WHEREIN X is a halogen atom, R1, R2, R3 and R4 are a hydrogen atom, a hydrocarbon group or a halogenated hydrocarbon group, R1 may be a group having the formula
WHEREIN R is an aliphatic, alicyclic or aromatic radical, and R3 and R4 may be a group consisting of -CH2OH or its esters; is produced by reacting an organic halide (2) having the formula:
D R A W I N G
wherein R is an aliphatic, alicyclic or aromatic hydrocarbon radical, preferably an alkyl radical of one to six carbon atoms, phenyl radical or benzyl radical, and X is a halogen atom, preferably chlorine or bromine. Representative examples of the compound represented by the formula (3), which may be used as the other starting material of the present invention, include 2-alkyl-1-alkene such as isobutene, 2-methyl-1-butene, 2-methyl-1-pentene, 2-methyl-1hexene, 2-methyl-1-heptene, 2-ethyl-1-butene, 2-ethyl-1-pentene, 2-ethyl-1-hexene, 2-ethyl-1-heptene or 2-n-propyl-1-pentene; 2.6dimethyl-1-heptene, 2.6-dimethyl-1.5-heptadiene, 2-ethyl-6methyl-1.5-heptadiene. Other examples are the compounds whose R3 or R4 is -CH2OH group, such as isopropenyl ethyl alcohol, and the ester thereof. It is preferable to use the esters of isopropenyl alcohol instead of isopropenyl alcohol itself in the practice of the invention, since cationic catalysts are used in the present invention. The ''''cationic catalyst'''' used in the invention means a material, such as Lewis acids, which can accelerate a cationic polymerization. Examples of the cationic catalysts are: (1) such metal halides as AlCl3, FeCl3, SnCl4, SbCl5, TiCl4, TeCl2, TeCl4, BiCl3 and ZnCl2 which are commonly known as Friedel-Crafts catalysts, (2) complexes of the foregoing metal halides and electron donors, (3) boron halides and complexes of said boron halides and electron donors, (4) quarternary ammonium salts, (5) organic electron acceptors such as tetracyanoethylene, and (6) charge-transfer complexes of organic electron acceptors and electron donors. These catalysts can be used singly or in combination of at least two species. Particularly suitable cationic catalysts are aluminum chloride, ferric chloride, stannic chloride and zinc chloride. The amount of the catalyst to be used in the reaction may be varied within the range where the telomerization reaction can proceed without being inhibited by the impurities being present in the telomerization reaction system. It is generally effective on the reaction to use the catalyst in amounts of at least 0.001 mole, preferably 0.005 to 0.1 mole per mole of the organic halide (2). In cases where the reaction is carried out in a solvent medium, the solvent should be a material which can neither deactivate the catalyst nor readily undergo a Friedel-Crafts reaction with the halide. For example, pyridine, thiophene and the like which have a high basicity can not be used as the solvent. On the other hand, by adding to the reaction system a suitable amount of ethyl alcohol, diethyl ether or the like whose basicity is not so strong it is possible to lower the activity of the catalyst and control the progress of the reaction. The materials which can be generally used as the solvent in the reaction are, for example, acyclic ethers such as diethyl ether and diisopropyl ether, cyclic ethers such as dioxane and tetrahydrofuran, halogenated hydrocarbons such as 1.2-dichloroethane and dichloromethane, and such aromatic compounds as benzene which is relatively free from a Friedel-Crafts reaction. The temperature for the telomerization reaction may be lower than the ceiling temperature for polymerization of isobutene. The preferred reaction temperature ranges from -78* to 80* C. especially from 0* to 60* C. This reaction is considerably exothermic, and therefore it is necessary to cool the reaction system itself and/or carrying out the reaction in a reactor equipped with a reflux condenser or an autoclave in which the reaction system can be sealed, so as to prevent the volatilization of the reaction system. In a preferred embodiment of the invention, the reaction is carried out using an ether having a low boiling point as the solvent and a reactor equipped with a reflux condenser, whereby excessive elevation of the temperature of the reaction system and consequent increase of side reactions as well as the volatilization of the reaction system can be easily prevented.
WHEREIN X, R1, R2, R3 and R4 represent the same as above. This reaction can be carried out in the presence of a cationic catalyst, such as Lewis acids, and in the presence or absence of a solvent under normal or increased pressure, by bringing the organic halide (2) into contact with the excess aMount of the olefin (3). In the description of Zhurnal Organicheskoj Khimii 1 2105-2114 (1965), it has been proposed that the molar ratio of olefin to organic halide should be regulated in the range of 1 : 1 or below 1 : 1 to obtain the additive products consisting of 1 mol of the telogen and 1 mol of the taxogen, and there 2.6-dimethyl-2heptenyl-6-halide is obtained from 3-methyl-2-butenyl-1-halide as the organic halide and isobutene as the olefin by the telomerization reaction. But in this case, the yield of said additive product is only in the range of 12.5 to 14.0 per cent based on the weight of used 3-methyl-2-butenyl-1-halide in spite of the degree of the reaction, i.e., the degree of the telomerization, is up to 80 to 86 per cent. And it is also known that the yield of the additive product from 1 mol of telogen and 1 mol of taxogen is decreased, and the poly additives such as dimers or trimers are increased, when the molar ratio of olefin to organic halides regulated in the range of more than 1.0; that is, heretofore the molar excess of olefin to that of organic halide has been used in the telomerization reaction system. Therefore, many prior art workers have attempted to carry out the telomerization reaction under the condition of molar excess of organic halide. But, contrary to the mode of the known process, it is found that the yield of the additive product from 1 mol of the organic halide (2) as the telogen, and 1 mol of the olefin (3) as the taxogen is remarkably increased under the conditions of reacting the telogen in the presence of the molar excess of the taxogen and regulating the temperature of said reaction in the range of about -78* C to about 80* C., preferably 0* to 60* c. The following processes may be applicable to the practice of the present invention. One of the processes comprises mixing the solution consisting of the organic halide (2) and a molar excess of olefin (3) with the cationic catalyst and starting the telomerization reaction. Another process comprises mixing the organic halide (2) dropwise into the solution consisting of olefin (3) and the cationic catalyst and starting the telomerization reaction. In the practice of the present invention, the latter process is the most preferable since the organic halide (2) is more unstable in the reaction system and the desired product can be obtained more effectively by the latter process. In the organic halide (1) represented by the general formula described above, 2.6-dimethyl-2-heptenyl-6-halide; which is the reaction product of 3-methyl-2-butenyl-1-halide and isobutene, wherein said R1, R2, R3 and R4 radicals in the above described general formula are hydrogen atoms; is the known product as described in Zhur. Org. Khim., 1 2105-2114 (1965), but other products are novel products which are not described in the prior art. Representative examples of the organic halide (2) used as one of the starting materials in the present invention include: a. Organic halides, whose said R1 and R2 are a hydrogen atom, hydrocarbon groups, preferably, alkyl groups or alkenyl groups having the carbon numbers of from one to six, halogenized hydrocarbon groups, preferably halogenated alkyl groups or halogenated alkenyl groups having the carbon numbers of from one to six; such as 3-methyl-2-butenyl-1-halide, 3-methyl-2-pentenyl1-halide, 3-methyl-2-hexyenyl-1-halide, 3-methyl-2-heptenyl-1halide, 3.7-dimethyl-2-octenyl-1-halide, 3,7-dimethyl-2-nonenyl1-halide, 2.3-dimethyl-2-butEnyl-1-halide or 3-methyl-2-pentenyl1.5-dihalide, and b. Organic halides whose said R is a ester group, such as 5halo-3-methyl-3-pentenyl carboxylate having the following formula:
WHEREIN R3 and R4 represent a hydrogen atom, a hydrocarbyl group, a halogenated hydrocarbon group or a group consisting of CH2OH or its esters, which is abridged hereinafter as ''''olefin (3);'''' in the presence of a cationic catalyst, such as Lewis acids. The reaction according to the present invention is a telomerization reaction in which the organic halide (2), such as 5-halo-3-methyl-3-pentenyl carboxylate serves as the telogen and olefin (3) such as isobutene as the taxogen. This reaction can be expressed by the following equation:
WHEREIN R is an aliphatic, alicyclic or aromatic group; which is abridged hereinafter as ''''organic halide (2),'''' with the compound having the formula:
WHEREIN X, R1 and R2 are the same as above, and R1 may be a group having the formula
WHEREIN R is an aliphatic, alicyclic or aromatic group, and R3 and R4 may be a group -CH2OH or its esters; which is abridged hereinafter as ''''organic halide (1),'''' and a method of producing the same. The organic halides (1) provided according to the present invention are industrially useful, for example, as intermediates for preparation of perfume materials, medicinal materials and the like, especially intermediates for the synthesis of terpenes. The inventors have now found that an organic halide (1) can be easily obtained with a low cost by reacting an organic halide having the following formula:
WHEREIN X, R1 and R2 is the same as above, respectively; with the compound having the formula:
WHEREIN R3 and R4 is the same as above, respectively, in the presence of a cationic catalyst at a temperature of from -78* to 80* C. This invention relates to a novel product which is industrially useful and a method of preparing the same, and more particularly to the organic halides having the following generic formula:
D R A W I N G
WHEREIN X is a halogen atom, such as chlorine or bromine, R1, R2, R3 and R4 represent a hydrogen atom, a hydrocarbon group or a halogenated hydrocarbon group, R1 may be a group having the formula
