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MindMap Gallery organic chemistry
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organic chemistry
Compilation of basic organic chemistry, including basic concepts, spectral analysis, reaction mechanisms, biomolecules, carbanions, acid derivatives, etc.
Edited at 2023-12-15 17:22:54
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organic chemistry
- Valentine's Day marketing campaign
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- Outline
organic chemistry
basic concepts
Compound naming
common nomenclature
n-heptane, isopropyl alcohol
Succinic acid, tartaric acid
Systematic nomenclature (IUPAC)
Determine the main functional group: -COOH>-SO3H>-CO2R>-COX>-CONH2>-(C=O)2O>-CN>-CHO>-C=O>-OH(alcohol)>-OH(phenol)> -NH2>-OR>Alkynes>Alkenes>-R>-X>-NO2>-NO
Determine the main chain: more main functional groups → longer main chain → more side chains → smaller side chains → more carbon atoms in each side chain → fewer side chain branches
Minimum series principle: Make the position of the substituents as small as possible
Order rules: Arrange by atomic number, put small groups first (English naming is in English alphabetical order)
Naming of special structures
Bridge ring: Numbering starts from the bridgehead carbon and is numbered from the large ring to the small ring. The bridgehead carbon is not counted. Example: Bicyclic【1.1.0】butane
Spiro ring: Numbering starts from the carbon adjacent to the spiro atom, from small rings to large rings, and the spiro atoms are counted, for example: spiro [4.5] decane
Biphenyl: The numbering starts from the bridgehead carbon, and the number of the second benzene ring is added with ‘
Heterocycle: Numbered starting from the heteroatom. When there are multiple heteroatoms, they are arranged according to O, S, Se, Te, N, P, As, Sb, Bi, Ge, Sn, Pb, B, and Hg (rough rule: low valence to high, atomic number from small to large)
chemical bond
Atomic orbital theory: Pauli exclusion principle (each orbit can accommodate up to two electrons), minimum energy principle (electrons occupy low-energy orbits first), Hund's rule (degenerate orbits must be filled with one electron each before they can accommodate the second electron)
Chemical bonds: ionic bonds (electronegativity difference>1.7), covalent bonds (electronegativity difference<0.6), metallic bonds
Valence bond theory: valence, orbital hybridization
Molecular orbital theory: bonding orbitals, antibonding orbitals
Polarity: dipole moment μ=charge value q*distance between two charge centers d, the direction is from positive charge to negative charge
The bond length of the covalent bond (single bond > conjugated double bond > double bond > triple bond), bond angle (109.5° for regular tetrahedron), bond energy (bond dissociation energy, average bond energy)
conformation
Cis-trans isomerism: Z (cis), E (trans)
Optical isomerism
Specific optical rotation (= optical rotation/tube length/density of test solution), molecular specific optical rotation (specific optical rotation*molecular weight/100)
Relative configuration (D-glyceraldehyde is D, L-glyceraldehyde is L)
Absolute configuration (hydrogen is farthest, other groups are in order from large to small, clockwise R, counterclockwise S)
Enantiomeric excess ee (integrated area difference/area sum), diastereomeric excess de
Conformation: rotational energy barrier, conformation distribution, equatorial bond e, upright bond a
Acid-base theory
Proton theory: conjugate acids and bases, the one that can donate a proton is an acid
Electron theory: Lewis acid, acid can accept electrons
Soft and hard acid-base theory
The central atom with small size, high charge number and low polarizability is hard acid.
High electronegativity, low polarizability, and hard base atoms that are difficult to oxidize
Spectral analysis
Ultraviolet (UV)
Principle: Electronic transition, △E=hv
Molar absorption coefficient k: determined by the electron transition probability. The smaller the binding of electrons by the atomic nucleus, the larger the k value. Generally, the k value for π→π* transition is larger, and the k value for n→π* transition is smaller.
Influencing factors: chromophore (ππ conjugation) and auxochromophore (p-π conjugation), steric hindrance, solvent, PH
Auxiliary color effect: p-π conjugation shifts the absorption wavelength to a longer wavelength and deepens the color. -OH, -OR, -NH2-NR2, -SR, -X, etc. are all auxiliary color groups.
Infrared (IR)
Principle: Molecular vibration energy level transition
Detection: Fourier transform spectrometer (FTS), gas, liquid and solid can be measured
Functional group area (4000~1350cm-1), fingerprint area (1350~650-1)
Influencing factors: electronic effects, vibration coupling, sample state (solid, liquid, gas), test conditions
Nuclear Magnetic (NMR)
Principle: Nuclear energy state transition (spin quantum number, saturation, relaxation)
Detection: Instruments with high frequency have good resolution and high sensitivity. Sweep frequency, sweep field (fix electronic wave frequency, change magnetic field strength)
chemical shift
shielding effect, deshielding effect
Influencing factors: electronegativity, anisotropy, hydrogen bonding (mostly producing a deshielding effect), solvent effect (great influence on active hydrogen), Van der Waals effect (the internuclear distance is smaller than the van der Waals radius, producing a deshielding effect)
coupling constant
Conditions for spin coupling:
Proton magnetism is not equivalent
The distance between protons does not exceed three single bonds (remote coupling can occur by inserting double or triple bonds)
Coupling constant J=Split peak distance*sweeping field frequency (coupling constant does not change with changes in external magnetic field)
Benzene ring: J(1-2)=7~10, J(1-3)=0~3
Alkenes: 3J cis=11~14, 3J trans=11~18
Interpret spectrum
First-order spectrum: conforms to the n 1 rule (this is only true when the chemical shift difference Δν of the two groups of protons is divided by the coupling constant J≥6) and the same group of nuclei is magnetically equivalent
Advanced spectrum: A hydrogen spectrum that does not meet the conditions of the first-level spectrum and requires complex calculations to calculate coupling constants and chemical shifts.
Impurity peak
solvent peak
Rotating edge peak: generated by the rotation of the sample tube
13C isotope edge peak: generated by coupling with 13C, only visible when the concentration is very high
carbon spectrum
The coupling spectrum is complex, and protons are generally used to decouple the spectrum.
Features of 13C spectrum: no integration, large chemical shift (obvious features), 13C-13C coupling does not need to be considered, long relaxation time, weak spectral line intensity
DEPT (135°) spectrum: Level 1 carbon, level 3 carbon has an upward peak, level 2 carbon has a downward peak, and level 4 carbon has no peak.
DEPT (90°) spectrum: only the third-order carbon peak appears
two-dimensional spectrum
NOESY (i.e. two-dimensional NOE): the correlation peak reflects the spatial distance relationship between the core and the core, regardless of the number of chemical bonds between the two.
H-H COSY: The correlation peaks reflect the 3J coupling relationship. Sometimes there are a few correlation peaks that reflect the long-range coupling. When 3J is very small (such as the dihedral angle is close to 90°, yes 3J is very small), there may not be a corresponding cross peak.
ROESY: Incomplete correlation peaks indicate spatial adjacent relationships, and some reflect coupling relationships.
Mass Spectrometry (MS)
Principle: Mass-to-charge ratio of ion fragments
Instrument: Mass spectrometer
Quadrupole mass spectrometer, magnetic mass spectrometer, time-of-flight mass spectrometer, Fourier transform ion cyclotron resonance mass spectrometer, ion trap mass spectrometer
Ion source: electron bombardment source (EI source), fast atom bombardment source (FAB source)
Interpret spectrum
Nitrogen Rule: Even-numbered nitrogens have even molecular weights, and odd-numbered nitrogens have odd-numbered molecular weights.
Isotope peak: 35Cl: 37Cl=3:1, 79Br: 81Br=1:1
Fragmentation into fragment ions
Generation of oxygen cations: aldehydes and ketones generate oxygen cations and then undergo α-cleavage; alcohols and ethers generate oxygen cations and then undergo β-cleavage.
Generate carbocation: common benzyl type, allyl type, tertiary carbon cation
Remove stable neutral small molecules (often accompanied by rearrangements)
reaction mechanism
electrical effect
induction effect
Electron-withdrawing group: NO2>C=O>SO2>COOR>CN>F>Cl>Br>I>C three C>OCH3>OH>C6H5>C=C>H
Electron donating group: (CH3)3C>(CH3)2CH>CH3CH2>CH3>H
conjugation effect
Electron-withdrawing conjugation effect: -NO2, -CN, -COOH, -CHO, -COR
Electron donating conjugation effect: -NH2(R),-NHCOR,-OH,-OR,-OCOR,Ph
reaction type
free radical reaction
There is no obvious solvent effect, and acid and alkali have no obvious effect. Oxygen will consume free radicals and cause an induction period in the reaction.
Free radical stability: 3°C·＞2°C·＞1°C·＞H3C· (the lower the bond dissociation energy, the more stable the free radical)
nucleophilic reaction
Carbocation stability: 3°＞2°, allyl＞1°＞CH3
nucleophilicity
In protic solvents: RS-≈ArS->CN->I->NH3(RNH2)>RO-≈OH->N3->Br->ArO->Cl->F->H2O
In dipolar solvent: F->Cl->Br->I-
Leaving group property: p-nitrobenzene sulfonic acid>benzenesulfonic acid>Tos>I>OH2≈Br>Cl>F
SN1
Both electronic effects and steric hindrance affect the reaction rate, the nucleophilicity of the nucleophile has little effect, and the protic solvent is conducive to the reaction.
Winstein ion pair mechanism: used to explain the incomplete racemization of products in SN1.
SN2
The main reason is that steric hindrance affects the reaction rate, the nucleophilicity of the nucleophile reagent has a great influence, and dipolar solvents are conducive to the reaction (protic solvents easily solvate the nucleophile reagent)
SN1 and SN2 compete
Primary halogenated hydrocarbons are prone to SN2, tertiary halogenated hydrocarbons are prone to SN1, and secondary halogenated hydrocarbons are somewhere in between.
Benzyl halides and allyl halides can be either SN1 or SN2, and diphenyl halides and triphenyl halides react according to SN1
Ethylene and benzene halides are not prone to nucleophilic reactions
Halogens linked to the bridgehead carbon are difficult to undergo nucleophilic reactions
SN2 competes with E2
The reagent is highly alkaline, has high concentration, large volume, and high reaction temperature, which is beneficial to E2
The reagent has strong nucleophilicity, weak alkalinity and small size, which is beneficial to SN2
SN1 and E1 compete
The reagent has strong affinity and small steric hindrance, which is beneficial to SN1
The reagent is highly alkaline and has large steric hindrance, which is conducive to E1 (generally, E1 occurs only when tertiary solvents are solvolyzed in polar solvents)
electrophilic reaction
aromatic electrophilic substitution
Mechanism of aromatic cations: activation group, passivation group, positioning effect
SE1 mechanism (single molecule electrophilic substitution)
Electrophilic addition of alkenes
rearrange
wittig rearrangement: Alkyl lithium or LDA rearranges ethers into secondary alcohols
subtopic
subtopic
protecting group
Protect hydroxyl group
Benzyl chloromethyl ether (BOM)
THP: Resistant to alkali but not acid (has certain stability to aprotic acid)
Tos: stable to acid, use HBr/PhOH or Mg/MeOH for removal
Silicone:
The difference between silyl ethers mainly lies in the difference in steric resistance and electrical properties. Acidic ones with smaller steric hindrance can deprotect faster, while those with larger steric hindrance can selectively protect primary alcohols.
When using TMS protection on HMDS, a small amount of iodine can be added to catalyze it
For slow-reacting secondary and tertiary alcohols, 2,6-dimethylpyridine or DMAP can be used as catalyst
Benzyl
There are electron-withdrawing groups on the benzene ring that are difficult to remove, but electron-donating groups are easy to remove.
Hydrogen debenzylation is closely related to the solvent, the rate is: toluene < methanol < ethanol < isopropyl alcohol < THF
Protected amino group
Cbz: remove ① palladium carbon hydrogenation ② HBr/HOAc or HBr/Diox or HBr/TFA ③ Na/NH3
Protect carboxylic acid
asymmetric synthesis
asymmetric oxidation
Alkene oxide is cis 1,2 diol: OsO4-K3Fe(CN)6, dilute cold KMnO4, I2/silver acetate
Alkene oxide is trans 1,2 diol: I2/silver benzoate, peroxyacid
Asymmetric epoxidation of olefins: Historian reagent, DDO (dimethyl or ketone oxide)
asymmetric reduction
Noyori asymmetric hydrogenation
RuOAc2(BINAP): For unsaturated carboxylic acids, enamide performs better
RuX2(BINAP): performs better on β-keto acid esters
RuCl2(BINAP)(diamine): Very effective on simple ketones
coupling reaction
Heck reaction: coupling of aromatic halides and vinyl compounds using organic Pd and ligands
Afraid of oxygen and often sensitive to water
Suzuki-Miyaura reaction: coupling of aryl halides and aryl/alkenylboronic acids/borates with organic Pd and ligands
Not sensitive to water, afraid of oxygen
Songashira reaction: coupling of aromatic halides and or halogenated alkenes with terminal alkynes under Pd-Cu catalysis
Stilll coupling: palladium-catalyzed coupling of aromatic halides and organotins
Negishi coupling: coupling of aromatic halide and organozinc under palladium or nickel catalysis
Biomolecules
sugar
Fischer projection formula: aldehyde is at the top, alcohol is at the bottom, and the hydroxyl group of the bottom chiral carbon is to the right, which is D
α sugar: the hemiacetal hydroxyl group and the C-5 hydroxyl group are on different sides of the ring plane; β sugar: the hemiacetal hydroxyl group and the C-5 hydroxyl group are on the same side of the ring plane
Metarotation phenomenon: ring structure and chain structure reach equilibrium in solution
Glucose: The product of the reaction between sugar and phenylhydrazine
Amino acids, peptides, proteins, nucleic acids
Fischer projection: acid is at the top, R is at the bottom, and the position of the amino group is on the right, which is D.
Amino acids with free amino groups and ninhydrin form a purple substance
Phenols and Quinones
Overview
Phenol is weakly acidic
reaction
Claisen rearrangement: allyl aryl ether rearranges to o-allylphenol at high temperature
Fries rearrangement: Phenolic ester and Lewis acid are heated together and rearrange to hydroxyaromatic ketone
Bucherer reaction: naphthol reacts with ammonia in the presence of sodium bisulfite to form naphthylamine
ether
reaction
Auto-oxidation to peroxide
Carbon-oxygen bond cleavage: the order of cleavage is tertiary alkyl>secondary alkyl>primary alkyl>aryl
synthesis
Williamson synthesis: sodium alcohols and alkyl halides
Dehydration between alcohols: acid catalyzed
Heterocycle
Naming: start numbering from the heteroatom, make the heteroatom number as small as possible, and then make the substituent number as small as possible
Pyrrole, furan, and thiophene are all prone to electrophilic substitution, and the α position is active, and the reactivity is pyrrole > furan > thiophene
Furan is easily protonated and then ring-opened
The sulfur of thiophene is easily protonated but the ring is stable
Pyridine is difficult to undergo electrophilic substitution and is prone to nucleophilic substitution. The nucleophilic substitution sites are at the α and γ positions. The pyridine ring is not easily oxidized and can be reduced by hydrogenation. The α hydrogen in the pyridine side chain is acidic.
Pyridine nitrogen oxide compounds can undergo electrophilic substitution and nucleophilic substitution, and the reaction sites are all at the α and γ positions.
Diazines are more difficult to undergo electrophilic substitution than pyridine, and can undergo nucleophilic substitution, which occurs at the ortho-para position of nitrogen. Diazines are not easily oxidized, and the side chain α hydrogen is active.
Indole, benzofuran, benzothiophene
Position 3 is active, hydrogen is acidic
Electrophilic substitution is mainly in heterocycles
Quinoline and isoquinoline electrophilic substitutions are mainly on the benzene ring, and nucleophilic substitutions are at positions 2 and 4
Fishcher Indole Synthesis: Phenylhydrazine and ketone are heated under acidic conditions to form indole.
amine
Overview: The alkalinity of amines is affected by the solvation effect and induction effect. The greater the degree of solvation, the stronger the alkalinity. The stronger the electron-donating induction effect, the stronger the alkalinity.
reaction
Hofmann elimination: quaternary ammonium base is decomposed into olefins by heating
Oxidation
Hydrogen peroxide or peracid oxidizes to amine oxide
Cope elimination: amine oxide is heated to decompose into hydroxylamine and alkenes
Vilsmeier reaction, N,N dialkylbenzenes are formylated with DMF/phosphorus oxychloride
Benzidine rearranges; rearranges to aminobiphenyl under acidic conditions
Diazotization
Sandmeyer reaction: diazonium salt reacts with hydrogen chloride to form aromatic halide using cuprous chloride catalysis
Gattermann reaction: metallic copper replaces cuprous chloride as catalysis
Diazonium salt will slowly hydrolyze into phenol, which can be reduced to aromatic hydrocarbons using ethanol or hypophosphorous acid, and reduced to hydrazine using sodium thiosulfate, sodium sulfite, etc.
Schimann reaction: diazonium salt and fluoroboric acid generate fluorobenzene
Gomberg-Bachmann reaction: coupling of diazonium salt and aromatic ring to biphenyl under basic conditions
preparation
Gabriel synthesis method: reaction between potassium phthalamide and alkyl chloride and then hydrolysis or hydrazinolysis
Aromatic nitro reduction: iron powder, zinc powder, stannous chloride, ammonium sulfide, sodium hydrogen sulfide, sodium sulfide (first reduced to nitroso, then hydroxylamine, and finally reduced to amino)
reductive amination
Hofmann degradation
Curtius rearrangement
Schmidt reaction
pericyclic reaction
Overview: No free radicals or ionic intermediates, not affected by acid, alkali and solvent polarity, generally requires heating or light
Classification
Electrocyclization reaction: self-ring closure of conjugated alkenes
Cycloaddition reaction: ring closing between two or more molecules with double bonds
Diels-Alder reaction
1,3 dipole cycloaddition
delta migration reaction
carbanion
Overview
Alpha hydrogen acidity: acid chloride>aldehyde>ketone>ester≈nitrile>amide
The generation of enol anions is controlled by thermodynamics and kinetics, and the hydrogen extraction by large sterically hindered bases tends to produce kinetic products.
reaction
Aldol condensation: acid catalyzed or base catalyzed, mostly base catalyzed, the reaction is reversible, low temperature is conducive to the forward reaction
Claisen-Schumidt reaction: the condensation of aromatic aldehydes without alpha hydrogen and aliphatic aldehydes and ketones with alpha hydrogen
Mannich reaction: Aldehydes, ketones and formaldehyde add amines to form amine methylation products in water, alcohol or acetic acid under acidic conditions.
Robinson ring expansion: the quaternary ammonium salt of cyclohexanone and Mannheim's base generates a six-membered ring under the action of a base
Claisen condensation: base-catalyzed ester condensation, reversible
Dieckmann reaction: intramolecular ester condensation
Perkin reaction: Under high temperature and strong alkali conditions, aromatic aldehydes and acid anhydrides generate aryl unsaturated carboxylic acids.
Knoevenagel reaction: catalyzed by a weak base, aldehydes, ketones and compounds containing active methylene groups undergo dehydration condensation.
Darzen reaction: aldehydes and ketones react with alpha halogenated carboxylic acid esters under strong base to form epoxy carboxylic acid esters
Benzoin condensation: benzaldehyde is condensed under the catalysis of cyanide anions, and cyanide anions can be replaced by safer thiazole salts
carboxylic acid derivatives
reaction
Nucleophilic substitution of carbonyl carbon
Leaving group: I->Br->Cl->-OCOOR>-OR>-OH>-NH2
Hydrolysis: Under acid catalysis or base catalysis, acid halides, acid anhydrides, esters, amides, and nitriles are all hydrolyzed into acids. Nitriles can be hydrolyzed into amides under controlled conditions.
Alcoholysis: Under acid catalysis or base catalysis, acid halides, acid anhydrides, amides, and nitriles can be alcoholyzed into esters, and the esters undergo transesterification (ester exchange can be catalyzed by tetraisopropyl titanate)
Aminolysis: Under acid catalysis or base catalysis, acid halides, acid anhydrides, and esters can be ammonolyzed to amides, and amide exchange reactions occur.
Reaction with organic metals: acid halides, acid anhydrides, esters, amides and active organic metals generate tertiary alcohols (there are steric hindrances that can stay in ketones), and inactive organic metals generate ketones. Organozinc reagents can react with aldehydes and ketones but do not react with esters
Catalytic hydrogenation: acid halide, acid anhydride, ester is reduced to alcohol, amide is difficult to be reduced, nitrile is reduced to amine
Metal hydride reduction: Lithium aluminum tetrahydride can be reduced, lithium borohydride can reduce esters, and lithium alkoxy aluminum hydride epoxy can stay in aldehydes.
Alpha hydrogen reaction: the alpha hydrogen of the acid halide is more active than the ester
preparation
Preparation of esters
Preparation of acid halides
Amide preparation
Preparation of acid anhydride: acid chloride plus carboxylate
Preparation of nitrile: amide is dehydrated with phosphorus pentoxide, phosphorus oxychloride, thionyl chloride, etc.
Alkenes
participative response
Electrophilic addition (Markovitch's rule): halogens, hydrogen halides, sulfuric acid, water, organic acids, alcohols, phenols, hypohalous acids
Free radical addition (anti-Markovsky rule)
Oxidation
Oxidation to epoxy compounds: peracid
Oxidation to o-diol: dilute cold potassium permanganate, osmium tetroxide
Hydroboration
Oxidation: adding hydrogen peroxide to obtain primary alcohol
Reduction: Add carboxylic acid to obtain alkanes
hydrogenation
The smaller the double bond substituent, the easier it is to adsorb on the catalyst surface and the easier it is to hydrogenate.
Reversible, easy to dehydrogenate at high temperatures
Homogeneous catalytic hydrogenation: Wilkinson catalyst
Reaction with carbene/carbene-like: preparation of three-membered rings
Alpha Hydrohalogenation: NBS
Diels-Alder reaction: dienophile, dienophile, reversible
Preparation
Alcohol water loss: heating with sulfuric acid
Dehydrohalogenation of halogenated hydrocarbons
Dehalogenation of dihalocarbons: zinc or magnesium
huffman elimination
Amine Oxide Thermal Cracking
Thermal cracking of xanthate ester: alcohol is treated with carbon disulfide alkaline into xanthate acid, then treated with methyl iodide to form xanthate ester, and heated to decompose into olefins
wtting reaction and witting-horner reaction
Olefin metathesis reaction: under the action of a catalyst, two molecules of olefin synthesize one molecule of olefin and release one molecule of ethylene.
Alkynes
Overview:
Alkynes generally have higher melting and boiling points and densities than corresponding alkenes
Electrophilic addition is more difficult than alkenes (electronegativity: sp>sp2>sp3)
participative response
terminal alkyne hydrogen
Reacts with aldehydes and ketones to form alkynyl alcohols (base catalyzed)
Reacts with hypohalous acid to form alkynyl halide
Reacts with base to form metal alkyne
reduction
Catalytic hydrogenation: lindla catalyst cis hydrogenation to obtain olefins
Hydroboration reduction: react with borane and then add acid to form Z-type olefins
Reduction of lithium aluminum tetrahydride to E-type olefins
Electrophilic bonus
Addition with halogen, hydrohalic acid, water
Free Radical Addition: Anti-Markov's Rule
nucleophilic addition
Addition of hydrocyanic acid to enonitrile (catalyzed by copper chloride)
Addition to organic matter containing active hydrogen
Oxidation
Polymerization (catalyzed by cuprous chloride)
Preparation
Dehalogenation of dihaloalkyl
Terminal alkynes react with Grignard reagents to form new alkynes
alcohol
Overview: The exchange of hydroxyl hydrogen can occur between alcohol molecules. If the purity is high, the exchange will be slow. If the exchange is fast, the nuclear magnetic splitting of the alcohol will disappear.
participative response
Reacts with hydrohalic acid, phosphorus halide, and thionyl chloride to form alkyl halide
Oxidation to aldehyde: manganese dioxide, Jones reagent, Ofenol oxidation method, DCC/DMSO
O-diol oxidation: periodic acid, lead tetraacetate
Rearrangement of pinacol: vicinal diol rearranges to ketone under the action of acid
Preparation
Alkene hydration
Grignard reagents react with epoxides or carbonyl compounds
subtopic
aromatic ring
Overview
Aromaticity: Huckel's rule (4n 2)
The α position of naphthalene is active, and the 9 and 10 positions of anthracene and phenanthrene are active.
reaction
replace
aromatic electrophilic substitution
Positioning effect: In most cases, when multiple substitutions occur, the activating group plays a greater role than the passivating group.
Nitrification: concentrated nitric acid, concentrated sulfuric acid, heating
Halogenation: fluorination with XeF2, iodination with thallium trifluoroacetate and KI, or iodine plus nitric acid
Sulfonation: heating with fuming sulfuric acid, the reaction is reversible
Freidel-Crafts reaction
reaction reversible
Just add a small amount of Friedel-Crafts alkylation catalyst, and add an equivalent amount of Friedel-Crafts acylation catalyst.
Lewis acid activity: AlCl3>FeCl3>BF3>TiCl4>ZnCL2
Chloromethylation reaction: benzene, formaldehyde, and hydrogen chloride are heated under the action of anhydrous ZnCl2 to form chlorotoluene.
Gattermann-Koch reaction: benzene reacts with carbon monoxide and hydrogen chloride under the action of Lewis acid to form benzaldehyde
Aromatic nucleophilic substitution (SNAr): the electron-withdrawing group is an active ortho-positioning group
reduction
Birch reduction: alkali metal reduces benzene ring to 1,4-cyclohexadiene in a mixture of liquid ammonia and alcohol.
Catalytic hydrogenation: high temperature and high pressure
Oxidation: the naphthalene ring is easier to oxidize than the side chain
aldehydes and ketones
reaction
addition
Reacts with Grignard reagent to form secondary alcohol (side reaction: reduction to alcohol, 1, 4 addition)
Reacts with hydrocyanic acid to form α-hydroxynitrile
Strecker reaction: reacts with ammonium chloride and sodium cyanide to form α-aminonitrile
reacts with alkynes to form acetylenic alcohols
Reacts with amines to form imines (Sievert's base)
Reacts with hydrazine to form hydrazone
Reacts with hydroxylamine to form oxime (oxime will undergo Beckmann rearrangement into amide in strong acid)
Reacts with semicarbazide to form semicarbazone
Reacts with alcohol or orthoformate to form ketal (aldehyde) or hemiketal (aldehyde)
Reacts with sodium bisulfite to form salt
It reacts with mercaptans to form thioketal (aldehyde) (which can be catalyzed by phosphorus oxychloride). The thioketal (aldehyde) is stable and can be desulfurized into methylene with Ni.
α,β unsaturated ketone conjugate addition
1,2 addition on the carbon-carbon double bond (with soft acids, such as halogens, hypohalous acids), 1,2 addition on the carbon-oxygen double bond (with hard bases), 1,4 addition (with hard acids /Soft base)
The carbon-carbon double bond is a soft base, and the carbon-oxygen double bond is a hard acid.
reduction
Clemmensen reduction: zinc amalgam and concentrated hydrochloric acid are refluxed together to reduce to methylene.
Huang Minglong reduction: heating potassium hydroxide and hydrazine, reducing to methylene
Catalytic hydrogenation to alcohols
Reduction of metal hydrides to alcohols
Borane reduction: When reducing α, β unsaturated ketones, reduce the carbonyl group first
Meerwein-Ponndorf reaction: reduction of aluminum isopropoxide to alcohol
Bimolecular reduction: Ketones undergo bimolecular reduction coupling in aprotic solvents under the catalysis of sodium, aluminum, magnesium, aluminum amalgam or low-valent titanium reagents.
alpha active hydrogen reaction
Under the catalysis of acid or base, α hydrogen is halogenated by halogen
Aldol condensation (adlol reaction)
Oxidation
Cannizzaro oxidation: disproportionation under strong base
Baeyer-Villiger oxidative rearrangement: peroxyacid inserts oxygen into ester
other
Favorski rearrangement: base-catalyzed, α-haloketone loses halogen atom and rearranges into carboxylic acid ester
Diphenylene glycol is catalyzed by a base and rearranged by heating to benzoglycolic acid.
wittig reaction: react with phosphorus ylide reagent to form alkenes
wittig-Horner reaction: reacts with phosphite to generate olefins, the product is mainly E type
Reacts with sulfur ylide to produce propylene oxide (α, β unsaturated ketone generates cyclopropane)
Stetter reaction: 1,4 addition of benzaldehyde and α, β unsaturated ketones catalyzed by cyano anions. The cyano anions can be replaced by safer thiazole salts
preparation
Rosenmund reduction: reduction of acid chloride using partially deactivated palladium catalyst
Reduction of acid chloride with dialkyl copper lithium (dialkyl copper lithium reacts very slowly with ketones)
Reduction of acid chloride with lithium alkoxyaluminum hydride
Nenitshesku reaction: Acid chlorides and alkenes react at low temperature to form ketones under the action of aluminum trichloride.
Acyl chloride reacts with alkyne to form halogenated enone
Nitrile reacts with Grignard reagent to form ketone
Alcohol oxidation
Pfitzner-moffatt oxidation: DCC/DMSO oxidation
Dess-Martin Oxidation
Svern oxidation: oxalyl chloride/DMSO, low temperature
Oppenauer oxidation: acetone/Al[OC(CH3)3]
Active MnO2 (DCM is often used as a solvent, and the reaction is slow if polar solvents are used)
Duff reaction: active aromatic compounds and methenamine are catalyzed by acid to generate imine intermediates which are then hydrolyzed into benzaldehyde.
carboxylic acid
Overview
Electron-withdrawing groups make carboxylic acids more acidic
reaction
alpha hydrogen reaction
Hell-Volhard-Zelinski reaction: phosphorus trihalide catalyzes alpha hydrogen substitution of carboxylic acids by halogens
Esterification
decarboxylation
Hunsdiecker reaction: the silver salt of a carboxylic acid reacts with bromine to decarboxylate an alkyl halide with one carbon less
Kochi reaction: Carboxylic acid adds lead tetraacetate, and the metal halide is heated and decarboxylated to an alkyl halide with one carbon less
preparation
Nitrile or amide hydrolysis: strong acid and strong alkali reflux
Ester hydrolysis: esters of primary and secondary alcohols are catalyzed by bases, and esters of tertiary alcohols are catalyzed by acids.
Halogenated hydrocarbons
Overview
Fluorinated alkanes with less than 4 carbons, chloroalkanes with less than 2 carbons and methyl bromide are gases, and generally haloalkanes are liquids.
participative response
Nucleophilic substitution: hydrolysis, alcoholysis, NH3, CN-, N3-, etc.
Elimination reaction: strong base
Reduction: LiAlH4, NaBH4, Zn/HCl, H2/Pd
Haloform exposure to light/air decomposition: peroxidation and then removal of hypochlorous acid
Preparation of organometallic reagents (Greg's reagent, organolithium)
Preparation
Alcohol Hydrogen halide or halogenating reagent
Halogen atom exchange (sodium iodide is soluble in acetone, while sodium chloride and sodium bromide are insoluble in acetone)
Alkene and hydrogen halide addition