DE1804071C3 - Process for the preparation of butyn- (1) -one- (3) - Google Patents

Description

50 Torr, remove from the reaction mixture, wherein it is advantageous to the reaction product by a

₂₅ to subtract the reflux coolant at about 0 to 5 ° C.

This also changes the reaction mixture withdrawn butynol-water azeotrope near-

From the Journal of the Chemical Society. London, condensed too completely on the reflux condenser and 1946, p. 43, it is already known that butyn- (1) -one- (3) can be returned to the reaction vessel, while this is distilled over by adding sulfuric acid and a stoichio- 30 butmone and in a frozen Vormetriscrt.n amount of chromic acid can be collected to an aqueous layer. Order a particularly pre-solution of butyne- (1) -ol- (3) at room temperature! in that manufacture. According to this process, however, the butynone is obtained by removing 40 " _o .

In addition, 1 000 805 35 mixed has been removed from the German patent application. Come as inert extractants described, butyn- (l) -one- (3) on electrochemical e.g. ether, aliphatic, optionally Ways to produce by anodic oxidation of butyne- (l) -oI- (3) chlorinated hydrocarbons and especially aro. According to this process, too, the matic, optionally nitrated or halogenated Butyn- (1) -one- (3) only in moderate yield he hydrocarbons into consideration, it being expedient keep. 40 extractants with boiling points above

A method of producing about 80 ° C was now used. For example, butyn- (l) -one- (3) by oxidation of an aqueous η-hexane, cyclohexane, hexamelhylene oxide, solution of butyn- (l) -ol- (3) with chromic acid and dibutyl ether, benzene, toluene, chlorobenzene , Found trichlorosulfuric acid, which is characterized by benzene and in particular o-dichlorobenzene. The existence of a 10 to 40 percent strength by weight aqueous 45 traction agent can be withdrawn during the reaction with the butynone formed continuously at temperatures between 15 and 50 'C with an approximately 45 to 120 weight and to the extent that it is withdrawn, replaced by a percentage excess of chromic acid, based on the new extractant. However, it is possible to oxidize the hydroxyl group to the keto group, and to add all of the extraction medium to Bc and sulfuric acid at a concentration of 30 to the start of the reaction. After separation, at least 30 percent by weight, based on that of the aqueous phase; the butynone can be obtained from the organic phase by means of a distill mixture of chromic acid and sulfuric acid, oxylation. dated and the butyn- (1) -one- (3) formed in accordance with the stipulation, however, the solution of the butinone can be continuously removed from its formation. An advantageous one in the extractant directly for subsequent reactions

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indicates that the bulin- (l) -on- (3) formed with an extractive agent is the oxidation in the

removed with the help of an inert extractant. generally carried out at atmospheric pressure.

According to the process according to the invention, the butyn- (l) -one- (3) is a valuable intermediate

Butyn- (l) -one- (3) in good to very good yields for the production of dyes and optical receive. 60 brighteners.

In accordance with the method of the invention, the chrome die parts mentioned in the following examples

acid and sulfuric acid at 10 to 40 parts by weight are parts by weight. They relate to room lines

percentages, preferably 5 to 25 percentages by weight, such as kilograms to liters, the percentages mentioned are

aqueous butyne- (1) -ol- (3) solution added. The water weight percent,

The remaining butynol solution can be neutral. However, it can be 65 B e i s η i e I 1

be advantageous if the submitted aqueous solution ^p

has an acidic pH. To adjust this In a reaction vessel with reflux cooling,

acidic pH can be any inert inorganic thermometer and inlet is provided with a

3 4

A mixture of 420 parts of butyne- (l) -ol- (3), 500 parts contains 45 parts of a 19.6% butyne- (l) -one- (3) -

Water and 2ÜO parts of concentrated sulfuric acid solution, corresponding to a yield of the end product

submitted. The temperature in the reaction vessel, that of 76% of theory.

is in a water bath, is set to 20 to for comparison in place of the one presented

Maintained 27 C. At a pressure of about 30 Torr 5 butynol-water-sulfuric acid mixture 408 parts of a

is allowed in a Mi- 55 weight percent butyne- (1) -ol- (3) solution within 4 to 5 hours and

A mixture of 708 parts of sodium dichromate, 993 parts, the procedure otherwise described above is obtained

Water and 1160 parts of concentrated sulfuric acid, a yield that is 21% of theoretical.
(D - 1.84) flow.

The reflux, cooled with water from 0 to 5 ° C, is ρ ie I 4
cooler is connected to the vacuum pump via a deep-freeze reservoir. Under the reaction conditions The procedure described in the first paragraph of Example 3 is the one described in the reflux condenser, almost 432 parts of toluene being used instead of the o-dichlorobenzene butynol-water azeotrope. 587 parts are obtained continuously condensed, and the condensate flows back into the reaction mixture of a 26% strength by weight butyn- (1) -one- (3) solution. The butyn- (l) -one- (3) is not retained by the reflux condenser, corresponding to a yield of 70% of theory

and condensed in Example 5 cooled to -20 to -30 ° C
Frozen template. After the addition has ended, the mixture is stirred

another half an hour in a water bath

temperature of 40 C to achieve the total butynone reaction conditions 2600 parts of the oxidation

to drift into the freezer. In the original stock solution according to Example 2 to form a mixture

312 parts of 97 percent by weight Bu- of 408 parts of butyn- (1) -ol- (3) (55 percent by weight),

tin- (l) -one- (3) collected, corresponding to 301 parts of 500 parts of water and 325 parts of o-dichlorobenzene

Butinone (calculated 100%). From the reaction as and works as described in Example 2 on. Man

mixture are obtained by distillation at 40 to 60 "C 0I6 parts of a 32.5% butyn- (l) -one- (3) -

in total 82 parts of butyne- (l) -oI- (3) as an aqueous solution, corresponding to a yield of 77% of the

Get mixture. The yield of butyne- (1) -one- (3) theory.

is 92% of theory, based on converted. 325 parts of o-dichlorobenzene are substituted for

Butyne- (1) -ol- (3). _3O 215 parts of toluene in and vc, - goes as described,

Example 2 this gives 391 parts of a 43.7% strength Butm- (l) -

on (3) solution, corresponding to a yield of

In a reaction vessel, a mixture of 78% of theory.

408 parts of 55% by weight Bulin- (1) -oI- (3), example 6
1000 parts of water and 200 parts of concentrated 35

Sulfuric acid together with 867 parts η benzene added to the mixture of 612 parts by weight. Percent butyn- (1) -ol- (3), 750 parts of water and, in the course of 2 to 3 hours, 2600 parts of 678 parts of o-dichlurbenzene are added in the course of a mixture of 2000 parts of ice, 2000, with stirring and external cooling Parts of concentrated 2 hours -inter the trated sulfuric acid described in Example 2 (D = - = 1.84) and 1200 parts of 40 conditions 3900 parts of oxidizing stock solution (ge-sodium dichromate ("oxidizing stock solution") to 3example 2) and works ti't reaction running. The temperature of the mixture reaction mixture, as described in Example 2, on. The temperature is 25 to 30 ° C. After the feed has ended, 872 parts of a 28.2% strength butyn- (1) -one- (3) are obtained. Cooling and stirring for 2 hours in room solution, corresponding to a yield of 84% temperature according to. The aqueous theory is then separated.

Sulfuric acid ί hrom (III) sulfate solution as the lower one replaces 678 parts of o-dichlorobenzene

Layer off and receives 1025 parts of a 17.1 weight-580 parts of chlorobenzene and otherwise proceeds as

percent butyne- (l) -one- (3) solution (determined from described, so you get butyne- (l) -one- (3) in one

the carbonyl number), corresponding to a yield of yield of 81% of theory.
80% of theory, based on the butyne- (l) - 50 used

ol- (3). The characterization of the end product is B is ρ ie 1 7
follows from his 2,4-dinitrophenylhydrazone

Melting point 180 to 181 ° C. In the mixture of 408 parts 55 weight percent

For comparison, instead of the centiger butir .- (1) -oI- (3) solution submitted, 1000 parts of water are used

Butynol-water-sulfuric acid mixture 408 parts of 55 and 650 parts of o-dichlorobenzene are left under the

55 percent by weight butynol and instead of the conditions mentioned in Example 2, 2630 parts

2-600 parts of oxidation stock solution, 1450 parts of a chromosulfuric acid of that described in Example 2

and if you proceed as described, you get the composition and work according to the example

Butyn- (l) -one- (3) only in a yield of 39% of game 2. 813 parts of a 20.1% strength are obtained

Theory. 60 butynone solution, corresponding to a yield of

B e i s ρ i e 1 3 75% of theory.

For comparison, instead of the 2630 parts

For a mixture of 408 parts of 55gcwichts- chromosulfuric acid according to Example 2, a mixture

percent bulin - (!) - oI- (3), 500 parts of water, of 560 parts of sodium dichromate, 2140 parts of water

200 parts of concentrated sulfuric acid and 650 parts of 65 and 529 parts of concentrated sulfuric acid and

O-dichlorobenzene is 2600 parts of the procedure as described in Example 2, so you get only 700 parts

Oxidation stock solution described is added. an 8, l% butinone solution, corresponding to a

The procedure is as described in Example 2 and the yield is 25% of theory.

Example 8

The mixture is left under the stated in Example 2 Reaktionsbcdineungen to the mixture of 408 parts 55gewichtspr '"- ntigem butyne (l) -OL- (3) un 500 parts of water 3ö2Teilen trichlorobenzene 3160Teile the Chromsc'nwefelsäure according to Example 2 and ^act..! works up as described in Example 2. 530 parts of a 31.6% strength butynone solution are obtained, corresponding to a yield of 77% of theory.

Use only 480 parts instead of the 3160 parts of chromosulfuric acid according to Example 2 and proceed otherwise as described, mar receives butinone- (l) -

on- (3) only
Theory.

in a yield of 50 "· ,, the

Example 9

With 2010 parts of the chromosulfuric acid according to Example 2, the mixture of 408 parts is 55 percent by weight Butyne- (l) -oI- (3), 500 parts of water and 385 parts of n-dibutyl ether among those in Example 2 ίο the specified reaction conditions oxidized. Man obtained after work-up 538 parts of a 28.5% strength butyne solution, corresponding to a yield of 70%. the theory.

Claims (2)

niche acids can be used. Appropriate patent claims: however, if sulfuric acid is used. In the mixture used for the implementation 1. Process for the production of butyne-Π) - from chromic acid and sulfuric acid, the on- (3) by oxidation of an aqueous solution is 5 sulfuric acid concentration preferably 35 to M) Gevon butyne- (l) -oI- (3) with chromic acid and sulfur weight percent, the chromic acid concentration is pre-acid, characterized in that preferably 15 to 25 percent by weight. The Chromman a 10 to 4Öeewichtsprozentiee aqueous acid is used in amounts, based on butyne (l) -OL- (3) -Lösun _e ~ at a temperature between the oxidation of the hydroxyl group to the keto group, ^c 15 and 50 C with a ~ m about 45 to 120 weight percent, preferably between 80 to 120 percent by weight, excess chromic acid. attracted to the oxidation of the hydroxyl group to The implementation is preferably at lempe- Keto group and sulfuric acid with a concentration between 20 and 40 ° C.
mourn by at least 30 percent by weight, to the butmon formed from the reaction zoeen to remove the mixture of chromic acid and 15 mixture, one can, for example, a Sulfuric acid, oxidized and the BuUn- (I) -stream of an inert gas, for example air, nitrogen- (3) According to the measure of its formation, substance or carbon dioxide is continuously removed through the mixture. "direct or suck through and which the butir.on with- 2. The method as claimed in claim 1, characterized in that gases are passed through a deep cool template or a draws that the butyne- (l) -one- (3) 20 formed is passed through the absorption vessel. Preferably will with the help of an inert extractant, however, the butmone formed is removed by application separates. of reduced pressure, suitably from 20 to