DE852541C - Process for the production of ethers of alcohols of the allyl alcohol type with halogen-containing substituted carbinols - Google Patents

Description

Process for the preparation of ethers of alcohols of the allyl alcohol type with halogen-containing substituted carbinols The present invention relates relate to a process for carrying out a new reaction between hydrocarbon halides of the kind of all-, ilhalides and organic epoxy compounds by which valuable, new, unsaturated ethers of alcohols of the allyl alcohol type with halogen-containing substituted carbinols are obtained for the most diverse Applications are useful.

The hydrocarbon halides of the allyl halide type, which are reacted with organic epoxy compounds according to the invention, are the olefinic hydrocarbon halides in which a halogenator is bonded directly to a saturated carbon atom and is arranged opposite an olefinic C — C bond as in allyl chloride. These halides can also be referred to as fl, y-olefinic halides because they have an olefinic bond in the β, y-position to the halogen atom. In a more limited sense they can be defined as 2-alkenyl halides. Although the alkenyl group is generally an open-chain alkenyl group, it can also be a closed-chain alkenyl group, e.g. B. a cycloalkenyl group.

The hydrocarbon halides of the allyl halide type represent a class of reactive unsaturated compounds which undergo reactions which clearly distinguish them from the halogen-substituted hydrocarbons which do not have an arrangement of a halogen atom and an olefinic bond corresponding to the allyl halides. Unlike, for example, the saturated or aromatic hydrocarbon halides, the hydrocarbon halides of the type used herein can easily be polymerized to form high molecular weight polymers. They are further distinguished by their unique chemical properties from other hydrocarbon halides such as the alkyl halides, the aryl halides and the aralkyl halides, e.g. B. by their tendency to form dimeric condensation products. In many cases, they respond in a way that due to reactions of other hydrocarbon halides can not be foreseen.

As far as is known, the only attempt to react hydrocarbon halides of the allyl halide type with organic epoxy compounds, e.g. B. alkylene oxides and substituted Al.kylene oxides, previously carried out by Lopatkin (journal for practical chemistry, N.F. 30, 390 [18841). By reacting allyl iodide and epichlorohydrin in the presence of zinc at o #, he obtained an unsaturated alcohol according to one of the possible formulas CH, Cl - CH (OH) - CH2 - CH, - CH: CH2 and CH, CI - CH (CH.OH ) - CH, - CH: CH .. This product was only of laboratory or theoretical interest. It was not found to have properties which made it technically important.

It has now surprisingly been found that valuable products can be produced if a hydrocarbon halide of the allyl halide type is reacted in the liquid phase at about 100 to 350 ', preferably between 130 and 25o', with an organic epoxy compound. The products which are produced by this process differ from the alcohols which are produced by the above-mentioned known process and represent valuable unsaturated ethers in which a residue bound to the ether oxygen atom is the hydrocarbon residue of the hydrocarbon halide of the type of allyl halides and the other radical bonded to the ether oxygen atom is the halohydrocarbon radical of a halogen-substituted alcohol which contains at least one carbon atom bonded directly to the carbon atom of the carbinol group and has a halogen atom on a carbon atom which is bonded directly to the carbon atom of the carbinol group. If you z. B. heated allyl chloride with epichlorohydrin, the valuable a, y-dichloro-fl- (allyloxy) -propane is obtained in excellent yield, which, as will be explained in more detail below, can be used for the production of new and improved resins and many others offers important application possibilities. This reaction, which enables the production of useful and valuable, new organic compounds, proceeds essentially in the sense of the following equation: When methallyl chloride and epibromohydrin are allowed to react with one another by the process of the invention, they essentially combine according to the following equation with formation of the valuable a-chloro-y-bromo-fl- (methallyloxy) propane.

Another example of the implementation carried out according to the method of the invention is as follows: It is seen that in the illustrated implementation products, the ether bond of the halogen-substituted hydrocarbon residue is located on the ß-carbon atom, db there ether are generated which are derived from alcohols of the kind of the allyl alcohol and secondary or tertiary halogen-substituted alcohols. This was a surprising result of the process when one takes into account that various alcohols when reacted with epoxy compounds, which one Group contain, provide the ether of a primary alcohol , which is derived from the epoxy compound. It is also known that the reaction between even BeiizN, Iclilorid and propylene oxide, the chlorprop ## l, '# tlier is formed, and not the chloroisopropyl ether. 'Because according to the method according to the invention from Epox # A compounds which the group contain, eters of alcohols of the allyl alcohol type and secondary or tertiary halogen-substituted alcohols can be obtained, the invention provides an effective method of producing new and useful ethers, many of which have hitherto only been produced with much greater difficulty and cost as far as this was possible at all.

The process according to the invention can be used for the reaction of any hydrocarbon halide of the allyl halide type with any organic epoxy compound which contains a 1,2 or 1,3 epoxy ring to produce ethers of alcohols of the type of allyl alcohols and halogen-substituted alcohols. The reaction can be expressed by the following general equation: wherein X represents a halogen atom, preferably bromine or chlorine.

Examples of compounds which contain 1,2 and / or 1,3 epoxy rings and which can be reacted with hydrocarbon halides of the all # Ihalide type by heating in the liquid phase according to the present process are the alkylene oxides, such as ethylene oxide and propylene oxide , 1, 2-Epoxybutane, 2,3-Epox # .butane, Isobutvienoxyd, 1, 3-Epoxvbutan, Butadienmonox # -d, Butadiendioxyd, Styroloxyd, Cyclopentenoxyd, I, 3-Epoxycyclopentan, as well as substituted alkylene oxides including the epoxy ethers, like Glycidäther , Glycidyl ethyl ether, glycid #, iprop #, ether, fl-methylglycidyl isopropyl ether, glycidyl neofentyl ether and glycidyl naphthyl ether; Ni'troepox # -de, such as 3-nitro-i, 2-epoxypropane, 3-nitro-2-; ittl # '1-1,2-epoxvbutati, and nitrostyrene oxide; Epoxy esters, such as 2, 3-epoxypropionic acid methyl ester, glycidyl acetate; fl-meth # -lglvcidviisobutyrat and glycidylnaplitlieiiat; Furthermore, epoxy compounds containing sulfur, such as glycidyl ethyl thioether and a - #% ethylgl # .ci (1 # -Ic #, clolioxyltliioether. In the context of the invention it has also been found that hydrocarbon halides of the type of allyl halides can even be reacted with epoxy compounds by the new process which, in addition to the epoxy ring, contain a reactive group or a reactive atom, in particular with epoxy compounds with a reactive halogen atom, such as the epihalohydrins and - the substituted epihalohydrins, whereby, for example, valuable ethers are formed which differ from an alcohol of the type of allyl alcohol and a dihalosubstituted secondary and tertiary carbinol. Representatives from the group of epihalohydrins which can be used in this sense are, for example, epichlorohydrin, epibromohydrin, ß-methylepichlorohydrin, a, a'-dimethylepibromohydrin, ß- Methylepibromohydrin, fl-Ethylepibromohydrin, Cyclohexylepichlorohydrin, Phe nylepichlorohydrin and i-bromo-3, 4-epoxybutane. It is not always necessary that the halogen atom in the epihalohydrin is bonded to a carbon atom which in turn is bonded directly to a carbon atom of the epoxy group, because the hydrocarbon halides of the allyl halide type can also be successfully reacted with epihalohydrins in which the carbon atom is present to which the halogen atom is bonded is one or more carbon atoms removed from the epoxy group. In addition, the method is also not limited to epihalohydrins which contain 1,2-epoxy groups, since epihalohydrins with 1,3-epoxy groups can just as well be used.

A preferred sub-group of epoxy compounds, of the invention can be used which according consisting of epihalohydrins, in which the epoxy group, a 1 represents 2-epoxy group containing in the ring one - containing group 'and a halogensubstituiexte methylene group directly attached - CI-I, to the other carbon atom of the epoxy ring, like the compounds of the glycerol-epihalohydrin type. These preferably used epoxy compounds can be represented by the formula in which X is a halogen atom, i.e. H. Bromine or chlorine, and R is a hydrogen atom or a hydrocarbon group, such as alkyl (examples of these are: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, the pentyl groups, the hexyl groups), an aryl group (examples of these are are: phenyl, phenethyl, xylyl, tolyl, benzyl) or a cycloaliphatic group (examples are: cyclopentyl, cyclohexyl, methylcyclopentyl, ethylc # lclohex # 11). The reaction of the hydrocarbon halides of the allvihalide type with the GI \ -cerol-epihalohydrins in the process according to the present invention proceeds essentially according to the following scheme: It will be seen that the product so formed contains a greater number of halogen atoms than any of the reactants. It also contains the halogen atoms in the activated positions, which are characterized by being bonded to a carbon atom, which in turn is directly bonded to a secondary or tertiary carbon atom. The high yields of these products, with no significant further condensation of these products with any of the reactants or with themselves, were not only an unexpected result in the process according to the invention, but these results also prove the essential difference in reactivity (as far as possible the process according to the invention is concerned) between hydrocarbon halides in which the halogen atom is arranged opposite the olefinic bond as in the allyl halides, and hydrocarbon halides which have no halogen atom in such a position.

In the case of the allyl-type hydrocarbon halides, the saturated carbon atom to which the halogen atom is directly attached may be a primary, secondary or even a tertiary carbon atom, although in general the primary hydrocarbon halides of the allyl halide type, particularly the aliphatic, are preferred. The hydrocarbon halides used, of the allyl halide type, may contain more than one halogen atom. In this case, the additional halogen atom or the atoms in the allyl position can be relative to an olefinic bond. B. be arranged as in vinyl chloride. Examples of halides of the allyl type which can be used in the process according to the invention are the primary monohalides, such as allyl chloride, methallyl chloride, crotyl chloride, 2-ethy1-3-chloro-i-propene, 2-isopropyl-3-chloro-i-propene, 2-n-propyl-3-chloro-i-propene, i-chloro-2-pentene, i-chloro-3-methyl-2-pentene, i-chloro-2-ethyl-2-butene, i-chloro 2-butyl-2-butene, i-chloro-2-isobutyl-2-butene, i-chloro-2-pentyl-2-pentene, i-chloro-2-butyl-3-methyl-2-butene, i- Chloro-2-methyl-2-octene, 3-chloro-2-neopentyl-i-propene, 3-chloro-2-hexyl-i-propene, i-chloro-2-ethY1-3-methyl-2-butene, i-chloro-2-tetradecene, i-chloro-2-heXVI-2-pentene and the corresponding bromine compounds; aliphatic secondary monohalides, such as. B. 3-chloro-i-butene, 3-bromo-i-butene, 3-chloro-pentene, 3-bromo-i-pentene, 3-chloro-i-hexene, 4-chloro-2-hexene, 4- Chloro-5-methyl-2-liexen and 5-chloro-3-heptene. Further examples of usable hydrocarbyl halides of allyl 3-chlori-cyclohexene, 3-bromo-i-cyclohexene, I, 4-dichloro-2-butene, 1, 4-dibromo-2-pentene, cinnamyl chloride, cinnamyl bromide, 3-chloro- 2-phenyl-i-propene, 3-bromo-2-phenyl-i-propene, i-chloro-2, 4-pentadiene, allylidene chloride, 2-furyl-3-chloro-i-propene and 5-methyl-3- chlori-cyclohexene.

A preferred embodiment of the invention is limited to the use of aliphatic, primary monohalides of-methylene hydrocarbons, such as allyl chloride, allyl bromide, methallyl chloride, methallyl bromide, 3-chloro-2-ethyl-i-propene and 3-bromo-2-isopropyl-i-propene. This preferably used group, which contains a methylene group, CH, =, bonded directly to carbon atom No. 2 or in the β-position, is characterized on the one hand by the great reactivity of the olefinic bond and the tendency to polymerize, on the other hand by the desired properties of the resulting from the process according to the invention received products from. It can be represented by the formula in which X is a halogen atom, d. H. Bromine or chlorine, and R is a hydrogen atom or a monovalent aliphatic hydrocarbon group, e.g. B. an Alkvlgruppe represent.

The process according to the invention can be carried out by heating a mixture of the selected reactants to an elevated temperature. After the desired conversion has taken place to a substantial extent, the product formed is isolated from the resulting mixture. Since the reaction takes place in the liquid phase, the reaction mixture must be kept wholly or partly in the liquid phase during the reaction. The temperature used depends, to a limited extent, on the particular reactants used and also on other reaction bodies, e.g. B. the Z2it and the quantitative ratio of the reaction components. It has been found that if the temperature is too low, the desired reaction does not occur, while at excessively high temperatures, polymerization, decomposition and / or other undesirable side reactions are generally obtained and unsatisfactory yields of the desired product are obtained. The lowest, generally usable temperature is about 100 '; Temperatures of at least 130 'are preferred. While temperatures up to 350 ' can be used in some cases, the preferred temperatures are below 250' for the best yields of the desired products.

The allyl halide type hydrocarbon halides and the epoxy compounds can be used in approximately equimolecular proportions. A moderate excess of the epoxy compound in relation to the hydrocarbon halide of the allyl type has a beneficial effect on the reaction rate and, under otherwise identical conditions, favors higher conversions to the desired product. In general, molar ratios of olefinic halide to epoxy compounds of from about io : i to about i : io can be used; a preferred range is approximately between 2: 1 and i : 2. If desired, inert solvents can be added to the reaction mixture, e.g. B. if one of the reactants is gaseous or solid at the reaction temperature and it is appropriate to use this reaction component in the form of a solution and not by itself.

The reaction proceeds without the addition of catalysts, although higher Reaction rates can be achieved by keeping the process in attendance a suitable catalyst for the reaction. Because of the slope of the Organic compounds used in the process to polymerize must be the catalyst one that does not undergo excessive polymerization of the reactants and / or the reaction product brings about, but still the desired reaction favored. Small amounts of copper or copper compounds, especially cupro salts, increase the reaction rate significantly when using the reaction mixture be brought into contact without significantly promoting the formation of polymers. It can therefore, in comparison to working without a catalyst, under otherwise constant Higher conversions into the desired products can be achieved by using conditions the process is carried out in the presence of copper or a copper salt. Under The copper compounds that can be used include: the copper halides, including the bromides, chlorides and iodides, copper sulfate, copper nitrate, copper borate, azurite and cuprocarbonate and organic copper salts, e.g. B. copper acetate, naphthenate, benzoate, palmitate and salicylate, as well as complex compounds of copper, such as the cuprous chloride-tributyl phosphite complex compound. Cuprobromide is a special one effective and preferably used catalyst.

The catalyst can be added to the reaction mixture as such, or it can be carried by a solid support material such as diatomaceous earth, alumina, silicon carbide, carbon, sintered glass, etc., the reaction mixture being in intimate contact with the catalyst on the support during heating is brought. When a copper salt, e.g. B. a copper halide is used as a catalyst, an excess can advantageously be used so that solid catalyst is present during the reaction. You can work with catalyst amounts of about 0.05 to about 50 OM, preferably from about 0.5 to about 10, calculated on the weight of the reaction components.

The solid material has proven to be a particularly effective catalyst, which as a residue after carrying out the process in the presence of an excess of a solid copper salt remains. The first time you run the Method heat the reaction mixture in contact with metallic copper. Some of this copper reacts to form a solid residue. Or one can be a copper salt as such, e.g. B. a copper halide, use as a catalyst. At the end of the heating time, the remaining solid is allowed to settle; the liquid is separated for the purpose of obtaining the reaction product. If this solid residue is used as a catalyst in a subsequent operation, with freshness Adding reactants and heating as described above, this residue is Calculated to the same weight, more effective than a copper salt that was not previously has been used in the method according to the invention.

The method can be carried out in any appropriate facility known to those skilled in the art. Since the reaction mixtures have a corrosive effect on certain metals, the apparatus must be made of or lined with a corrosion-resistant material, such as glass, porcelain, nickel, gold, tantalum, molybdenum, iridium, palladium, chromium, platinum, cadmium or suitable alloys of these substances. Rubber or synthetic organic, chemical-resistant surface coatings can also be used. Certain ferrous building materials are less desirable. Thus it has been found that the presence of iron, in the pure state or in the various carbon steels, favors the formation of polymers and of tars which evidently arise from hydrocarbon halides of the allyl halide type; Surprisingly, iron also promotes the conversion of the epoxy compound, e.g. B. in the case of epichlorohydrin in glycerol dichlorohydrin. This undesirable effect of iron can be reduced or prevented by using alloyed nickel from about 5 percent by weight upwards, with or without other alloying elements. Accordingly, stainless steels, e.g. B. nickel-chromium steels, or iron-containing alloys with at least 50 / ' nickel' are advantageously used as building materials for the device which is used to carry out the method according to the invention.

'Can hear the Verfa be carried out in batches, batchwise or continuously. A suitable batch implementation is that a mixture of the reactants is prepared, which may be preheated, after which the catalyst, if such is used, is added and the mixture is then heated in a corrosion-resistant vessel which is provided with means for condensing, e.g. B. a reflux condenser, if the reaction components boil at or near the reaction temperature. Or you work in a closed autoclave when the reaction components boil at temperatures below the reaction temperatures. In the case of reaction components which are immiscible with one another and / or with the catalyst, it is desirable to move the reaction mixture during heating in order to bring about intimate contact between the reaction components or between the reaction components and the catalyst. The course of the reaction can be followed by withdrawing samples from the reaction mixture and analyzing them. In the case of continuous operations, preheated streams of the reaction components can optionally be mixed, whereupon the mixture is kept at the desired temperature for a suitable time. The catalyst, if one is used, can be either action components prior to mixing one of Re 'or both are added to the mixture, or the reaction components. According to another embodiment, the catalyst, e.g. B. a supported catalyst, be arranged in a reaction zone and the reaction mixture are brought into contact therewith.

The pressure on the reaction mixture can be at, above or below the Atmospheric pressure, but care must be taken that the mixture is liquid Phase is held. If pressures above atmospheric are used, can it does this automatically when the reaction mixture is heated in a closed vessel occurring, or they can be generated in addition, z. B. by application mechanical pressure or by the action of an inert gas (e.g. argon, nitrogen, Methane or Helitim) under pressure on the reaction mixture.

After the implementation has taken place to the desired extent, can recover the product from the reaction mixture by any suitable method will. The catalyst can when it is suspended as a solid in the mixture or has been dispersed by filtration, settling, centrifugation, or the like Treatments are removed. As stated above, it can be used with advantage in a further implementation of the procedure can be used. The product can be made from the Reaction mixture can be obtained by fractional distillation, treatment with selective solvents, crystallization or other suitable methods. The fractional Distillation is generally preferred. Unreacted hydrocarbon halides of the type of allyl halides and / or epoxy compounds can be recovered and wholly or partially fed back into the process. will.

The invention is illustrated in more detail by the following examples. Example i A mixture of 93 9 (IJ MOI) epichlorohydrin and 84 9 (1.1 mol) allyl chloride was introduced into a pressure-resistant cylindrical glass vessel with an inner diameter of about 3.8 cm and a length of about 25 cm, in which 5 g of copper foil (thickness 0.05 mm) were suspended. The jar was closed and its contents heated by immersion in a heated oil bath for from 180 to 185 minutes for 15 hours. The jar was then removed from the oil bath and cooled. The solid suspended in the liquid was allowed to settle. The copper foil had converted, and a non-metallic solid body remained, from which the liquid was poured off and then subjected to fractional distillation. The fraction distilling below 45 mm Ilg at 104 'was collected separately and turned out to be a, y-dichloro-fl- (allyloxy) -propane of the formula: With the following properties: refractive index (n 2o / D) 1.4672; Density (d 20/4) 1.166. Analysis: Found 41.8 % Cl, 42.4% C and 5.95 11/0 H; calculated on Co HIOO 02, 41.98 0 /, Cl, 405 0 /, C and 5.92 0 /, H. The conversion of the reaction components used to α, γ-dichloro-β- (allyloxy) propane was 62, 9 ojo, calculated on the epichlorohydrin, and 57.1 0 / -, calculated on the allyl chloride. The yield was 70.5 %, calculated on the epichlorohydrin consumed, and 0.010 / "# calculated on the allyl chloride consumed. Example 2 This example illustrates a cycle process in which a catalyst previously used to cause the reaction between an allyl type hydrocarbon halide and an epoxy compound is reused. The moist, solid residue or sludge which had remained in the glass vessel after decanting according to Example i above was used as the catalyst. A further 93 g of epichlorohydrin and 84 g of allyl chloride were added to this residue. The jar was closed and heated to 16o to 163 'for 15 hours. After cooling, the liquid part of the mixture was separated and distilled. There was a 420% conversion into α, γ-dichloro-fl- (allyloxy) propane, calculated on the epichlorohydrin used.

Since the temperature in this experiment was not comparable to the temperature used in example i, a further experiment was carried out according to the procedure of example i, but at a temperature of 165 to 172 '. The α, γ-dichloro-β- (allyloxy) propane was obtained in a yield of 27 %, calculated on the epichlorohydrin used. This shows the strong superiority of that used in the first experiment in this example (paragraph i) Example 3 In a glass-lined autoclave, 552 9 (5.97 moles) of epichlorohydrin and 502 9 (6.56 moles) of allyl chloride were mixed in. A piece of copper foil (thickness 0.05 mm, size 212 cm2) was added. The autoclave was closed and heated to 147 to 166 'for 66 hours. In the fractional distillation of the resulting mixture, α, γ-dichloro-β- (allyloxy) propane was calculated in a yield of 700 / " and 63.60 /", respectively on the epichlorohydrin or allyl chloride used, and in a yield of 77.5 0 /, or 82.6 ", 1. ' calculated on the consumed epichlorohydrin or allyl chloride, obtained, Example 4 0.3, d-2r copper compound of the diacetoacetic ester was added to a mixture of 93 g epichlorohydrin and 84 g allvI chloride in the vessel used in Example 1. The mixture was added for 15 hours heated to 165 to 169 # and then fractionally distilled, a, y-dichloro-β- (allyloxv) -propane being obtained in the following yields: Conversion: Yield: l ", on ver 0,". on turnedReact.- needed React.- Component component AllvIchloride ....... 22.5 go Epichlorti # -drin .... 24.8 65.7 Example 5 In the absence of added catalyst 111 in a glass-lined autoclave, the reaction of allvIchloride and epichlorohydrin, which were present in the molar ratio ij : i, for 15 hours at 164 to 170'a, y-dichloro-β- (allyloxy) propane in a conversion of 6.4 or 5.80 / " calculated on the epichlorohydrin or allyl chloride used. As in the previous examples, the formation of polymers was insignificant.

Example 6 A mixture of 103 9 epichlorohydrin, 97 g of allyl chloride and 28 - cuprous chloride was heated in a nickel autoclave to 162 to 166 'for 25 hours. The autoclave was then cooled, the contents drawn off and the liquid distilled after the catalyst had been separated off. The conversion of the allyl chloride or epichlorohydrin used to a, y-dichloro-fl- (all # lloxy) -propane resulted in 47.5) /, and 54.40 / ,.

EXAMPLE 7 A mixture of 279 g epichlorohydrin, 252 g allyl chloride and 6 g cuprous chloride was heated to 148-154 ° with agitation for 18 1/2 hours in a stainless steel autoclave equipped with a powerful stirrer. During this time, the pressure that was originally created automatically fell from 9.1 at to a final value of 2.8 at. The a, y-dichloro-ß- (allyloxy) propane was obtained in the following yield: Conversion: Yield: 0.0 to ver 0. , on ver used React needed React.- Component components Allyl chloride ....... 53.8 86.7 Epichlorohydrin .... 59.2 87.1 The fact that it is desirable to bring about intimate contact between the solid catalyst and the liquid reaction mixture results from the fact that if the above-described experiment is repeated without stirring the reaction mixture during the heating period, the conversion into a, y-dichloro-fl- (allyloxy) -propane about 8 0 / "calculated on the used epichlorohydrin was. from this result, it can be concluded that the mechanism of the catalysis is heterogeneous catalysis, in the main, not a homogeneous catalyzed by dissolved copper compounds in the liquid mixture.

Example 8 In a glass reaction vessel similar to that used in Example I, 64 9 (IJ MOI) of propylene oxide, 92 g (1.2 mol) Allylcblorid and 2 g of cuprous chloride were mixed. The mixture was heated to 165-169 'in the closed jar for 15 hours. The cooled liquid was then poured off from the remaining solids in the vessel and fractionally distilled. The product, which was found to have a boiling point of 64 to 65 ' at 50 mm Hg, was identified as an allyl (i-chloro-2-propyl) ether with the formula The product was obtained with a conversion percentage of 710 / "calculated on the propylene oxide used, and 660 /" calculated on the allvIchloride used.

Example 9 By heating a mixture of gi g (0.8 mol) of allyl chloride, 68 g (0.89 mol) of glycidyl allyl ether and 2 g of cuprous chloride for 15 hours in a closed glass vessel, to 165 'and fractional distillation of the resulting mixture was with a Yield of 870 / "calculated on the allyl chloride consumed, and with a conversion of 65 ° /" calculated on the glycidyl allyl ether used, the diallyl ether obtained from glycerol-a-monochlorohydrin. It distills under a pressure of 50 mm Hg from 126.5 to 128.5 ' and has a refractive index (n 2o / D) of 1.4570 and a specific gravity (d 20/4) of 1.0357.

Example 10 This example illustrates the reaction of a hydrocarbon halide of the allyl halide type, which contains 2 halogen atoms, one of which is arranged opposite the olefinic bond as in the allyl halides and the other as in the vinyl halides, with an epoxy compound. That used in Example I in a glass vessel, similarly, III G (i, o mol) were I, 3-dichloropropane, mixed 839 (0,9M01) of epichlorohydrin and 2 g of cuprous chloride. By heating the mixture for 15 hours in a closed vessel to 165 to 170 'and fractional distillation of the resulting liquid mixture, a, y-dichloro-(, y'-chlorallyloxy) -propane with a conversion of 110 /., Calculated on the ET used) ichlorhvdrin 27.5 0 "used calculated on 1, 3-dichloropropene, receive, and /. The thus prepared a, y * dichloro-fl- (y'-chloroallyloxy) propane distilled under 2o mm Hg at 125 to 127 ' . It has a refractive index (n 2o / D) determined by 1.4930 and a specific gravity (d 20/4) of 1.3048 In the analysis were obtained for the product. 51.9 '/ o Cl, 4 5 0 /, H and 35.2 0 /, C, versus 5 2.3 0 /, Cl, 4.4 0 /, H and 35.4 0 /, C, calculated on the formula Example ii When methallyl chloride and epichlorohydrin were heated according to the procedure explained in the preceding examples in the presence of cuprous chloride for 15 hours to 165 to Uo ', methallyl (a, y-dichloro-fl-propyl) ether was formed, which under pressure boils from So mm Hg at 116 to 117 '. Upon analysis, this product was found to contain 38.0% Cl, 6.67% H and 46.9% C , versus 38.8% Cl, 6.55% H and 45.9 0 /, C, calculated on the formula The process according to the present invention enables the reaction for the first time by bringing together hydrocarbon halides of the allyl type, which contain a reactive olefinic bond, with organic epoxy compounds which contain an activated and labile halogen atom which is attached to a carbon atom which is directly connected to a carbon atom of the epoxy ring is bonded without a change in said olefinic bond occurring and without said labile halogen atom being influenced. Many of the compounds obtained are new. Of particular interest are the ethers of fl, y-olefinic alcohols and bis (halomethyl) carbinols, which are represented by the formula can be shown in which R-0- is the optionally halogen-substituted oxy radical of a fl, y-olefinic alcohol (examples of such fl, yolefinic alcohols are allyl, methallyl, 2-ethyl-2-propenyl, crotyl, cinnamyl , 2-cyclohexenyl, 4-chloro-2-butenyl, 3-chloro-2-octenyl, 3-chloroallyl, 3-bromoallyl, 3-chloro-z-methylallyl, 2-pentenyl, tert. -Pentenyl-2-phenyl-2-propenyl-, and 2-EthY1-3-methyl-2-butenyl alcohol). R 'is a hydrogen atom or a hydrocarbon group, such as an alkyl, aryl or cycloalkyl group, and X represents bromine or chlorine, it being possible for the halogen atoms in the CH2X groups to be identical or different. A subgroup of the above-mentioned ethers includes the ethers of the aliphatic ß-methylene alcohols with aliphatic bis (halomethyl) carbinulums, which are represented by the last-mentioned formula when R is an aliphatic ß-methylene hydrocarbon group in the sense explained above (see p. 4, third Paragraph), R 'is a hydrogen atom or an alkyl group and X is bromine or chlorine, preferably chlorine.

When the allyl-type hydrocarbon halide contains two or more halogen atoms, novel and useful ethers of halogen-substituted allyl-type alcohols with bis- (halomethyl) -substituted carbinols can be obtained by the process of the present invention. A valuable subgroup of these substances can be represented by the formula in which R2 represents a 3-halo-2-alkenyl group (examples are 3-chloroallyl, 3-chloro-2-isopropylallyl, 3-bromo-i-dodecylallyl, 3-chloro-2-butenyl, 3-chloro-i- propyl-2-hexenyl and 3-BroM-2-iS0-propyl-2-butenyl) and X is chlorine or bromine.

Of particular interest and value, not only because of the availability of the starting materials, but also because of their excellent and desirable properties, are the ethers composed of primary aliphatic β-methylene alcohols and aliphatic bis (halomethyl) carbinols, which can be represented by the formula In this formula, R is a hydrogen atom or an alkyl group; X is chlorine or bromine, preferably chlorine. Rx is the hydrocarbon group of a primary, aliphatic alcohol substituted in the β-position by a methylene group. A subgroup of these ethers includes those compounds which are represented by the above formula when the radical Rx represents the hydrocarbon group of an allyl alcohol or the 2-propenyl group. This subgroup includes the allyl ethers of bis (halomethyl) -substituted carbinols, such as: a, y-dichloro-β- (allyloxy) -propane, a ,, y-dibromo-β- (allyloxy) -propane, a, y-dichloro fl-ethyl-ß- (allvlox #,) - propane, a, y-dibromoß-methyl-fl- (allyloxy) -propane, a, y-dichloro-fl-propyl-fl- (allyloxy) -propane, a- Chlor-y-bromo-ß-butyl-fl- (allyloxy) -propane, a, y-dichloro-ß-neopentyl-ß- (allyloxy) -propane, a, y-dibromo-ß-hexyl-ß- (allyloxy ) -propane, a "y-dichloro-fl-isooctvi-fl- (allyloxy) -propane, a, y-dichloroß-decyl-fl- (allyloxy) -propane. Another subgroup of compounds that offer particular interest because of the The clear, branched-chain structure of the hydrocarbon radical which is bonded directly to the ether oxygen atom includes those ethers which are represented by the last-mentioned structural formula when Rx is the hydrocarbon group of a primary, aliphatic alcohol which is substituted in the β-position by a methylene group and which is a tertiary olefinic alcohol Carbon atom in has the fl position. These ethers can be represented by the formula Herein, R represents the hydrogen atom or an alkyl group, X represents chlorine or bromine and Rc represents an alkyl group which can contain from 1 to 10 carbon atoms. The following are mentioned as examples of compounds from this preferred subgroup: a, y-dichloro-β- (methallvloxy) -propane, a, y-dibroi-n-β- (methallyloxy) -propane, fl-methyl-a, y -dichlor-ß- (methallyloxy) -propane, a, Z-dichloro-ß- (ß'-ätliyl-ß ', y'-propenyloxy) -propane, ß-butyl-a, y-dichloro-ß- (ß '-äthvl-ß', y'-propenyloxN7) -propane, ß-pentyl-a-chloro-, y-bromo-fl- (methallyloxy) -propane, fl-octyl-a, y-dichloro-ß- (ß '-butyl-ß', y'-propene #, loxy) -propane, ß-decyl-a, y-dichloro-fl- (ß'-neopent #, # l-ß ', y'-propenyloxy) -propane , ß-tert-butyl-a, y-dibromo-ß- (ß'-octyl-ß ', y'-propenyloxy) -propane, ß- (a', y'-dimethylbut% 11) -a, y -dichlor-fl- (methallvioxy) -propane.

The presence of two halomethyl groups (in which each halogen bonded to a primary carbon atom) attached to the carbon atom, that is bonded directly to the ether oxygen atom confers those discussed above Compounds desirable properties. These properties are in ethers of halogen-substituted carbinols in which only one halogen atom is present, or in which, in the presence of two halogen atoms, one is attached to a primary carbon atom and another is bonded to a secondary or tertiary carbon atom, does not ascertain. The presence of the fl, V-olefinic bond in the ether oxygen Bound hydrocarbon residue also gives the new compounds unique properties Properties. These properties are found in ethers of halogen-substituted carbinols, by substitution of the hydrogen atom of the carbinols mentioned For example, an alkyl group, an aryl group or a Cvcloalk-ylgruppe formed cannot be ascertained.

The compounds obtainable by the process according to the invention represent valuable, versatile intermediate products. For example, the halogen atoms replaced by hydroxyl, e.g. B. by hydrolysis; so can valuable monoethers trihydric alcohols with allyl type alcohols e.g. B, ether of glycerine will. Thus obtained fl-ethers of glycerol of the allyl type can be used for the production improved alkyd resins can be used. Such glycerine ethers can also be used Can be polymerized exposure to oxygen at elevated temperature. Or you can be reacted with monobasic carboxylic acids for the purpose of obtaining more valuable ones polymerizable ester. Products obtainable by the process of the invention can also be used as biologically active compounds and as preliminary products for such products.

The ethers of #, y-olefinic alcohols with bis (halomethyl) carbinols, especially the ethers of aliphatic primary 2-methylene alcohols and saturated aliphatic bis- (chloromethyl) -substituted carbinols, which are produced according to the new process available have proven to be valuable for making new and useful sulfur-containing high molecular weight products. Such ethers in particular the allyl or methallyl ethers of bis (chloromethyl) carbinol or a hornologic ether, which is preferably a 2-alkyl-2-propenyl group directly contains bound to the ether oxygen atom, z. B. in an aqueous or an alcoholic medium with water-soluble sulfides and polysulfides, such as sulfides and polesulfides of alkali metals, ammonium and alkaline earth metals will. One can only use one or a majority of the unsaturated halogenated ethers condense with the alkaline polysulfides. In addition, co-condensation products are produced by the joint condensation of one or more of the above unsaturated ether and one or more halogen-substituted compounds, which are known to form with alkaline polysulfides condense high molecular weight sulphurous products.

The sulfur-containing products, which are derived from the ethers of fl, y-olefinic Alcohols and bis (halometh ## 1) carbinols that can be produced are waxy to rubber-like to hard materials and can, for. B. as Cb.2rzugmaterial for Surfaces, for electrical insulation, for the production of corrosion-resistant pipes and used as additives for synthetic rubbers or resins.

Claims (2)

PATENT CLAIMS: i. Process for the preparation of ethers of alcohols of the allyl alcohol type with halogen-containing substituted carbinols, characterized in that a hydrocarbon halide of the allyl halide type is reacted in the liquid phase at about 100 to 35o ', preferably between 130 and 250c, with an organic epoxy compound . 2. The method according to claim i, characterized in that the reaction in the presence of copper or a copper compound, preferably a cuprous halide, is carried out as a catalyst. 3, method according to claim i or 2, characterized in that the reaction components are heated in contact with an excess of a solid copper compound, whereupon the liquid mixture containing the desired ether is separated from the excess of the copper compound and this is used as a catalyst for converting new proportions of the reactants into the desired ether is used. 4. The method according to claim i to 3, characterized in that the olefinic halide and the epoxy compound are used in molar ratios of about io : i to i : io, preferably from 2: 1 to I : 2. 5. The method according to claim i to 4, characterized in that, in the case of the production of an ether from a preferably aliphatic bis (halomethyl) carbinol with a preferably aliphatic, advantageously primary, substituted in ß-position by a methylene group A fl, γ-olefin alcohol, the hydrocarbon halide of the allyl halide type, is reacted with a glycerine pihalohydrin. 6. The method according to claim i to 5, characterized in that in the case of the preparation of an ether of a bis (halomethyl) carbinol with a halogen-substituted A fl, y-olefin alcohol, a hydrocarbon halide of the allyl halide type which contains two or more halogen atoms , is reacted with a glycerine pihalogen, hydrin.