ALQUINOS

NOMENCLATURA
 1-hexino cyclooctino
 3-octino propino

ALQUINOS
IMPORTANTES
Síntesis

1. Por eliminaciones con bases fuertes, dos E2 seguidas.

2. Por sustitución con acetiluros (partir de un alquino)
Qué se obtiene por reaccion de bromuro de t-butilo con acetiluro de litio?
Reactividad
Mecanismo

1. Hidrohalogenación

Por qué es más estable?

Reacción con HI de 1-pentino y 2-pentino?

2. Halogenación
3. Hidratación de alquinos. MARKOVNIKOV
4. HIDRATACION ANTIMARKOVNIKOV
HIDROGENACIONES

Alqueno Cis Alqueno trans

COMPUESTOS AROMÁTICOS
aromatic
1.In the traditional sense, 'having a chemistry typified by benzene'.

2.A cyclically conjugated molecular entity with a stability (due to

delocalization ) significantly greater than that of a hypothetical localized
structure (e.g. Kekulé structure ) is said to possess aromatic character.
If the structure is of higher energy (less stable) than such a
hypothetical classical structure, the molecular entity is 'antiaromatic'.
The most widely used method for determining aromaticity is the
observation of diatropicity in the 1H NMR spectrum.
See also: Hückel (4n + 2) rule, Möbius aromaticity

3.The terms aromatic and antiaromatic have been extended to describe

the stabilization or destabilization of transition states of pericyclic
reactions The hypothetical reference structure is here less clearly
defined, and use of the term is based on application of the Hückel (4n +
2) rule and on consideration of the topology of orbital overlap in the
transition state. Reactions of molecules in the ground state involving
antiaromatic transition states proceed, if at all, much less easily than
those involving aromatic transition states.
Gold book
NOMENCLATURA

1. NOMENCLATURA o,m,p
2. MEMORIZAR LAS POSICIONES
A planar (or near planar) cycle of sp2 hybridized atoms, the p-orbitals of which
are oriented parallel to each other. These overlapping p-orbitals generate an
array of π-molecular orbitals.

These π-orbitals are occupied by 4n+2 electrons (where n is an integer or

zero). This requirement is known as The Hückel Rule.
antiaromaticity (antithetical to aromaticity)
Those cyclic molecules for which cyclic electron delocalization provides
for the reduction (in some cases, loss) of thermodynamic stability
compared to acyclic structural analogues are classified as antiaromatic
species. In contrast to aromatic compounds, antiaromatic ones are
prone to reactions causing changes in their structural type, and display
tendency to alternation of bond lengths and fluxional behavior (see
fluxional molecules) both in solution and in the solid. Antiaromatic
molecules possess negative (or very low positive) values of resonance
energy and a small energy gap between their highest occupied and
lowest unoccupied molecular orbitals. In antiaromatic molecules, an
external magnetic field induces a paramagnetic electron current.
Whereas benzene represents the prototypical aromatic compound,
cyclobuta-1,3-diene exemplifies the compound with most clearly defined
antiaromatic properties.

4n electrones pi
Resumen reglas para compuesto aromático
1) Su estructura debe ser cíclica y debe contener enlaces dobles conjugados.
2) Cada átomo de carbono del anillo debe presentar hidridación sp2, u
ocasionalmente sp, con al menos un orbital p no hidridizado.
3) Los orbitales p deben solaparse para formar un anillo continuo de orbitales
paralelos. La estructura debe ser plana o casi plana para que el solapamiento
de los orbitales p sea efectivo.
4) Además debe cumplir la regla de Hückel

Clasifiquelos en aromaticos y antiaromaticos

REACTIVIDAD
1.Sustitucion electrofílica
REACTIVIDAD

Plantee los mecanismos

SEGUNDA SUSTITUCION ORIENTADORES
C6H6 (large excess) + CH3CH2CH2-Cl + AlCl3 ——> C6H5-CH(CH3)2 + HCl
Cómo entra un Tercer grupo?

Básicamente se obedece al grupo más activante

 Los anillos muy activados dan polihalogenaciones, polinitraciones etc
Para evitarlo se debe hacer el anillo menos activado el anillos (fenol y
anilina)

pyridine (a
HNO3 , 5 ºC H3O(+) & heat
base)
C6H5–NH2 + H3CO)2O C6H5–NHCOCH3 p-O2N–C6H4–NHCOCH3 p-O2N–C6H4–NH2

Qué se obtiene por la reacción directa de la anilina?

2. OXIDACIONES Y REDUCCIONES
a. Oxidaciones de aril-alquilos

No importa el tamaño del grupo alquilo, siempre que tenga un

hidrogeno bencílico al menos
b. Reducciones de aromáticos: Difícil, por qué?
c. Reducciones de nitros y carbonilos
SUSTITUCION NUCLEOFILICA
AROMATICA
SOLO OCURRE EN ANILLOS MUY DESACTIVADOS O EN
CONDICIONES MUY FUERTE
 Intermedio bencino

En el mecanismo primero se da una

eliminación y luego una adición
Ejerccios finales