Problem Set 2

Honors Chemistry
DUE : Friday November 10th

On this work I have upheld Groton’s Honor Code.

NAME:

COLLABORATORS :

Problem Score
1.  __________ / 20
2.  __________ / 20
3.  __________ / 20
4.  __________ / 20
5.  __________ / 20
___________________ / 100
 Honors Chemistry 2017
Pset 2 1
Brianna is studying volcanic activity on the island of Java. She collects samples on three layers of igneous rock from the island
and measures the amount of 40K and 40Ar in the samples.

a.  Using Brianna’s data, calculate the age of the three layers of igneous rock. The data will be sent to you Surface
directly by LV in an excel file named HCHEM_PSET2_2017_1_LastName.xlsx.
A
Make sure to use the data that I sent you. Send the file back to LV with your analysis included. (17 pts)
b.  Write a brief explanation of what the data tells us about the rock layers. (3 pts) B

Core

________ / 20 pts
 Honors Chemistry 2017
Pset 2 2
You are given a 12.10 g mixture of an unknown metal X complexed with sulfate, Xn(SO4)m , and with chloride, XpClq.
•  The mixture is dissolved in 100 mL of water.
•  When an excess of 1 mol/L BaCl2 is added to the mixture 15.911 grams of sulfate salt are collected.
•  When an excess of 1 mol/L AgNO3 is added to the mixture 3.428 grams of chloride salt are collected.
a.  Determine the identity of the unknown metal. (10 pts)
b.  Calculate the concentration of the metal in the original 100 mL solution. (5 pts)
c.  Provide a detailed experimental method for confirming the identity of unknown metal X. (5 pts)

________ / 20 pts
 Honors Chemistry 2017
Pset 2 3
Ryan Shenvi’s lab at the Scripps Research Institute recently published total syntheses of two natural product analogs. 20-nor-
salvinorin A is a kappa-opioid receptor agonist that may find use as a non-addictive analgesic. 11-O-debenzoyltashironin is a
small molecule that promotes the growth of neuronal projections known collectively as neurites.

Based on the structures and combustion analysis determine the molecular formula and molecular mass of 20-nor-salvinorin A
and 11-O-debenzoyltashironin. Make sure to show all your work. (20 pts)
O

O O
H H HO
O
20-nor-salvinorin A 11-O-debenzoyltashironin.
O Combustion Analysis. OH
O
Combustion Analysis.
H
O Mass of Sample = 0.1000 g Mass of Sample = 0.1000 g
O
Mass of CO2 = 0.2314 g Mass of CO2 = 0.2376 g
O O HO
Mass of H2O = 0.0560 g Mass of H2O = 0.0729 g
20-nor-salvinorin A 11-O-debenzoyltashironin.

Ohtawa, Masaki, et al. J. Am. Chem. Soc 139.28 (2017): 9637-9644.

Roach, Jeremy, et al. ChemRxIV (2017) doi:10.26434/chemrxiv.5318188.v2 ________ / 20 pts
 Honors Chemistry 2017
Pset 2 4
Shown below are the last five steps in the Shevni lab’s synthesis of 11-O-debenzoyltashironin.
In paranthesis is the percent yield for each step.

O N
O
1. K 2CO3, MeI 1. Me 2NH, Me 3 Al, PhMe,
O OH O
acetone, 22 oC 100 oC
O
O H O O oC
2. 2 M NaOH (aq) 2. TMSCl, Et 3N, CH 2Cl 2, 0
O O
22 oC then SOCl 2, -78 oC
O (76%) then MeOH, CH(OMe)3
p-TsOH H 2O, 22 oC
A B (42%) C
LiNMe 2, HMPA
THF, 0 to 22 oC
then O 2, P(OEt) 3, 0 oC
(82%)

H N
HO O HO
1. Co(acac) 2, PhSiH 3, O 2 4 M HCl (aq)
OH HO O O
O PhMe/CH 2Cl 2, 22 oC THF, 80 oC
O O
O 2. pTsOH H 2O, 22 oC (49%)
O
(72%)
HO
11-O-debenzoyltashironin. E D

a.  How many moles of A would the lab need to start with to produce 2.25 mmol of 11-O-debenzoyltashironin? (10 pts)

b.  Identify the steps that involve an oxidation of the reactant. (hint, compare the products and the reactants). (10 pts)

Ohtawa, Masaki, et al. J. Am. Chem. Soc 139.28 (2017): 9637-9644. ________ / 20 pts
 Honors Chemistry 2017
Pset 2 5
Mass spectrometry is used to calculate the molecular mass and to elucidate the structure of molecules.

73
100
C3H5BrO2
90

80

70
Relative Intensity

60

50

40
152 154
30

20
107 109 135 137
28 45 55
10

0
1 11 21 31 41 51 61 71 81 91 101 111 121 131 141 151 161
M/Z (amu)

a.  Assign each of the labeled peaks in the mass spectra with a chemical formula (e.g. 15 amu = CH3). (10 pts)
b.  Based on your analysis which of the following structures matches the mass spectra. Briefly explain your logic. (5 pts)
A H H B H H C O
H
Br C O O C Br HO C
C C H H C C C C H
H H O H H O H H Br

c.  Set up the following calculation. How many milliliters of 0.52 mol/L C3H5BrO2and how many milliliters of water do you
need to prepare 0.012 L of 0.032 mol/L C3H5BrO2? (5 pts)

________ / 20 pts