WORKBOOK FOR ORGANIC SYNTHESIS: DISCONNECTION APPROACH
THE BASICS CHAPTER ALKANES CYCLOALKANES REACTION BASICS ALKENES AND CARBOCATIONS ALKYNES STEREOCHEMISTRY ALKYL HALIDES AND RADICALS SN1, SN2, E1, AND E2 REACTIONS NMR CONJUGATED SYSTEMS AROMATICS ALCOHOLS ETHERS ALDEHYDES AND KETONES CARBOXYLIC ACIDS CARBOXYLIC ACID DERIVATIVES CARBONYL ?-SUBSTITUTION REACTIONS AND ENOLATES CHAPTER 19 CARBONYL CONDENSATION REACTIONS CHAPTER 20 AMINES SOLUTIONS TO PROBLEMS CHAPTER 1 THE BASICS CHAPTER 2 ALKANES CHAPTER 3 CYCLOALKANES CHAPTER 4 REACTION BASICS CHAPTER 5 ALKENES AND CARBOCATIONS CHAPTER 6 ALKYNES CHAPTER 7 STEREOCHEMISTRY CHAPTER 8 ALKYL HALIDES AND RADICALS CHAPTER 9 SN1, SN2, E1, AND E2 REACTIONS CHAPTER 10 NMR CHAPTER 11 CONJUGATED SYSTEMS CHAPTER 12 AROMATICS CHAPTER 13 ALCOHOLS CHAPTER 14 ETHERS CHAPTER 15 ALDEHYDES AND KETONES CHAPTER 16 CARBOXYLIC ACIDS CHAPTER 17 CARBOXYLIC ACID DERIVATIVES CHAPTER 18 CARBONYL ?-SUBSTITUTION REACTIONS AND ENOLATES THE BASICS 1 1 HYBRIDIZATION, FORMULAS, PHYSICAL PROPERTIES 1 SELDANETM IS A MAJOR DRUG FOR SEASONAL ALLERGIES; RELENZATM IS A COMMON ANTIVIRAL O O OH NH NH H2N OH OH OH NH O RELENZATM C D O O H BENADRYLTM (ANTIHISTAMINE) CL ZINGERONE (A CONSTITUENT OF THE SPICE GINGER) O N H 3 A ONE TYPE OF CARBENE, [:CH2], A VERY REACTIVE SPECIES, HAS THE TWO UNSHARED ELECTRONS IN THE SAME ORBITAL AND IS CALLED “SINGLET” CARBENE IDENTIFY THE ORBITAL AND PREDICT THE HCH BOND ANGLE B ANOTHER TYPE OF CARBENE IS CALLED “TRIPLET” CARBENE AND HAS A LINEAR HCH BOND ANGLE IDENTIFY THE ORBITALS HOUSING THE TWO LONE ELECTRONS 4 A WHICH HAS THE HIGHER BP? B LOWER MP? N H N OR OR HO OH HO OH CATECHOL HYDROQUINONE 7 PENICILLIN V AND THE ANTIULCERATIVE CIMETIDINE (TAGAMETTM – THE FIRST BILLION DOLLAR ETHICAL DRUG) HAVE THE STRUCTURES BELOW: N O H N S O CO2H HN N S N H N H N C N PENICILLIN V CIMETIDINE A B C D A COMPLETE THE MOLECULAR FORMULAS FOR EACH PENICILLIN V: C_____H_____N_____O_____S CIMETIDINE: C_____H_____N_____S B IDENTIFY THE TYPE OF ORBITAL (S, P, SP, SP2, SP3) THAT HOUSES THE LONE ELECTRON PAIRS ON THE ATOMS INDICATED BY ARROWS A, B, AND C IN THE ABOVE STRUCTURES A ________ B ________ C ________ C THE BOND BETWEEN THE CARBONYL CARBON AND NITROGEN (INDICATED BY ARROW D) IS SOMEWHAT STRONGER THAN A SINGLE BUT WEAKER THAN A DOUBLE BOND GIVEN THAT FACT, WHAT TYPE OF ORBITAL HOUSES THE LONE PAIR OF ELECTRONS ON THAT NITROGEN? (SUGGESTION: DO THIS PROBLEM AFTER STUDYING RESONANCE ) D HOW MANY LONE PAIRS OF ELECTRONS ARE IN EACH STRUCTURE? PENICILLIN V: ________ CIMETIDINE: ________ WORKBOOK FOR ORGANIC SYNTHESIS: THE DISCONNECTION APPROACH H2N WORKBOOK FOR ORGANIC SYNTHESIS: THE DISCONNECTION APPROACH NH O O O TAMIFLUTM (ANTIVIRAL) A B C N N NH F O HO2C CIPROTM (ANTIBIOTIC) HO OH C CH YASMINTM COMPONENT (OCP) 1 2 ACIDS AND BASES THAT CAN EXIST IN AMMONIA? BOVE ANSWER WRITE A REACTION TO DESCRIBE WHAT USING CURVED ARROW NOTATION, WRITE LEWIS ACID/BASE EQUATIONS FOR EACH OF THE FOLLOWING REMEMBER TO WHAT IS THE STRONGEST BASE ODIUM HYDRIDE (NAH) IS, IN FACT, A STRONGER BASE THAN THE A S HAPPENS WHEN NAH IS ADDED TO NH3 USE ARROWS TO SHOW THE FLOW OF ELECTRONS HICH IS THE STRONGER BASE: (CH3)2NH OR CH3-O-CH3? 2 W C PLACE FORMAL CHARGE ON ALL APPROPRIATE ATOMS LABEL THE REACTANTS ON THE LEFT OF THE ARROW AS LEWIS ACIDS B WORKBOOK FOR ORGANIC SYNTHESIS: THE DISCONNECTION APPROACH N C S: E LYNESTRENOL, A COMPONENT OF CERTAIN ORAL CONTRACEPTIVES, HAS THE STRUCTURE O HA HB C C ORMULA: C___H___O RESPECTIVELY, AND THE PKA OF AMMONIA IS ABOUT 35 HE CONJUGATE BASE OF LYNESTRENOL WITH AMMONIA IS THE KEQ FOR THE ABOVE REACTION ABOUT EQUAL TO, GREATER THAN, OR LESS THAN 1? THE STRUCTURE OF IBUPROFEN (A A CALCULATE THE MOLECULAR F B THE PKAS OF HYDROGENS A AND B ARE ABOUT 16 AND 25, WRITE A BRØNSTED-LOWRY EQUATION FOR THE REACTION OF T C ) AND ACETAMINOPHEN (B) ARE DRAWN BELOW CO2H A HO NH O B A WRITE A REACTION FOR THE CONJUGATE BASE OF A WITH B WORKBOOK FOR ORGANIC SYNTHESIS: THE DISCONNECTION APPROACH WHICH SPECIES HAS THE ABILITY TO QUANTITATIVELY (COMPLETELY) REMOVE THE PROTON HA (PKA 22) FROM B C IS KEQ ABOUT EQUAL TO, LESS THAN, OR GREATER THAN A ETOH B HOAC C CA OF HYDRIDE D CB OF ETOH STRESS LEVELS IN HORSES MAY BE MONITORED BY MEASURING URINE ESTRADIOL COMMENT ON THE KEQ FOR THE ACTION OF THE CONJUGATE BASE OF NITROMETHANE (PK 10 3) WITH ESTRADIOL ESTRADIOL NITROMETHANE 0 PYRIDINIUM CHLORIDE IS DRAWN BELOW PLACE THE APPROPRIATE FORMAL CHARGE ON THE ATOMS THAT BEAR IT A N H CL THE PKAS FOR PYRIDIN M CHLORIDE AND SODIUM BICARBONATE (NAHCO3) ARE 5 2 AND 10 2, RESPECTIVELY RITE A BRØNSTED-LOWRY EQUATION FOR THE REACTION OF PYRIDINIUM CHLORIDE WITH THE CONJUGATE BASE OF IS KEQ GREATER THAN, LESS THAN, OR ABOUT ONE? B IU W BICARBONATE USE CURVED ARROW NOTATION TO SHOW THE FLOW OF ELECTRONS C WORKBOOK FOR ORGANIC SYNTHESIS: THE DISCONNECTION APPROACH 1 3 RESONANCE ORBITAL HOUSING THE ELECTRONS SPECIFIED BY THE ARROWS 1 IDENTIFY THE TYPE OF CH N O C O H3C H HICH SPECIES HAS THE LOWER PKA, H C N OR H O C N ? 2 W HOW MANY NUCLEI CAN REASONABLY BEAR THE CHARGE IN EACH OF THESE IONS? D THE COMPOUND BELOW CAN BE PROTONATED AT ANY OF THE THREE NITROGEN ATOMS TO GIVE A GUANIDINIUM ION ERIVATIVE (CREATINE PHOSPHATE AND THE AMINO ACID ARGININE POSSESS THIS MOIETY) ONE OF THESE NITROGENS IS EN NH WORKBOOK FOR ORGANIC SYNTHESIS: THE DISCONNECTION APPROACH 5 DRAW A RESONANCE STRUCTURE THAT IS MORE STABLE THAN THE ONE GIVEN USE CURVED ARROWS TO DERIVE H A B O O O OZONE N C D C C N: H H OH HOW MANY NUCLEI CAN REASONABLY BEAR THE CHARGE IN EACH OF THE FOLLOWING IONS? O C D RECALLING THAT RESONANCE IS A STABILIZING FORCE, EXPLAIN WHY THE PKA OF HA IN A IS (ONLY!) ABOUT 10 H HA O O A 8 EITHER XYGEN IN ACETIC ACID (HOAC) COULD, IN THEORY, BE PROTONATED TO PRODUCE TWO DIFFERENT CONJUGATE ACID FORM DRAW EACH AND EXPLAIN WHICH IS MORE FAVORED O S WORKBOOK FOR ORGANIC SYNTHESIS: THE DISCONNECTION APPROACH HOW MANY NUCLEI CAN REASONABLY BEAR THE CHARGE OR ODD ELECTRON IN EACH OF THE FOLLOWING? O H I CH3O H CL N H N A B C 0 B ’S MOLECULAR DIPOLE MOMENT (P) IS LARGER THAN A’S EXPLAIN O O A B 1 BIOLUMINESCENCE IN FIREFLIES IS A RESULT OF THE CONVERSION OF CHEMICAL ENERGY (IN ATP) TO LIGHT ENERGY PECIFICALLY, ATP, O , AND THE ENZYME LUCIFERASE CAUSE LUCIFERIN (~ 9 MG CAN BE COLLECTED FROM ABOUT + HV N S S N HO O WORKBOOK FOR ORGANIC SYNTHESIS: THE DISCONNECTION APPROACH