Show how to convert alkenes, alkyl halides, and carbonyl compounds to alcohols.
For the synthesis of alcohols with carbon skeletons, use organometallic reagents.
Menthone is produced by the most common and useful compounds in nature, in industry and around the plant as single enantiomers.
The essence of wine was considered to be ethyl alcohol, which is still used to treat distilled wine.
Ethyl alcohol is found in alcoholic beverages, cosmetics, and drug preparations.
Wood alcohol is used as a fuel and solvent.
rubbing alcohol is the most popular in the world.
The hydroxy group can be converted to most other functional groups by a wide variety of methods.
Alcohols are versatile synthetic intermediates.
The physical properties of alcohols are discussed in this chapter.
In the next chapter, we will continue our study of the central role that alcohols play in organic chemistry as reagents, solvents, and synthetic intermediates.
The structure of water is similar to that of alcohol, with an alkyl group replacing one of the hydrogen atoms.
The H bond angle in water is because the methyl group is larger than the hydrogen atom.
The bond angle compression is caused by oxygen's nonbonding pairs of electrons.
The O bond is larger than the hydrogen bond.
The OH group is made of tertiary carbon.
The primary, secondary, and tertiary halides reacted differently when we studied them.
It's the same for alcohols.
We need to know how these classes of alcohols react under certain conditions.
The properties of phenols are similar to those of alcohols.
In this chapter, we look at the properties of phenols that are similar to alcohols.
The aromatic nature of phenols is considered in Chapter 16.
The IUPAC system gives unique names for alcohols based on rules that are similar to those for other compounds.
Give all the substituents their numbers, as you would for an alkane or alkene.
Alcohols are classified according to the type of carbon atom they have.
There is a carbon atom in a benzene ring.
The OH group is on the second carbon atom.
The complete name is 1-bromo-3,3-dimethylbutan-2-ol.
The following alcohol has a systematic name.
The longest chain has six carbon atoms, but not the carbon bond to the hydroxy group.
The OH group contains five carbon atoms.
The chain is numbered from right to left to give the lowest possible number.
The compound is called 3-(iodomethyl)-2-isopropylpentan-1-ol.
The alcohols carbon atom is bonded to the hydroxy group.
The multiple bonds numbers were once Summary of Organic Nomenclature.
The new and old placements of the numbers are shown in the figure.
The order of precedence of functional groups is shown in Table 10-1.
Inside the back cover is a table called the "Summary of Functional Group Nomenclature".
The main group is considered the highest priority, and the others are considered substituents.
The IUPAC decided that the term "hydroxyl" should only refer to the.
Common usage often ignores this new rule.
The names of the alcohols should be given to IUPAC.
The system shows an alcohol as a molecule of water with an alkyl group replacing one of the hydrogen atoms.
The IUPAC nomenclature should be used if the structure is complex.
The common name for each alcohol should be given with the IUPAC name.
Draw all the possible constitutional isomers of alcohols with each formula.
Give the name of the alcohol.
The preferred method for naming diols is this one.
The hydroxylation of alkenes is the most common method of synthesis of glycols.
Their common names reflect the synthesis of glycols.
We will use the "diol" name for diols, but be aware that the names "ethylene glycol" and "propylene glycol" are universally accepted for these common diols.
Give a name for each diol.
The systematic names and common names "carbolic acid" are shown in the following examples.
Deep, painless burns are caused by O potent neurotoxin and skin exposure.
The names of the compounds will be systematic.
Most of the alcohols are liquids at room compounds.
The ring of volatile liquids is cleaved by them and degrades the fruity odors.
Some of the highly branched isomers are solid at room temperature, and the higher alcohols are products further to water and carbon.
The soil around highways has higher alcohols but still fruity odors.
Propan-1-ol and propan-2-ol fall in the middle, with a barely noticeable viscosity and a characteristic odor on the run off of hydrocarbons often associated with a physician's office.
The physical properties of the vehicles are listed in Table 10-2.
The boiling points of ethyl alcohol and propane are different.
The boiling point of dimethyl ether is intermediate.
The difference in boiling points between propane and ethanol suggests that they are attracted to each other more strongly.
The two important intermolecular forces are hydrogen bonding and dipole-dipole attractions.
The high boiling point is caused by hydrogen bonding.
The oxygen atom of another alcohol molecule can cause a hydrogen bond with a pair of nonbonding electrons.
H hydrogen atoms form bonds.
The strength of hydrogen bonds is 21 kJ per mole, which is weaker than typical bonds of 300 to 500 kJ, but stronger than dipole-dipole attractions.
The attractions contribute to the high boiling points of alcohols and ethers.
O bonds and the nonbonding elec trons add to produce a dipole moment of 1.69 D in ethanol, compared with 0.08 D in propane.
The positive and negative ends of the dipoles align to produce attractive interactions.
The effects of hydrogen bonding and dipole-dipole attractions can be compared with the effects of dimethyl ether.
The boiling point of dimethyl ether is about 17 degrees higher than that of propane, but still 103 degrees lower than that of ethanol.
The hydrogen bonds are stronger than the dipole-dipole attractions.
Water and alcohols have the same hydroxy groups that can form hydrogen bonds.
Alcohols are better for polar substances than hydrocarbons.
Some of the lower alcohols can be dissolved with significant amounts of ionic compounds.
The structure and synthesis of alcohols lend themselves to nonpolar organic solvents.
There are some simple alcohols in water.
Each hydrogen-bonding group can carry up to four carbon atoms into the water.
The boiling point of Dimethylamine is 7.4 degC.
Alcohols are one of the most important chemical commodities.
Each year, millions of tons of various chemicals are produced and used.
These alcohols are among the most versatile chemicals, used as fuels, solvents, antiseptics, beverages, and starting materials for chemical synthesis.
Methanol was originally produced by the destruction of wood chips in the absence of air.
Many cases of blindness and death were caused by this practice.
Methanol is made by a reaction of carbon monoxide with hydrogen.
This reaction requires large, complicated industrial reactor and uses high temperatures and pressures.
The amount of water added allows production of synthesis gas with the correct fuel for automotive engines.
The racers have used E85, which is 85% alcohol, and Methanol, which is 2% alcohol, in the past.
It is cheap and 15% gasoline.
Government subsidies have helped.
In the 1960's and 70's, all the ily corn was used to make fuel.
After a crash in 1964, a bad fire caused the increase to methanol.
The price of food grains is lessflammable than gasoline, and water is effective against fires caused by Methanol.
As with any alternative fuel, there are advantages and disadvantages.
Methanol is hard on rings, seals, and plastic because of its excellent solvent properties.
Foods are part of the fuel system.
Its tendency to burn with little or no visible flame can allow danger more valuable commodities than fuels.
When rotten fruit falls into a pattern, it's likely that the prehistoric discovery of ethanol occurred.
This discovery probably led to the creation of the most valuable and waste tional medicines.
The primitive wine that resulted could be stored in a sealed container without the risk of decomposition, and it also served as a safe, unpolluted source of water to drink.
Beer has been used as a safe source of drinking water in many societies.
There are many different fuels that can be used to make Ethanol.
Brewer's less valuable starting materials are added to the solution and the yeast cells convert simple more valuable products.
It is possible to waste sugars, such as glucose, to other things.
In some cases, T 2C2H5OH + 2 CO2 to fuels.
yeast cells cannot survive higher concentrations in the alcoholic solution that results from fermentation.
Distillation increases the amount of fuel that can be used as a motor fuel.
The structure and synthesis of alcohols can't increase the concentration above 85% because of the solution is water and not pure water.
When traces of water don't affect the reaction, the alcohol produced by distillation can be used as a solvent and reagent.
The catalyzed high-temperature, high-pressure, gas-phase reaction of water with ethylene has been used since World War II to make most industrial ethanol.
There are various specially treated clays.
Ethanol is an excellent solvent that is cheap to use.
The tax on liquor makes it more expensive.
It is possible to use untaxed ethanol, but it requires extensive record keeping and purchase of a special license.
It is a good motor fuel with similar advantages.
If the car is to run on pure ethanol, the car's carburetor must be adjusted and alcohol-resistant seals must be fitted.
Many people think that Ethanol and Methanol are toxic.
Methanol is about twice as toxic as ethanol.
The toxicity depends on the amount and the concentration.
The nerve in the eye may be damaged.
We consider these solvent to be relatively safe compared to hazardous solvent such as benzene and chloroform.
Propan-2-ol is made by hydration of propylene.
Both alcohols are used by the government.
Rubbing alcohol is an effective antiseptic.
In the early 1920s, people used rubbing alcohol as a safe and effective antiseptic because of the presence of Ethanol.
It's safer for use in mouthwashes than it is for taking it orally.
The alcohols kill the skin because they are not as easy to pass through.
The hydroxy protons of water and alcohol are weakly acidic.
Some alcohols are as acidic as water, while others are less acidic.
Table 10-4 compares the acid-dissociation constants of some alcohols with those of water and other acids.
The acid-dissociation constants for alcohols vary depending on their structure, from about 10-16 for methanol down to about 10-18 for most tertiary alcohols.
As the substitution on the alkyl group increases, the acidity decreases because a more highly substituted alkyl group decreases the stability of the alkoxide ion.
Table 10-4 shows that substitution by electron-withdrawing halogen atoms enhances the acidity of alcohols.
The electron-withdrawing chlorine atom helps to stable the 2-chloroethoxide ion.
The following compounds should be ranked in decreasing order of acidity.
These examples show large classes of compounds that are different in acidity.
We have already seen many of the useful reactions of alkoxide ion.
When an alkoxide ion is needed in a synthesis, it is formed by the reaction of sodium or potassium metal with alcohol.
The metal is oxidation and the hydrogen ion is reduced to form hydrogen gas.
The alkoxide ion is left behind by the hydrogen that bubbles out of the solution.
The more acidic alcohols react quickly to form methoxide and ethoxide.
Propan-2-ol, a secondary alcohol, reacts more slowly.
Butyl alcohol reacts very slowly with sodium.
Secondary and tertiary alcohols can be done in a convenient amount of time with the use of Potassium.
Some alcohols react slowly.
In some cases, a useful alternative is sodium hydride.
Even with difficult compounds, sodium hydride reacts quickly to form the alkoxide.
Since their structures are similar, we might expect phenol to have the same acidity as cyclohexanol.
The prediction is wrong because phenol is more acidic than cyclohexanol.
A typical acid-dissociation constant for an alcohol is cyclohexanol.
It must be something special about phenol that makes it acidic.
The phenoxide ion is more stable than a typical alkoxide ion because the negative charge is not confined to the oxygen atom but is delocalized over the oxygen and three carbon atoms of the ring.
The oxygen atom is the most negatively charged of the four atoms sharing the charge.
A more stable ion can be created by the ability to spread the negative charge over four atoms.
The following equilibrium lies to the right, as the reaction of phenol with sodium hydroxide is exothermic.
Adding the phenol to the solution EPM of phenoxide ion of sodium hydroxide is how phenoxide anions are prepared.
There is no need to use either metal.
The negative charge on an adjacent carbon atom can be stable through resonance with an aqueous phenol solution.
The precipitated proteins are + O.
The DNA can be collected if the O is present.
Two of the nitrophenols are more acidic than phenol.
The third compound is slightly more acidic than phenol.
To show why two of the anions should be stable, use resonance structures of the appropriate phenoxide ion.
One of the compounds is very soluble in a solution of sodium hydroxide, which is slightly smilly smilly smilly smilly smilly smilly smilly smilly smilly smilly
There is a difference in the solubility of these compounds.
Show how a separatory funnel can be used to separate the two compounds.
Alcohols are important synthetic intermediates because they can be made directly from a wide variety of other functional groups.
We looked at the conversion of alkyl halides to alcohols by substitution and the conversion of alkenes to alcohols by hydration in Chapters 6 and 8.
References for review are included in the summarized reactions.
The largest and most versatile group of alcohol syntheses are the nucleophilic additions to carbonyl compounds.
The SN2 mechanism is used to compete with elimination.
In contrast to alkyl halides, Organometallic reagents have nucleophilic carbon atoms.
M bond has a partial positive charge on metal and a partial negative charge on carbon.
The table shows the electronegativities of some metals.
One type of organometallic compound with a nega tive charge on carbon has already been encountered.
Terminal alkynes are weakly acidic, and they are converted to sodium acetylides by treatment with a strong base.
New carbon-carbon bonds can be formed with the reaction of alkyl halides and carbonyl compounds.
Most alkyl and alkenyl groups are not acidic enough to be deprotonated, but they can be made into Grignard reagents and organolithium reagents.
Some of the best ways of forming carbon-carbon bonds are provided by these reagents.
The reaction of an alkyl halide with organic chemistry results in grignard reagents.
We are going to use magnesium metal.
This reaction is always carried out in a dry (anhydrous) ether solvent, where Grignard reactions are needed to form which are needed to stable the reagent as it forms.
The most common solvent for these reactions is CH2 CH3.
Grignard reagents can be made from primary, secondary, and tertiary alkyl halides, as well as from vinyl and aryl halides.
bromides and chlorides are the most reactive halides.
Alkyl fluorides don't react.
The reactions show the formation of Grignard reagents.
Organometallic compounds are formed when alkyl halides, vinyl halides, and aryl halides react with lithium.
This reaction does not need ether.
The map of the potential of methyllithium is shown in the 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 888-666-1846 The blue color of the metal is due to its partial positive charge, while the red color is due to its partial negative charge.
The structure and synthesis of alcohols are similar to carbanions.
Adding carbonyl (C " O) groups is one of their most useful reactions.
The carbonyl group has a partial positive charge on carbon and a partial negative charge on oxygen.
The positively charged carbon has a negative charge on the oxygen atom.
The alkoxide ion is a strong base.
Adding water or acid in a second step causes the alkoxide to give alcohol.
A Grignard reagent or an organolithium reagent can serve as the nucleo phile in this addition to a carbonyl group.
The discussions refer to Grignard reagents, but also to organolithium reagents.
Key Mechanism 10-1 shows that the Grignard reagent adds carbonyl to form an alkoxide ion.
The alkoxide is given the alcohol by the addition of dilute acid.
We are interested in the reactions of Grignard reagents.
There is an electron-rich region around oxygen and an electron-poor region near carbon on the EPM of formaldehyde.
Some of the best methods for assembling a carbon skeleton are provided by Grignard and organolithium reagents.
The alkoxide ion is given by the addition of ketones and aldehydes to the alkoxide.
Magnesium reacts with an anhydrous ether solution.
An alkoxide salt is formed by attacking a carbonyl compound.
After the first reaction is complete, water or acid is added to the alkoxide to give it alcohol.
phenylmagnesium bromide is given when magnesium reacts with bromobenzene in an ether solution.
An alkoxide salt is formed by attacking a carbonyl compound.
After the first reaction is complete, water or acid is added to the alkoxide to give it alcohol.
Adding a Grignard reagent to formaldehyde gives a primary alcohol with one more carbon atom than in the Grignard reagent.
The reagent is Grignard.
aldehydes are added to by grignard reagents.
The alkyl group from the Grignard reagent and the alkyl group from the carbonyl group of the aldehyde are the two alkyl groups of the secondary alcohol.
Adding on the carbinol carbon atom could be used to synthesise each of the secondary alcohols.
The carbonyl carbon atom of a ketone has two alkyl groups bonding to it.
A tertiary alcohol with three alkyl groups bonding to the carbinol carbon atom is given by the addition of a Grignard reagent.
Two of the alkyl groups were originally bonds to the ketone carbonyl group.
The Grignard reagent is the third alkyl group.
Any one of the three alkyl groups can be added to this tertiary alcohol in the form of a Grignard reagent.
The first, second, and third are all likely to work, but only the third begins with no more than five carbon atoms.
Further steps would be required to generate the ketones from compounds with no more than five carbon atoms.
A tertiary alcohol has three groups reagent to a ketone.
The Grignard reagent was added to each of the groups.
The OH group of a carboxylic acid is replaced by other groups.
The hydroxy group of acid is replaced by a chlorine atom.
Acid chlorides and esters react with two equivalents of Grignard reagents to give tertiary alcohols.
Adding the first equivalent of the Grignard reagent causes an unstable intermediate that expels a chloride ion or alkoxide ion from the acid chloride or the ester to give a ketone.
The alkoxide ion is a suitable leaving group in this reaction because of its stabilizing effect on a negatively charged intermediate.
The magnesium salt of a tertiary alkoxide is formed when the ketone reacts with a second equivalent of the Grignard reagent.
One of the alkyl groups derived from the acid chloride or ester is used to make a tertiary alcohol.
An example would be using an ester.
When making alcohol with propiophenone.
Adding a second equivalent and two identical alkyl groups gives a tertiary alcohol.
There is a mechanism for the reaction of acetyl chloride with phenylmagnesium bromide.
Secondary alcohols with two identical alkyl groups are given after a formate ester reacts with an excess of a Grignard reagent.
A mechanism to show how the reaction of ethyl formate with an excess of allylmagnesium bromide gives is proposed.
The following secondary alcohols would be synthesised using reactions of Grignard reagents with ethyl formate.
The ring strain is relieved by the attack by the Grignard reagent.
The only Grignard ethylene oxide is the reaction of a Grignard reagent.
The OH group appears on the second carbon from the new bond.
The same way as Grignard and organolithium reagents, acetylide ion add to carbonyl groups.
Like Grignard and organolithium reagents, Acetylide ion adds to ethylene oxide.
Predict the products obtained by adding the acetylide ion to the ethylene oxide.
Acetylide ion are alkylated by the displacement of alkyl halides.