1. PRIMERA SECCIÓN: EN BUSCA DE LA REPRESENTACIÓN PERDIDA
1.4. UNE: SENTIDOS E INTERESES SINDICALES DE LA REPRESENTACIÓN CORPORATIVA
To a flask containing concentrated hydrochloric acid (12cm3) and an equal amount of water was added the o-haloaniline substituent (0.03 moles) which was dissolved by heating. The reaction mixture was then cooled in
an ice bath to below 5°C, whereupon a solution of sodium nitrite (0.033 moles ca 10% w/v) was added dropwise over a period of 5 minutes. Since the diazotisation reaction is exothermic, the following conditions must be observed during the procedure
a) Acidity to congo-red paper
b) A positive reaction to starch-iodide paper c) A temperature <10°C
After continuous stirring for 15 minutes in the presence of excess nitrous acid, sulphamic acid was added to the solution until a negative test on starch iodide paper was observed. The diazonium salt solution was filtered into a solution of the diethylaniline
component (0.03 moles) dissolved in water (22 cm3) and concentrated hydrochloric acid (22 cm3) at 10°C. The
resulting mixture was then stirred for a further 10 minutes.
Sodium acetate crystals were added until the reaction mixture was no longer acid to congo-red paper. The
mixture was left standing overnight. The resulting solid dye was filtered, washed with water, and left to dry
in air. The crude azodye was then recrystallised from ethanol. The following azodyestuffs were prepared:
1-(2-Chlorophenylazo)-4-N,N-diethylaminobenzene (7, X=C1) This was isolated as red crystals (52%) m.p. 60°C (From EtOH) (Found C 66.12, H 6.41, N 14.56: CjgHjgClj^ requires C 66.77, H 6.30, N 14.60%) ^HfCDClg) 7.9-6.8
([AX]2 system, 4ArH), 7.75-7.2(m,4ArH), 3.5(q,4H) 1.2(t ,6H)ppm.
1-(2-Bromophenylazo)-4-N,N-diethylaminobenzene (7, X=Br) This was obtained as red crystals (53%) m.p. 61% (From EtOH) (Found C 57.87, H 5.53, 12.62: CjgH^BrjNg requires C 57.84, H 5.46, N 12.64%) 61h(CDC13) 7.9-6.7([AX]2 system,
4ArH), 7.6-7.1(m,4ArH), 3.5(q,4H), 1.25(t,6H)ppm.
1-(2-Iodophenylazo)-4-N,N-diethylaminobenzene (7, X=I) This was isolated as red crystals (41%)m.p. 71°C (From EtOH) (Found C 50.21, H 4.72, N 10.97:'CigHigI^ 3 requires
C 50.67, H 4.78, N 11.08%) 6^ (0 0 0 1 3) 8 . 0-6 . 9 ( [ AX] 2 system,
4ArH), 7.8-7.2(m,4ArH), 3.5(q,4H), 1.25(t,6H)ppm.
1-(2-Chlorophenylazo)-2-acetylamino-4-N,N-diethylaminobenzene (8, X=C1) This was isolated as red crystals (42%) m.p.
99°C (From EtOH) (Found C 62.42, H 6.37, N 16.34: C 18H21CI1 N^Oi requires C 62.69, H 6.13, N 16.24%)
S^tCDClg) 8 . 3 ( s, lArH) , 7.8(d,2ArH), 7.4(m,4ArH), 6.5(d,lH),
3.5(q,4H), 2.3(s,3H), 1.3(t,3H)ppm.
1-(2-Bromophenylazo)-2-acetylamino-4-N,N-diethylaminobenzene (8, X=Br) This was isolated as red crystals (75%) m.p.
101°C (From EtOH) (Found C 55.13, H 5.31, N 14.08:
C18H 2iBr jN^O j requires C 55.53, H 5.43, N 14.39%) ^HtCDCls) 8.3(s,lArH), 7.75(d,2ArH), 7.3(m,4ArH), 6.5(d,lH), 3.5(q,4H),
2.3(s,3H), 1.25(t ,3H)ppm. - 169 -
1-(2-Iodophenylazo)-2-acetylamino-4-N,N-diethylaminobenzene (8, X=I) This was obtained as red crystals (47%) m.p.
111°C (From EtOH) (Found C 49.88, H 4.72, N 12.90
C 18H 21IiN 4°i re(3uires c 49.55, H 4.85, N 12.84%) <$1H(CDC13)
8.35(s,lArH), 7.8(d,2ArH), 7.4(m,4ArH), 6.5(d,lH), 3.55
(q,4H), 2.3(s,3H), 1.2(t,3H)ppm.
3.8.3 Preparation of Phosphonium Salts
The template (10“3mole), tertiary phosphine (3x10“ 3
moles) and nickel (II) bromide (2xl0-if moles) were heated together under reflux in ethanol (10 cm3) in a nitrogen
atmosphere for 5-8 hours. The reaction mixture was then poured into water (50cm3) containing KBr or KI (0.5g), and extracted with ether (2x20 cm3) in order to remove
any non-ionic impurities. The aqueous layer was then extracted with chloroform (3x10 cm3) and discarded. The chloroform layer was dried (MgSO 4) and evaporated. The oily residue was then triturated several times with
sodium - dried ether until it solidified. After filtration, the majority of salts were recrystallised using a chloroform/ ethylacetate mixture. All the butylphosphonium salts
became hygroscopic on contact with the atmosphere and therefore no microanalytical data has been obtained on these salts. During the kinetic study the following salts have been characterised:
4-Methyl-N-(2-triphenylphosphoniobenzylidene)aniline iodide (16, R=Me) This was isolated as yellow crystals (42%)
m.p. >300°C (From CHCl3/EtOAc) (Found C 68.41, H 4.77,
N 3.49, C37H30IiN2Pi Requires C 67.27, H 4.57, N 4.24%)
63lP (CDC13 ) 25.94 ppm. 6lH(CDCl3), 8.5(s,lH), 7.65(m,19ArH),
6.85-5.95([AX]2 system, 4ArH), 2.15(s,3H)ppm.
N-(2-triphenylphosphoniobenzylidene)aniline iodide (16, R=H) This was obtained as yellow crystals (35%) m.p. >300°C
(From CHCI3/ether) (Found C 63.63, H 4.35, N 2.18:
C 35H3t+ Ij^Pj . H 20 requires C 63.37, H 4.60, N 2.39%)
631P(CDC13 ) 26.05 ppm. fiiHfCDCl^ 8.6(s,lH), 8.1-7.1
(m,24ArH)ppm.
4-Bromo-N-(2-triphenylphosphoniobenzylidene)aniline iodide (16, R=Br) This was collected as light brown coloured crystals (56%) decomp. 200-202°C (From CHCl3/ether) (Found
C 57.23, H 3.85, 2.21: C31 H2IfBrl I1 W P requires C 57.43,
H 3.73, N 2.16%) 631P(CDC13) 26.17ppm. fiiHfCDClg) 8.8(s,lH)
8.2-7.3(m,19ArH) 7.15-6.00([AX]2 system, 4ArH)ppm.
4-Phenylamino-N-(2-triphenylphosphoniobenzylidene)aniline iodide (16, R=NHPh) This was isolated as bright orange crystals (78%) decomp. 106°C (From CHC13/ether) (Found
C 67.63, H 4.82, N 4.12: C37 H N 2P^ requires C 67.27,
H 4.57, N 4.24%) 631P(CDC13 ) 25.72ppm. S^CDClg) 8.5(s,lH)
8.2-7.3(m,24ArH), 6.85-6.00([AX]2 system, 4ArH) 5.7(s,1H)ppm. 4-Hydroxy-N-(2-triphenylphosphoniobenzylidene)aniline
iodide (16, R=OH) This was isolated as a yellow solid (21%) m.p. >300°C (From CHCl3/ether) (Found C 61.29,
H 4.13, N 2.32: C31H2 511NjOJP1. H20 requires C 61.69,
H 4.47, N 2.32%) 631P (TFA/D20 ) 26.56ppm 61H(TFA,D20) 8.7(s,1H)
8.1-7•2(m,19ArH) 7.0-6.1([AX]2 system, 4ArH) 5.2(s,1H)ppm.
4-Diethylamino-N-(2-triphenylphosphoniobenzylidene)aniline iodide (16, R=NEt2) This was obtained as orange crystals
(65%) m.p. 255°C (From CHCl3/EtOAc) (Found C 64.52, H 5.31,
N 4.21: C 35H3 k I 1N2P1. H20 requires C 63.83, H 5.47, N 4.26%)
631P(CDC13 ) 25 .68ppm. fiiHtCDCl^ 8.5(s,lH) 8 .1-7 .1 (m, 19ArH)
7.3-6.2(m[AX]2 system, 4ArH), 3.3(q,4H), 1.2(t,6H)ppm.
4-Carboethoxy-N-(2-triphenylphosphoniobenzylidene)aniline iodide (16, R=C02Et) This was isolated as light green
crystals (35%) decomp. 120°C (From CHCl3/EtOAc) (Found
C 61.57, H 4.50, N 1.77: C H I N 0 P. H O requiresod zy 1 1 1 1 2 C 61.21, H 4.79, N 1.55%) 631P(CDC13 ) 26 .07ppm. e ^ C D C l ^ 8.5(s,1H) 8.1-7.2(m,23ArH), 4.3(q,2H), 1.3(t,3H)ppm.
All the azodyestuff salts prepared during this kinetic study were isolated and characterised with the iodide
counter-anion as standard. This was achieved by adding potassium iodide crystals in the salt-isolation procedure. 4-(2-Triphenylphosphoniophenylazo)-N,N-diethylaniline iodide (12, R ^H, R^Ph) This was obtained as red crystals (83%) m.p. 220°C (From CHCl3/EtOAc) (Found
C 62.78, H 5.13, N 6.18: C3IfH33I NgP H2O requires C 61.91,
H 5.31, N 6.37%). 631p(CDCl3 ) 23.74ppm. 61H(CDC1 ) 8.2-7.4
(m,19ArH), 6.95-6.4([AX] 2 system, 4H), 3.4(q,4H), 1.2
(t,6H)ppm.
4-(2-Tributylphosphoniophenylazo)-N,N-diethylaniline
iodide (12, R1=H, R2=Bu) This was obtained as a hygroscopic
red solid (43%) <$31p (CDC13 ) 31.63 ppm. S ^ C D C ^ ) 8.5(s,4ArH),
7.1-6.6([AX] 2 system, 4ArH), 3.4(q,4H), 2.85(m,6H), 1.5-0.8
(m,27H) ppm.
2-Acetylamino-4-(2-triphenylphosphoniophenylazo)-N,N- diethylaniline iodide (12; R1=NHCOCH3, R2=Ph) This was
isolated as purple crystals (87%) m.p. 235°C (From CHC13 ,
EtOAc) (Found C 61.93, H 5.29, N 7.44: C36 H 36I N^O 1 'P1
requires C 61.89, H 5.16, N 8.02%) 631P(CDC13) 23.43 ppm
S^tCDCl ) 8.3-7.4(m,23ArH), 6.1(d,lH), 3.4(q,4H), 2.3(S 1.2(t,6H)ppm.
2-Acetylamino-4-(2-tributylphosphoniophenylazo)-N,N- diethylaniline iodide (12; R1=NHCOCH3 , R2=Bu) This was
isolated as a hygroscopic purple solid (42%). 631P(CDC13)
31.05 ppm. 6iH(CDC13), 8.1-7.5(m,7ArH), 6.0(d,lH),
3.4(q,4H), 2.9(m,6H ), 2.35(s,3H) 1.4-0.8(m,27H)ppm.
3H) ,
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