DE1768299B2 - - Google Patents

Description

I 768 299 if

3-4

The dispersion of the deuterium gas in the so-

Hydrocarbon liquid is accomplished, intopene effects determine.

the deuterium through a porous glass For a more complete understanding of the invention

disk in the stationary catalyst layer, which is a method according to the figure,

Grain size of about 0.42 to 4.00, preferably 5, in which a device is shown that is suitable for

0.59 to 2.00 well, at the rate of performing the method of the invention

preferably 40 to 50 cc / min. can flow in, is suitable. A reaction chamber 10, which with a

although there are also higher or lower flow buoys constructed from a porous pane of glass 12

speeds are applicable. If you leave it equipped, it is put on with the charcoal

Deuterium gas fed continuously for 30 to about 5000 hours. The headboard is

flow through the liquid hydrocarbon, provided with the thermometer 11, which is in the open

the period of time is inserted with the number of carbon atoms tion 13, which is obtained by removing the

in which the hydrocarbon, the degree of its un- thermometer, can also be used as a sample opening

saturation and the percentage of deuterium that can. The lower part of the reaction vessel 10 has

to be introduced into the hydrocarbon, 15 has a section 16, the diameter of which is larger

varies. is than that of the reaction vessel 10, so that the

• As soon as the reaction has ended, the deute catalyst 14 can be kept practically stationary, A deuterium gas line 18 is provided with a flow path, depending on whether the deuterated hydrocarbon regulator 20 is equipped to control the flow of the Deustoff Is liquid or solid at room temperature, isolates 20 terium gas through the porous glass surface 12 to will. When the deuterated hydrocarbon at regulate. The upper TeU of the reaction vessel 10 Room temperature is liquid, it is equipped with a low- is equipped with a line 22, which the verseende Hydrocarbon, e.g. B. Penian or hexane, bond with a not shown. Reflux condenser, extracted, the solvent is prepared by distillation which is arranged on line 24. Practically distant, and the deuterated hydrocarbon becomes 25 table through the entire reaction vessel 10 and the Ab Purified distillation in vacuo. When the section 16, which contains the catalyst 14, stand in Deuterated hydrocarbon at room temperature in an oil bath 26 fixed to that temperature it will also be provided with a low-boiling point, which is necessary in order to z. B. pentane, extracted to liquefy the soldered Kohlf waterploF and on solvent is removed by distillation, and the 30 to bring the desired reaction temperature. That solid residue is obtained from a low-boiling oil bath 26 can alternatively also be carried out by electrical Solvent, such as pentane, recrystallized. Elements are replaced.

Although those for the production of certain deuterated hydrogen atoms are very stable and have proven to be particularly useful in radiolytic experiments, the time span required as compounds can be about 3 weeks in 35, petrochemistry demands the method in investigations as soon as it works the micro- very little maintenance, except for the periodic biological oxidation, the nuclear magnetic resonance. Taking samples for analysis.
in the case of mass spectrometric and ultra-red spectro Another advantage of the mixing according to the invention. Working and as a solvent at high driving is that unsaturated hydrocarbon temperature has been proven. In particular, the substances according to the invention, such as 1,5,9-cyclododecatriene and trans-stilbene, result in the compounds obtainable in accordance with the if necessary, finally their complete saturation of the deuterium nuclear magnetic resonance, result in deuterated counterparts. Probably manure. In the investigation, too, the unsaturated starting hydrocarbon is reduced to the spectrometric cracking processes, and in the first with deuterium to the saturated, partial investigation of the influence of the presence of dcuterized compounds, which then, deuterium, is used in these processes. as shown in the following equations 1 and 2, By means of comparative methods, an exchange reaction can be subjected to this:

D ₂ iPd / 'CD ₂ ; Pd; C

rfi.i D ₃ ; Pd IC \

_ ■ ' D ₂ ; Pd ic _y

^{C >} 185 ⁰ C

Another advantage of the process according to the invention is that under the conditions of Exchange, neither cracking nor isomerization of the substrate is observed. The won According to vapor phase chromatography, deuterated products are homogeneous and possess sharp melting points and regular boiling points. Furthermore, it was found that the mass spectra confirm the structures of the fully deuterated compounds. However, epimerization occurs asymmetric carbon atoms, as shown by the results obtained with decalin in Equation 3 will be shown:

»5

(3)

Starting from either pure cis- or trans-decalin, an equilibrium mixture of the two isomers is obtained, which contains about 92% trans-decalin-d ₁₈ and 8% cis-decalin-d ". These equilibrium values obtained at 448 ° K agree well with those given by A 11 i η ger inter alia in J. Chem. Soc, Vol. 81 (1959), p. 4080. These authors measured the cistrans equilibrium catalyzed by 5% Pd on carbon in a hydrogen atmosphere at 531 "K and found the equilibrium composition to be 8.96% cis-decalin and 91.04% trans-decalin.

example 1
n-hexadecane-d ^,

With the deuterium inlet opening completely closed, 3.5 g of 2% Pd on activated carbon (particle size 0.59 to 2.00 mm) and then 2.5 g of catalyst (particle size 2.00 to 4.00 mm) and a layer of glass beads were on the way Introduced into the cell through the thermometer opening. 32 g of n-hexadecane were added, the thermometer insert was installed in the cell, and a cooling system with water cooling was attached to the radiator arm and provided with an outlet tube for escaping deuterium gas. Then, deuterium gas was passed through the regulator at a rate of 40 cc / min. blown into the cell. The apparatus containing the cell was lowered in a controlled with a thermostatic oil bath and held at 19O ⁰ C.

Analysis samples were taken periodically by lifting the cell out of the bath Deuterium flow is switched off and a sample is taken through the thennometer opening with a syringe became. The system was then restarted as described above.

After 316 hours of operation, it was determined by mass spectrometric analysis that the n-hexadecane contained 99.4% D. The contents of the cell were then extracted with pentane and poured into a 100 ml round bottom flask. The pentane was removed by distillation under atmospheric pressure and the deuterated n-hexadecane was distilled in vacuo. Yield: 20 g (54%) n-hexadecane-d ^; Sp. 102 to 117 ^° C. at 2 to 5 mm; Mp. 14 to 15 ° C.

Example 2
n-tetracosane-d ₅₀

n-Tetracosane-d ₆₀ was prepared according to the method of Example 1, except that 20 g of the n-tetracosane used as the starting material were melted before the deuterium gas was passed through the cell. After 596 hours, the material, as determined by nuclear magnetic resonance, was 98.6% deuterated. It was extracted from the cell using n-pentane (spectroscopic quality) at room temperature, pumped dry and then recrystallized from n-pentane. Yield: 11g (48%). Mp. 45 to 46 ⁰ C.

Example 3
Cyclododecane-d ₂₄

20 g of 1.5 g-cyclododecatriene were treated in the same way as the n-hexadecane of Example 1, only that the process was carried out at about 100 ° C. The material proved itself after 48 hours than fully saturated as it crystallized easily. The connection was then made in the same way as treated the n-tetracosane. After 1210 hours it was determined by mass spectrometric analysis 99.51% deuterated. It was extracted with n-pentane and recrystallized from n-pentane.

In another experiment, 20 g of cyclododecane was used as the starting material. To An exchange of 452 hours gave 13.4 g (59%) of cyclododecanes (99% D, U. R .; m.p. 60 to 62 ° C).

Example 4

Decalin-d ₁₈

The procedure of Example 1 is carried out with 16 g of cis-decalin, but at 165 ^° C. The 13.6 g (75%) decalin-d ₁₈ obtained after 496 hours of exchange, determined by nuclear magnetic resonance, were 99% deuterated and consisted of 92% of the trans and 8% of the cis form. Similarly, starting from trans-decalin, after about 500 hours decalin-d ₁₈ (99 atomic percent D) was obtained as a mixture of cis-decalin-d ₁₈ (8%) and trans-decalin-dj ₈ (92%).

B is ρ ie 1 5
1,2-dicyclohexylethane-d _2e

12 g of trans-stilbene was made in the same manner as

Treated n-hexadecane. After 4720 hours at 185 ° C were 5 g (37%) l ^ -Dicyclohexyläthan-d.;, (98.1% D) determined by mass spectrometric analysis.

Examples 6-11

If essentially the same as in Examples 1 or: is followed, other deuterated products are obtained. The following table I illustrates the starting material « which can be used, the deuterated products obtained with it, the caialysato used: the duration of the exchange reaction in hours and the reaction temperature:

Table I Perdeuterated hydrocarbons produced by exchange with deuterium gas

at
game Raw material Product and atomic percent D Catalyst =) exchange
duration Temp. Hours. ⁰ C 6th
7th n-decane
n-dodecane
n-dodecane
n-dodecane
n-dodecane n-decane-d _a2 ^a ), 96% D.
n-dodecane-d ₂₆ ^a ), 98.6% D.
n-dodecane-d ₂ " ^a ). 48% D.
n-dodecane-d ₂₀ "), 24% D.
n-dodecane-d ₂₆ ^a ), 35% D. Pd on C
Pd on C
Pt on C
Rh on C
Pd on C 282
430
60
42
60 170
195
195
195
195 8th 2,2,4,4,6,8,8-heptamethyl-
nonan 2,2,4,4,6,8,8-heptamethyl-
nonane-d;,., ·· ¹ ), 95% D Pd on C 700 195 9 1,5,9-cyclododecatriene Cyclododecane-dj ^), 99.5% D. Pd on C 1210 195 10 li-octacosan n-octacosane dgs "), 97.5% D. Pd on C 1500 195 11th Squalane (2,6,10,15,19,23-He-
xamethyltetracosane) Squalane-d " ₂ ^a ), 99.5% D. Pd on C 1465 195

") Carried out in a manner as described in Example 1 for the preparation of n-hexadecane.

^b ) Carried out in the same way as was described in Example 1 for the preparation of n-tetracosane.

^c ) All catalysts consist of 2 percent by weight metal on activated carbon, and their grain sizes are in the range from 0.42 to 4.00 mm.

Example 12
n-dodecane-d ₂₀

There was followed the procedure of Example 1, except that 64 g of the starting material n-dodecane and 7 g platinum on 5 g of activated carbon was used as a catalyst at a reaction temperature of 195 ⁰ C. After 304 hours of operation, it was then determined by mass spectrometric analysis that the n-dodecane contained 99.74% D. The yield was 32 g (43%; Sp. 94 ⁰ C at 14 mm).

Example 13
n-octadecane-d _M

The procedure of Example 2 was followed, except that 16 g of n-octadecane and 3 g of palladium were added 2 g of activated charcoal were used as a catalyst at a reaction temperature of 195 ° C. To 1360 hours of operation was determined by mass spectrometric analysis that the n-octadecane

Contained 97.9% D. The yield was 6 g (33%; melting point 28 to 29 ° C.).

Example 14
n-hexatriacontane-d., 4

Working method of example 2 followed,

Initial

It was di

and 20 g of n-hexatriacontane were used as g
material used. After replacement reaction time of 500 hours at 195 ^C 'C was determined by mass spectrometric analysis that the n-hexatriacontane contained 99.5% D. The yield was 15 g (65%).

15th

example
Pristan-d ₄₀

16 grams of pristane were used and the procedure of Example 1 was followed for a period prior to 500 hours at 195 ° C. 8 g (43%) pristane-d _4l were generated (Sp 128 mm 3 to 135 ° C;. 99.5 ° / _o ig <deuteration).

1 sheet of drawings

Claims (1)

high temperatures, for example higher than 35O ⁰ C, claim: are required, occur in addition to the exchange cracking and isomerization. Process for the preparation of deuterated From British patent 798 030 it is Compounds of saturated or unsaturated, known, alkanes and cycloalkanes in the presence of cyclic or acyclic hydrocarbons metals on carriers in the liquid phase with gaseous with 10 to 36 carbon atoms like to deuterium by exchange. With the process of hydrogen atoms by means of deuterium and, in contrast to the British patent, it is not possible to obtain any substantial addition of deuterium, in the liquid borrowed completely deuterated product. State and in the presence of metals on io. The known process has the further disadvantage of using carriers as catalysts, which means that it has to be carried out at excess pressure. draws that the exchange and, if necessary, the addition in the British patent at 100 to 200 ° C in preferably mentioned aluminum oxide catalyst is not the presence of palladium, platinum or rhodium suitable for the deuteration of aliphatic and activated carbon as a catalyst so long through- 15 cycloaliphatic hydrocarbons,
leads that up to 99.7% of the hydrogen atoms The invention is a method for have been replaced by deuterium atoms. Making deuterated compounds from ge saturated or unsaturated, cyclic or acyclic Hydrocarbons with 10 to 36 carbon 20 atoms by exchanging the hydrogen atoms Deuterium and possibly the addition of deuterium, in the liquid state and in the presence of The object of the invention is the production of deuterating metals on supports as catalysts, which thereby ler, saturated, cyclic and acyclic carbon is characterized by the exchange and Hydrogen with 10 to 36 carbon atoms, possibly the addition at 100 to 200 ° C with any desired isotopic purity up to in the presence of palladium, platinum or rhodium 99.7 atomic percent D. on activated carbon as a catalyst for so long. It is known that low molecular weight carbons that up to 99.7% of the hydrogen atoms have been replaced by hydrogen atoms with less than 10 carbon atoms,
with deuterium by gas phase reaction via metal 30 As compounds which film through the invention and can be produced on metal catalysts applied to supports, for example the catalysts can be perdemerated. The following could be mentioned: n-decane d ₂₂ , n -Dodecane-d. ^. N-pentane, η-hexane, n-heptane, n-octane, 3-methyl- n-hexadecane-d ^, n-octadecane-dag, n-tetracosane-d = ,,, pentane , Cyclcbutane, cyclopentane and methylcyclo- n-hexatriacontane-d ^, 2,2,4,4,6,8,8-heptamethylnohexane with an isotopic purity of 98% D 35 nan-d _34. Pristan-d ₄₀ (i.e. 2 , 6,10,14-tetramethylpenta- or above. Decane-d ₄₀ ), cis-decalin-d ₁₈ , trans-decalin-d _ls , cyclo- In J. Am. Chem. Soc, Vol. 84 (1962), p 925, 2-Dicyclohexyläthan-d is dodecane-d _24, L, ₂₆ and reported Squalanüber attempts to hexene, zl ^{1> 9} -octalin d _e2. These compounds have an isotopic pure and J ° ^a0 octaline in the liquid phase by introducing up to 99.7 atomic percent D on.
of deuterium gas into a mixture of carbon. The starting materials are branched, straight-chain, hydrogen and a suspended Pd or Pt cyclic or acyclic hydrocarbons, which are used to deuterate the catalyst at 24.5 ° C. As a result, which may be both saturated and unsaturated, some of the saturated compounds will use one. In all cases, the deuterated obtained contained a greater number of deuterium atoms than the fully saturated equivalent of the starting material for the reduction of the unsaturated compound 45. As an example of suitable output were necessary; However, there was no evidence of hydrocarbons, such as n-decane, n-dodecane, n-hexada, that high yields of perdeuterated compounds were obtained under the conditions used , 4,4,6,8,8-heptamethylnonane, pristane (ie fertilizing were obtained or that an exchange occurred with 2,6,10,14-tetramethylpentadecane), cis-decalin, trans-saturated substances. Furthermore, 50 decalin, 1,5,9-cyclododecatriene, cyclododecane, trans attempts failed, decalin mentioned in such a system stilbene and squalane,
by treatment with deuterium gas over a The hydrogen-deuterium exchange between To deuterate platinum catalyst at 25 ^{0 C;} there was no exchange of deuterium gas and the liquid hydrocarbon. is used below the boiling point In J. Org. Chem., Vol. 28 (1963), p. 3085, 55 hydrocarbons and in a temperature range are reported that an investigation has shown that from 100 to 200 ^° C., preferably from 150 to 200 ^° C., the liquid phase exchange of n-octane and carried out. When working at a temperature 2,2,4-trimethylpentane with deuterium in comparison below the boiling point of the hydrocarbon for gas phase exchange ur, is suitable. G ο rd ο η the cracking of the hydrocarbon is negligible * and Madison have ir US Atomic Energy 60 permeable, since 1% or less of the deuterated pro-comm. Conf. 398-1 (Chr. Abstr., Vol. 61 (1964), products have a higher or lower boiling point than p. 15 615 d) a disV '-. Continuous process to have the desired hydrocarbon.
Deuterating before C ₈ -C hydrocarbons Palladium was found to be particularly effective indicated, b;>. the either deuterium oxide or catalyst. The amount of catalyst is not critical, gaseous deuterium as a source of deuterium and a 65. In general, an amount of 2% of the Cobalt molybdenum sulfide-on-alumina-catalyst ver catalyst on activated carbon the conversion of the be turned. This procedure is disadvantageous, the starting material is effective in the deuterated product the process is discontinuous, and since it is catalyzed.