Fluorene 2-bromo

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. 

Bromo-9-phenylfluorene 9H-Fluorene, 9-bromo-9-phenyl- (9) (55135-66-5) Butyllithium, lithium, butyl- (8,9) (109-72-8)... 

Bromo-9-phenylfluorene 9H-Fluorene, 9-bromo-9-phenyl (9) (55135-66-5) (S)-Dimethyl aspartate hydrochloride Aspartic add, dimethyl ester, hydrochloride, L- (8) L-Aspartic acid, dimethyl ester, hydrochloride (9) (32213-95-9) 9-Methoxy-9-phenylfluorene 9H-Fluorene, 9-methoxy-9-phenyl- (9) (56849-87-7) 9-Phenyl-9-fluorenol Fluoren-9-ol, 9-phenyl- (8) 9H-Fluoren-9-ol, 9-phenyl- (9) (25603-67-2)... 

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. 

Figure 14 The structure of 9-bromo-9-[(bromomagnesium)methylene]fluorene 30. 

It appears that neither the lithium carbenoid pathway nor the cyclopropanation of buta-trienes are general routes to [3]radialenes. More successful is the cyclotrimerization of 1,1-dihaloalkenes via copper or nickel carbenoids, provided the substituents at the other end of the C=C double bond are not too small. Thus, tris(fluoren-9-ylidene)cyclopropane 27 was formed besides butatriene 28 from the (l-bromo-l-alkenyl)cuprate 26 generated in situ from (9-dibromomethylene)fluorene (Scheme 3)10. The cuprate complexes formed... 

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 Ad -E mechanism proposed to account for the kinetics of substitution of 9-(a-bromo-a -arylmethylene)fluorenes by thiolate ions in aqueous acetonitrile also features elimination of the leaving group in a fast step following rate-determining carbanion formation (by nucleophilic addition). ... 

The substitution of 9-(Q -bromo-Q -arylmethylene)fluorenes by MeS and / -TolS ions in MeCN-H,0 (4 1) is a second-order reaction and its rate decreases on increasing the water content of the medium. With MeS, for the change of the a-aryl group. 

N 20.29% crysts, mp 43-44°. First prepd by treating 9 bromo-9 trimethylsiIyl-fluorene with sodium azide in hot methanol, more recently by treating 9-bromofluorene itself under the same conditions. Its expl props are not described in CA... 

The structures of three monomeric organomagnesium bromides in which the magnesium center is penta-coordinate have been established in the solid state. These compounds are MeMgBr(THF)(TMEDA) (156) , 9-bromo-9-[(bromomagnesium)methylene]fluorene tris-THF complex (157) and MeMgBr(THF)3 (158) . 

Solvolysis of the R,R and R,S isomers of 2-bromo-9-(l-X-ethyl)fluorenes, X = Cl, Br, I, or OBs, in 25% (v/v) acetonitrile in water has been studied with respect to rates of formation of elimination products and of substitution products (X = OH or NHCOMe).142 The parent 9-(l-X-ethyl)fluorenes and the 2,2/-dibromo-9-(l-X-ethyl)-fluorenes were also studied. Various effects of leaving group and of the presence of nucleophiles on the competition between the reactions were observed and the Bronsted equation was applied to the results for the elimination reactions. A related study of solvolysis of 9-(X-methyl)fluorenes, X = I, Br, or Bs, was also carried out, in which the Swain-Scott equation was applied to nucleophilic selectivities in the S 2 reactions.143... 

A 50-ml Schlenck tube equipped with a stirring bar containing bis(l,5-cyclooc-tadiene)-nickel(O) (4.48 mmol), 2,2 -bipyridyl (4.48 mmol), and 1,5-cycloocta-diene (4.48 mmol) was treated with 5 ml of DMF and the ensuing deep blue/ purple solution stirred at 60°C for 30 minutes. The mixture was then treated with 2,7-diiodo-9,9-bis(2-ethylhexyl)fluorene (1.68 mmol) and 2,5-bis(p-bromo-phenyl)-A-(p-hexylphenyl)pyrrole (0.56 mmol) in 20 ml of toluene by syringe and then stirred for 5 days at 75°C. The solution was cooled to ambient temperature and precipitated into a mixture of 100 ml apiece of methanol and acetone and 5 ml concentrated hydrochloric acid. After of the mixture was stirred for 2 hours, it was filtered the solid residue was dissolved in chloroform and re-precipitated in methanol and acetone solution, and re-filtered. The residue was successively washed with methanol, water and methanol, and dried the product was isolated having a Mj, of 47,200 daltons. 

C12H26S ethyl decyl sulfide 19313-61-2 537.00 54.833 2 25508 C13H9Br 2-bromo-9H-fluorene 1133-80-8 474.15 41.406 2... 

A procedure better adapted to operation on a large scale is described by Bavin. A solution of 1 mole of fluorene in 500 ml. of ether is added with stirring under reflux to an ethereal solution of phenyllithium prepared from 1.5 moles of bromo-benzene. After 1 hr. more the orange solution of metallated hydrocarbon is poured as rapidly as possible into powdered dry ice which has been slurried with ether. The mixture is acidified, the solvent removed by steam distillation, and the solid is dissolved in aqueous potassium carbonate solutioa Clarification with Norit gives a pale yellow solution which is poured into excess 30% hydrochloric acid. The colorless, crystalline product on reaction with methanol and hydrogen chloride gave the pure methyl ester, m.p. 64-65°. The yield was generally over 70% and occasionally reached 90%. ... 

Phenylation of carbanions derived from olefins such as 1,3-pentadiene and l-(p-anisyl) propene and aromatics such as indene and fluorene are possible by the SrnI route in ammonia solvent. From the 1,3-pentadiene a mixture of mono-olefins and dienes is produced along with a small amount of di- and triphenylated material. Hydrogenation of the mixture gives 1-phenylpentane in 74% yield.106) Phenylation of 2- and 4-picolyl anions is conveniently effected in ammonia. When bromo- or iodobenzene is used for this purpose, reaction probably occurs by both SrnI and benzyne routes.111)... 

When toluene (9.5 g) is treated with dioxan Br2 (from 15.1 g of bromine) and heated at 35-40°, the mixture is rapidly decolorized after dilution with 10% NaOH solution,p-bromo-toluene (16.8 g) is obtained. Naphthalene can be similarly monobrominated at the 1-position, anthracene at the 9- and fluorene at the 2-position. 

It is surprising that, to the best of our knowledge. X-ray structures have only been published for diazomethanes in which the two H-atoms are replaced by a hydrocarbon, namely 2-bromo-9-diazofluorene (5.2 Griffiths and Hine, 1970) and 9-diazo-fluorene (5.3 Tulip et al., 1978). There is also an X-ray analysis of the heteroaromatic diazo compound 3-diazoindazole (5.4 Leban et al., 1978). 

The only example of rod-rod copolymers with polyphenylene-based rods are the polymers 230 and 231, in which two polyfluorene blocks are separated by a short arylene vinylene unit (Scheme 105). These were prepared by Suzuki polycondensation of a fluorene monoboronic acid 232 in the presence of the bromo-substituted oUgo(arylene vinylene) units 233 and 234 [321], From the molecular masses of the polymers, the total number of fluorene units in both 230 and 231 is about 18. 

Recently, a new synthetic protocol for synthesis of 9-arylfluorenes or 9,9-diarylfluorenes was reported wherein these products were furnished in good to excellent yields by Pd-catalyzed cross-coupling reactions of fluorene with haloarenes [141]. This synthetic method was also applied in the preparation of aryl-substituted sumanenes. Palladium-catalyzed arylation of sumanene (2) was conducted with l-bromo-2,6-dimethylbenzene, and the desired xylylsumanene 124-xyl was... 

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