alkylation of acetylene & terminal alkynes

               H X

RC-CR' +2Na NH2 -> RC CR' +2NaX

               H X

double dehydrohalogenation of vicinal dihalides

                H H

RC-CR' + 2NaNH₂ ->RC   CR' + 2NaX

                 X  X

Hydrogenation of alkynes to alkanes

RC CR' + 2H₂ metal catalyst> RCH₂CH₂R'

hydrogenation of alkynes to alkenes 

                                        R        R

RC CR' + H₂ Lindlar/Pd> C=C

                                H           H 

metal-ammonia reduction

                                R          H           

RC CR' + 2Na + NH3-> C=C + 2NaNH2

                                   H          R                   

ozonolysis of alkynes 

                  O           O

RC CR' --> RCOH + HOCR'

addition of hydrogen halides

                                              X

RC CR' ___> RC=CR' ___> RCH2CR'

                          X                  X

acid catalyzed hydration

  O

RC CR' + H₂O ---> RCH₂CR'

halogenation of alkynes

                                      R      X      X     X                     

                     RC     CR' X_2> C=C X₂> RC-CR'

       X     R'      X    X

Ka of alkynes

10^-26

Ka of alkenes

10^-45

Ka of alkanes 

10^-62

Ka of p-toluenesulfonic acid 

10²

Ka of carboxylic acid

10^-5

Ka of phenol

10^-10

Ka of water

10^-16

Ka of alcohols

10^{-16 to} 10^-18

Ka of ammonia

10^-35

allyl

H₂C=CHCH₂-

allylic halogenation

H₂C=CHCH₂- + X₂ heat /light>  H₂C=CHCH₂X + HX

allene

H2C=C=CH2

addition of hydrogen halides to conjugated dienes

[image]

halogen addition to dienes

1,4-addition predominates when Cl₂ & Br₂ add to conjugated dienes

vinyl

-CH=CH₂

diels-alder reaction

• conjugate addition of an allene to a conjugated diene
• gives cyclohexene
• concerted & stereospecific
• [image]

toluene

benzoic acid

benzaldehyde

aniline

anisole

styrene

acetophenone

[image]

xylenes

biphenyl

[image]

naphthalene

anthracene

[image]

phenol

phenanthrene

[image]

birch reduction

halogenation of alkylbenzenes

[image]

oxidation of alkylbenzenes

[image]

benzylic halide substitution

[image]

preparation of alkenyl & alkynylbenzenes

dehydrogenation: ArCH2CH3 630C/ZnO> ArCH=CH2 + H2

dehydration : ArCHOHCH3 KHSO4/heat>ArCH=CH2

electrophilic addition 

ArCH=CH2 E-Y> ArCHY-CH2E

electrophilic aromatic substitution

Ar-H + E-Y -> Ar-E + H-Y

nitration

ArH + HNO3 H2SO4/30-40> ArNO2 + H2O

sulfonation

ArH + HOSO2OH heat> ArSO2OH + H2O

halogenation

ArH + X2 FeX2> ArX + HBX

friedel-crafts alkylation 

ArH + RX AlCl3> ArR + HX

friedel-crafts acylation

ArH + RCOCl AlCl3> ArCOR + HCl

ArH + RCOOCOR AlCl3> ArCOR + RCOOH

limitations on fridel crafts reactions

• organic halide that reacts w/ arene must be an alkyl halide or an acyl halide -no vinylic or aryl haldes
• rearrangement of alkyl groups can occur
• strongly deactivating aromatic rings do not under FC
• sometime difficult to limit FC alkylation to monoalkylation

 very strongly activating

effect on orientation:ortho, para-directing

subs: NH2, NHR, NR2, OH

strongly activating

• effect on orientation: ortho, para
• subs: NHCOR, OR, OCOR

activating

• effect on orientation: ortho, para
• subs: R, Ar, CH=CR2

standard of comparison

H

deactivating

• effect on orientation: ortho, para
• subs: X= F, Cl, Br, I. & CH2X

strongly deactivating

• effect on orientation: meta
• subs: COH, COR, COOH, COOR, COCl, C N, SO3H

very strongly deactivating 

• effect on orientation: meta
• subs: CF3, NO2

nuclear magnetic resonance spectroscopy (NMR)

tells us about the carbon skeleton & the environments

of the hydrogens attached to it

infrared (ir) spectroscopy

reveals presence or signals the abscence if key functional groups

ultra violet (UV-IS) spec

probes electron distribution, especially in molecules that have conjugated PI systems

mass spec

gives molecular weight & formula, both of molec itself & various structural units w/in it

H NMR

• chemical shifts: (position of signal-position of TMS peak) /spectrometer freq X 10⁶ 
• downfield =decreased shielding(more electronegative)
• upfield = increased shielding
• # of signals: how many different kinds of protons we have 
• intensity of signals: area under peak, relative ratiosof diff kinds of proteins
• splitting of each signal: tells how may protons are vicinal to the one giving the signal , n+1
  

factors that affect 13C shifts 

• electronegativity of groups attached to carbon
• hybridization of carbon

index of hydrogen deficiency

1/2(C_nH_2n+2-C_nH_x)

pyridine 

[image]

pyrrole

[image]

furan

[image]

phenyl

[image]

benzyl

ex: benzyl alcohol

[image]

preparation of organolithium

RX + 2M (CH3CH2)2O> RM + MX 

prep of organomagnesium compounds: grignard reagents

RX Mg/(CH3CH2)2O> RMgX

grignard reagent rxn w/ formaldehyde

RMgX + HCOH 1.(CH3CH2)2O> RCH2OMgX 2.H3O+> RCH2OH

grignard reagent rxn w/ aldehydes

RMgX + R'COH (CH3CH2)2O>  RCHR'OMgX H3O> RCHR'OH

grignard reagent rxn w/ ketones

RMgX + R'COR'' (CH3CH2)2O> RCR"R'OMgX H3O>  RCR"R'OH

adding D2O to grignard example

CH3CH=CHBr Mg/THF> CH3CH=CHMgBr D2O> CH3CH=CHD

synthesis of acetylenic alcohols 

RC CNa+ R'COR" NH3> RC    CCR"R'ONa H3O> 

RC CCR"R'OH

prep of 3 OHs from esters & grignard reagents

2RMgX+R'COOR" (CH3CH2)2/H3O> RCR'ROH

lithium dialkylcuprates 

2RLi + CuX (CH3CH2)2O> R2CuLi + LiX 

iodomethylzinc idodide

CH2I2 + Zn (CH3CH2)2O/Cu> ICH2ZnI

prep of alkanes using lithium dialkylcuprates

R2CuLi + R'CH2X (CH3CH2)2O> RCH2R'

simmons-smith rxn

alcohol

ROH

ROR'

ether

aldehyde

RCOH

ketone

RCOR'

carboxylic acid

RCOOH

acid catalyzed hydration of alkenes 

R2C=CR2 + H2O H+> R2CHCOHR2

hydroboration-oxidation of alkenes

R2C=CR2 1.B2H6/2.H2O2,OH-> R2CHCOHR2

hydrolysis of alkyl halides

RX + HO- H2O,Ca(OH)2/heat> ROH + X-

sodium borohydride reduction of an aldehyde or ketone

RCOH NaBH4/H2O,CH3OH,or ETOH> RCH2OH

              aldehyde

RCOR' NaBH4/H2O,CH3OH, ETOH> RCHOHR' 

Ketone

lithium aluminum hydride reduction of an aldehyde or ketone

RCOH 1.LiAlH4,(CH3CH2)2O/2.H2O>  RCH2OH

aldehyde

RCOR' 1.LiAlH4,(CH3CH2)2O/2. H2O>  RCHOHR'

ketone

prep of alcohols by reduction of carboxylic acids & esters

RCOOH 1.LiAlH4,(ch3ch2)2o/2.h2o> RCH2OH

                  carboxylic acid

RCOOR' 1.LiAlH4,(ch3ch2)2o/2.h2o> RCH2OH + R'OH

               ester

prep of alcohols from epoxides

[image]

prep of alcohols with osmium tetroxide

dihydroxylation of alkenes

alcohol rxn w/ hydrogen halides

ROH + HX -> RX + H2O

conversion of alcohols to ethers

2RCH2OH H+> RCH2OCH2R + H2O

alcohol rxn w/ thionyl chloride

ROH + SOCl2 -> RCl + SO2 + HCl

alcohol rxn w/ phosphorus tribromide

3ROH + PBr3 -> 3RBr + H3PO3

acid catalyzed dehydration of alcohol

R2COHCHR2 H+> R2C=CR2 +H2O 

conversion to p-toluenesulfonates

ROH + R'COOH H+> R'COOR + H2O

rxn of alcohols w/ acyl chlorides

ROH + R'COCl pyridine> R'COOR + HCl

rxn of alcohols with acid anhydrides

ROH + R'COOCOR' -> R'COOR + R'COOH

esters of inorganic acids

ROH + HONO2 -> RONO2 + H2O

oxidation of alcohols

RCH2OH oxidize> RCOH oxidize> RCOOH

K2Cr2O7/H2SO4,H2O or PCC/CH2Cl2

oxidative cleavage of vicinal diols

[image]

ethylene oxide (oxirane)

[image]

propylene oxide

tetrahydrofuran

[image]

1,4-dioxane

acid catalyzed condesation of alcohols

2RCH2OH H+> RCH2OCH2R + H2O

limited to symmetrical ethers from primary alcohols

williamson ether synthesis

RO- + R'CH2X -> ROCH2R' + X-

like Sn2

limited to methyl or primary halides 

no limitation on alkoxide 

only important rxn of ethers:

cleavage by hydrogen halides

ROR' + 2HX -> RX + R'X + H2O

hydrogen halide reactivity: HI>HBr>HCl

crown ethers

peroxy acid oxidation of alkenes

R2C=CR2 + R'OOOH -> R2C-CCR2 + R'COOH

syn addn

sharpless epoxidation 

R2C=CR2 + (CH3)3COOH

Ti[OCH(CH3)2]4/diethyl (2R,3R)- or

(2S,3S)-tartrate> 

R2C-CR2 + (CH3)3COH

conversion of vicinal halohydrins to epoxides

[image]

epoxidation of alkenes

[image]

acid catalyzed ring opening of epoxides

[image]

prep of sulfides 

RS- Na+  + R'-X Sn2> RSR' + Na+X-

alkylation of sulfides

RSR' + R"X sn2> RSR"X