DE1668405C3 - - Google Patents

Description

characterized in that the rectification can be used to win the peroxides

planning of having carbonylated products Toggle ^{be ^!} S ™ _{fi dut Au} f e _was based on

ESSTSÄSSfiTuJ ^ u ^ dTefeLTm ciJS ^ U ^ fi

Pressure of 5 mm of mercury carried out 35

in order to increase the proportion of carbonylated products.

According to the invention, this problem is solved by 40 that the oxidation of turpentine oils at constant i d ^ ah before. 70 «> C ^^ F ^

40 that the oxidation de p

The invention relates to a method for continuous temperature in the vicinity. 70 «> C

naturally conducted catalytic oxidation of "^ and that the terpene notes for

mainly containing terpene hydrocarbons - undesirable decay "ν ^

the turpentine oils, borrowed to the cobalt abbey em by blowing in large air

gene and under ultraviolet radiation in countervates of nickel, vanadium,. ^

was added to a cobalt abyss with intensive penetration of niobium, rhenium, selenium and tellurium

mixing the feed as well as subsequent. Pildiin «.

Distillation and / or rectification for recovery On the basis of this suggestion, w.rddieMdung

of peroxides enriched in carbonylated products and that

Oxidation products of the terpenes. 50 terpenes enriched with carbonylated products

Promoted the use of oxides Terpcnoxyden in the veterinary, the direct P ^"3 ™ ³ ^ · ⁵ f comparable

Medicine and human medicine are well known. One gains are maneuverable without having to reduce the load

these oxides from turpentine oil, conifers and there- side of the content of certain η not water-

bintus excerpts and applies them e.g. B. in the form of soluble components additional substances

Add syrup, suppositories, coated tablets, injection solutions, 55 are The procedure is thus. "" J

Aerosols, capsules and the like are more effective; the products obtained in this way can

^ d ^ 'o? yditio ™ TOrgi.g of components that can be used directly due to their degree of purity

Turpentine oils can be found in very different reactions.

The distillation to the representation directly m the

tion required. To the sensitivity of the 60 therapy usable J ^erD 5 ^nox y * * J ^ ™:

initially forming terpene oxidation products, e.g. B. moderately above 75 ° C with emem D k _ w, n about

Peroxides or epoxies, compared to the different 10 mm cross silver column after the removal of the

most influences, such as B distilled water to distill the products that escape first.

take into account, is carried out with one from the German.

Auslegeschrift 1032 736 known method for 65 The rectification for the extraction of carbo-

Production of unsaturated terpene alcohols prenylated products enriched oxidized terpene

beaten! that one can use an oxidation mixture that can penen according to a further proposal by Erdurch Treating a pinene or 1,2-p-menthene discovery at a temperature between 72 C and

75 - C and at a pressure of 5 mm of mercury be performed.

The invention is described in detail below ! au``> rt. The first procedural stage to the intensive Oxidation of turpentine oils is by working together marked with the following conditions:

a) Continuous injection of large quantities

compressed air
b, exposure to light, especially ultraviolet radiation

c) Heating the oil of turpentine to around 70 ° C and maintaining this temperature

d) constant movement of the liquid with the help of a stirrer, for example in a Speed of 3200 rpm

c) Presence of cobalt abietate as an oxidation catalyst that you can get through the action of

represents! ^{Present of Wasserstoftsuperoxvd} t) addition of one or more derivatives of Nkls, vanadium, tungsten, tantas, niobes,

'Hp Tt Jr ^zum _v ^K f ^altablfe -? ^ IRS $ T Γ ^r improving katalyüschen effect and BeschleumgungdesZerfallsunerwunschterHydroperoxyde.

These conditions favor the oxidation processes with simultaneous destruction of the undesired ones Hydroperoxides, so that their subsequent chemical removal is not necessary. About it In addition, a maximum yield of terpene oxides is achieved in a very short time. The process flow is finished in less than 15 hours. .

As a surprising result, one can also see that under the effect of the intense Oxidation with simultaneous decomposition of the undesired hydroperoxides, thermal decomposition processes are considerably reduced in the course of the distillation and that the acidity of the products produced and the amount of residues remaining in the still remains minimal. From it it follows that a single distillation is sufficient to produce preparations that can be used directly in pharmacy.

For this reason, the second process stage consists of a simple fractional distillation of oxidized turpentine under reduced pressure. The untransformed alpha and beta pinene escape first during the distillation, and the fraction that is above 75 ° is collected subtracts a pressure of 10 mm cross column of silver.

The product presented in this way can be used directly in any pharmaceutical form with the exception of injectable solutions, so that the known methods on chemical Can save paths necessary cleaning processes.

The third process stage is used to prepare practically neutral terpene oxides, those with carbonylated ones Derivatives are enriched and can be used directly in pharmaceutical therapy it in its pure state or in combination with other preparations. The application of the pure or Combined end product is in any form, including injectable solutions for administration by intramuscular or intravenous route.

For this purpose, the fraction separated out in the course of the second process stage is between 72 and 75 ° C rectified under a pressure reduced to 5 mm of mercury. Man In this way, e maintains a product with a degree of purity that is no longer chemically post-treated

ernndungsgemaßen method can ^thus be ^{a e "f an} L ^{ache 'el sch."'} - economic and ^{sicnere "else} Terpenoxyde produced which can be enriched with karbonylierten products or ^{mcht U" d dnek)} '^{"P harmaz} ^ ^t's! Therap.e are usable

According to the invention, the oxidizing process of the ^Ter Penole ^at gleichze.tiger destruction of the Hydro-Γ ° ^ΧΥ verstärkturd g, calibration time, the for this oxy-

^datio " ^ss ^ ^{fe er} / P ^rde , ^rIlc _A ^h ,, ^{e Zeuda} ™ ^dadl f ^ ¹¹ !" gert that the KobaU Abietat has one or more denominations

* at ^{the foI} 8 ^{ends metals or} semi-metals are added at _ao * _{; κ} ^ _{vanadium>tungsten> tantalum} niobium, rhenium, selenium or tellurium. These take over the role ^of accelerators (promoters) in the catalytic effect of the abietate.

_Are "Assuming a terpene oil (called Essence _{de Bordeaux <() from> in} ^ m as components _{(_)} ,. p _inen. (L ^ ^ .p _and traces of lime ^ _{tna, th} \ _g g _{depends on you} fa _gmdsT mix:

Compound carbonyls (25%)

Verbenone 18 to 20 ⁰ O

Myrtenal 5 to 6 per cent

Hydroxyls (52%)

Verbenol 40 to 45 »/ 0

Pinocarveol / '°

Different

PineDoxvd 1

Campholene aldehyde ". '.". ".'.! '.'. '.'.) ^{4 bU 5} ° ^{/ o Light} carbon compounds .. 3 to 4 · /. Heavy carbon compounds

(Sesquiterpone) 10%

Sobrerol 1%

Unknown 1%

Residues 3%

This essence or this oil is according to the invention at a temperature of 70 ° C by blowing in subjected to intense oxidation of large quantities of compressed air, and that at the same time Exposure to ultraviolet rays and one of the aforementioned catalysts, one or more Accelerators (promoters) are added, which are made from derivatives of nickel, vanadium, tungsten, tantalum, Niobium, rhenium, selenium or tellurium exist. All substances become in the course of the oxidation thoroughly stirred, for example with the aid of an agitator rotating at 3200 rpm.

At the beginning of this oxidation stage, hydroperoxides are formed, starting from the ethylene compounds, and peroxides, starting from the aldehydes formed under these conditions or Ketones. The peroxides can act on the camphotene aldehyde and form radicals lead, so that ketones of the type of camphor or dihydiocamphenone are formed in very small amounts.

It is found that in addition to the acceleration

of the oxidation processes and the decomposition of the hydroperoxides, an equalization of the reactions occurs, resulting in an improvement in efficiency and leads to a steady course of the procedure.

After the oxidation are in the course of the second process stage, in which under reduced pressure a fractional distillation is carried out, which reduces the processes of thermal decomposition in such a way that there is very little residue in the distillation vessel remain. As is common practice, products that escape at the beginning of the distillation contain Pinenes not yet oxidized and minor ones formed in the course of the previous oxidation stage Amounts of formic acid and acetic acid are excreted.

A fraction now arises which ^{distills above 75 l} C under a pressure of 10 mm of mercury. The effect of the above-mentioned catalysts with one or more of the promoters mentioned means that the scrap of the substances initially escaping in the distillation remains to a minimum. In this way the following substances are created: Verbenone, Myrtenal. -Vbenol. Myrtenol-Pinocarveol, Pinene-Epoxy. Kampholene aldehyde, while the resin-forming terpene products unsuitable for pharmaceutical use remain in the still.

With the method according to the invention can be a very high speed of conversion of the oils in oxygenated terpene derivatives. a more complete conversion, a constant efficiency and a major amount of in pharmaceutical therapy following distillation directly usable products.

Claims (2)

1 2 - ■ ■ »c with an acidic gas such as S h ^ eS wurSc, treated with an aqueous alkali and the cnt- 1. A process for continuously guided kata- tiouimuieb ^"lu" _{ioilsnroduktc} by fractional lytic oxidation of mainly terpene 5 standenen ^"r _{The bci} this process corresponds' hydrocarbon containing Terpentinölen ^DCSL ° f ⁿ _p rawde need in a second Siafe by blowing large amounts of air and subject to re '*; ultraviolet irradiation in the presence to be eliminated _tionsmitle j _s, one with Hilie a - ₀ ^ _{their since the} p _he oxyde with cobalt Abietats with intensive mixing result ergeioei ™..' _{o "£} occurring Teivpeder feed as well as by subsequent io den at ^R ^ ^u ^ " _{! lair} ^ _e n. Distillation and / or rectification for the production of ^ ^ _known processes in accordance with the wetting of carbonylated products 375 829 for the recovery of enriched oxidation products of the terpenes, French r <~ , *, _{derivatives from} Terpend adurchgeke η η ζ eich η et that the oxy- of hydroxy1- ^ and ^ _en -> _{essential oils in opposition} . dation of the turpentine oils at a constant temperature 15 konk.iwas..rsi - _ie blowing air in the vicinity of 70 ° C is carried out for a ^ taiysaio. ^ _Ange ließend the oxy and that the Terpentinölen to accelerate and ^S f '^ ™ ° separated _by distillation, wähdes decay unwanted hydroperoxides ^DATL to-? ⁿ ? P ^Iodl * ^tl ' _R S _on svcrlauf not covered Οι in addition to the cobalt abietate one or more rend uas vorr' Kejkiio ^ ^ ^ derivatives of nickel, vanadium, tungsten, 20 the first seduced ^S «J" ^ _{before Trough all} tantalum, niobium, rhenium, selenium or tellurium ^{B smoke} ^ ^k ^ _r f _a ^ _SZ e _itd except impaired, for be attached a "c gr" u "- J _v j _at ionsgases is first.. 2. The method according to claim 1, characterized in that the blowing in cks O ^ dat 1 S ^ _ms indicates that the distillation to represent 1 1 mouths ang, vv raut α ^ ^^ ^^ directly usable in therapy terpene oxides 25 further .4 Stunotn _slu - _{the Ternp} perature above 75 ° C at a pressure of about 10 mm by Zugabt dg _"h ^ j _be