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Organic Synthesis Techniques Overview

The document summarizes several organic chemistry reactions and techniques. It describes the borohydride reduction of 9-flourenone to reduce a ketone to an alcohol using sodium borohydride. It also discusses the carbocation rearrangement of benzopinacolone which forms rearranged products through a bridged intermediate. Finally, it outlines the oxidation of methoxybenzyl alcohol to methoxybenzaldehyde using phase transfer catalysis with sodium hypochlorite and a phase transfer catalyst.

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Geetha Vipulanandan
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31 views3 pages

Organic Synthesis Techniques Overview

The document summarizes several organic chemistry reactions and techniques. It describes the borohydride reduction of 9-flourenone to reduce a ketone to an alcohol using sodium borohydride. It also discusses the carbocation rearrangement of benzopinacolone which forms rearranged products through a bridged intermediate. Finally, it outlines the oxidation of methoxybenzyl alcohol to methoxybenzaldehyde using phase transfer catalysis with sodium hypochlorite and a phase transfer catalyst.

Uploaded by

Geetha Vipulanandan
Copyright
© Attribution Non-Commercial (BY-NC)
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as DOC, PDF, TXT or read online on Scribd

Borohydride reduction of 9-flourenone Sodium borohydrde is one of the most convenient and safest way to reduce a ketone or aldehyde

hyde into the corresponding alcohol Ketones and aldehydes can be selectively reduced in the prescence of the less reactibe carbonyl groups (esters and amides) Methods used vacuum filtration with cold methanol Note: LAH or dihydrogen with Pt, Pd or Ni could have also been used

Carbocation Rearrangement of Benzopinacolone Formation of products with structures substantially different from those of the starting materials Bridged intermediate To test for the prescence of hydroxyl group methyl red DIC test which turns the compound orange red when the hydroxyl group reacts Methods used reflux, suction dry Ethanol removes iodine color Reflux is the process of boiling reactants while continually cooling the vapor returning it back to the flask as a liquid. It is used to heat a mixture for extended periods and at certain temperatures. The reflux apparatus is shown below. A condenser is attached to the boiling flask, and cooling water is circulated to condense escaping vapors.

Oxidizing methoxybenzyl alcohol to methoxybenzaldehyde using phase transfer catalysis Microscale oxidation Oxidation occurs when oxygen is added to or hydrogen is lost from an organic molecules Primary to carboxylic groups > Chromium in the +6 oxidation state is commonly used Secondary alcohols to ketones Collins reagent > toxic, CrO3-Pyridine2 > it contains no water so it can be used to oxidize a primary alcohol to an aldehyde without further oxidation to a carboxylic acid KMnO4 > basic solution, does not work with alcohols that contain double or triple bonds and does not work with secondary alcohols to make ketones NaOCl is a substitute for the toxic collins reagent. It oxidizes aromatic and aliphatic secondary alcohols to ketones and primary aromatic alcohols to aldehydes. It selectively oxidizes secondary alcohols in the presence of primary alcohols Mechanism is still unknown

Phase transfer catalyst TBAS = starting alcohol is soluble in organic solvents but not soluble in water. NaOCl is soluble in water but not in organic solvents > can be used to bring the two reactants together > shuttle moving back and forth between the layers > TBAS is a quaternary ammonium salt = the alkyl groups render TBAS soluble in ethyl acetate but it is also a salt that is water soluble Methods used stirring, decant, extraction (NaCl, water), dry with anhydrous magnesium sulfate, rotovap to get rid of excess ether Extraction is a very common laboratory procedure used when isolating or purifying a product. Organic chemistry employs solid-liquid, liquid-liquid, and acid-base extractions. The following applies to liquidliquid extractions, which will be used in this course. It is very common for organic products synthesized in a reaction to be purified by liquid-liquid extraction. A separatory funnel (see picture) is used for this process. In this procedure, the organic product is isolated from inorganic substances. The organic product will be soluble in an organic solvent (organic layer) while the inorganic substances will be soluble in water (aqueous layer). Although the criteria states that the organic solvent chosen should not be miscible with water, some solvents dissolve a small amount. Thus, water must be removed before separating the organic product from the organic solvent or else the product will be contaminated with water. A drying agent must be used. There are a number of drying agents available to the organic chemist: we will be using sodium sulfate and magnesium sulfate in this course. Placing the organic solvent containing the dissolved product in contact with the chosen drying agent will allow the agent to absorb any dissolved water. The agent can then be removed from the solvent and then the product can be isolated.

Synthesis of Phenacetin Williamson Ether Synthesis Contains both an ether group and an amide group substituted para on benzene ring Williamson ether synthesis formation of an ether by reaction of an alkyl halide with the conjugate base of an alcohol or phenol The number of moles of methoxide ion must be the same as the number of moles of p-acetamidophenol used for Williamson synthesis because if not enough methoxide ion is used, some of the p stuff will not be converted to its conjugate base and thus will not react. If too much methoxide ion is used, it will compete as a nucleophile with the p stuff, reducing the yield of phenacetin. The boiling point of the recrystallization solvent should be lower than the melting point of the compound to be recrystallzied. If the solvents boiling point is higher than the compounds melting point, the compound will oil out. Oiling out occurs when a compound is insoluble in a solution at a temperature above the compounds melting point. As a result, the compound is deposited as an oil and not as crystals Methods used reflux, vaccum filtration, purification

Diels- Alder Reaction Form bridged polycyclic anhydride [4 + 2] cycloadditions In one step, the reaction forms a six-membered ring with one or two double bonds from an open-chain compound

Diene 4pi, electron rich, nucleophile > alkyl groups enhance reactivity Dienophile double or triple bonds Concerted Xylene 140C boiling temperature provides good reaction temperature, does not freeze in ice cold water, reactants are more soluble than the product Favors center ring because there is better pi bond interaction, most thermodynamically stable, retain resonance stabilized system Methods used reflux, vacuum filtration, recrystallization Do not recrystallize with water because a different product will form

Friedel Crafts Reaction Unsaturated hydrocarbon is alkylated or acylated using a lewis acid catalyst PPA serves as the solvent and results in high yields and as catalyst Clear to amber Extraction, dry, decant, vacuum filtration, recrystallize Water hydrolyzes PPA

Common questions

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'Oiling out' occurs when a compound becomes insoluble at a temperature above its melting point, leading to its separation as an oil rather than solid crystals. This phenomenon significantly disrupts the purification process, as the desired product does not form well-defined crystals for filtration. To prevent oiling out, the choice of solvent with a boiling point lower than the compound's melting point is crucial, allowing for controlled crystallization during cooling .

In the Diels-Alder reaction, dienes, being electron-rich due to conjugation and alkyl substituents, act as nucleophiles, whereas dienophiles are electron-poor, often due to electron-withdrawing groups, making them electrophilic. This electron density difference drives the reaction as the diene donates electrons to the electron-deficient dienophile, facilitating a concerted cycloaddition that forms a stable product with favorable pi bond interactions .

Reflux involves boiling the reaction mixture while continuously condensing the vapor back to liquid, maintaining a constant temperature conducive to the reaction. This setup allows for prolonged heating without solvent loss, ensuring that reactions requiring higher temperatures proceed effectively. In the oxidation of methoxybenzyl alcohol, reflux ensures that the reactants are heated uniformly and continuously, facilitating reaction completion by providing sustained energy input .

Sodium borohydride is a mild reducing agent that selectively reduces ketones and aldehydes to their corresponding alcohols without affecting less reactive carbonyl groups like esters and amides. This selectivity is due to the higher reactivity of ketones and aldehydes compared to other carbonyl groups, allowing sodium borohydride to target them preferentially .

Bridged intermediates stabilize carbocations during rearrangement by providing an alternate structure that distributes the positive charge more evenly. In the rearrangement of benzopinacolone, this intermediate can significantly alter the pathway of the reaction, leading to products with structures substantially different from the starting materials. This changes the outcome by shifting the reaction toward more stable conformations or products .

NaOCl is a less toxic alternative to Collins reagent for oxidizing secondary alcohols to ketones and primary alcohols to aldehydes. It offers a safer and more environmentally friendly option due to its reduced toxicity. However, it might be less selective under some conditions compared to Collins reagent, which can specifically stop at the aldehyde stage without further oxidation. Despite these differences, NaOCl is advantageous for its safety profile and wide applicability .

KMnO4 offers simplicity and high reactivity for oxidizing alkenes and other functional groups in a basic solution. However, it does not efficiently oxidize secondary alcohols to ketones or alcohols with double/triple bonds, unlike chromium-based reagents, which are more versatile in handling various types of alcohols. Chromium reagents, though toxic, allow for precise control over the oxidation state to stop at aldehydes or proceed to acids .

In Williamson ether synthesis, the solvent must dissolve both the alkyl halide and methoxide ion efficiently while maintaining proper stoichiometry. Using insufficient or excessive methoxide disturbs the balance, either failing to convert the p-acetamidophenol to its conjugate base or decreasing the yield by competing as a nucleophile. Thus, the solvent must not only support the reaction thermally and kinetically but also ensure accurate concentration and reaction conditions, preventing side reactions and maximizing ether yield .

A phase transfer catalyst like TBAS facilitates the reaction between reactants in different phases by shuttling them across the phase boundary. In the oxidation of methoxybenzyl alcohol, TBAS helps bring the alcohol, which is soluble in organic solvents, and sodium hypochlorite, soluble in water, together. TBAS, being a quaternary ammonium salt, is soluble in both water and organic solvents, thus bridging the reactants and facilitating the oxidation process .

Electrophilic aromatic substitution in the Friedel-Crafts reaction involves the formation of an electrophile that attacks the aromatic ring. The Lewis acid catalyst, such as AlCl3, enhances this process by forming a complex with the alkyl or acyl halide, generating a more potent electrophile. This boosted electrophilic character allows the aromatic ring to be alkylated or acylated, making the catalyst pivotal for activating the electrophile and facilitating substitution .

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