SU1397424A1 - Method of producing cyclohexanecarboxylic acids - Google Patents

Abstract

The invention relates to cyclocarboxylic acids, in particular the production of cyclohexanecarboxylic acid (CK), which can be mono- or di-substituted by methyl, ethyl and is used as a plasticizer, a component of paints, varnishes, lubricants and catalysts. The increase in the output of CC and the simplification of the process of its production occurs due to a change in the modes and the use of the promoting agent. - Preparation of CK occurs by carbonipylation of the corresponding cyclohexane at a pressure of 50-100 atm in a medium of water (molar ratio of water to cyclohexane is 5-12.5) in the presence of a palladium-catalyst complex of the general formula PdCljLj, where L (CbH) P, pyridine, poly - (2-vinylpyridine),. C H5 - CN with the addition of HI. The promoter (HI) is used in an amount of 0.5-1.5% by weight of the reaction mixture. The method provides the output of the Central Committee up to 97%. 2 tab. about SS cl

Description

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with

four

tNd

four;

The invention relates to organic synthesis, in particular, to a process for the preparation of cyclohexanecarboxylic acids of the general formula

1 G - € UN

RI-XJ

where R is H, CH, CdH .; and R - H, CH, by carbonylation of cyclohexene or its alkyl derivatives in the liquid phase in the presence of a catalyst, Cshs lexanecarboxylic acids can be used as plasticizers, components of paints, varnishes, lubricants, agricultural preparations, color extractants, rare, noble; metals and scattered elements, ink components, and also as components of catalysts.

The aim of the invention is to increase the yield of the target product and simplify the process by changing the modes of the process and other promoting agent.

As a catalyst, palladium complexes of the general formula are used (where L is PPH3, Py, poly- (2-vinyl pyridine), PhCN), with the addition of a promoter — hydroiodic acid in an amount of 0.5-1.5% by weight of the reaction mixture.

Due to the found molar ratio of water to cycloolefin equal to 50-12.5, the reaction mixture after the reaction is in two phases: in the upper phase, the reaction product and the catalyst in the form of a suspension, and in the lower aqueous organic acid and. promoter (HI). The catalyst from the top layer is easily separated from the product.

the reaction is filtered or decanted and can be reused without reducing its effectiveness.

Example 1 A glass ampoule was placed in a stainless steel autoclave with a capacity of 0.15 l and loaded with: water 4.5 g (0.25 mol), acetic acid 3 g (0.05 mol), cyclohexene 4.1 g (0.05 mol), Pd (PPh,) j, Cli 70 mg (Ruhl) and 47% HI 0.25 g (1% by weight of the reaction mixture). The molar ratio cyclohexene: water is 1: 5. The autoclave is flushed with carbon monoxide twice at 5 atm and then released into the atmosphere. Then in the autoclave create a pressure of CO to 100 atm. The reactor is heated during its rotation (90 rpm) to 150 ° C. The reaction is carried out for 4 hours. The autoclave is cooled, the excess pressure is released. The reaction product (upper layer) is separated from the catalyst and analyzed by GLC. 6.3 g (99% yield) of cyclohexane-carboxylic acid are obtained, t, bale, 128 mm Hg, ct, t, pl. S4 with. The conversion of cyclohexene is 100%, and the selectivity is 99%,

Examples 2-23, In Example 1, carbonylation of cyclohexene or its alkyl derivatives is carried out with the difference that some process parameters are changed in the carbonylation process of cyclohexenes.

In tab. I shows the carbonylation of cyclohexene and its alkyl derivatives (reaction time 4 h), in table. 2 - carbonylation of cyclohexene with repeated use of the catalyst PdCl2 (PPH) g,

.Table

PdCl, (PPh4) g AcOH 5.0 fsO 100 95 97

V

  L.O. 150 150 95

95

V- I, 4-dimethyl-dicloxaxen

Cyclohexene

fsO 100 95 97

150 100 95

150 150

100, 95

100 75

95

96,100

92 90

9

75

ten

li

 2

13 14 J5 16 17 IB 19 20

21

22-23- - -

. AND

. -. - -Tl.

lt

-, -

m

.-, -

PdCljPya PdClj (PhCN) t

PdClt {(nonH- - (2-VINIL-pnridine) |

PdCli PPh,) i

2.5

5.0

10.0

12.5

15.0

5.0

5.0

3.0

5.0

5.0

5.0

5.0

5.0

5.0

5.0

EtCOOB 5.0 K-PrCOOH 5.0 H-BuCOOH 5.0

if

- Carbonic acids contain mixtures (1: 6.3: 4.5: 2) 1-methyl, 3-methyl, and methyl methylohexaccarboxylic acids, t, kip. 130-135 C / 13.

 Carboxylic acids contain mixtures of (, 5: 405) 1-step-, 2-ethyl, 3-ethyl, and th-ethnylnclogexancarCo ovis

acids, t. Kip. 132-137 C / 13.

 Carboxylic acids contain a mixture of (1: 9) 1,4-imethyl- to G. 3-dimershislohexaccarboxylic acids, t. Kip. U5-13l ° C / 2t. At the indicated ratios, the biphasicity of the systems disappears.

Examples 24-27. The experiments were carried out as in Example 1 with the difference that after the test, the reaction product was removed from the upper organic layer and analyzed by GLC. The catalyst, separated from the upper organic layer from the reaction product, together with the addition of standard quantities of water, AcOH, aqueous HI and cyclohexene, was introduced into the autoclave in the following experiment. The catalyst is used in four repeated experiments (Table 2).

From tab. 2, it can be seen that the catalyst can be re-used without decreasing its efficiency, while the palladium-1 leaving the catalyst into the volume is insignificant (about 1.5-2% after each experiment).

Continuation of table 1

M

150 150 150

tso

150 150

too

120 160 180 200 220 130 130 130

150 30 ISO

100 100

100 100

too

50

100

100

100

100

100

100

too,

100 100

91

99

98

97

96

96

78

98

98

100

100

100

97

97

100 98 too 97 too 96

100

100

too

98

90

98.4

99

97

98

95

92

86

99

97

99

98 99 97

 91 99 98 95 86

94.5 77 95 96 95 92 87 96

91.2 96

96 96 93.

table 2

 Determined from the aqueous acid layer after the experiment by atomic absorption spectrophotometry using a Saturn-2 instrument.

Carbonylation of cyclohexenes according to the proposed method is carried out with a CO pressure of less than 50 atm impractical because of a lack of CO for carrying out the reaction and the shortness of the disturbance of the existence of a liquid phase. It is also inexpedient to carry out the synthesis of cyclohexanecarboxylic acids at a pressure above 100 atm from an economic and technical point of view.

soon

where R is N.CH, CjHg and R is N.CH, by carbonylation of cyclohexene or its alkyl derivatives with carbon monoxide at elevated temperature and increased pressure in the presence of a catalyst, a palladium complex, characterized in that, in order to increase the yield of the target product and simplify the process , the latter is carried out at a temperature of 120–200 ° C and a pressure of carbon monoxide of 50–100 atm in aqueous C – C-organic acid with the addition of hydroiodic acid at a molar ratio of water and cycloolefin equal to 5–12.5,

Claims (1)

Soo claims 1 2. 3 4 5 26 94 97 91 2.0 '27 92 96 88 1.9 The method of obtaining cyclohexanecarboxylic acids of the general formula * It is determined from the aqueous acid layer after the experiment by atomic absorption spectrophotometry on a Saturn-2 device. Carbonylation of cyclohexenes according to the proposed method is carried out at a CO pressure of less than 50 atm due to a lack of CO for the reaction and the inadmissibility of the existence of a liquid phase. To carry out the synthesis of cyclohexanecarboxylic acids at pressures above 100 atm is also impractical from an economic and technical point of view. where R is H, CH ₃ , C ₂ H _S and R ₄ is H, CH _L , by carbonylation of cyclohexene or its alkyl derivatives with carbon monoxide at elevated temperature and $ 1 elevated pressure in the presence of a catalyst - palladium complex, characterized in that, with In order to increase the yield of the target product and simplify the process, the last ₂ θ ns are conducted at a temperature of 120-200 ^₽ C and a pressure of carbon monoxide of 50-100 atm in aqueous C ^ -C ^ -organic acid with the addition of hydroiodic acid in a molar ratio of water to cycloolefin, equal to 5-12.5.