C A T A L Y T I C A L K Y L A T I O N OF T E T R A L I N

COMMUNICATION 10. POSSIBILITY OF THE USE OF NONANE-DEHYDROGENATION CATALYZATES FOR THE ALKYLATION OF TETRALIN

(UDC 542. 97)

N. I . S h u i k i n , N. A . P o z d n y a k , a n d T . P. D o b r y n i n a

N. D. Zelinskii Inst i tute of Organic Chemistry, Academy of Sciences, USSR Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3,

pp. 530-534, March, 1964 Original a r t i c le submitted September 17, 1962

In previous investigations [1, 2] we have shown that alkenes, including nonenes, when diluted with alkanes to a nonene content of 13% react with te t ral in at 95 ~ in presence of a luminum and a l i t t le a lkyl bromide as act ivator with formation of alkyl tetral ins . One of us in col laborat ion with Timofeeva and others [3-5] has found conditions for the dehydrogenation of nonane in presence of oxide catalysts with formation of ca ta lyza tes containing 8-16% of nonenes and 1-25% of aromatic hydrocarbons. It is well known that there are as yet no simple and accessible methods for the isolation of the middle and higher olefins from their mixtures with other hydrocarbons. It was therefore of

interest to examine the possibility of using the alkenes in the mixtures formed by the dehydrogenation of alkanes

without isolat ion.

We here report our first results on the ut i l iza t ion of olefins obtained in the dehydrogenation of nonane for the a lkylat ion of te t ra l in and also on the ut i l izat ion of the mixture of aromat ic hydrocarbons formed together with a l - kenes as a result of the part ia l dehydrocycl izat ion of alkanes. The experiments were carried out in presence of a lu - minum, of which we took 0.04 g -a tom per mole of tetral in, with 0.09 mole of heptyl bromide as act ivator . In the a lkyla t ion of tetral in with nonane ca ta lyzates containing traces of aromat ic hydrocarbons the yield of nonyltetral in

at tained 80%, based on the nonenes taken:

- H t C~H~o - - * CgHIs K--5, 500 ~

( [ ~ 6 f)-"lS0~ ( [~--C9H19 "t- C9H:8 AI-I-CTI-I,sB;

As a result of the a lkyla t ion of aromat ic hydrocarbons in the nonane-dehydrogenat ion ca ta lyza tes with the nonenes

present we obtained 2 - e t h y t - 4 - i s o n o n y l - l - m e t h y l b e n z e n e in 60% yie ld:

2C9H2o

CHs CHs --5H2 / 100 ~ /

, CgHIs q- C~H4 ~ C6H3--C~Hs 500--600 ~ ~ AIq-CTH~sBr C2H5 C~HI~

E X P E R I M E N T A L

For the investigation we took nonane-dehydrogenat ion ca ta lyza tes obtained over various oxide catalysts. From these we first separated a fraction corresponding in boil ing point to C 9 hydrocarbons: i t c a m e over in the range 140- 151" (748 ram) and consisted of nonane, nonenes in which the double bond was not at the end of the molecule , and

alkylbenzenes, probably 1 - e t h y l - 4 - m e t h y l - and 1 -e thy l -3 -methy l -benzenes .*

The ca ta lyza te fractions used in the experiments were prepared and character ized by a group led by E. A. Timofeeva.

4 9 2

f Composition of | ,

oataly ate, $ _ _ . l y . ~ ~

Io o = I ~ ~ ~ �9

oo m ~ % ~ - ~ < , ~

of Tetral in with Nonane-dehydrogenation CataD

14.0

14.0

15.7

15.7 15.7

10.0

10.0

65.1

64.5

89.0

O

2

A m o u n t obtained of

fraction of b. p. 140-!51 ~

(748 mm), g

inc 1 udin_!p_.$__ - r i l l 03 at

total o ~ ~ o o = o ooo=

56.1 1.4 -

60.1 2.4 --

50.5 Nil -

57.3 Ditto -

z a t e s

0 r176 �9

d

O

4

4

4

4

4

5

5

5

5

3.1

3.1

Traces

Ditto

7.2 7.2

70.0

70.0

65.0

65.0 79.0

78.0

i00

3 : 2

3 : 2

5 :3

5 :3

I:I

2 : 1 3 : 2

6.2

7.2

4.8

6.8

52 55 70 66 80 23 31

6.1

5.3

3.5

3.0

3.5

0.5

1.0

0

0

O

TABLE 2. Alkylation of the Aromatic Hydrocarbons of the Nonane Catalyzate with the

Nonenes Present

lation

TABLE 1. Alkylation

tuct

60.0

50.0

38.9

39.2

41.5

65.0

55.5

65.7

65.0

For the alkylation oftetral in we took catalyzate fractions with the following compositions: 1) 15.7% of nonenes

and traces of aromatic hydrocarbons; 2) 14.~0 of nonenes and 3o70 of aromatic hydrocarbons; 3) 10.0% of nonenes and 7~ of aromatic hydrocarbons. For the alkylation of the aromatic hydrocarbons of the catalyzate formed s imultane-

ously with the nonenes we used the cataIyzates: 4) 6% of nonenes and 6~ of aromatic hydrocarbons; 5) 11% of nonenes

and 13% of aromatic hydrocarbons. The iodine values of the catalyzates were determined by the bromometric method

[6], and the content of aromatic hydrocarbons was determined by the relative dispersion method [7].

The alkylation of tetralin was carried out at 100 ~ for 4 h in presence of the above-stated small amounts of a lu-

minum and heptyl bromide by a procedure that we have described earlier [2]. In each experiment we took 0.125 mole of tetralin; the amounts of catalyzate taken are given in Table 1. Unchanged catalyzate and tetralin were

driven off at atmospheric pressure through a column of 15-plate efficiency. The nonyltetralin fraction was distilled off through the same column in the range 155-164 ~ (6 ram). From Table I it will be seen that the nonenes of Frac- tion 1 of the catalyzate, which contained 15.707o of nonenes with traces of aromatic hydrocarbons, reacted completely with tetralin. The yield of nonyltetralin, b. p. 155-164 ~ (6 ram) and n~ 1.5095, was 80~

493

Analysis of the nonyltetral in obtained in the experiments with the aid of its infrared spectrum showed that i t was 6-isononyhetral in. From the combined residues, which came over above 164", we isolated about 40% of d inonyl- te t ral in fraction, b. p. 215-235" (6 mm) and n~ 1.5180; according to the infrared spectrum this fraction corresponded to 4,6-di isononyltetral in. We sulfonated the monononyltetral in, and the sulfonate obtained gave a stable copious foam; we sent a sample for testing as a detergent.

Alkylat ion of the aromat ic hydrocarbons of ca ta lyza te Fraction 4. This was carried out by mixing the compo- nents and stirring the mixture at 100" in an atmosphere of nitrogen. Reaction set in after an induction period, which amounted to 1 - I0 h, depending on the re la t ive amounts of the components. The best results were obtained when 0.135 g of a luminum and 1 g of heptyl bromide were taken to 50 g of ca ta lyza te (Table 2).

To remove the induction period, with Fraction 5 of the ca ta lyza te the experiments were carried out as follows. A glass flask, from which air had been displaced with nitrogen, was heated, and first a luminum turnings were intro- duced and then heptyl bromide. The la t ter then reacted with the aluminum, probably as follows:

2A1 q- 3CTHI~Br ~ CTH15A1Br2 ~- (C~H15h A1Br.

The ca ta lyza te was then added to the compounds formed. The mixture was stirred in an atmosphere of nitrogen at 100" for 4 h.

In both cases the react ion products were disti l led through the 15-pla te column. Unchanged original fraction was dist i l led off at 140-151" at atmospheric pressure, and its content of nonenes and aromat ic hydrocarbons was de - termined. A 11 that came over above 151" was taken to be a lkyla t ion product. Table 2 shows that under the given conditions the yields of a lkylat ion products vary from 39 to 60%, based on the nonenes taken for reaction.

The combined alkylat ion products from experiments with Fractions 4 and 5 were dist i l led through the 15-pla te column at a residual pressure of 6 mm. About 90~ of the a lkyla t ion product c ame over in the range 135-147" (6 mm). Narrow fractions coming over in this range were analyzed on an IKS-14 infrared spectrometer in the region of X = 2800

3000 cm "l. The spectra of a l l the fractions contained bands characteris t ic for 1 ,2 ,4- t r ia lkylbenzenes . We de te r - mined the intensities of the absorption bands at 2926 cm "1 (e l ) and 2956 cm "1 (ez), and from these we ca lcula ted

the numbers of CH 2 and CH s groups in the hydrocarbon molecules of the fractions investigated (Table 3).

According to the infrared data the alkylbenzenes obtained consisted mainly of 2 - e t h y l - 4 - i s o n o n y l - l - m e t h y l - benzene. This product was sulfonated, and as the sulfonate obtained gave a good stable foam a sample was sent for tests to determine the possibility of its use as a detergent.

The infrared spectra were determined by I. N. Lifanova, whom the authors thank.

TABLE 3. carbons

B. p. (*C at 6 ram)

135-140 140-145 145 -147

Results of Spectral Investigation of Fractions of Alkylaromat ic Hydro-

1.4910 1.4920 1.4910

559 467 4"/7

No. of CH 2 groups

7.5 6.3 6.3

8, 2

360 343 352

No. of CH s groups

4 3.4 3.5

S U M M A R Y

1. It was shown that nonyltetralins can be obtained in yields of up to 80%, based on the nonenes taken, by the a lkyla t ion of tetral in with nonane-dehydrogenat ion ca ta lyzates containing 10-16% of nonenes.

2. From nonane-dehydrogenat ion cata lyzates containing 6-11% of nonenes and 6-13% of C 9 alkylbenzenes, by the alkylat ion of one of these components by the other 1 ,2 ,4- t r ia lkylbenzenes can be obtained in about 60% yield,

based on the nonenes taken for reaction.

1.

L I T E R A T U R E C I T E D

N. I. Shuikin and N. A. Pozdnyak, Izv. AN SSSR. Otd. khim. n., 1962, 1455.

494

2, 3. 4. 5.

6. 7.

N. I. Shuikin and N. A. Pozdnyak, Izv. AN SSSR. Otd. khim. n., 1961, 1156. N. I. Shuikin, E. A. Timofeeva, and V. M. Kleimenova, Izv. AN SSSR. Otd. khim. n., 1961, 653. E. A. Timofeeva, N. I. Shuikin, and T. P. Dobrynina, Kinetika i kataliz, 2, No. 4, 5'/4 (1961). Yu. P. Plomikov, V. S. Smirnov, E. A. Timofeeva, V. M. Kleimenova, and N. I. Shuikin, Kinetika i kataliz,

2, No. 2, 267 (1961). G. D. Gal'pern, Tr. Inst. nefti AN SSSR, 4, 141 (1954). B, V. Ioffe, Zh. obshch, khimii, 1_6, 1119 (1946).

All abbreviations of periodicals in the above bibliography are letter-by=letter transliter-

ations of the abbreviations as given in the original Russian journal. Some or all of this peri-

odical l i t e ra ture m ay we l l be a v a i l a b l e in E n g l i s h t rans la t ion . A complete list of the cover-to- cover English translations appears at the back of this issue.

495