DE1950935C3 - Process for the production of alpha glycols - Google Patents

Description

The tjon temperature is generally between 50
ynd 200 ⁰ C, preferably between 80 and 130 ⁰ C.

The reaction is at a pH equal to or In a tube are tertiary butyl hydroperoxide,

less than 7 carried out The yields are water, butene (2) and molybdenum naphthenate J ^a ^ ¹¹ "

increased when given in a slightly acidic medium 5 zol solution as a catalyst. The molar

is being worked on. The proportion of molybdenum naphthenate is 4 · ΙΟ " ⁸ Mo

In the method according to the invention (calculated as metallic molybdenum per molecule

a catalyst is used. Tertiary butyl hydroperoxide is used as a catalyst.

preferably a Ti, Cr, Se, Zn, Nb, Ta, Te, The proportions of the various reactants

U-, W- and / or Re-connection used, vor- io are as follows:

but preferably a vanadium or molybdenum mmol

Catalyst. As a rule, organic salts are tertiary butyl hydroperoxide IM

of molybdenum or vanadium, such as water 35.3

Naphthenates, stearates, octoates, carboxyl compounds, butene 42.8

fertilize. Preferably molybdenum or Vana 15

diumcarboxylate and molybdenum or vanadium The ratio of olefin / hydroperoxide is therefore the same

carboxyl compounds are used, but the invention is 3.7, the water / hydroperoxide ratio is 3.

application is not limited to these compounds. It the tube is sealed and then under

_{Instead of this, Mo, O 3} , can also be used as catalysts to bring movement to 120 ^° C. in an autoclave

MoO, MoO ₃ , molybdic acid, molybdenum chlorides and ao These conditions are maintained for 1 hour.

oxychloride, molybdenum fluoride, molybdenum phosphate. After cooling down, the remaining amount of gas will be

Molybdenum sulfide can be used. In the same way, the various components can and will be measured

NEN molybdenum-containing heteropoly acids and / or their liquid phase is determined. The result is

Salts in the process according to the invention use the following reaction products:

find application, also analog or similar compounds 35 mmol

fertilize the other metals mentioned above. Glycol 9.6

Finally, powdered, metallic epoxy 0.3

Molybdenum can be used as a catalyst. Butene- (2) (not converted) 10.1

There must be such an amount of catalyst in the case of tertiary butyl hydroperoxide

Reaction according to the invention are used that 30 (converted) IM

the proportion of metal atoms in the catalyst each

Molecule of hydroperoxide above 10- *, preferably The hydroperoxide conversion is therefore g ^ icn

between 0.002 and 0.03. 97.8 mole percent and the glycol yield based on

It is also advantageous if the hydroperoxide of the converted hydroperoxide is 85.3%.

limit the concentration in the reaction medium so that 35

that the olefin compound is present in excess. _R. . .,

Preferably, the amount of hydroperoxide does not exceed B e 1 s ρ 1 e
30 percent by weight of the mixture consisting of

Hydroperoxide and olefin compound, namely unab- Cyclohexene is according to the invention for 2 hours

depending on any inert solder that may be present on tertiary butyl hydroperoxide at 90 ⁰ C in counter-

solvent. Preferably, said hydration of vanadium naphthenate is used as a catalyst.

peroxide content between 10 and 15 percent by weight, left to act. There are about 9 · 10 ^-3 V atoms per

based on the mixture, consisting of hydro- Molecule tertiary butyl hydroperoxide present. the

peroxide and olefin compound. The following groups of respondents are involved:

The reaction time is not critical. It can be 45 mmol

vary within wide limits, but in all tert-butyhydroperoxide is 27.8

mean the reaction is allowed to proceed so long, _v ser 555.3

until the hydroperoxide has completely disappeared. hex 39.6

On the other hand, it is advantageous to always use an excess

to have an olefin compound, which 50 Nuu 'kr reaction is the organic phase through

as a diluent for the hydroperoxide an- üifo ..- ographie analyzed for cyclohexene and

see is. by chemical analysis (periodic acid) on the

The water can be examined in exactly stoichiometric deten diol. 16.3 mmol of tert-butyl

Amount to be added, but the hydroperoxide to be added is 11.5 mmol of cyclohexene

The amount of water is also not critical, and you can convert 55, and 10.5 mmol of glycol as well

Add excess water. The excess water 0.3 mmol of epoxy have formed,

at the end of the reaction it can be used to build the hydroperoxide has converted to 58.6%,

deten oxygen-containing products by means of decane and the yield of glycol, based on the

The ratio of the unconverted olefin compound-converted hydroperoxide is equal to 64.4%.

fertilize to separate which in a new reaction 60

cycle can be used. _. . . .

The method according to the invention is particularly suitable
special for the production of glycerin from allyl alcohol, of butanediol- (2,3) from butene- (2), by Hs glycerin is produced from allyl alcohol. Cyclohexanediol from cyclohexene and from 2-methyl-65 28.4 mmol of cumene hydroperoxide, butanediol (2,3) from isoamylene. 556.6 mmoles of water and 39.8 mmoles of allyl alcohol

The following examples serve to explain when entered into a pipe,

the invention. After closing the tube, these

Substances left to react for 1 hour at 120 ^° C. and with movement. The reaction products are then analyzed: 11.17 mmol of cumene hydroperoxide and 17.07 mmol of allyl alcohol are converted. 10.55 mmol of glycerine and only 0.62 mmol of the corresponding epoxide were formed.The glycerine thus formed represents 94.4% of the hydroperoxide converted during the reaction.

Examples 4 to 8

2-methyl-butanediol- (2,3) is oxidized synthesized from isoamylene with tert-butyl hydroperoxide using molybdenum naphthenate as a catalyst. The details and results of the experiments are summarized in the table below.

5 example 7th 8th 4th 120 6th 100 120 90 1 100 4th 1 1 20.97 1 64.36 25.95 27.86 93.27 56.20 75.34 114.05 38.24 0.1 75.12 0.1 0.1 0.1 419 0.1 155 77.80 553 154 CH ₃ CO ₁ H 0 20.27 CH ₃ CH ₁ H 59.14 25.62 15.34 0.06 37.33 0.35 1.20 0.35 2.67 1.84 8.81 2.12 2.01 16.21 5.25 49.98 22.32 12.98 96.6 30.24 91.9 98.72 55.1 80.0 66.4 84.5 87.10 84.6 81.0

Temperature ( ⁰ C) Duration (lockers) Starting materials:

tert-butyl hydroperoxide (mMcl)

2-methytbuteh- (2) (mmol)

Molybdenum naphthenate (mmol)

H _t O

acid

Results: Converted tert-butyl hydroperoxide

Epoxy formed (mmol) Carbonyl formed (mmol)

2-methyl-butanediol- (2,3) (mmol)

Conversion of tert-butyl hydroperoxide yield of diol (% mol)

Examples 4 and 5 show that with increasing temperature, the conversion increases at the expense of the yield. Examples 6 and 7 make it clear that when working in a slightly acidic medium, very high diol yields can be achieved. The conversion obviously increases with the reaction time However, the diol yield remains unaffected.

Finally, Example 8 shows that a high conversion of tert-butyl hydroperoxide and At the same time, a very high diol yield can be achieved if with an excess of olefin (based on the hydroperoxide) and with a small amount of water.

Example 9

2-Methyl-butanediol- (2,3) is produced by the oxidation of isoamylene with tert-amyl hydroperoxide, i.e. with a hydroperoxide having the same carbon structure as the oxidized olefin, synthesized under the conditions according to the invention.

The reaction is carried out with the following proportions of reactants:

mmol

tertiary amyl hydroperoxide 62.3

Isoamylene 72.9

Molybdenum naphthenate 0.25

H O _t 140

The reaction medium is adjusted to a slightly acidic pH by adding Acetic acid.

After 4 hours at 100 ⁰ C 54 tertiary mmol Amylhydroperoxyd are converted and the following substances educated:

mmol

tertiary amyl epoxide 0.35

Methyl isopropyl ketone 8.02

2-methylbutanediol- (2,3) 40.35

87% of the hydroperoxide involved has thus been converted, and the diol yield (% mol), based on the converted hydroperoxide, is 74.5%.

This reaction enables the synthesis of 2-methylbutanediol- (2,3) without consumption of isoamylene. It can be assumed that isopentane, which is oxidized to isoamylhydroperoxide, which acts on the isoamylene to give the 2-methylbutanediol (2,3) and the tertiary amyl alcohol. The latter can be converted into isoamylene by simple dehydration, which is returned to the isoamyl hydroperoxide-operated oxidation stage.

The same reaction cycle is possible with all olefins if they are the same with the hydroperoxide Carbon skeleton are oxidized.

Claims (5)

To hydrolyze oxides, which correspond to the patent claims to be won: «-Glycols eat. It has also already been proposed to convert olefins directly to α-glycols 1. Process for the production of "-glycols to oxidizeea, namely by means of hydrogen peroxide, by reaction of an organic hydroperoxide 5, the yields are always a: nr low with an aliphatic or alicyclic olefin, (S. B. M s kh t i e ν, A. A. B a k shi-Zad e and which may be substituted by hydroxyl groups S. I. Mekhtiev, Azerbaijan, Khun. Zer 1960, can, characterized in that No. 6, 33-8, according to C.A. 55, 22 113). the reaction is carried out in the presence of water in order to seduce the yields in the oxidation will. ίο improve, is suggested by different sides 2. The method according to claim 1, characterized in that the olefins are oxidized by the draws that in the presence of a catalyst, hydroperoxide exists in an anhydrous medium and in the ocean from a Ti-, Cr-, Se-, Zu-, Nb-, Ta-, wart of boric acid or boric acid anhydride by-Te-, U, W and / or Re connection, preferential feed. In the latter case, the first thing you get is the wise in the presence of a V- and / or Mo-Ver 15 boric acid ester and only then the «-Glycols commitment, work is done. even by hydrolysis. So it must be with this 3. The method according to claim 1 or 2, thereby driving an intermediate product, namely the borate, characterized in that in the liquid phase in counter-forms, which is then to be hydrolyzed. Was such a catalyst tonnage worked the object of the invention is to provide a is that the number of catalyst metal atoms ao process which the immediate oxidation of per mole of hydroperoxide involved above 10 "* aliphatic or alicyclic olefins by means of hydroliegt, preferably between 0.002 and 0.03, peroxides to «-Glycols, with amounts to. increased yields. 4. The method according to any one of claims 1 to 3, this is achieved according to the invention in that marked in that with such as the reaction is carried out in the presence of water Hydroperoxide concentration is worked that is. Surprisingly, it has been found the ratio of hydroperoxide to the sum that, contrary to the general view, the question of Hydroperoxide and olefin carried out below 30Ge- borrowed reaction in an aqueous medium Weight percent, preferably between 10 and can and that under these conditions 30% by weight, 30 ° glycols are formed, but not epoxies 5. Process according to one of the above or esters as in the known processes.
Claims, characterized in that with the process according to the invention, all reaction mediums can be oxidized to a temperature between aliphatic olefins to «-Glycols, 50 and 200 ⁰ C, preferably between 80 and both the normally gaseous, 130 ⁰ C, is kept . 35 such as ethylene, propylene and butenes, as well as the liquid olefins and even the high molecular weight solid olefins whether these olefins are branched or are not branched or are «-olefins acts or not. Alicyclic olefins can also 40 are oxidized to «-glycols in the manner according to the invention, such as cyclohexene, the cyclooctene, the cyclododecene. Likewise, according to the invention, all aliphatic or cyclic The invention relates to a process for seeing di- and poly-olefins being oxidized, wherein Production of -glycols by reaction of a 45 it does not matter whether the double bonds organic hydroperoxide are conjugated with an aliphatic or not. or alicyclic olefin, in particular one by Furthermore, according to the invention, hydroxyl groups substituted olefin. also drive olefins which are oxidized by In this context, α-glycols are used to denote hydroxyl groups (unsaturated, i.e. olefinic, alcohols) only the actual glycols are substituted with two adjacent 50). Bare carbon atoms bonded hydroxyl groups can be used according to the invention are all hydroperoxides stood, but in particular also those of it by all those compounds which the structure substitution of a hydrogen atom by a white formula ROOH, where R is an alkyl, tere hydroxyl group-derived derivatives. Alkenyl, aryl, alkaryl, aralkyl, cycloalkyl, The «-glycols are organic cycloalkenyl radicals or a similar radical which represents compounds in many ways, which may also be useful, both as end products and as functional groups. For example, tertiary is also used as intermediate products in syntheses. Butyl hydroperoxide, tertiary methjrl-butyl hydroperdie diols are used as antifreeze agents, oxide, cyclohexyl hydroperoxide, ethylbenzene hydroda they have a high boiling point and a very low 60 peroxide, cumene hydroperoxide.
Show freezing point. The reaction is carried out in the liquid phase. As synthesis intermediates, they are very If the olefin at reaction temperature is gaseous reactive substances. In particular, if it is, then work is carried out with sufficient pressure, as a starting material in the manufacture of plastic so that the mixture is completely in a liquid state resin is of great importance. 65 exists. There are already many methods of preparation The reaction can be carried out in the presence of a solvent known from «-Glycols. One of the most widespread means to be carried out is that of the preposterous Method consists in making those ephandenen reactants inert. The Rea-