Chem 546: Lab 9 – Sodium Borohydride Reduction of Benzophenone

Procedure
Introduction
Aldehydes and ketones can easily be reduced to alcohols through the addition of a hydride ion
(H -). Metal hydride reagents, like sodium borohydride and lithium aluminum hydride, Figure 1)
are common sources of a hydride ion used in these reactions because hydrogen is more
electronegative than both boron and aluminum.

Figure 1. Common metal hydride reducing agents.

Lithium aluminum hydride is a very powerful reducing agent that can reduce aldehydes and

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ketones, esters, carboxylic acids, and nitro groups. This can be very useful in synthesis, but it

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also can be difficult to work with as it reacts violently with water and can spontaneously catch on

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fire when exposed to air.

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Sodium borohydride (NaBH4) is more selective than lithium aluminum hydride because it is less

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reactive. It will reduce aldehydes and ketones to alcohols easily, but will not react with most
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other functional groups. This selectivity and reactivity can be an advantage or a disadvantage,
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depending on the reaction. Sodium borohydride is much easier to work with than lithium
aluminum hydride. It can be used in its solid form, but it will slowly decompose with air, so it
should be noted to keep the container capped when not in use.
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In a sodium borohydride reduction, the hydride ion acts as a nucleophile and adds to the
electrophilic carbonyl carbon. No free hydride ions are formed, rather the hydride is transferred
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directly from the metal (Figure 2). In the case of sodium borohydride, this will eventually form
borate salts as by-products1 after all 4 hydride ions from the BH4- are used. Technically, you
only need 1 equivalent of sodium borohydride for every 4 equivalents of aldehyde or ketone, but
it is best to use a 50 – 100% excess to compensate for any that reacts with the solvent of
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decomposes. This reaction is first order with respect to sodium borohydride, so adding excess
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will also increase the reaction rate. After reaction with sodium borohydride, the oxygen of the
carbonyl must be protonated (Figure 2). This typically occurs by adding acid.
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Figure 2. Sodium borohydride reduction of an aldehyde or ketone.

After reaction, unreacted sodium borohydride can be decomposed by acidifying the reaction
mixture to a pH of 6 or lower by adding dilute acid. This acid will also protonate any
deprotonated alcohol product and any neutralized acidic functional groups in your starting
material. Depending on the properties of the product and the solvent used, the product can be

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 separated by filtration or extraction. Any borate salt by-products that are formed will be soluble
in water.
In this experiment, you will use sodium borohydride to reduce the benzophenone, forming
diphenyl methanol (Figure 3). Physical properties for the chemicals used can be found in Table
1.

Figure 3. Sodium borohydride reduction of benzophenone.

Table 1. Relevant physical constants.

Compound MW (g/mol) MP (°C)

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Benzophenone 182.2 119
NaBH4 38 -

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Diphenyl methanol 184.2 68 - 69

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Procedure

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In a 25 mL round bottom flask, place 0.55 g of benzophenone (AKA diphenyl ketone) and add a
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slurry of 0.06 g of sodium borohydride in 3 mL of 2-propanol while stirring. Top the round bottom
flask with a condenser and heat the mixture to reflux for 30 minutes. After 30 minutes, allow the
mixture to cool to room temperature.
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To decompose the borate ester complex, add 3 mL of 10% aqueous sodium hydroxide and stir
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until the precipitate is dissolved. You can break up any resistant clumps and add 1 - 2 mL of
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water to get them to dissolve. Transfer this solution to a conical vial and add 5 mL of
dichloromethane to extract the product. Remove the organic layer and extract the aqueous layer
one more time with 5 mL of dichloromethane. Combine both dichloromethane extracts and dry
them with sodium sulfate.
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Tare weigh a clean, dry 25 mL round bottom flask transfer the dried organic solution to it.
Concentrate the solution by rotary evaporation to yield solid diphenylmethanol. Get a mass, MP,
and IR of your product. The TA will give you an IR of the starting material. Before disposing of
your product, show it to your TA for evaluation.
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**Adapted from: Experimental Organic Chemistry: A Small Scale Approach by Charles R. Wilcox, Jr. and Mary F. Wilcox

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