المحاضرة الأولى

‫ﺍﻟﻔﺭﻗﺔ ﺍﻻﻭﻟﻰ‬

‫ﺍﻟﻣﺣﺎﺿﺭﺓ ﺍﻷﻭﻟﻰ‬

‫ﻛﻳﻣﻳﺎء ﻋﺿﻭﻳﺔ‬

‫ﺩ‪/‬ﺣﻧــــــــﺎﻥ‬

‫ﺍﺣﻠ ُ ْﻝ‬ ‫ﺳ ْﺭ ِﻟﻲ ﺃَ ْﻣ ِﺭﻱ َﻭ ْ‬ ‫ﺏ ﺍﺷ َْﺭﺡْ ِﻟﻲ َ‬ ‫ﺻﺩ ِْﺭﻱ َﻭﻳَ ِ ّ‬ ‫َﺭ ّ ِ‬ ‫ﺳﺎﻧِﻲ ﻳَ ْﻔﻘَ ُﻬﻭﺍ ﻗَ ْﻭ ِﻟﻲ‬ ‫ﻋُ ْﻘﺩَﺓً ِﻣ ْﻥ ِﻟ َ‬ ‫ﺍﻟﺳﻼﻡ ﻋﻠﻳﻛﻡ ‪...‬ﺍﺯﻳﻛﻡ ﻳﺎ ﺷﺑﺎﺏ ﺍﻟﻣﺳﺗﻘﺑﻝ ‪ ....‬ﺍﻟﻑ ﻣﺑﺭﻭﻙ ﻋﻠﻰ ﻧﺗﺎﻳﺞ ﺍﻟﺗﺭﻡ ﺍﻻﻭﻝ ﻭﺍﻥ‬ ‫ﺷﺎء ﷲ ﺍﻟﺗﺭﻡ ﺍﻟﺗﺎﻧﻰ ﻳﻛﻭﻥ ﺍﻓﺿﻝ ﻛﻣﺎﻥ ‪ .......‬ﻭﺍﻟﻠﻰ ﻣﺵ ﺣﺎﻟﻔﻪ ﺍﻟﺣﻅ ﻳﺑﺩﺃ ﻳﺫﺍﻛﺭ ﻣﻥ‬ ‫ﺑﺩﺭﻯ ﺑﻘﻰ‬ ‫ﻓﻳﻪ ﻛﻼﻡ ﻓﻰ ﺍﻟﺑﺩﺍﻳﺔ ﻋﻥ ﺍﻛﺗﺷﺎﻑ ﺍﻟﺑﻧﺯﻳﻥ ﻭﻏﻳﺭﻩ ‪ .....‬ﺩﻩ ﺍﻧﺎ ﻫﺷﺭﺣﻪ ﻣﻊ ﺷﺭﺡ ﺍﻟﺑﻧﺯﻳﻥ‬ ‫ﻋﻠﺷﺎﻥ ﻣﺵ ﺍﺩﺧﻝ ﻛﻠﻪ ﻓﻰ ﺑﻌﺿﻪ ‪ .......‬ﻫﻧﺑﺩﺃ ﻣﻌﺎﻛﻡ ﺑﻣﺭﺍﺟﻌﺔ ﺑﺳﻳﻁﺔ ﻋﻠﻰ ﺍﻟﺗﻬﺟﻳﻥ‬ ‫ﻋﻠﺷﺎﻥ ﻫﻧﺣﺗﺎﺟﻪ ﻭﺑﻌﺩﻫﺎ ﻧﺩﺧﻝ ﻋﻠﻰ ﺍﻟﻣﻁﻠﻭﺏ ^_^‬

‫‪Hybridization‬‬ ‫• ﻛﻧﺎ ﺑﻧﻌﺭﻑ ﻧﻭﻉ ﺍﻟﺗﻬﺟﻳﻥ ﻋﻥ ﻁﺭﻳﻕ ﻣﺟﻣﻭﻉ ‪:‬‬ ‫‪Number of sigma bond + lone pair of electrons‬‬

‫‪Sp3‬‬ ‫‪Sp2‬‬ ‫‪Sp‬‬

‫‪• =4‬‬ ‫‪• =3‬‬ ‫‪• =2‬‬ ‫‪• EX:‬‬

‫‪Sp3‬‬ ‫ﺃﺣﻣﺩ ﺍﻟﻌﺎﻳﺩﻯ‬

‫‪Sp2‬‬ ‫‪1‬‬

‫‪sp‬‬ ‫‪Dr\Ahmed Al3yde‬‬

• Atoms Have lone pair of electrons :

HeteroAtoms : O , N , S Halogens : F , CL , Br , I

Sp3

Sp3

‫ــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــ‬ • Hybridization of ions : • Carbocation C

+

• Free radical C• • Carboanion C •

Sp2 Sp2 Sp3 Except in Resonance

EX:

Sp2

CH3

Sp2

-

Sp3

CH3

Sp2 C H

-

Sp2 N H

H2C

-

CH CH2

Dr\Ahmed Al3yde

Sp2

2

‫ﺃﺣﻣﺩ ﺍﻟﻌﺎﻳﺩﻯ‬

‫ ﻧﺩﺧﻝ ﺑﻘﻰ ﻋﻠﻰ ﺍﻟﺷﺭﺡ‬... ‫ ﻁﺑﻌﺎ ﺍﻧﺗﻭ ﻋﺎﺭﻓﻳﻥ ﻛﻝ ﺍﻟﻠﻰ ﻓﻭﻕ ﻭﺷﺭﺣﻧﺎﻩ ﻛﺗﻳﺭ ﺍﻟﺗﺭﻡ ﺍﻻﻭﻝ‬o

o What is the difference between aliphatic and aromatic compound ?

Aliphatic compound : • Open Chain Hydrocarbon : Alkane , Alkene , Alkyne • Cyclic Hydrocarbon : cyclo alkane , cyclo alkene ‫ﻛﻝ ﺍﻟﺣﺎﺟﺎﺕ ﺍﻟﻠﻰ ﺍﺧﺩﻧﺎﻫﺎ ﺍﻟﺗﺭﻡ ﺍﻻﻭﻝ‬ ‫ـــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــ‬

Aromaticity

• The compound to be aromatic it must fulfill the following requirements : 1- Cyclic 2- Planar 3- Complete conjugation (sp2 hybride) 4- Obey Huckel’s rule : ‫ ﺷﺭﻭﻁ ﺩﻯ‬٤ ‫• ﻳﻌﻧﻰ ﻋﻠﺷﺎﻥ ﺍﻟﻣﺭﻛﺏ ﻳﺗﻘﺎﻝ ﻋﻠﻳﻪ ﺍﺭﻭﻣﺎﺗﻰ ﻻﺯﻡ ﺗﺗﻭﻓﺭ ﻓﻳﻪ ﺍﻝ‬ ‫ ﺣﻠﻘﻰ‬: Cyclic -١ ‫ ﻣﺳﻁﺢ‬:Planar -٢ ‫ ﻳﻌﻧﻰ ﺗﺗﺑﺎﺩﻝ ﻓﻳﻪ ﺍﻟﺭﻭﺍﺑﻁ ﺍﻻﺣﺎﺩﻳﺔ ﻣﻊ‬: Complete conjugation -٣ ‫ﺍﻟﺛﻧﺎﺋﻳﺔ ﻓﻰ ﻛﻝ ﺍﻟﺣﻠﻘﺔ‬ Dr\Ahmed Al3yde

3

‫ﺃﺣﻣﺩ ﺍﻟﻌﺎﻳﺩﻯ‬

‫‪ -٤‬ﻭﺍﺧﻳﺭﺍ ﻻﺯﻡ ﻳﺗﺑﻊ ﻗﺎﻧﻭﻥ ‪Huckel‬‬ ‫ﻳﻼ ﻧﺷﺭﺡ ﻛﻝ ﻧﻘﻁﺔ ﺑﺎﻟﺗﻔﺻﻳﻝ‬ ‫‪1-cyclic‬‬ ‫ﻣﺭﻛﺏ ﺣﻠﻘﻰ‬

‫ﻣﺭﻛﺏ ﻏﻳﺭ ﺣﻠﻘﻰ‬

‫ ﻳﻌﻧﻰ ﺍﻳﻪ ﻣﺭﻛﺏ ﺣﻠﻘﻰ ‪ ...‬ﻳﻌﻧﻰ ﻳﺣﺩﺙ ﺗﺩﺍﺧﻝ ﺑﺎﻟﺭﺃﺱ ﺑﻳﻥ ﺟﻣﻳﻊ ﺫﺭﺍﺕ ﺍﻟﻣﺭﻛﺏ‬‫ﻟﺗﻛﻭﻳﻥ ﺣﻠﻘﺔ )ﺭﻭﺍﺑﻁ ﺳﻳﺟﻣﺎ (‬ ‫ ﻋﻧﺩﻙ ﻋﻠﻰ ﺍﻟﺷﻣﺎﻝ ﺩﻯ ﺣﻠﻘﺔ ﺍﻟﺑﻧﺯﻳﻥ ‪ ....‬ﺣﺻﻝ ﻓﻳﻬﺎ ﺗﺩﺍﺧﻝ ﺑﺎﻟﺭﺃﺱ ﺑﻳﻥ ‪ ٦‬ﺫﺭﺍﺕ‬‫ﻛﺭﺑﻭﻥ ﻭﻛﻭﻧﻭﺍ ﺣﻠﻘﺔ ﺑﻧﺯﻳﻥ ‪ ...‬ﻭﺍﻟﺟﺯء ﺍﻟﻌﻣﻭﺩﻯ ﻋﻠﻰ ﺍﻟﻛﺭﺑﻭﻧﺎﺕ ﺩﻩ ﻋﺑﺎﺭﺓ ﻋﻥ‬ ‫ﺍﻭﺭﺑﻳﺗﺎﻝ ‪ p‬ﺍﻟﻠﻰ ﻣﺵ ﺍﺷﺗﺭﻙ ﻓﻰ ﺍﻟﺗﻬﺟﻳﻥ ﻻﻧﻧﺎ ﻋﺎﺭﻓﻳﻥ ﺍﻥ ﺟﻣﻳﻊ ﺫﺭﺍﺕ ﺍﻟﺑﻧﺯﻳﻥ‬ ‫ﺗﻬﺟﻳﻧﻬﺎ ‪ ) sp2‬ﺍﻭﺭﺑﻳﺗﺎﻝ ‪ 2 + S‬ﺍﻭﺭﺑﻳﺗﺎﻝ ‪( P‬‬ ‫ ﻁﺑﻌﺎ ﺍﻭﺭﺑﻳﺗﺎﻝ ‪ Pz‬ﺩﻩ ﻫﻭ ﺍﻟﻣﺳﺋﻭﻝ ﻋﻥ ﺗﻛﻭﻳﻥ ﺭﻭﺍﺑﻁ ﺑﺎﻯ ﻋﻥ ﻁﺭﻳﻕ ﺍﻟﺗﺩﺍﺧﻝ‬‫ﺑﺎﻟﺟﻧﺏ‬ ‫ ﺍﻣﺎ ﺍﻟﻣﺭﻛﺏ ﻋﻠﻰ ﺍﻟﻳﻣﻳﻥ ﻓﻬﻭ ﺃﻟﻛﻳﻥ ﻋﺎﺩﻯ ‪ .....‬ﻭﻣﻭﺿﺣﻳﻥ ﺍﻥ ﻣﺵ ﺣﺻﻝ‬‫‪ overlap‬ﺑﻳﻥ ﺍﻻﻭﺭﺑﻳﺗﺎﻻﺕ ‪ .....‬ﻓﺗﻛﻭﻧﺕ ﺳﻠﺳﻠﺔ ﻣﻔﺗﻭﺣﺔ ‪ ...‬ﻭﻻ ﻳﻣﻛﻥ ﻳﻛﻭﻥ ﻓﻳﻪ‬ ‫ﻣﺭﻛﺏ ﺍﺭﻭﻣﺎﺗﻰ ﺑﺳﻠﺳﻠﺔ ﻣﻔﺗﻭﺣﺔ ‪ ...‬ﻳﺎ ﺭﺏ ﺗﻛﻭﻥ ﻭﺻﻠﺕ‬ ‫ﺃﺣﻣﺩ ﺍﻟﻌﺎﻳﺩﻯ‬

‫‪4‬‬

‫‪Dr\Ahmed Al3yde‬‬

‫ﻣﺳﻁﺢ‬

‫‪2- planar‬‬

‫• ﺍﻳﻪ ﺍﻗﺭﺏ ﻣﺛﺎﻝ ﻟﻠﻣﺭﻛﺏ ﺍﻟﻣﺳﻁﺢ ‪:‬‬ ‫ ﺍﻟﺳﺑﻭﺭﺓ ﻣﺳﻁﺣﺔ ‪ ...‬ﻻﻥ ﺟﻣﻳﻊ ﺍﺟﺯﺍﺋﻬﺎ ﻓﻰ ﻣﺳﺗﻭﻯ ﻭﺍﺣﺩ‬‫ ﻧﻔﺱ ﺍﻟﺣﻛﺎﻳﺔ ﻻﺯﻡ ﺍﻟﻣﺭﻛﺏ ﺍﻻﺭﻭﻣﺎﺗﻰ ﻳﻛﻭﻥ ﻣﺳﻁﺢ ‪ ....‬ﻳﻌﻧﻰ ﺟﻣﻳﻊ‬‫ﺍﻟﺫﺭﺍﺕ ﺍﻟﻣﻛﻭﻧﺔ ﻟﻠﺣﻠﻘﺔ ﻳﻛﻭﻧﻭﺍ ﻓﻰ ﻧﻔﺱ ﺍﻟﻣﺳﺗﻭﻯ‬ ‫‪• EX:‬‬ ‫ﺫﻯ ﻣﺎ ﺍﻧﺗﻭ ﺷﺎﻳﻔﻳﻥ ﺩﻯ ﺣﻠﻘﺔ ﺑﻧﺯﻳﻥ ‪....‬‬ ‫ﺟﻣﻳﻊ ﺫﺭﺍﺕ ﺍﻟﻛﺭﺑﻭﻥ ﻭﺍﻟﻬﻳﺩﺭﻭﺟﻳﻥ ﻓﻰ‬ ‫ﻧﻔﺱ ﺍﻟﻣﺳﺗﻭﻯ‬ ‫ـــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــ‬

‫)‪3- complete conjugation (Sp2 hybride‬‬

‫ ﻋﻠﻰ ﺍﻟﺷﻣﺎﻝ ﻓﻳﻪ ﺣﻠﻘﺔ ﺍﻟﺑﻧﺯﻳﻥ ﺍﻟﻠﻰ ﺑﺗﺗﺑﺎﺩﻝ ﻓﻳﻬﺎ ﺍﻟﺭﻭﺍﺑﻁ ﺍﻟﺛﻧﺎﺋﻳﺔ ﻣﻊ ﺍﻻﺣﺎﺩﻳﺔ ‪...‬ﻭﺟﻣﻳﻊ‬‫ﺫﺭﺍﺕ ﺍﻟﺑﻧﺯﻳﻥ ﺗﻬﺟﻳﻧﻬﺎ ‪ Sp2‬ﻳﺑﻘﻰ ﺍﻟﻣﺭﻛﺏ ﺩﻩ ﻓﻳﻪ ‪complete conjugation‬‬ ‫ ﺍﻟﻣﺭﻛﺑﻳﻥ ﺍﻟﺗﺎﻧﻳﻳﻥ ﻓﻳﻪ ﺫﺭﺓ ﻓﻰ ﺍﻟﺣﻠﻘﺔ ﺗﻬﺟﻳﻧﻬﺎ ‪ Sp3‬ﺑﺗﻭﻗﻑ ﺍﻝ ‪conjugation‬‬‫ ﻳﻌﻧﻰ ﻧﻘﺩﺭ ﻧﻘﻭﻝ ﻟﻭ ﺍﻟﺣﻠﻘﺔ ﺗﺣﺗﻭﻯ ﻋﻠﻰ ﺫﺭﺓ ﻭﺍﺣﺩﺓ ﺗﻬﺟﻳﻧﻬﺎ ‪ Sp3‬ﻳﺑﻘﻰ ﺍﻟﻣﺭﻛﺏ ‪not‬‬‫‪) aromatic‬ﻭﺧﻠﻰ ﺑﺎﻟﻙ ﺍﻧﺎ ﻗﻠﺕ ﺍﻟﺫﺭﺍﺕ ﺍﻟﻣﻛﻭﻧﺔ ﻟﻠﺣﻠﻘﺔ ﻫﻰ ﺍﻟﻠﻰ ﺗﻬﺟﻳﻧﻬﺎ ‪( Sp2‬‬

‫ﺃﺣﻣﺩ ﺍﻟﻌﺎﻳﺩﻯ‬

‫‪5‬‬

‫‪Dr\Ahmed Al3yde‬‬

‫ﺑﺱ ﻳﻌﻧﻰ ﺍﻳﻪ ‪complete conjugation‬‬ ‫‪Contineous or nearly continuous overlapping of all p‬‬ ‫‪orbitals‬‬ ‫ﻳﻌﻧﻰ ﺗﺩﺍﺧﻝ ﻣﺳﺗﻣﺭ ﻷﻭﺭﺑﻳﺗﺎﻻﺕ ‪ P‬ﺩﻩ ﻣﻌﻧﺎﻩ ﺍﻥ ﻻﺯﻡ ﻛﻝ ﻛﺭﺑﻭﻣﺔ ﺗﺣﺗﻭﻯ ﻋﻠﻰ‬ ‫ﺍﻭﺭﺑﻳﺗﺎﻝ ‪ P‬ﻏﻳﺭ ﻣﻬﺟﻥ‬ ‫ ﻭﺫﻯ ﻣﺎ ﺍﺧﺩﺗﻭﺍ ﺍﻟﺗﺭﻡ ﺍﻻﻭﻝ ﺍﻥ ﺍﻟﻛﺭﺑﻭﻧﺔ ﺍﻟﻠﻰ ﺗﻬﺟﻳﻧﻬﺎ ‪Sp3‬‬‫ﻻﺗﺣﺗﻭﻯ ﻋﻠﻰ ﺍﻭﺭﺑﻳﺗﺎﻝ ﻏﻳﺭ ﻣﻬﺟﻥ ‪ ...‬ﻋﻠﺷﺎﻥ ﻛﺩﻩ ﻣﺵ ﺑﺗﻌﻣﻝ‬ ‫‪conjugation‬‬ ‫ ﻁﻳﺏ ﻳﺎ ﺩﻛﺗﻭﺭ ﻣﺎ ﺍﻟﻛﺭﺑﻭﻧﺔ ﺍﻟﻠﻰ ﺗﻬﺟﻳﻧﻬﺎ ‪ Sp‬ﺗﺣﺗﻭﻯ ﻋﻠﻰ‬‫ﺍﻭﺭﺑﻳﺗﺎﻟﻳﻥ ‪ P‬ﻏﻳﺭ ﻣﻬﺟﻧﻳﻥ ‪ ...‬ﻫﻝ ﻳﻧﻔﻊ ﺗﻌﻣﻝ ‪ conjugation‬؟‬ ‫ ﺍﻛﻳﺩ ﻁﺑﻌﺎ ﻳﻧﻔﻊ ‪ ...‬ﻳﻌﻧﻰ ﻣﻣﻛﻥ ﻧﻘﻭﻝ ﻻﺯﻡ ﺟﻣﻳﻊ ﺫﺭﺍﺕ ﺍﻟﺣﻠﻘﺔ‬‫ﺗﻬﺟﻳﻧﻬﺎ ‪ Sp2‬ﺍﻭ ‪ SP‬ﺍﻭ ﺍﻻﺗﻧﻳﻥ ﻣﻌﺎ ‪ ....‬ﺍﻩ ﻳﻧﻔﻊ ﺑﺱ ﻣﺵ ﻫﺩﻳﻠﻛﻡ‬ ‫ﺍﻣﺛﻠﺔ ﺍﻻ ﻟﻭ ﺩ‪/‬ﺣﻧﺎﻥ ﺷﺭﺣﺗﻬﺎ ﻟﻳﻛﻡ‬ ‫ـــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــ‬

‫‪4- Huckel’s rule‬‬ ‫‪Number of ࣊ electrons = 4n+2‬‬ ‫‪• n = 0,1,2,3,…..‬‬ ‫ ﺭﻛﺯ ﻣﻌﺎﻳﺎ ﺑﻘﻰ‬‫ ﺑﻳﻘﻭﻟﻙ ﻻﺯﻡ ﻋﺩﺩ ﺍﻻﻟﻛﺗﺭﻭﻧﺎﺕ ﺍﻟﻣﻛﻭﻧﺔ ﻟﻠﺭﺍﺑﻁﺔ ﺑﺎﻯ ﻳﺳﺎﻭﻯ ‪ 4n+2‬ﺑﺣﻳﺙ ‪ n‬ﺗﻛﻭﻥ‬‫ﻋﺩﺩ ﺻﺣﻳﺢ‬ ‫‪ -‬ﺗﻌﺎﻟﻰ ﻧﻔﻬﻡ ﺑﻣﺛﺎﻝ‬

‫ﺃﺣﻣﺩ ﺍﻟﻌﺎﻳﺩﻯ‬

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‫‪Dr\Ahmed Al3yde‬‬

‫‪2 electrons‬‬

‫‪EX:‬‬ ‫‪2 electrons‬‬

‫‪2 electrons‬‬ ‫‬‫‬‫‪-‬‬

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‫ﺫﻯ ﻣﺎ ﺍﺣﻧﺎ ﻋﺎﺭﻓﻳﻥ ﺍﻥ ﺍﻯ ﺭﺍﺑﻁﺔ ﺑﺗﻛﻭﻥ ﻣﻛﻭﻧﺔ ﻣﻥ ﺍﻟﻛﺗﺭﻭﻧﻳﻥ )ﺍﻟﻛﺗﺭﻭﻥ ﻣﻥ ﻛﻝ ﺫﺭﺓ (‬ ‫ﻳﻌﻧﻰ ﺍﻯ ﺭﺍﺑﻁﺔ ﺑﺎﻯ ﻓﻰ ﺣﻠﻘﺔ ﺍﻟﺑﻧﺯﻳﻥ ﻫﺗﻛﻭﻥ ﻣﻛﻭﻧﺔ ﻣﻥ ﺍﻟﻛﺗﺭﻭﻧﻳﻥ )ﺍﻟﻛﺗﺭﻭﻥ ﻣﻥ ﻛﻝ ﺫﺭﺓ‬ ‫ﻛﺭﺑﻭﻥ ﺑﺗﺷﺎﺭﻛﻪ ﻣﻊ ﺍﻟﺫﺭ ﺍﻟﻣﺟﺎﻭﺭﺓ ﻭﺗﺗﻛﻭﻥ ﺭﺍﺑﻁﺔ ﺑﺎﻯ (‬ ‫ﻗﺎﻟﻙ ﺑﻘﻰ ﺍﻧﺕ ﺗﻌﺭﻑ ﻋﺩﺩ ﺍﻻﻟﻛﺗﺭﻭﻧﺎﺕ ﺍﻟﻣﻛﻭﻧﺔ ﻟﻠﺭﻭﺍﺑﻁ ﺑﺎﻯ ﻓﻰ ﺍﻟﺣﻠﻘﺔ ﻭﺗﻌﻭﺽ ﺑﻳﻬﺎ ﻓﻰ‬ ‫ﺍﻟﻘﺎﻧﻭﻥ ‪ 4n+2‬ﻭﻟﻭ ‪ n‬ﻁﻠﻌﺕ ﻋﺩﺩ ﺻﺣﻳﺢ ﻳﺑﻘﻰ ﺗﻣﺎﻡ ﻭﺍﻟﻣﺭﻛﺏ ﻳﺗﺑﻊ ﻗﺎﻧﻭﻥ ‪huckel‬‬ ‫‪...‬‬ ‫ﻛﻝ ﺍﻟﻠﻰ ﻋﻠﻳﻙ ﺍﻧﻙ ﺗﻌﺩﺩ ﺭﻭﺍﺑﻁ ﺑﺎﻯ ﻭﺗﺿﺭﺑﻬﺎ ﻓﻰ ﺍﺗﻧﻳﻥ ‪ ....‬ﻳﻌﻧﻰ ﻣﺛﻼ ﺍﻟﺑﻧﺯﻳﻥ ﻳﺣﺗﻭﻯ‬ ‫ﻋﻠﻰ ‪ ٣‬ﺭﻭﺍﺑﻁ ﺑﺎﻯ ‪ .....‬ﻳﺑﻘﻰ ﻳﺣﺗﻭﻯ ﻋﻠﻰ ‪ ٦‬ﺍﻟﻛﺗﺭﻭﻧﺎﺕ ﻣﻛﻭﻧﻳﻥ ﻟﻬﺫﻩ ﺍﻟﺭﻭﺍﺑﻁ ‪....‬‬ ‫ﻧﻌﻭﺽ ﺑﻘﻰ‬ ‫‪• 4n+2 = 6‬‬ ‫‪• n=1‬‬ ‫‪• Aromatic‬‬ ‫ﻋﻭﺿﻧﺎ ﻓﻰ ﺍﻟﻘﺎﻧﻭﻥ ﺑﺭﻗﻡ ‪ 6‬ﻓﻁﻠﻌﺕ ‪ n‬ﻋﺩﺩ ﺻﺣﻳﺢ ‪ ...‬ﻋﻠﺷﺎﻥ ﻛﺩﻩ ﺍﻟﻣﺭﻛﺏ‬ ‫ﺍﺭﻭﻣﺎﺗﻰ‬ ‫ ﻭﻁﺑﻌﺎ ﻣﻼﺣﻅﻳﻥ ﺍﻥ ﺍﻟﺷﺭﻭﻁ ﺍﻻﺭﺑﻌﺔ ﺗﻧﻁﺑﻕ ﻋﻠﻰ ﺍﻟﺑﻧﺯﻳﻥ ﻋﻠﺷﺎﻥ ﻛﺩﻩ‬‫ﻫﻭ ﺍﺷﻬﺭ ﺍﻟﻣﺭﻛﺑﺎﺕ ﺍﻷﺭﻭﻣﺎﺗﻳﺔ‬ ‫ ﻳﺑﻘﻰ ﻛﺩﻩ ﻻﺯﻡ ﺍﻝ ‪ ٤‬ﺷﺭﻭﻁ ﺗﻛﻭﻥ ﻣﻭﺟﻭﺩﺓ ﻓﻰ ﺍﻟﻣﺭﻛﺏ ﻋﻠﺷﺎﻥ ﻧﻘﻭﻝ‬‫‪... Aromatic‬ﻭﻟﻠﻌﻠﻡ ﺍﻟﻣﺭﻛﺑﺎﺕ ﺍﻟﻐﻳﺭ ﻣﺳﻁﺣﺔ ﻫﺗﻌﺭﻓﻬﻡ ﺑﺎﻻﺳﻡ ﻓﻣﺵ‬ ‫ﺗﻘﻠﻕ ﻣﻥ ﺍﻟﻧﻘﻁﺔ ﺩﻯ ‪ ....‬ﺗﻌﺎﻟﻰ ﻧﺎﺧﺩ ﻣﺛﺎﻟﻳﻥ ﻋﻠﻰ ﺍﻟﺳﺭﻳﻊ‬

‫ﺃﺣﻣﺩ ﺍﻟﻌﺎﻳﺩﻯ‬

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‫‪Dr\Ahmed Al3yde‬‬

‫‪4n + 2 = 18‬‬

‫‪4n + 2 = 14‬‬

‫‪n=4‬‬

‫‪n=3‬‬

‫‪Aromatic‬‬

‫‪Aromatic‬‬

‫ ﺍﻟﻣﺭﻛﺑﻳﻥ ﺍﻟﻠﻰ ﻓﻭﻕ ‪ cyclic , planar ,‬ﻭﻛﻝ ﺫﺭﺍﺗﻬﻡ ﺗﻬﺟﻳﻧﻬﺎ ‪Sp2‬‬‫ ﻭﻛﻣﺎﻥ ﻋﺭﻓﻧﺎ ﻋﺩﺩ ﺭﻭﺍﺑﻁ ﺑﺎﻯ ﻭﺿﺭﺑﻧﺎﻫﻡ ﻓﻰ ﺍﺗﻧﻳﻥ ‪ ...‬ﻭﻋﻭﺿﻧﺎ ﻓﻰ ﺍﻟﻘﺎﻧﻭﻥ ﻭﻁﻠﻊ ‪n‬‬‫ﻋﺩﺩ ﺻﺣﻳﺢ ‪....‬ﻳﺑﻘﻰ ﺧﻼﺹ ﺍﻟﻣﺭﻛﺏ ‪Aromatic‬‬ ‫ ﻫﻧﻌﺭﻑ ﻳﻌﻧﻰ ﺍﻳﻪ ‪ Annulene‬ﻣﺵ ﺗﺳﺗﻌﺟﻝ ^_^‬‫ـــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــ‬

‫ ﻁﻳﺏ ﺍﻣﺗﻰ ﺍﻗﻭ ﻻﻥ ﺍﻟﻣﺭﻛﺏ ‪not aromatic‬‬‫ ﺍﻛﻳﺩ ﻳﻌﻧﻰ ﻟﻭ ﺣﺻﻝ ﻧﻘﺹ ﻓﻰ ﺍﻯ ﺷﺭﻁ ﻣﻥ ﺍﻟﺷﺭﻭﻁ ﺍﻻﺭﺑﻌﺔ ﺍﻟﻠﻰ ﺍﺧﺩﻧﺎﻫﻡ ‪...‬‬‫ﺗﻌﺎﻟﻰ ﻧﺎﺧﺩ ﻣﺛﺎﻝ ﻟﻠﺗﻭﺿﻳﺢ ﺩﻟﻭﻗﺗﻰ‬

‫ﺍﻟﻣﺭﻛﺏ ﺍﻟﻠﻰ ﻓﻭﻕ ﺩﻩ ﻋﻠﻰ ﺍﻟﺭﻏﻡ ﺍﻧﻪ ﺣﻠﻘﻰ ﻭﺟﻣﻳﻊ ﺫﺭﺍﺗﻪ ﺗﻬﺟﻳﻧﻬﺎ ‪sp2‬‬ ‫ﺍﻻ ﺍﻧﻪ ﻣﺵ ﺍﺭﻭﻣﺎﺗﻰ ؟!!!‬ ‫ﺃﺣﻣﺩ ﺍﻟﻌﺎﻳﺩﻯ‬

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‫‪Dr\Ahmed Al3yde‬‬

‫ ﻻﻥ ﺍﻟﻣﺭﻛﺏ ﻣﺵ ﻣﺳﻁﺢ ‪ ...‬ﻳﻌﻧﻰ ﻓﻳﻪ ﺫﺭﺍﺕ ﻛﺭﺑﻭﻥ ﻓﻭﻕ ﻣﺳﺗﻭﻯ ﺫﺭﺍﺕ‬‫ﻛﺭﺑﻭﻥ ﺗﺎﻧﻳﺔ ‪ ...‬ﻣﺵ ﻛﻝ ﺍﻟﺫﺭﺍﺕ ﻧﻔﺱ ﺍﻟﻣﺳﺗﻭﻯ ﻳﻌﻧﻰ ﺍﻟﻣﺭﻛﺏ ‪non-‬‬ ‫‪ planar‬ﻳﺑﻘﻰ ﻋﻠﻰ ﻁﻭﻝ ‪not aromatic‬‬ ‫ ﻫﻧﺎﺧﺩ ﺍﻟﻣﺭﻛﺏ ﺩﻩ ﺑﺎﻟﺗﻔﺻﻳﻝ ‪ ...‬ﺍﻧﺎ ﺣﻁﻪ ﻫﻧﺎ ﻛﻣﺛﺎﻝ ﻟﻠﻔﻬﻡ‬‫ ﺍﻣﺗﻰ ﺍﻗﻭﻝ ﻋﻠﻰ ﺍﻟﻣﺭﻛﺏ ‪ Anti-Aromatic‬؟؟؟‬‫ ﺭﻛﺯ ﻣﻌﺎﻳﺎ ﺑﻘﻰ ﻋﻠﺷﺎﻥ ﻧﻔﺭﻕ ﺑﻳﻥ ‪Aromatic , not aromatic ,‬‬‫‪anti aromatic‬‬ ‫ـــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــ‬

‫‪Anti Aromatic‬‬

‫‪• Requirements :‬‬ ‫‪1- Cyclic‬‬ ‫‪2- Planar‬‬ ‫‪3- Complete conjugation‬‬ ‫‪4- Number of ࣊ electrons = 4n‬‬ ‫ ﻭﺍﺿﺢ ﺟﺩﺍ ﺍﻧﻪ ﺫﻯ ﺍﻝ ‪ Aromatic‬ﻟﻛﻥ ﻫﻣﺎ ﻋﺩﺩ ﺍﻻﻟﻛﺗﺭﻭﻧﺎﺕ ﺍﻟﻠﻰ ﻓﻰ‬‫ﺍﻟﻣﺭﻛﺏ ﻫﻳﺳﺎﻭﻯ ‪ 4n‬ﺑﺣﻳﺙ ‪ n‬ﺗﻛﻭﻥ ﻋﺩﺩ ﺻﺣﻳﺢ‬ ‫ ﺗﻌﺎﻟﻰ ﻧﻔﻬﻡ ﺑﺎﻷﻣﺛﻠﺔ‬‫‪Cyclo butadiene‬‬ ‫ ﺩﻩ ﻣﺭﻛﺏ ﻫﻧﺗﻌﺎﻣﻝ ﻣﻌﺎﻩ ﻋﺎﺩﻯ ﺟﺩﺍ ﺫﻯ ﻣﺎ ﺍﺗﻌﻭﺩﻧﺎ‬‫ ﻫﻧﻼﻗﻳﻪ ‪ cyclic , planar ,‬ﻛﻝ ﺫﺭﺍﺗﻪ ﺗﻬﺟﻳﻧﻬﺎ ‪sp2‬‬‫ ﻋﻧﺩﻩ ﺭﺍﺑﻁﺗﻳﻥ ﺑﺎﻯ ‪ ......‬ﻳﺑﻘﻰ ﻋﺩﺩ ﺍﻻﻟﻛﺗﺭﻭﻧﺎﺕ ﺍﻟﻣﻛﻭﻧﺔ ﻟﻠﺭﻭﺍﺑﻁ ﺑﺎﻯ = ‪٤‬‬‫ ﺗﻌﺎﻟﻰ ﻧﻌﻭﺽ ﻓﻰ ﻗﺎﻧﻭﻥ ‪huckel‬‬‫ﺃﺣﻣﺩ ﺍﻟﻌﺎﻳﺩﻯ‬

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‫‪Dr\Ahmed Al3yde‬‬

4n = 4

4n + 2 = 4

n=1

n=0.5

anti aromatic ‫ﺑﻛﻝ ﺑﺳﺎﻁﺔ ﺗﻌﺎﻟﻰ ﻧﻔﻬﻡ‬ ‫ ﻓﻛﺩﻩ ﺍﻟﻣﺭﻛﺏ ﺩﻩ‬... ‫ ﻋﺑﺎﺭﺓ ﻋﻥ ﻛﺳﺭ‬n ‫ ﻁﻠﻌﺕ‬huckel ‫ﻓﻭﻕ ﻟﻣﺎ ﻋﻭﺿﻧﺎ ﻓﻰ ﻗﺎﻧﻭﻥ‬ huckel ‫ﻣﺵ ﺑﻳﺗﺑﻊ ﻗﺎﻧﻭﻥ‬ ‫ ﺍﻟﻠﻰ ﻫﻭ ﻋﺩﺩ ﺍﻻﻟﻛﺗﺭﻭﻧﺎﺕ‬anti-aromatic ‫ﻓﺩﺧﻠﻧﺎ ﻋﻠﻰ ﺍﻟﻘﺎﻧﻭﻥ ﺍﻟﺗﺎﻧﻰ ﺑﺗﺎﻉ ﺍﻝ‬ 4n = ‫ﺍﻟﻣﻛﻭﻧﺔ ﻟﻠﺭﺍﺑﻁﺔ ﺑﺎﻯ‬ ‫ ﻋﺩﺩ ﺻﺣﻳﺢ‬n ‫ﻟﻣﺎ ﻋﻭﺿﻧﺎ ﻁﻠﻌﺕ‬ anti aromatic ‫ﻳﺑﻘﻰ ﺧﻼﺹ ﺍﻟﻣﺭﻛﺏ ﺑﺗﺎﻋﻰ‬

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Aromatic , not , anti ‫ﺗﻌﺎﻟﻰ ﻧﺟﻣﻊ ﺍﻟﻔﺭﻕ ﺑﻳﻥ ﺍﻝ‬ Aromatic Not aromatic (non-aromatic) Anti Aromatic

cyclic, planar, completely conjugated compound with 4n + 2 π electrons. (stable) compound that lacks one (or more) of the requirements for aromaticity: being cyclic, planar, and completely conjugated. (less stable) cyclic, planar, completely conjugated compound with 4n π electrons. (very unstable)

Aromaticity increase stability

Dr\Ahmed Al3yde

10

‫ﺃﺣﻣﺩ ﺍﻟﻌﺎﻳﺩﻯ‬

‫‪-‬‬

‫‬‫‬‫‬‫‪-‬‬

‫ﺍﻯ ﻣﺭﻛﺏ ﺍﺭﻭﻣﺎﺗﻰ ﺑﻳﻛﻭﻥ ﻋﻧﺩﻩ ﺛﺑﺎﺗﻳﻪ ﻋﺎﻟﻳﺔ ‪ .....‬ﻳﻌﻧﻰ ﺍﻟﻣﺭﻛﺑﺎﺕ ﺍﻟﺗﺭﻡ ﺩﻩ‬ ‫ﺛﺑﺎﺗﻳﺗﻬﺎ ﺍﻋﻠﻰ ﻣﻥ ﻣﺭﻛﺑﺎﺕ ﺍﻟﺗﺭﻡ ﺍﻻﻭﻝ ﻛﻠﻪ )ﺗﻔﺎﻋﻼﺕ ﺍﻟﺗﺭﻡ ﺍﻻﻭﻝ ﻣﺵ ﺗﻧﻔﻊ‬ ‫ﻣﻌﺎﻫﺎ(‬ ‫ﻭﺍﻧﺎ ﻓﻰ ﺍﻟﺟﺩﻭﻝ ﻓﺭﻗﺗﻠﻙ ﺑﻳﻥ ﺍﻝ ‪ ٣‬ﻓﻰ ﺍﻟﺛﺑﺎﺗﻳﻪ‬ ‫ﺍﻟﻣﺭﻛﺑﺎﺕ ﺍﻻﺭﻭﻣﺎﺗﻳﺔ ﺍﻋﻼﻫﻡ ﻓﻰ ﺍﻟﺛﺑﺎﺗﻳﻪ‬ ‫ﻭﺑﻌﺩﻫﺎ ﺍﻟﻣﺭﻛﺑﺎﺕ ‪ not aromatic‬ﺫﻯ ﺍﻻﻟﻛﺎﻥ ﻭﺍﻻﻟﻛﻳﻥ‬ ‫ﻭﺍﻗﻝ ﺣﺎﺟﺔ ﻓﻰ ﺍﻟﺛﺑﺎﺗﻳﻪ ﻫﻰ ﺍﻝ ‪ anti aromatic‬ﻋﻠﺷﺎﻥ ﻛﺩﻩ ﺑﻳﻘﻭﻟﻙ ﺍﻥ‬ ‫ﺍﻟﻣﻭﺍﺩ ﺩﻯ ﻣﻥ ﻛﺗﺭ ﻋﺩﻡ ﺍﻟﺛﺑﺎﺗﻳﻪ ﻣﺵ ﻣﻭﺟﻭﺩﺓ ﻻﻧﻬﺎ ﺑﺗﺗﻔﺎﻋﻝ ﻋﻠﻰ ﻁﻭﻝ‬

‫ـــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــ‬ ‫‪Examples‬‬

‫ـــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــ‬

‫ﺃﺣﻣﺩ ﺍﻟﻌﺎﻳﺩﻯ‬

‫‪11‬‬

‫‪Dr\Ahmed Al3yde‬‬

‫‪Sp3 carbon‬‬

‫‪Not Aromatic‬‬ ‫ــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــ‬

‫‪Aromaticity of ions‬‬ ‫‪• requirements :‬‬ ‫‪1-Cyclic‬‬ ‫‪2-Planar‬‬ ‫)‪3-Complete conjugation (sp2 hybride‬‬ ‫‪4-Obey Huckel’s rule‬‬ ‫‬‫‬‫‬‫‪-‬‬

‫‪-‬‬

‫ﺍﻻﺧﺗﻼﻑ ﻫﻧﺎ ﺑﻘﻰ ‪ ...‬ﺍﻣﺗﻰ ﺍﺣﺳﺏ ﺍﻟﺷﺣﻧﺔ ﻓﻰ ﻗﺎﻧﻭﻥ ‪huckel‬‬ ‫ﺑﻛﻝ ﺑﺳﺎﻁﺔ ﻟﻭ ﺍﻟﺷﺣﻧﺔ ﺍﻟﺳﺎﻟﺑﺔ ﺩﺍﺧﻠﺔ ﻓﻰ ﺍﻝ ‪ resonance‬ﻣﻊ ﺍﻟﺣﻠﻘﺔ ﻳﺑﻘﻰ ﻫﺗﺣﺳﺏ‬ ‫ﺍﻟﺷﺣﻧﺔ ﺍﻟﺳﺎﻟﺑﺔ ﺏ ‪ ٢‬ﺍﻟﻛﺗﺭﻭﻥ‬ ‫ﻭﻟﻭ ﻣﺵ ﺩﺧﻠﺕ ﻓﻰ ﺍﻝ ‪ resonance‬ﻳﺑﻘﻰ ﻣﺵ ﻫﻧﺣﺳﺑﻬﺎ ‪...‬‬ ‫ﻁﺑﻌﺎ ﺩﻩ ﻋﻛﺱ ﻛﻼﻡ ﺗﺣﺩﻳﺩ ﻧﻭﻉ ﺍﻟﺗﻬﺟﻳﻥ ﻓﻰ ﺍﻟﺷﺣﻧﺔ ﺍﻟﺳﺎﻟﺑﺔ ‪ .....‬ﻛﻧﺕ ﺑﻧﻘﻭﻝ ﻟﻭ‬ ‫ﺍﻻﺷﺎﺭﺓ ﺍﻟﺳﺎﻟﺑﺔ ﺩﺧﻠﺕ ‪ resonance‬ﻣﺵ ﺑﻧﺣﺳﺑﻬﺎ ﻓﻰ ﺗﺣﺩﻳﺩ ﻧﻭﻉ ﺍﻟﺗﻬﺟﻳﻥ ‪ ...‬ﺍﻥ‬ ‫ﺷﺎء ﷲ ﺗﻛﻭﻥ ﻓﺎﻛﺭ ﺍﻟﺗﻬﺟﻳﻥ ^_^‬ ‫ﺗﻌﺎﻟﻰ ﻧﺎﺧﺩ ﻣﺛﺎﻝ ﻋﻥ ﺗﺣﺩﻳﺩ ﺍﻷﺭﻭﻣﺎﺗﻳﺔ ﻓﻰ ﺍﻟﻣﺭﻛﺏ ﻟﻠﻰ ﻋﻠﻳﻪ ﺷﺣﻧﺔ‬

‫ﺃﺣﻣﺩ ﺍﻟﻌﺎﻳﺩﻯ‬ ‫ﺃﺣﻣﺩ ﺍﻟﻌﺎﻳﺩﻯ‬

‫‪٠١٠٢٦٢١٨٨٦١‬‬ ‫‪12‬‬

‫‪Dr\Ahmed Al3yde‬‬

‫‪2‬‬

‫‪1‬‬

‫ ﺗﻌﺎﻟﻰ ﻧﻌﺭﻑ ﺍﻟﻔﺭﻕ ﺑﻳﻥ ﺍﻟﻣﺭﻛﺏ ‪ ١‬ﻭﺍﻟﻣﺭﻛﺏ ‪٢‬‬ ‫ﻣﺭﻛﺏ ﻭﺍﺣﺩ‬ ‫ﺍﻟﻣﺭﻛﺏ ﺍﻟﻠﻰ ﻗﺩﺍﻣﻙ ‪ cyclic , planar‬ﻭﺟﻣﻳﻊ ﺫﺭﺍﺗﻪ ﺗﻬﺟﻳﻧﻬﺎ ‪Sp2‬‬ ‫ ﺍﻻﺷﺎﺭﺓ ﺍﻟﺳﺎﻟﺑﺔ ﻣﺷﺗﺭﻛﺔ ﻓﻰ ﺍﻝ ‪ resonance‬ﻣﻊ ﺍﻟﺣﻠﻘﺔ ﻭﺫﻯ ﻣﺎ ﺍﺣﻧﺎ‬‫ﻋﺎﺭﻓﻳﻥ ﻣﻥ ﺍﻟﺗﺭﻡ ﺍﻻﻭﻝ ﺍﻥ ﺍﻻﺷﺎﺭﺓ ﺍﻟﺳﺎﻟﺑﺔ ﺗﻣﺛﻝ ﺍﻟﻛﺗﺭﻭﻧﻳﻥ‬ ‫ ﻋﻠﺷﺎﻥ ﻛﺩﻩ ﻭﺍﺣﻧﺎ ﺑﻧﺷﻭﻑ ﻋﺩﺩ ﺍﻻﻟﻛﺗﺭﻭﻧﺎﺕ ﺍﻟﻠﻰ ﻫﻧﻌﻭﺽ ﻓﻳﻬﺎ ﻓﻰ ﻗﺎﻧﻭﻥ‬‫‪ huckel‬ﻻﺯﻡ ﻧﺣﺳﺏ ﺍﻝ ‪ ٢‬ﺍﻟﻛﺗﺭﻭﻥ ﻟﻺﺷﺎﺭﺓ ﺍﻟﺳﺎﻟﺑﺔ‬ ‫ ﻳﻌﻧﻰ ﻓﻰ ﺍﻟﻣﺭﻛﺏ ﻭﺍﺣﺩ ﻫﻧﻼﻗﻰ ﻓﻳﻪ ﺭﺑﻁﺗﻳﻥ ﺑﺎﻯ ‪ ....‬ﻳﻌﻧﻰ ‪ ٤‬ﺍﻟﻛﺗﺭﻭﻧﺎﺕ ‪...‬‬‫ﻭﻧﺿﻳﻑ ﻋﻠﻳﻬﻡ ‪ ٢‬ﺍﻟﻛﺗﺭﻭﻥ ﺍﻟﺷﺣﻧﺔ ﺍﻟﺳﺎﻟﺑﺔ ‪ ....‬ﻳﺑﻘﻰ ﺍﻟﻣﺟﻣﻭﻉ ‪٦‬‬ ‫ ﻧﻌﻭﺽ ﻓﻰ ﻗﺎﻧﻭﻥ ‪ huckel‬ﻟﻘﻳﻧﺎ ‪ n‬ﻋﺩﺩ ﺻﺣﻳﺢ ‪...‬ﻳﺑﻘﻰ ﺍﻟﻣﺭﻛﺏ ﺍﺭﻭﻣﺎﺗﻰ‬‫ﻣﺭﻛﺏ ‪٢‬‬ ‫ﺍﻟﻣﺭﻛﺏ ‪ cyclic , planar‬ﺟﻣﻳﻊ ﺫﺭﺍﺗﻪ ﺗﻬﺟﻳﻧﻬﺎ ‪sp2‬‬ ‫ ﺍﻝ ‪ resonance‬ﺍﻟﻠﻰ ﻓﻰ ﺍﻟﺣﻠﻘﺔ ﺑﻳﺗﻡ ﻋﻥ ﻁﺭﻳﻕ ‪ ٣‬ﺭﻭﺍﺑﻁ ﺑﺎﻯ ‪...‬‬‫ﻭﺍﻻﺷﺎﺭﺓ ﺍﻟﺳﺎﻟﺑﺔ ﻣﺵ ﻣﺷﺗﺭﻛﺔ ﻓﻰ ﺍﻝ ‪ resonance‬ﺩﻩ ‪.‬‬ ‫ ﻳﺑﻘﻰ ﻣﺵ ﻫﻧﺣﺳﺏ ﺍﻟﻛﺗﺭﻭﻧﺎﺕ ﺍﻻﺷﺎﺭﺓ ﺍﻟﺳﺎﻟﺑﺔ ﻭﺍﺣﻧﺎ ﺑﻧﻌﻭﺽ ﻓﻰ ﻗﺎﻧﻭﻥ‬‫‪huckel‬‬ ‫ ﻳﺑﻘﻰ ﻓﻳﻪ ‪ ٣‬ﺭﻭﺍﺑﻁ ﺑﺎﻯ ‪ .....‬ﻳﻌﻧﻰ ‪ ٦‬ﺍﻟﻛﺗﺭﻭﻧﺎﺕ‬‫ ﻁﻠﻌﺕ ‪ n‬ﻋﺩﺩ ﺻﺣﻳﺢ ‪......‬ﻳﺑﻘﻰ ﻣﺭﻛﺏ ﺍﺭﻭﻣﺎﺗﻰ‬‫ﺃﺣﻣﺩ ﺍﻟﻌﺎﻳﺩﻯ‬

‫‪13‬‬

‫‪Dr\Ahmed Al3yde‬‬

‫ ﺍﻭﻋﻰ ﺣﺩ ﻳﺗﻠﺧﺑﻁ ‪ ......‬ﻭﺍﻟﻠﻰ ﻳﺗﻠﺧﺑﻁ ﻳﻌﺭﻑ ﺍﻥ ﻟﻭ ﺍﻻﺷﺎﺭﺓ ﺍﻟﺳﺎﻟﺑﺔ ﻋﻠﻰ ﺫﺭﺓ‬‫ﻣﺭﺗﺑﻁﺔ ﺑﺭﺍﺑﻁﺔ ﺛﻧﺎﺋﻳﺔ ﻓﻣﺵ ﻫﻧﺣﺳﺏ ﺍﻻﺷﺎﺭﺓ ﺍﻟﺳﺎﻟﺑﺔ‬ ‫ ﻟﻛﻥ ﻟﻭ ﺍﻻﺷﺎﺭﺓ ﺍﻟﺳﺎﻟﺑﺔ ﻋﻠﻰ ﺫﺭﺓ ﺟﻣﻳﻊ ﺭﻭﺍﺑﻁﻬﺎ ﺍﺣﺎﺩﻳﺔ ‪ ....‬ﻳﺑﻘﻰ ﻧﺣﺳﺏ‬‫ﺍﻻﺷﺎﺭﺓ ﺍﻟﺳﺎﻟﺑﺔ ﻓﻰ ﻗﺎﻧﻭﻥ ‪huckel‬‬ ‫• ﺳﺅﺍﻝ ﺍﻣﺗﺣﺎﻥ ﻫﺎﻡ ﺟﺩﺍ‬ ‫‪Give reasonable explanation‬‬ ‫‪- The anion of benzene is aromatic although it‬‬ ‫? ‪contains total 8 free electrons‬‬

‫‪- Answer : the negative charge is found in Sp2‬‬ ‫࣊ ‪orbital prependicular on the 2Pz orbitals of‬‬ ‫‪electrons of the double bonds , so can not‬‬ ‫‪enter in conjugation in ring ,so the number of‬‬ ‫‪࣊ electrons inside the ring is still 6 , so obey‬‬ ‫‪huckel rule‬‬ ‫ﻳﻌﻧﻰ ﺍﻻﺷﺎﺭﺓ ﺍﻟﺳﺎﻟﺑﺔ ﺑﺗﻛﻭﻥ ﻋﻣﻭﺩﻳﺔ ﻋﻠﻰ ﺍﻭﺭﺑﻳﺗﺎﻝ ‪) 2pz‬ﻳﻌﻧﻰ ﺍﻻﺷﺎﺭﺓ‬ ‫ﺍﻟﺳﺎﻟﺑﺔ ﺑﺗﻛﻭﻥ ﻓﻰ ﻧﻔﺱ ﻣﺳﺗﻭﻯ ﺫﺭﺍﺕ ﺍﻟﻛﺭﺑﻭﻥ ( ‪ ...‬ﻟﺫﻟﻙ ﻣﺵ ﺑﺗﻘﺩﺭ ﺗﺩﺧﻝ ﺍﻝ‬ ‫‪ conjugation‬ﺍﻭ ﺍﻻﻧﺗﻘﺎﻝ ﺍﻻﻟﻛﺗﺭﻭﻧﻰ ﺍﻟﻠﻰ ﻓﻰ ﺍﻟﺣﻠﻘﺔ ‪....‬ﻟﺫﻟﻙ ﻣﺵ‬ ‫ﺑﻧﺣﺳﺑﻬﺎ ﻭﺑﻳﻔﺿﻝ ﻋﺩﺩ ﺍﻻﻟﻛﺗﺭﻭﻧﺎﺕ ﺩﺍﺧﻝ ﺍﻟﺣﻠﻘﺔ ‪ ٦‬ﺍﻟﻛﺗﺭﻭﻧﺎﺕ ‪...‬ﻟﺫﻟﻙ ﺍﻟﻣﺭﻛﺏ‬ ‫ﻳﺗﺑﻊ ﻗﺎﻧﻭﻥ ‪ huckel‬ﻭﺑﻳﻛﻭﻥ ﺍﺭﻭﻣﺎﺗﻰ‬ ‫ﺍﻻﺷﺎﺭﺓ ﺍﻟﺳﺎﻟﺑﺔ ﺑﻌﻳﺩﺓ ﻋﻥ ﺍﻝ‬ ‫‪ conjugation‬ﻭﻓﻰ ﻧﻔﺱ ﻣﺳﺗﻭﻯ ﺫﺭﺍﺕ‬ ‫ﺍﻟﻛﺭﺑﻭﻥ ‪ .....‬ﻳﺎ ﺭﻳﺕ ﻟﻭ ﺗﻌﺭﻓﻭﺍ ﺗﺭﺳﻣﻭﺍ‬ ‫ﺍﻟﺭﺳﻣﺔ ﻓﻰ ﺍﻻﻣﺗﺣﺎﻥ ﻟﻭ ﺟﺎﻟﻙ ﺍﻟﺳﺅﺍﻝ‬

‫ﺃﺣﻣﺩ ﺍﻟﻌﺎﻳﺩﻯ‬

‫‪14‬‬

‫‪2Pz‬‬ ‫‪Sp2‬‬

‫‪Dr\Ahmed Al3yde‬‬

‫‪ -‬ﺗﻌﺎﻟﻰ ﻧﺎﺧﺩ ﻣﺛﺎﻝ ﻋﻠﻰ ﺍﻻﺷﺎﺭﺓ ﺍﻟﻣﻭﺟﺑﺔ‬

‫• ﺗﻌﺎﻟﻰ ﻧﻌﺭﻑ ﻟﻳﻪ‬ ‫ﺍﻟﻣﺭﻛﺏ ﻋﻧﺩﻙ ‪ cyclic , planar‬ﺟﻣﻳﻊ ﺫﺭﺍﺗﻪ ﺗﻬﺟﻳﻧﻬﺎ ‪Sp2‬‬ ‫• ﺍﻻﺷﺎﺭﺓ ﺍﻟﻣﻭﺟﺑﺔ ﺗﻌﻧﻰ ﻧﻘﺹ ﻓﻰ ﺍﻻﻟﻛﺗﺭﻭﻧﺎﺕ ﻋﻠﺷﺎﻥ ﻛﺩﻩ ﺑﻧﻌﺗﺑﺭﻫﺎ ﻣﺵ‬ ‫ﻣﻭﺟﻭﺩﺓ ﻭﺍﺣﻧﺎ ﺑﻧﺷﻭﻑ ﻋﺩﺩ ﺍﻻﻟﻛﺗﺭﻭﻧﺎﺕ ﺍﻟﻠﻰ ﻫﻧﻌﻭﺽ ﺑﻳﻬﺎ ﻓﻰ ﻗﺎﻧﻭﻥ‬ ‫‪huckel‬‬ ‫• ﺍﻟﻣﺭﻛﺏ ‪ ١‬ﻋﻧﺩﻩ ﺭﺍﺑﻁﺗﻳﻥ ﺑﺎﻯ ‪ ......‬ﻳﻌﻧﻰ ‪ ٤‬ﺍﻟﻛﺗﺭﻭﻧﺎﺕ ﻣﻛﻭﻧﻳﻥ ﻟﻬﺫﻩ‬ ‫ﺍﻟﺭﻭﺍﺑﻁ‬ ‫• ﺑﺎﻟﺗﻌﻭﻳﺽ ﻓﻰ ﺍﻟﻘﺎﻧﻭﻥ ﻫﺗﻼﻗﻰ ‪ n‬ﻛﺳﺭ‬ ‫• ﻋﻠﻰ ﻁﻭﻝ ﻧﺩﺧﻝ ﻋﻠﻰ ﻗﺎﻧﻭﻥ ‪ ....... 4n‬ﻟﻘﻳﻧﺎ ‪ n‬ﻋﺩﺩ ﺻﺣﻳﺢ‬ ‫• ﻳﺑﻘﻰ ﺍﻟﻣﺭﻛﺏ ﺑﺗﺎﻋﻰ ‪anti-aromatic‬‬ ‫ ﺗﻌﺎﻟﻰ ﻧﺎﺧﺩ ﺍﻣﺛﻠﺔ ﻟﻠﺗﺩﺭﻳﺏ‬‫‪Cyclo propene‬‬

‫ﺣﻠﻘﺔ ﻣﻥ ‪ ٣‬ﺫﺭﺍﺕ‬

‫‪Anti aromatic‬‬

‫‪Three membered ring‬‬

‫‪Aromatic‬‬

‫‪Not aromatic‬‬ ‫ﻻﻥ ﻓﻳﻪ ﺫﺭﺓ ﺗﻬﺟﻳﻧﻬﺎ‬ ‫‪sp3‬‬

‫ﺃﺣﻣﺩ ﺍﻟﻌﺎﻳﺩﻯ‬

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‫‪Dr\Ahmed Al3yde‬‬

‫ ﻁﺑﻌﺎ ﻓﻰ ﺍﻟﻣﺭﻛﺏ ﺍﻟﻠﻰ ﻋﻠﻰ ﺍﻟﻳﻣﻳﻥ ﺣﺳﺑﻧﺎ ﺍﻻﺷﺎﺭﺓ ﺍﻟﺳﺎﻟﺑﺔ ﻻﻧﻬﺎ ﺩﺧﻠﺔ ﻓﻰ‬‫ﺍﻝ ‪ resonance‬ﻭﺍﻟﻣﺭﻛﺏ ﻋﻧﺩﻩ ﺭﺍﺑﻁﺔ ﺑﺎﻯ ﻭﺍﺣﺩﺓ ‪.....‬ﻓﺎﻟﻣﺟﻣﻭﻉ‬ ‫ﻫﻳﻛﻭﻥ ‪٤‬‬ ‫‪five membered ring‬‬

‫‪Cyclo pentadienyl‬‬ ‫‪anion‬‬

‫‪Cyclo pentadienyl‬‬ ‫‪cation‬‬

‫‪Cyclo pentadiene‬‬

‫‪Not aromatic‬‬

‫ ﻓﻳﻪ ﻣﻠﺣﻭﻅﺗﻳﻥ ﻣﻬﻣﻳﻥ ‪:‬‬‫• ﺍﻭﻻ ‪ :‬ﺍﻟﺷﻛﻝ ﺍﻟﻠﻰ ﺗﺣﺕ ﺩﻩ ﺍﻟﻠﻰ ﻫﻭ ﻋﺑﺎﺭﺓ ﻋﻥ ﺩﺍﻳﺭﺓ ﻭﺟﻭﺍﻫﺎ ﺍﺷﺎﺭﺓ‬ ‫ﺩﺍﺧﻝ ﺍﻟﻣﺭﻛﺏ ‪ ....‬ﻣﻌﻧﺎﻩ ﺍﻥ ﺍﻟﻣﺭﻛﺏ ﻳﺣﺗﻭﻯ ﻋﻠﻰ ﺍﺷﺎﺭﺓ ﺗﺗﺑﺎﺩﻝ ﻣﻊ‬ ‫‪complete conjugation‬‬ ‫ﺍﻟﺭﻭﺍﺑﻁ ﺍﻟﺛﻧﺎﺋﻳﺔ ﻓﻰ ﺍﻟﺣﻠﻘﺔ ﻣﻛﻭﻧﺔ ‪conjugatio‬‬

‫ﺃﺣﻣﺩ ﺍﻟﻌﺎﻳﺩﻯ‬

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‫‪Dr\Ahmed Al3yde‬‬

‫ﺍﻟﻣﻠﺣﻭﻅﺔ ﺍﻟﺗﺎﻧﻳﺔ ﻋﺑﺎﺭﺓ ﻋﻥ ﻣﻌﻠﻭﻣﺔ ﻋﻥ ﺍﻟﺣﻠﻘﺎﺕ ﺍﻟﺧﻣﺎﺳﻳﺔ‬ metallocenes

Sandwich like compounds

They are compounds in which two cyclo pentadienylidiene ringsform sandwich around ametal ion .the most known of these is ferrocene ‫ﻳﻌﻧﻰ ﺣﻠﻘﺗﻳﻥ ﺧﻣﺎﺳﻳﺗﻳﻥ ﻟﻣﺎ ﻳﺷﻭﻓﻭﺍ ﻣﻌﺩﻥ ﺑﻳﻌﻣﻠﻭﺍ ﺳﻧﺩﻭﺗﺵ ﻋﻠﻳﻪ )ﺑﻳﺭﺗﺑﻁﻭﺍ ﺑﻪ‬ ( ‫ﻳﻌﻧﻰ‬ ‫ ﺫﻯ‬ferrocene ‫ ﻫﻳﺗﻛﻭﻥ ﻣﺭﻛﺏ ﺍﺳﻣﻪ‬... ‫• ﻭﻟﻭ ﺍﻟﻣﻌﺩﻥ ﺩﻩ ﻋﺑﺎﺭﺓ ﻋﻥ ﺣﺩﻳﺩ‬ ‫ﻣﺎ ﻭﺍﺿﺢ ﻓﻰ ﺍﻟﺭﺳﻣﺔ‬

ferrocene

• It is stable compound because the two rings are freely rotate • The most stable form : staggered form

Dr\Ahmed Al3yde

17

‫ﺃﺣﻣﺩ ﺍﻟﻌﺎﻳﺩﻯ‬

‫‪Cyclo heptatriene‬‬

‫‪seven membered ring‬‬

‫‪Not aromatic‬‬

‫‪Tropylium cation‬‬

‫‪Tropylium anion‬‬

‫• ﺧﻠﻰ ﺑﺎﻟﻙ ﺍﻥ ﺍﻳﻭﻥ ﺍﻟﺣﻠﻘﺔ ﺍﻟﺳﺑﺎﻋﻳﺔ ﺍﺳﻣﻪ ‪tropylium‬‬ ‫• ﻫﻧﺎ ﺑﺭﺩﻩ ﻓﻳﻪ ‪ ... metallocenes‬ﻋﺑﺎﺭﺓ ﻋﻥ ﺣﻠﻘﺔ ﺳﺑﺎﻋﻳﺔ ﻣﻊ‬ ‫ﺧﻣﺎﺳﻳﺔ ﺣﻭﻟﻳﻥ ﻣﻌﺩﻥ ‪ ....‬ﺍﻋﺭﻑ ﺍﻟﻣﻌﻠﻭﻣﺎﺕ ﺩﻯ ﻋﻠﺷﺎﻥ ﻣﻣﻛﻥ‬ ‫ﺗﺗﺳﺄﻝ ﻓﻳﻬﺎ )ﻣﺵ ﺑﻌﻳﺩﺓ (‬

‫ﺃﺣﻣﺩ ﺍﻟﻌﺎﻳﺩﻯ‬

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‫‪Dr\Ahmed Al3yde‬‬

metallocenes • Metallocenes that contain tropylium ion have been prepared recently ‫ ﻟﻠﺣﻠﻘﺔ ﺍﻟﺳﺑﺎﻋﻳﺔ ﻟﺳﻪ ﻣﺣﺿﺭﻳﻧﻪ ﺣﺩﻳﺛﺎ )ﺍﻛﺗﺷﻑ‬metalocenes ‫• ﻳﻌﻧﻰ ﺍﻝ‬ (‫ﺣﺩﻳﺛﺎ‬

M=metal

‫ــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــ‬ Eight membered ring

Cyclo octatetraene

‫ﻣﻬﻡ ﺟﺩﺍﺍﺍﺍﺍﺍﺍﺍﺍﺍﺍﺍﺍﺍﺍﺍﺍ‬

Not aromatic !

‫ ﻟﺳﺑﺑﻳﻥ ﻣﻬﻣﻳﻥ ﺟﺩﺍ‬not aromatic ‫• ﺍﻟﻣﺭﻛﺏ ﺩﻩ‬ 1- Not plannar (tube – like shape)

Tube – like shape Dr\Ahmed Al3yde

19

‫ﺃﺣﻣﺩ ﺍﻟﻌﺎﻳﺩﻯ‬

‫‪2- Not obey Huckel's rule‬‬ ‫‪• 4n+2=8‬‬ ‫‪• n=1.5‬‬ ‫• ﻁﺑﻌﺎ ﻣﺵ ﻳﻧﻔﻊ ﻫﻧﺎ ﻧﻘﻭﻝ ﺍﻟﻣﺭﻛﺏ ‪ anti aromatic‬ﻻﻥ ﺍﺻﻼ ﺍﻟﻣﺭﻛﺏ‬ ‫‪non-planar‬‬ ‫• ﻳﺑﻘﻰ ﺍﻟﻣﺭﻛﺏ ﺍﺻﻼ ﻏﻳﺭ ﻣﺳﺗﻭﻯ ﻭﻛﻣﺎﻥ ﻻ ﻳﺗﺑﻊ ﻗﺎﻧﻭﻥ ‪huckel‬‬ ‫• ﺍﻛﺗﺷﻔﻭﺍ ﻁﺭﻳﻘﺗﻳﻥ ﻳﺣﻭﻟﻭﺍ ﺍﻟﻣﺭﻛﺏ ﺩﻩ ﻝ ‪ aromatic‬ﺗﻌﺎﻟﻰ ﻧﺷﻭﻑ ﺍﺯﺍﻯ‬ ‫‪To be Aromatic‬‬ ‫)‪1- Reaction with potassium metal to obtain (dianion‬‬

‫•‬ ‫‪2K‬‬

‫‪Dianion‬‬ ‫‪Aromatic, Stable , diatropic and plannar‬‬

‫‪1,3,5,7 tetramethyl‬‬ ‫‪cyclo octatetraene‬‬

‫ ﻓﺎﻋﻠﻧﺎ ﺍﻟﻣﺭﻛﺏ ﻣﻊ ﺑﻭﺗﺎﺳﻳﻭﻡ ﻓﻧﺗﺞ ﻣﺭﻛﺏ ﻋﻠﻳﻪ ﺷﺣﻧﺗﻳﻥ ﺳﺎﻟﺑﺗﻳﻥ ‪ .....‬ﺗﺗﻭﻓﺭ ﻓﻳﻪ‬‫ﺍﻟﺧﻭﺍﺹ ﺍﻻﺭﻭﻣﺎﺗﻳﻪ‬ ‫‪ -‬ﺗﻌﺎﻟﻰ ﻧﺷﻭﻑ ﺍﻟﻁﺭﻳﻘﺔ ﺍﻟﺗﺎﻧﻳﺔ‬

‫ﺃﺣﻣﺩ ﺍﻟﻌﺎﻳﺩﻯ‬

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‫‪Dr\Ahmed Al3yde‬‬

2- By dissolving in conc.H2SO4 to obtain Homo tropylium ion

H+

Homo-tropylium ion • A proton adds to one of double bonds to form a homotropylium ion , and in this case the aromatic sextet is spread over seven carbons , as in tropylium ion • The eight carbon is Sp3 carbon and so can not take part in aromaticity ‫ ﺗﻡ ﺍﺿﺎﻓﺔ ﻫﻳﺩﺭﻭﺟﻳﻥ ﻟﻠﺭﺍﺑﻁﺔ ﺍﻟﻣﺯﺩﻭﺟﺔ‬... ‫• ﻫﻧﺎ ﺑﻌﺩ ﻣﺎ ﺍﻟﻣﺭﻛﺏ ﺗﻔﺎﻋﻝ ﻣﻊ ﺍﻟﺣﻣﺽ‬ ‫ ﻭﻛﺭﺑﻭﻧﻪ ﻭﺍﺣﺩﺓ ﺑﻌﻳﺩﺓ‬..... ‫ ﻛﺭﺑﻭﻧﺎﺕ ﺟﻧﺏ ﺑﻌﺿﻬﺎ‬٧ ‫ ﻓﺗﻛﻭﻥ ﺣﻠﻘﺔ ﺗﺣﺗﻭﻯ ﻋﻠﻰ‬.... ‫ ﻟﻠﺣﻠﻘﺔ ﺍﻟﺳﺑﺎﻋﻳﺔ ﻭﻁﺑﻌﺎ‬tropylium ion ‫ ﻓﺎﻟﻣﺭﻛﺏ ﺑﻳﺗﺣﻭﻝ ﻛﺈﻧﻪ‬.... ‫ﻋﻥ ﺍﻟﺣﻠﻘﺔ‬ ‫ﺩﻯ ﺍﺭﻭﻣﺎﺗﻳﻪ ﺫﻯ ﻣﺎ ﺍﺧﺩﻧﺎ‬

‫ـــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــــ‬ nine membered ring

1,3,5,7 Cyclo nona-tetra-ene

Dr\Ahmed Al3yde

21

‫ﺃﺣﻣﺩ ﺍﻟﻌﺎﻳﺩﻯ‬

‫ ﺳﺅﺍﻝ ﻣﻬﻡ‬How could 1,3,5,7 cyclo nonatetraene be converted into an aromatic substance ? . indicate the reactions that would be used and draw the structure of the starting material and te product Sp3 ‫ ﻻﻥ ﻓﻳﻪ ﺫﺭﺓ ﺗﻬﺟﻳﻧﻬﺎ‬not aromatic ‫• ﻳﻌﻧﻰ ﺍﻟﻣﺭﻛﺏ ﺍﻟﻠﻰ ﻓﻭﻕ ﺩﻩ‬ ‫• ﺑﻳﻘﻭﻟﻙ ﻓﻰ ﺍﻟﺳﺅﺍﻝ ﺍﺯﺍﻯ ﺗﺧﻠﻳﻪ ﺍﺭﻭﻣﺎﺗﻰ ﻭﻭﺿﺢ ﺍﻟﺗﻔﺎﻋﻝ ﻣﻊ ﺭﺳﻡ ﺍﻟﻣﺎﺩﺓ‬ ‫ ﻭﺍﻟﻧﺎﺗﺞ‬.... ‫ﺍﻟﺩﺍﺧﻠﺔ‬ • Answer : - By reaction with base

Base

Not aroma c has Sp3 carbon

Anion , aromatic , planar and

, not planar , and has 8 ࣊ electrons

contain 10 ࣊ electrons

‫ ﻭﻟﻣﺎ ﻧﺧﻠﺹ ﺍﻯ ﻣﻭﺿﻭﻉ ﻫﻧﺯﻟﻛﻡ ﺍﺳﺋﻠﺔ ﻋﻠﻳﻪ ﺍﻥ ﺷﺎء ﷲ‬.... ‫ ﺩﻯ ﺍﺟﺎﺑﺔ ﺍﻟﺳﺅﺍﻝ‬hetero atom ‫ ﻧﺩﺧﻝ ﻋﻠﻰ ﺟﺯﺋﻳﺔ ﺟﺩﻳﺩﺓ ﻭﻫﻰ ﺍﻻﺭﻭﻣﺎﺗﻳﺔ ﻓﻰ ﺍﻟﺣﻠﻘﺎﺕ ﺍﻟﻠﻰ ﻓﻳﻬﺎ‬-

Dr\Ahmed Al3yde

22

‫ﺃﺣﻣﺩ ﺍﻟﻌﺎﻳﺩﻯ‬

‫‪Hetero cyclic aromatic compounds‬‬ ‫ﺣﻠﻘﺔ ﺗﺣﺗﻭﻯ ﻋﻠﻰ ﺫﺭﺓ ﻧﻳﺗﺭﻭﺟﻳﻥ ﺍﻭ ﺍﻛﺳﺟﻳﻥ ﺍﻭ ﻛﺑﺭﻳﺕ ﺑﺟﺎﻧﺏ ﺍﻟﻛﺭﺑﻭﻥ‬ ‫ﻭﺍﻟﻬﻳﺩﺭﻭﺟﻳﻥ ‪...‬ﺍﺯﺍﻯ ﺍﻋﺭﻑ ﺍﻟﺣﻠﻘﺔ ﺍﻻﺭﻭﻣﺎﺗﻳﻪ ﻣﻥ ﻏﻳﺭﻫﺎ ؟‬ ‫ﻧﻔﺱ ﺍﻟﻠﻰ ﻗﻭﻟﻧﺎﻩ ﺑﺎﻟﺿﺑﻁ‬ ‫ﻳﻌﻧﻰ ﻻﺯﻡ ﺍﻟﻣﺭﻛﺏ ﻳﻛﻭﻥ ‪:‬‬ ‫‪Cyclic , planar , complete conjugation , obey huckel's rule‬‬ ‫• ﺍﻻﻫﻡ ﺑﻘﻰ ﺍﻣﺗﻰ ﺍﺣﺳﺏ ﺯﻭﺝ ﺍﻻﻟﻛﺗﺭﻭﻧﺎﺕ ﺍﻟﻠﻰ ﻋﻠﻰ ﺍﻟﺫﺭﺍﺕ ﺩﻯ‬ ‫• ﻗﺎﻟﻡ ﻧﻔﺱ ﻣﻭﺿﻭﻉ ﺍﻻﺷﺎﺭﺓ ﺍﻟﺳﺎﻟﺑﺔ‬ ‫• ﻟﻭ ﺯﻭﺝ ﺍﻻﻟﻛﺗﺭﻭﻧﺎﺕ ﺷﺎﺭﻙ ﻓﻰ ﺍﻝ ‪ conjugation‬ﻳﺑﻘﻰ ﻫﻧﺣﺳﺑﻬﻡ‬ ‫ﻭﺍﺣﻧﺎ ﺑﻧﻌﺩ ﻋﺩﺩ ﺍﻻﻟﻛﺗﺭﻭﻧﺎﺕ ﻋﻠﺷﺎﻥ ﻧﻌﻭﺽ ﻓﻰ ﻗﺎﻧﻭﻥ ‪huckel‬‬

‫‪pyrrol‬‬

‫‬‫‬‫‬‫‪-‬‬

‫ﻓﻰ ﺍﻝ ‪ pyrrol‬ﻫﻧﻼﻗﻰ ﺍﻥ ﺍﻟﻧﻳﺗﺭﻭﺟﻳﻥ ﻋﻠﻳﻬﺎ ﺫﻭﺝ ﻣﻥ ﺍﻻﻟﻛﺗﺭﻭﻧﺎﺕ ‪ ....‬ﻭﺍﻟﺯﻭﺝ ﺩﻩ‬ ‫ﺑﻳﺷﺎﺭﻙ ﻓﻰ ﺍﻝ ‪ conjugation‬ﺍﻟﻠﻰ ﻓﻰ ﺍﻟﺣﻠﻘﺔ‬ ‫ﻳﺑﻘﻰ ﻫﻧﺣﺳﺏ ﺯﻭﺝ ﺍﻻﻟﻛﺗﺭﻭﻧﺎﺕ ﺩﻭﺍ ‪ +‬ﺍﻻﻟﻛﺗﺭﻭﻧﺎﺕ ﺍﻟﻣﻛﻭﻧﺔ ﻟﺭﻭﺍﺑﻁ ﺑﺎﻯ‬ ‫ﻫﻧﺎ ﻓﻳﻪ ﺭﺍﺑﻁﺗﻳﻥ ﺑﺎﻯ ﻳﺑﻘﻰ ﻓﻳﻪ ‪ ٤‬ﺍﻟﻛﺗﺭﻭﻧﺎﺕ ‪ + ......‬ﺯﻭﺝ ﺍﻻﻟﻛﺗﺭﻭﻧﺎﺕ ﺍﻟﺣﺭﺓ ﺍﻟﻠﻰ‬ ‫ﻋﻠﻰ ﺍﻟﻧﻳﺗﺭﻭﺟﻳﻥ ‪ ......‬ﻳﺑﻘﻰ ﺍﻟﻣﺟﻣﻭﻉ ‪٦‬‬ ‫ﻳﺑﻘﻰ ﺍﻟﻣﺭﻛﺏ ‪ aromatic‬ﻻﻧﻪ ﺗﺗﻭﻓﺭ ﻓﻳﻪ ﻛﻝ ﺍﻟﺷﺭﻭﻁ‬

‫ﺃﺣﻣﺩ ﺍﻟﻌﺎﻳﺩﻯ‬

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‫‪Dr\Ahmed Al3yde‬‬

‫‪ o‬ﺍﻣﺎ ﻓﻰ ﺍﻝ ‪pyridine‬‬

‫‪N‬‬ ‫ﻫﻧﻼﻗﻰ ﺍﻥ ﺍﻝ ‪ resonance‬ﺍﻭﺍﻝ ‪ conjugation‬ﺍﻟﻠﻰ ﻓﻰ ﺍﻟﺣﻠﻘﺔ ﺑﻳﺗﻡ ﻋﻥ‬ ‫ﻁﺭﻳﻕ ‪ ٣‬ﺭﻭﺍﺑﻁ ﺑﺎﻯ ‪ ....‬ﻭﺯﻭﺝ ﺍﻻﻟﻛﺗﺭﻭﻧﺎﺕ ﺍﻟﻠﻰ ﻋﻠﻰ ﺍﻟﻧﻳﺗﺭﻭﺟﻳﻥ ﻟﻡ ﻳﺷﺎﺭﻛﻭﺍ ﻓﻰ ﺍﻝ‬ ‫‪ resonance‬ﻳﺑﻘﻰ ﻣﺵ ﻫﻧﺣﺳﺏ ﺯﻭﺝ ﺍﻻﻟﻛﺗﺭﻭﻧﺎﺕ ﺍﺛﻧﺎء ﺍﻟﺗﻌﻭﻳﺽ ﻓﻰ ﻗﺎﻧﻭﻥ‬ ‫‪huckel‬‬ ‫ ﻳﺑﻘﻰ ﺑﺭﺩﻩ ﻓﻳﻪ ‪ ٣‬ﺭﻭﺍﺑﻁ ﺑﺎﻯ ‪ ...‬ﻳﺑﻘﻰ ‪ ٦‬ﺍﻟﻛﺗﺭﻭﻧﺎﺕ‬‫ ﻳﺑﻘﻰ ﺍﻟﻣﺭﻛﺏ ﺗﺗﻭﻓﺭ ﻓﻳﻪ ﻛﻝ ﺍﻟﺷﺭﻭﻁ ‪ ...‬ﻭﻁﺑﻌﺎ ﺍﻟﻣﺭﻛﺏ ﺍﻟﻠﻰ ﻓﻭﻕ ﻭﺍﻟﻣﺭﻛﺏ‬‫ﺩﻩ ﻛﻝ ﺫﺭﺍﺗﻬﻡ ﺗﻬﺟﻳﻧﻬﺎ ‪Sp2‬‬ ‫‪ -‬ﻭﺩﻯ ﺻﻭﺭﺓ ﺗﻭﺿﺣﻠﻙ ﺍﺯﺍﻯ ﺯﻭﺝ ﺍﻻﻟﻛﺗﺭﻭﻧﺎﺕ ﺑﺭﻩ ﺍﻝ ‪conjugation‬‬

‫• ﻁﻳﺏ ﻟﻭ ﺑﺩﻝ ﺍﻟﻧﻳﺗﺭﻭﺟﻳﻥ ﻓﻳﻪ ﺍﻛﺳﺟﻳﻥ ﺍﻭ ﻛﺑﺭﻳﺕ ﺍﻟﻠﻰ ﻋﻧﺩﻫﻡ ﺯﻭﺟﻳﻥ ﻣﻥ‬ ‫ﺍﻻﻟﻛﺗﺭﻭﻧﺎﺕ ﺍﻟﺣﺭﺓ‬

‫ﺃﺣﻣﺩ ﺍﻟﻌﺎﻳﺩﻯ‬

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‫‪Dr\Ahmed Al3yde‬‬

‫‬‫‪-‬‬

‫‬‫‪-‬‬

‫‪S‬‬

‫‪O‬‬

‫‪Thiophene‬‬

‫‪Furan‬‬

‫ﻫﻧﺎ ﻛﻝ ﺫﺭﺓ ﻣﻥ ﺍﻻﻛﺳﺟﻳﻥ ﺍﻭ ﺍﻟﻛﺑﺭﻳﺕ ﻋﻠﻳﻬﻡ ﺯﻭﺟﻳﻥ ﻣﻥ ﺍﻻﻟﻛﺗﺭﻭﻧﺎﺕ ﺍﻟﺣﺭﺓ‬ ‫ﻓﻳﻪ ﺯﻭﺝ ﻣﻧﻬﻡ ﻫﻳﺷﺎﺭﻙ ﻓﻰ ﺍﻝ ‪ conjugation‬ﻭﺯﻭﺝ ﺗﺎﻧﻰ ﻣﺵ ﻫﻳﺷﺎﺭﻙ‬ ‫‪..‬ﻟﺫﻟﻙ ﻫﻧﺣﺳﺏ ﺯﻭﺝ ﻭﺍﺣﺩ ﺑﺱ ﻣﻊ ﺍﻟﻛﺗﺭﻭﻧﺎﺕ ﺑﺎﻯ ﻋﻠﺷﺎﻥ ﻧﻌﻭﺽ ﻓﻰ ﻗﺎﻧﻭﻥ‬ ‫‪huckel‬‬ ‫ﻳﻌﻧﻰ ﻛﻝ ﻣﺭﻛﺏ ﻓﻳﻪ ﺭﺍﺑﻁﺗﻳﻥ ﺑﺎﻯ ‪ ٤ ......‬ﺍﻟﻛﺗﺭﻭﻧﺎﺕ ‪ .....‬ﻣﻊ ﺯﻭﺝ ﻣﻥ‬ ‫ﺍﻻﻟﻛﺗﺭﻭﻧﺎﺕ ‪......‬ﻳﺑﻘﻰ ﺍﻟﻣﺟﻣﻭﻉ ‪٦‬‬ ‫ﻳﺑﻘﻰ ﺍﻟﻣﺭﻛﺏ ‪Aromatic‬‬

‫ﻣﻠﺣﻭﻅﺔ ﻫﺎﻣﺔ ‪:‬‬ ‫‪Aromaticity‬‬

‫ﺃﺣﻣﺩ ﺍﻟﻌﺎﻳﺩﻯ‬

‫‪Electronegativity‬‬

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‫‪Dr\Ahmed Al3yde‬‬

‫ﻳﻌﻧﻰ ﻟﻭ ﻫﻧﺭﺗﺏ ﺍﻟﻣﺭﻛﺑﺎﺕ ﺍﻟﻠﻰ ﻓﻭﻕ ﻋﻠﻰ ﺣﺳﺏ ﺍﻝ ‪aromaticity‬‬ ‫ﻫﻧﻼﻗﻰ ﺍﻥ‬ ‫‪in aromaticity‬‬

‫‪Thiophene > pyrrol > furan‬‬

‫ ﺍﻧﺎ ﻋﻣﻠﺗﻠﻛﻡ ﺗﺭﺗﻳﺏ ﻣﺧﺗﻠﻑ ﻋﻥ ﺍﻟﺩﻛﺗﻭﺭﺓ ﺷﻭﻳﺔ ﻭﻓﻳﻪ ﺣﺎﺟﺎﺕ ﺫﻯ ﺍﻝ‬‫‪ annulene‬ﻣﺵ ﻗﻠﺗﻬﺎ ﺩﻟﻭﻗﺗﻰ ‪ ....‬ﻣﺵ ﺗﻘﻠﻕ ﻛﻝ ﻛﻠﻣﺔ ﺍﻟﺩﻛﺗﻭﺭﺓ ﺷﺭﺣﺗﻬﺎ‬ ‫ﻫﻘﻭﻟﻬﺎ ﻟﻛﻥ ﻓﻰ ﻭﻗﺗﻬﺎ ‪ ....‬ﺍﻧﺎ ﻣﺵ ﻫﺯﻭﺩ ﻋﻥ ﻛﺩﻩ ﻭﻫﺩﻳﻠﻙ ﺷﻭﻳﺔ ﺍﻣﺛﻠﺔ ﻋﻠﺷﺎﻥ‬ ‫ﺗﺛﺑﺕ ﺍﻟﻠﻰ ﺍﺧﺩﻧﺎﻩ ﺍﻟﻧﻬﺎﺭﺩﻩ ﺩﻩ ﺑﺱ‬

‫‪N‬‬

‫‪N‬‬

‫ ﻓﻰ ﺍﻟﻣﺛﺎﻝ ﺩﻩ ‪ ....‬ﺯﻭﺝ ﺍﻻﻟﻛﺗﺭﻭﻧﺎﺕ ﺍﻟﻠﻰ ﻋﻠﻰ ﺍﻟﻧﻳﺗﺭﻭﺟﻳﻥ ﻣﺵ ﺷﺎﺭﻙ‬‫ﻓﻰ ﺍﻝ ‪) resonance‬ﻭﻗﻠﺗﻠﻙ ﻣﻣﻛﻥ ﺗﻌﺭﻓﻬﺎ ﻟﻭ ﻓﻳﻪ ﺭﺍﺑﻁﺔ ﺛﻧﺎﺋﻳﺔ‬ ‫ﻟﻠﻧﻳﺗﺭﻭﺟﻳﻥ(‬ ‫ﺃﺣﻣﺩ ﺍﻟﻌﺎﻳﺩﻯ‬

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‫‪Dr\Ahmed Al3yde‬‬

‫ ﻟﻛﻥ ﺯﻭﺟﻳﻥ ﺍﻻﻟﻛﺗﺭﻭﻧﺎﺕ ﺍﻟﻠﻰ ﻋﻠﻰ ﺍﻻﻛﺳﺟﻳﻥ ‪....‬ﺷﺎﺭﻙ ﻣﻧﻬﻡ ﺯﻭﺝ‬‫ﻭﺍﺣﺩ ﻓﻰ ﺍﻝ ‪conjugation‬‬ ‫ ﻳﺑﻘﻰ ﻛﺩﻩ ﺭﺍﺑﻁﺗﻳﻥ ﺑﺎﻯ ‪ +‬ﺯﻭﺝ ﺍﻟﻛﺗﺭﻭﻧﺎﺕ ﺍﻻﻛﺳﺟﻳﻥ ‪ .....‬ﻳﺑﻘﻰ ﻛﻠﻪ ‪٦‬‬‫‪ ....‬ﻳﺎﺭﺏ ﺗﻛﻭﻥ ﺍﺗﻔﻬﻣﺕ‬

‫ ﻫﻧﺎ ﺍﻟﻧﻳﺗﺭﻭﺟﻳﻥ ﺟﻣﻳﻊ ﺭﻭﺍﺑﻁﻪ ﺍﺣﺎﺩﻳﻪ ﻓﺯﻭﺝ ﺍﻻﻟﻛﺗﺭﻭﻧﺎﺕ ﺷﺎﺭﻙ ﻓﻰ ﺍﻝ‬‫‪ ٤ + conjugation‬ﺭﻭﺍﺑﻁ ﺑﺎﻯ‬

‫‪Anti Aromatic‬‬

‫• ﻛﻔﺎﻳﺔ ﻋﻠﻳﻛﻡ ﻛﺩﻩ ﺍﻟﻧﻬﺎﺭﺩﻩ‬ ‫• ﻭﺍﻥ ﺷﺎء ﷲ ﻧﺧﻠﺹ ﺍﻟﻣﻭﺿﻭﻉ ﺩﻩ ﻣﻊ ﺍﻻﺳﺋﻠﺔ ﺍﻟﻣﺣﺎﺿﺭﺓ ﺍﻟﻠﻰ ﺟﺎﻳﺔ ﻭﻧﺩﺧﻝ‬ ‫ﻋﻠﻰ ﺍﻟﺑﻧﺯﻳﻥ ﻭﺗﻔﺎﻋﻼﺗﻪ ‪ ....‬ﺩﻣﺗﻡ ﻓﻰ ﺭﻋﺎﻳﺔ ﷲ ‪ ...‬ﻭﺫﺍﻛﺭﻭﺍ ﻛﻭﻳﺱ‬

‫ﻛﻭﺭﺱ ﺍﻟﻌﺿﻭﻳﺔ‬ ‫ﺍﻟﺳﺑﺕ ﻭﺍﻟﺛﻼﺛﺎء‬ ‫ﺍﻟﺳﺎﻋﺔ ‪ ١‬ﻭﺍﻟﺳﺎﻋﺔ ‪٢:٣٠‬‬ ‫ﺳﻧﺗﺭ ﺍﻟﺟﺎﻣﻌﺔ‬ ‫ﺃﺣﻣﺩ ﺍﻟﻌﺎﻳﺩﻯ‬

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‫‪Dr\Ahmed Al3yde‬‬