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CHM 102
| Question | Answer |
|---|---|
| Carbocation is a___and___. | Electrophile lewis acid |
| Leaving group tendency-Strong bases are___. strong acids are___leaving group. | Poor leaving group strong |
| Leaving group tendency-F-,OH-,NH2-,CH3- | (F-)>OH->NH2->CH3- |
| Leaving group tendency-RO-,PhO-,MeCOO-,CF3COO-,OH- | (CF3COO-)>(MeCOO-)>PhO->OH->RO- |
| Leaving group tendency-CH3COO-,CH3SO3-,CF3SO3- | [CF3SO3-]>(CH3SO3-)>(CH3COO-) |
| Leaving group tendency-N2 NH3 H2O | [N2]>[H2O]>NH3 |
| Leaving group tendency-Halogens | (I-)>(Br-)>(Cl-)>(F-) |
| Leaving group tendency-Nosylate,brosylate,tosylate | (NsO-)>(BsO-)>(TsO-) |
| Diazotization reaction___. | RNH2->(NaNO2+HCl)R+ + N2 |
| CR OF carbocation 1- | Combination of nucleophile |
| CR OF carbocation Comb degree order___elimin degree order___. | 1>2>3 3>2>1 |
| CR OF carbocation Comb depends on temperature as___and elimn. as___. | Inversly directly |
| CR OF carbocation Comb depends on nucleophilicity as___and basic strength as___. | Directly Inversly |
| If during a reaction more than one alkene is produced then the most stable alkene is___. | Zaitsev rule |
| C+ + Halogen ->C + E C/E ratio is in order | F->Cl->Br->I- |
| Tert-butyl-C-C(+)(-C)-C | Hoffman product is major |
| Rearangement produces a___and if the step is RDS or shift is stabilised by backbonding then__. | More stable carbocation Better electron donor |
| Cyclopentane-CH2+->(rearrangement)___ | Cyclohexane carbocation |
| Cyclopropane-CH2+->(rearrangement)___ | Not rearranges |
| RI CARBOCATION CH3CH2OH+Conc H2SO4 110 C 140 C 170 C | CH3CH2HSO4 Et-O-Et CH2=CH2 |
| In dehydration of alcohol after formation of carbocation-at low temperature___,at high temperature___. | Nucleophile attack Base attack |
| E1 lg__first and then___takes proton. | Leaves base |
| E1 rate directly proportional to concentration of substrate and___. | Independent of base |
| E1 rate is___to lg tendency. | Directly proportional |
| E1 rate for different substrate___. | Benzyl>allylic>3>2>1 |
| E1 mechanism is favored by___. | Good lg,polar solvent,poor base,poor nucleophile,high temperature |
| E1 C-C(-OH,-C)-C(-OH,-C)-C ->(conc H2SO4,heat)___. | Pinacolon Tert butyl-C(=O)-C |
| Cyclopentane(OH)-Cyclopentane-E1 | Decalin with bridge double bond |
| E1 reagents that take halogens | SbCl5,AlCl3,AlBr3,AgNO3 |
| E1 C-C-NH2(NaNO2,HCl)->___. | C-C-ONO,C-C-Cl,C-C-O-C-C,major C-C-OH |
| Ae Classical carbocation mechanism | >C=C<->(RDS)E->C-C<+->E-C-C-Nu |
| Ae Classical carbocation mechanism Rate is__and proportional to___. | Second order electrophilicity of electrophile |
| Ae Alenylation of alkene C=C->(Catalytic H2SO4)___. | Formation of carbocation,attack on alkene,deprotonation. |
| Ae Alkylation of alkene->(HF 0 C)___. | Formation of carbocation,attack on alkene,rearrangement |
| Ae Hyrohalogenation of alkene___. Rate for different halogen___. | RDS formation of carbocation,attack of nucleophile I>Br>Cl>F |
| Anti-Markonikoff addition___. | ROOR->2RO'+HBr->ROH + Br'->formation of carbon radical |
| HF,HCL,HBr,HI__only shows Kharash-Peroxide effect. | HBr |
| Rate of Ae >=< >= \= = | >=< > >= > \= > = |
| Rate of Ae =-Ph__(para). OMe Me H CN NO2 | OMe>Me>H>CN>NO2 |
| Rate of Ae =-Ph__ OMe(meta,para),NO2(meta,para),H | OMe(p)>H>OMe(m)>NO2(m)>NO2(p) |
| Rate of Ae Styrene and stillbene | Stillbene>styrene |
| Ae Triple bond___react when not in conjugation, but when it is in conjugation the triple bond___. | Will not is first to react |
| In peroxide reaction the -ve part in following reagents CCl4 CBr4 CCl3Br CBr3-Cl H-CF3 I-CF3 H-CI3 EtSH is___. | |
| Prins reaction Alkene+___(dil. H2SO4)->___by___. | HCHO 1,3 diol alkene C attack HCHO then OH attacks positive charged carbon |
| Non classical carbocation mechanism___ | First Br attacks on double bond and then other Br attacks |
| Ae KCP__when___,___ | Ea,energy barrier is less low temperature |
| Ae C_=C-H+HCl(HgCl2) to get___only because___ | C=C-Cl it is attached to HgCl2 as it has lost its nucleophilicity |
| Ph-CH(OH)-C_=CH + H+ ->___. | Cinnamaldehyde Ph-CH=CH-CH=O |
| C_=C->(CH2N2 hv)___ C_=C->(CH2N2)___ | Cyclopropene 1,2 azacyclopentane |
| C=C-CN self polymer___. C=C-CN polymer with But-3-yne-1-ene | Orlon Buna N |
| C2H2 +AsCl3,AlCl3___which counteracted by___. | Cadet bunsen Lewsite(Cl-C=C-AsCl2) BAL |
| NCM Ae Rate is proportional to___. | Electrophilicity of electrophile Nucleophilicity of nucleophile |
| NCM Ae Rate in halogens | F2>Cl2>Br2>I2 |
| Cis on anti addition gives___. | Threo |
| NCM Ae In HOBr reaction the nucleophile is___. | H2O |
| NOCl___ NCM Ae Cyclic ion opens from that end which is___. | Tilden reagent Gives more stable carbocation |
| Br2 on Anthracene gives___.Cyclic compound which reacts with Br2 | 9-10 product cylopropane |
| 1,3,5Cycloctatriene with Br2 gives___. | Trans 7,8 dibromo Bicyclo[4,2,0]octane. |
| 1,5Cyclooctadiene + Br2 gives | 2,6 dibromo bicyclo[3,3,0]octane |
| >= + X2 at 25 C gives__. | Major product by Sae Cl>= |
| Diels Alder reaction follow cyclic transition state mechanism,concerted mechanism,pericyclic. Rate is proportional to___. | EDG in diene EWG in dienophile 1/stearic hindrance |
| Out of Furan pyrrole thiophene which is not giving Diels alder? | Pyrrole thiophene |
| HCl+ Na___NaNH2___RONa___NaOH___NaHCO3___. | Y Y Y Y Y |
| RCOOH+ Na___NaNH2___RONa___NaOH___NaHCO3___. | Y Y Y Y Y |
| PhOH+ Na___NaNH2___RONa___NaOH___NaHCO3___. | Y Y Y Y N |
| ROH+ Na___NaNH2___RONa___NaOH___NaHCO3___. | Y Y Y N N |
| 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 |
| 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 |
| C_=C->(__)-(Me-CO-Me)-H2O-ConcH2SO4->H2 Pd | Benedicts reagent Isoprene |
| Terminal alkyne+ NaNH2__ KOH___. | Yes No |
| 2-alkyne+ NaNH2__ KOH___. | No Yes |
| 2alkyne NaNH2 heat___ | Terminal alkyne 1-C- 2-resonance 3- |
| C_=C+Cu2Cl2 NH4Cl heat___. | Vinyl addition |
| 3C2H2(Fe Red hot tube)___. | Benzene |
| 4C2H2(Ni(CN)4)___. | COT |
| RC_=C-H+ NaOCl___ +I2 liqNH3 0 C | RC_=C-Cl RC_=C-I |
| CaC2+H2O___ Mg2C3+H2O___ Al4C3+H2O___ | Acytelene Propyne Methane |
| Generation of Grignard reagent | R-X + (Et2O Mg) R-Mg-X |
| Reactivity,nucleophilicity,basicity in decreasing order of organometallic reagents | RNa(Wurtz) RMgX(Grignard) R2Zn(Frankland) R2CuLi(Coreyhouse) |
| Characteristic reactions of carbanion___. | Reactions as a base Reactions as a nucleophile nucleophilic addition nucleophilic addition elimination |
| 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 |
| Monochlorides possible Isobutane | 2 2 |
| Monochlorides possible Isopentane Neopentane | 6 4 1 1 |
| Monochlorides possible Hexane 3 methylpentane | 5 3 8 5 |
| Monochlorides possible Methyl cyclohexane | 12 8 |
| Monochlorides possible 2Methoxy propane 3Ethoxy pentane | 4 3 10 6 |
| Dichlorides possible Propane Butane Isobutane | 5 2 2 1 10 2 5 3 3 1 1 1 |
| Dichlorides possible pentane isopentane neopentane | 17 3 6 8 18 4 6 8 2 1 0 1 |
| Dichlorides possible Hexane | 26 3 9 14 |
| Chloroderivatives possible Methane ethane propane | 4 9 35 |
| Decreasing rate in substrate of Grignard reagent | RCOCl RCHO RCOR RCOOR RCONR2 RCOO- |
| Bu-Cl+Mg Et2O___ Bu-Cl+Na Et2O___ Bu-Cl+.5 Mg Et2O___ | Bu-Mg-Cl Bu-Bu Bu-Bu |
| 1,4 dichlorobutane+ Mg Et2O___. 1,4 dichlorobutane+ Mg(excess) COCl2___. | Cyclobutane Cyclopentanone |
| Grignard reagent + acidic H compound___ Grignard reagent + acidic H-lone pair(NH2Cl RONH2)___ | RH R-acidic H part 1-RH |
| RCOOR + H3O+___ | RCOOH addition of H+,then H2O,-ROH,-H2O |
| Soda lime + RCOOH->___.Mechanism___. | RH Acid base reaction then Cao+CO2->CaCO3+RH |
| Rate of oakwood degradation is___. | Proportional to stability of carbanion |
| RCOO-+ MnO/CaO/BaO ->___. Ph-CHBr-C(COOH)-Br heat___ | R- Ph-C=C-Br |
| Compounds like Beta-Keto,Beta-amino acids,Gem dicarboxylic acid,beta-gamma unsaturated acid___. | Lose CO2 only on heating |
| 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 |
| 2MeCOOH+Conc H2SO4 heat___ 2MeCOOH+CaO/MnO/BaO heat___. | Anhydride Acetone |
| RCOOH->(Ca(OH)2)___->(heat)___. | (RCOO)2Ca RCOR |
| COOH-C-C(OH COOH)-C-COOH->(heat)___. | C=C(COOH)-C |
| 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)) |
| ALDOL Cyclopropanone___ Bicyclo[2,2,1]octane-8-one___ Me2CH-CH=O___. | No aldol No self aldol No self aldol |
| 14 carbon-NO2 | Moth repellant |
| C-CO-C+(NaNO2 HCl)___. | C-CO-C=N-OH First tautomerise then attack NO+ then tautomerise |
| C-CO-C +Br2(excess) Acidic medium___. C-CO-C +Br2(excess) basic medium___. | Tautomerise attack of Br2 -HBr Carbanion attack of Br2 |
| 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 |
| C-CO-C +Br2(excess) basic(excess) medium___. | CHX3 + C-COO-Na+ |
| Ph-CH(OH)-Me->(CaOCl2 H2O) | Do first oxidation |
| 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 |
| Me3-C-C(=O)-Me___not formed and fluoroform are formed | I Br Cl form not formed |
| Acetyl acetone ->(iodoform reaction)___. | 1 CHI3 |
| Lactic acid | Me-C(OH)-COOH |
| Victor meyer test___. | RCOH->(Red P I2)->R-C-I->(AgNO2)R-C-NO2 |
| Mennich reaction Me-CO-Me+HCHO+R-NH2->___by___. | Me-CO-C-C-NH-R 1st tautomerise then form carbanion from HCHO then attack |
| Darzen reaction___. | ROH+SOCl2->RCl+HCl+SO2 |
| +I decreasing order | CH2->NH->O->COO->CMe3>CHMe2>CH2Me>Me>H |
| +I decreasing order between isotopes of hydrogen | T>D>H |
| -I decreasing order | NF3+>NMe3+>NO2->CN->CHO>COOH>F>Cl>Br>I |
| -I decreasing order between F,OH,NH2 | F>OH>NH2 |
| Basic strength is directly proportional___. | EDG 1/EWG steric hindrance |
| On moving left to right in period or up to down in a group___. | Basicity decreases |
| EtNH2 Et2NH Et3N basicity | GP 1<2<3 SP 1<3<2 |
| CH2(COOH)2 | |
| CH bond energy | Proportional to 1/stability of F.R. |
| +M effect decreasing order | CH2->NH->O->OR>OH>OPh NH2>OH>F F>Cl>Br>I OR>SR |
| -M effect decreasing order | Ch2>BH2>PH2 NO2>CN>CHO>COR>COOR>CONH2>COO- |
| -N=O___SO2H | +M as well as -M |
| Hyperconjugation between H,D,T | H>D>T |
| Order of H M I effects | M>H>I |
| CF3+ CCl+ ion stability order CF3- CCl- ion stability order | I>IIp orbital resonance II>Id orbital resonance |
| C-C(-)-NMe3+ C-C(-)-PMe3+ stability order | I>II |
| The more delocalised are the electrons___. | The less basic it is |
| SIR operates only on bigger groups like___. | NO2 SO3H COOH NR2 |
| When group is ortho to basic site in benzene then__. | SIP acts |
| 1,8diethylamine naphthalene | H protonates then H bond |
| Stability of butenes | >= > TransC-C=C-C > CisC-C=C-C > C=C-C-C |
| Vitamin C | CH2OH-C(OH)-cyclic(C-O-C(=O)-C(OH)=C(OH)) |
| Acidic order of common organic acids | HCl>RCOOH>H2CO3>PhOH>H2O>ROH>RC_=CH>NH3>RC=C>CH3 |
| CHCl3 CHF3 acidity order | I>II |
| PhOH squaric acid acidic order | Squaric acid |
| Ortho meta para halophenol acid order | Meta>para>ortho |
| Ortho meta para Ph-F,Ph-Cl,Ph-Br,Ph-I acidic order | Cl>Br>F>I |
| COOH-Ph-SO3H COOH-Ph-NO2 acidic order | COOH acidic order II>I Total acidic order I>II |
| 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 |
| Groups of nucleophile - charged neutral LP pi electron | |
| On going left to right in a period___. | Nucleiphilicity basicity decreases |
| On going up to down in a group___. | Nucleophilicity increases in polar protic solvent Nucleophilicity decreases in polar aprotic solvent |
| Polar aprotic solvents | DMF HMPT DMA DMSO crown ether |
| Nucleophilicity order | SH->P(CH3)3>CN->I->OCH3->OH->Br->Cl->NH3>OAc- |
| Lg tendency order | NH3+>I->H2O+=Br->Cl->>F- |
| Carbocation stability | 3>2>allylic>benzylic>1 |
| ___solvents increase the rate of E2 reaction. | Polar aprotic |
| Increasing rate for E2 reaction | 3>2>1 strong bases |
| A reaction is___when it yields predominantly or exclusively one constitutional isomer when more than one is possible. | Regioselective |
| A reaction is___when it forms predominantly or exclusively one stereoisomer when two or more are possible. | Stereoselective |
| The E1 and E2 mechanisms both involve the same number of bonds broken and formed. The only difference is___. | Timing |
| E1 CHARACTERISTICS | 1st order 2steps 3>2>1 weak base good lg polar protic solvent |
| 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 |
| ___favor E2 mechanism. ___favor E1 mechanism. | Strong bases,order of reactivity weaker bases,1 C carbocations |
| With strong bases and 3 C carbon___. | E2 mechanism |
| With weak nucleophiles or bases and 3 C Carbon | Sn1 and E1 mechanism |
| With 1 C Carbon and strong nucleophiles | Sn2 |
| With 1 C Carbon and strong sterically hindered bases | E2 mechanism |
| With 2 C Carbon and strong bases and nucleophiles | Sn2 E2 mechanism |
| With 2 C Carbon and strong sterically hindered bases | E2 mechanism |
| With 2 C Carbon and with weak nucleophiles or bases | Sn1 and E1 mechanism |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| Non-electrophillic case example | H-H S-S C-H C-C |
| Electrophilic case example | X2 R-X Ar-X H-X O2 |
| Reductive elimination | Two cisoidal anionic ligands on a metal center couple together |
| Migratory insertion | Cisoidal anionic and neutral ligand on a metal complex couple together |
| In migratory insertion what is not changed? | Oxidation state or d electron-count but the overall electron-count on metal decreases by 2e- |
| Which anions and neutral molecules can perform migratory insertion? | H- R- Ar- acyl- O2- CO alkenes alkynes carbenes |
| 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 |
| Fe(C5H5)EtPPH3CO->(CH3NO2)____. (HMPA)___. | Et migrates CO inserts |
| Alkene manafacturing by Zr(C5H5)2CH3 involves____. | Migratory insertion |
| An alkene and a hydride usually react via a___to the coordinated alkene ligand | Migration of the hydride |
| RNH2->(NaNO2 HCl)___(CAN)___. R2NH->(NaNO2 HCl)___ R3N->(NaNO2 HCl)___ | ROH red R2N-N=O oily liquid No effect |
| Ph-NH2(NaNO2 HCl)___(alkaline beta napthol) Ph-NHR(NaNO2 HCl)___ | Ph-N2+Cl- Red Ph-N(-N=O)-R oily liquid |
| ROH+Lucas reagent(ZnCl2+HCl)->___ alcohol turbidity time 3 degree___2 degree | |
| ROR(HI anhydrous)->___ ROR(Conc HI)->___. ROR(dilute HI)->___. | Sn2 Sn1 Sn1 |
| R-X+NH3 which type reaction where R-1 degree___ R-3 degree___ | Sn2 elimination |
| NCH3 NPh3 PCH3 PPh3 which does not react with MeI___. | NPh3 |
| R1-O-R2 (dil H2SO4)->___. | Follow Sn1 reaction |
| Me-NH-Et(anhydrous HI)___ "(anhydrous HI)___ "(conc HI)___ | (MeNH2Et)+I- Me-I EtNH2 Me-I EtNH2 Hurzig mayer method |
| OH-C-C-OH(HCl+ZnCl2)->____. | Cl-C-C-Cl No adjacent carbocation |
| R-I+NaI(acetone)->___. | R-I Finkelstein reaction |
| R-Cl+KF(DMF)->___. | R-F Swarts reaction |
| MeCl+RONa->___. | ROMe williamson synthesis |
| Me-Cl+(KCN,AgCN,AgCN(DMF))->___. Me-Cl+(KNO2,AgNO2)->___. | Me-CN Me-NC Me-CN MeONO MeNO2 |
| R-C_=N->(H2O H+)___ R-C_=N->(H2O OH-)___ | RCOOH NH4+ RCOO- NH3 |
| RCONH2(H2O,H+/OH-)___. | RCONH2 |
| RCN+H2___. R-C_=N(Sn+HCl)___. RCN(stephen reagent)->___. | RCH=NH RCH2-NH2 RC=NH |
| MeCl+ alc AgNO3->___ MeCl+ aqAgNO3->___ | Me-ONO2 NO3- is more solvated |
| Me3C-Cl+(alcAgNO3,aqAgNO3)->___,___ | Me3ONO2 AgCl major Me3COR Me3COH major |
| For anchimeric assistance conditions are___. | Internal Nu,anti,concentration of external Nu must be low |
| Me3N+OH- ->___ Me3S+OH- ->___ Me3S+I- ->___ NMe4+I- -> | Sn2 Sn2 Sn1 Sn2 |
| Me-C-(OMe)3___. | Methyl orthoacetate |
| All halogen compounds burn with green edge flame___. | Belstein test |
| ROH+RedP/I2___. | P(ROH)3->RI Sn2 mechanism |
| ROH+Red P/HI->___. | RH+H3PO3 |
| In propagation step the polymer chain growth happens from___. | Migratory insertion |
| Sum(niMi)/sum(ni) Sum(niMi^2)/sum(niMi) Mw(avg)/Mn(avg) | Mn(avg)=___Mw(avg)=____PDI=___. |
| What is the basis of M(w)? | More weighty molecules contribute more to the properties of the polymer |
| As the distribution narrows the dispersivity approaches___. | 1 |
| What factor most effect stereochemistry if the polymerization? | Steric environment around the metal corner |
| C2 symmetry(chiral) produces___environment. Bulky small catalyst environment produces___. Small ligands that offer little steric directing effect produce___. | Isotactic syndiotactic atactic |
| SBR rubber is made from | Styrene butadiene |
| 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 |
| 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 |
| Olefin metathesis constitutes a catalytic methods for both___C=C double bonds.The reaction is generally___. | Cleaving and forming reversible |
| 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 |
| 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 |
| 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 |
| One loop through the catalyst cycle.Typically one equivalent of reactant is converted to one equivalent of product(per equivalent of catalyst) | Turnover |
| 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) |
| 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]- |
| 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 |
| Coordination environment of Fe(II)in deoxymyoglobin and oxymyoglobin___. | (Poryphyrin)Fe-Proximal His-F helix on another side-distal His-E helix |
| 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 |
| 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 |
| Fe is___above the poryphyrin plane. | .4 A* |
| ___and___are nonheme comoounds in which the metal is bound directly to the protein | Hemerythrin hemocyanic |
| Hemerythrin is found in___.Hemocyanin,a copper protein is found in___. | Marine animals mollusks and arthopods |
| Aquatic mammals are particularly rich in myoglobin;the concentration in some cases is so high that skeletal muscles appear___. | Almost black in color |
| Monomeric hemoglobins also occur in blood of___and___. | Invertebrates roots of legumes |
| 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 |
| Invertebrates don't seem to follow___.Sea ccumber Molpadia arenicola bleeds profusely but___doesn't contain. | Any evolutionary scheme Close relative starfish |
| Hemerythrins___/Fe MW___. Hemocyanins___/Cu MW___. | 7000 40000-108000 Mollusk=25000 4-9x10^6 Arthopod=37000 .5-3x10^6 |
| 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 |
| 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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