Related to hydrogen bonds, alkyl groups in alcohol molecules have hindering hydrogen bond association. The larger the hydrocarbon group, the stronger the hindrance.

Cannot use CaCl2 and MgCl2CuSO4 to dry lower alcohols

pKa=16～18

Primary alcohol > Secondary alcohol > Tertiary alcohol

Main influencing factors: Solventization of alkoxy anions

Preparation of sodium alkoxide

Preparation of magnesium alcohol and Mg in I2

Alcohol and aluminum amalgam to produce aluminum alcohol

syllium salt

Reaction mechanism

Relative activity

Lucas reagent identification of primary and secondary tertiary alcohol

Reactions involving neon-group participation

Alcohol acts with PBr3 and PI3 to form halogenated hydrocarbons and phosphorous acids (conformation flip)

Carbon atoms connected to hydroxyl groups are chiral and have a configuration maintained

In nucleophilic solvent, configuration remains

Add pyridine and turn the configuration

Reaction mechanism

Relative reaction activity

Dehydration orientation

SN2

Generally speaking, low temperatures produce ethers and high temperatures produce ethers

For tertiary alcohols, the main olefins are largely dispelled.

Alcohol and hydrohalogenic acid SN1 are prone to rearrangement

Both dehydration of primary and secondary tertiary alcohols is E1, which is prone to rearrangement.

Alcohol reacts with sulfuric acid to form hydrogen sulfate, nucleophilic substitution

The product is olefin during the reaction of tertiary alcohol

Primary alcohol tertiary alcohol tertiary alcohol

Cannot directly obtain esters, alcohol and phosphoryltrichloride react to obtain esters

Reaction of alcohol and sulfonyl chloride to obtain ester

Sulfonate negative ions are weak bases, good leaving groups

Preparation of sulfonate from alcohols does not involve carbon-oxygen bond breakage, and the configuration remains

In K2Cr2O7-H2SO4, it is first oxidized to form aldehyde, and then oxidized to carboxylic acid

Stop in the aldehyde stage

Generally stable, under peroxy acid or KMnO4 conditions, it may continue to oxidize to carboxylic acid.

Without α-hydrogen, it is difficult to oxidize Under severe acid oxidation conditions, dehydrate to an olefin first, and then the olefin oxidizes and breaks to form a mixture of small molecule carboxylic acids and ketones

C-C bond breaks, forming two molecules of carbonyl compounds and iodine acid Add silver nitrate to produce white precipitate

After removing the hydroxyl group, it generates more stable carbopositive ions to determine the rearrangement direction

pKa=10

Phenol is more acidic than alcohols

Generate blue-purple complexes

Reaction with enol

Due to the stability of p-π conjugation, it is difficult to dehydrate into ethers.

Sodium phenol and halogenated hydrocarbons

With more active acid chloride or acid anhydride

Phenol and bromine water form white precipitate of tribromophenol at room temperature

Nitration with dilute nitric acid, o-nitro and p-nitrophenol at room temperature (low yield)

2,4,6-Trinitrophenol: sulfonation of concentrated sulfuric acid, introduction of sulfonic acid groups, enhance antioxidant ability (introduce electron-absorbing groups on the benzene ring, generally enhance antioxidant ability), add nitric acid, nitration, heating, Nitric acid substitutes the sulfonic acid group to form picric acid.

Phenol and nitrite acid effect to produce p-nitrosophenol

Room temperature ortho-substitution Paraposition substitution at 100℃

Without AlCl3 as a catalyst, complexes will be formed Commonly used H3PO4, HF, BF3 and polyphosphate as catalysts

In the acylation reaction, BF and ZnCl2 are used as catalysts, and the acylating reagent can be directly used with carboxylic acid rather than acid chloride.

Under AlCl3 catalyzed, the acyl group is transferred from the oxygen atom to the ortho- or para-position of the benzene ring to form phenolone ketones

Acid or alkaline conditions, phenol condensates with formaldehyde, and is used in the preparation of phenolic resins in industry.

Phenol reacts with acetone to form bisphenol A under acid catalysis

Phenol and chloroform react in sodium hydroxide solution, and an aldehyde group is introduced at the ortho-position of the aromatic ring, and after acidification, it forms ortho-hydroxybenzaldehyde.

Alkaline conditions are more likely to occur

The addition direction of asymmetric olefins and water complies with the Marshmallow rule. Adding hydroxyl groups to double bond carbon atoms with less hydrogen, except for ethanol, all secondary and tertiary alcohols are obtained.

Carbon positive ions are generated and rearranged

Ethylene reacts with aqueous mercury acetate to form hydroxymercury compounds, and then treats NaBH4 to obtain alcohol without rearrangement.

Secondary or tertiary alcohol, Martha

Preparation of primary alcohols from endogenic alkenes, anti-Markanium addition

First add, R-to the carbonyl carbon, Mg X is connected to oxygen

The addition product is magnesium alcohol, hydrolyzed to obtain alcohol and basic magnesium halide

Step by step ~ Addition and hydrolysis

Olefins are oxidized in dilute KMnO4 alkaline solution to form cis 1,2-diol

Open ring stereochemistry is trans