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Ch. 6 - Stereoisomerism: Arrangement of Atoms in Space
Mullins - Organic Chemistry: A Learner Centered Approach 1st Edition
Mullins1st EditionOrganic Chemistry: A Learner Centered ApproachISBN: 9780137566471Not the one you use?Change textbook
Chapter 5, Problem 32

Imagine a sample that is enriched in the R enantiomer. If the % ee of the sample is 83%,
(a) what percent of the mixture is racemic?
(b) What is the ratio of R to S?

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1
Step 1: Understand the concept of enantiomeric excess (% ee). Enantiomeric excess is defined as the difference in percentage between the two enantiomers in a mixture. Mathematically, % ee = |%R - %S|, where %R and %S are the percentages of the R and S enantiomers, respectively.
Step 2: Recognize that a racemic mixture contains equal amounts of R and S enantiomers (50% R and 50% S). If the sample is enriched in the R enantiomer, the % ee represents the excess of the R enantiomer over the racemic portion of the mixture.
Step 3: To determine the percentage of the mixture that is racemic, use the relationship: % racemic = 100% - % ee. Substitute the given % ee value (83%) into this equation to calculate the racemic portion.
Step 4: To find the ratio of R to S, first calculate the percentages of R and S in the mixture. Use the formula: %R = (% ee + % racemic / 2) and %S = (% racemic / 2). These equations account for the enantiomeric excess and the racemic portion.
Step 5: Once you have %R and %S, calculate the ratio of R to S by dividing %R by %S. This will give you the ratio of the R enantiomer to the S enantiomer in the mixture.

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Key Concepts

Here are the essential concepts you must grasp in order to answer the question correctly.

Enantiomers and Enantiomeric Excess (ee)

Enantiomers are pairs of molecules that are non-superimposable mirror images of each other, often referred to as R and S configurations. Enantiomeric excess (ee) quantifies the purity of one enantiomer over the other in a mixture, expressed as a percentage. An ee of 83% indicates that the sample is predominantly composed of one enantiomer, which is crucial for determining the composition of the mixture.
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Calculating Enantiomeric Excess and Observed Rotation

Racemic Mixture

A racemic mixture contains equal amounts of both enantiomers, resulting in a 50% ee. To find the percentage of a racemic component in a mixture with a known enantiomeric excess, one can use the formula: % racemic = 100% - % ee. This concept is essential for calculating the proportion of the racemic mixture in the given sample.
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Calculating EE, percent of each enantiomer, and sketching mixture

Ratio of Enantiomers

The ratio of R to S enantiomers in a mixture can be derived from the enantiomeric excess. If the ee is known, the ratio can be calculated using the formula: R:S = (ee + 100)/2 : (100 - ee)/2. This ratio provides insight into the relative amounts of each enantiomer present, which is critical for understanding the stereochemistry of the sample.
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Related Practice
Textbook Question

Using a 1.0-cm polarimeter cell and a solution prepared by dissolving 2.54 g of glucose in 1 L of H₂O, the specific rotation of d-glucose was calculated to be +52.7° at 20 °C using the sodium D line as the source of light. What was the observed rotation of the solution?

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Textbook Question

A student wanted to measure the specific rotation of the following propionate derivative (density = 1.12 g/ml).

A sample of the pure compound was placed in a 10.0-cm polarimeter tube, and using the sodium D line, the observed rotation at 20°C was determined to be +46.6° . What is the specific rotation of the propionate derivative?

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Textbook Question

(S)-Propranolol, a drug used for the treatment of anxiety, has a specific rotation of -25.5° . Attempting to prepare it in enantiopure form, a chemist produced a compound that gave a specific rotation of -18.3° . What is the ratio of (S)- to (R)-propranolol produced by the chemist?

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Textbook Question

(R)-Selegiline, a monoamine oxidase (MAO) inactivator, was approved by the FDA in 1989 for the treatment of Parkinson's disease. In pure form, it has a specific rotation, [α]²⁰D = - 11.0°. What is the expected specific rotation of a mixture containing 64% S and 36% R?

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Textbook Question

Cholesterol (50 mg) was dissolved in 10 mL of chloroform and placed in a 1.0-cm polarimeter cell. This solution produced an observed rotation (using the sodium D line at 20°C ) of - 1.58° . What is the specific rotation of cholesterol?

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Textbook Question

For the molecules shown,

(i) count the number of stereocenters present and

(ii) draw all possible stereoisomers.

(iii) Identify the relationships between stereoisomers as enantiomers or diastereomers.

(a)

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