Contents Chapter 1 Chapter 2 Chapter 3 Chapter 4 Chapter 5 Chapter 6 Chapter 7 Chapter 8 Chapter 9 Chapter 10 Chapter 14 Chapter 12 Chapter 13 Chapter 14 Chapter 15 Chapter 16 Chapter 17 Chapter 18 Chapter 19 Chapter 20 Chapter 21 Chapter 22 Chapter 23 Chapter 24 Chapter 25 Chapter 26 Chapter 27 Chapter 28 Chapter 29 Chapter 30 Structure and Bonding Acids and Bases Introduction to Organic Molecules and Functional Groups Alkanes Stereochemistry Understanding Organic Reactions Alkyl Halides and Nucleophilic Substitution Alkyl Halides and Elimination Reactions Alcohols, Ethers, and Related Compounds Alkenes Alkynes, Oxidation and Reduction Mass Spectrometry and Infrared Spectroscopy Nuclear Magnetic Resonance Spectroscopy Radical Reactions Conjugation, Resonance, and Dienes Benzene and Aromatic Compounds Reactions of Aromatic Compounds Carboxylic Acids and the Acidity of the O-H Bond Introduction to Carbonyl Chemistry; Organometallic Reagents; Oxidation and Reduction Aldehydes and Ketones—Nucleophilic Addition Carboxylic Acids and Their Derivatives— Nucleophilic Acyl Substitution ‘Substitution Reactions of Carbonyl Compounds at the a Carbon Carbonyl Condensation Reactions Amines Carbon-Carbon Bond-Forming Reactions in Organic Synthesis Perioyclic Reactions Carbohydrates Amino Acids and Proteins Synthetic Polymers 17-4 20-4 24-4 224 23-4 24-4 25-1 26-1 274 28-4 29-1Structure and Bonding 1~1 Chapter 1: Structure and Bonding Chapter Review Important facts © The general rule of bonding: Atoms strive to attain a complete outer shell of valence electrons (Section 1.2). H “wants” 2 electrons. Second-row elements “want” 8 electrons, nonbonded electron pair Usneuralaone "1 ‘ 8 2 1 Number of nonbonded ‘electron pare 2 [The sum (# of bonds + #of lone paits) = 4 for all elements except H, © Formal charge (FC) is the difference between the number of valence electrons on an atom and the number of electrons it “owns” (Section 1.3C). See Sample Problem 1.3 for a stepwise example. - _ {number of electrons Daniton: . ‘an atom “owns” Examples : wo ae = oo I. i I i sc share tecrons. + C hare 9 elcome 1S ehars 6 letons. LERane Aclecrons, 16 Syne electrons TERRE Sunshaied eccrons tree 1eoaet Some" closer © Curved arrow notation shows the movement of an electron pair. The tail of the arrow always begins at an electron pair, either in a bond or a lone pair. The head points to where the electron pair “moves” (Section 1.6). Use an electron pir to form a double bond. Mow a lain sancti / © Electrostatic potential plots are color-coded maps of electron density, indicating electron rich (red) and electron deficient (blue) regions (Section 1.12).Chapter 1-2 The importance of Lewis structures (Sections 1.3-1.5) A properly drawn Lewis structure shows the number of bonds and lone pairs present around each atom ina molecule. Ina valid Lewis structure, each H has two electrons, and each second-row element has no more than eight. This is the first step needed to determine many properties of a molecule. p—[seomeiny_} Tinea, trigonal pianar, or tetrahedral} (Section 1.7) ee ent eee ees toh a Lewis Resonance (Section 1.6) The basic principles: © Resonance occurs when a compound cannot be represented by a single Lewis structure, ‘* Two resonance structures differ only in the position of nonbonded electrons and x bonds. The resonance hybrid is the only accurate representation for a resonance-stabilized compound. A hybrid is more stable than any single resonance structure because electron density is delocalized. . - \a ict evecare nase ‘The difference between resonance structures and isomers: © Two isomers differ in the arrangement of both atoms and electrons. * Resonance structures differ only in the arrangement of electrons. ig & on OCH eh 2Q-CH, SO-H tom! tmee}! Geometry and hybridization The number of groups around an atom determines both its geometry (Section 1.7) and hybridization (Section 1.9). Number of Geometry Bond angle‘) Hybridization Examples groups _ 2 linear 180 Bella, HC=CH Sp 3 trigonal planar 120 sp BPs, CHz=CH2 4 tetrahedral 109.5 p> CH, NHa, H20Structure and Bonding 1-3 Drawing organic molecules (Section 1.8) Shorthand methods are used to abbreviate the structure of organic molecules. oO ee oh ey so ence vescare cre ee A carbon bonded to four atoms is tetrahedral in shape. The best way to represent a tetrahedron is to draw two bonds in the plane, one in front, and one behind. Four equivalent drawings for C H # HH 4 I I y oy ce pee a Hey f Each drawing has two solld lines, one wedge, and one dashed wedge. Bond length ‘* Bond length decreases as you go from left to right across a row and increases down a column of the table (Section 1.7A). gh > stew > SoH eek Belectrons TN" x Selections per N BS olectons 10 x electrons perO == Bolectons 22 electrons total [3] Use the shortcut to figure out how many bonds are needed. * Number of electrons needed if there were no bonds: ais x Zelectons perH = 6 electrons 4 second-ow elements x Belton pereloment «= + 2 electrons 38 electrons needed it there were no bonds: * Number of electrons that must be shared: 98 electrons 22 electrons 16 electrons must be shared © Every bond requires two electrons, so 16/2 = 8 bonds are needed. [4] Draw all possible Lewis structures. * Draw the bonds to the H’s first (three bonds). Then add five more bonds. Arrange them between the C’s, N, and O, making sure that no atom gets more than eight electrons. There are three possible arrangements of bonds; that is, there are three resonance structures. * Add additional electron pairs to give each atom an octet and check that all 22 electrons are used. 4 4 i H-G-N 4 HEN CO 4 : Bonds to's sdded. 7 Hoon at H Allbonds craw in Electron pals dawn in. ‘Three arrangements possible, Every atom has an octaChapter 1-6 © Calculate the formal charge on each atom. * You can evaluate the Lewis structures you have drawn. The middle structure is the best resonance structure, because it has no charged atoms. Note: This method works for compounds that contain second-row elements in which every element gets an octet of electrons. It does NOT necessarily work for compounds with an atom that does not have an octet (such as BF), or compounds that have elements located in the third row and later in the periodic table. Practice Test on Chapter Review 1a, Which compound(s) contain a labeled atom with a +1 formal charge? All lone pairs of electrons have been drawn in, Ore OR tpn 4, Both (1) and (2) have labeled atoms with a +1 charge, 5. Compounds (1), (2), and (3) all contain labeled atoms with a +1 formal charge. b. Which of the following compounds is a valid resonance structure for A? Gots A dels SoH, Oct Bor inl Soren a Soo ait A 4, Both (1) and (2) are valid resonance structures for A. 5. Cations (1), (2), and (3) are all valid resonance structures for A. c. Which species contains a labeled carbon atom that is sp® hybridized? eee Orres sO) 4. Both (1) and (2) contain labeled sp” hybridized atoms. 5. Species (1), (2), and (3) all contain labeled sp” hybridized carbon atoms.Structure and Bonding 1-7 d. Which of the following compounds has a net dipole? 1, CHsCH2NHCH2CHs 4. Compounds (1) and (2) both have net dipoles. 2. CHsCH2CH20H 5. Compounds (1), (2), and (3) all have net dipoles, 3, FCH2CH2CHaF 2. Rank the labeled bonds in order of increasing bond length. Label the shortest bond as 1, the longest bond as 4, and the bonds of intermediate length as 2 and 3. Ho=e 3. Answer the following questions about compounds A~D. CO or or a. What is the hybridization of the labeled atom in A? b. What is the molecular shape around the labeled atom in B? c. In what type of orbital does the lone pair in C reside? . What orbitals are used to form bond [1] in D? €. Which orbitals are used to form the carbon-oxygen double bond [2] in D? 4, Draw an acceptable Lewis structure for CHsNO3. Assume that the atoms are arranged as drawn, Hoo HCONO 4 Answers to Practice Test Lad 2A-1 0 3.asp 4. One possibility: 5, bl B-4 ». trigonal planar cl c-2 c. sp? a5 D-3 . Cap-Cop? ©. Csp-Oxp?, Cp-OpChapter 1-8 Answers to Problems 1.1 Two isotopes differ in the number of neutrons. Two isotopes have the same number of protons and electrons, group number, and number of valence electrons. The mass number is the number of protons and neutrons. The atomic number is the number of protons and is the same for all isotopes. Nitrogen-14 | Nitrogen-13 ‘a, number of protons = atomic number for N=7 7 7 ‘b. number of neutrons = mass number — atomic number 7 6 ‘c. number of electrons = number of protons 7 fi <. group number 5A 3A e. number of valence electrons 5 3 1.2 Tonic bonds form when an element on the far left side of the periodic table transfers an electron to an element on the far right side of the periodic table. Covalent bonds result when two atoms share electrons. nt 7 a Br H-G-C-H Naty Nat b. H-¢-6-# i oN ‘onic ne | Fao n-# bonds are ‘AIC-H end c-c oovalent joie Aone bonds Bonds ae covalent, ‘Tonio a cova 1.3. Atoms with one, two, three, or four valence electrons form one, two, three, or four bonds, respectively. Atoms with five or more valence electrons form [8 — (number of valence electrons)] bonds. a. O 8~6 valence e- = 2 bonds c. Br 8~7 valence e~ b. Al 3 valence e-=3 bonds d. Si 4 valence e~= bond bonds 1.4 [1] Arrange the atoms with the H’s on the periphery. [2] Count the valence electrons. [3] Arrange the electrons around the atoms. Give the H’s 2 electrons first, and then fill the octets of the other atoms. [4] Assign formal charges (Section 1.3C) M1 HH 22} Count valence &: 1 HH ante e-used a “HOCH 2Cxde= 8 H-G-G-H Al second-ow elements x ie ave anon wn Sueen i" mere » mH {21 Count valence e 4 4 HONH 10xde= 4 H-G-N-H + H-G-Hi-H Sixt im a) HH Hy ha Ha veal 12.6 used. Neneeds 2 more electrons for an octet,Structure and Bonding 1-9 mou [21 Count vatenes mH 4 Hoa tCx4e- H-G-cl = + H-G-d: SHxte- ie H tone ie a ‘otal 8. used. Complete octet Clneeds 6 more ‘lecrons for an octet. 1.5 Follow the directions from Answer 1.4. a. HON HON ‘Count valence @- H-C-N > H~ 1Cx4e- THxte b. HCO Hoo 4 Ho & HOCH.COH =H OCC OH 4 Complete octets. 1.6 Formal charge (FC) = number of valence electrons — [number of unshared electrons + (4\(number of shared electrons)] x 5-[0+ 126) =+1 o-R empl =s a | HON-H b, {CHs-N. /s S-[0+(VQNe=+1 — 4-(0+ (120) OH [+ (iVa=0 — 6-[8+ (12) 17 H a. CHO™ [1] HC © 2} Count valence e~ fey Ai 4Chapter 1-10 b. Hoe IN] H © C2} Count valence e- I) H-c-¢ ——+ H-c 20x4e-=8 detuecd THxte=1 totale” = 9 [Add 1 for) charge = 10 (CH NHS)’ ot] HH 8 WH HONH wb HH aa ‘Subtract 1 for (+) charge = 14 er ined, (CHW) Ut] [2] Count valence e- 8 4 M icraleaman ce ecaT4 =i i diate 4 ¢ H ANx5 5 H Toate Te toe sed Compt att and Pai for (9) charge = 14 Som sage 18 . ® ee eR s(iee=1 eRe tigei=1 8+ (0 19 a. CzH,Clz (two isomers) Court valence eH eortes 8 fh ainie = 4 H-G-¢ eH 340 tre isomers) Count vance " Sorte way eon ie Hp ppEn wen up P-G-fw ha han ieee ©. Cats (two isomers) ‘Count valence &- 3Cx4e-=12 GHxte-=6 totale =18 1.10 Two different definitions: © Isomers have the same molecular formula and a different arrangement of atoms, * Resonance structures have the same molecular formula and the same arrangement of atoms,Structure and Bonding 111 atthe end Nin the midlo 2lone pais Stone pairs j itferont arrangement of tome = Isomers same arrangement of atom: resonance structures, 1.11 Isomers have the same molecular formula and a different arrangement of atoms. Resonance structures have the same molecular formula and the same arrangement of atom: 2ione pairs Slone pars ‘same arrangement of stom 183 b. GH CHy—C~GH Ww A a ce CHO, (C2Hts02)- L a ferent molecular formulas = neither ferent arrangement of atoms = isomers 1.12. Curved arrow notation shows the movement of an electron pair. The tail begins at an electron pait (a bond or a lone pair) and the head points to where the electron pair moves. rad) Sax >) " one a hoa CH, H ‘The net charges the same ‘The net charge isthe same Inboth resonance structures, in both resonance structures. 1,13 Compare the resonance structures to see what electrons have “moved.” Use one curved arrow to show the movement of each electron pair. o-Ps_5-OHs a a oe om dnp ae setae H Two electron pairs move: ‘wo curved arrows,Chapter 1-12 1.14 To draw another resonance structure, moye electrons only in multiple bonds and lone pairs and keep the number of unpaired electrons constant. 1.13 A “better” resonance structure is one that has more bonds and fewer charges. The better structure is the major contributor and all others are minor contributors. To draw the resonance hybrid, use dashed lines for bonds that are in only one resonance structure, and use partial charges when the charge is on different atoms in the resonance structures. H 4 4 i Cy oN Hy Ne, HOC HoeG. UH 2 Meee Mow on, GHG oe efg 4 4 Hon HOW Alatoms have ces “These wo resonance stuctres ae equivalent yi: one more bond ‘Tey both have one erarge and te sare nub ie major contbutor of pos” Thay ar equal eontibutrs foto hoi. ts yt 4 Hab be aCe age aoa 1.16 ot, om le a hans ony oH a b. The N atom in B has four atoms and no lone pairs, so there is no way to move the electrons to give the N another bond. 1.17 To predict the geometry around an atom, count the number of groups (atoms + Ione pairs), making sure to draw in any needed lone pairs or hydrogens: 2 groups = linear, 3 groups = trigonal planar, 4 groups = tetrahedral‘Structure and Bonding 1-13, Nas 2 atoms + 2 lone pas 4 groups =lelranedral or bent molecular 3 groups = wigonal planar | shape) 4 groups = teahedeal {4 oroups = ternal ue \ a. ‘CHy-6-CHy ae ans ‘3 groups = trigonal planar 2 groups = tnear 4 groups = tetrahedral 4 groups = tetrahedral 4 groups = tetrahedral 7} ee co b. CHs—O-CHy i ' 4 groups = tetrahedral (or bent molecular shape) ee 1.18 To predict the bond angle around an atom, count the number of groups (atoms + lone pairs), making sure to draw in any needed lone pairs or hydrogens: 2 groups = 180°, 3 groups = 120°, 4 groups = 109.5°. “This Chas 3 groups, so 2 groups = 180" both angles se 120" Nb “This Chas 4 groups, so both angles are 109.5" 1.19 To predict the geometry around an atom, use the rules in Answer 1.17. 4 groups oe bent molecular shape) 4 4 groups HH HOP HH /tevaneta: i ee! (8-G-6-$-6-0% cy H0-¢-¢ oo anda 44 i Sgrouns ‘groups, groups al plan tovahodral roa eee (or bent molecular shape) ‘enanthotoxin 1.20 Reading from left-to-right, draw the molecule as a Lewis structure. Always check that carbon has four bonds and all heteroatoms have an octet by adding any needed lone pairs,Chapter 1-14 (Cri CCHIOHICHCHs (HOCH, ,CHICH,,CICH),CH.CH, " / (cHy),cHoHo \ =e Uh ea eH-G-e-8H | CHyCHS).CHICHs)2 1.21 Draw the Lewis structure of lactic acid. H Lee CHCHOH|CO;A — H-G-C—C~ Ha 1.22 In shorthand or skeletal drawings, all line junctions or ends of lines represent carbon atoms. The carbons are all tetravalent. fo feo ectnorte (2-atryheny ¢ethoxychnamate) svobenzone ye TOs CatesOs 1.23 In shorthand or skeletal drawings, all line junctions or ends of lines represent carbon atoms. Convert by writing in all carbons, and then adding hydrogen atoms to make the carbons tetravalent, Hotty Wo Ect H-0-G-H Aa 1.24 Ho. Ho. ] auine Sw CattedaOe molecu formulaStructure and Bonding 1-15 1.25 A charge on a carbon atom takes the place of one hydrogen atom. A negatively charged C has one lone pair, and a positively charged C has none. positive charge negative charge positive charge negative charge no lone pas ‘one lone pair no lone pals ‘one lone pair no H's needed one H needed one H needed lone H needed 1.26 Draw each indicated structure, Recall that in the skeletal drawings, a carbon atom is located at the intersection of any two lines and at the end of any line. ° & (CHa), =CH(CH,).CHy = Nw Ai = ersstorscomen A 4} cok eee oes “ i HO|oH.CHeCHCO.CHIC b. . sone OK = HO[CH,),cH« CHale - ~ oe) Oe 4 Ho ° RO Ha 1.27 To determine the orbitals used in bonding, count the number of groups (atoms + lone pairs): 4 groups = sp*, 3 groups = sp”, 2 groups = sp, H atom = 1s (no hybridization). igle bonds are G, and all double bonds contain one and one 7 bond. All covalent Keone’ ® "HH Yu sng bond Cats a 1H tha snglebonds are [ Each G-0 bonais H7o-G-C"H Chongs, Each G-H bond is Gams, wha Tota of 10 o bonds Each © hée 4 groups and is sp" hybridized. 1.28 [1] Draw a valid Lewis structure for each molecule. [2] Count the number of groups around each ato1 H atom = Ls (no hybridization). groups = sp*, 3 groups = sp*, 2 groups = sp, Note: Be and B (Groups 2A and 3A) do not have enough valence e* to form an octet, and do not form an octet in neutral molecules. 4 a. [1] H-CBe- unt groups around e AIC bor se (i) H-C—Be—H [2] Count groups around each atom: BB) tC stone: Oost 4 Bo-H bond: Bear Hie Bo has 2 bonds.Chapter 1-16 CH b. [1] CHy—B-CHy {2} Count groups around each atom: [8]. ACH bonds: Caste ee OSE eS B forms 3 bonds. CHy-B-CH, seroups 3 groups sp sp? 1a GNP H-C-8-¢-H a Count groups around each atom: 11 ALC bode Cute face ee Stance Sixt aa KH 476-8-6-H Suid seibe 2 sgrae 2 1.29 To determine the hybridization, count the number of groups around each atom: 4 groups = sp, 3 groups = sp”, 2 groups = sp, H atom = 1s (no hybridization). a CH © Che cra iF Soups soups groupe 2 groups 4 roups 2 gcups 7 ae) st set - 1,30 a ), $0 It is sp* hybridized. Fe 9 hyvzed Co are labeled. d, e. Draw in all H atoms to count 6 bonds. Each C-H and C-C single bond is a bond. Each double bond has one ¢ bond and one m bond. WH 8 bt coe-bn Aadawana sobons ps 1.31 Single bonds are weaker and longer than double bonds, which are weaker and longer than triple bonds. Increasing percent s-character increases bond strength and decreases bond length.‘Structure and Bonding 1-17 “ H A ( ) c \ eit / or of On t ot a ple bond SShover bond 25% charactor The tripe bond is shorter ‘than the double bond, is ey ag «OOF c Ora N Notts NatHie 25% s-character 5% scharactor ‘The CaN bond ie shortr Shorts bond than the C-N bond, 1.32 Electronegativity increases from left-to-right across a row of the periodic table and decreases down a column. Look at the relative position of the atoms to determine their relative clectronegativity. most electropositve ‘most lectroposive most eloctroposive most slecroposive | most ‘aaa [remepeoreome most ateeaate m= rare Y Se<8<0 p, NaxP, NH, (2.1) CH=CH Lewis acid (2.8) electron pair _—_a proton, or an unfilled BPs, AICh, HCI, acceptor _valence shell, or a partial CHsCO2H, H20 (+) charge Lewis base (2.8) electron pair alone pairora bond — “OH, “OCH, H, “NE, donor CH=CH? ‘Acid-base reactions [1] A Bronsted-Lowry acid donates a proton to a Bronsted-Lowry base (2.2). oH acid base conjugate base conjugate acid == wes ‘* Electron-rich species react with electron-poor ones. ‘* Nucleophiles react with electrophiles. Important facts © Definition: pX,=—log K,. The lower the pKa, the stronger the acid (2.3).Chapter 2-2 © The stronger the acid, the weaker the conjugate base (2.3). Increasing pK, Increasing pK, of the conjugate acid ee > CH=CH, ch, Hel : - eae or Hyco; cH,=CH Pky = 44 Pke= 48 — Increasing acilty Increasing basicity ‘© In proton transfer reactions, equilibrium favors the weaker acid and the weaker base (2.4), as Taaareauioconarow] weed + Anacid can be deprotonated by the conjugate base of any acid having a higher pis (2.4). Acid Pky Conjugate base CHCO-H 48 cHCO- CHYCH.O-H 16 Crh CH.0 ‘These bases HO=cH 25 Ho=o- ‘can deprotonate HH 35 ce CHLCOnH. higher pk than (CH,CO;-H Factors that determine acidity (2.5) [1] Element effects (2.5) ‘The acidity of H—A increases both left-to-right across a row and down a column of the periodic table. Increasing electronegativty en nen es ahi Increasing acilty HF H-ol HBr HHI Increasing size Increasing acidityAcids and Bases 2-3 [2] Inductive effects (2.5B) ‘The acidity of HA increases with the presence of electron- withdrawing groups in A. ‘CH3CH,OH —_ CHyCH,O- weaker acd No alana tctronegatve atone slice ie conoeds bax - & fal crenon ——~ hed seongor alt i CF, withdraws electron density, stabilizing the conjugate base. [3] Resonance effects (2.5C) The acidity of HA increases when the conjugate base A:~ is resonance stabilized. caso 4 onsen arel strode conivgate base &

Answers to Practice Test lad 2.a.D 3.a.C 4a. b.4 bA bB Ni i: es) eBD cor « (oryeen—O—o14 A Answers to Problems 2.1 Bronsted-Lowry acids are proton donors and must contain a hydrogen atom. Bronsted—Lowry bases are proton acceptors and must have an available electron pair (either a Ione pair or a x bond). a tie iy seid seid cro, (CH C8 rotons pan fone pe eee wo folabess Baa bese nbonds é f : crore, on, Yoon, rot abase=ro lone pas basen pals on 0 Sextonde base—lone pa on Ox bod SST, ats Soe ame MaMa 2.2 A Bronsted—Lowry base accepts a proton to form the conjugate acid. A Bronsted-Lowry acid loses a proton to form the conjugate base. a Nis NHe » Hor Be o> ——— Hoi Hs0,- ———+ soe (CHys0=0 ———» (ci,0-0H CHs0H oH0-Chapter 2-6 23a, True. OHy=CHy + HY ——» cH,CHS base conjugate acis . False. CHyCH2" cannot be the conjugate base of CHsCHs" because they both have the same number of H’s and a conjugate base must have one fewer H. c, False, CH2=CHlz and CHsCH2 differ by the presence of H’, not H d. True. Remove Ht F cH,=cH, | OE cHy=CH acid conjugate base e. True, CHycH, + HY > CH.CH, base conjugate aig 2.4 The Bronsted-Lowry base accepts a proton to form the conjugate acid. The Bronsted-Lowry acid loses a proton to form the conjugate base. Use curved arrows to show the movement of electrons (NOT protons), Re-draw the starting materials if necessary to clarify the electron movement. a aa + NOL Ke SS 5 NXE 2.5 To draw the products: [1] Find the acid and base. [2] Transfer a proton from the acid to the base. [3] Check that the charges on each side of the arrows are balanced. 9 a a + HO—CH (-)1 charge on each side of b + He (-)1 charge on each side acid base Ly - a © Otte Bg Dot + GF etree onenensice acid ae & AB oso EAL Bt + “O80 etna one so — aAcids and Bases 2-7 2.6 Draw the products in each reaction as in Answer 2.4. ; H .OH OH) | VV aT en, He Wb ce 4 BO HL 8 ee © Qu Dine 2.7 The smaller the pKa, the stronger the acid. The larger the Ke, the stronger the acid. on om a CHOC, or OHCHOH Cr Cr ph=i8 pk,=50 i 10-10 40-4 smaller PK stronger acid larger Ki, stronger acid 2.8 To convert from Ka to pK, take (-) the log of the Ks; pKa =—log Ka. To convert pXs to Ka, take the antilog of (-) the pKs. a. Ky=10- 10% Ky=52x10% —b. pKee7? —pky=t— pky=3.2 | PKA=10 | pK= 21 pK =4.3 echo K, ie Ky=saxt04 2.9 Since strong acids form weak conjugate bases, the basicity of conjugate bases increases with increasing pKa of their acids. Find the pKs of each acid from Table 2.1 and then rank the acids in order of increasing pKs. This will also be the order of increasing basicity of their conjugate bases. a. ___ Increasing aciaty » Increasing acy ——_—“_“" a nssing acidity HzO NHs CH, HCeCH CH=CH, CH, PK. 157 38 50 Phe= 25 ak 80 ‘conjugate bases: OH -NHp “CHy ‘conjugate bases: “CaCH -CH=CHe “CHy es eee Increasing basicly Inereasing basicly 2.10 Use the definitions in Answer 2.9 to compare the acids. The smaller the pK, the larger the Ks and the stronger the acid. When a stronger acid dissolves in water, the equilibri the right, HOH (CHyycoout formic cia pivalie aid PK= 98 Phy =50 ‘a. smaller pky = larger Ke . weaker acid = stronger conjugate baseChapter 2-8 2.11 To estimate the pKa of the indicated bond, find a similar bond in the pKs table (H bonded to the same atom with the same hybridization). Oe owl For NH pk Is 38. For CH,CH.OH, For CH,COOH, pK, is 4.8. estimated pi, = 38 PKI 16 ‘estimated pK, = 5 estimated px, = 16, 2.12 Label the acid and the base and then transfer a proton from the acid to the base. To determine if the reaction will proceed as written, compare the pK; of the acid on the left with the conjugate acid on the right. The equilibrium always favors the formation of the weaker acid and the weaker base. a nC Equilibrium favors base conjugate base conjugate acid —_‘the starting materials, 38 weaker acid + OH boo + bee ki m Eauibvium favors acid base conjugate base conjugate acid the starting materia. PK, = 50 PK,= 15.7 weaker acid a & CHCO.H + © CHCH AF «= = CHO} + HCH GH Equibrum favors acid base conjugate base conjugate acid «(MP Poduets. PK= 48 PK = 16 weaker acid 4 + CHCH OH = HG + chon: Equilium favors the starting materials. conjugate acid ‘conjugate base PK 2.13 An acid can be deprotonated by the conjugate base of any acid with a higher pKs. HCN Base Conjugate acid pK, pk, = 25 NaH io 35 ‘Any base having a conjugate NazCO5 Hod 10.2 |OnlyNaH and NaNH, are ‘cid with ap higher than NaOH Hd 187 _|stotgenouan te dovictonate 25 can his acd Nani Nig 'S7__Jacetonite Baas NaHCO, H.08, a 2.14 The acidity of HZ increases left-to-right across a row and down a column of the periodic table. Sa Ceol ein (@), ope cm choomn Sta tei iis farther to the right in only C-H bonds ORES SYN mr sementatyteaam e ara penta ree et the stronger acid,Acids and Bases 2-9 215 i Because sid neoases across a A S.,, tom and down a eau the oer at me slay a NH eO-H CoH 2.16 Look at the element bonded to the acidic H and decide its acidity based on the periodic trends, Farther to the right and down the periodic table is more acidic. most acidic most acide rome a NOH b HO Ne SON n | Molecule contains C-H Molecule contains C-H, Molecule contains C-H and N-H bonds, and O-H bonds. N-H, and O-H bonds, Nis farther ight; therefore, ls farther right therefore, Os farthest right therefore, N-H hydrogen is the most acl. (0-H hydrogen isthe most acicic (0-H hydrogen is tho most acidic 2.17 The acidity of HA increases left-to-right across the periodic table, Pseudoephedrine contains C-H, N-H, and O-H bonds. The O-H bond is most acidic. pseudoephedtine Skeletal structure 2.18 Compare the most acidic protons in each compound to determine the stronger acid. / 4 Am on > op ACOH Sits ' c-Hbond peli: ¢-Hbend © aarti Ni tar oth gt in ‘nope ae poe al venge ald stronger acid 2.19 More electronegative atoms stabilize the conjugate base, making the acid stronger. ‘Compare the electron-withdrawing groups on the acids below to decide which is a stronger acid (more electronegative groups = more acidic). ° ° "OH it ca .OH ‘oH a i. C4 7 » gAlon oo Mie Tore asic a iis closer Is farther rom tho F is more slacronegative than Cl, making the tone BF bona, i fatner ram (O-Hibond inthe acid on theright more acide. ‘more actaChapter 2-10 2.20 2.21 2.22 2.23 2.24 No, more acidic 'NOgis electron withdrawing, making the ‘0-H band in the acd on the right more acil More electronegative groups stabilize the conjugate base, making the acid stronger. HOCH,CO.H CH,CO.H an achydroxy acid ‘acetic acid ‘The extra OH group contains an electronegative 0, which ‘stablizes tho conjugate base, ‘stronger acid, HBr is a stronger acid than HCI because Br is farther down a column of the periodic table, and the larger Br” anion is more stable than the smaller CI- anion. In these acids the H is bonded directly to the halogen. In HOC! and HOBr, the H is bonded to O, and the halogens Cl and Br exert an inductive effect. In this case, the more electronegative CI stabilizes “OCI more than the less electronegative Br stabilizes OBr. Thus, HOCI forms the more stable conjugate base, making it the stronger acid. The acidity of an acid increases when the conjugate base is resonance stabilized. Compare the conjugate bases of acetone and propane to explain why acetone is more acidic. Pe a i Bt ot anata eis ¢ 2b * os more sane conjugate base HCH, cry * “Ci Os” “CHe —"Restone fe more acide. acetone ne resonance structure places the (-) charge on the more pk, = 192 ‘stacronegative Owlom, Tiss eepedisly good bose fs cnjcH.ct, —2—- cryctiite only one Lows stucture less Sabie conjgate base propane Peeso (Poy C-H born te starting ‘material can be removed ) The acidity of an acid increases when the conjugate base is resonance stabilized. Acetonitrile has a resonance-stabilized conjugate base, which accounts for its acidity. 4 peb-can: 2. ‘Te negave charge i stabized by ; b>a lamrt eet Te mos! sole poon has acted econance esto won u a itis removed, making its conjugate base the most stable, ho ab 0: ae sh sche resonance stbitzaion cookgate base — negative cary on et rserae Sevres ere : inate (mes ale er er Nw ‘TRS aes) ost ce ‘9 conjugate base OH no resonance stabization, but by toss of (): negative charge on O, an electronegative atom e - - 1s,, This conugate base has two resonance conyte base we Ain Structures, but one places a negate. ba ae charge on. 2 62 Lh G2 i Cort Supivacaine This lone pair is delocalized by resonance, so itis ess ‘avaliable o donate to an acid, making I less bas. 2.63 Lewis bases are electron pair donors: they contain a lone pair or a x bond. Brensted-Lowry bases are proton acceptors: to accept a proton they need a lone pair or a x bond. This means Lewis bases are also Bronsted-Lowry bases. 20:-— one pats on © a i . 6 Hoon lone psig onci nether =nolone pairs Bonds ‘both ‘oembonds both 2.64 A Lewis acid is an electron pair acceptor and usually contains a proton or an unfilled valence shell of electrons. A Bronsted-Lowry acid is a proton donor and must contain a hydrogen atom. All Bronsted—-Lowry acids are Lewis acids, though the reverse may not be true. a. Ho bole «. 80 oF; both Lewis aca Lewis aca nether confine a unfit vlence untied valonce vo tf erunled ‘shollon C shell on 8 Valence shell‘Chapter 2-22 2.65 Label the Lewis acid and Lewis base and then draw the products. f & ofa 8 A u new bond 108:6H Coe > NE naw bone Lewis base Lewis acid Lewis base Lewis acid 2.66 A Lewis acid is also called an electrophile. When a Lewis base reacts with an electrophile other than a proton, it is called a nucleophile, Label the electrophile and nucleophile in the starting materials and then draw the products. “ACh, ae ‘ i a 8 Oe > HE ae ao ructopnie lca peas ES rucleophile olectrophile 2.67 Draw the product of each reaction. ° N - H SoH, + — 3 7CHs ae e. Ks Hy a. A conjugate acid-base pair differ in the presence of a proton. A and B (or B and D) represent a conjugate acid-base pair. b. A and D are resonance structures because the atom placement is the same, but the electron pairs are placed differently. c. Aand C (or C and D) are constitutional isomers because they have the same molecular formula (CsH»NO), but the bonds are different. A and D have an N-H bond, and C has an 0-H bond.Acids and Bases 2-23 2.69 ra cin] _ ton transfer 7G 2 Los he = oi rs + HBr nucleophile electrophile 2.70 Draw the products of each reaction. In part (a), OH pulls off a proton and thus acts as a Bronsted-Lowry base. In part (b), OH attacks a carbon and thus acts as a Lewis base. ee fe 2.71 Answer each question about esmolol. most acidic Esmolol contains C-H, N-H, and O-H bonds. Since t oh F olen meee eres, 1 OH bond is most acidic, ° esmolol [Al sp? C's are indicated with an arrow. Theis the ony tigonal pyramidal atom. The d+ O's are indicated with a ().Chapter 2-24 i fs n CY) CO Bafta . i 272 Se . Ni i Ne N “OO @—Bw Ls " Path [2] is favored because a resonance-stabilized conjugate acid is formed. The N that is part of the C=N is therefore more basic. 2.73. Draw the product of protonation of either O or N and compare the conjugate acids. When acetamide reacts with an acid, the O atom is protonated because it results in a resonance- stabilized conjugate acid. a) ALeey voor Ly ‘only a minor contributor to the hybrid because of charges. | Sih eee | is less resonance stabilized than N oH a>icu, N has two resonance structures with the same number of bonds and charges, so both contribute approximately equally to the hybrid. This makes N more resonance stabilized than its conjugate base, and less willing to give up a proton than M, which has no similar resonance stabilization. Thus Mis a stronger acid than N. (Resonance structures that break the C=O bond are not drawn in this solution, because they are possible for both compounds.)Introduction to Organic Molecules and Functional Groups 3-1 Chapter 3: Introduction to Organic Molecules and Functional Groups Chapter Review Classifying carbon atoms, hydrogen atoms, alcohols, alkyl halides, amines, and amides (3.2) © Carbon atoms are classified by the number of carbons bonded to them; a 1° carbon is bonded to one other carbon, and so forth. Hydrogen atoms are classified by the type of carbon atom to which they are bonded; a 1° hydrogen is bonded to a 1° carbon, and so forth. Alkyl halides and alcohols are classified by the type of carbon to which the OH or X group is bonded; a 1° alcohol has an OH group bonded to a 1° carbon, and so forth. Amines and amides are classified by the number of carbons bonded to the nitrogen atom; a 1° amine has one carbon-nitrogen bond, and so forth, ‘Types of intermolecular forces (3.3) ‘Type of force Cause Examples __ van der Waals (VDW) Due to the interaction of temporary dipoles All organic compounds £ © Larger surface area, stronger forces 2 © Larger, more polarizable atoms, £ stronger forces B dipole-dipole (DD) _Due to the interaction of permanent dipoles (CH:):C=0, H2O 3 hydrogen bonding Due to the electrostatic interaction ofa H & (HBor H-bonding) atom in an O-H, N-H, or H-F bond with 2 another N, O, or F atom. ion-ion Due to the interaction of two ions NaCl, LiF Physical properties Property | Observation Boiling | © For compounds of comparable molecular weight, the stronger the forces the higher point the bp. GAA) Increasing strength of i ‘Increasing boling pointChapter 3-2 For compounds with similar functional groups, the larger the surface area, the higher the bp. Incroasing surface area Increasing Boling point For compounds with similar functional groups, the more polarizable the atoms, the higher the bp. CHst °c Increasing polarizability Increasing boling point Melting | For compounds of comparable molecular weight, the stronger the forces the higher point the mp. G.4B) eee vow, D> VOW, DD, HB Mw =72 Mw = 74 mp =-96°C, mp =-90 80, Increasing strength of intermolecular forces increasing melting point For compounds with similar functional groups, the more symmetrical the compound, the higher the mp. symmetry Increasing molting pointIntroduction to Organic Molecules and Functional Groups 3-3 Solubility | Types of water-soluble compounds: (3.40) | © Tonic compounds * Organic compounds having < 5 C’s, and an O or N atom for hydrogen bonding (for a compound with one functional group) Types of compounds soluble in organic solvents: + Organic compounds regardless of size or functional group «Examples: (Gente) — ~~ A rae eae Se | Key: VOW = van der Waals, DD = dipole-dipole, Hi MW = molecular weight hydrogen Bonding Reactivity (3.8) ‘* Nucleophiles react with electrophiles, ‘+ Electronegative heteroatoms create electrophilic carbon atoms that react with nucleophiles. ‘* Lone pairs and x bonds are nucleophilic sites that react with electrophiles. = ch.cH, <1 OF e 4 CH City electrophilic site Practice Test on Chapter Review 1.a. Which of the following compounds exhibits dipole-dipole interactions? 1. CHC 4, Compounds (1) and (2) both exhibit dipole-dipole interactions. 2 (cHy:0 8, CHxCHgCHz—oH 5S, Compounds (1), (2), and (3) all exhibit dipole-dipole interactions. b. Which of the following compounds can hydrogen bond both to another molecule of itself and to water? 0, och, . £ = 4. Compounds (1) and (2) can each hydrogen bond to another g molecule like itself and water. 2 WH O 5. Fach of the three compounds, (1), (2), and (3), can hydrogen bond to another molecule like itself and to water. 3. CHEN‘Chapter 3-4 c. Which of the following compounds has the highest boiling point? 1, CH3CH2CH20CH2CHs 4. (CHs):CHCH(CH:)NE2 2. CHs(CH)sCH3 5. (CHs)2CHCH(CH:)2 3. CHs(CH2)sNE2 d. Which statement(s) is (are) true about the following compounds? 1. The boiling point of A is higher than the 2 ae boiling point of B. A c 2. The melting point of B is higher than the melting point of C. 3. The boiling point of A is higher than the boiling point of D. . > 4, Statements (1) and (2) are both true. 5. Statements (1), (2), and (3) are all true. 2. Consider the anti-hypertensive agent atenolol drawn below. : cq wo; a = 8 LAA Fhe a, What is the hybridization of the N atom labeled with A? b. What is the shape around the C atom labeled with F? c. What orbitals are used to form the bond labeled with E2 4. Which bond (B, C, or D) is the longest bond? e. Would you predict atenolol to be soluble in water? £ Which of the labeled H atoms (Hs, Hp, or He) is most acidic? Answers to Practice Test Las asp b.2 trigonal planar C3 6. Cy Cys a5 4D eyes fHIntroduction to Organic Molecules and Functional Groups 3-5 Answers to Problems 3a H804 + HHH, “S28. po reaction CHcH—-BENar + Hp cHyoHy —MH po reaction 3.2 To classify a carbon atom as 1°, 2°, 3°, or 4°, determine how many carbon atoms it is bonded to (1° C = bonded to one other C, 2° C = bonded to two other C’s, 3° C = bonded to three other C’s, 4° C = bonded to four other C’s). Re-draw if necessary to see each carbon clearly, To classify a hydrogen atom as 1°, 2°, or 3°, determine if it is bonded to a 1°, 2°, or 3° C (a 1° H is bonded to a 1° C; a 2° H is bonded to a 2° C; a 3° H is bonded to a 3° C), Re-draw if necessary. re Ne re a eo! eee g aw a i Ean 0 | Pcate Or we Ke ze8 Allother Os are 2° c's, a Allothor Cs are 1" c's. ve redraw oe , [now ce He ' VHe 1H i ots cn cH AA SH ae b. [1] CHsCH_CH-CH, 2 ot)—O-H I cHy-¢—c-cHy ly one” en by OH, Wy He HH aie ny ire ae Nva ‘Alothers are 2"Chapter 3-6 3.4 A 1° ROH or RX has the functional group bonded to a 1° C; a 2° ROH or RX has the functional ‘group bonded to a 2° C; a 3° ROH or RX has the functional group bonded to a 3° C. yp Of RoR 2 3.5 Use the definitions from Answer 3.4. dexamethasone 3.6 Amines are classified as 1°, 2°, or 3° by the number of alkyl groups bonded to the nitrogen atom. 1? amine 29 amine a ba ». Rl 2° amine 12 amine 37 MO amine. ao ve ba a seateonat So? 412 alcoho! 3.8 A 1° amide has one carbon-nitrogen bond; a 2° amide has two carbon-nitrogen bonds; a 3° amide has three carbon-nitrogen bonds.Introduction to Organic Molecules and Functional Groups 3-7 3.9 Identify the functional groups based on Tables 3.1, 3.2, and 3.3. 2 alkene aT oo (Gouble bond) Ho, ctr eb, nf cto yo" Ola se _ 20H shikimie acts amie setae oonois tl (hycroxy groups) 3.10 One possible structure for each functional group: ° a aldehydo= 6 ceabonyicadd= Ge aideryde= Oa, a~A vf non oe 9 ° b. ketone = co d. ester = é UR non AL acto 3.11 One possible structure for each description: ° ° ecto NAA A ketone aldehyde ° 9 ee ha ketone A / kone kone 3.12 Summary of forces: * All compounds exhibit van der Waals forces (VDW). * Polar molecules have dipole-dipole forces (DD). * Hydrogen bonding (H-bonding) can occur only when a H is bonded to an O, N, or F. -O re » AK, - cay agate o-¢ “VOW tone ‘ outeTeans “pt nds oo YO forges Wbvvony 2h rir nae Toney amegt gese ° Soi b 4 Aa f. ie “ei portar-H and - vow co - VOW fren eur _SPMet eS on “yaa 2S na 00 ow sip ‘ane pse 0D snort no bondingChapter 3-8 3.13 3.14 3.15 3.16 One principle governs boiling point: «Stronger intermolecular forces = higher bp. Increasing intermolecular forces: van der Waals < dipole-dipole < hydrogen bonding ‘Two factors affect the strength of van der Waals forces, and thus affect bp: ‘Increasing surface area = increasing bp. Longer molecules have a larger surface area. Any branching decreases the surface area of a molecule. © Increasing polarizability = increasing bp. 2» yee 6 NNN RR t i longer molecule, more surtaco area ‘only VOW OW and 0D. higher bolting point polar, stronger intermolecular forces higher bolting point aa mas Set Oa crearaee ee (| t ‘VOW, DD, and H-bonding stronger intormolecuiar forces ‘higher boiling point 1is more polarizable. ro H-bonding higher Botting point Increasing intermolecular forces: van der Waals < dipole-dipole < hydrogen bonding g g o 8. CH HsCHy “oN Won Hy 1N-H bonds aon or hyérogen bonding no hydrogen bonding skongor Intermolecular forces weaker intermolecular forces ‘higher baling point a NN i. o } ana more polar stronger intermolecular forces ora spharcal (bonding) packs beter higher mp Tlgher mp ‘Compare the intermolecular forces to explain why sodium acetate has a higher melting point than acetic acid 2 g a A, ots 0H CcHiy""0-Nar cele ald sodium acetate 2. VOW, 0D, and H-bonding 8. VOW, DD, ionic bonds not ionic, ower meting point Bone bonds are the strongest: higher melting point.Introduction to Organic Molecules and Functional Groups 3-9 3.17 A compound is water soluble if it is ionic or if it has an O or N atom and < 5 C’s. oa ea NON oo ‘an 0 atom that nonpolar an N atom that can can Hibond with Water not water soluble bond to H.0, but >508 not water soluble 3.18 Hydrophobie portions will primarily be hydrocarbon chains. Hydrophilic portions will be polar. Circled regions are hydrophilic because they are polar. All other regions are hydrophobie because they have only C and H. ‘can H-bond to soit can H-bond to H,0 ‘ N can H-bond to H,0 D norethindrone arachidonic acid 3.19 Like dissolves like, * To be soluble in water, a molecule must be ionic, or have a polar functional group capable of H-bonding for every 5 C’s. ‘* Organic compounds are generally soluble in organic solvents regardless of size or functional group, nonpolar long hygroearon chin ° va mR - » CoO os vitamins nonpolar © viaminK, ‘ncn (ohytonuinone) soluble in water ue 10 soluble inorganic solvents to poarunatonal groups fhe polar O-3 bonds bu he and.only8 Csi the maacule impound has 10 Ce Veter insoluble 3.20 a. aes or HO” ° b. The amide, carboxylic acid, and both alcohols can all hydrogen bond with water. c. Since pantothenic acid has only nine carbons with four functional groups that can hydrogen bond, pantothenic acid is a water-soluble vitamin.Chapter 3-10 3.21 A soap contains both a long hydrocarbon chain and a carboxylic acid salt. : . . Aon CAR short chain a ‘carboxylic acid salt {onic salt t long chain Thisis a soap because it contains both @ Tong chain and a carboxylic acid sal. 3.22. Detergents have a polar head consisting of oppositely charged ions, and a nonpolar tail consisting of C-C and C-H bonds, just like soaps do. Detergents clean by having the hydrophobic ends of molecules surround grease, while the hydrophilic portion of the molecule interacts with the polar solvent (usually water). mn oO. wo { polar head este ea on ae sare ranean Water x isla Smaseatieatege Sarees ecaeaaea 3.23 . & B q = \ we norte nee ie Pare Lean rene Sardine cree Ee tron een b. Heroin can cross the blood-brain barrier more readily because it is less polar than morphine, and therefore more soluble in the nonpolar interior of the cell membrane. 3.24 The noble gas xenon consists of uncharged atoms that exhibit only van der Waals interactions, so it is very soluble in the nonpolar interior of the cell membrane. It can thus cross the blood~brain barrier and act as an anesthetic. 3.25 Because the interior of a cell membrane is nonpolar, aspirin crosses a cell membrane as a neutral carboxylic acid, by the general rule that “like dissolves like.”Introduction to Organic Molecules and Functional Groups 3-11 3.26 Electronegative heteroatoms like N, O, or X make a carbon atom an electrophile. A lone pair on a heteroatom makes it basic and nucleophilic. Pi (x) bonds create nucleophilic sites and are more easily broken than bonds, ‘nucleophilic nucleophilic. 8 i nucleophile nl be ‘835 Allone pairs—nucleophilic ses. me ‘Al stoms abled wth br ave Ye ; sloctrophiic ses C bonded to Br t electrophilic nucleophilic an C's bonded to $ are ad ‘electrophilic. 3.27 Electrophiles and nucleophiles react with each other. ° er : : ee Pa en ca cc oe lees ee ale leads acon elocrope o =<) + a) vei ruse 3.28 arise . ’ of S aromate tng vgs oot POW amine "COOH cater I J carry ai a is nat ae boxed can hogan bono Oo 0. baal ats canfyataoe sont ocd 3.29 ke 8. HOCH, oct CHO ‘Three OH's allow for H-bonding. ‘Stronger intermolecular forces mean a Pigher bp and mp. Etectrophilc carbons are labeled with").Chapter 3-12 3.30 akene ‘oH ‘The most electrophilic Cs labeled with. ‘his isomer has an OH, giving more opportunites for H-bonding (through both O and H atoms), and probably making it more HzO soluble. 3.31 Use the rules from Answer 3.2. 4 hy cr HH ae 2b, Sana bot chy “QO Hs Pl Wc. H cHs H POM i Cen Alchiyshavet"Hs.—cH,-9 ‘alGrshave 2H 4 ACH have 3 H's. 3.32. Identify the functional groups based on Tables 3.1, 3.2, and 3.3. sromaticring, ees = nang Neg j , lel Ay - anys FADO crete oun ‘romaticinge ster ‘ibuprofen pectin 6 carbone acd a amine na G if i ALi ee A at Ft be i OH 1 aero” t t signs eB eohel aare car iced places Netionctonn 3.33 A cyclic ester is called a lactone. A cyclic amide is called a lactam. amine eher ester amideIntroduction to Organic Molecules and Functional Groups 3-13 3.34 alkene £ P alcohol 2 amide he ester —) 5 Cl —1" akylhalice salinosporamide A 3.35 Draw the constitutional isomers and identify the functional groups. ° on ale eee woe ° Ay ‘carboxylic acid t emer why el 9 ‘i ser oo sont Is ; ue 3.36 Use the rules from Answer 3.12. ° P . - orn oom 0 “0 : ow ey vt vow vow dipole-dipole dipole-dipole dipole-dipole no dipole-dipole no H-bonding (no 0-H bond) no H-bonding (no N-H bond) (nonpolar GC, CH bonds) ‘no H-bonding (no O,N, F) H-bonding (OH bond) 3.37 Increasing intermolecular forces: van der Waals < dipole-dipole < H-bonding ‘a. Increasing intermolecular forces: b. Increasing intermolecular forces: Py wo ta vow vow ; ai le dipole-dipole elected Spoe-dple ciple dleChapter 3-14 3.38 1 fou] 9. b OO = (oH) M4 SO O India Indinavir can hydrogen bond to another molecule of itself at boxed-in sites. Indinavir can hydrogen bond to water at both the boxed-in sites and the sites labeled with an arrow. 3.39 ‘VDW forces; B = H-bonding; C = ion-ion interactions; D = H-bonding; E = H-bonding; F=VDW forces. °. a H _Yy ae a CY Aan 6 adohyce ketone ether leohol b. The alcohol is the highest boiling, because it is the only isomer that can hydrogen bond with another molecule of itself. 3.40 3.41 Use the principles from Answer 3.13. ~ GH Ait loa males surace area largest sutace area ‘most branching eee Increasing bolling point : OOP El vow vow vow. ata ee qr ‘H-bonding a Increasing 3.42 In CHsCH2NHCHS, there is a N-H bond, so the molecules exhibit intermolecular hydrogen bonding, whereas in (CH3)sN the N is bonded only to C, so there is no hydrogen bonding. The hydrogen bonding in CHsCH2NHCHs makes it have much stronger intermolecular forces than (CH))N. As intermolecular forces increase, the boiling point of a molecule of the same molecular weight increases.3.43 Stronger forces, higher mp. Introduction to Organic Molecules and Functional Groups 3-15 0 OH smenthone rmonthol ‘vow vow sipclea tpol-cipole tower mel pint one. higher meting pont 3.44 Stronger forces, higher mp. vow vow vow Increasing melting point 3.45 Boiling point is determined solely by the strength of the intermolecular forces. Because benzene has a smaller size, it has less surface area and weaker VDW interactions and therefore a lower boiling point than toluene. The increased melting point for benzene can be explained by symmetry: benzene is much more symmetrical than toluene, More symmetrical molecules can pack more tightly together, increasing their melting point. Symmetry has no effect on boiling point. cold toluene bp = 80°C, ‘and mp =5°C vory symmetrical ‘loser packing In soli form higher mp 3.46 Increasing polarity = increasing water solubility. O+ O- O- poet polar lar and nottbondng —Hetondng toHs0, bonding note More opportitios for H-bonding with its ‘O atom and is Hon 0.Chapter 3-16 3.47 Look for two things: © To H-bond to another molecule of itself, the molecule must contain a H bonded to O, N, or F. * To H-bond with water, a molecule needs only to contain an O, N, or F. ‘Only (¢) can H-bond to another molecule Ike ist. “These molecules can H-bond with water, All ofthese ©. CHsCH;CONHs molecules have an O orN atom. b.(CHSCHN © CHsCH.CONH, 6. CH;CH;COOCH, 3.48 Draw the molecules in question and look at the intermolecular forces involved. ‘90 H bonded 0. © on H bonded to 0: Loa od hydrogen bonding lath ether butanol VOW forces VOW forces. dipole-dipole forces atl tres * Both have < 5 C's and an electronegative O atom, so they can H-bond to water, making them soluble in water. * Only butan-1-ol can H-bond to another molecule of itself, and this increases its boiling point. 3.49 Use the solubility rule from Answer 3.19. on 04 ° oH a «Ho ° 0 Ho” “on le catfeine sucrose ‘many polar bonds with O ‘many polar bonds with N and O atoms 10's and 12 Cs ‘many opportunites for H-bonding ‘many opportunites for H-bonding with HzO water soluble water soluble on ‘carotatoxin smestranol + polar funcional group oy but >10 C's 2 polar functional groups ot water soluble ‘but> 10.08. rot water solubleIntroduction to Organic Molecules and Functional Groups 317 3.50 Water solubility is determined by polarity. Polar molecules are soluble in water, while nonpolar molecules are soluble in organic solvents. ee er — ba l 2 ; Ey vane oom ee eea aoe ea ray EE ee ancy eee ay aati Itis also soluble in organic solvents because it Is organi, but is probably more soluble in HzO. 3.51 Compare the functional groups in the two components of sunscreen. Dioxybenzone will most likely be washed off in water because it contains two hydroxy groups and is more water soluble. — dioxybonzone {wo ketones two hyaroxy groups fone ether cone ketone ‘one other ‘more water soluble 3.52 Because of the O atoms, PEG is capable of hydrogen bonding with water, which makes PEG water soluble and suitable for a product like shampoo. PVC cannot hydrogen bond to water, so PVC is water insoluble, even though it has many polar bonds. Because PVC is water insoluble, it can be used to transport and hold water. a” i on 4 10 H-bonding tbond ~~ pro 04 woe aaaa polyethylene alyco)) polyviny! chore) PEG PVC. water soluble water insoluble 3.53 Molecules that dissolve in water are readily excreted from the body in urine, whereas less polar molecules that dissolve in organic solvents are soluble in fatty tissue and are retained for longer periods, Compare the solubility properties of THC and ethanol to determine why drug screenings can detect THC and not ethanol weeks after introduction to the body.Chapter 3-18 a CD ' a ioe fH as ener nc ee fae tice orice fn, ty se ore eee sea Soluble in organic solvents and therefore soluble in fatty tissue. Due to their solubilities, THC is retained much longer in the fatty tissue of the body, being slowly excreted over many weeks, while ethanol is excreted rapidly in urine after ingestion. 3.54 Compare the intermolecular forces of crack and cocaine hydrochloride. Stronger intermolecular forces increase both the boiling point and the water solubility. onic bord _ 4 a Hy Sy a 4 Bx axe ae) LY Q 8 ceca vc cotsin cere igh el a oe The molecules are identical except for the ionic bond in cocaine hydrochloride. Ionic forces are extremely strong forces, and therefore the cocaine hydrochloride salt has a much higher boiling point and is more water soluble. Because the salt is highly water soluble, it can be injected directly into the bloodstream, where it dissolves. Crack is smoked because it can dissolve in the organic tissues of the nasal passages and lungs. cawohl iy oes aa OAR te ‘i OA ee r~nAy aA u i ° at Pe b. ° o _ ° OL ALN 18 mf nee T ' fie functional groups that have lonic sat many opportunites far H-bonding more water soluble ‘water soluble ¢. Because the hydrochloride salt is ionic and therefore more water soluble, it is more readily transported in the bloodstream. 3.553.56 3.57 3.58 3.59 3.60 Introduction to Organic Molecules and Functional Groups 3~19 Use the rules from Answer 3.26. aie ae - elie ws EEE meet a a a. CHa Gr lecrophie t electophic eae Allthe C=C's are ‘electrophilic ae (All one pairs on O and Care nucleophile.) » Ove —« . +o ——+ no coe rucleohic ruceopile nlephi » Cy th me ot . Per nacleoptise ueolnue o=>e=nie electopie More rigid cell membranes have phospholipids with fewer in the molecule, making the phospholipids pack less tightly. Phospholipids without C= pack very tightly, making the membrane less fluid and more rigid. ‘The double bonds introduce kinks in the chain, ‘making packing ofthe hydrocarbon chains less fffciont. This makes the cell membrane formed fe Pa tennn| iy / / SS Bis ionic, so it does not “dissolve” in the nonpolar interior of a cell membrane and it cannot cross the blood-brain barrier. A is a neutral organic molecule with polar bonds, so it can enter the nonpolar interior of the cell membrane and cross the blood-brain barrier. 2 amine a ao eee 3 amie = aromatic ing aromatic lng —*Chapter 3-20 ©. Quinapril can hydrogen bond to water at all N and O atoms (boxed in). 4. Quinapril can hydrogen bond to acetone at its 0-H and N-H bonds (shown with arrows). e. The most acidic H is the lone H bonded to O, which is part of a carboxylic acid. £. The most basic site is the N atom of the amine (circled). 3.61 v armatietng ab. 7 “i ener —> 0f N=" amine oN ketone —+ 0 \ done 3” lho! c. The lone OH proton is the most acidic site. d. The lone N atom is the most basic site, e. The N atom is surrounded by three atoms and a lone pair (four groups), so it is sp? hybridized. £. Oxycodone contains seven sp” hybridized C’s labeled with gray circles. 3.62 Because the O atom in tetrahydrofuran is in a ring, the C atoms bonded to it are kept away from the lone pairs on O. This allows the O atom to more readily hydrogen bond with water, thus increasing its solubility in water. \g’ + — Electron pairs are more exposed. This facitates H-bondingIntroduction to Organic Molecules and Functional Groups 3-21 3.63 amide amine cei at v4 ©: font aan nope tnd sto N ic) Sh | hysrogen bonding possible ° WH N somatic ting i O aromatic rng : most basic atom bets [6 i ‘TheN atom ofthe amide is ess basic because the lone pails par of resonance with the G=0. C ‘Aloms that can hydrogen bond to H,0 are boxed in. Elecrophiis carbone ae labeled wih (). ost acct H, pky~ 25, 'AIHS are bonded to C's. Removal of th Hon the C adjacent othe C=O resus ina resonance ‘sabilzed anion, d.Fentanyt exhibits van der Waals and iple-dpole interactions but no hydrogen bonding, because tore no H bonded f0O oN 3.64 oH Onn OH Oy ot. OY ‘cHo F 4 CHO et O ‘The OH and CHO groups are close enough that they can The OH and the CHO are too far intramolecularly H-bond to each other. Because the two _apart to intramolecularly H-bond polar functional groups are involved in intramolecular H- to each other, leaving more bonding, they are less available for H-bonding to H20. opportunity to H-bond with, This makes A less H20 soluble than B, whose two solvent. functional groups are both available for H-bonding to the H20 solvent. 3.65 «2. melting point ZA 0H Fumatc acid he its two larger COOH groups on opposite Ho” ‘ends of the molecule, and in this way lean pack betlor inf Inallatice than maleic acid, giving ita higher mp. fumarie acid . solubity Hott Stow Maleic acid is more polar, giving it yoaterH,0 solubly. The bond apoles in 0° hi 1 mars afd cancel maleic acidChapter 3-22 ©, removal ofthe fist proton (pK) wo" yo 0 0 [os 01 proton oo \i alee sl nstnleurH boing stbcn tn coop base sr eves ‘omoved, main fai sed more sede ha ran oo 4. removal ot the second proton (oK2) oo ‘0,0 t Now the sianion i holdin close proximity inmalec ci, and this destabilizes the conjugate base. Thus, removing the second H in male ‘0s harder, making ft @ weaker acd than ‘marie aca Tor emoval of tho second proton. Intramolecular H-bonding ‘snot possible here. “The two negative charges are much farther ‘apart. This makes the dianion trom fumatie ‘acid more stable and thus pk, is lower for fumarie acid than malele acAlkanes 4-1 Chapter 4: Alkanes Chapter Review General facts about alkanes (4.1-4.3) Alkanes are composed of tetrahedral, sp? hybridized C’s. There are two types of alkanes: acyclic alkanes having molecular formula CyH2y +25 and cycloalkanes having molecular formula CyHz». © Alkanes have only nonpolar C-C and C-H bonds and no functional group, so they undergo few reactions. © Alkanes are named with the suffix -ane. Names of alkyl groups (4.44) a ee wo om _ cnoncny, = ont -™ c aa coh une A | meso cone ‘isobutyl (Hy. eg it isopropyl tertbuty i Conformations in acyclic alkanes (4.9, 4.10) a © Alkane conformations can be classified as staggered, eclipsed, anti, or gauche depending on the relative orientation of the groups on adjacent carbons. HH 4 | CHy H a H H 4. 4 HK. H Oy | et | et | fe, H CH CH © Dihedral angle=0° |e Dihedral angle= 60° |e Dihedral angle of |* Dihedral angle of 2 2 CHs’s = 180° CHs’s = 60° # A staggered conformation is lower in energy than an eclipsed conformation. «An anti conformation is lower in energy than a gauche conformation.Chapter 4-2 ‘Types of strain © Torsional strain—an increase in energy due to eclipsing interactions (4.9). © Steric strain—an increase in energy when atoms are forced too close to each other (4.10), ® Angle strain—an increase in energy when tetrahedral bond angles deviate from 109.5” (4.11). ‘Two types of isomers [1] Constitutional isomers—isomers that differ in the way the atoms are connected to each other (4.1). [2] Stereoisomers—isomers that differ only in the way atoms are oriented in space (4.13B). Oo Lie trans aaa Tsomere, stereoisomers ‘Conformations in cyclohexane (4.12, 4.13) Cyclohexane exists as two chair conformations in rapid equilibrium at room temperature, Each carbon atom on a cyclohexane ring has one axial and one equatorial hydrogen. Ring-flipping converts axial H’s to equatorial H’s, and vice versa. ‘An axial H fips equatorial be rot An, SO yin Te An equtl ips ax + In substituted cyclohexanes, groups larger than hydrogen are more stable in the more roomy equatorial position, wae CH pn oat | Bp ae OH 95% 5%Alkanes 4-3 * Disubstituted cyclohexanes with substituents on different atoms exist as two possible stereoisomers. * The cis isomer has two groups on the same side of the ring, either both up or both down. ‘¢ The trans isomer has two groups on opposite sides of the ring, one up and one down, CH, 1, Aand C are stereoisomers. 4, Statements (1) and (2) are both true. 2. Band D are identical 5. Statements (1), (2), and (3) are all true. 3. A and B are stereoisomers. b, Which of the following statements is true about cis-I-isopropyl-2-methyleyclohexane? 1. The more stable conformation has the isopropyl group in the equatorial position and the methyl group in the axial position, 2. The more stable conformation has both the methyl and isopropyl groups in the equatorial position, 3. cis-1-Isopropyl-2-methyleyclohexane is a stereoisomer of trans-1-isopopyl-3-methyl- cyclohexane. 4, Statements (1) and (2) are true. Statements (1), (2), and (3) are all trueChapter 4—4 c. Rank the following conformations in order of increasing energy. cH Hy Lorch, ace chic. 4 Chet, CHG Gu.cHs a e c L.CAlkanes 4-5 5. Consider the following disubstituted cyclohexane drawn below: OL a. Draw the more stable chair conformation for the cis isomer. b. Draw the more stable chair conformation for the trans isomer. Answers to Practice Test Lad 2... S-isobutyl-2,6- 3. a. identical 4A3 Sa, dimethyl-6- B4 propyldecane C2 bl b. L-sec-butyl-4- b. constitutional = D-I propyleyclooctane isomers 2 ¢. stereoisomers b. Answers to Problems 4.1 The general molecular formula for an acyclic alkane is CnH2n+2- Number of C atoms =n 2n+2 [Number of H atoms 23 2(23) +2 48 25 2(25) + 52 27 227) +2= 56 4.2. 2-Methylbutane has 4 C’s in a row with a 1 C branch.Chapter 4-6 4.3. Constitutional isomers differ in the way the atoms are connected to each other. To draw all the constitutional isomers: [1] Draw all of the C’s in a long chain, [2] Take off one C and use it as a substituent, (Don’t add it to the end carbon: this re-makes the long chain.) [3] Take off two C’s and use these as substituents, etc. Five constitutional isomers of molecular formula CeHyg [11 ong chain [2] with one C as a substituent fefteiy wo Co's cabethuert ee ee ae 4.4 Draw each alkane to satisfy the requirements, we reorn Fe neers ie 45 per wien ce ¢ NY f ee a esto eons eae a 4.6 Use the steps from Answer 4.3 to draw the constitutional isomers. Five constitutional isomers of molecular formula C,H having one ring: QO oF ale a A Ne Le 4.7 Follow these steps to name an alkane: [1] Name the parent chain by finding the longest C chain. [2] Number the chain so that the first substituent gets the lower number. Then name and number all substituents, giving like substituents a prefix (di, tri, etc.). [3] Combine all parts, alphabetizing the substituents, ignoring all prefixes except iso.