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R-X by Mind Map: R-X

1. R-X

1.1. Preparation:

1.1.1. Alkane: Free radical 3°>2°>1°

1.1.2. Alkene (reacting with HCL, HBR, HI, H+-OH-)

1.1.3. Alcohol (reacting with PCl5, PCl2, PBr3 or PI3, SOCl2 (thionyl chloride, darzen's rxn), Lucas reagent(an.zncl2+HCl))

2. aq. KOH

2.1. R-OH

3. alc.KOH

3.1. R=R

4. Elimination rxn (Dehydrohalogenaion:loss of H and halogen): product is alkene

5. Action with metals

5.1. 1. With Na (Wurtz rxn) R-X -Na/dry ether,𝛥 → R-R+NaX

5.2. Mg

5.2.1. R-MgX

5.2.1.1. Grignard's reagent:

5.2.1.2. 1. H+-OH-

5.2.1.3. 2. i) CO2 ii) H+ Product: RCOOH

5.2.1.4. 3. i) HCOOH (Formaldehyde) ii)H2O/H+ Product: 1°-alcohol

5.2.1.5. 4. Aldehyde, H2O/H+ Product: 2°-alcohol

5.2.1.6. 5. Ketone, H2O/H+ Product: 3°-alcohol

5.2.1.7. 6. R*-OH Product: R-H + MgX-OR*

5.2.1.8. 7. R-C-OR’+RMgX+H₂O ----> R-C-R’(OH)+Mg(OH)X

5.2.1.9. 8. KCN/R*CN, H2O/H+ Product: Aldehyde/ Ketone

6. Nucleophilic substictution rxn

6.1. 1. With aq. KOH or aq.NaOH R-X+KOH ---> R-OH+KX R-X+NaOH ---> R-OH+NaX

6.2. 2. With moist Ag2O R-X+AgOH ---> R-OH+AgX (unstable)

6.3. 3. With RONa (sodium alkoxide) (Williamson's rxn) R-X +RONa --𝛥-> R-O-R+NaX

6.4. 4. With KCN or NaCN R-X+KCN --𝛥-> R-CN+KX R-X+NaCN --𝛥-> R-CN+NaX

6.4.1. Properties of R-CN:

6.4.2. a. Complete hydrolysis or acidic hydrolysis R-CN -H2O/H+→RCOOH

6.4.3. b. Partial hydrolysis (incomplete hydrolysis R-CN -c.HCl→R-CO-NH2

6.4.4. c. Reduction of R-CN reducing agents :H2/Ni :H2/Pd :H2/Pt :LiAlH4

6.5. 5. With AgCN R-X+AgCN -𝛥→R-NC+AgX

6.6. 6. With AgNO2 R-X+AgNO2 -𝛥→ R-NO2+AgX

6.7. 7. With KNO2 or NaNO2 R-X+KNO2 -𝛥→ R-ONO+KX

6.8. 8. With NH3 (Hoffmann's ammonolysis) R-X+NH3 -sealed tube 100°C→ R-NH2+HX

6.9. 9. With RSNa (sodium alkyl sulphide/sodium alkyl mercaptide. IUPAC name: sodium alkanethiolate) R-X+RSNa -𝛥→R-S-R+NaX

6.10. 10. R-X+KSH-𝛥→R-SH+KX

6.11. 11. R-X+R*COOAg -𝛥 → R*COOR+AgX

6.12. 12. R-X+CH≡CNa -𝛥→ CH≡C-R+NaX