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UNITED STATES PATENT OFFICE2,666,083 2,666,083 Process of PRODUCING A-HALO-W- TRHALOPROPY, ETHERS John W

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UNITED STATES PATENT OFFICE2,666,083 2,666,083 Process of PRODUCING A-HALO-W- TRHALOPROPY, ETHERS John W Patented Jan. 12, 1954 UNITED STATES PATENT OFFICE2,666,083 2,666,083 PROCESs OF PRODUCING a-HALO-w- TRHALOPROPY, ETHERS John W. Copenhaver and Donald E. Sargent, Easton, Pa., assignors to General Aniline & Film Corporation, New York, N.Y., a corporation of Delaware No Drawing. Application November 23, 1948, Serial No. 61,736 Claims. (C.260-614) 2 This invention relates to a novel method etc.). However, the process is operative with the Wherein a tetrahalomethane is reacted with a higher alkyl or cycloalkyl vinyl ethers, such as cy vinyl ether in the presence of peroxidic catalysts clohexyl vinyl ether, lauryl vinyl ether, steary or ultraViolet light to produce 1-halo-3-trihalo vinyl ether, etc. and if desired, such vinyl ethers propyl ethers. as benzyl vinyl ether, phenyl vinyl ether, creSyl We have discovered that when a vinyl ether, vinyl ether, etc. may be employed. In addition preferably containing a small annount of an ace to vinyl ethers, related alkyl or arylaf-ethyleni tal, and a tetrahalomethane are mixed in the cally unsaturated ethers of the type indicated in presence of a Small amount of an organic per the above equation may be employed to produce Oxide, or when subjected to the influence of ultra it) correspondingly substituted i,3,3,3-tetrahalo violet light, the halomethane adds on to the dou propyl ethers. As examples of such ethers may be ble bond of the vinyl ether to produce 1-halo-3- mentioned methyl propenyl ether, methyl iso trihalopropyl ether. This reaction may be for propenyl ether, methylbutenyi ether, methyl-a- mulated as follows: pheny vinyl ether, methyl-6-phenyl vinyl ether Equation I: R. R. O.R. 15 and the corresponding ethyl, propyl, butyl, amyl and phenyl ethers and the like. CX4 - R O CR'ss-CE - ox. He As stated, the preferred catalyst employed for R X the reaction is an organic peroxide and it is be Wherein X represents halogen (e. g. chlorine or lieved that any organic peroxide which is soluble bromine), the R, represents hydrogen or the 20 in the halomethane employed is operative in the same or different alkyl or aryl hydrocarbon radi present process. As examples of usual and pre cals, and R represents the hydrocarbon residue of ferred peroxidic catalysts for the present inven an alcohol or phenol, preferably lower alkyl (i.e. tion may be mentioned benzoyl peroxide, lauroyl methyl, ethyl, propyl, isobutyl, n-butyl). How peroxide, and the like. - Relatively small amounts ever, so far as operability of the process is con 25 of catalyst are effective, the amount employed cerned, R may also be higher alkyl (i.e. lauryl, generally being about 0.001% by weight of the stearyl, etc.), aryl (i. e. phenyl, naphthyl, cresyl, vinyl ether. However, amounts up to 0.1% may etc.) or alkaryl (i.e. benzyl). The thus obtained be employed, if desired. Ultraviolet ight also 1-halo-3-trihalopropyl ethers are novel con catalyzes this reaction and if desired may be en pounds Which are of interest as chemical inter 30 ployed as the sole catalyst or along with peroxide mediates for the production and the synthesis of catalysts. Organic compounds. For example, as described It has been found that in addition to the 1: in the copending application of John W. Copen adduct which is obtained as illustrated in the haver, Serial No. 58,623, filed November 5, 1948, Equation. It above, there is formed a certain now Patent No. 2,556,905, these tetrahalo 'ethers 35 amount of higher boiling material. The produc may be reacted with an alcohol to produce ace tion of such higher boiling materials may be for tals of trihalo-propionaldehyde, which are of in mulated as follows: terest as insecticides and as intermediates in the C cla--, niOROCH-CH2) - - - Synthesis of insecticidal materials by condensa "r OR tion with chlorobenzene, etc. 40 H. The reaction proceeds readily on heating a Cls C- -CH-i- =CH-CH mixture of a tetrahalomethane and a vinyl ether, OR til C the reflux temperature of the mixture and at wherein Risas defined above. - mospheric pressure having been found to be suit It was found that when working with samples able with vinyl ethers boiling above about 35° C.; of vinyl ethers which had been stored for some with lower boiling ethers pressure is necessary. time, 80-85% yields of the 1:1 adduct; were ob It has also been found that the yield of tetrahalo tained and only minor amounts of higher boiling ether which is obtained is improved by employing materials were produced, while when freshly dis some excess of halomethane in the reaction and , tilled pure vinyl ethers were emiployed in the in general from 2 to 5 molar proportions of haio 50 reaction, only. 20-40% yields of the l: is adduct methane are employed per mol of vinyl ether, were obtained and substantially larger amounts As examples of vinyl ethers which may be em of high molecular weight materials were formed. ployed in the present invention to produce the It has been found that small amounts of acetals, corresponding ethers of 1-chloro-3-trichloro which are frequently present in impure or old propanol may be mentioned the lower alkyl vinyl samples of vinyl ethers, appear to activate the ethers in which the alkyl group contains from 1 reaction and result in a very substantial increase to 5 carbon atoms (i.e. methyl vinyl ether, ethyl in the amount of the 1:1 adduct, which is formed. vinyl ether, propyl vinyl ether, isopropyl vinyl Therefore, in the preferred embodiments of this ether, n-butyl vinyl ether, isobutyl vinyl ether, 'invention, -a, -small amount of an acetal which tertiary butyl vinyl ether, isoamyl vinyl ether, 60 advantageously should correspond to the vinyl 2,666,088 3 4. ether employed is included in the reaction mix bon tetrachloride was removed and the concen ture. Amounts of acetal equal to from 1-2% of trate was distilled at reduced piessure to give the vinyl ether employed are sufficient. Thus, 1,3,3,3-tetrachloropropy; butyl ether (boiling if butyl vinyl ether is employed in the reaction, point 77° at 1.4 min.). preferably from 1-2% of dibutyl acetal is incor 5 It will be understood that the foregoing ex porated therein, while if methyl vinyl ether is annples are illustrative of preferred embodiments employed in the reaction, preferably from 1-2% of the present invention and that various modi of dimethyl acetal is incorporated therein. The fications of the type previously indicated may be production of the i:1 adduct as the principal made therein without departing from the Spirit product and the formation of only very minor of this invention or the scope of the appended amounts of higher molecular Weight products is claims. It will also be apparent that in place a surprising result, in that in most reactions of . of the carbon tetrachloride. Specified in the fore halo-alkanes with unsaturated compounds, the going examples, other tetrahalomethanes such higher molecular weight products are formed in as carbon tetrabromide, trichlorobroinonethane, great amounts as the principal reaction product. dichlorodibromonethane or tribronochlorometh The following specific exampies, in which the ane may be employed. in the event that mixed parts are by weight, will illustrate specific pre halomethanes are employed in the reaction, the ferred embodiments of the present invention: product obtained will presumably be a 1-bromo Eacample I 3,3,3-trihalo compound, although the possibility that an isomeric 3-bromo-1,3,3-trihalo compound 1232 parts by weight (8 moles) of redistilled may be formed is not precluded. carbon tetrachloride were heated to reflux and We claira: a solution of 0.24 part by Weight of benzoyl per'OX 1. The process of producing ethers of 1-halo ide in 280 parts by weight (2.8 moles) of n-butyl 3-trihalopropyl ethers, which conprises subject vinyl ether, which had been stored for several ing a mixture of a vinyl etheir selected from the months and contained 1-2% of dibutyl acetal, group consisting of alkyl-, aryl and aikaryl vinyl slowly added thereto during 2 hours. During ethers with a tetrahalo methane, said inixture the addition of the vinyl ether, the temperature being substantially free of polymerizable con of the refiuxing reaction mixture gradually in rounds other than the vinyl ether specified; to creased from 76-92 C. On completion of the the action of heat and in the piesence of free addition of the n-butyl vinyl ether, the exceSS radicals selected from the class consisting of free carbon tetrachloride was reinoved by distilla adicals formed by peroxy conjouinds acting oil tion and the reaction product, then distilled under the reaction inixture and free radicals formed by reduced pressure to give 568 parts by Weight (ap ultraviolet light acting on the reaction inixture. proximately 80% of theory) of 1,3,3,3-tetrachlo 2. The process as defined in claim 1, wherein ropropylbutyl ether boiling at 80° C./2.3 in., the vinyl ether contains a Small annount of an n25 1.4685. acetal selected from a group consisting of di In addition to the tetrachloroether a snai alkyl-, aryl- and alkaryl-acetals in which the amount of higher boiling material was present alkyl, aryl and alkaryl groups correspond to the in the still-pot residue. This higher boiling rina 40 Similar groups in the vinyl ether enployed. terial was believed to be largely 15,5,5-tetra 3. The process as defined in clair. 1, wherein chloro-3-butoxyamyl n-butyl ether and higher the halo-nethane is carboi tetrachloride.
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