DE647192C - Process for the simultaneous introduction of halogen and alkyl radicals into organic compounds with at least one olefinic double bond - Google Patents

Description

Process for the simultaneous introduction of halogen and alkyl radicals into organic compounds with at least one olefinic double bond It is generally not possible to add simple haloalkyls to multiple carbon bonds. According to the currently valid theoretical views, there is an exception only for molecules with particularly reactive double bonds, such as are found in the enols, in which the reactivity of the adding molecule is changed by a special type of substitution. It has now been found that alkyl halides of the general formula where R is hydrogen, an alkyl, aralkyl or aryl radical, R 'is an alkyl radical and X is halogen, can be added to organic compounds having at least one olefinic double bond to form halogen-substituted ethers.

Suitable compounds with olefinic double bonds are, for example, the compounds of ethylene, such as isobutylene and trimethylethylene, cyclohexene, butadiene and its homologues and r, α-dihydrobenzene. Examples of alkyl chlorides that can be used for the reaction are: monochlorodimethyl ether C H3 0 C H2 Cl, monochloromethyldodecyl ether C12 H25 0 C H2 Cl, a-methoxybenzyl chloride C6 H5 (; H (O CH3) Cl and its core substitution products, such as p-chloro-a- methoxybenzyl chloride Cl C3 H4 CH (0 C H3) Cl, p-methyl-a-methoxybenzyl chloride C H3 C; H4 CH (OC H3) Cl, a-methoxycinnamenyl chloride CH, CH - CH - CH (OC H3) Cl; a-methoxy -a-chloro-β-phenylethane C, H5 CH. CH (OC H3) Cl a-methoxynaphthomethyl chloride C1oH7 CH (OCH3) Cl. Instead of the chlorides, other halides, for example the corresponding bromides, can also be used or without dilution with a suitable solvent, such as benzene or acetylenetetrachloride: Depending on the combination chosen, the additions take place at different rates, depending on both the structure of the unsaturated compound and the construction of the. All: ylchlorids depends. You k Can be accelerated by suitable catalysts; as such, anhydrous metal halides, especially mercury halides, have proven useful.

Instead of the a-all .: oxyallyl chlorides purified by distillation, the crude products can often also be used directly, as they are after the conversion of the with the compounds suitable for replacing alkoxyl with chlorine, after removing any volatile accompanying substances as far as possible, remain behind as residue.

It is known (see Blanchard, Bull. Soc. Chim. France [4] 39/1119 and 1263 [1926]) that nlonochlorodimethyl ether is the oxide ring of epichlorohydrin able to explode under addition; but it could not be deduced from this that this class reactive alkyl chlorides are added to unsaturated carbon bonds can. Nor could this be inferred from the well-known fact that Acid chlorides adhere to monounsaturated hydrocarbons, such as Cy cloliexen, with the help of tin tetrachloride or aluminum chloride are able to add (see D a rz e n s, Com. rend. Acad. Sciences 15o / 707 figio]), since there are two very different classes of organic halogen compounds are involved.

The compounds made accessible by the process are on other way up to now not or only very difficult to get; through the in Halogen and alkoxyl in their molecule are various modifications accessible form a valuable starting material for further syntheses.

Example i 16.g of liquefied butadiene and 52 g of 493/203 [r932]) remain with the addition of a few (Liebigs Annalen stand tenths of a gram of mercury chloride for 2 days at room temperature. Klan decomposes with dilute sodium chloride solution and isolated in the usual way with ether. The i-phenyl - i = methoxy-5-chloropentene-3, Co H5 - CH (OCH3 ) - CH. - CH: CH - CH. C1, is a colorless, viscous, pleasant, acetal-like smelling liquid that boils below 0.06 mm at 93 °. -D; °: = .0657. Without the addition of the catalyst under otherwise identical conditions, the yield of addition product drops to a fifth.

EXAMPLE 2 27 g of monochlorodimethyl ether and 10.5 g of liquefied butadiene react in the presence of 3 to 4 g of mercury chloride, when the mixture comes to room temperature, with a dark color and self-heating, which must be kept below 30 ° by cooling. It is left to stand for a further 24 hours and worked up as indicated in Example i. The i-methoxy-5-chloropenten-3: CH30-CH2-CH2-CH: CH -CH2C1, which can be isolated in a yield of 60 to 7001, is a colorless, easily mobile liquid with a sharp, radish-like odor, boiling under normal pressure at iiS °. d °: x, oo22. Example 3 36 g of crude α-methoxybenzyl bromide, as is left behind according to Liebigs Annalen 49S / 124 (1932) by the conversion of benzaldelium dimethyl acetal and acetyl bromide after the volatile accompanying products have been pumped off, are mixed with 6 g of liquid butadiene without the addition of a catalyst. After standing for 3 days at room temperature, the work-up carried out according to Example i gave i-plienyl-i-methoxy-5-bromopenten-3: C6 H5 - CH (OC H3) - C H2 - CH: CH - C H2 Br with 30% yield. Boiling point at 0.05 mm 92 °. Example 4 279 cyclohexene, 45 g of α-methoxybenzyl chloride and 149 g of mercury chloride are stirred for 32 hours with exclusion of moisture, gradually turning brown. The addition of the chloride is much slower in this case. The attacked cyclohexene is filtered off with suction in vacuo, isolated in the manner described and the crude addition product is oxidized in acetone solution with permanganate until the color of the latter is obtained. The io: methoxybenzyl-2-chlorocyclohexane boils below 0.01 mm at 94.5 °. Colorless liquid. -Cyclohexene reacts with monochlorodimethyl ether when the two components are shaken for several days in the presence of mercury chloride. The resulting i-methoxymethyl-2-chlorocyclohexane boils below 0.25 mm at 3o to 31 '. Example 5 Molecular amounts of i, 2-dihydrobenzene and α-methoxybenzyl chloride are combined in the presence of a few centigrams of mercury chloride. At room temperature, a violent reaction occurs with strong self-heating, which is moderated by cooling. You let stand for a while and work up according to example i. The addition product, an α-methoxybenzylchlorocyclohexene with the position of the substituents to the double bond of the hydrogenated nucleus still unclear, is produced in almost quantitative yield and is a colorless, almost odorless liquid with a boiling point of 0.05 mm 1i2 °: d4 °: r, zo66. Without a catalyst, the addition proceeds less energetically, and after 2 days a conversion of 40 to 50% is achieved.

Molar amounts of monochlorodimethyl ether and i, 2-dihydrobenzene react in the presence of larger amounts (up to a few grams) of mercuric chloride, also under intense heating. The resulting methoxymethylchlorocyclohexene boils at 80 ° under 10 mm pressure. d'4'- =, o636. EXAMPLE 6 To a mixture of: 21 g of a-methoxybenzyl chloride and 0.2 g of mercury chloride, 10.5 g of trimethylethylene are allowed to slowly flow in while cooling with ice. The reaction sets in rapidly with heating. As soon as it is finished, work on in the manner given in example i. The i-phenyl-i-methoxy-2,3-dimethyl-3-chlorobutane obtained in very good yield is a colorless, pleasant-smelling liquid; which boils under 16 mm pressure at 133 to i35 °. d4 °: z, o278. If one works without the addition of oxysilver chloride, the same reaction occurs, albeit more slowly. Example 7-Molecular amounts of monochlorodimethyl ether and trimethylethylene are brought together in the presence of oxysilver chloride, i-methoxy-2, 3-dimethyl-3- chlorobutane is obtained, which boils under a pressure of 1 3 to 14 mm at 45 to 46 °. d4 °: 0.9528.

Example 8 24 parts of monochlorodimethyl ether and 18 parts of liquefied Isobutylene reacts in the presence of 2 parts of mercury chloride on standing for 3 days at room temperature with each other until the hydrocarbon has almost completely disappeared. The up to 60 ° passing from is separated by distillation at 1s to 14mm pressure Catalyst off and fractionated. The i-methoxy-3-methyl-3-chlorobutane formed, a colorless, easily mobile liquid, boils under 127 mm pressure at 8 °. d4 °: 0.9455 The yield reaches 60 to 70%.

Claims (1)

Claim Process for the simultaneous introduction of halogen and alkyl radicals into organic compounds with at least one olefinic double bond, characterized in that alkyl halides of the general formula are applied to these compounds in which R is hydrogen, an alkyl, aralkyl or aryl radical, R 'is an alkyl radical and Y is halogen. Corrigendum to patent specification 647 192 class 12o group 2/05. In patent specification 647 192, on page 1, line 49, the word "halogen" is replaced by the word j- "homolo en", on page 2, line 15, the word "acetate" is replaced by the word 'acetals "and on page 2, line 71 replace the word "A-methoxylbenzyl chloride" with the word Ca4-methoxybenzyl chloride ".