. | H2O
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| NOCl___ NCM Ae Cyclic ion opens from that end which is___. | Tilden reagent
Gives more stable carbocation
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| Br2 on Anthracene gives___.Cyclic compound which reacts with Br2 | 9-10 product
cylopropane
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| 1,3,5Cycloctatriene with Br2 gives___. | Trans 7,8 dibromo Bicyclo[4,2,0]octane.
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| 1,5Cyclooctadiene + Br2 gives | 2,6 dibromo bicyclo[3,3,0]octane
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| >= + X2 at 25 C gives__. | Major product by Sae Cl>=
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| Diels Alder reaction follow cyclic transition state mechanism,concerted mechanism,pericyclic. Rate is proportional to___. | EDG in diene
EWG in dienophile
1/stearic hindrance
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| Out of Furan pyrrole thiophene which is not giving Diels alder? | Pyrrole thiophene
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| HCl+ Na___NaNH2___RONa___NaOH___NaHCO3___. | Y Y Y Y Y
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| RCOOH+ Na___NaNH2___RONa___NaOH___NaHCO3___. | Y Y Y Y Y
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| PhOH+ Na___NaNH2___RONa___NaOH___NaHCO3___. | Y Y Y Y N
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| ROH+ Na___NaNH2___RONa___NaOH___NaHCO3___. | Y Y Y N N
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| C_=C ->(Na) only in NH3 there is good yield | Other protic solvents can't be used for they are more acidic than terminal alkene
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| C-C-C_=C+NaNH2->___ AgNO3 NH4OH Cu2Cl2 NH4OH | C-C-C_=C(-) Na+
C-C-C_=C(-) Ag+ dirty white
C-C-C_=C(-) Cu+ red ppt
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| C_=C->(__)-(Me-CO-Me)-H2O-ConcH2SO4->H2 Pd | Benedicts reagent
Isoprene
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| Terminal alkyne+ NaNH2__ KOH___. | Yes
No
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| 2-alkyne+ NaNH2__ KOH___. | No
Yes
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| 2alkyne NaNH2 heat___ | Terminal alkyne 1-C- 2-resonance 3-
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| C_=C+Cu2Cl2 NH4Cl heat___. | Vinyl addition
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| 3C2H2(Fe Red hot tube)___. | Benzene
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| 4C2H2(Ni(CN)4)___. | COT
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| RC_=C-H+ NaOCl___ +I2 liqNH3 0 C | RC_=C-Cl
RC_=C-I
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| CaC2+H2O___ Mg2C3+H2O___ Al4C3+H2O___ | Acytelene
Propyne
Methane
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| Generation of Grignard reagent | R-X + (Et2O Mg) R-Mg-X
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| Reactivity,nucleophilicity,basicity in decreasing order of organometallic reagents | RNa(Wurtz) RMgX(Grignard) R2Zn(Frankland) R2CuLi(Coreyhouse)
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| Characteristic reactions of carbanion___. | Reactions as a base
Reactions as a nucleophile
nucleophilic addition
nucleophilic addition elimination
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| Strong bases as___and attacks irreversibly to give___.Eg___. Weak bases as___and attack reversibly to give___.Eg___. | Hard nucleophile KCP 12 product RNa RLi NaBH4 LiAlH4
soft nucleophile TCP H2S R2CuLi NH2NH2 R2Zn
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| Monochlorides possible Isobutane | 2 2
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| Monochlorides possible Isopentane Neopentane | 6 4
1 1
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| Monochlorides possible Hexane 3 methylpentane | 5 3
8 5
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| Monochlorides possible Methyl cyclohexane | 12 8
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| Monochlorides possible 2Methoxy propane 3Ethoxy pentane | 4 3
10 6
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| Dichlorides possible Propane Butane Isobutane | 5 2 2 1
10 2 5 3
3 1 1 1
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| Dichlorides possible pentane isopentane neopentane | 17 3 6 8
18 4 6 8
2 1 0 1
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| Dichlorides possible Hexane | 26 3 9 14
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| Chloroderivatives possible Methane ethane propane | 4
9
35
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| Decreasing rate in substrate of Grignard reagent | RCOCl RCHO RCOR RCOOR RCONR2 RCOO-
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| Bu-Cl+Mg Et2O___ Bu-Cl+Na Et2O___ Bu-Cl+.5 Mg Et2O___ | Bu-Mg-Cl
Bu-Bu
Bu-Bu
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| 1,4 dichlorobutane+ Mg Et2O___. 1,4 dichlorobutane+ Mg(excess) COCl2___. | Cyclobutane
Cyclopentanone
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| Grignard reagent + acidic H compound___ Grignard reagent + acidic H-lone pair(NH2Cl RONH2)___ | RH
R-acidic H part 1-RH
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| RCOOR + H3O+___ | RCOOH
addition of H+,then H2O,-ROH,-H2O
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| Soda lime + RCOOH->___.Mechanism___. | RH
Acid base reaction then Cao+CO2->CaCO3+RH
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| Rate of oakwood degradation is___. | Proportional to stability of carbanion
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| RCOO-+ MnO/CaO/BaO ->___. Ph-CHBr-C(COOH)-Br heat___ | R-
Ph-C=C-Br
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| Compounds like Beta-Keto,Beta-amino acids,Gem dicarboxylic acid,beta-gamma unsaturated acid___. | Lose CO2 only on heating
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| Heating effect beta dioc__ Gamma dioc___ delta dioc___ epsilon and one more dioc___ | CO2 eliminated to 1 carbon less carboxylic acid
H2O eliminated to cyclic anhydride
H2O eliminated to cyclic anhydride
CO2 H2O eliminated to cyclopentanone
CO2 H2O eliminated to cyclohexanone
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| 2MeCOOH+Conc H2SO4 heat___ 2MeCOOH+CaO/MnO/BaO heat___. | Anhydride
Acetone
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| RCOOH->(Ca(OH)2)___->(heat)___. | (RCOO)2Ca RCOR
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| COOH-C-C(OH COOH)-C-COOH->(heat)___. | C=C(COOH)-C
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| Alpha hydroxy carboxylic___ Beta hydroxy carboxylic___ Gamma hydroxy carboxylic___ Delta hydroxy carboxylic___ more longer polymerise on heating. | Lactide Cyclic(C-O-C(=O)-C-O-C(=O))
-C=C-COOH
Gamma lactone cyclic(C-C-C-O-C(=O))
Delta lactone cyclic(C-C-C-C-O-C(=O))
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| ALDOL Cyclopropanone___ Bicyclo[2,2,1]octane-8-one___ Me2CH-CH=O___. | No aldol
No self aldol
No self aldol
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| 14 carbon-NO2 | Moth repellant
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| C-CO-C+(NaNO2 HCl)___. | C-CO-C=N-OH
First tautomerise then attack NO+ then tautomerise
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| C-CO-C +Br2(excess) Acidic medium___. C-CO-C +Br2(excess) basic medium___. | Tautomerise attack of Br2 -HBr
Carbanion attack of Br2
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| C-CO-C +Br2 basic(excess) medium___. | C-C-COONa 1st C-CO-C-Br then cyclopropanone then OH- attack then acid base Faversky reaction
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| C-CO-C +Br2(excess) basic(excess) medium___. | CHX3 + C-COO-Na+
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| Ph-CH(OH)-Me->(CaOCl2 H2O) | Do first oxidation
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| Me-C-NO2+NaNO2 HCl___. Me2-C-NO2+NaNO2 HCl___. Me3-C-NO3+NaNO2 HCl___. | C-C(=N-OH)-NO2 Red
Me2-C(-N=O)-NO2 Blue
White
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| Me3-C-C(=O)-Me___not formed and fluoroform are formed | I Br Cl form not formed
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| Acetyl acetone ->(iodoform reaction)___. | 1 CHI3
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| Lactic acid | Me-C(OH)-COOH
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| Victor meyer test___. | RCOH->(Red P I2)->R-C-I->(AgNO2)R-C-NO2
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| Mennich reaction Me-CO-Me+HCHO+R-NH2->___by___. | Me-CO-C-C-NH-R
1st tautomerise then form carbanion from HCHO then attack
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| Darzen reaction___. | ROH+SOCl2->RCl+HCl+SO2
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| +I decreasing order | CH2->NH->O->COO->CMe3>CHMe2>CH2Me>Me>H
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| +I decreasing order between isotopes of hydrogen | T>D>H
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| -I decreasing order | NF3+>NMe3+>NO2->CN->CHO>COOH>F>Cl>Br>I
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| -I decreasing order between F,OH,NH2 | F>OH>NH2
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| Basic strength is directly proportional___. | EDG 1/EWG steric hindrance
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| On moving left to right in period or up to down in a group___. | Basicity decreases
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| EtNH2 Et2NH Et3N basicity | GP 1<2<3
SP 1<3<2
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| CH2(COOH)2 |
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| CH bond energy | Proportional to 1/stability of F.R.
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| +M effect decreasing order | CH2->NH->O->OR>OH>OPh
NH2>OH>F
F>Cl>Br>I
OR>SR
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| -M effect decreasing order | Ch2>BH2>PH2
NO2>CN>CHO>COR>COOR>CONH2>COO-
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| -N=O___SO2H | +M as well as -M
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| Hyperconjugation between H,D,T | H>D>T
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| Order of H M I effects | M>H>I
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| CF3+ CCl+ ion stability order CF3- CCl- ion stability order | I>IIp orbital resonance
II>Id orbital resonance
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| C-C(-)-NMe3+ C-C(-)-PMe3+ stability order | I>II
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| The more delocalised are the electrons___. | The less basic it is
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| SIR operates only on bigger groups like___. | NO2 SO3H COOH NR2
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| When group is ortho to basic site in benzene then__. | SIP acts
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| 1,8diethylamine naphthalene | H protonates then H bond
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| Stability of butenes | >= > TransC-C=C-C > CisC-C=C-C > C=C-C-C
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| Vitamin C | CH2OH-C(OH)-cyclic(C-O-C(=O)-C(OH)=C(OH))
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| Acidic order of common organic acids | HCl>RCOOH>H2CO3>PhOH>H2O>ROH>RC_=CH>NH3>RC=C>CH3
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| CHCl3 CHF3 acidity order | I>II
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| PhOH squaric acid acidic order | Squaric acid
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| Ortho meta para halophenol acid order | Meta>para>ortho
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| Ortho meta para Ph-F,Ph-Cl,Ph-Br,Ph-I acidic order | Cl>Br>F>I
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| COOH-Ph-SO3H COOH-Ph-NO2 acidic order | COOH acidic order II>I
Total acidic order I>II
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| Four groups of electrophiles + incomplete octet 0 incomplete octet 0 expanded octet o complete not expanded | H+ R+ X+ NO2+ NO+ Me-CO
BH3>BX3 BF3<BCl3 free radicals
PCl3 FeCl3 ZnCl2 SbCL3
XX RX CO2 SO3 CCl4
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| Groups of nucleophile - charged neutral LP pi electron |
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| On going left to right in a period___. | Nucleiphilicity basicity decreases
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| On going up to down in a group___. | Nucleophilicity increases in polar protic solvent
Nucleophilicity decreases in polar aprotic solvent
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| Polar aprotic solvents | DMF HMPT DMA DMSO crown ether
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| Nucleophilicity order | SH->P(CH3)3>CN->I->OCH3->OH->Br->Cl->NH3>OAc-
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| Lg tendency order | NH3+>I->H2O+=Br->Cl->>F-
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| Carbocation stability | 3>2>allylic>benzylic>1
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| ___solvents increase the rate of E2 reaction. | Polar aprotic
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| Increasing rate for E2 reaction | 3>2>1 strong bases
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| A reaction is___when it yields predominantly or exclusively one constitutional isomer when more than one is possible. | Regioselective
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| A reaction is___when it forms predominantly or exclusively one stereoisomer when two or more are possible. | Stereoselective
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| The E1 and E2 mechanisms both involve the same number of bonds broken and formed. The only difference is___. | Timing
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| E1 CHARACTERISTICS | 1st order 2steps 3>2>1 weak base good lg polar protic solvent
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| For E2 elimination, the C-Cl bond must be anti periplanar to the C—H bond on a β carbon, and this occurs only when the H and Cl atoms are both in the axial position. The requirement for__means that elimination must occur. | Trans diaxial geometry
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| ___favor E2 mechanism. ___favor E1 mechanism. | Strong bases,order of reactivity
weaker bases,1 C carbocations
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| With strong bases and 3 C carbon___. | E2 mechanism
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| With weak nucleophiles or bases and 3 C Carbon | Sn1 and E1 mechanism
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| With 1 C Carbon and strong nucleophiles | Sn2
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| With 1 C Carbon and strong sterically hindered bases | E2 mechanism
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| With 2 C Carbon and strong bases and nucleophiles | Sn2 E2 mechanism
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| With 2 C Carbon and strong sterically hindered bases | E2 mechanism
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| With 2 C Carbon and with weak nucleophiles or bases | Sn1 and E1 mechanism
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| Methyl 1 C Carbon Weak base/poor Nu,poor base/good Nu,strong base/good Nu,strong base/poor Nu | NR Sn2 Sn2 Sn2
NR Sn2 Sn2 E2
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| 2 C Carbon Weak base/poor Nu,poor base/good Nu,strong base/good Nu,strong base/poor Nu | Sn1,E1 Sn2 Sn2,E2 E2
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| 3 C Carbon Weak base/poor Nu,poor base/good Nu,strong base/good Nu,strong base/poor Nu | Sn1,E1 Sn1,E1 E2 E2
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| 1 C Benzylic 2 C Benzylic 3 C Benzylic Weak base/poor Nu,poor base/good Nu,strong base/good Nu,strong base/poor Nu | Sn1 Sn2 Sn2 Sn2
Sn1,E1 Sn2 Sn2,E2 E2
Sn1,E1 Sn1,E1 E2 E2
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| 1 C allylic 2 C allylic 3 C allylic Weak base/poor Nu,poor base/good Nu,strong base/good Nu,strong base/poor Nu | Sn1 Sn2 Sn2 Sn2
Sn1,E1 Sn2 Sn2,E2 E2
Sn1,E1 Sn1,E1 E2 E2
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| What is an oxidative addition? | A neutral ligand adds to a metal center and oxidizes the metal and oxidizes the metal at least one anionic ligand becomes attached to metal center
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| Non-electrophillic case example | H-H S-S C-H C-C
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| Electrophilic case example | X2 R-X Ar-X H-X O2
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| Reductive elimination | Two cisoidal anionic ligands on a metal center couple together
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| Migratory insertion | Cisoidal anionic and neutral ligand on a metal complex couple together
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| In migratory insertion what is not changed? | Oxidation state or d electron-count but the overall electron-count on metal decreases by 2e-
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| Which anions and neutral molecules can perform migratory insertion? | H- R- Ar- acyl- O2-
CO alkenes alkynes carbenes
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| A migration is when the___and performs a nucleophillic-like intramolecular attack on the electrophillic neutral ligand. An insertion is when the neutral ligand moves and___. | Anionic ligand moves
"inserts” into the bond between the metal and anionic ligand
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| Fe(C5H5)EtPPH3CO->(CH3NO2)____. (HMPA)___. | Et migrates
CO inserts
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| Alkene manafacturing by Zr(C5H5)2CH3 involves____. | Migratory insertion
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| An alkene and a hydride usually react via a___to the coordinated alkene ligand | Migration of the hydride
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| RNH2->(NaNO2 HCl)___(CAN)___. R2NH->(NaNO2 HCl)___ R3N->(NaNO2 HCl)___ | ROH red
R2N-N=O oily liquid
No effect
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| Ph-NH2(NaNO2 HCl)___(alkaline beta napthol) Ph-NHR(NaNO2 HCl)___ | Ph-N2+Cl- Red
Ph-N(-N=O)-R oily liquid
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| ROH+Lucas reagent(ZnCl2+HCl)->___ alcohol turbidity time 3 degree___2 degree |
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| ROR(HI anhydrous)->___ ROR(Conc HI)->___. ROR(dilute HI)->___. | Sn2
Sn1
Sn1
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| R-X+NH3 which type reaction where R-1 degree___ R-3 degree___ | Sn2
elimination
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| NCH3 NPh3 PCH3 PPh3 which does not react with MeI___. | NPh3
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| R1-O-R2 (dil H2SO4)->___. | Follow Sn1 reaction
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| Me-NH-Et(anhydrous HI)___ "(anhydrous HI)___ "(conc HI)___ | (MeNH2Et)+I-
Me-I EtNH2
Me-I EtNH2
Hurzig mayer method
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| OH-C-C-OH(HCl+ZnCl2)->____. | Cl-C-C-Cl
No adjacent carbocation
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| R-I+NaI(acetone)->___. | R-I
Finkelstein reaction
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| R-Cl+KF(DMF)->___. | R-F
Swarts reaction
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| MeCl+RONa->___. | ROMe williamson synthesis
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| Me-Cl+(KCN,AgCN,AgCN(DMF))->___. Me-Cl+(KNO2,AgNO2)->___. | Me-CN Me-NC Me-CN
MeONO MeNO2
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| R-C_=N->(H2O H+)___ R-C_=N->(H2O OH-)___ | RCOOH NH4+
RCOO- NH3
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| RCONH2(H2O,H+/OH-)___. | RCONH2
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| RCN+H2___. R-C_=N(Sn+HCl)___. RCN(stephen reagent)->___. | RCH=NH
RCH2-NH2
RC=NH
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| MeCl+ alc AgNO3->___ MeCl+ aqAgNO3->___ | Me-ONO2
NO3- is more solvated
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| Me3C-Cl+(alcAgNO3,aqAgNO3)->___,___ | Me3ONO2 AgCl major Me3COR
Me3COH major
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|
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| For anchimeric assistance conditions are___. | Internal Nu,anti,concentration of external Nu must be low
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|
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| Me3N+OH- ->___ Me3S+OH- ->___ Me3S+I- ->___ NMe4+I- -> | Sn2
Sn2
Sn1
Sn2
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|
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| Me-C-(OMe)3___. | Methyl orthoacetate
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|
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| All halogen compounds burn with green edge flame___. | Belstein test
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|
||||
| ROH+RedP/I2___. | P(ROH)3->RI Sn2 mechanism
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|
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| ROH+Red P/HI->___. | RH+H3PO3
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|
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| In propagation step the polymer chain growth happens from___. | Migratory insertion
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|
||||
| Sum(niMi)/sum(ni) Sum(niMi^2)/sum(niMi) Mw(avg)/Mn(avg) | Mn(avg)=___Mw(avg)=____PDI=___.
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|
||||
| What is the basis of M(w)? | More weighty molecules contribute more to the properties of the polymer
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|
||||
| As the distribution narrows the dispersivity approaches___. | 1
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|
||||
| What factor most effect stereochemistry if the polymerization? | Steric environment around the metal corner
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|
||||
| C2 symmetry(chiral) produces___environment. Bulky small catalyst environment produces___. Small ligands that offer little steric directing effect produce___. | Isotactic
syndiotactic
atactic
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|
||||
| SBR rubber is made from | Styrene butadiene
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|
||||
| Metathesis refers to the reaction of two unsaturated substances that leads to a___. | Switching of the atom groups on each end of the bond with unsaturation
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|
||||
| Which reaction is used to produce 11-tetradecenyl acetate which is used in orange protection? | 3-Hexene+Eicosenyl acetate Metathesis
🗑
|
||||
| LnM-Cl+AlR3/MAO/ZnR2->___. | LnM-R+AlR2Cl Initiation
🗑
|
||||
| Polymerization propagates through___. | Migratory insertion
🗑
|
||||
| M-CH3+C2H2->___->(___)->so on. | M(C2H2)-CH3 M-CH2-CH2-CH3
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|
||||
| Olefin metathesis constitutes a catalytic methods for both___C=C double bonds.The reaction is generally___. | Cleaving and forming
reversible
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|
||||
| Chauvin mechanism for metathesis___. | R-C=CH2->(R-C=[M])R-C(-M-CH2-)C-R->(R=Rout)M=CH2->(R-C=CH2)R-CH(-M-CH2-)-CH2
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|
||||
| In 1995 Grubbs reported the synthesis of RuCl2(=CHPh)(PCy3)2 in high yield and purity.This complex is obtained as a___.It is very famous for ease synthesis,high catalytic activity,it constitute the___. | Purple microcrystallne
The most useful catalysts
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|
||||
| Homogeneous catalysis are good because___. | More selective,more active,more easily studied,easily modified for optimizing selectivity
🗑
|
||||
| Homogeneous catalysis are bad because___. | Senstitive to permanent deactivation,difficulty in separation
🗑
|
||||
| Exposure to elemental Hg will___whereas exposure to polythiols will___. | Poison heterogeneous catalyst
poison homogeneous catalyst
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|
||||
| One loop through the catalyst cycle.Typically one equivalent of reactant is converted to one equivalent of product(per equivalent of catalyst) | Turnover
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|
||||
| The absolute number of passes through the catalytic cycle before the catalyst become deactivated. | Turnover number
🗑
|
||||
| The number of passes through the catalytic cycle per unit time | Turnover frequency=n(products)/(n(catalysts)t)
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|
||||
| Hydrogenation process step1 three methods___. | Oxidative addition LnM+H2<=>LnM(H,H)
hydrogenolysis LnM-X+H2<=>LnM-X+HX
heterolytic cleavage LnM+H2+B-<=>[LnM-H]-
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|
||||
| Hb MW=___,alpha___,beta___,active site___. | 64,500 g 141 146 Fe
A tetramer of hemoglobin
🗑
|
||||
| Mb MW=___,alpha___,active site___. | 17,800 g 161 Fe
🗑
|
||||
| Reaction of Fe with O2___. | Fe(II)+O(2)->Fe(II)-O(2)
Fe(II)-O2+Fe(II)->peroxocomplex(III)
Fe(III)-O-O-Fe(III)->2Fe(IV)=O
Fe(IV)=O+Fe(II)->oxo complex
Fe
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|
||||
| Coordination environment of Fe(II)in deoxymyoglobin and oxymyoglobin___. | (Poryphyrin)Fe-Proximal His-F helix
on another side-distal His-E helix
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|
||||
| Fe(N(poryphyrin))4N(His) Fe(N(poryphyrin))4N(His)O2- | x2-y2(|) z2(|) xy(|) xz(||)yz(||)
xy(||) xz(|)yz(|)
🗑
|
||||
| Role of distal base in hemoglobin | Sterically weaken CO bond
🗑
|
||||
| S shaped hyperbolic | Hemoglobin(percent O2 vs partial pressure of O2)___,Myoglobin___.
🗑
|
||||
| The role of Myoglobin is to store___. | Store the oxygen and release it for metabolic
🗑
|
||||
| Why Fe doesnt' forms oxo complex with oxygen with in hemoglobin? | Because of steric hindrance of proteins
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|
||||
| The coordination environment comprises of four nitrogens from the porphyrin ring, one___arising out of the amino acid residue, histidine, of the protein chain, and possibly a second distant imidazole nitrogen or a water molecule. | Imidazole nitrogen
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|
||||
| Fe is___above the poryphyrin plane. | .4 A*
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|
||||
| ___and___are nonheme comoounds in which the metal is bound directly to the protein | Hemerythrin hemocyanic
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|
||||
| Hemerythrin is found in___.Hemocyanin,a copper protein is found in___. | Marine animals
mollusks and arthopods
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|
||||
| Aquatic mammals are particularly rich in myoglobin;the concentration in some cases is so high that skeletal muscles appear___. | Almost black in color
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|
||||
| Monomeric hemoglobins also occur in blood of___and___. | Invertebrates
roots of legumes
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|
||||
| These high molecular weight hemoglobins, which may contain up to 200 hemes per molecule. are also called___. | Erthrocruorins
🗑
|
||||
| Which in exception of all vertebrates have hemoglobin? | Ice fish
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|
||||
| Invertebrates don't seem to follow___.Sea ccumber Molpadia arenicola bleeds profusely but___doesn't contain. | Any evolutionary scheme
Close relative starfish
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|
||||
| Hemerythrins___/Fe MW___. Hemocyanins___/Cu MW___. | 7000 40000-108000
Mollusk=25000 4-9x10^6
Arthopod=37000 .5-3x10^6
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|
||||
| Myoglobins___/Fe MW___. Legheglobbins___/Fe MW___. Invertebrate hemo___/Fe MW___. Vertebrate hemo___/Fe MW___. Chlorocruorins___/Fe MW___. | 18000 18000
16000 16000
16000-40000 16000-6x10^6
16000 65000
22000-35000 3x10^6
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|
||||
| Four of the six coordination spaces around the metal are occupied hv the nitrogens of the poryphyrin.In the fifth space is the___of a histidine residue,the 8th amino acid of the helical region laheled F | Four
Imidazole nitrogen
🗑
|
||||
| In O2-free hemoglobin the iron is in the___and has a high spin configuration | +2 oxidation state
🗑
|
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