Organic Compounds Notes PDF

# Organic Compounds ## Carboxylic Compounds - C-H - R-Z - R-X - R-C-OH - R-C-NH2 - R-C-OR Ester ## Alcohols / Ethers - R-OH - R-O-R | Compound | Formula | |---|---| | Methanol | CH3OH | | Ethanol | CH3CH2OH | ## Naming Alcohols - 1-methyl butanol (CH3-CH2-CH2-CH2OH) - 2-Bromo-4-Pentanol (CH3-C...

# Organic Compounds ## Carboxylic Compounds - C-H - R-Z - R-X - R-C-OH - R-C-NH2 - R-C-OR Ester ## Alcohols / Ethers - R-OH - R-O-R | Compound | Formula | |---|---| | Methanol | CH3OH | | Ethanol | CH3CH2OH | ## Naming Alcohols - 1-methyl butanol (CH3-CH2-CH2-CH2OH) - 2-Bromo-4-Pentanol (CH3-CH2- CH-CH2-OH) ## Preparation of Alcohols - **Hydration of Alkene:** - CH3CH=CH2 + H20 - > CH3CH-CH3 - (2-propanol) - **Oxymercuration - demercuration** - CH3-CH=CH2 + Hg(OAc)2 - > CH3-CH-CH2 + H+ + HgOAc - H20, TAF - CH3-CH-CH2 + NaBH4 - > CH3-CH-CH3 + Hg+ + OAc- - OH, Hg(OAc) OH - **Nu-Substitution** - CH3CH2-BY + OH - > CH3-CH2OH+Br - SN1 - CH3CH2-BY + OCH3 - > CH3-CH2-O-CH3 + Br - SN2 ## Reduction of Aldehyde and Ketone - R-C=O + H2/ Ni, Pt, Pd - > R-CH2-OH - RC=O + (Ni, NaBH4, LiAlH4) - > R-CH-R ## Reduction of Carboxylic Acid - R-C-O + LiAlH4 or NaBH4 - > R-CH2OH ## Reactions of Alcohols - R-OH is a weakly acid. - R-OH has a poor leaving group ## Alkoxide Formation - CH3CH2OH + Na+ - > CH3CH2ONa + H+ - Sodium Ethoxide ## Ester Formation - CH3CH2OH + C-C-CH3 + H2SO4conc. - > CH3-CH2-O-C-CH3 - COOH + CH3OH + H2SO4conc. - > C-OCH3 ## Reaction with - HBr - CH3CH2OH + H-Br - > CH3CH2OH + Br - SN1 - CH3CH2Br + H2O - CH3-C-OH + H-BY - > CH3-C + Br + H2O - SN1 - SoCl2 (Thionyl chloride) - CH3CH2OH + SOCL2 - > CH3CH2O-Cl + CH3CH2Cl + SO2 + Cl + H+ - Ethyl Chloride ## Dehydration of Alcohol - CH3CH2OH + H2SO4 → CH2=CH2 - 180°C - β-elimination Alkene ## Oxidation of Alcohol - CH3CH2OH - > CH3-C-OH - Mild Oxidative Reagent (Corey Reagent, PCC, ChloroChromate, Cr03, KMnO4, Na2Cr207, Ag20, ZnO, HNO3, OsO4) - CH3-C-H → CH3 - C-CH3 - 350°C - Ketone # Ether (R-O-R) Preparation - **Williamson ether Synthesis** - Nu-Substitution - CH3CH2OH + Na - > CH3CH2ONa + H+ - Sod. Ethoxide - CH3CH2ONa + CH3BY - > CH3 CH2-OCH3 + Na By - From halide Alkyle. - Dehydration of Al Cohol - 2CH3CH2OH + H2SO4 → CH3CH2-O-CH2CH3 + H2O ## Reactions of Ethers - **Hydration of ether** - CH3CH2O CH2CH3 + H2SO4dil - > 2CH3CH2OH - **Cleavage of ether** - CH3CH2O-CH2CH3 + 2HBY - > 2CH3 CH2 BY+ H2O - Reaction with HBr, HI # Carbonyl Compounds - R-E-H(R') Aldehyde and Ketone - Organic Acid derivatives: - R-C-OH (Cl, OR, NH2) - Electronegative atom - R-C-R ketone - R-C-H Aldehyde - CH3OH Acid - CH3-Cl Acyl chloride - CH3-COCH3 Aromatic Ester - CH3-C-NH2 Amide | Compound | Formula | Category | |---|---|---| | Formaldehyde | H-C-H | Aliphatic Aldehyde | | Acetaldehyde | CH3-CH | Aliphatic Aldehyde | | Benzaldehyde | C6H5-CH | Aromatic Aldehyde | | Propanal | CH3-CH2-CH | Aliphatic Aldehyde | | Acetone | CH3-C-CH3 | Aliphatic Ketone | - CH3-CH=CH-C-CH3 3-Pentenone (unsaturated) - CH3CH3-CH3 2-butanone (saturated) - CH3CH=CH-C-H 2-butenal (unsaturated) - CH3-CH2-CH 2-propanal ## Aldehyde and Ketones Synthesis - **Ozonlyzation of Alkene (Reaction with O3)** - CH3CH=CH-CH3 + O3 - > CH2-C+ + CH2-C-H - CH3-C=CH-CH3 - > CH2-C-H + CH3-C-CH3 - CH3 - **Oxidation of Alcohol** - CH3CH2OH + [O] - > CH3-C-H - (CrO3, PCC, KMnO4, Na2Cr207, Ag20, ZnO) ## Reduction of Carboxylic Acid and Derivatives - CH3-C-H - > LiAlH4 or NaBH4 - > CH3-CH2OH - Aldehyde only - R-C-OH - R-C-Cl - R-C-OR - R-C-NH2 - R-C≡N - > DIBAL-H - > R-C-H - Aldehyde - Di isobutyl Aluminum Hydride (DIBAL-H) - strong reducing reagent - -78°C # Ether (R-O-R) Preparation - Williamson ether Synthesis - Nu-Substitution - From Halide Alkyle - Dehydration of Al Cohol ## Reactions of Ethers - Hydration of ether - Cleavage of ether # Carbonyl Compounds - **Aldehydes and Ketones** - **Oxidation of Alcohol** - Swern Oxidation - **Ozonlyzation of Alkene** - **Reduction of carboxylic Acid and derivatives** - Ketones swern oxidation ## Reactions of Aldehyde and Ketone - **Nu-Substitutions** - Carboxylic Acid (Cl, OR, NH2) - Electrophilic carbon reacts with nucleophiles - **Nu Addition (Aldehydes and Ketones)** - Protonation: - H20 + R-C-H(R) - > R-C-H(R) + OH ## Reduction of Aldehyde and Ketone - R-C-H(R) + LiAlH4, - > R-C-H(R) + OH - CH3-C-H + LiAlH4 - > CH3-C-H - 2HOH - CH3-C-CH3 + LiAlH4, - > CH3-C-CH3 - 2HOH ## Selective Reduction - 2-cyclo hexenone + LiAlH4/NaBH4 - > 2-Cyclo Hexenol - 2 HOH - allylic Alcohol - 2-cyclo Hexenone + H2 (1 eqav) - > Ketone - 2-cyclo Hexenone + H2 (excess) - > Cyclo Hexanol - Pd-C - CH3 - Wolff-Kishner - ZACH9) - Clemenson ## Oxidation - R-C-H - > R-C-OH ## Reaction with Grignard Compound - CH3BY + Mg - > CH3. Mg Br - Ether - R-C-H(R) + CH3MgBr - > R-C-H(R) - 2HOH - 1,2 Alcohol - H-C-H + CH3MgBr - > H-CH - 2HOH - 1, 1 Alcohol ## Reactions With Amines (loss of Water) - **Amine (Enamins)** : - R2-NH - CH3-C-CH3 - NHR+ - **i Amine (Imins)** - R-NH2 - CH3-C-CH3 - R-NH-H - CH3-C-CH3 - NH-R - CH3-C-CH3 - N-R2 - CH3-C-CH2-H - N-R2 - CH3-C=CH2 - N-Re - CH3-C-CH3 - > CH3-C-CH3 - N-R - > NH-R - Imins (Shiff bases) - Carbinol amine ## Reaction with R-OH - R-C-H(R') + RO-H - > R-C-H(R') - Hemi acetal - R-C-H(R') - > R-C-H(R') - acetal ## Halogenation at α carbon - R-C-H + C12 - > R-C-CH2 + HCl - -Halo Aldehyde - or Ketone - CH3-C-H + C12 - > CICH2-C-H - 2-Halo Acetaldehyde - 2-Chloro Acetaldehyde - CH3-C-CH3 + C12 - > CICH2-C-CH3 - 2-Chloro Acetone ## Haloform formation - CH3-C-H + 3NaOI - > IC- 3NaOH + CH3-C-ONa + CHI - Halogenation - > CH3I - Iodic Acid - Iodoform - Sodium acetate ## Aldol Condensation - 2CH3-C-H + NaOH - > CH3-C-CH2-C-H - 3-hydroxy butanal - Enolate ion (Nu) - -H20 - -SN2 # Carboxylic Compounds - Z an electronegative atom - Z= OH - > carboxylic Acid ( R-C-OH) - Z= Cl, Br, I - > Acyl chloride, Bromide, Iodide - ( R-C-Cl) - Z= OR - > Ester - (R-C-OR) - Z= NH2 - > Amide - (R-C-NH2) - **R= an Alkyl group"** | Compound | Formula | Category | |---|---|---| | Propanoic Acid | CH3-CH2-C-OH | Carboxylic Acid | | Ethanoyl Chloride | CH3-C-Cl | Acyl Chloride | | Ethanamide | CH3-C-NH2 | Alkanamide | | Methyl Ethanoate | CH3-C-OCH3 | Ester | | Ethanamide | CH3CH2-C-NH2 | Alkanamide | | Ethenyl Ethanoate | CH2C-O-CH3 | Ester | | N,N di methyl ethanamide | CH3-C-N-CH3 | Alkanamide | - **iso pentyl ethanoate )رائحة الموز (** - CH3-C-O-(CH3)3-CH3 - **iso pentyl pentanoate )رائحة الفناج** - CH3-C-O-(CH3)3_CH3 - **octanyl ethanoate )رائحة البرتقال** - CH3-C-O-(CH3)7- CH3 - **methy Butanoate )رائحة الأناناس** - CH3-C-O-CH3 ## Nu-Acyl Substitution - *Nu attack* - loss of leaving group - R-C-Nu + Z ## Nu-Addition - *Nu attack* - Protonation - R-C-Nu ## Increasing ability of leaving group - OH < NH2 < OR < CI - lowest reactive - > most reactive ## Increasing activity - Preparation of Acid - **Alkene oxidation** - RR KMnO4 - > 2R-C-OH - RR - > 2R-C-OH - CH2C12, 2 HOH, H2O2 ## Aldehyde and i Alcohol oxidation - CH3-C-H + CrO3 - > CH3-C-OH - CH3CH2OH + CrO3 - > CH3CH2-C-OH ## Alkyl benzene oxidation - Toluene (CH3) x KMnO4 - > benzoic Acid (COOH) ## Hydrolysis of cyanohidrine, Nitriles - R-C-H(R) + HCN - > R-C-H(R) + H2O - R-CH2-CN + H2O - > R-C-OH ## Carboxylation of Grignard Reagent = Grignard carboxylation - CH3-Cl + Mg - > CH3 Mg Cl - Ether - 0℃ - *Nu attack* - *Protonation* - CH3MgCl + CH3-C - > MgCl + CH3-C-OH + CH3MgCl ## Reactions of carboxylic Acid - H2O + R-C-NH2, - > R-NH3 + R-C-OH - Amide - LiAlHy + R-C-OH - > R-C-H - Reduction - R-C-H - > R-C-OR + H20 - i Alcohol - R-C-Cl + SOCL2 - > *R-C-Cl+SO2↑ + HCl* - Acyl chloride - R-C-CL + H20, - > R-C-OH - *Alpha halogenation* - R-C-OR + H20 - > R-C-OH + Acyl Cl + SO2 - Ester ## Preparation of Acyl chloride - HCl + POCL3 + R-C-OH - > R-C-Cl + SO2 + HCl - PCC (phosphorus perchloride) - PCl3 - 3R-C-Cl + H3PO3 - (*Phosphorus Tri Chloride*) ## Reactions of Acyl chloride - R-C-Cl + HCl + R-NH2 - > R-C-NH2 - Amide - i Amide - Hydrolysis - R-C-Cl + R-OH - > R-C-OR + HCI - Ester - R-C-OH + HCI - > carboxylic Acid ## Ester - R-E-OR - R-C-OH + R-OH - > R-C-OR + H2O - Ester - **Estrification = condensation Reaction** - CH3-C-OH + R-OH, - > CH3-E-OR - H2SO4 conc. - CH3OH + H2SO4conc. - > C-OCH3 - Ester - CH3OH + C-COOH - > C-OCH3 ## Reactions of Ester. - R-C-OR + HOH, - > R-C-OH + ROH - Hal hydrolysis - carboxylic Acid - R-C-Cl + ROH - > Acyl Chloride ## Reduction of carboxylic Acid, Acyl Chloride, Ester - LiAlHy, NaBH4 strong Reducing Reagent. - Di isobutyl Aluminum Hydride - (DIBAI-H) - mild reducing reagent - Lithium tri-tert-butoxy Alumanium Hydride - mild Reducing Reagent ## Reactions of Propanoyl Chloride - DLIAIHY + CH3CH2CH2OH - 2 HOH - i Alcohol propanol - DIBAL-H + CH3-CH2-C-H - 2 HOH - Propanal - DLIAI HY + CH3CH2CH2-OH - 2 HOH - Propanol - DLIAIHY + CH3-CH2-CH2-OH + R-OH (CH3-OH) - 2 HOH - Propanal - DIBAI-H + CH3-CH2-C-H - 2 HOH - Propanal