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Show how you would accomplish the following transformations. Some of these examples require more than one step.

Short Answer

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(a)

(b)

(c)

(d)

(e)

Step by step solution

01

Synthesis of epoxides

Epoxides can be easily made from alkenes and they undergo a number of useful synthetic reactions. Epoxides are known as valuable synthetic intermediates.

02

Peroxyacid epoxidation

Peroxyacids can be used to convert alkenes to epoxides. The epoxides are known to open to a glycol if the reaction occur in an aqueous medium. For this reason, strong acids are avoided for the synthesis of epoxides. meta-chloroperoxybenzoic acid (mCPBA) can be used for epoxidations process because of its desirable soluble properties. mCPBA is weakly acidic peroxy acid and is soluble in aprotic solvent like CH2Cl2. The reaction proceeds in a one-step concerted manner where the stereochemistry of any substituents around the double bond is maintained.

03

Synthesis

(a) 2-methylpropene reacts with meta-chloroperoxybenzoic acid (mCPBA) in a one-step concerted process to give 2,2-dimethyloxuirane.

(b) 1-phenylethanol on treatment with H2SO4 forms styrene, which on further treatment with meta-chloroperoxybenzoic acid (mCPBA) gives 2-phenyloxirane .

(c) 5-chloropent-1-ene on treatment with BH3, THF/H2O2, OH- forms 5-chloropent-1-ol which loses a hydroxide ion to give tetrahydropyran

(d) 5-chloropent-1-ene on treatment with Hg(OAc)2, H2O/NaBH4 forms 5-chloropent-2-ol which loses a hydroxide ion to give 2-methyltetrahydrofuran.

(e) 2-chlorohexan-1-ol loses a hydroxide ion to give 1,2-epoxyhexane.

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Most popular questions from this chapter

Mustard gas, Cl-CH2CH2-CH2CH2-Cl, was used as a poisonous chemical agent in World War I. Mustard gas is much more toxic than a typical primary alkyl chloride. Its toxicity stems from its ability to alkylate amino groups on important metabolic enzymes, rendering the enzymes inactive.

  1. Propose a mechanism to explain why mustard gas is an exceptionally potent alkylating agent.
  2. Bleach (sodium hypochlorite,NaOCl, a strong oxidizing agent) neutralizes and inactivates mustard gas. Bleach is also effective on organic stains because it oxidizes colored compounds to colorless compounds. Propose products that might be formed by the reaction of mustard gas with bleach.

Write structural formulas for the following compounds

  1. methyl isopropyl ether (b) di-iso-butyl ether (c) 2-methoxyoctane

(d) diallyl ether (e) allyl ethyl ether (f) cycloheptane oxide

(g) trans-2,3-epoxyheptane (h) (2R,3S)-2-ethoxypentan-3-ol (i) cis-2,3-dimethyloxirane

(Another true story) An organic lab student carried out the reaction of methyl magnesium iodide with acetone (CH3COCH3), followed by hydrolysis. During the distillation to isolate the product, she forgot to mark the vials she used to collect the fractions. She turned in a product of formula C4H10Othat boiled at 350C.The IR spectrum showed only a weak O-Hstretch around 3300 cm-1, and the mass spectrum showed a base peak at m/z 59.The NMR spectrum showed a quartet (J = 7Hz) of area 3at δ1.3Propose a structure for this product, explain how it corresponds to the observed spectra, and suggest how the student isolated this compound.

Show how you would synthesize the following ethers in good yields from the indicated starting materials and any additional reagents needed.

(a) Cyclopentyl n propyl etherfromcyclopentanolandpropan-1-ol.

(b) n-butyl phenyl etherfromphenolandbutan-1-ol.

(c) 2-ethoxyoctanefrom anoctene

(d) 1-methoxydecanefrom adecene

(e) 1-ethoxy-1-methylcyclohexanefrom 2-methylcyclohexanol.

(f) trans-2,3-epoxyoctane from octane-2-ol.

In 2012, a group led by Professor Masayuki Satake of the University of Tokyo reported the isolation and structure determination of a toxin from a marine algal bloom that decimated the fish population off the New Zealand coast in 1998. Extensive mass spectrometry and NMR experiments ultimately led to the structure shown below, named Brevisulcenal-F. (See Journal of the American Chemical Society, 2012, 134, 4963-4968.) This structure holds the record for the largest number of fused rings, at 17.

Brevisulcenal-F

a. How many ether groups are present?

b. How many alcohol groups are present? Classify the alcohols as 1o or 2o or 3o.

c. Are there any other oxygen-containing functional groups? Which, if any?

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