CHEM 2370 DANDEKAR

Solomons Chapter 8 (9th ed)

CHAPTER 8
ALKENES & ALKYNES : REACTIONS
- INTRODUCTION - REGIOCHEMISTRY : MARKOVNIKOVS RULE - ADDITION OF : Br2 , Cl2 - OXIDATION - CARBENES - SYNTHETIC STRATEGIES

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Solomons Chapter 8 (9th ed)

INTRODUCTION:
ADDITION REACTIONS : A-B >C=C< > CA CB <

sp

ALKENES A-B CC CA = CB A-B

sp ? ALKYNES

CA2 CB2

(ALKYNES : TWO BONDS: ADD 2 AB ) WHY ? HOW ? - THE BOND IS EASILY BROKEN - SO ? - IS ADDITION LIKELY TO BE ENDOTHERMIC OR EXOTHERMIC ? - ALKENES & ALKYNES CAN ACT AS e RICH SPECIES ( i.e., LEWIS ACID OR BASE ? )

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Solomons Chapter 8 (9th ed)

- SO ? - LIKELY TO REACT WITH : e RICH SPECIES ? OR e POOR SPECIES ? ELECTROPHILIC ADDITION REACTIONS : SEE p 312 ADDITION OF HX: - CONSIDER THE FOLLOWING EXAMPLE :
H H H OR H H H I H H I H H H

HI

REGIOCHEMISTRY:
- HOW TO PREDICT WHICH PRODUCT IS LIKELY TO BE THE MAJOR PRODUCT ?

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Solomons Chapter 8 (9th ed)

- APPLY MARKOVNIKOVS RULE : A+ B + > C = CH > CB CHA (MAJOR) > CA CHB (MINOR)

cf. A & B (A B)

cf. # H AT EACH sp2 CARBON

EXAMINE:

WHICH CARBON ADDS A & WHICH CARBON ADDS B

IMPLICATIONS ? - IN GENERAL, UNSYMMETRICAL REAGENT (A+ B) + UNSYMMETRICAL ALKENE / ALKYNE

A+ : ELECTROPHILIC PREFERENTIALLY ADDS TO THE CARBON HAVING MOST HYDROGENS B : ?

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Solomons Chapter 8 (9th ed)

WHY THIS REGIOCHEMISTRY ? - WHAT HAPPENS WHEN ELECTROPHILE (A+) REACTS WITH ALKENE ? - FORMS INTERMEDIATE : C+ ION - REACTS FURTHER WITH (B) TO GIVE FINAL PRODUCT - SO ? - MAJOR PRODUCT: DETERMINED BY RELATIVE EASE OF FORMATION OF INTERMEDIATE CARBOCATION - SO ? - CONSIDER CARBOCATION STABILITY 3 TO - PREDICT LIKELY MAJOR / MINOR PRODUCTS - SEE MECHANISM: p. 316, 318 - SEE FIG. 8.1, 8.2 p. 316 317 > 2 > 1 >
+

CH3

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Solomons Chapter 8 (9th ed)

- DO PROBLEMS: 8.1 8.3 p. 318 319 - STEREOCHEMISTRY: p. 320 - ADDITION TO sp2 CARBON RACEMIC PRODUCT (NOTE: OTHER CHIRAL CENTERS UNAFFECTED!) - ADDITION OF H2SO4: ( A + B ) = H+ - SEE p. 320 - DO PROBLEM: 8.4 p. 321 - ADDITION OF H2O: ( A + B ) = H+

O-SO2OH

OH

- SEE p. 321 322 - ACID-CATALYSED REACTION NOTE: POTENTIAL FOR REARRANGEMENTS! DO PROBLEMS: 8.5 8.8 p. 322 323

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Solomons Chapter 8 (9th ed)

SOSOLUTION ? - 2-STEP REACTION: OXYMERCURATION DEMERCURATION NO REARRANGEMENTS ! (WHY?) BUT USE CAUTION : Hg-COMPOUNDS ARE TOXIC ! - MECHANISM: p. 324 325 - REAGENTS: 2-STEP PROCESS i) Hg(OAc)2 / THF , H2O ii) NaBH4 , OH - REGIOCHEMISTRY: LIKE MARKOVNIKOV ADDITION OF H2O - STEREOCHEMISTRY: OVERALL, NOT STEREOSPECIFIC HOW ABOUT ANTI-MARKOVNIKOV REGIOCHEMISTRY? - 2-STEP PROCESS: HYDROBORATION OXIDATION - REAGENTS: i) THF , BH3 ii) H2O2, OH

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Solomons Chapter 8 (9th ed)

- HYDROBORATION MECHANISM: p. 328 3317 - EXAMINE THE CURVED ARROWS - IS THE BORON IN BH3 AN ELECTROPHILE / NUCLEOPHILE? - REGIOCHEMISTRY: ANTI-MARKOVNIKOV ADDITION OF BH3 ALKYLBORANE (RBH2) DIALKYLBORANE (R2BH) TRIALKYLBORANE (R3B) ( EACH R- COMES FROM THE ALKENE) SO? STOICHIOMETRY: 1 MOL BH3 : 3 MOL ALKENE NOTE: SOMETIMES, R2BH IS USED AS THE HYDROBORATION REAGENT INSTEAD OF BH3 STOICHIOMETRY? 1 MOL BH3 : 1 MOL ALKENE

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Solomons Chapter 8 (9th ed)

- STEREOCHEMISTRY: SYN - CONCERTED REACTION VIA CYCLIC TRANSITION STATE - WHAT IF THE REACTION WERE NOT CONCERTED? - SYN STEREOCHEMISTRY WOULD NOT BE OBSERVED - WHY? - OXIDATION MECHANISM: p. 329 - EXAMINE MIGRATION OF R- cf. CARBOCATION REARRANGEMENT - EXAMINE LEAVING GROUP - GOOD / BAD ? - DRIVING FORCE FOR REACTION? - WEAK OO BOND - STEREOCHEMISTRY: - CONFIGURATION OF MIGRATING GROUP UNCHANGED - HYDROLYSIS: p. 330 - CONFIGURATION OF ROUNCHANGED

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SO? OVERALL STEREOCHEMISTRY IS SYN (RELATIVE TO STARTING ALKENE) SEE FIG. 8.3, p. 331 SO, THREE WAYS TO ADD WATER TO ALKENES: A] MARKOVNIKOV (REARRANGEMENT!) H3O+, H2O B] MARKOVNIKOV (NO REARRANGEMENT!) i) Hg(OAc)2 / THF , H2O ii) NaBH4 , OH C] ANTI-MARKOVNIKOV (SYN) i) THF , BH3 ii) H2O2, OH - PROTONOLYSIS OF ALKYLBORANES - REAGENT: CH3CO2H - PRODUCT: B REPLACED BY H TO GIVE R H (cf. CATALYTIC HYDROGENATION ) - APPLICATION IN ISOTOPE LABELING WITH DUTERIUM - REAGENT: CH3CO2D

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- PRODUCT: B REPLACED BY D TO GIVE RD DO PROBLEMS: 6.14 p 332; - ADDITION OF X2: ( IN CCl4 ) ( A+ B ) = X+ X ( ?! ) REACTION IS OBSERVED TO BE STEREOSPECIFIC PRODUCT FROM Z ISOMERS IS DIFFERENT FROM PRODUCT FROM E ISOMERS HOW COME ? - NOT EXPLICABLE BASED ON CARBOCATIONMEDIATED MECHANISM ! SO ? - MUST PROPOSE NEW / MODIFIED MECHANISM CONSISTENT WITH EXPERIMENTAL OBSERVATIONS ( - WHY ? ) 6.33 p 357

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MECHANISM: SEE p. 333 - FIRST: FORMATION OF HALONIUM ION ( WITH X+ FROM X+ X- ), RELEASING X (Nu: ) - 3-MEMBERED RING- STRAINED! - WHY DOES IT EVEN FORM? - THEN: X APPROACHES IN SN2 FASHION: BACK-SIDE ATTACK - RING OPENS - RESULTS IN ANTI ADDITION OVERALL - SUCCESSFULLY ACCOUNTS FOR DIFFERENT PRODUCTS OBTAINED FROM E AND Z ISOMERS - SEE p 336 337 DO PROBLEMS: 8.46 c), d) p 358 - ADDITION OF X2: ( IN H2O ) ( A+ B ) = X+ OH ( ?! ) - PRODUCT: HALOHYDRIN - REGIOCHEMISTRY: ? - STEREOCHEMISTRY: STEREOSPECIFIC, ANTI

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Solomons Chapter 8 (9th ed)

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MECHANISM : SEE p. 337 - FIRST: FORMATION OF HALONIUM ION - THEN: BACK-SIDE ATTACK BY H2O - PRODUCT: HALOHYDRIN COMPARE WITH: X2 / CCl4 ( BACK-SIDE ATTACK BY X ) WHY THE DIFFERENCE ?! - EXAMINE THE ABILITY OF SOLVENT TO ACT AS Nu: H2O NUCLEOPHILIC SOLVENT - SO ? - cf. STATISTICAL PROBABILITY OF THE HALONIUM INTERMEDIATE ENCOUNTERING ( & REACTING WITH ) X v. H2O SOLVENT v. CCl4 NON-NUCLEOPHILIC

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Solomons Chapter 8 (9th ed)

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- SO ? - DIFFERENT PRODUCTS OBTAINED DEPENDING ON WHETHER THE SOLVENT IS NUCLEOPHILIC : HALOHYDRINS OR NON-NUCLEOPHILIC : DIHALIDES - DO PROBLEMS: 8.17 p. 338 8.48 p. 359 8.27 (h) p. 376

OXIDATION:
C COLD C C HOT C O + O C OH C OH ( SYN )

( HYDROXYLATION )

( OXIDATIVE CLEAVAGE )

REAGENTS: HYDROXYLATION: KMnO4, OH , H2O OR 1) OsO4 , PYRIDINE 2) NaHSO3 (OR Na2SO3 ), H2O

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OXIDATIVE CLEAVAGE:

1) O3, CH2Cl2 2) Zn , HOAc

cf. PRODUCTS OBTAINED WITH THE TWO REAGENTS:

C O + O C H OZONOLYSIS C C H C O + O C O H WITH KMnO4

OZONOLYSIS KETONES ALDEHYDES

v.

HOT, ALKALINE KMnO4 KETONES ACIDS OR (CO2 + H2O)

WHY THE DIFFERENCE? - KMnO4 IS A STRONG OXIDIZING AGENT - SO ?

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ANY ALDEHYDE INITIALLY FORMED IS (QUICKLY!) FURTHER OXIDIZED: TO ACID (1-CARBON ACID DECOMPOSES TO CO2 AND H2O) - DO PROBLEMS: 8.21-23 p. 342, 345 8.27 ( j, k, l) p. 376

REACTIONS OF ALKYNES:
- ADDITION: - EXAMINE ADDITION OF - X2: SEE p. 345 - HX: SEE p. 346 - STOICHIOMETRY - STEREOCHEMISTRY - REGIOCHEMISTRY - H2O: DETAILS CHAPTER 16 - ADD TO ONE BOND ONLY ENOL , WHICH QUICKLY EQUILIBRATES TO KETO ( MORE STABLE ) - OXIDATIVE CLEAVAGE: SEE p. 347 - PRODUCTS : ACIDS VIA: OZONOLYSIS & KMnO4

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DO PROBLEM: 8.25 p. 347

CARBENES: >C:
- REACTIVITY ? - e DEFICIENT OR e RICH ? - HIGHLY REACTIVE INTERMEDIATES - SYNTHESIS OF CARBENES - FROM DIAZOMETHANE: :CH2 N N: (RESONANCE HYBRID) - SEE p. 358

IS ( N N:) A GOOD LEAVING GROUP ?

- BY - ELIMINATION: - SEE p. 339: REAGENT: BASE ( RO K+) (- HX ) CHCl3 :CCl2

cf. : - ELIMINATION OF RX - - ELIMINATION OCCURS ONLY IF - ELIMINATION IS NOT POSSIBLE

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- REACTIONS OF CARBENES - VERY SHORT-LIVED SPECIES! - ADDITION TO: > C = C< - FORMATION OF CYCLOPROPANES - SEE p. 339 - STEREOSPECIFIC REACTION - IMPLICATIONS ? - CONCERTED MECHANISM - SIMMONS-SMITH REACTION: - CYCLOPROPANATION : SEE p. 340 CH2I2 + Zn (Cu) ICH2ZnI

A CARBENOID - POTENTIAL SOURCE OF: :CH2 - SYNTHETIC STRATEGIES: - SEE p. 347 350 : LEARN ! - CAREFULLY GO THROUGH SECTION 8.21 ON YOUR OWN - DO LOTS OF PROBLEMS !!