Патент USA US3093699код для вставки
ice United States atent 1 W 3,093,689’ Patented June 11, 1963, 2 is apparently responsible for the different type of product 3,093,689 HYDROXY HALOGENATED ETHER ‘ _ PRODUCTION Kenneth B. Cofer, Pasadena, and Robert W. Fourie, Houston, Tex., assignors to Shell Oil Company,‘ New York, N.Y., a corporation of Delaware N0 Drawing. Filed July 8, 1960, Ser. No. 41,475 6 Claims. (Cl. 260-613) which is produced in high yield. These are halo-substi tuted hydroxy ethers of predetermined composition which are not only useful as solvents and as plasticizers for resins but also advantageous intermediates for the produc tion of other desirable compounds, particularly epoxy ethers which are starting materials ‘for resins and other products. ' ,Any of the numerous ethylenic alcohols can be used in This invention relates to the production of halo-substi 10 the new process. One especially preferred subgroup of tuted hydroxy ethers and especially to the manufacture of starting alcohols are the water soluble beta,gamma-mono these compounds from unsaturated alcohols. ethylenic monohydric alcohols having three to ?ve carbon There are several routes whereby halo-substituted hy atoms per molecule. Typical examples of alkenols of this droxy ethers can be made'using conventional chemical kind are, allyl alcohol, methallyl alcohol, crotyl alcohol, operations. For instance, an ether can be halogenated to 15 methyl vinyl carbinol, dimethyl vinyl carbinol, 3-methyl-2 introduce a plurality of halogen atoms per molecule and buten-l-ol, methyl isopropenyl carbinol, and the like. a part of these halogen atoms can be hydrolyzed to hy Examples of other suitable starting ethylenic alcohols are, droxy groups by reacting with sodium hydroxide or the for instance, S-buten-l-ol; 3-pen-ten-l-ol; 3-methyl-3 like. Alternatively a polyhydroxy ether can be reacted butene-l-ol; Z-methyl-B-butene-l-ol; methyl allyl carbinol; producing mixed products since there is no way of con 4-methyl-4-penten-l-ol; 2,3-dimethyl crotyl alcohol; ethyl allyl carbinol; 1-heptene-4-ol; methyl ethyl allyl carbinol; dimethyl allyl carbinol; 2,4-dimethyl-lshepten-4-ol; 1 decen-4-ol; 3,7-dimethy1-2-octen-1-01; IO-undecen-l-ol; 11 trolling which of the halogens and hydroxyl groups will be dodecen-l-ol; oleyl alcohol, etc. Instead of the foregoing with dry hydrogen halide or with phosphorous pentahalide to partly replace the hydroxyl groups by halogen. Besides low yields, these methods have the disadvantage of usually converted in the different operations. On this account it 25 open chain aliphatic hydrocarbon alcohols, cyclo aliphatic hydrocarbon alcohols such as 2-cyclohexenol; 3-cyclo is customary to rely upon reaction of an epihalohydrin hexenol; 2 - ethylidene - 1 - cyclohexanol; 3-cyclohexenyl with an alcohol for production of halogenated hydroxy ethers. The limited availability of low cost epihalohydrins methanol, and the like can be used. Another subgroup of suitable starting ethylenic alcohols are the aryl-substi seriously restricts the usefulness of this method and makes tuted ethylenic alcohols and the alkenyl-substituted aro it prohibitively expensive in most cases where the starting matic alcohols of which the following are representative epihalohydrin must be especially synthesized for the reac tion. \ An important object of the invention is the provision of examples, alpha-vinyl-benzyl alcohol; l_-phenyl-3-buten-2 o1; 2-phenyl-4-penten~2-ol; para-vinyldbenzyl alcohol and 3-phenyl-3-pcnten-2-o1. a new and economically attractive method for the produc tion of hydroxy halogenated ethers from unsaturated alco 35 Starting alcohols which contain more than one hydroxyl group and/ or more than one ethylenic double bond in the hols. Another object is the direct production in a single step, of halogenated hydroxy ethers from ethylenic alco molecule can be used in the new process although halo substituted hydroxy ether mixtures of greater complexity hols. Still another object is to provide a new process whereby halo-substituted hydroxy ethers of predetermined will be obtained. Polyhydric ethylenic alcohols which ?xed composition can be efficiently produced. A special 40 can be employed ‘are, for instance, 2~butene-l,4-diol;nl object is the production of halogen-substituted hydroxy butene - 3,4 - diol; Z-ethyl-l~phenyl-3-butene-1,2-diol; 5 ethers which can be either symmetrical or unsymmetrical vinyl-1,3-dimethanol benzene; 1,4-dihydroxycyclohexene ethers depending upon the choice of the starting alcohol (reactants. Further objects and advantages of the invention will be apparent from the following description of the new 2; 1,2-dihydroxycyclohexene-3 and the like. Examples of process. polyethylenic ‘alcohols which can be similarly used are, vinyl allyl carbinol; allyl propenyl carbinol; diallyl methyl carbinol; geraniol; linalool, 2,4-cyclohex-adienylmethanol; In accordance with the invention halo-substituted hy droxy ethers are produced by reacting an ethylenic alcohol with a hypohal-ogenous acid. Ethers having halogen and divinylbenzyl alcohol; and 3,4-dihydroxy-1,5-hex-adiene. hydroxy substituents on both groups attached to the ether oxygen atom are produced when the alcohol reactant is of the foregoing alcohols which are seen to be alcohols of up to 18 carbon atoms per molecule containing only carbon, hydrogen and hydroxyl oxygen atoms. Halo gen, ether, ketone, ester and like substituents which are unreactive under the conditions of the new reaction are ehylenic alcohol exclusively. By adding a non-ethylenic ‘ alcohol to the reaction mixture an unsymmetrical halo substituted hydroxy ether in which one of the groups Substituted ethylenic alcohols can be employed as starting materials in the process of the invention instead’ attached to the ether oxygen is the same as that linked to 55 the preferred type of substituents. the hydroxyl group of the non-ethylenic alcohol is pro Examples of such substituted ethylenic alcohols are, for instance, l-chloro duced by the new process. In both cases products may be obtained which are mixtures of isomeric ethers in which halogen is linked to one of the carbon atoms of the methoXy-Z-propen-l-o-l; 1-allyloxy-2-hydroxybutene-3; 3-. hydroxy-4-cyclohexene-l-one; 1-acetoxybutene-2-ol-4 and ethylenic group of a starting ethylenic alcohol and an ether 60 oxygen is linked directly to the other carbon atom of that group in one ether and the halogen and ether oxygen link ages are reversed in their attachments to the carbon atoms of that‘ethylenic group in an isomeric ether product. Production of halo-substituted hydroxy ethers in this way is readily "carried out on a commercial scale in an e?icient and economical manner. It was unexpected to 3-buten-2-ol; 5 - chloro - 3 - methyl-2,4-hexadien-l-ol; the like. 1 a When using ethylenic alcohols which have a solubility in Water ofless than about 25 percent by weight, at ordi nary temperature, it is advantageous to add to the reac tion mixture a mutual solvent for the ethylenic alcohol and the hypohalogenous acid solution with which it is to be reacted. Su?icient of the mutual solvent should be used to make the concentration of the ethylenic alcohol in hypohalogenous acid solution at least equal to 50 per ?nd that this single step‘ process will give these useful cent by weight. products. Instead halohydrination products of the start 70 The hypohalogenous acid with which the ethylenic ing ethylenic alcoholrnight have been predictedas the alcohol is reacted is preferably an aqueous solution of predominant product. A diiferent mechanism of reaction hypochlorous or hypobromous acid although hypo?uo; 3,093,689 rous or hypoiodous acids can also be used. The hypo~ halous acid can be made in the usual way by reacting the corresponding halogen with water. Instead of a pre formed solution of the acid, the hypohalogenous acid can. be formed in the reaction mixture during the process of the invention by feeding halogen and water to the re actor. Preferably a large molar excess of water to halo gen, for example, about 5 to about 50 or more moles per mole of halogen, is used. Alcohol hypohalites, such, for example as ethyl hypochlorite, tertiary butyl hypochlo In the same way when methallyl alcohol is reacted, an equally good yield of bis-(2-chloro-3-hydroxy-2-methyl propyl) ether and isomers is obtained and from crotyl alcohol and hypobromous acid bis(2-bromo-3-hydroxy butyl) ether and isomers are obtained. By using methyl vinyl carbinol in place of the allyl alcohol of Example I, a good yield of bis(3-chloro-4 hydroxy-Z-butyl) ether and isomers is realized. With either 2-rnethyl-2~buten-l-ol or methyl isopropenyl car 10 binol and hypobromous acid as the reactants the product rite, n-butyl hypobromite, and the like are another source of hypohalogenous acid for the reaction of the invention. The hypohalogenous acid, whether preformed or made in situ is desirably used in an overall ratio of about one mole per mole of ethylenic alcohol to be reacted. is 3 - (Z-bromo - 3 - hydroxy-Z-methylbutoxy)~2-bromo-2 Higher proportions of alcohol can be employed although usually at a sacri?ce of plant capacity. Higher propor tions of hypohalogenous acid, or of halogen when in situ the same way, reaction of alpha-vinyl-benzyl alcohol hypohalogenous acid production is being used, to alcohol chloro-3,4-dihydroxy - 1 - butoxy) - 3 - chloro-1,4-butane methylbutanol-l and isomers in good yield. When using 2-cyclohexenol as the ethylenic alcohol in the method of Example I the ether product is bis(2 chloro-3-hydroxycyclohexyl) ether and its isomers. In gives bis(2-chloro~3-hydroxy-l-phenylpropyl) ether and isomers. With 2-butene-1,4-diol the product is 2(2 are feasible in the process but are less preferred because 20 diol and isomeric hydroxy-chloro ethers. of the greater danger of by-product formation. An ex With a substantial molar excess of divinyl carbinol to ception to this rule is in reactions with polyethylenic al hypochlorous acid at all times in the reaction one can cohols where higher ratios of hypohalogenous acid will obtain bis(1-vinyl-2-chloro-3~hydroxypropyl) ether and be desirable when one wishes to obtain a halohydrinated isomers in signi?cant yield or by the use of larger amounts product instead of a halo-hydroxyether containing one or 25 of hypochlorous acid, the chlorohydrination products of more ethylenic groups. As a general rule mole ratios this unsaturated chlorohydroxy ether, particularly bis(2,4— used will be in the range of about 0.5 :l to about 2:1, idichloro-l,5-dihydroxy-3-amyl) ether and isomers can more preferably about 0.9:1 to about 1.1:1 when react be obtained in substantial yield. ing monoethylenic alcohols. The new reaction is carried out advantageously in the liquid phase, preferably at ordinary temperatures, but As previously pointed out, the reaction can be carried out having in the reaction mixture another alcohol or a phenol which takes part in the reaction as well as the higher or lower temperature can also be used. Tem ethylenic alcohol. In this modi?cation of the invention peratures in the range of about 0° to about 100° C. are the product will be an unsymmetrical ether in which one suitable. Atmospheric or elevated pressures can be used of the groups attached to the ether oxygen atom cor and either batch, continuous or intermittent method of 35 responds to the other alcohol or phenol minus a hydroxyl reaction can be employed successfully. The following examples illustrate in more detail, suit able methods for applying the process of the invention. Example I group while there is also linked to the ether oxygen atom a halo hydroxy radical derived from the ethylenic alco ?ux condenser, and chlorine-dispensing tube. The ?ask equal mole ratios of the two different types of hydroxy compounds is advantageous. However, ratios of the hol. This method of reaction can be carried out under the same conditions as used in reacting a single ethylenic 40 alcohol or mixtures thereof with hypohalous acid as This example illustrates the production of di-(chloro previously described. Lower alkanols are an example hydroxypropyl) ethers by reacting allyl alcohol, chlorine of one subgroup of saturated alcohols useful in this and water. modi?cation of the invention. One hundred and seventy grams of allyl alcohol, along The ratio of ethylenic alcohol to other alcohol or with ?fty grams of water, were charged to a one-liter phenol which can be used in this modi?cation of the reaction ?ask equipped with a stirrer, thermometer, re invention can be varied widely. Usually approximately was immersed in a water bath for temperature control. Approximately 142 grams of chlorine were bubbled into the reaction ?ask over a two~hour reaction period. During the reaction the contents were rapidly stirred while the temperature was controlled between 0° C. and 25° C. by the addition of ice to the water batch. After reaction the hydrochloric acid produced from the reaction of chlorine with water to form HOCl and order of about 0.121 to about 1.5:1 more preferably about 0.9:1 to about 1.1:] moles of ethylenic alcohol to other hydroxyl compound, i.e. alcohol or phenol, are suitable. The following examples illustrate this modi?cation of the invention in more detail. Example II HCl was neutralized with about 70 grams of NaOH dis solved in 200 cc. of water. During the neutralization This example illustrates the production of 2-chloro-3 the contents of the ?ask were kept at about 0“ C. to pre hydroxypropyl n-butyl ether and 2-butoxy-3-chloropro vent reaction of the chlorohydrin ethers with the NaOH. panol from n-butanol, allyl alcohol and hypochlorous After neutralization, the water and excess allyl alcohol 60 acid. were distilled off under Vacuum (200 mm. Hg). The Two hundred grams of normal butyl alcohol, along product was then stabilized by heating to about 110° C. with 50 grams of water and 58 grams of allyl alcohol, at 200 mm. Hg pressure for a period of 30 minutes. were charged to a one-liter reaction ?ask equipped with a After stabilization the crude ether product was ?ltered to stirrer, thermometer, re?ux condenser, and chlorine-dis remove solid salt. The product was further puri?ed by 65 pensing tube. The ?ask was immersed in a water bath distilling off the dichlorohydrin and monochlorohydrin for temperature control. Approximately 71 grams of contaminants by stabilizing to a temperature of 110° C. chlorine was bubbled into the reaction ?ask over a two— at 10 mm. pressure. About 180 grams of product was hour reaction period, during which time the contents were obtained, which was identi?ed as chlorohydrin ethers. rapidly stirred and the temperature was controlled be The chief components of the product appear to be bis(2 70 tween O" C'. and 25° C. by the addition of ice to the water chloro-3-hydroxypropyl) ether and its isomers 2-chloro bath. 3-hydroxypropyl 3-chloro-2-h},’droxypropy1 ether, 2-chlo After reaction the hydrochloric acid produced during ro-3-hydroxypropy1 1-hydroxymethyl-2-chloroethyl ether the reaction was neutralized with about 40 grams of and 3-chloro-2-hydroxypropyl l-hydroxymethyl-Z-chlo NaOH ‘dissolved in about 150 cc. of water. During the 75 neutralization step, the contents of the reaction ?ask were roethyl ether. 3,093,689 5 6 kept at about 0° C. to prevent reaction of the chloro hydrin ethers with the NaOH. After neutralizationthe We claim as our invention: 1. A process for producing an unsymmetrical halo water and excess normal butyl alcohol were distilled oli substituted hydroxy ether which comprises reacting at under vacuum. The product was then stabilized by heat ing to 110° C. at 200 mm. Hg pressure for about 30 minutes. After stabilization the product was ?ltered to about 0° to about 100° C. an ethylenic alcohol having up to 18 carbon atoms per molecule and a member of the group consisting of phenol and a lower alkanol with an aqueous hypohalogenous acid solution using a mole ratio of said acid to ethylenic alcohol of about 0.5:1 remove the solid salt. Approximately 150 grams of light amber product was obtained, which was identi?ed as chlorohydrin ether of normal butyl alcohol. to about 2:1 and a mole ratio of ethylenic alcohol to By substituting methallyl and ethyl alcohols for the 10 said group member of about 01:11 to about 1.511,.the allyl and butyl alcohols in the above process, a good yield concentration of the ethylene alcohol in the hypohalog of 3-ethoxy-2-chloro-2-methyl-1 propanol and its isomer enous acid solution as calculated Without said group 2-ethoxy-2-met-hyl-3-chloro-l-propanol is obtained. Using member being initially at least 50% by weight, and said isopropyl alcohol with crotyl alcohol and hypobromous alcohols containing only carbon, hydrogen and hydroxyl acid under the same conditions, the products are 3-iso propoxy-Z-bromo-labutanol and its isomer 2-isopropoxy 3-bromo-1abutanol. Similar reaction of dimethyl vinyl carbinol with tert. butyl alcohol and H001 formed in situ gives 4-chloro ' oxygen atoms whereby an unsymmetrical ether having attached to the ether oxygen atom (a) the radical cor responding to said group member minus OH, and (b) a halo hydroxy radical derived from the ethylenic alcohol is produced. 3-tert. butoxy-Z-methylbutanol-Z and 3-chloro-4-tert. butoxy-Z-methylbutanol-Z. With 3-butene-l-ol and n-pro panol reacted with bromine and water, one obtains 3 2. A process for producing an unsymmetrical halo substituted hydroxy ether which comprises reacting at about 0° to about 100° C. an ethylenic alcohol having up to 18 carbon atoms per molecule and a lower alkanol with an aqueous hypohalogenous acid solution using a bromo-4-propoxy-l-butanol and 4-bromo-3-propoxy-1 butanol. l-cyclohexenylmethanol and methanol reacted with hy 25 mole ratio of said acid to ethylenic alcohol of about pochlorous acid as in Example 11 results in the produc 0.5:1 to about 2:1 and a mole ratio of ethylenic alcohol tion of l-chloro-l-hydroxymethyl-Z-methoxy cyclohexane to saturated alcohol of about 0.1:1 to about 1.5:1, the and 2-chloro~1-hydroxymethy1 - 1 - methoxycyclohexane. concentration of the ethylenic alcohol in the hypohalo Analogous reaction of 1-phenyl-34buten-2~ol and ‘ethanol yields 1-pheny1-3-chloro-4-ethoxybutanol-2 and l-phenyl 4-chloro-3-ethoxybutanol-2. ‘From 3-hexene-2,5-diol and isopropanol the chief product is 3-isopropoxy-4-bromo hexane~2,5-diol when using hypobromous acid under the same conditions. 30 genous acid solution as calculated without the saturated alcohol being initially at least 50% by weight, and said alcohols containing only carbon, hydrogen and hydroxyl oxygen atoms whereby an unsymmetrical ether having attached to the ether oxygen atom (a) the radical cor By substituting phenol for the n-butanol of Example 35 responding to said saturated alcohol minus OH, and (b) a halo hydroxy radical derived from the ethylenic alcohol H there can be produced 3-phenoxy-2~chloro-l-propanol is produced. and its isomer 2~phenoxy-3—chloro-1-propanol. Use of a polyol for reaction with the ethylenic alcohol and hypohalous acid makes it possible to produce either 3. A process in accordance with claim 2 wherein the unsymmetrical halo-substituted ether is recovered by neu mono- or polyethers as predominant product depending 40. tralizing the reaction mixture at a temperature below that at which the ether reacts under the existing conditions and upon the proportions of the reactants which are employed. then distilling. 'I‘hus reaction of allyl alcohol with ethylene glycol and hypochlorous acid according to the method of Example 4. A process in accordance with claim 2 wherein an II gives 2-chloro-3abeta-hydroxyethyl-l-propanol with its alkyl 2-chloro-3-hydroxyalkyl ether is produced by re isomer 3-chloro-Z-betaahydroxyethyl-1-propanol and 1,2 45 acting a lower alkanol with a beta,gamma~ethylenic al kenol having 3 to 5 carbon atoms per molecule and hypo chlorous acid. and hypobromous acid in aqueous acetone solution, the 5. A process in accordance with claim 4 wherein the chief products are Z-(parahydroxypheny-l) -2 [4-(ch1oro-3 alkenol is allyl alcohol and the hypochlorous acid is 50 hydroxypropoxy) phenyl] propane and its isomer Z-(para formed in the reaction mixture by reacting chlorine with hydroxyphenyl)-2[4-»( 1-hydroxymethy-1-2 - chloroethoxy) water. phenyl] propane or 2,2~bis[4-(2-chloro-3-hydroxypro 6. A process for producing a phenyl 2-chloro-3-hy poxy)phenyl] propane and isomers depending on the droxyalkyl ether which comprises reacting at about 0° proportions of the reactants employed. Still other variations can be made in the process of the 55 to about 100° C., phenol and a beta,gamma-ethylenic alkenol of 3 to 5 carbon atoms per molecule with aqueous invention which is not limited to the reactions which hypochlorous acid solution using a mole ratio of said have been given by way of illustration only nor by the acid to ethylenic alcohol of about 0.5 :1 to about 2:1 examples which have been used to show suitable pro and a mole ratio of ethylenic alcohol to phenol of about cedures for conducting these new reactions. Nor is the invention limited by any theory proposed in explanation 60 0.1:1 to about 1.5 :1, the concentration of the ethylenic alcohol in the hypohalogenous acid solution, as calculated of the new and improved results which are produced without the phenol, being initially at least 5 0% by weight by the new method. whereby an ether having attached to the ether oxygen atom The halo-hyd-roxy ethers whose e?icient production bis(2-chloro - 3 - hydroxypropyl(ethane and isomers. Using 2,2-bis(parahydroxyphenyl)propane, allyl alcohol from ethylenic alcohols is made commercially feasible (a) the phenyl radical, and (b) a chloro hydroxy alkyl by the new process have a number of important uses. radical derived from the alkenol is produced. The liquid halo-hydroxy ethers are solvents ‘for resins and the like and are useful in surface coating composi References Cited in the tile of this patent tions. These and higher molecular halohydroxy ethers are convertible by reaction with sodium hydroxide or other 70 Read et al.: Jour. Chem. Soc. (London), vol. 121 base to epoxyethers which, especially in the case of the (1922), pages 989-999‘. polyepoxy products, are starting materials for resinous Taylor et al.: Canadian Jour. of Research, vol. 4 products of various kinds. It will accordingly be seen (1931), pages 119-133. that the new process of the invention offers many ad Williams et al.: Chem. and Met. Eng; vol. 47 (1940), vantages and can be applied in many ways. 75 pages 834—838.