Exam 2. CH310N Spring Anslyn March 23, Please PRINT the first three letters of your last name in the boxes below. PRINT Full Name UT-EID _

Transcription

1 CH310N Spring 2010 Anslyn March 23, 2010 Exam 2 Please PRINT the first three letters f yur last name in the bxes belw. k y PRINT Full Name UT-EID _ 1) ( 8 pts ) 2) ( 5 pts ) 3) ( 5 pts ) 4) ( 22 pts) 5) ( 4 pts) 6) ( 8 pts) 7) ( 7 pts ) 8) ( 6 pts ) 9) ( 8 pts ) 10) ( 8 pts ) 11) ( 7 pts ) 12) ( 12 pts) Bnus) ( 2 pts ) Ttal Scre ----:-_ (100 pts)

2 1. a) Give the cmmn names fr the fllwing mlecules. (Frm ntes, 2 pints) OH _B_en _1._t)_'L_A_Ct_c_t I 1 Ac.eJl1r+r-; Ie. b) Give the IUPAC name fr the fllwing mlecule. (Frm hmewrk, prblem 18.13h, 2 pints) 0 CI CI c) Draw the chemical structures fr the fllwing cmmn names. (Frm ntes, 2 pints) DMF (N, N-Dimethyl frmamide) Acetic Anhydride 2

3 d) Draw the chemical structure fr the fllwing IUPAC name. (2 pints) Z-isprpyl hex-3-enate 2. The fllwing questin is in regards t the equilibrium established by disslving sdium acetate in methanethil (CH 3 SH, pka=10.4), as shwn belw. Which side fthis reactin dminates at equilibrium? Why? (5 pints) CHsSH... e SCHs!i{C) lsi S ti~'1 It< ~ +-4 >fn,~.- 01 del S. The s i dr f tfv. e t u-,-i, l'/lv Lih r~pt t h 'i ~ +~ we.,. -e.v-.:'~ (1 J \') f~~ J S flu J.eft dovvtf't7q-+es. 3

4 3. In class, we talked at length abut the hydrlysis f carbxylic acid derivatives, where reactin with water gives the parent carbxylic acid. Please explain the bserved reactivity trend f the carbxylic acid derivatives tward hydrlysis. (5 pints) c~l~ 15 nt '1~1.(e~s6\~k/ white ~ ca.tl/hk hvr1~ 1\ 11-n>~ I s f~ t.eu-ej. fhe bek, ('('sy"''tr (Q. Pe d (Q. VJ Y"\ ~.lj,"1 +~ fk Hie en bd Yl'jl ~) (es ~ e[ecknp ~\lll fa-1'\) f-(.a(i~ ~l 'u 1 I --;) we( W>'l ~., \A.C lt~h; l 5Vt (h a: \ ~ver~ r ~ 4

5 4. Fill in the bx with the apprpriate reactant, reagent, r prduct. Sme bxes require mre than ne step. (22 pints) A) Frm hmewrk, prblem NaOEt,.. EtOH 1. NaOH 2eq~ ~ OEt 2. HCI/H HCI/H 2 0. heat B) 1. LOA, -78 C ~ )lci 0 C) D) ~MgBr ~OCH' (2 equiv) ~ 5

6 E) ~N/ H F) 1. NaOEtlEtOH 2. CH 3 -Br 3. NaOH 4. HCI 5. Heat G) Frm hmewrk, prblem ~H 1. NaOH.. H) Frm hmewrk, prblem 18.25D :J... )~H ~OEt

7 I) Frm hmewrk EtO~OEt NaOEt.. J) Frm hmewrk, prblem 17.18D Br I. fr\~b I Q;~aY" 2. c";). 'J.\1C\(H':l0 0QOH 1'-'::: OCH 3 OCH 3 5. In the presence f a base such as NaGEt, the fllwing reactin prceeds t frm the bicyc1ic prduct that is shwn belw. Sme f the carbn atms have been labeled frm 1-9 in the starting material. Number the atms in the prduct that crrespnd t thse numbered in the starting material. (4 pints) a 4 3 Eta a 7

8 l~i;;xl, UJC1W LUI;; HJt:\';HC1HJ~JH IUJ UJt: Jt:C1\"UUH HJ jjjuuji;;hj J \. VVHJ"'JJ JJa~ U~~JJ J"'-UJQVYJJ U,-JUvv h including all participating lne pairs, applicable frmal charges, and required arrw pushing t indicate flw f electrns. (8 pints) 8

9 7. (Frm hmewrk, prblem 19.26) Shw hw yu might bring abut the fllwing cnversin. (7 pints) a CP ) W () CJ II 9

10 8. An ester can be hydrlyzed t the parent carbxylic acid under acidic cnditins. Draw this mechanism, making sure t shw all participating lne pairs, applicable frmal charges, and required arrw pushing t indicate flw f electrps. (6 pints) ).l~ 10

11 9. Treatment f an acid chlride with an alchl in the presence f pyridine frms an ester, as shwn belw. Draw the mechanism fr this reactin, including all participating lne pairs, applicable frmal charges, and required arrw pushing t indicate flw f electrns. Be sure t accunt fr the frmatin f the side prduct. (8 pints) a ~OH a.- + GJ ~CI )lo~ 0 H Ne CI 1\1 O e 0 0~7 ~U > A~ ~ U( tj.~ ft., U: 8 ~ OH ~ /-... ~( 11

12 10. Using nly benzyl alchl as a surce f carbn atms, shw hw yu might bring abut the fllwing cnversin. (8 pints) V OH ~~(J ~~r ll? ~1fJk \)~8r (1. ~t,) ~) fif//hl 12

13 11. Using nly ethyl acetate as a surce f carbn atms, shw hw yu might bring abut the fllwing cnversin. (7 pints) 0 )(OEt 0 0 ~~Et OEt 0 ~L+ Na.O + C(+O~ ""7 C> Q ~[t D ~ +- ~ 0 ~O(t OK CJ E+ 6r00[-( 13

14 12. Using a retrsynthetic apprach, give the letters (A-L) and the name f the reactin (a list f reactins names is prvided) needed t make each f the prducts listed. Each letter can be used nce, mre than nce, r nt at all. There is an extra cpy f the bx f ptins n the last page f the test fr yu t tear ff and use. (12 pints) a ~ H A a B a ~ ~H ~8' D E F a 0 a a ~~ 0/ G H I a /'--)U~ ~OH ~ J K L List f Pssible Reactin Names: Aldl Reactin Claisen Cndensatin Acetacetic Ester "Like" Synthesis Malnic Ester Synthesis Michael Additin Malnic Ester Synthesis Michael Additin Acetacetic Ester "Like" Synthesis Rbinsn Annulatin Enamine Alkylatin 14

15 I) [ Reactin Name: 1(0P'fI'50 1 fhlnlj. \~~ > Starting Material Letters: t D \ II) HO > Starting Material Letters: I f F III) I H > Reactin Name: Il,I ~'*I, Ii (J~, ~lhn I Starting Material Letters: E (Xd) Starting Material Letters: IV) > L /< \ Reactin Name: (J7 lyhcuj. IMd N-rbY\ AceJt>qUJk'c Eskf ill)' ke 11 5t ~; r$ 15

16 Starting Material Letters: V) ~ > \ y 1 G Reactin Name: L~C\~~ ~rv1f15~;hry'\ Starting Material Letters: VI) HO > I {1 f< Reactin Name: (h ~0h~ MJ-\tlOh Iha lafl1e f)~<?r 5vrrtits~ 5, BONUS QUESTION: What is the name f the greatest rck band in histry, aptly titled s by their biggest fan Dr. Anslyn? (2 pints) 16

17 ~ A B ~ ~H D E ~B' F H G H I ~OH ~ J K L List f Pssible Reactin Names: Aldl Reactin Claisen Cndensatin Acetacetic Ester "Like" Synthesis Malnic Ester Synthesis Michael Additin Malnic Ester Synthesis Michael Additin Acetacetic Ester "Like" Synthesis Rbinsn Annulatin Enamine Alkylatin 17