DAT Organic Chemistry Reactions etc. – Flashcards
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Aromatic Sulfonation
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Fuming sulfuric Acid (SO?/H?SO?) + Heat
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Aromatic Nitration
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Nitric and Sulfuric acids (H?SO?/HNO?), nitronium intermediate
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Aromatic Acylation (Friedel-crafts)
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Carbocation electrophile (usually acyl) is incorporated into aromatic ring, catalyzed by AlCl?
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Activating Groups
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ortho/para-directing NH?>NR?>OH>NHCOR>OR>OCOR>R
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Deactivating Groups (para)
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F>Cl>Br>I
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Deactivating (Meta)
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(e? withdrawing): NO?>SO?H>carbonyl, COOH, COOR, COR, CHO
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SN2
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Requires a good nucleophile
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E2
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Requires a strong base
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Alcohol Addition
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Addition of water to double bonds to form an alcohol
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Alcohol Addition (Grignard)
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RMgBr + carbonyl -> Alcohol
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Alcohol Reduction
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Aldehyde/Ketone/Carbox acid/Ester + LiAlH? or NaBH? -> Alcohol
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Phenol Synthesis
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Hydrolysis of diazonium salts
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Alcohol Dehydration
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Requires Strong acid i.e. H?SO? and heat
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Alcohol Substitution
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-OH is not a good leaving group so hard to do. Best to add change -OH into a H?O or add tosyl chloride and form a tosylate (great leaving group)
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Alcohol Substitution (alkyl halide)
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Can also be done with PBr? to create alkyl bromides
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Alcohol Oxidation
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PCC yields aldehydes, KMnO? will create a carboxylic acid or ketone
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Ether Synthesis
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Condensation of R-OH in ACID
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Williamson Synthesis
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Follows SN2 mechanism
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mCPBA
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Used to form an oxirane, can also be used on a hexene (1 double bond)
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Aldehyde Oxidation
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Produces a carboxylic acid. KMnO?, CrO?, Ag?O or TOLLEN's Reagent
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Ketone Oxidation
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Does not exist
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Enolization
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Michael Addition
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Hydration of Carbonyl
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H?O acts as the nucleophile
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Cyanohydrin Formation
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Aldehyde and ketone react with HCN
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Hydrazone Formation from Carbonyl
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Reagent = H?NNH?
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Wittig Reaction
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C=O ?C=C
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Carboxylic Acid Synthesis From 1° OH
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Reagents: KMnO?, K?Cr?O?, CrO?
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Carboxylic Acid Synthesis from Alkene
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CH?CH=CHCH?CH? ?1)KMnO?, OH?, heat 2)H?? CH?COOH + CH?CH?COOH Yields two carboxylic acids at site of cleavage
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Carbonation of Grignard Reagents
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(CH?)?CBr ?Mg/ether?(CH?)?MgBr ? 1.CO? 2. H?, H?O ? (CH?)?CCOOH
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Hydrolysis of Nitriles
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Yields carboxylic acid and NH??
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Nucleophilic Substitution of Carboxylic Acid (general)
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Yields a ketone where the Nu? takes the place of the alcohol
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Reduction of Carboxylic Acids (general)
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Results in corresponding primary alcohol
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Ester Formation from Carboxylic Acids
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Requires an alcohol under acidic conditions, yields an ester and water. Water is used as a leaving group
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Acyl Halide Formation
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Reagents: Carboxylic acid and SOCl? or other halide
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Soap Formation
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Carboxylic acids react with NaOH to form salts, organize non-polar tails around a non-polar substance and polar heads facing water. Spherical structure is called micelles.
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Decarboxylation
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Results in loss of CO? and thus loss of entire carboxyl when heated
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Hydrolysis of Acyl Halide
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Very rapid reaction
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Anhydride Formation from Acyl Chloride
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Reaction of carboxylate salt (RCOO?) and acyl chloride (RCOCl) produces an anhydride
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Acyl Halide ? Ester
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Nucleophilic attack by an alcohol results in replacement of the halide in an acyl halide with an ester EtOH + CH?COX -; CH?COOEt + HX
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Acyl Halide ? Amide
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Nucleophilic substitution CH?COX + 2NH? ? CH?CONH? + NH?Cl
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Acyl Halide Reduction
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CH?COX + H?/Pd/BaSO?/quionoline/Lindlar's Catalyst ? CH?OH
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Cyclic Anhydride Self-condensation
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Only 5 and 6 membered rings are easily made
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Condensation of 2 Carboxylic Acids
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Carboxylic acids under anhydrous conditions results in an anhydride and loss of H?O
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Hydrolysis of Anhydrides
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Results in 2 equivalents of carboxylic acids when exposed to water
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Anhydride ? Amide
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Cleaved by NH? to produce an amide and a carboxylic acid. The COOH and NH? can react further to create an ammonium carboxylate
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Anhydride ? Ester + Carboxylic Acids
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Reacting with -OH will produce one ester and one molecule of COOH. "Splits" the original molecule
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Anhydride acylation
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Reagents: AlCl? or other Lewis acid will produce an aryl ketone (benzene with a ketone) and a carboxylic acid
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Transesterification
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Transform one ester into another, -OH acts as a nucleophile and displaces alkoxy on original ester
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Grignard Addition to Ester
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Results in a tertiary alcohol if enough reagent is added and the intermediate ketone is not too bulky (MgBr)
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LAH Reduction of Ester
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Produces two different alcohols
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Amide Hydrolysis
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Results in COOH + NH?, occurs under acidic conditions via nucleophilic substitution
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Hofmann Rearrangement
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Converts amides to 1° amines with loss of carbonyl as CO?
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Amide Reduction
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Reagent: LAH, results in corresponding amine, no C atom is lost
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Acyl Halides
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Most reactive (least stable) carboxyl derivative, can do Friedel-Crafts acylation, and can be reduced to alcohols or aldehydes
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Anhydrides
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Second most reactive carboxyl derivative, can be formed via substitution or condensation and can perform Friedel-Crafts acylation
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Esters
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Not very reactive carboxyl derivative, hydrolyze to yield acids + alcohols, can react with Grignard reagents to produce a 3° alcohol
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Amides
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Least reactive carboxyl derivative, can be formed by reacting many substrates with amines or ammonia, can be transformed to 1° amines via Hofmann rearrangement
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Amine Synthesis from -NO?
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Iron or Zn as a catalyst
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Nitrile ? Amine
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LAH = lithium aluminum hydride, produces a primary amine
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Imine ? Amine
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Aldehyde or ketone reacted with ammonia, then reduced with hydrogen and a Ni catalyst
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Amide ? Amine
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Reacting an amide with LAH produces RCH?NH?
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Exhaustive Methylation
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Amine ? ammonium iodide ?ammonium hydroxide ? least substituted alkene
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C=O IR Peak
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1750-1800 (sharp)
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O-H IR Peak
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3200 - 3600 (broad)
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N-H IR Peak
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3400 - 3500 (sharp)
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What is the relationship between the H and LG during an E2 reaction?
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They must be anti-periplanar to one another
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When determining a molecules stero-center configuration (R+S), what direction should the lowest priority group face?
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The lowest priority group (usually H) should be facing away from you in a Fischer projection
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OsO4 / t-BuOOH / base
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Syn-diol addition
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COOH IR Peak
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Peak at ~1710 cm?¹
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What does non-volatile refer to in organic chemistry?
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A substance that does not turn into a gas easily, i.e. thing layer chromatography is a method sufficient for separating non-volatile substances
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Geometric isomer
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isomer that differs in the placement of groups around a double bond; cis/trans isomerism
