9-phenyl fluorene

The relative amounts of 9-phenyl-9-fluorenol and 9-bromo-9-phenyl-fluorene were determined as follows A 13C NMR spectrum (CDCI3 solution, Bruker 400 MHz) of an authentic sample of 9-bromo-9-phenylfluorene was recorded and then doped in 1% increments with authentic 9-phenyl-9-fluorenol. A 13C NMR spectrum (CDCI3 solution, Bruker 400 MHz) was recorded after each doping, and the heights of the peaks at 120.3 ppm (bromide) and 120.0 ppm (alcohol) were monitored. These spectra were compared with a 13C NMR spectrum (CDCI3 solution, Bruker 400 MHz) of the sample in question. Application of this technique to an evaporated aliquot of the reaction mixture in Step B, indicated >97% conversion of alcohol to bromide after 24 hr. 

The volume concludes with the preparation of four useful starting materials. The highly electrophilic tricarbonyl reagent DIMETHYL MESOXALATE finds application as a two-electron component in various pericyclic processes. 9-BROMO-9-PHENYL-FLUORENE is becoming increasingly used for the protection of primary amines, particularly amino acids and amino esters. Two methods for introducing the 9-phenylfluorenyl group are illustrated in the preparations of (S)-N-(9-PHENYLFLUOREN-9-YL)ALANINE AND (S)-DIMETHYL N-(9-PHENYLFLUOREN-9-YL)ASPARTATE. 

Values up to pKa 33 (diphenylmethane) are those reported for equilibrium methods, and were measured either directly using the H acidity function or by comparing acidity with 9-phenyl-fluorene. Above pA 33, we assume a = 0.3 for toluene, cumene, and tripticene, and base other values on pKa = 43 for benzene and an assumed a of 0.9. The scale is based on the Langford and Burwell value of 18.5 for pKa of 9-phenylfluorene. 

Dagegen werden l,2-Bis-[triphenylmethyl]- bzw. l,2-Bis-[9-phenyl-fluorenyl-(9)]-hy-drazin durch Natrium/Ammoniak/0° in guten Ausbeuten zu Triphenylmethan (90% d.Th.) bzw. 9-Phenyl-fluoren (—100% d.Th., F 147°) reduziert6. 

Sfethozy-l. 2-benzo-anthracen 6 II704. 9-Oxy-9-phenyl-fluoren 6,725, 1357, II704. 9-[4-Oxy-phenyl]-fluoren 6 I 357. 

Hydroxy-9-phenyl-fluorene (0.01) H2SO4 (0.1) Acetic acid 25 72 9-p-Hydroxyphenyl-9-phenylfluo-rene (95%) 221, 325... 

Hydroxy-9-phenyl-fluorene (0.02) HCl (0.6) Acetic acid 115 1 9-p-Aminophenyl-9-phenylfluorene (80%) 325... 

Dimethylaniline 0.012 9-Hydroxy-9-phenyl-fluorene (0.004) Ha(-) Acetic add 115 4 9-p-IHmethylaminopheDyl-O-phenylfluorene (90%) 325... 

Bis[4-(2-Bromotetrafluoroethoxy)phenyl]Fluorene. This product was prepared according to Method I using 9,9-bis(4-hydroxyphenyl)fluorene... 

Barriers to Rotation and Equilibrium Constants at 0°C for 9-(o-Substituted Phenyl)fluorene Rotamers (63) in Chloroform- ... 

Buttressing effects are known to raise the barrier to rotation in the biphenyl series by preventing bond angle deformations of a substituent involved in direct interaction in the transition state. Similar effects were found in the 9-arylfluorene series (108). The barrier to rotation of 9-(3-bromo-6-methoxy-2,4-dimethyl-phenyl)fluorene (67, X = H) in chloroform-d at 56.3°C is 25.7 kcal/mol for... 

The foregoing examples of differential reactivities of rotamers may be summarized by saying that the reactivity is controlled by the steric factor. The difference in the reactivities of rotamers of 9-(2-bromomethyl-6-methyl-phenyl)fluorene (56) in SN2 type reactions falls in the same category (176). However, the substituent effect is not limited to a steric one there can be conformation-dependent electronic effects of substituents as well. A pertinent example is found in the reactivity of the bromomethyl compound (56) when the rotamers are heated in a trifluoroacetic acid solution (Scheme 10). The ap form gives rise to a cyclized product, whereas the sp form remains intact (176). The former must be reacting by participation of the it system of the fluorene ring. 

Preparation of 9,9-dioctyl-2,7-( V-4 -bronmphenyl)(4- V-phenylamino) phenyl)fluorene... 

Borsenberger et al. (1996e) measured hole mobilities of a series of donor glasses N,N/-diphenyl-N,N,-(2-naphthyl)-(p-terphenyl)-4,4/,-diamine (NDNTP), N,N -dipheny l-N,N -(2-naphthy l)-( 1,1 -phenyl)-4, -diamine (NDNPD), 9,9-bis 4-[N-(4-tolyl)-N-(2-naphthyl)amino]phenyl fluorene (BTNAF), and 2,5-bis(4-diethylaminophenyl)-l,3,4-oxadiazole (OXD). For OXD, the photocurient transients were dispersive. Nonetheless, transit times could readily be determined from the intersection of the two linear regions of the transients. In all glasses, the field and temperature dependencies were described as lo u /3E 2 and -(T0IT)2. The results are summarized in Table 6. 

Recently, another pathway was used to synthesize indolo [ 3,2-ft ] carbazole-based molecules containing aromatic substituents on both ends of the material. First, octyl side chains are added on the nitrogen atoms then, aromatic substituents can be added by using either Suzuki or Stille cross-coupling starting with 2,8- or 3,9-dibromo-5,ll-dioctylindolo[3.2-b]carbazoles. As shown in Scheme 11, the addition of phenyl, thiophene, biphenylamino-phenyl, fluorene, and even carbazole units has recently been reported in the literature [20,93]. 

Both polysulfone and the polyetherimide are thermojdaslics whieh withstand higher temperatures than epoxies such as DGEBA. The effect of (43) a polysulfone (Udel, 43a) and polyetherimide (Ultem, 43b) thermoplastics on the properties of a tetra-2,3-epoxypropylamine, N,N,N, N -tetra-2,3-epoxypropyl-, -bis(4-aminophenyl)-p-diiso-propenylbenzene (HPT Resin 1071,43c) has been studied and also the effect of these thermoplastics on the resin di-2,3-epoxypropyl-9,9-bis (hydro phenyl)fluorene (HPT Resin 1079,43d). Both these resins have a stiff backbone and were developed for use as amatrix resin for advanced composites. They can be cured with the aromatic dianune, -bis(3,5-dimethyl-4-aminophenyl)-p-diisopropylbenzene (43e). These resin curing agent combinations exhibit greatly improved hot/wet performaiKe over that of traditional epoxies. 

S. Kazama, T. Teramoto, K. Haraya, Carbon dioxide and nitrogen transport properties of w(phenyl)fluorene-based cardo polymer membranes, J. Memb. Sci. 207 (1) (2002) 91-104. 

C.-P. Yang, H.-C. Chiang, Organosoluble and light-colored fluorinated polyimides based on 9,9-( /5[4-(4-amino-2-trifluoromethylphenoxy) phenyl] fluorene and aromahc dianhydrides, CohoidPolym. Sci. 282 (12) (2004) 1347-1358. 

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