Oxidation of cyclododecene with molecular oxygen in the presence of boric acid

78

K. M. So~rovA et al. SUMMARY

1. A s t u d y was made of the effect of temperature, pressure, contact time and the ratio of initial olefins on co-disproportionation of propylene and isobutylene on a silica-tungsten catalyst, in order to obtain isoamylenes. 2. I n the presence of a catalyst containing 4.4% wt. WOs/SiO~ at a temperature of 435 °, a pressure of 22 atm, a gravimetric rate of raw material supply of 50 hr -1 and a molar ratio of initial olefins of 1 : 1 propylene conversion is about 50%, isobutylene conversion, 27%, Cs-olefin yield 16% wt. and isoamylene concentration, 98o/0. REFERENCES

1. 2. 3. 4. 5. 6. 7. 8.

R. L. BANKS and R. B. REGIER, Ind. Engng. Chem. Prod. Rcs. Devel. 10, 46, 1971 U.S.A. Pat. 3697613, 1972; Izobreteniya za rubezhom, No. 20, 38, 1972 U.S.A. Pat. 3702827, 1972; RZhKhim. 16N 10P, 1973 Brit. Pat. 1159054, 1969, RZhKhim. 5N 14P, 1970 Brit. Pat. 1159055, 1969; RZhKhim. 5N, 13P, 1970 U.S.A. Pat. 3590096, 1971; RZhKhim. 6N, 15P, 1972 U.S.A. PaL. 3590098, 1971; RghKhim. 6N, 17P, 1972 V. Sh. FEL'DBLYUM,T. I. BARANOVA and T. A. TSAILINGOL'D,Zh. organ, khimii 9, 870, 1973

OXIDATION OF CYCLODODECENE WITH MOLECULAR OXYGEN IN THE PRESENCE OF BORIC ACID* ~ K. M. So,ovA, G. A. ZELENAYA and A. N. BASHKIROV A. V. Topchiyev Institute of Petrochemical Synthesis, U.S.S.R. Academy of Sciences (Received 7 October 1975)

CYCLIC olefin oxides are reactive compounds used for preparing valuable organic products such as diols, dicarboxylic acids, amino-alcohols, etc. Therefore, finding simple methods for the synthesis of olefm oxides is of definite interest. Methods of preparing olefin oxides involve mainly the interaction of olefinns with per-acids or alkylhydroperoxides in the presence of catalysts [1-6]. This paper seeks to examine oxidation of cycloolefins with molecular oxygen in the presence of boric acid, in order to explain the possibility of synthesizing cyclene oxides and unsaturated cyclic alcohols by this method. I t was shown previously [7-9] in connection with liquid-phase oxidation of olefins * •eftokhimiya 16, No. 3, 445-451, 1976.

Oxidation of cyclodecene with molecular oxygen

79

of aliphatic series that the addition of boric acid has a positive effect on t h e yield of olefin oxides. A s a result of recent studies [10-16] concerning the mechanism of action of additives containing boron during oxidation of hydrocarbons with molecular oxygen it was established that additives containing boron, particularly metaboric acid, perform two functions during oxidation: 1) the function of acid catalyst resulting in heterolytic decomposition of hydroperoxides to form alcohol borates and isolate active oxygen ROOH~HOB~-O-,[-HOB~O -]-~ROB~O~H=O+ : O :,

J

OOH

(1)

which in the case of unsaturated hydrocarbons interacts with the double bond to form hydrocarbon oxides [17] and 2) the function of an esterifying agent which b y interacting with intermediate compounds containing hydroxyl changes them into less reactive alkoxy-boric compounds. The reactivity of the latter depends on the ratio between the boron atom and alkoxyi groups [18]. Hemolytic breakdown of hydroperoxides R O O H - * R 1 0 . -F-" OH, (2) %~. 5~

b %wt.

30 40

1~1

20 2O 10

0

2

q

8

8 hr,

0

2

¢

I 6

1 8 hr,

FIG. 1. Kinetic curves of using hydrocarbons in liquid phase oxidation (a) and hydrocarbon consumption, % of contents in the initial mixture (b): 1, 1', /" -- trans-cyclododecane; 2, 2', 2"--c/8-cyclododeceno; 3', 3" -- cyclododecano. In Figs. 1-3: O--without boric acid; × --3% wt.; A--5% wt. boric acid.

80

K . M . SoxovA ¢¢ ~.

competes w~th reaction (1), resulting in a different composition of reaction products. The ratio of these reactions ((1) and (2)) depends on reaction conditions and mainly on the proportion of compound containing boron, added. EXPERIMENTAL

A stereoisomer mixture of cyclododecene (80% we.) and cyclododecane (20% wt.) was used for the investigation. The ratio of eyclododecene stereoisomers was as follows, %: trans-isomer 66, cis-isomer 34. Using a hydrocarbon mixture for the investigation enabled a comparative evaluation to be made of reactivity in relation to molecular oxygen in the presence of boric acid of isomeric cyclic olefins and naphthenes. Oxidation was carried out in a conventional oxidizing cell using a nitrogen-oxygen mixture containing 4% 03 at a feed rate of 600 1./kg.hr and at temperatures of 165 and 180 ° in the presence of different amounts of boric acid. Reaction products were analysed by gas-liquid chromatography using a Khrom-31 chromatograph with a flame-ionization detector. Polyethylene glycol adipate was used as stationary liquid phase, applied in the proportion of 10% on "risorb C", the fraction being 0.2-0.3 ram. Standard vis- and transcyclododecenes were obtained by dehydration of cyclododecanol and pyrolysis of its acetate [19]. Cis-and trans-oxides of cyclododecene were synthesized by interaction of cyclododecene with perbenzoic acid [20] and cyclododecenol was obtained by the Rosenblum method [21]. When considerable amounts of ketone were present in the reaction mixture (oxidation without boric acid) the product examined was treated before analysis with hydroxylamine in order to combine compounds with the carbonyl group [22]. Cyclododecene oxides and cyclododecenol were isolated from oxidized products obtained under different conditions of oxidation. Compounds which had not reacted with boric acid were distilled off in vacuum from the oxidized products and the remainder--boric acid esters of compounds containing hydroxyl were saponified with hot water and the alcohol concentrate obtained was separated to mono- and poly-functional compounds by vacuum distillation. Compounds, which had not reacted with boric acid were separated into unreacted hydrocarbon and compounds containing oxygen, by displacement chromatography on SiO~. The oxygen compounds obtained--the concentrate of cyclododecene oxides--were subjected to vacuum distillation. Figure 1 shows kinetic curves of consumption of cyclododecenes and cyclododecane during oxidation at 180° in the presence of various amounts of boric acid and kinetic curves of hydrocarbon consumption expressed as percentages of contents in the initial mixture. Experimental results indicate that the addition of boric acid during oxidation of cyclic unsaturated hydrocarbons, as with oxidation of naphthene hydrocarbons, inhibits the reaction. With an increase in the amount of boric acid, the rate of oxidation decreases as a consequence of a reduction in the

Oxidation o f cyclodecene with molecular oxygen Ioq -ooI~ + op!xo ,~ spunod - ~ o o Xz~puooos I~UO!'~ounjououz 0 0 r..j r..) 0 0

a N

0 r~

i

s~onpoad.~q uo.~%o~oz i~m.I!oq-qi~!q lOUOOOpOpoIo-~o op.Txo OUOOopopo[oZo ~//o "[Ol:II

'uoqa~ooap.~q 3° uo!sao.*.uoo $o ooa~o~I

ff 0

!°:

IouooopopoIo,~o op!xo ouooopopoloXo

.oo 0

I~uoqa~o u~

[Xxoap-~q

0

zoqso

•~

%'*O~tH

aq 'om!~

Do ',~ ~ u o u ~ , s o d x o j o "oK

,.~ ~ ~ .~

81:

K. M. SOKOVAet a/.

$2

concentration of hydroperoxides ensuring degenerate chain branching, i.e. with an increase in the amount of boric acid, reaction (1) prevails over reaction (2).

%~

%~"

1o~

o I

I

I

2

0

6

b

I

8hr

2

¢

8

8 hr

l~xo. 2. Kinetic curves showing the formation of cyclododecane (a) and eyelododecenol oxide (b) during oxidation of cyclododecene: 1-3-- 180; 4-- 165°C. Results in Fig. 1 show t h a t in spite of the iact t h a t the concentration of cyclododecane in the initial mixture is close to the concentration of cis-cyclododecene (21 and 27%), the rate of oxidation of cyclododecane is much lower t h a n the rate of oxidation of cis-cyclododecene. These results also confirm T~LE 2.

EFFECT

OF THE

AMOUNT

OF BORIC

ACID

OF OXIDATIOI~" OF CYCLODODECENE

Time, hr

Amoun~ Degree of of H,BO,, conversioI of eyclo%wt. dodecene 16 19 21 22

ON THE

SELECTIVITY

AT 170 °

Selectivity of the reaction, reel. °/o oxide

alcohol

total

49.6 17"3

36.1 6.8 28.5 32.3

85.7 24.1

39-5

48"5

68.0

80-7

t h a t ¢is- and trans-isomers of cyclododecene have the same reactivity in relation to molecular oxygen in the presence of boric acid. Table 1 shows the composition of oxidized products obtained under different conditions of oxidation of cyclododecene.

Oxidation of cyclodecene with molecular oxygen

83

Cyclododecene oxide isolated from the oxidized product in experiment 3 had the following characteristics: b.p. 100-101°/3 mm; n~ 1.4802; d~° 0.9470. Found, %: C 79.08, H 12-19 CI~H~O. Calculated, %: C 79.06, H 12.16. Gas-chromatographic analysis shows that the oxide separated is a stereoisomer mixture in the ratio: trans-isomer 66.7%, c/s-isomer 33.3~/o. Results in the literature [20, 23]: trans-epoxycyclododecane--b.p. 100-102°/3 mm; n~° 1.4775; d~° 0.9424, cis-epoxycyclododecane--b.p. 88-90°/1.5 ram; n ~ 1.4837. Figure 2 shows kinetic curves of the formation of cyclododecene oxide and cyclododecenol during oxidation. Figure 3 and Table 2 show results obtained when determining the effect of the amount of boric acid and the degree of oxidation on the selectivity of oxidation of cyclododecene at 180 °. The amount of hydrocarbon used for forming oxide and alcohol, related to the overall amount of hydrocarbon was used to determine the selectivity of t h e reaction. mole %

50- ~

A

z~

y,~

Z

X/.x

% 2

4

6

Bhr

:FIG. 3. Selectivity of oxidation of cyclododecene: 1, 2--cyclododocene oxide; 3, 4--cycle. dodecenol. Experimental results indicate that reaction conditions have a considerable effect on the rate of formation of compounds containing oxygen and the selectivity of oxidation. During oxidation of cyclododecene at 180 ° an increase in the amount of boric acid has a marked effect on the selectivity of oxidation. Thus, if in the absence of boric acid the selectivity of the reaction is 24 mol. ~ , in the presence of 3 ~ H3BO 3 with about the same degree of transformation of cyclododecene (Table 2) the selectivity of the reaction increases 2-8-fold a n d in the presence of 5 ~ H3BO 3 it increases 3.3-fold and is 80% in terms of t h e hydrocarbon converted.

84

K . M . So~rovA et al.

Figure 3 shows t h a t the selectivity of the reaction in relation to oxides, both with oxidation with 5% H3B0 3 and with oxidation with 3% HsB08 remains practically unchanged during 8 hr oxidation, which is evidence of the high stability of cyclododecene oxides in this reaction system. The cyclododecenol formed during oxidation, in spite of the fact t h a t it is in alkylborate form in the reaction mixture, is a reactive compound. This, apparently, takes place as a result of the presence of a double bond in the molecule, consequently the selectivity of the reaction in relation to alcohol decreases over a period of time. From curves showing a reduction in the selectivity of the reaction it is clear t h a t an increase in the amount of boric acid in the reaction mixture slows down the rate of consumption of alkyl borates, which is probably due to a change in the ratio between the boron atom and alkoxyl groups [22]. A reduction in reaction temperature from 180 to 165 ° reduces the rate ©f oxidation. An increase in the a m o u n t of boric acid from 3 to 5% has no marked influence on the selectivity of oxidation, which is due apparently to the m a x i m u m dependence of the selectivity of oxidation on the amount of boric acid added, which had previously been established during oxidation o f paraffin hydrocarbons in the presence of additives containing boron [16]. Experimental results indicate t h a t oxidation at a temperature of 180 ° in the presence of 5% HsB03 for 2-3 hr creates the most favourable conditions for obtaining cyclododecene and cyclododecenol oxide. The overall select i v i t y of the reaction in this case is 80-86 mol. % in terms of the cyclododecene conver~ed with a degree of conversion of 16-22%, Results in Table 1 indicate t h a t an increase in the selectivity of the reaction in the presence of boric acid takes place mainly as a result of a reduction in the a m o u n t of high-boiling reaction by-products. i T A B L E 3. C H A R A C T E R I S T I C S OF H I G H - B O I L I I ~ G R E A C T I O N P R O D U C T S

Functional analysis, number mg KOH/g No. of experiment

acid

30 17 17 6

ester

40 53 32 57

carbo- hydro- iodnyl xyl ine 82 71 69 52

85 188 180 257

39 64 72 79

groups containing 0 237

329 298 372

[ Elementary analysis, %* 0 (from the C H differ-

/

ell,ce )

77.50 75.66 79-95

11.57 10.58 10.96

11.15 13.76 13.10

* Calculated for C,,H,,O,,~ooC 72"72; H 11-11 0 16.16 hydroxyl; number 560.

Functional and elementary analyses of the compounds indicated are shown i n Table 3. I t is clear from Table 3 t h a t high-boiling reaction products are polyfunctio-

Oxidation of cyclodecene with molecular oxygen

85

n a l c o m p o u n d s containing o x y g e n . C o m p a r a t i v e l y low c o n t e n t s of f u n c t i o n a l g r o u p s containing o x y g e n a n d d e t e r m i n e d b y c o n v e n t i o n a l m e t h o d s (particu l a r l y b y o x i d a t i o n w i t h o u t boric acid) a n d t h e low iodine n u m b e r confirm t h a t during o x i d a t i o n c o n d e n s a t i o n t a k e s place b o t h a t t h e double b o n d a n d a p p a r e n t l y as a result of i n t e r a c t i o n b e t w e e n i n d i v i d u a l g r o u p s c o n t a i n i n g o x y g e n . T h e possibility of i n t e r a c t i o n b e t w e e n c o m p o u n d s containing h y d r o x y l a n d c o m p o u n d ~ w i t h oxide g r o u p s resulting in t h e f o r m a t i o n of e t h e r b o n d s has b e e n i n d i c a t e d p r e v i o u s l y [7]. SUMMARY

1. A s t u d y was m a d e of liquid p h a s e o x i d a t i o n o f c y c l o d o d e c e n e w i t h molecu l a r o x y g e n in t h e presence of boric acid. I t w a s f o u n d t h a t u n d e r g i v e n conditions e p o x y c y c l o d o d e c a n e m a y be o b t a i n e d w i t h a yield of 4 9 % mol. in t e r m s of t h e e y e l e d o d e c e n e c o n v e r t e d w i t h a d e g r e e of conversion of 16-20~/o b y liquid-phase o x i d a t i o n o f cyclododecene w i t h m o l e c u l a r o x y g e n in t h e presence o f boric acid. T h e yield of cyclododecenol is 3 2 - 3 6 % mol. 2. I t was e s t a b l i s h e d t h a t cis- a n d trans-cyclododecenes h a v e t h e s a m e r e a c t i v i t y in liquid-phase o x i d a t i o n w i t h m o l e c u l a r o x y g e n in t h e p r e s e n c e o f boric acid. '

1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17.

REFERENCES

G. WILKE, Angew. Chem. 69, 397, 1957; 75, 10, 1963 E. G. E. HAWKINS, J. Chem. Soc., 2169, 1950 W. F. BRILL and N. INDICTOR, J. Organ. Chem. 29, 710, 1964 N. INDICTOR and W. F. BRILL, J. Organ. Chem. 80, 2074, 1965 J. B. LEE and B. C. UFF, Quart. Rev. (London) 21, 429, 1967 R. LANDAU, 7th World Petroleum Congress, Mexico City, 1967 V. V. KAMZOLKIN, A. N. BASHKIROV, Yo. V. KAMZOLKINA and S. A. LODZIK, Neftekhimiya 11, 750, 1962 A. N. BASHKIROV, Ye. V. KAMZOI.KINA, S. A. LODZIK and V. V. KAMZOLKIN, Dokl. AN SSSR 184, 597, 1969 V. A. ZAKUPRA, A. Ye. MYSAK, Ye. V. LEBEDEV, "N. D. CHELOK'YAN and T. N. PLIYEV, Neftekhimiya 10, 385, 1970 F. BROICH and H. GRASEMANN, ErdS1 und Kohle 18, 360, 1965 F. I. NOVAK, V. V. KAMZOLKIN, Yu. A. TALYZENKOV and A. N. BASHKIROV, Neftekhimiya 7, 248, 1967 F. I. NOVAK, V. V. KAMZOLKLN, A. N. BASHKIROV and Yu. A. TALYZENKOV, l~eftekhimiya 11, 888, 1971 F. I. NOVAK, A. N. BASHKIItOV, V. V. KAMZOLKIN and Yu. A. TALYZENKOV, Dokl. AN SSSR 196, 149, 1971 F. I. NOVAK, A. N. BASHKIROV, V. V. KAMZOLKIN and Yu. A. TALYZENKOV, Dokl. AN SSSR 207, No. 4, 874, 1972 N. TAKAMITSU and T. HAMAMOTO, Nippon Kagaku Kaishi, No. 6, 1156, 1973 V. V. KAMZOLKIN and A. N. BASHKIROV, Sb. Teoriya i praktika zhidkofaznogo okisleniya (Theory and Practice of Liquid-Phase Oxidation). Nauka, Moscow, 1974 P. F. WOLF and R. K. BARNES, J. Organ. Chem. 34, 3441, 1969

A . N . KAM~-EVA et a/.

86

18, F. I, NOVAK, A. N. BASHKIROV. YU. A. TALYZENKOV and A. N. BASHgIROV Dokl. AN SSSR 214, No. 6, 1346, 1974 19. AI. A. PETROV, K. M. SOKOVA. V. V. KAMZOLKIN and A. N. B A S ~ I R O V , /)old. AN SSSR 203, 113, 1972 20. H. NOZAKI and R. NOYORI, J. Organ. Chem. 30, 1652, 1965 21. M. ROSENBLUM, J. Amer. Chem. Soe. 79, 3179, 1957 22. V. S. JOHNSON, R. D. SHENNAN and R. A. REED, Organicheskiye reaktivy dlya organieheskogo analiza (Organic Reagents for Organic Analysis) Izd. inostr, lit. Moscow, 1948 23. L. I. ZAKHARKIN and V. V. KORNEVA, Dokl. AN SSSR 132, 1078, 1960

ACTIVITY OF HETEROGENEOUS CATALYSTS IN LIQUID-PHASE OXIDATION OF TETRALIN* A. N. ~ v x ,

V. I. ZAKWAROVA, A. V. ART~MOV, V. A. SET,~ZNEV and YE. N. ~ARTYNOVA

D. I. Mendeleyev Chemico-Technological Institute, Moscow

(Received 9 September 1975) HETEROGENEOUS c a t a l y s t s in liquid-phase o x i d a t i o n of h y d r o c a r b o n s h a v e several a d v a n t a g e s o v e r h o m o g e n e o u s catalysts. U s i n g h e t e r o g e n e o u s c a t a lysts t h e r a t e o f i n t e r m e d i a t e p r o d u c t f o r m a t i o n a n d process selectivity increase. This p a p e r is concerned w i t h t h e s t u d y of t h e c o m p a r a t i v e c a t a l y t i c a c t i v i t y a n d s e l e c t i v i t y o f v a r i o u s h e t e r o g e n e o u s c a t a l y s t s m a d e f r o m activ a t e d charcoal a n d c a r b o n b l a c k w i t h m e t a l ions o f v a r i a b l e v a l e n c y applied on t h e i r surfaces: m a n g a n e s e , cobalt, iron a n d nickel in liquid-phase o x i d a t i o n o f tetralin. B A U , AG-3, S K T , K A D a n d A G N a c t i v a t e d charcoals a n d c h a n n e l g a s b l a c k w i t h a specific surface o f 150 m2/g (KS-150), channel gas b l a c k w i t h a specific surface of 300 m~/g (KS-300) a n d PM-70 c a r b o n b l a c k were used as carriers. TABLE 1. COMPARISON

OF CATALYTIC A C T I V I T I E S OF VARIOUS

METAL CATIONS A P P L I E D ON K S - 1 5 0

W X 10 4,

Cation

mole/1. • see

Cation

W × 10', mole/1. • see

CoS+

0.005 5"950 2.610

Fe z+ Ni *+

0.373 0.012

MnS+

* IWeftekhimiya 16, No. 3, 452-456, 1976.