MindMap Gallery Summary of Medical Organic Chemistry Reactions
Summary of medical organic chemistry reactions, including chain hydrocarbons, cyclic hydrocarbons, halogenated hydrocarbons, alcohols, phenols, ethers, aldehydes, carboxylic acids, carboxylic acid derivatives, amines, hybrid rings, amino acids, and disaccharides. The main reactions are here~
Edited at 2022-07-08 08:50:12One Hundred Years of Solitude is the masterpiece of Gabriel Garcia Marquez. Reading this book begins with making sense of the characters' relationships, which are centered on the Buendía family and tells the story of the family's prosperity and decline, internal relationships and political struggles, self-mixing and rebirth over the course of a hundred years.
One Hundred Years of Solitude is the masterpiece of Gabriel Garcia Marquez. Reading this book begins with making sense of the characters' relationships, which are centered on the Buendía family and tells the story of the family's prosperity and decline, internal relationships and political struggles, self-mixing and rebirth over the course of a hundred years.
Project management is the process of applying specialized knowledge, skills, tools, and methods to project activities so that the project can achieve or exceed the set needs and expectations within the constraints of limited resources. This diagram provides a comprehensive overview of the 8 components of the project management process and can be used as a generic template for direct application.
One Hundred Years of Solitude is the masterpiece of Gabriel Garcia Marquez. Reading this book begins with making sense of the characters' relationships, which are centered on the Buendía family and tells the story of the family's prosperity and decline, internal relationships and political struggles, self-mixing and rebirth over the course of a hundred years.
One Hundred Years of Solitude is the masterpiece of Gabriel Garcia Marquez. Reading this book begins with making sense of the characters' relationships, which are centered on the Buendía family and tells the story of the family's prosperity and decline, internal relationships and political struggles, self-mixing and rebirth over the course of a hundred years.
Project management is the process of applying specialized knowledge, skills, tools, and methods to project activities so that the project can achieve or exceed the set needs and expectations within the constraints of limited resources. This diagram provides a comprehensive overview of the 8 components of the project management process and can be used as a generic template for direct application.
reaction summary
chain hydrocarbon
Alkanes
Halogenation reaction (sunlight, high temperature, free radicals)
Oxidation reaction (combustion)
Cleavage reaction, △
In addition to the breakage of the C chain, there is also the removal of H2,
Alkenes and alkynes
addition reaction
hydrogenation
catalyst
Add halogen
Add halogenated hydrocarbon
Following Markov's rule, H is added to C atoms with more H atoms.
Anti-Markovitch rule: In the presence of peroxide, the reaction between asymmetric olefins and HBr follows the anti-Markovnkish rule, and only HBr is a special case. Other chlorides do not have similar properties.
add water
Follow Markov's rules
Catalysis by acids – sulfuric acid and phosphoric acid
Electronic rearrangement occurs during the addition of alkynes and water
Acetylene reacts to form acetaldehyde
The hydration products of other alkynes are ketones
oxidation reaction
Oxidation of osmium tetroxide, alkenes are quantitatively oxidized to vicinal diols
Potassium permanganate oxidation
When dilute and cold, o-diol
When concentrated by heat, the double bonds are broken to form carboxylic acids and ketones
ozone oxidation
in inert solvent
Double bonds break to form aldehydes or ketones
Break the triple bond to form carboxylic acid
Special reactions of alkynes
Hydrogen atoms in alkynes are replaced by metal ions (alkyne-gan reaction)
Acetylene silver, white
Acetylene subone, brick red
Characteristic reactions of conjugated dienes
conjugate addition
1,2 bonus
1,4 bonus
Diels–Alder reaction
△
Ring formation reaction of conjugated dienes with alkenes or alkynes
cyclic hydrocarbons
Alicyclic hydrocarbons (macrocyclic alkane-like, small cyclic alkene-like)
Reacts with hydrogen, opens the ring (small ring-like alkene), only applicable to 3, 4, 5-membered rings, 5 does not react
Ni,△
Reacts with halogen, 3, 4, and 5-membered rings open, and 5+ substitution reaction occurs
Add CCl4/△, replace hv
Reacts with hydrohalic acid, 3-membered ring, addition and ring opening, 3 does not react
The only difference between small rings and alkenes is that they cannot be oxidized by common oxidants like alkenes.
When cycloalkanes react with strong oxidants under heating conditions, the rings break and generate dibasic acids.
△
Aromatic hydrocarbons
Electrophilic substitution reaction (benzene homologues react more easily than benzene)
Halogenation reaction
Fe,△
nitrification reaction
Sulfuric acid, △
At 95°C, using fuming nitric acid and concentrated sulfuric acid, nitrobenzene can be converted into m-dinitrobenzene
Sulfonation reaction
Concentrated sulfuric acid, 75~80℃
Fuming sulfuric acid (SO3, concentrated H2SO4)
Friedel-Crafts alkylation reaction
AlCl3, 0~25℃
Friedel-Crafts acylation reaction
AlCl3
oxidation reaction
As long as there is α-H, it will be oxidized to the carboxyl group connected to the benzene ring.
addition reaction
Ni,180~250℃(△)
Free radical substitution of side chains
hv or △
α–H is more easily substituted than β–H
Halogenated hydrocarbons
nucleophilic substitution reaction
Substituted by hydroxyl group to form alcohol
△, NaOH/KOH
Substituted by alkoxy to form ether
Williamson method for making ether: sodium alcohol and primary alkyl halide; if it is a secondary alkyl halide or a tertiary alkyl halide, elimination reaction is likely to occur
Substituted by cyano group to form nitrile
Ethanol, △
Only applicable to primary alkyl halides, secondary or tertiary halogenated hydrocarbons will produce olefin by-products
Replaced by nitrate to form nitrate ester and AgX precipitation
Ethanol, △
Different types of halogenated hydrocarbons can be identified based on different reaction speeds
Allyl halohydrocarbons (immediate reaction)
Tertiary alkyl halide (shock)
Secondary halogenated alkyl(heating)
Primary halogenated alkyl (long time heating)
Ethylene halohydrocarbon (non-reactive)
Benzene halide (non-reactive)
Substituted by amino group to form amine
The reaction has by-products (substitution products of all levels are mixed together), which has limitations in synthesis.
β-elimination reaction
Following Zaitsev's rule: hydrogen atoms are mainly removed from β-carbon atoms that contain less hydrogen.
Strong base, alcohol as solvent, heating
Reacts with metals to form organometallic compounds
Generate format reagents
Rate: first, second, third, iodine, bromine, chlorine (decreasing);
alcohol
Weakly acidic, reacts with active metals to release hydrogen and generate sodium alkoxide. It is easily hydrolyzed and can be stored without water.
The electron-donating induction effect weakens the acidity, and the alkalinity of sodium alcohol is the opposite. This property can be used to test
esterification reaction
C-O bond breaking (nucleophilic substitution)
Reaction with hydrohalic acid (halogenation reaction)
Primary alcohols are Sn2 reactions, others are Sn1, and Sn1 has rearrangement products
Lucas reagent is used to identify alcohols with less than 6 carbon atoms.
Tertiary alcohol, immediately turbid
Secondary alcohol, cloudy after 10 minutes
Primary alcohol, reacts when heated
Reacts with phosphorus halide or sulfoxide chloride
Can avoid the formation of rearrangement products
dehydration reaction
Intramolecular dehydration (to form alkene)
High reaction temperature
rearrangement product
To form conjugated products
More stable carbocation
When dehydrating some unsaturated alcohols, first consider whether an alkene containing a stable conjugated system can be generated. In this case, Zaitsev's rule is not followed.
Intermolecular dehydration (to ether)
Reaction temperature is low
oxidation reaction
Oxidation by strong oxidants
Selective oxidizing agent (only oxidizes alcohol, not double bonds)
PCC
Sarit
Active MnO2
Catalytic dehydrogenation to aldehydes or ketones
Characteristic reactions of adjacent diols (adjacent hydroxyl groups)
Reacts with Cu(OH)2 to reveal dark blue color
Reacts with HIO4 to break bonds and detect quantitatively
phenol
Acidic, stronger than carbonic acid
Electron-withdrawing groups, acidity enhancement
Electron-donating group, weakening acidity
Substitution reaction
Generate phenol ether
Williamson ether synthesis method, generated by reaction with alkylation reagent in alkaline solution
Generate phenolic ester
Phenol reacts with carboxylic acid derivatives to form phenolic esters
oxidation reaction
Generate p-phenylene chloride
Electrophilic substitution reaction on benzene ring
Halogenation reaction
Polar solvent (H2O) is a polysubstitution product
Non-polar solvent (CS2) is a monosubstituted product
nitrification reaction
Sulfonation reaction
Heating Alignment
room temperature ortho
Color reaction (properties of phenolic hydroxyl and enol-type compounds)
Color development with FeCl3
ether
Formation of salt
Concentrated hydrochloric acid, concentrated nitric acid
When the salt meets water, it decomposes into the original ether to achieve separation and purification.
Ether bond breaking
Hydrohalic acid, heated
Produce alcohols and halogenated hydrocarbons
Oxidation of alkyl ethers
Ring-opening reaction of epoxy compounds
Reagents containing active hydrogen, acidic conditions
When it comes to C cations, before considering steric hindrance, electronic rearrangements will occur to obtain the most stable C cations.
alkaline conditions
The ring can also be opened. In this case, the C positive ion is not considered, but the smallest steric hindrance is given priority.
aldehyde
nucleophilic addition reaction
Bonus with HCN
Steric hindrance (the main factor affecting aliphatic)
Electronic effect (main influencing factor of aromatics)
Addition with NaHSO3 produces a white precipitate of sodium α-hydroxysulfonate
Used for identification (compounds that meet the reaction conditions and compounds that do not meet the reaction conditions)
Used to purify certain aldehydes and ketones
Addition to alcohol
Generate acetal
Ketones and ethylene glycol smoothly generate cyclic ketals
It can protect the carbonyl group and can be hydrolyzed with dilute acid.
Addition to water
Reacts with amines ammonia and its derivatives
The product is easily hydrolyzed by dilute acid and protects the carbonyl group
react with format reagent
Generate alcohol, which is also a good way to synthesize alcohol
α-H reaction
Enolization
α-halogenated
alkaline conditions
Haloform reaction may occur
Identify whether there is a methyl ketone or a methyl group connected to the hydroxyl C in the structure
Synthesis of carboxylic aldehydes with one less carbon atom than methyl ketone
aldol condensation reaction
alkaline conditions
Growing carbon chain
Intramolecular condensation to form cyclized compounds
Products containing α-H can be dehydrated by heating, but if the benzene ring and carbonyl group work together, they can be dehydrated at room temperature.
Disproportionation reaction (Cannizzaro reaction)
reduction reaction
reduced to alcohol
Catalytic hydrogenation (double bonds are also added)
Metal hydride reduction (double bonds are not added)
reduced to hydrocarbons
Zn/Hg, HCl (Clemson reduction method) stable to acid
Alkaline, hydrazine, heating
oxidation reaction
Toulon's reagent
Fehling's reagent
carboxylic acid
Acidic
Electron-withdrawing groups enhance acidity
Electron-donating groups weaken acidity
Nucleophilic substitution reaction on carbonyl group
Acid halide (similar to the halogenation of alcoholic hydroxyl group)
PCl3
PCl5
SOCl2 (the by-product is gas and is easy to remove)
Anhydride
P2O5,△
ester
Reaction rate is affected by steric hindrance
Amide
decarboxylation reaction
Carboxylic aldehydes with electron-withdrawing groups on α(β)-C are unstable
Oxalic acid, malonic acid, removes one carboxyl group and retains one
Succinic acid, glutaric acid and phthalic acid are heated and dehydrated to form cyclic anhydride
When adipic acid and pimelic acid are heated, they lose water and decarboxylate to form a ketone with one less carbon.
Hensdike reaction
decarboxylation
In two steps of AgNO3, KOH and Br2/CCl4
Cozy reaction
Decarboxylate and generate halogenated hydrocarbons
reduction reaction
LiAlH4, reduces acid to alcohol, double bonds are not affected
α-H substitution
P as catalyst
Hydroxy acid
Acidic
alkyd acidic
Hydroxyl electron-withdrawing induction effect (acidity enhancement)
Molecular hydrogen bonding (enhanced)
phenolic acid acidic
Hydroxy conjugation effect (weakened)
Intramolecular hydrogen bonding (enhanced
oxidation reaction
Toulon's reagent, dilute nitric acid, hydrogen peroxide
Thermal reaction of hydroxy acids
Alpha-hydroxy acid, bimolecular dehydration, forming lactide
β-Hydroxy acid, intramolecular dehydration, generating unsaturated acid
γ-, δ-hydroxy acid, intramolecular dehydration to form cyclic lactone
w – Hydroxy acid, polyester
Thermal decarboxylation of phenolic acids
Carbonyl acid
alpha-keto acid
Ag(NH3)2 →decarboxylation
H2SO4,△→decarboxylation
Concentrated H2SO4, △→Decarbonylation (CO)
beta-keto acid
Decarboxylation to ketone by heating
Tautomerism ~ keto and enol
π–π conjugation
A six-membered ring is formed through hydrogen bonding
carboxylic acid derivatives
Degree of p-π conjugation
Acid halide<anhydride<ester<amide
p-π conjugation reduces C
Acyl nucleophilic substitution reaction
electronic effect
spatial effect
order of reactivity
Acid halide > acid anhydride > ester > amide
hydrolysis
Alcoholysis
Transesterification reaction
Ammonolysis
Under alkaline conditions (NaOH, pyridine, triethylamine)
Claisen ester condensation reaction
The condition is that sodium alkoxide
amine
alkaline
Secondary > Primary > Tertiary > Ammonia > Pyridine > Aniline
The electron-withdrawing group becomes less alkaline and the electron-donating group becomes more alkaline.
Acylation reaction of amines (aminolysis reaction of carboxylic acid derivatives)
There is no H on N of the tertiary amine, and no acylation reaction occurs.
Acylation reaction can be used to protect amino groups
Alkylation of amines
Generates a mixture of amines
Reaction of amines with nitrous acid (identification)
Primary amines generate diazonium salts and release hydrogen gas quantitatively.
Aromatic amines do not release N2 at room temperature and need to be heated to release it.
Secondary amine, produces yellow oil or solid
Tertiary amine, no obvious phenomenon
Hinsberg reaction (identification, separation) of amines "sulfonylation reaction"
Primary amine, white solid, soluble in NaOH
Secondary amine, white solid, insoluble NaOH
Tertiary amine, unreactive
Halogenation reaction
With bromine water, 2,4,6-tribromoaniline, white solid
Friedel-Crafts reaction of aromatic amines
Primary and secondary amines should be protected with acylating reagents
Tertiary amines can undergo Friedel-Crafts reaction directly
Nitrogen evolution reaction of diazobenzene chloride (substitution reaction)
Diazo is a chromogenic group used in the synthesis of pigments
application
Introduce hydroxyl group at specified position of benzene ring
"Occupancy, positioning" at a specific position on the benzene ring
Water, △→Ph-OH
CuCl,HCl→Ph-Cl
CuCN,KCN→Ph-CN
KI→Ph-I
C2H5OH/H3PO2→Ph-H
hybrid ring
Pyrrole, furan, thiophene
5 member ring
Electrophilic substitution (α-position)
Pyrrole is weakly acidic
Pyridine
alkaline
Electrophilic substitution mainly attacks the β-position
Mustard gas S(CH2CH2Cl)2
Boil alkaline water and oxidize and disinfect with bleaching powder
Lewis gas (Cl2AsCH=CHCl)
Hydrolysis ClCH=CHAs
Acts with alkaline substances
Ethylene, sodium arsenate
oxidation
Amino acid (L form)
Both sexes
Formation of inner dipolar salt (minimum solubility)
Isoelectric point pI, the concentration of anions and cations is equal
pH>pI, negative charge
pH<pI, positive charge
Features
At this time, the solubility of amino acids in water is minimum
The concentration of dipole ions is the largest, and the concentration of positive and negative ions is the smallest.
Not moving towards the poles
use
Separation and purification (using the difference in isoelectric point of different amino acids)
Dehydration into peptides (dehydration condensation)
decarboxylation reaction
Ba(OH)2,△
Reacts with nitrous acid to release N2 (property of primary amine)
Color reaction with ninhydrin hydrate
α-Amino acid reacts with ninhydrin to produce a purple color
The reaction product of proline and ninhydrin is yellow
Reaction with 2,4-dinitrofluorobenzene (amino-substituted fluorine)
For the determination of polypeptide or protein structure (dinitrobenzene method, DNP method)
peptide
When naming, the N end is in front and the C end is on the right.
Structural determination
Complete hydrolysis method
Determine sort order
N-terminal
2,4-dinitrofluorobenzene
Isothiocyanate method (ring formation)
C-terminal
A. Carboxypeptidase method
B. Hydrazide method
Enzyme catalyzes partial hydrolysis of peptide bonds
Sugar (D type)
structure
α-waving style, less stable
β-surrender, more stable
alkaline isomerization
Conversion between Keto and Enol
epimerization
Epimers (only one chiral carbon atom has the opposite configuration, and the other chiral carbon atoms have the same configuration)
Glycoside formation
Name: Ligand Residue of Sugar Glycoside
Dry HCl catalysis
Oxidation reaction (carried out in open chain form)
Toulon's reagent, Fehling's reagent
Bromine water oxidation (acidic), no isomerization
Can oxidize aldose, but cannot oxidize ketose (cannot isomerize to aldose)
Nitric acid oxidation
Oxidize aldose to glycocaric acid
enzymatic oxidation
All monosaccharides are reducing
adult reaction
Monosaccharide and excess phenylhydrazine, heating
Glucose, yellow crystals
Sugar phenylhydrazine→hydrazone→hydrazine
Different sugars have different crystal forms and melting points. Use sugars to identify different sugars.
Esterogenesis
Dehydration reaction (to form ether, to form double bonds)
The product reacts with phenols to produce colored substances, which are used for sugar identification.
disaccharide
sucrose
Hydrolyzed into glucose and fructose
There is no optical rotation phenomenon, it cannot form reagents, and it cannot reduce Toulon's reagent and Fehling's reagent.
fructose
Hydrolyzed into two molecules of glucose
Reducibility: reduction of Toulon's reagent and Fehling's reagent
Can form maltose with phenylhydrazine
variable rotation phenomenon
lactose
Hydrolyzed into galactose and glucose