Process for the production of cycloalkanecarboxylic acids

Details Process for the production of cycloalkanecarboxylic acids Process for the production of cycloalkanecarboxylic acids

1987-05-26

1989-03-28

Shippen, Michael L.

Organic compounds -- part of the class 532-570 series

Organic compounds

Carboxylic acids and salts thereof

562400, C07C 5100

Patent

active

048166022

DESCRIPTION:

BRIEF SUMMARY
As is known, the cycloalkanecarboxylic acids of general Formula I are valuable intermediate products used, inter alia, for the manufacture of sweeteners (European patent application No. 01 28 654). The production of these compounds according to the known state of the art, however, is very expensive. Compounds of formula I have the general formula ##STR2## wherein n means the number 1 or 2, atoms.
The process of this invention makes it possible to synthesize these compounds by a substantially simpler route.
The starting compounds for the process of this invention can contain as the alkyl groups R.sub.1 through R.sub.4, for example, methyl groups, ethyl groups, propyl groups, isopropyl groups, or butyl groups. Based on the commercial exploitability of the products of the process, those starting compounds are preferred wherein the substituents R.sub.1 through R.sub.4 are identical. Especially preferred starting compounds are those carrying methyl groups as substituents R.sub.1 through R.sub.4. The starting compounds can carry identical or differing groups as the substituents X and X'. These groups can be polar substituents which can be split off with the formation of carbenium ions. Such substituents are preferably chlorine atoms, bromine atoms, alkylsulfonyloxy groups (such as the methanesulfonyloxy group or the trifluoromethanesulfonyloxy group), or arylsulfonyloxy groups (such as the benzenesulfonyloxy group, the p-bromobenzenesulfonyloxy group, or the p-toluenesulfonyloxy group). These starting compounds can be prepared in a simple way from the corresponding diols by esterification or by exchange of the hydroxy groups for chlorine or bromine. Preferred starting compounds are those carrying as substituents X and X' methanesulfonyloxy groups or, in particular, chlorine atoms or bromine atoms.
In the first stage of the process of this invention, the compounds of general Formula II are reacted under conditions known per se with 1,1-dichloroethylene (see, for example: Angew. Chemie 78: 932 [1966] and 91: 169 [1980]; Tetrahedron Letters 1968, 4979 and 1973, 1569; Chem. Ber. 100: 978 [1967], 103: 3851 [1970] and 106: 2513 [1973]; J. Chem. Soc. Perk. Ed. I, 1973, 2559; Acta Chem. Scand. 34b: 621 [1980]; and Synth. Comm. 14: 113 [1984]; J. Amer. Chem. Soc. 67: 1152 [1945], 68: 1650 [1946], 46: 1655 [1946], and 71: 698 [1949]; as well as J. Org. Chem. 48: 1159 [1983]). Compounds of formula II have the general formula --X'(II), alkylsulfonyloxy group, or an arylsulfonyloxy group. Thus, the compounds of Formula II can be reacted in 1,1-dichloroethylene as the solvent with the addition of strong Lewis acids (such as, for example, iron(III) chloride, iron(III) bromide, tin(IV) chloride, tin(IV) bromide, zirconium(IV) chloride, boron trichloride, boron trifluoride, zinc(II) chloride, gallium(III) chloride or, in particular, aluminum(III) chloride) at a reaction temperature of -50.degree. to +100.degree. C., thus obtaining the compounds of Formula III. Compounds of formula III have the general formula --CH.sub.2 --CCl.sub.2 X' (III), given above. On the other hand, however, it is also possible to perform this reaction step with the use of other solvents inert under the reaction conditions (for example chlorinated hydrocarbons.
Hydrogen chloride or, if applicable, also HX is split off from the thus-prepared compounds of general Formula III in a second reaction step which can be performed under the conditions likewise described in the above-mentioned publications. For the splitting-off step, aqueous bases, such as sodium hydroxide solution or potassium hydroxide solution, are utilized for economical reasons. It is frequently suitable, for increasing the reaction velocity, to add also phase transfer catalysts (such as, for example, "Aliquat") to the reaction mixture. This reaction step is advantageously conducted at a reaction temperature of 20.degree. to 100.degree. C.
Hydrogen chloride and, if applicable, also HX' can be split off, depending on the type of substituent X and on the reaction conditions, as early as during t

REFERENCES:
patent: 3450782 (1969-06-01), Connor

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