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ORGANIC FALL 2019 LANEY COLLEGE CHEM 12A (L1/L1LA/L1LB) INSTRUCTOR: STEPHEN CORLETT EXAM 1, Part II (150 points) Page 1 of 5

Name ______Key ORGANIC CHEMISTRY FALL 2019 LANEY COLLEGE CHEM 12A (L1/L1LA/L1LB) INSTRUCTOR: STEPHEN CORLETT EXAM 1, Part II (150 points) Page 2 of 5

1. The compound called DMAP is shown below.

a. Indicate the hybridization for each of the atoms. b. Identify what type of orbital each of the lone pair of is in. c. Indicate whether each lone pair of electrons is localized or delocalized. (15 points)

a ~ . a lone pair -

is in a orbital 2 p ← 2 and delocalized go

2 ← lone pair is go 2$ in an spa orbital and is localized

2. For the structure shown below, push electrons to show the other form. Circle the major resonance form and provide the reason for your choice. (15 points)

" " o? - .

f ¥7man.

3. Consider the three compounds below. Indicate which compound has the largest pKa and which has the smallest pKa. Use ARIO to justify your answers (don’t forget about the conj. bases) (20 points) smallest middle pka largest pka pka

O O O It H H ① ~ o_O →NH 150

Is more least stable most stable since than element is electronegative 3rd row and more able N so better able to , ingest a -0 support -0 charge to support charge ORGANIC CHEMISTRY FALL 2019 LANEY COLLEGE CHEM 12A (L1/L1LA/L1LB) INSTRUCTOR: STEPHEN CORLETT EXAM 1, Part II (150 points) Page 3 of 5

4. Given the information about the equilibrium (Keq), answer the following:

a. Which ion, A or B, is the stronger ? - B

b. Which , or DMAP, is the stronger ? - DMAD c. Suggest a reason for the difference in acidity of A and B. d. Use pushing to show the proton transfer in the acid/base reaction. (20 points)

→

to resonance c . enhanced A due the stability of

÷:*:*.mu - hence less acidic acid

i÷÷÷i

5. Trifluoromethanesulfonic acid (aka triflic acid) is one of the strongest known . Use ARIO to explain the difference in acidity between methanesulfonic acid and trifluoromethanesulfonic acid (don’t forget about the conjugate base). (15 points)

atom effect and are resonance effect the same for both

buses conjugate O H -0 IF I

- - s - o * - s o_O ttzc t H F y , O ft o

←

of *dative effect of , group base so stabilizes this conjugate , than methane sulfonic more stable from

- is mid so the acid stronger ORGANIC CHEMISTRY FALL 2019 LANEY COLLEGE CHEM 12A (L1/L1LA/L1LB) INSTRUCTOR: STEPHEN CORLETT EXAM 1, Part II (150 points) Page 4 of 5

6. Strychnine is an exceedingly toxic compound – ingesting as little as 20 mg can be fatal. Circle and name as many of the common functional groups as you can. (25 points)

wrought gamine ① alkene O o amide ether

7. The two valid resonance structures for trimethylphosphine oxide are shown below. Which one is the major one. Clearly explain the reasoning for your choice. (20 points)

0

the structure is best charge separated because

3rd 2nd elements do not form row and row

stable it bonds which is shown in the structure , on the right .

Mm " A atween and so . very poor weep extra orbital node orbitals due to the 3p ggg ④ of the 3p orbital . ORGANIC CHEMISTRY FALL 2019 LANEY COLLEGE CHEM 12A (L1/L1LA/L1LB) INSTRUCTOR: STEPHEN CORLETT EXAM 1, Part II (150 points) Page 5 of 5

8. For the following reactions, for the reactants (items on the left), identify the Lewis acid and the Lewis base. Show with electron pushing how the reaction proceeds. For question c., also show what the expected product would be – the Lewis acid/base complex that is formed. (20 points)

= L = acid . A L . Lewis base . B Lewis .

L - L A . B . . ←-•*a ④

L . A L - . B V .

: El :

. . -0 . . @

- :c - Atl - c! oh ! , * I L - B :c . : ✓ . ! k " . A . " complex ORGANIC CHEMISTRY FALL 2019 LANEY COLLEGE CHEM 12A (L1/L1LA/L1LB) INSTRUCTOR: STEPHEN CORLETT t EXAM 1, Part I (-150 points) so points Page 1 of 5

Name ______key (Lao B ) ORGANIC CHEMISTRY FALL 2019 LANEY COLLEGE CHEM 12A (L1/L1LA/L1LB) INSTRUCTOR: STEPHEN CORLETT EXAM 1, Part I (150 points) Page 2 of 5

1. The natural product citral is found in many essential oils, particularly in citrus oils. You might guess what it smells like. (10 points)

° ← 2 lone pairs of . % electrons were not shown originally !

a. What is the molecular formula for citral? Go Hyo

b. How many electrons does citral have? Are they all shown in the structure above? If not, what’s missing? Go 40

16 72 valence elections His o id - 2 lone pairs on ! > z oxygen 2. Draw a that has the molecular formula C4H6O2 that has only the “common” functional groups discussed in Chapter 2 (it could have more than one!).

a. It should be drawn using bond-line structures with any lone pairs of electrons clearly shown. b. Label the functional groups

Only draw one molecule! (points will be lost for multiple structures…) (20 points)

O O acid H carboxylic H # # H OH H alkene # aldehy other lots of possibilities

ORGANIC CHEMISTRY FALL 2019 LANEY COLLEGE CHEM 12A (L1/L1LA/L1LB) INSTRUCTOR: STEPHEN CORLETT EXAM 1, Part I (150 points) Page 3 of 5

3. For the following ,

i. Draw bond-line drawings that show the expected geometry (use dashes and wedges where necessary). ii. In your structures, clearly show any lone pairs of electrons. iii. Indicate whether the molecule has a permanent moment (µ ≠ 0 D), if it does, then indicate the direction of the overall dipole, or if it doesn’t have a permanent dipole moment (µ = 0 D) (30 points)

a. C2H5NO2 ② d i 1nF ? . M¥0 :& : Xs -0

b. C3H5Br " s i : : *

or or Erna ofFit D- in : . . TB all m to

c. CH2N2 H her . . . or W - CEN : N=c=N/ or ' ¥m=÷i0 ' ' I-D H d Td H = o m # O m

4. Assign formal charges (if non-zero) to the appropriate atoms in the following molecules (or ions). (Note that all lone pairs of electrons are shown in each structure) (10 points)

to -0 @

5. (NH3) has a dipole moment (µ) of 1.42 D, whereas nitrogen trifluoride (NF3) has a value of 0.234 D. Suggest a reason for the dramatic difference between these two otherwise similar molecules. (Hint: carefully consider the structure, polarity, and geometry) (15 points)

A. at m=h4D - at N X m 0.23413 µ µ¥µ ¥ , +1 n'Hit :r÷¥¥?i÷ : H have -f all bond the n bond dipoles partially subtract the lone components in the same cancel ( ) from are which reduces direction so additive pair dipole , the and contribute to the large mall dipole of the molecule dipole moment ORGANIC CHEMISTRY FALL 2019 LANEY COLLEGE CHEM 12A (L1/L1LA/L1LB) INSTRUCTOR: STEPHEN CORLETT EXAM 1, Part I (150 points) Page 4 of 5

6. Consider the structure shown below. (20 points)

sea see ← ?⇐ I ¥÷ ( gp2 2 Sp

a. Label the hybridization for each of the atoms (except ).

b. What type of (s) do the three lone pairs on the oxygen occupy? (are they all the same?) is Two lone pairs are in orbitals - the third Lone pair spa in orbital so that c. Show the other resonance form using electron pushing. a 2p it resonance can be in with the it bond .

7. Ketene, shown below, is a very reactive compound used for preparing esters and amides, and also, derivatives of amino acids. For every bond in the molecule, indicate which type of bond it is (π or s) and what atomic orbitals are used to form them (hybridized orbitals are considered atomic orbitals). Also, what type of orbitals are the oxygen lone pairs of electrons in (are they both in the same type?). (note: there are 5 unique bonds that need identifying). (25 points)

)

m.bneggpairszfofwocspzt.gs ? o + Is orbital ← ( sp )

↳ 82 Sp Spa ←

up -, Zp )

± + ) . Zp

ORGANIC CHEMISTRY FALL 2019 LANEY COLLEGE CHEM 12A (L1/L1LA/L1LB) INSTRUCTOR: STEPHEN CORLETT EXAM 1, Part I (-150 points) 130 pointy Page 1 of 4

Name ______key (Iof A ) ORGANIC CHEMISTRY FALL 2019 LANEY COLLEGE CHEM 12A (L1/L1LA/L1LB) INSTRUCTOR: STEPHEN CORLETT EXAM 1, Part I (150 points) Page 2 of 4

1. The natural product carvone is found in many essential oils, particularly in spearmint oil. You might guess what it smells like. (10 points)

These lone pair of

< e- not . electrons were

' a shown originally

a. What is the molecular formula for carvone?

cloth 40 b. How many valence electrons does carvone have? Are they all shown in the structure above? If not, what’s missing? " ° Go " ' 4 so violence elections Hey . O de

2. Draw a molecule that has the molecular formula C5H8O3 that has only the “common” functional groups discussed in Chapter 2 (it could have more than one!).

a. It should be drawn using bond-line structures with any lone pairs of electrons clearly shown. b. Label the functional groups.

Only draw one molecule! (points will be lost for multiple structures…) (20 points)

e - : i. OH :O "

. . It " \ OH ? tons of TX" IT other ↳,

' . . possibilities - O :

ORGANIC CHEMISTRY FALL 2019 LANEY COLLEGE CHEM 12A (L1/L1LA/L1LB) INSTRUCTOR: STEPHEN CORLETT EXAM 1, Part I (150 points) Page 3 of 4

3. For the following molecules,

i. Draw bond-line drawings that show the expected geometry (use dashes and wedges where necessary). ii. In your structures, clearly show any lone pairs of electrons. iii. Indicate whether the molecule has a permanent dipole moment (µ ≠ 0 D), if it does, then indicate the direction of the overall dipole, or if it doesn’t have a permanent dipole moment (µ = 0 D) (30 points)

a. CO2 - co - o : m

- b. C2H2 - CIC H H = m 0

c. CH2N2 (this one has formal charges, that must be shown) but there are other , possibilities k " Mc=N①=n÷° - en : H i - ' . mini . ,m=c=n H µ = # O M¥0 µ o m 4. Assign formal charges (if non-zero) to the appropriate atoms in the following molecules (or ions). (Note that all lone pairs of electrons are shown in each structure) (10 points)

④ -0

5. Ammonia (NH3) has a dipole moment (µ) of 1.42 D, whereas nitrogen trifluoride (NF3) has a value of 0.234 D. Suggest a reason for the dramatic difference between these two otherwise similar molecules. (Hint: carefully consider the structure, polarity, and geometry) (15 points)

AE TIE N * ← * ' " H * * f. ¥s" ¥ F * H E F

the N- F bond dipoles all bond and " dipoles ' ' subtract from the (one pair contribute in direction and reduce the same cone pair overall dipole ORGANIC CHEMISTRY FALL 2019 LANEY COLLEGE CHEM 12A (L1/L1LA/L1LB) INSTRUCTOR: STEPHEN CORLETT EXAM 1, Part I (150 points) Page 4 of 4

6. Consider the structure shown below. (20 points)

2 ' q2 ( a- go - O ! \ . as It ° D -01 \-\ 3 ✓ . . Sp £ E ① gp3

a. Label the hybridization for each of the atoms (except hydrogen).

b. What type of atomic orbital(s) do the three lone pairs on the oxygen occupy? (are they all the same?)

2 two in is in of them are go orbitals one a 2p orbital , c. Show the other resonance form using electron pushing.

is on the left ) ( major form

7. Cyanogen bromide, shown below, is a reagent used for cleaving proteins at specific locations and is useful for protein sequencing. For every bond in the molecule, indicate which type of bond it is (π or s) and what atomic orbitals are used to form them (hybridized orbitals are considered atomic orbitals). Also, what type of orbital is the nitrogen lone pair of electrons in. (note: there are 4 unique bonds that need identifying). (25 points)

f r ( sp + sp )

go orbital Nb it ( zp ) , Ny FA ← Sf - it ( Zpz t2pz)

o ( gp2 - sp ) 4

hate the Br is hybridized 2 resonance with Sp since it can have the neighboring [is?⇐n? - ii.⇒ai:o)