CHE 331.800 11.14 - Le w M E 13" 4‘00 W404 Draw the...

Info icon This preview shows pages 1–7. Sign up to view the full content.

View Full Document Right Arrow Icon
Image of page 1

Info icon This preview has intentionally blurred sections. Sign up to view the full version.

View Full Document Right Arrow Icon
Image of page 2
Image of page 3

Info icon This preview has intentionally blurred sections. Sign up to view the full version.

View Full Document Right Arrow Icon
Image of page 4
Image of page 5

Info icon This preview has intentionally blurred sections. Sign up to view the full version.

View Full Document Right Arrow Icon
Image of page 6
Image of page 7
This is the end of the preview. Sign up to access the rest of the document.

Unformatted text preview: Le w, M E 13%!" 4‘00 W404 11/11/13 Draw the structure of the major product of each reaction. A. \/\/\ + HBr —> B. \7‘\/ + HC] —__> C. Chapter 8 l 1 0 Addition of Sulfuric Acid to Alkenes I} Addition of concentrated sulfuric acid to alkenes leads to alkyl hydrogen sulfates. The addition follows Markovnikov’ 5 rule. H H H \ \ l C=CH7 ——') C-CH,—l1 —> H;C-C—CH; / ‘ / E ' i ’ “it Q .. “1C \ - .. rosofi 11 H )3“ »_ 2 980311 2° Cnrbocation Isopropyl hydrogen (more stable carbocationl sulfate I) The sulfate can be hydrolyzed by heating with water i The net result Is Markovnikov addition of water to an alkene = Id , I”). he: C1~1¢YCH=CH2 CHXLI‘HCH1 CH‘SHCH1 + H3304 050‘.“ 0“ 1/1 " Chapter 8 800‘6 It fit" Aifi .29 A. + r r -€fl -(NM’§ “A *‘ °mCWc I WA 33 ' 'ra) Cfiflvlflf | -. “31w xix-«ct 09 a c, ‘ "" mev 30 'No chi(\ CCOW ~\> o 'r J. nonfiomofs‘VnDHS ° ND A K{OJ} CUM-U ° 0 DIN 61“” 1N0 Q, . hulk 0 Addition of Water to Alkenes: Acid-Catalyzed Hydration ID The reaction of alkenes with dilute aqueous acld leads to Markovnikov addition of water. CH‘ €le (7:ch + mm (EHI—C—(THl—ll CH1 (m tert-Butyl alcohol H, \ I I} Mechanism: N / 0 f \ § \ . f___\ C / C 5 C -— L H ~ ‘ 7— / 7 4 <’ / ‘ “$1: ¥* hxi~ t1 #Lfi’ ’3 . U179“) 3 (QfiOm » Chapter 8 13 ->Theor alkenes and the dehydration of alcohols are sump y reverse reactions of one other. * Hydration Is favored by addition of a small amount of acid and a large amount 91 water. * 's favored by concentrated acid with ver water Eresent (removal of water produced also helps favor ehydration). I) Carbocation rearrangements can occur. CH3 OH I H 50 I CH3-(|3—CH=CH2 CH3—(13—(lo‘H—CH3 It 2 CH3 \Otfi’g'flrét‘) CH3 CH} 3,3-Dimethyl-1-butene 2,3-Dimethyl-2-butanol (major product) Chapter 8 (x Vii/Lg ‘ V f H MATH WU: ,. __ C H ,_ {M " C "C H :7 Z ' u ' l \ VLLQ. _ H W “h LO I 1C“ 11/11/13 1 “L mQ hum Cite? $11 bi“ fi‘ 11/11/13 O Alcohols from Alkenes Through Oxymercuration- Demercuration: Markovnikov Addition I¢ The procedure gives high yields ot alcohols and avoids rearrangements. Shy) I: U rymr'r'r‘unm'nn 0 LI) \ /-" (n )W 1| /C‘—“~C\ 41110 + H; UCCH. » 9 " Ll ’ L" 0 + CII‘COU 4: )4} WU: ( [J “fit-Nu} “Limutm‘ 0L 0 (1 <1 Sly v 2: I) ‘nmu'umlirm ,” L I 1 Wk 0 I —l‘—J‘— 0 + ()H + MBIL % ~(‘—(I‘— ~ Hg 7» (‘Hxlto' 03m 5 no l1! r’ ’ p1 '- s H V > 'RLE. ”‘ ? WEN DU" " CKOCICU \ (kn/19 u xx ID The reaction shows Markovfiov selectivity ‘w‘ Lg k L! a V (3H1 (TH‘ I (ll llglOAcL/THFlLO I CH.;C—-CH=CH2 ‘ CH‘C—CHCH, I [2) NHBH‘. OH ' i I CH3 CH; OH 3.3-Dimelhyl-l-butene 3.3-Dimethyl-2-butanol 15 (94%) CH C C (“C ’“2 RD f ""1 H210 CLfld H Como 3 Wm No 951M O Alcohols from Alkenes through Hydroboration- Oxidation: Anti-Markovnikov Syn Hydration (M310 <3 “lo M9 I) The reaction leads to syn and anti-Markovnikov addition of water ,A , I, ' WA is ‘l 1”“ to alkenes. It is atwo-step process. L (’11 \L/C'l l Lth * _ . a CH‘ -1 Wu (ggl 6L why it CH (1) Miami 7W _ A f i,” . 3 (3) “EUPHO‘ DE H “(ft long , H 1 J S (‘2 r '" W t ~ J H on m] A 0 1m step: Hydroboration: Synthesis of Alkylboranes \C=C/ + H—B/ __C|_é_ / \ \ I I H /B\ Alkene Boron hydride Alkylborane Chapter 8 1 16 THH (woman <52ij {‘16P 1°» hgcuctx«(LUCW> o Mechanism of Hydroboration I} Boron hydride adds successively to three molecules of alkene. Mnrv [m ~ulhtllulml mmlmmi rurlxm mum" H ILZCH—CH‘ ' ' if ' —(‘H ll..(?(?ll=(ill: #qu‘u-u m ‘" u ‘ —~+ u n + ‘ » i.u<|c<|ul\| i / \ H,C(‘H *" ("H. II in mi. ” "u: H_(‘(‘H--CH« H . _r ‘ 1 1 .(LH (H u n H II Null-mm; l / \ H .L'L'H ~CH: (3H:# (“HCH‘ 'I'riprupyllmrnnv I} Boron becomes attached to the |_e_s_s_substituted carbon of the double bond. * This orientation leads to antl-Markovnlkov product. I) The boron and hydride add with syn (cis) stereochemistry. 11/11/13 :7 l 1., A M. V CH; ‘ s 'n at lllUll ‘ -" CH“ ,1 / ~ anu~Murkmmkm J + cnantiomcr [I H B / ‘\ H H cnaprens 17 ,r‘ \ 1 l ‘l‘ k ‘ ‘K ‘ 1 l I V . w’ l 5‘ \ \l(' 11 \ \k;\ ‘141, l \ Ll 1 1 9 Hydroboration of methylcyclopentene gives the anti-Markovnikov product with syn addition of the elements of water. ‘ CH 15‘ step: CH llllpTHF ‘ ‘ llulmlmratiml: + enumiumer Ann-Murkmmkm and H syn addition ‘ "10,. mr —. H Hudaunn‘ " Burun group I3 rcpiuux’i u Ill-1 2“‘1 step: ()Il / x H H umiligurzilmn ll _\ lulcnlinn ul' ,3 LQRH fetCLUN CfiflhégycflfinO“ 0L71”U3 Cm CL mum. ‘ Chapter 8 lcnzinnomcr E I I ” SWQ (LL/("W UL“ T‘i (10(13 cwmxzhnus Summary of Alkene Hydration Methods: - Acid-catalyzed hydrolysis: Markovnikov addition (Beware of rearrangements!) ° Oxymercuration/demercurationz Markovnikov addition (No rearrangements) ° Hydroboration-Oxidation: anti-Markovnikov and syn (cis) addition. Chapter 8 l9 9 Addition of Bromine and Chlorine to Alkenes I) Addiiion produces vicinal dihalides. Br 5 at "Will H ‘ _ + Brim-a H + cnunuomcr (95%) Br trans-l .2-Dihromocyclohexane {as a racomic form) "YYLUW <5 Cx (:1 (Milti). I. Used used as a test for alkenes. \C B room lCank/l' lilll’C é ‘=, + r —," *“‘7— ' n ‘ ‘ / \ 2 in mg dark. CO; | I Rapid decolorllzation B B of Brz/LU4 Is a r r test for alkcnes An alkene ric-Dibromide and alkvnes. (colorless) (a colorless ’ compound) Chapter 8 20 wiry-m bommom 1‘3 Cirmcup “(M33 0“) Cl 111% ‘ 11/11/13 10 / Alb) N > A f _ m 7 MO 7 v m 7 7 QFCLMGQMM ...
View Full Document

{[ snackBarMessage ]}

What students are saying

  • Left Quote Icon

    As a current student on this bumpy collegiate pathway, I stumbled upon Course Hero, where I can find study resources for nearly all my courses, get online help from tutors 24/7, and even share my old projects, papers, and lecture notes with other students.

    Student Picture

    Kiran Temple University Fox School of Business ‘17, Course Hero Intern

  • Left Quote Icon

    I cannot even describe how much Course Hero helped me this summer. It’s truly become something I can always rely on and help me. In the end, I was not only able to survive summer classes, but I was able to thrive thanks to Course Hero.

    Student Picture

    Dana University of Pennsylvania ‘17, Course Hero Intern

  • Left Quote Icon

    The ability to access any university’s resources through Course Hero proved invaluable in my case. I was behind on Tulane coursework and actually used UCLA’s materials to help me move forward and get everything together on time.

    Student Picture

    Jill Tulane University ‘16, Course Hero Intern