DE1116661B - Process for the production of organic manganese carbonyl compounds - Google Patents

Description

The invention relates to the preparation of organic manganese carbonyl compounds of the formula R Mn (CO) ₅ , where R is an alkyl, aryl, aralkyl, alkaryl or an unsaturated aliphatic, optionally aryl-substituted hydrocarbon radical, characterized in that alkali metal manganese pentacarbonyl Compounds treated with compounds introducing the above radicals, which react with the alkali metal manganese pentacarbonyl compounds to form an alkali metal salt, or an acyl manganese pentacarbonyl compound which can be obtained by treating an alkali metal manganese pentacarbonyl compound with an acylating agent, under Cleavage of carbon monoxide is pyrolyzed, with high yields of hydrocarbon-manganese pentacarbonyl compounds being obtained in both cases.

In the above formula, the radicals R preferably have 1 to about 17 carbon atoms. Examples are benzyl manganese pentacarbonyl, Phenyl manganese pentacarbonyl, o-ethylphenyl manganese pentacarbonyl, m-t-butylphenyl manganese pentacarbonyl, p-AUylbenzyl manganese pentacarbonyl and methyl manganese pentacarbonyl. According to the invention The compounds that can be prepared are distinguished by a strong alkylating effect. The inventive Process is particularly suitable for the production of methyl manganese pentacarbonyl by reaction of potassium manganese pentacarbonyl with dimethyl sulfate or a methyl halide. Allyl manganese pentacarbonyl is made by reacting allyl chloride with sodium manganese pentacarbonyl and p-phenylbenzyl manganese pentacarbonyl by reaction a p-phenylbenzyl halide, especially p-phenylbenzyl iodide obtained with lithium manganese pentacarbonyl.

Also compounds in which the organic hydrocarbon residue is replaced by non-reactive Substituted radicals which are not hydrocarbon radicals are within the scope of the invention.

The alkali metal manganese pentacarbonyl compounds used as starting materials are produced by reacting an alkali metal with dimangandecacarbonyl in ether as a solvent.

The reaction between the alkali metal manganese pentacarbonyl compound and the compound introducing a hydrocarbon radical is expediently also carried out in an ether as solvent, it being possible to use the alkali metal manganese pentacarbonyl without isolation. In particular, high yields of organic manganese pentacarbonyl compounds are obtained in processes of manufacture
of organic manganese carbonyl compounds

Applicant:

Ethyl Corporation,
New York, NY (V. St. A.)

Representative: Dr. W. Beil and A. Hoeppener,
Lawyers, Frankfurt / M.-Höchst, Antoniterstr. 36

Claimed priority:
V. St. v. America, March 13, 1957 (No. 645 675)

Rex Dewayne Closson, Northville, Mich.,
and Thomas Hunter Coffield, Farmington, Mich.

(V. St. A.),
have been named as inventors

when the ether used as solvent has a boiling point above 25 ° C. It also turned out that that cyclic ethers, such as tetrahydrofuran and dioxane, lead to excellent yields of organic Manganese pentacarbonyl compounds lead and are therefore preferred as solvents.

Suitable solvents are very generally lower alkyl ethers, cyclic ethers or ethers, the contain a multitude of C-O - C bonds. Examples are ethyl butyl ether, dibutyl ether, Isobutyl isopropyl ether, methyl neopentyl ether, the diethyl ether and the dibutyl ether of diethylene glycol, Tetrahydrofuran, 1,4-dioxane, 1,3-dioxane and substituted Dioxanes. In general, a saturated, organic ether that is free from others is suitable is reactive groups, has no active hydrogen and contains at least 4 carbon atoms. Ethers with 4 to about 12 carbon atoms are most suitable. In the case of those introducing a hydrocarbon residue Reactants are hydrocarbon halides, sulfates and similar compounds, which react with the alkali metal to form a salt. Examples are dibenzyl sulfate, dimethyl

109 738/433

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sulfate, alkyl, aryl and aralkyl halides and was 59.5% of theory. The analysis showed pretty much

Alkali halides. exactly the calculated hydrocarbon F-Manganese

The implementation will depend on the content used.

Reactants at temperatures between analysis for

about 20 and 100 ° C, the top 5 being methyl manganese pentacarbonyl, CH ₃ Mn (CO) ₅ :

Limit of the boiling point of the solvent used as TWprVinpt r ία ί tti ^ Mn on ο ·

turned aether. The reaction already occurs Γ 34 <5 TT 1 Xl Mn? Fi 4
at room temperature after mixing the reaction

participant a. However, the infrared spectrum showed the manganese carbonyl

capable organic compounds with a high molar grouping and the presence of a methyl group,

kular weight used as reactant, so the substance was highly volatile and quickly evaporated in

it is expedient to carry out the reaction at a higher temperature in an air stream. The connection seemed to simmer

temperature up to the reflux temperature of the ether when they are in a tube to determine the boiling point

respectively. Reaction times of more than one hour point was heated to about 140 to 145 ° C,

Although they can be used, they are generally 15 The yield of methyl manganese pentacarbonyl was

but not necessary. As in other cases, also very good if instead of dimethyl sulfate

the reaction time depends on the activity of the re-methyl iodide was used,
participants and the temperature used.

If the reaction product is a crystalline solid Example 2
Substance, it is generally insoluble in water and 20

is therefore by diluting the ether with water, sodium manganese pentacarbonyl was made in 267 parts

and conveniently simply filtering the reaction tetrahydrofuran using 12.2 parts

mixed separately. The further purification can by Dimangandecacarbonyl and an excess of

Sublimation or crystallization take place. Is the 1% sodium amalgam made. The above-

If the reaction product is a liquid, then it will be expedient to stand still containing sodium manganese pentacarbonyl

moderately by fractional distillation of the reaction liquid was decanted and placed under nitrogen

mixed separately. held. Then it was mixed with 8 parts of benzyl chloride,

As mentioned above, the inventive C ₆ H ₅ CH ₂ Cl, treated and then 15 minutes on

Compounds also heated by pyrolysis of acyl manganese in a steam bath. It parted almost immediately

pentacarbonyl compounds, which have a carbon atom 30 after heating a light colored precipitate.

contain more. So goes z. B. By centrifugation and subsequent decanting

Benzoyl manganese pentacarbonyl pyrolytic destroying of the liquid gave a bright solid

carbonylation to phenyl manganese pentacarbonyl. substance that turned out to be sodium chloride. The liquid one

In the following examples, all parts relate to solution being dried to dryness under reduced pressure

and percentages - unless otherwise stated - 35 evaporated and the residue under pressure

on weight. less than 1 mm and temperatures up to 100 ° C

sublimated.

Example 1 15.75 parts of a pale yellow sublimate were obtained that with small amounts of a light-colored liquid

Was contaminated by conversion of 7.8 parts of Dimangandeca- 40. Careful resublimation at

carbonyl, [Mn (CO) ₅ J ₂ , with 2.5 parts at 50% room temperature reported a good yield

Sodium dispersion in mineral oil became a solution of crystals that melted at 37.5 to 38.5 ° C. the

from sodium manganese pentacarbonyl, NaMn (CO) ₅ , in analysis gave for that prepared in this way

Tetrahydrofuran produced. The following - Benzyl manganese pentacarbonyl 19.6% manganese, 49.7%

measured before: 45 carbon and 2.28% hydrogen. These values

One with gas inlet and outlet devices correspond roughly to the calculated ones. The infrared gene and devices for stirring, heating and spectrum shows a carbonyl group and a mono-cooling equipped reaction kettle was indicated with a stick-substituted benzene ring. The total yield of substance rinsed out and filled with 88 parts of tetrahydrofuran benzyl manganese pentacarbonyl amounted to 87.5% of the theo-dissolved dimanganese decacarbonyl. This was followed by 50 rie, based on the sodium manganese pentacarbonyl. the sodium dispersion was added and the resultant, based on the weight of the sodium mixture obtained, was stirred at 50 ° C. for 3 hours. Then chlorides were left and the yield was 91.5%.
drop. The supernatant liquid was decanted off and a small sample was titrated with hydrochloric acid. Example 3
The titration showed a high conversion to Na-55
trium manganese pentacarbonyl. 8.7 parts of NaMn (CO) ₅ in 88 parts of tetrahydrofuran

7.55 parts of dimethyl sulfate with 3.2 parts of allyl chloride were then added to the solution under nitrogen. The reaction occurred immediately and was cautiously refluxed for 1 hour at which point the temperature became cloudy with a rise in temperature and mixture. The removal of the solution thickening accompanied the mixture, with a slight precipitate formed by distillation over a spiral body. Overnight column and subsequent distillation of the residue, the mixture was left to stand in an inert atmosphere - under reduced pressure gave a low yield and then poured into 500 parts of ice water, a pale yellow liquid which was shaken vigorously on cooling and filtered. It had to be carefully set to ice bath temperature. This substance appeared to be air-dried, since the product is very oxidative to decompose in air. The analysis was volatile. The recrystallization from low boiling values corresponded almost exactly to a compound of the petroleum ether gave a crystalline product, the empirical formula C ₈ H ₇ MnO ₃ . Allyl manganese penta melted between 94.5 and 95 ° C. The carbonyl yield has the empirical formula C ₈ H ₅ MnO ₅ .

Example 4

Sodium manganese pentacarbonyl was made from 15.6 parts of dimanganese decacarbonyl, 175 parts of tetrahydrofuran and 4.32 parts of sodium amalgamated with 432 parts of mercury. After detaching of the supernatant solution of the amalgam, this was 3.8 parts of methallyl chloride in 44 parts Tetrahydrofuran added. The resulting mixture was left overnight under nitrogen and with exclusion of light ditched. A further 3.8 parts of methallyl chloride in tetrahydrofuran were then added. By Atmospheric distillation removed 142 parts of tetrahydrofuran. The reaction mixture was distilled under reduced pressure. The methallyl manganese pentacarbonyl transferred at a pressure of about 1 mm at 49 to 51 ° C. That Methallyl manganese pentacarbonyl was a light and air sensitive liquid at room temperature which solidified when cooled with dry ice. Yield 35 to 40%

Good yields of manganese pentacarbonyl compounds are also obtained if rubidium, Cesium and francium salts of manganese carbonyls used as reactants.

Example 5

100 parts of benzoyl manganese pentacarbonyl were heated to 100 ° C. under vacuum using an oil bath. At 90 ° C., the compound began to melt with vigorous evolution of gas. After the Gas evolution, the melt was cooled, whereupon solidification occurred. The evolved gas was collected and turned out to be almost pure carbon monoxide. The pale yellow obtained after cooling After sublimation, the solid had a melting point of 50 to 53 ° C. There were 78 parts recovered this yellow solid. Infrared and elemental analysis showed the compound to be was phenyl manganese pentacarbonyl.

Analysis for C ₁₁ H ₅ O ₅ Mn:

Calculated ... C 48.5, H 1.85, Mn 20.2;
found ... C48.9, H 1.95, Mn20.2.

Example 6

100 parts of acetyl manganese pentacarbonyl were placed in a sublimation unit and placed under vacuum pyrolyzed by gentle heating. When the compound melted (i.e. above 56 ° C) it was violent Observe gas evolution. As soon as the evolution of gas had subsided, the melt became cooled, whereupon solidification occurred. Sublimation gave 56 parts (66% yield) of methyl manganese pentacarbonyl obtained which had a melting point of 90 to 93 ° C. The material was identical with that obtained in Example 1.

The organic manganese pentacarbonyl compounds obtainable according to the invention are effective anti-knock agents in gasoline for internal combustion engines with spark ignition. B. 1.02 g of manganese as If methyl manganese pentacarbonyl is added to a gasoline with an octane rating of 80, the octane rating rises 94.3. If 2.01 g of manganese are added to this gasoline as methyl manganese pentacarbonyl, the obtained is Octane number at 100.

Claims (2)

PATENT CLAIMS: 1. Process for the preparation of organic manganese carbonyl compounds of the formula RMn (CO) ₆ , wherein R denotes an alkyl, aryl, aralkyl, alkaryl or an unsaturated aliphatic, optionally aryl-substituted hydrocarbon radical, characterized in that alkali metal-manganese pentacarbonyl compounds are treated with the above radicals introducing compounds which react with the alkali metal-manganese pentacarbonyl compounds React alkali metal salt formation, or that acyl manganese pentacarbonyl compounds are pyrolyzed with elimination of carbon monoxide. 2. The method according to claim 1, characterized in that the reaction is carried out at temperatures between about 20 and about 100 ° C in the presence of an ether, the upper temperature limit is below the boiling point of the ether used as the solvent. When the registration was announced, a priority coating was laid out. © 109 738/433 10.61