SU760995A1 - Homogenic catalytic system for selective hydrogenating of chloronitroaromatic compound of benzene series - Google Patents

Description

The invention relates to catalysts for the selective hydrogenation of chlorine nitroaromatic compounds of the benzene series. five

,-.-.one....,. A homogeneous catalyst is known for the hydrogenation of substituted nitrobenzenes, which is the complex compound Рс or Ρά with oxy-substituted naphthoquinones, dissolved in dimethylformamide. In the presence of this catalyst, 2,4-dinitrocholorbeneol is hydrogenated to form 2,4-diamino chlorobenzene with hydrogen [1].

However, this catalyst has. low stability and in the process of hydrogenation is destroyed with the release of metal.

Another known homogeneous catalyst for the hydrogenation of chlorine-substituted. nitrobenzenes is a complex compound C C [{C ₆ H ₅ ) s dissolved in a mixture of benzene-ethyl

.alcohol. In the presence of this catalyst, p-chloronitrobenzene is hydrogenated to 25 η-chloroaniline with a conversion of 100% and a selectivity of 86% at 105-135 ° C and pressure. hydrogen production is 80–100 atm [2].

The closest to the proposed is a homogeneous catalytic system

2 ...... '' '

for the selective hydrogenation of chloronitroaromatic compounds of the benzene series, consisting of a compound of a metal of group VIII (an iridium compound), a ligand (chloroanilic acid), an aliphatic alcohol and water.

In the presence of this system, chloronitroaromatic compounds are hydrogenated at atmospheric pressure and 22-90 ° C with a selectivity of 98.5-99.8%. For hydrogenation use 1 · 10 ' ² -5 10 ² g-at. iridium per 1 mol of the hydrogenated compound, and the specific activity of the catalytic system is 1.5-14.2 mol H ₂ / min-g-at [g].

The purpose of the invention is to increase the activity of the catalytic system.

This' aim is achieved in that the homogeneous catalyst system comprises a group VIII metal compound which is used as KS1 _minutes; ligand, which is used as an adduct of chloroanilic acid with an amine, of the general formula C ₆ H _g 0 ₄ C1 ₂ · 2C ₄ H ₅ MH ₂ or

C, H _g 0dC1 ₂ · p.SINDLk ^- , where n = 1-2; K = 0H, C1, H ₂ P0d, with the following molar ratio of components: rhodium chloride: adduct of chloroanilic acid with

h 760995

amine: aliphatic alcohol water (5 · 10 “ ⁷ τ 3,5-1СГ *): (5 <1 (G ⁷ -3,5 · 1 СГ ⁴ ):

: (0.109 - 1.98): (0.167 - d 5.56) • respectively. '

As a result of the use of the proposed ’catalytic system in the hydrogenation of chloronitroaromatic compounds with hydrogen, its specific selectivity increases on average by 12–10 times as compared to the known one.

A homogeneous catalytic system is prepared by the interaction of 1.14 "10 ~ ^a - 2.9 * 10'®, mol KNS1 $ with an equimolar amount of adduct of chloroanilic acid with an amine in water at 25-80 ° C in ₄ for 20-150 minutes in inertial pus atmosphere, after which the solution is cooled to 20-25 ° C, and aliphatic alcohol is added. Immediately by carrying out the hydrogenation reaction, the catalytic -system is treated with N a8H ₄ ι 1,3 amount of 1.3-51.3 mol per 1 g-at. rhodium. The hydrogenation reaction is carried out at atmospheric pressure of hydrogen and 25-80 ° C. For the hydrogenation use 4,63-Ю ' ⁴ - 4,64 · 10' ² g-at. KN per 1 mol of the hydrogenated compound. The yield of chlorinated anilines is quantitative, the conversion of chloronitrocompounds is 100%, the selectivity of the formation of the chloraminoaromatic compound is 99.2 - 100%, the reaction time is 3-120 minutes. The specific activity of the catalytic system is 14.5-143 mol N ₂ / min "g-at. Kh.

Example!. '2.0 g (9.55 mmol) of chloroanilic acid is dissolved in 150 ml of distilled water at 80 ° C. A solution of 1.02 g (19.1 mmol) of ammonium chloride is added to this solution and left for 24 hours at 2025 ° C. The precipitate in the form of fine black needles is filtered off, washed with ether, dried in air and recrystallized from water. The resulting product according to the elemental composition. Has the formula C ₆ ^and 2.0 ₄ C1 ₂ · 2HH ₄ C1.

Example 2. 4.18 g (0.02 mol) of chloroanilic acid is dissolved in 300 ml of distilled water at 60 ° C.

A solution of 3.64 ml (3.72 g, 0.04 mol) of aniline in 50 ml of distilled water is added to this solution. The resulting solution is left for 24 hours at 20-25 ° C. The precipitated violet crystals are filtered, washed with ether, dried in air and recrystallized from water. The resulting product according to elemental analysis has the composition C ₆ H ₂ 0 ₄ C1 ₂ <x2C ₆ H ₅ MN ₂ .

Example 3. 5.2 3 mg (2.5 · 10 ' ⁵ mol) rhodium chloride KK C1 _{3 is} dissolved in 200 ml (11.1 mol) of distilled' water "in a stream of inert gas (nitrogen or argon) at 25 C. A solution of 7.9 mg (2.8 "10" ⁵ mol) of chlorine adduct is added to this solution.

four

anilic acid with ammonium chloride in 215 ml (11.9 mol) of distilled water and stir the reaction mixture for 150 minutes.

To 85 ml of the resulting aqueous rast- thief poured 150 ml (1.98 mole) ^e isopropyl alcohol and stirred for 5 min. 23.5 ml of the prepared catalytic system containing 5Ί0 ' ⁷ mol KN C! _e, 5-10 ^'7 mole adduct hloranilovoy acid with ¹⁰ Risto ammonium chlorite, 0.198 mole of isopropyl alcohol and 0.472 mol of water are charged into a thermostatted glass reaction .sosud provided with a tube for hydrogen input produva15 dissolved hydrogen and administered 1.9 mg Νθ BH ₄ * * 2H ₂ 0 (51.3 mol of sodium borohydride; per 1 mole of KN). Then the reaction mixture is stirred for 2 minutes, after which 20 0.2 g of 3,4-dichloronitrobenzene are introduced in a stream of hydrogen and the reaction mixture is shaken at atmospheric pressure of hydrogen and 25 ° C.

The progress of the reactions is controlled by the absorption of hydrogen. The theoretical amount of hydrogen (78 ml) is absorbed in 120 minutes, the specific activity of the catalytic system is 17.5 mol H ₂ / min · g-at. 4,4-dichloroaniline is obtained, the yield is quantitative, the degree of dehalogenation is 0.10% {table, experience 7). The yield of 3,4-dichloroaniline. And the selectivity of the reaction is estimated by gas chromatography.

Example 4 73.1 mg

_ (3,5 · 10 * ⁴ mol) rhodium chloride KN C1 ₃

• 35 is dissolved in 20 ml (1.11 mol) of distilled water in a stream of inert gas at '40 ° C. A solution of 55.4 mg {3, 5 · 10 ' ⁴ mol) of chloroanilic acid adduct with ammonia-40 Kom C ₆ H ₂ 0 ₄ C1 ₂ · MN ₄ OH in 80 ml is added to this solution

(4.44 mol) of distilled water and stir the reaction mixture at 40 ° C for 20 minutes. Then to the resulting solution is poured 150 ml .. (2.41 mol) of isopropyl alcohol and

• get a catalytic system containing 3.5 <10 ' ⁴ mol KN C1 ₃ ,

3.5 "10 ' ⁴ - mol of chloroanilic acid adduct with ammonia, 5.56 mol of water and 2.41 mol of propyl alcohol.

The prepared catalytic system is loaded into a reaction vessel with a capacity of 500 ml, rinsed with hydrogen and injected 62.4 mg (8.43 · 10 ' ⁴ mol), sodium borohydride (2.41 mol 55 Na per 1 g-at. KN). After stirring the reaction mixture for 5 minutes at 25 °, 10 g of 3,4-dichloronitrobenzene is injected into the reactor in a stream of hydrogen, the reactor is heated to 50 ^σ 0 and shaken at 0 at atmospheric pressure of hydrogen. · The progress of the reaction is controlled by the absorption of hydrogen, the theoretical amount of which 3900 ml is absorbed in 26 minutes, specific selectivity of the catalytic system

760995

17.7 mol K ^ / mnH-at. Kh. Get it.

3.4-dichloroaniline, the yield is quantitative, the degree of dehalogenation is 0.20% (table, experiment 16), the yield of 3,4-dichloraniline and the selectivity of the reaction are evaluated by gas chromatography.

Example 5. 12.7 mg

(6.08 * 1O ^'5 mol) rhodium chloride KNS1 _and dissolved at 80 ° C in 20 ml (1.11 mol) of distilled water in an inert gas stream. A solution of 2 4.1 mg (6.08-10 ^-5 mol) of an adduct of chloroanilic acid with aniline 24 04204024 2С ₆ Н ₃ МН ₂ in 20 ml (0.344 mol) of ethanol is added to the obtained solution and the reaction mixture is stirred for 20 min. .

Prepared catalytic system containing 6.08 "10" ⁵ mol KN.C) \, 6.09 * 10 "^ mol of chloranilic acid adduct with aniline C ₆ H _g 0 ₄ C1 ₂ * 2ϋ _ό Η ₅ · ₂ , 0.344 moles of ethanol, 11 moles of water are loaded into the reactor and 0.2 g are hydrogenated

3.4-dichloronitrobenzene, as indicated in example 4 (sodium borohydride take 9.9 mg (11.34-10 ^-5 mol), 2.2 mol

Selective hydrogenation

25

I

chlorinitroaromatic

| Νβ В Η ₄ · 2Η ^ 0 on 1g-at, KN) (table ¹ , experiment 14).

ΪΙ p and me. 6 The catalytic system is prepared as indicated in example 3. To do this, take 4.19 mg

5 (2-10- ^ mol) rhodium chloride KN C1 _e ,

40 ml (2.2 mol) of distilled water, 6.32 mg (G-KG * mol) of chloroanilic acid adduct with ammonium chloride C ₆ H ₇ 0 ₄ C 1 ₂ · 2HN ₄ C 1, 45 ml

10 (2.5 mol) of distilled water and 150 ml (1.98 mol) of isopropyl alcohol.

23.5 ml of the prepared catalytic system containing 2 * 10 ^-6 mol of KN C1 _& 2, 2 * 10 ^-6 mol of chloroanolic acid adduct with ammonium chloride, 0.47 mol of water and 0.198 mol of isopropyl alcohol are loaded into the reactor and Hydrogenated with 0.2 g of 3,4-dichloronitrobenzol, as indicated in Example 4.

20 Sodium borohydride take 4.1 mg

(5.24-10 ^-5 mol, 26.2 mol NaVN ₄ -2N _g 0 per.1 g-at. KN). The specific activity of the catalytic system is 89.3 mol NS / minGH at KN (table, experiment 9).

The results of nitrobenzene hydrogenation are presented in the table. ^one

connections “

Experience

Ligand

If- Solvent, If- About- Specific Ste- honest- mole honest- should Naya stump IN Overall Alcohol Water in living assets- de- kata volume, ΝβΒ Н ₄ " tel- ness loidi Liza- ml "2H ₂ 0, ness mole ditch Torah, mole reactions, n ₂ % g-at? on * 10 ⁵ mole min min * Kh g-at. Kh

one

2

3

four

five

6

7

8 9

ten

eleven

12

13

14

15

sixteen

17

18

nineteen

20 21 22

C ₆ H ₂ 0 ₄ C1 ₂ 2ΝΗ ₄ 0Η The same

ο ₆ η ₂ ο ₄ ο _ζ · 2νη ₄ ο

Also

II

II

С ₆ Н ₂ 0 ₄ С) _Г 2МН ₄ Н ₂ Р0 ₄ ^С 6 ^Н 2 ° 4 ^С, 2 ' ^2С 6 ^Н 5 ^МН 2

с, н ₂ о ₄ С 1 ₂ · νη ₄ he С ₆ Н ₂ 0 _{4 2} · ₂ ΝΗ ₄ Ο The same ” ¹¹ -

2 ^C 6 ^H 4 ° ^C, 2 ^'2MN 4 ^0H Same

5.6 25 0.344 0.278 2.17 five 22.4 0.15 4.2 25 0.344 0.278 1,3 four 45.1 0.80 4.56 13 0.248 0.167 2.67 'five 23.5 0.10 4.56 13 0.172 0.167 Also five 27.4 0.12 4.56 13 0.132 0.167 ¹¹ - five 20.3 0.12 4.56 0.05 13 0.109 0.167 _ and __ five 23.5 0.15 23.5 0.198 0.472 51.3 120 17.5 0.10 0.10 23.5 0.198 0.472 27.4 55 44.7 0.10 0.20 23.5 0.198 0.472 26.2 25 89.3 0 0.50 23.5 0.198 0.472 15.3 ten 143.0 0 1.0 23.5 0.198 0.472 12.2 ten 58.0 0.10 6.0 20.0 0.198 0.278 2.1 20 35.8 0.10 6.08 14 . 0.132 0,222 2.0 15 14.5 0.10 0.15 6.08 40 0.344 1.11 2.2 five 16.2 35.0 250 1.98 5.56 2.41 26 17.7 0.20 4.56 13 0.172 0.167 2.67 3 23.3 0.20 4.56 13 0.172 0.167 2.67 four 20.2 0.10 4.56 13 0.172 0.167 2.67 3 21.2 0.20 5.6 25 0,228 0.462 2.17 thirty 4.3 2.0 5.6 25 0.26 0.278 2.17 35 3.5 8.3 5.6 25 0.344 0.278 2.17 25 5.3 1.7 5.6 2.17

and note. Hydrogenation conditions: PH? 760 mm Hg, those p

tour of the reaction medium 30 C, in the experience of 7-25 s, in the experience of 2-90 ° C, in the experience of 15-50 ° C.

76 (3995 8

For the preparation of the catalytic solution is used in experiment 3 methyl alcohol, in experiments 1,2,4,14, 16-18, 21 - ethyl alcohol, in experiments 5, 7-13, 15, · 22 - isopropyl alcohol, in experiment B - butyl alcohol, in experiment 19 — acetone, in experiment 20 — dimethylformamide.

Hydrogenated chloronitrobenzenes in experiment 16 — p-chloronitrobeneol (0.17 g), in experiment 17 — o-chloronitrobenzene (0.17 g), in experiment 18, m-chloronitro- ”*

benzene (0.17 g), in all other experiments - 3,4-dichloronitrobeneol, in experiments 1, 3, 19-22 - 0.3 g, in experiments 2, 7-11, 13, 14-0.2 g in experience 1? 1.15 g, in the experience of 15 - 10 g. 1

Claims (1)

Claim ; . < _ν Homogeneous catalytic system for the selective hydrogenation of chlorine nitroaromatic compounds ben- ² "* 3" of the series consisting of a compound of a metal of the VIII group of the periodic system, a ligand based on the chloroanic acid oxides, aliphatic alcohol and water, characterized in that ^g in order to improve catalyst system activity, 'as a group VIII metal compound used is rhodium chloride as ligang yes - hloranilovoy yisloty adduct with an amine of general formula ³ C $ NlO4S1 "* »2С ₆ Н ₅ МН ₂ or С ₆ Н ₂ 0 ₊ С1 _g · n (МН ₄ Г К", where n = 1-2 K = OH, C1, n ₂ ro _4G • with the following molar ratio of components: rhodium chloride “adduct of chloroanilic acid with amine: aliphatic alcohol: water - (5 · 10“ ⁷ -3.5 ”” 1 <G ⁴ ): ( 5-10-- ⁷ - 3.5 10 ' ⁴ ): : (0.109 - 1.98): (0.167 - 5.56), respectively.