Organic compounds -- part of the class 532-570 series – Organic compounds – Nitriles
Patent
1999-08-05
2000-04-04
McKane, Joseph
Organic compounds -- part of the class 532-570 series
Organic compounds
Nitriles
C07C25314
Patent
active
06046352&
DESCRIPTION:
BRIEF SUMMARY
The invention relates to a preparation process for 4-cyano-4'-hydroxybiphenyl. This compound is known as an intermediate and used, for example, in the synthesis of monomers of crystal liquid polymers (GB 2002767) (J. Polym. Sci., Part C: Polymer Letters, Vol. 28, 345-355 (1990); J. Mater, Chem., 1993, 3(6), 633-642) or for the formation of specific polysiloxanes (U.S. Pat. No. 5,262,052).
4-cyano-4'-hydroxybiphenyl can be prepared as described in the Application EP44759 or in J. Mater. Chem., 1933, 3(6), 633-642, by reacting 4-bromo-4'-hydroxybiphenyl with copper cyanide. Another preparation method described in the Application U.S. Pat. No. 5,262,052, consists of reacting di(4-methoxyphenyl)zinc with 4-bromobenzonitrile in the presence of Ni(PPh3).sub.4. The disadvantage of these processes is that they use toxic agents such as copper cyanide. A subject of the invention is a preparation process which does not use a toxic agent such as copper cyanide or which uses less toxic agents than those described in the state of the art.
The invention relates to a preparation process for 4-cyano-4'-hydroxybiphenyl, the process comprising: magnesium halide, 4-alkoxy-4'-formyl-biphenyl and conversion of the formyl group into cyano, and
The reactions are preferably carried out under an inert atmosphere. For example, the reactions can be carried out under a nitrogen atmosphere.
The aldehyde function can be protected by the standard methods known to a person skilled in the art. Thus, for example, protection can be carried out by using ethylene glycol, propylene glycol or dimethyl ether as agent.
The protected 4-bromobenzaldehyde can be reacted with a Grignard reagent in an aprotic solvent. The alkoxy group of p-alkoxyphenyl magnesium halide is preferably an alkoxy having at most 5 carbon atoms; the alkoxy group can be, for example, a methoxy or ethoxy group and preferably the methoxy group, and the halide used is preferably the chloride or bromide.
The nature of the deprotection reaction depends on the reagent used for the protection reaction. The deprotection can be a hydrolysis. The conversion of the formyl group into cyano can be carried out by the standard methods known to a person skilled in the art; hydroxylamine can be used as a reagent.
The hydrolysis of the alkoxy group can be carried out without hydrolysis of the cyano group by using an appropriate reagent such as pyridinium chloride.
The following examples are presented to illustrate the above procedures and must in no case be considered as a limit to the scope of the invention.
EXAMPLE 1
Preparation of 2-(4 bromophenyl)-1, 3-dioxolane
40 g (216 mmol) of bromobenzaldehyde, 39 ml (700 mmol) of ethylene glycol, 1.6 g (9.3 mmol) of p-toluene sulphonic acid and 670 ml of toluene are introduced into a 2 l three-necked flask equipped with a Dean-Stark apparatus under nitrogen. The reaction mixture is taken to reflux whilst eliminating the water formed. After 24 hours of reflux, the reaction mixture is hydrolized with a saturated solution of sodium carbonate (240 ml). The organic phase is recovered and washed twice with a saturated solution of sodium chloride (2.times.160 ml), then concentrated under vacuum. The crude product obtained is distilled under 40 mm/Hg (150-156.degree. C.).
EXAMPLE 2
Preparation of 2-[p-(4-methoxyphenyl)-phenyl]-1,3-dioxolane
0.8 g of magnesium, 1 ml of tetrahydrofurane (THF) and one crystal of iodine are introduced into a 50 ml three-necked flask under nitrogen. The reaction mixture is heated to 40.degree. C. and 4.75 g of 4-bromoanisole in solution in 25 ml of THF is poured in. The reaction mixture is taken to reflux for an hour and a half.
After returning to ambient temperature, this solution is poured onto a mixture of 2-(4-bromophenyl)- 1,3-dioxolane (5 g) in 50 ml of THF in the presence of a catalyst (Pd, 0.25%) whilst maintaining the temperature at 0.degree. C. The reaction mixture is left to return to ambient temperature and the second fraction of catalyst (0.25%) is added. The reaction mixture is then heated at 40.degree.
REFERENCES:
patent: 5262052 (1993-11-01), Rossiter et al.
Breton Christine Le
Cazaux Jean-Bernard
McKane Joseph
Societe d'Expansion Scientifique Expansia
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