Organic compounds -- part of the class 532-570 series – Organic compounds – Amino nitrogen containing
Patent
1986-02-27
1988-03-29
Reamer, James H.
Organic compounds -- part of the class 532-570 series
Organic compounds
Amino nitrogen containing
564291, C07C 8730
Patent
active
047345268
DESCRIPTION:
BRIEF SUMMARY
The object of this invention is a new category of fluoridation agents for organic compounds, especially acetylenic compounds, the process for their preparation and their utilization in addition or nucleophilic substitution reactions.
Organo-fluorine compounds present great interest, especially fluorovinyl compounds, including certain of them, such as fluorofumarate and its derivatives, which demonstrate appreciable fungicidal properties.
In addition, fluorovinyl compounds constitute valuable intermediaries which can serve as base products for various syntheses, especially for fluorine polymer synthesis.
Preparations proposed up to this time for fluorovinyl compounds are particularly long and thus are not economical.
To date, no fluoridation agent has been described as being suitable for HF addition with acetylenic compounds and thus leading solely to fluoro-olefins.
Indeed, known fluoridation agents such as hydrogen fluoride (HF) liquid, whose implementation, moreover, is especially delicate, as well as other reagents such as such as G. A. OLAH's reagent (pyridine, 10 HF) J. Org. Chem. (1979), 44 (22) 3872, whose reactivity is very similar to that of liquid HF, produces saturated fluorine derivatives coming from the bis-addition of HF.
It was also proposed by ZUPAN et al Journal of Fluorine Chemistry, 24 (1984) 291-302, to use HF carrying resins as fluoridation agents. Such resins are particularly difficult to use because their preparation requires the use of liquid HF and these resins, when applied to acetylenic compounds, do not produce fluorovinyl compounds.
As the result of work on hydrogenofluoride ions, it was noted that [F.sup.-,nHF] type ions with n.perspectiveto.2, which will henceforth be termed "dihydrogenotrifluoride" or "H.sub.2 F3.sup.- ", appear to be a good source of HF.
Studies conducted have indeed allowed it to be demonstrated that dihydrogenotrifluoride anions allowed the addition of HF with bi-activated or mono-activated triple bonds, thus producing mono-fluorine ethylenic compounds with good yields, and that they could also lead to nucleophilic substitution reactions.
Moreover, in a relatively surprising and unexpected manner, it was noted that, compared with certain known fluoridation agents, dihydrogenotrifluoride anions did not lead to HF addition in activated or non-activated ethylenic compounds.
This invention has the object, in the capacity of a new industrial product, a fluoridation agent, especially for acetylenic compounds, with said fluoridation agent corresponding to the following general formula:
Q+ represents either: (i) a cation having the formula: ##STR1## in which:
R1, R2, R3 and R4, identical or different, represent an alkyl radical having 1 to 20 carbon atoms, an aryl radical or an aralkyl radical, with the number of carbon atoms in R1+R2+R3+R4 being at least equal to 13 and preferably between 15 and 22,
or: (ii) a polymeric matrix carrying functions having the formula: ##STR2## in which:
R5, R6 and R7, identical or different, represent a lower alkyl radical having from 1 to 6 carbon atoms, and n is an average value between 1.5 and 2.5, preferably between 1.8 and 2.1.
As can be noted from the above formula, the number "n" of compounds having formula (I) is around 2, such that, for purposes of simplification, these compounds will henceforth be termed "dihydrogenotrifluorides".
"Dihydrogenotrifluorides" such as defined above present the advantage with respect to known agents of allowing HF addition with activated triple bonds and thus producing fluorovinyl compounds in a simple and economical manner.
This selectivity with respect to acetylenic bonds is completely remarkable and thus allows the production of different fluorovinyl compounds which, up to the present, could be obtained only at the price of especially long and low-yield syntheses.
Moreover, compared with known fluoridation agents, the agents in accordance with the invention are easily obtained, without resorting to the use of liquid hydrogen fluoride (HF), which is especially significant, taking account of
REFERENCES:
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Domijan et al., Inorganic Chem., vol. 8, #7, pp. 1534-1535, (1969).
Bensadat et al. (I), Chem. Abst., vol. 93, #238946h, (1980).
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Alieu et al., Chem. Abst., vol. 79, #91647m, (1973).
Domijan, Chem. Abst., vol. 75, #157602u, (1971).
Albert Patrice J.
Cousseau Jack
Reamer James H.
Universite d'Angers
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