/ Patented July 21, 1942 2,290,462

UNITED STATES2,290,462 PATENT OFFICE DHALOGENATED ETHERS Charles F. H. Allen and James Van Alan, Roch ester, N.Y., assignors to Eastman Kodak Com pany, Rochester, N. Y., a corporation of New Jersey W No Drawing. Application January 6, 1940, Serial No. 312,22 6 Claims. (C. 260-615) This invention relates to di-halogenated ethers ExAMPLE 1.-Heiamethylene-bis-oacylmethyl and their method of preparation, and more par cloride (C2CH2O(CHa)6OCHCl). ticularly to di-halogenated methyl ethers of polyhydric alcohols. A mixture of 3.9 parts of hexamethylene gly A number of halogenated ethers and particu col, 2.1 parts of trioxymethylene, and 15 parts of larly the mono-halogenated ethers are known 5 benzene is Cooled to 15° C., and hydrogen chlo and used industrially for various purposes. AS ride passed in for 2 hours. The Water layer is an example, the mono-halogenated ether separated and the benzene removed on a steam (lauryl-a-chloroethyl ether) may be mentioned. bath under vacuum, leaving 4.2 parts of chloride. Also a few di-halogenated ethers have been de O ExAMPLE 2-Decamethylene-bis-oacylmethyl scribed. However, these have generally com chloride (CICH2O (CH) 0OCHIC) prised the chloroethyl derivatives. A mixture of .100 parts of decamethylene gly We have found that new halogenated ethers col, 35 parts of trioxymethylene, and 1000 parts may be prepared by a relatively simple pro of benzene is cooled to 5-10 C., and While stir cedure, with excellent yields. Our new halo 5 ring, dry hydrogen chloride is passed in until genated ethers may be employed for a number of all the solid in Suspension has gone into Solution. purposes in the prior art wherein the afore This takes 3.5 to 4 hours. The separated aqueous mentioned ethers have been employed, and in layer is removed, the benzene removed in vacuo, particular our novel ethers possess a high de and the residue used directly or distilled in gree of utility because of the especially active 20 nature of the halogen atom therein. . vacuo. The yield of distilled product is 115 This invention has for One object to provide parts, B.P. 200-203.15 mm. new di-halogenated ethers of di-hydroxy ExAMPLE 3-Trimethylene-bis-oacylmethyl aliphatic compounds. Another object is to pro chloride (CICHO(CH2)3OCH2Cl) vide novel halogenated ethers containing a halo 25 A mixture of 7.6 parts of trimethylene glycol, gen atom possessing substantial activity. Still 5 parts of trioxymethylene, and 25 parts of ben another object is to provide novel halogenated Zene is cooled to 15 C., and hydrogen chloride ethers of glycols containing six or more carbon passed in for 2 hours. The Water layer is sepa- . atoms. Still another object is to provide novel rated and the benezene removed on a steam bath halogenated ether derivatives of glycols and Con 30 under vacuum, leaving 9.8 parts of chloride. taining at least one chloronethyl group, A still further object is to provide a simple and efficient ExAMPLE 4-Ethylene-bis-ocymethyl chloride method for the preparation of the afore-de (CCHOCH2CHOCH2C) scribed compounds. Other objects will appear A mixture of 310 parts of ethylene glycol, 300 hereinafter. parts of trioxymethylene, and 1000 parts of ben We have found that halogenated alkyl ethers, zene is externally cooled to 10-15 C., and dry and preferably the chloromethyl derivatives of hydrogen chloride is passed into the mixture di-hydroxy alcohols may oe prepared and that until it is satuated. This takes about 5 hours. these compounds exhibit excellent activity with The water formed during the reaction and any respect to the halogen attums. We have found 40 unused glycol form a layer which is separated. that the activity of the halogen atoms in our The solvent is removed from the residual solu preferred compound wherein the halogen aton tion on a steam bathin vacuo. The clear residual is attached to the methyl group, possesses con liquid (412 parts), is used directly. . . siderably greater activity than, for example, In a similar manner, other compounds such when attached to other groups as an ethyl group. as, for example, 8-in-amyloxyethoxymethyl chlo We have found that our novel compounds may ride (CsI11OCHAOCHgCl), B. P.108-111/23 mm., be easily prepared with excellent yields by re prepared from glycol-mono-n-amylether, may be acting the di-hydroxy compound with formalde prepared. hyde,'a solvent and dry hydrogen chloride, as As already indicated, our novel compounds may . will be set forth in detail hereinafter. 50 be employed for various purposes, wherein, for For a more detailed understanding of our in example, the prior art halogenated compounds vention, reference is made to the following ex have heretofore been employed. In particular, amples, which are set forth for the purposes of however, our novel halogenated ethers are useful, illustrating certain preferred embodiments, ss wherein an active halogen atom is desired.

t 2 2,290,462 For example, they form alkoxynitriles, and 3. The compound hexamethylene - bis - oxy salts with amines, sulfides, phosphines, etc. The methyl chloride. substances so formed may be surface-active, e.g. 4. The compound decamethylene - bis - oxy foaming and Wetting agents. methyl chloride. m The benzene used as a solvent may be replaced 5 5. A process for the manufacture of dichloro by ether, dioxane, or chloroform, and the like. methyl ethers of polyhydric alcohols, which Com From the foregoing, it is apparent that our prises reacting together a mixture of the poly invention is susceptible of some modification and hydric alcohol, para-formaldehyde and dry hy hence, We do not wish to be restricted, excepting drogen chloride for 1-8 hours in the presence of insofar as may be necessitated by the prior art 10 a solvent from the group consisting of benzene, and the spirit of the appended claims. dioxane, ether, and chloroform and separating What We claim and desire to be Secured by water from the reaction mixture to obtain the Letters Patent of the United States is: chloromethyl ether. 1. Compounds having the formula: 6. A process for the manufacture of dichloro methyl ethers of polyhydric alcohols, which Com CCEO (CB) OCBC prises reacting together a mixture of the poly Wherein is at least 5. hydric alcohol, para-formaldehyde and hydrogen 2. A process for the manufacture of halogenated chloride in the presence of a solvent from the ethers, which comprises reacting a mixture of a group consisting of benzene, dioxane, ether, and polyhydric alcohol, paraformaldehyde and dry 20 chloroform, and separating Water from the re halogen chloride, said reaction being carried out action mixture to obtain the chloromethyl ether. in the presence of a non-aqueous solvent for said mixture, and for a period of from one to eight CELARES F. H. A.E.N. hours. AMS WAN AIAN.