ChemistryAlcohols, Phenols And EthersFor JEE aspirants
The preparation of alcohols comes down to six reliable routes: hydration of alkenes (acid catalysed,
oxymercuration or hydroboration), hydrolysis of alkyl halides, reduction of aldehydes, ketones, esters and
acids, and addition of Grignard reagents to carbonyl compounds. Each route is chosen for what it controls:
acid hydration and oxymercuration give the Markovnikov alcohol, hydroboration the
anti-Markovnikov one, and only the Grignard route builds a new C−C bond. The
preparation of alcohols appears in almost every NEET and JEE Main paper.
On this page1All routes2From alkenes3From halides4Reduction5Grignard6Industry7Choose a route8Examples
Key Formulas - Quick Reference
★ Must learnAcid hydration: RCH=CH2+H2OH+Markovnikov alcohol (carbocation, so rearrangement is possible).
★ Must learnOxymercuration: Hg(OAc)2/H2O, then NaBH4. Markovnikov, no rearrangement.
★ Must learnHydroboration: B2H6, then H2O2/OH−. Anti-Markovnikov and syn.
Hydrolysis: R−X+aq. KOH→R−OH+KX (moist Ag2O is cleaner).
★ Must learnReduction: aldehyde →1∘ alcohol, ketone →2∘ alcohol, ester or acid →1∘ alcohol with LiAlH4.
★ Must learnGrignard: HCHO→1∘, RCHO→2∘, R2CO→3∘, epoxide →1∘ with two extra carbons.
Every Grignard reaction ends with an H3O+ work-up, and every Grignard reaction needs perfectly dry apparatus.
1. The Full Map of Routes to an Alcohol
Before learning any single method it helps to see all of them at once, because most exam questions are
really asking which route gives which alcohol, not how to run the reaction. The table lists all six; the flowchart and mind map in section 7 turn it into a decision you can make in seconds.
Start from
Reagent
Alcohol obtained
alkene
dil. H2SO4 (or H3PO4)
Markovnikov; skeleton may rearrange
alkene
Hg(OAc)2/H2O, then NaBH4
Markovnikov; no rearrangement
alkene
B2H6, then H2O2/OH−
anti-Markovnikov; syn addition
alkyl halide
aq. KOH or moist Ag2O
same skeleton, −OH replaces X
aldehyde, ketone, ester, acid
NaBH4 or LiAlH4
1∘ or 2∘ alcohol
carbonyl compound
RMgX in dry ether, then H3O+
1∘, 2∘ or 3∘, new C-C bond
2. From Alkenes
2.1 Acid catalysed hydration
Alkenes add water in the presence of a dilute acid such as H2SO4 or
H3PO4. The addition follows Markovnikov's rule, so the −OH group goes to the
more substituted carbon.
Figure 1: Acid catalysed hydration. Top: propene gives propan-2-ol, the Markovnikov alcohol. Bottom: the mechanism; protonation makes the more stable 2∘ carbocation, water attacks it and loses H+, so carbocation stability alone decides where −OH goes.
Every step of this mechanism is reversible. Dilute acid with plenty of water pushes the equilibrium
towards the alcohol; hot concentrated acid pulls it back and dehydrates the alcohol to the alkene. The same
two arrows, read in opposite directions, are the whole of acid catalysed hydration and acid catalysed
dehydration.
2.2 The limitation: carbocation rearrangement
Because a free carbocation is formed, a hydride or an alkyl group can migrate to give a more stable
cation before water ever attacks. The alcohol you isolate then has a different carbon skeleton from the one
you expected.
Figure 2: Why acid hydration can give the wrong skeleton. The 2∘ cation from 3,3-dimethylbut-1-ene becomes a 3∘ cation by a 1,2-methyl shift, so the major product is 2,3-dimethylbutan-2-ol, not the expected 3,3-dimethylbutan-2-ol.
2.3 Oxymercuration and demercuration
This two-step sequence gives the same Markovnikov alcohol but avoids the rearrangement problem
completely, because the intermediate is a bridged mercurinium ion and never a free carbocation.
Figure 3: Oxymercuration gives the same Markovnikov alcohol as acid hydration, but the bridged mercurinium ion prevents any carbocation rearrangement.
Exam Trick
If a question gives you a skeleton that could rearrange (a carbon next to a quaternary centre) and asks for the unrearranged Markovnikov alcohol, the answer is oxymercuration and demercuration.
Net addition is of H and OH with Markovnikov orientation, and typical yields are around 90 per cent.
2.4 Hydroboration and oxidation
Diborane or a BH3⋅THF complex adds across the double bond with boron going to the
less substituted carbon. Alkaline hydrogen peroxide then replaces boron by −OH with retention
of configuration, so the overall result is anti-Markovnikov hydration.
Figure 4: Hydroboration oxidation. Top: boron takes the less hindered carbon and H2O2/OH− swaps it for −OH with retention, giving propan-1-ol. Bottom: in the four-centre transition state δ+ builds on the more substituted carbon (which receives H) and boron (δ−) bonds to the CH2 end, both on the same face (syn).
JEE AdvancedHydroboration controls two kinds of selectivity at once. Regioselectivity: boron lands on the less
hindered carbon, so the −OH finally appears there. Stereoselectivity: the four-centre transition
state forces H and B onto the same face, so the addition is syn. Since the oxidation
step keeps the configuration at carbon, the stereochemistry set in the first step survives into the product.
Route
Reagents
Regiochemistry
Stereochemistry
Rearrangement
Acid hydration
H2O/H+
Markovnikov
not controlled
possible
Oxymercuration
Hg(OAc)2, then NaBH4
Markovnikov
not controlled
none
Hydroboration
B2H6, then H2O2/OH−
anti-Markovnikov
syn addition
none
Oxymercuration-demercurationHg(OAc)2/H2O, then NaBH4 bridged mercurinium ion Markovnikov, no rearrangement propene gives propan-2-ol
Hydroboration-oxidationB2H6, then H2O2/OH− four-centre transition state anti-Markovnikov, syn, no rearrangement propene gives propan-1-ol
2.5 Hydroxylation: making two hydroxyl groups at once
Cold dilute alkaline KMnO4 (Baeyer's reagent) or OsO4 followed by
NaHSO3 adds two −OH groups to the same face of the double bond, giving a cis diol.
Opening an epoxide with acidic water instead gives the trans diol.
Figure 5: Two ways to put two −OH groups on one double bond. KMnO4 or OsO4 give the cis (syn) diol; the epoxide route gives the trans (anti) diol.
Key idea
Same alkene, three reagents: acid and mercury put −OH on the more substituted carbon, borane on the less substituted one; only acid lets the skeleton rearrange.
Quick Recall: tap to checkPropene with B2H6, then H2O2/OH−?
Propan-1-ol (anti-Markovnikov).
Why does oxymercuration never rearrange?
Its intermediate is a bridged mercurinium ion, not a free carbocation.
Cyclopentene with cold dilute alkaline KMnO4?
cis-Cyclopentane-1,2-diol (syn hydroxylation).
3. From Alkyl Halides
An alkyl halide heated with aqueous alkali gives an alcohol by nucleophilic substitution. The reaction is
clean for primary halides but competes badly with elimination for tertiary ones.
Figure 6: Aqueous alkali converts an alkyl halide to an alcohol. For a 1∘ halide it is a clean SN2 attack from the back, so the configuration is inverted.
Aqueous KOH is both a nucleophile and a base, so tertiary halides mostly give alkenes. Moist silver
oxide, Ag2O/H2O, supplies OH− in a much less basic environment and
gives far better alcohol yields. This is why textbooks call the alkali method unsatisfactory for tertiary halides.
4. From Carbonyl Compounds by Reduction
4.1 Aldehydes and ketones
Figure 7: Reduction of aldehydes and ketones. Top: an aldehyde always gives a 1∘ alcohol and a ketone a 2∘ alcohol. Bottom: H− adds to the δ+ carbonyl carbon, then the alkoxide picks up H+ in the separate work-up.
Reagent
Reduces
Does not reduce
Note
NaBH4
aldehydes, ketones
esters, acids, C=C
can be used in water or alcohol
LiAlH4
aldehydes, ketones, esters, acids, amides
isolated C=C
violent with water, use dry ether
H2 with Ni, Pd or Pt
C=O and C=C
nothing much
not selective
NaBH4: gentlereduces aldehydes and ketones only leaves esters, acids and C=C alone safe in water or ethanol
LiAlH4: powerfulalso reduces esters, acids and amides leaves an isolated C=C alone reacts violently with water: dry ether, then work-up
Exam Trick
"Count the R's." Reduction only adds hydrogen, so the degree of the alcohol equals the number of carbon groups already on the carbonyl carbon: an aldehyde (one R) gives a 1∘ alcohol, a ketone (two R) a 2∘ alcohol. No reduction can ever give a 3∘ alcohol.
4.2 Esters and carboxylic acids
Figure 8: LiAlH4 pushes esters and acids all the way down to primary alcohols. NaBH4 cannot do this.
Catalytic hydrogenolysis of an ester needs far harsher conditions than ordinary hydrogenation: about
250∘C and very high pressure over copper chromite, CuO⋅CuCr2O4.
This is the industrial route to long chain primary alcohols used in detergents.
Key idea
Reduction keeps the carbon skeleton: aldehydes and esters end as 1∘ alcohols, ketones as 2∘, and only LiAlH4 can reach esters and acids.
5. From Grignard Reagents
Victor Grignard discovered organomagnesium halides in 1900 and received the Nobel Prize in 1912. Their
value is simple: they put a negative charge on carbon, and a carbon nucleophile can attack a carbonyl carbon
to make a new carbon to carbon bond.
Figure 9: The Grignard reagent. Top: R-X and Mg in dry ether; reactivity R-I>R-Br>R-Cl, and the C−Mg bond puts a negative charge on carbon. Bottom: that carbanion attacks C=O to build a new C−C bond; only the final hydrolysis brings in water.
5.1 Which carbonyl gives which alcohol
Figure 10: The one table you must know for Grignard questions. Methanal gives 1∘, any other aldehyde gives 2∘, a ketone gives 3∘, and ethylene oxide adds two carbons to give a 1∘ alcohol.
Exam Trick
Count the groups on the carbonyl carbon before the reaction. Methanal has none, so you get 1∘; one group gives 2∘; two groups give 3∘.
An ester with excess Grignard gives a tertiary alcohol with two identical alkyl groups, because the reagent adds twice.
An ester of formic acid with excess Grignard gives a secondary alcohol, again with two identical groups.
Ethylene oxide is the only common reagent that adds two carbons and still gives a primary alcohol.
5.2 Restrictions you must respect
Figure 11: A Grignard reagent is a strong base first and a nucleophile second. Any acidic hydrogen in the flask converts RMgX into the alkane RH and the synthesis fails.
5.3 Planning a Grignard synthesis
Work backwards. Look at the carbon carrying −OH, break one of the bonds to it, and the two
fragments tell you which carbonyl compound and which Grignard reagent to start from.
Figure 12: How to plan a Grignard synthesis: look at the carbon carrying −OH, cut one of its bonds, and the two pieces are your carbonyl compound and your Grignard reagent.
Key idea
Grignard synthesis is the only route that adds carbons: cut one bond at the −OH carbon, and the two pieces are the carbonyl compound and the Grignard reagent.
Quick Recall: tap to checkWhich carbonyl compound gives a 1∘ alcohol with RMgX?
Methanal, HCHO (or ethylene oxide, which adds two carbons).
Ethyl ethanoate with excess CH3MgBr, then H3O+?
2-Methylpropan-2-ol: the reagent adds twice.
Why must the ether be dry?
Water protonates RMgX to the alkane RH and destroys the reagent.
6. Industrial and Commercial Routes
Ethanol by fermentation. Starch or sugar is hydrolysed by the enzymes diastase and maltase, then zymase converts glucose into ethanol and CO2. Fractional distillation gives rectified spirit, about 95 per cent ethanol.
Ethanol by hydration of ethene.CH2=CH2+H2O over phosphoric acid at about 300∘C and 70 atm, the main modern route.
Methanol from synthesis gas.CO+2H2 over ZnO-Cr2O3 at high pressure.
The oxo process. An alkene with CO and H2 gives an aldehyde, which is then hydrogenated to a primary alcohol.
7. Choosing the Right Route
A synthesis question gives you a target and asks for the reagent. Ask four questions in order: does the target need new carbons, is the start an alkene (and which carbon should get −OH), is it a carbonyl compound, or is it a halide?
Figure 13: Flowchart: pick the route from the product you need. Ask first whether the target has more carbons than the starting material, because only the Grignard route builds a new C−C bond.Figure 14: Mind map: eight routes, each with its reagent and the alcohol it gives. The three alkene routes differ only in regiochemistry and rearrangement.
8. Solved Examples
Solved Example 1
Which reagent converts but-1-ene into butan-1-ol, and which converts it into butan-2-ol?
Solution:
Butan-1-ol is the anti-Markovnikov product, so use B2H6 followed by
H2O2/OH−. Butan-2-ol is the Markovnikov product, so use
H2O/H+, or better Hg(OAc)2/H2O followed by
NaBH4, which avoids any rearrangement.
Solved Example 2
3,3-dimethylbut-1-ene is treated with dilute H2SO4. Predict the major product
and explain.
Solution:
Protonation gives a secondary carbocation at C-2. A methyl group migrates from C-3 to C-2, converting it
into a more stable tertiary carbocation at C-3. Water then attacks there, so the major product is
2,3-dimethylbutan-2-ol and not 3,3-dimethylbutan-2-ol. This rearrangement is exactly why acid
hydration has limited synthetic value.
Solved Example 3
How would you prepare 2-phenylethanol, C6H5CH2CH2OH,
from bromobenzene?
Solution:
Make phenylmagnesium bromide from bromobenzene with magnesium in dry ether. React it with
ethylene oxide, which opens at the less substituted carbon and adds two carbons, then hydrolyse with
H3O+. The product is C6H5CH2CH2OH, a primary
alcohol two carbons longer than the reagent.
Solved Example 4
Suggest two different Grignard routes to 2-methylbutan-2-ol.
Solution:
The −OH carbon carries a methyl, an ethyl and another methyl group. Cutting one methyl gives
butan-2-one with CH3MgBr. Cutting the ethyl group gives
propanone with C2H5MgBr. Both are followed by H3O+ and both
give the same tertiary alcohol, so the choice is decided by which starting material is cheaper.
Solved Example 5
Why does CH3MgBr fail to convert
HOCH2CH2CHO into the expected alcohol?
Solution:
The molecule already contains an −OH group, whose hydrogen is acidic towards a Grignard reagent.
The first mole of CH3MgBr is consumed as a base, giving methane and the magnesium alkoxide,
so that first mole never reaches the C=O group. Either protect the hydroxyl first, or sacrifice an extra mole of CH3MgBr: with two moles the diol product does form.
Solved Example 6
An alkene C4H8 gives butan-2-ol on oxymercuration and demercuration,
and butan-1-ol on hydroboration and oxidation. Identify the alkene.
Solution:
The two products differ only in the position of the −OH group, so the alkene must be terminal and
unbranched. That gives but-1-ene, CH3CH2CH=CH2. Markovnikov addition
puts −OH on C-2 and anti-Markovnikov addition puts it on C-1.
Solved Example 7
Complete: ethyl benzoate +2C2H5MgBr, followed by
H3O+, gives what?
Solution:
An ester reacts with two moles of Grignard reagent. The first addition expels the ethoxide group to give
propiophenone, and the second adds to that ketone. After hydrolysis the product is
3-phenylpentan-3-ol, a tertiary alcohol carrying two identical ethyl groups, which is the signature of
the ester route.
Solved Example 8
Propene can be converted into propan-1-ol by (A) H2O/H+ (B) Hg(OAc)2/H2O, then NaBH4 (C) B2H6, then H2O2/OH− (D) aq. KOH
Solution:
Answer: (C). Propan-1-ol has −OH on the less substituted carbon, the anti-Markovnikov product, which only hydroboration-oxidation gives. (A) and (B) give propan-2-ol; (D) does not react with an alkene.
Solved Example 9
Which pair gives 2-methylpropan-2-ol after acid hydrolysis? (A) HCHO and (CH3)2CHMgBr (B) CH3CHO and C2H5MgBr (C) CH3COCH3 and CH3MgBr (D) HCHO and CH3MgBr
Solution:
Answer: (C). A 3∘ alcohol needs a ketone. Propanone plus a methyl group gives (CH3)3COH. (A) gives 2-methylpropan-1-ol, (B) butan-2-ol and (D) ethanol.
Solved Example 10
How many moles of CH3MgBr does one mole of 4-hydroxybutan-2-one, HOCH2CH2COCH3, consume? Name the product after hydrolysis.
Solution:
Two moles. The first is destroyed by the acidic O−H hydrogen (giving methane); the second adds to the C=O group. Hydrolysis gives HOCH2CH2C(OH)(CH3)2, 3-methylbutane-1,3-diol.
Practice Questions
Product of but-1-ene with B2H6, then H2O2/OH−?Answer: butan-1-ol.
Product of 2-methylpropene with dilute H2SO4?Answer: 2-methylpropan-2-ol.
Reagent that converts ethyl ethanoate into ethanol only.Answer: LiAlH4, then H3O+ (2 mol of ethanol per mole of ester).
CH3MgBr with ethylene oxide, then H3O+, gives?Answer: propan-1-ol, two carbons longer than the reagent.
Give one carbonyl compound and Grignard reagent pair that makes butan-2-ol.Answer: CH3CHO+C2H5MgBr (or propanal +CH3MgBr).
Cyclohexene with cold dilute alkaline KMnO4 gives?Answer: cis-cyclohexane-1,2-diol.
Which reagent turns CH2=CHCHO into CH2=CHCH2OH, and why not H2/Ni?Answer: NaBH4, which reduces only the C=O; H2/Ni would also saturate the C=C.
Common Mistakes to Avoid
Watch out
Writing the Markovnikov product for hydroboration. B2H6 followed by H2O2/OH− always gives the anti-Markovnikov alcohol.
Forgetting that acid hydration goes through a free carbocation, so the skeleton can rearrange.
Adding water along with LiAlH4 or a Grignard reagent. Water is added only in the separate work-up step.
Using NaBH4 to reduce an ester or a carboxylic acid. It is not strong enough.
Expecting a tertiary alkyl halide to give a good yield of alcohol with aqueous KOH. Elimination wins; use moist Ag2O.
Preparing a Grignard reagent from a molecule that contains −OH, −NH2, −COOH or a terminal alkyne hydrogen.
Saying hydroboration gives anti addition. It is syn addition with anti-Markovnikov regiochemistry, two separate ideas.
Forgetting that methanal is the only aldehyde that gives a primary alcohol with a Grignard reagent.
Frequently Asked Questions
Which method gives the anti-Markovnikov alcohol from an alkene?
Hydroboration oxidation. Diborane or BH3⋅THF adds with boron
on the less substituted carbon, and alkaline hydrogen peroxide then replaces boron by −OH. Propene
gives propan-1-ol, while acid hydration of the same alkene gives propan-2-ol.
Why is oxymercuration preferred over acid catalysed hydration?
Acid hydration forms a free carbocation, which can rearrange and give the wrong
carbon skeleton. Oxymercuration goes through a bridged mercurinium ion, so no rearrangement is possible, and
it gives the same Markovnikov alcohol in about 90 per cent yield under mild conditions.
What is the difference between NaBH4 and LiAlH4?
NaBH4 is a mild hydride donor that reduces only aldehydes and ketones and
can even be used in water or alcohol. LiAlH4 is far more powerful, reducing esters, carboxylic acids
and amides as well, but it reacts violently with water so it must be used in dry ether.
Why must Grignard reactions be carried out in perfectly dry conditions?
The carbon of a Grignard reagent behaves like a carbanion, which is a very strong
base. Any acidic hydrogen, including that of water, protonates it immediately to give the alkane
R−H, destroying the reagent before it can attack the carbonyl group.
Which carbonyl compound gives a tertiary alcohol with a Grignard reagent?
A ketone. The carbonyl carbon of a ketone already carries two alkyl groups, and the
Grignard reagent adds a third, so after hydrolysis you get a tertiary alcohol. Esters with excess Grignard
also give tertiary alcohols, but with two identical alkyl groups.
What is the difference between syn and anti hydroxylation?
Cold dilute KMnO4 or OsO4 delivers both oxygen atoms from one
cyclic intermediate, so the two −OH groups add to the same face and give a cis diol. Forming an
epoxide first and opening it with acidic water attacks from the opposite face, giving a trans diol.
Which preparation of alcohols questions are most common in NEET?
NEET mostly asks the product of acid hydration or hydroboration of propene or but-1-ene, the product of reducing an aldehyde or ketone with NaBH4 or LiAlH4, and which carbonyl compound gives a primary, secondary or tertiary alcohol with a Grignard reagent. Markovnikov versus anti-Markovnikov settles most of them.
What kind of Grignard problems appear in JEE Main?
JEE Main uses Grignard reagents in multi-step problems: choose the carbonyl compound and reagent for a target alcohol, count the moles used up when the molecule has an acidic hydrogen, or predict the tertiary alcohol from an ester and excess reagent. Always work backwards from the carbon carrying the OH group.
Previous year questions on Preparation of Alcohol
3 questions from past papers, each with a step-by-step solution.