DE2053736C3 - Process for the production of 1- and 2-formylindane by the oxo synthesis - Google Patents

Description

It has been found that 1- and 2-formylindan formylindan.

more advantageous than previously obtained when indene according to the method of the invention leads to both oxosynthesis with carbon monoxide and hydrogen game, from by reacting, in a high pressure vessel at temperatures of 80 to 18O ⁰ C and pressures of 45 in the optionally together with one of the BE -100 to! 000 at in the presence of rhodium carbonyl-written inert solvent and the complexes described. The new process has the advantage that 1-specified pressures and tempering with one and 2-formylindane are obtained in a simple manner in good yields in a mixture of carbon monoxide and hydrogen of the stage. 5 ° specified composition implements. The React-The new process is remarkable in that, after cooling and depressurization, the hydroformylation of indene in nes by distillation removes the presence of cobalt carbonyl complexes from the catalysts. From the mixture thus obtained, slight yields of 1- and 2-formylindane are then obtained, 1- and 2-formylindane by known methods, while most of the indene is hydrogenated to indane 55 z. B. fractional distillation isolated. Will be expedient. It was therefore not to be expected that the hydro- unreacted indene would be fed back into the reactivation of indene using rhodium.

dium carbonyl complexes is more specific. 1- and 2-formylindan, which is produced according to the method of

Carbon monoxide and hydrogen are produced in the eye-invention is suitable for production

my in a volume ratio 4: 1 to 1: 4, par- 60 of crop protection agents and dyes. Further

others in a volume ratio of 2: 1 to 1: 2 are used. can be obtained by hydrogenating 1- or 2-formylindane

It is possible to produce indene and the mixture of carbon easily 1- or 2-hydroxymethylindane, the

monoxide and hydrogen in stoichiometric quantities for the production of esters with a refreshing scent

to apply. It is advantageous to use that which is suitable.

named mixture of carbon monoxide and hydrogen 65 The process according to the invention is as follows

in excess, e.g. B. up to 100 mole percent. Examples illustrated. The parts mentioned are

The implementation is carried out at temperatures of 50 parts by weight. They relate to space

to 180 ⁰ C through. Dividing as kilograms to liters gives particularly good results.

I 93% consists of I- and 2-formylindane, isomers «

:; “ _UJ ratio: 77; 23,

In a high pressure vessel made of stainless steel of 1000

Volume parts are 250 parts indene, 250 parts Example 4
Benzene and 0.05 part of CycJooctadienyl-IS-rhodium-5

^ cblorid with an equimolecular mixture of As described in Example 2, 500 parts

ί Carbon monoxide and hydrogen under a pressure indene and 0.015 part RhpiCsH ^ iCOJCl 10 hours

of 700 at bit 10O ⁰ C implemented. After 6 hours at 14O ° C and 200 at with carbon monoxide and

₅ . The reaction time is cooled and the reaction hydrogen is converted, and 425 parts of the crude mixture obtained are depressurized. Fractional distillation distils io products. 196 parts are obtained

; 263 parts of a mixture of 1 and unreacted starting product are obtained back. Besides that

ι- 2-Formylindan in a ratio of 75: 25 from the boiling point are 172 parts of a mixture of 1- and 2-For-

ί point 130 to 131 ° C at 25 Torr. The yield is cylindane, the isomer ratio of which is 60:40

^ 84% of theory. amounts to

-i 15th

Example 5
ϊ Example 2

As described in Example 2, 500 parts are used

In a high pressure vessel of 1000 parts by volume of indene and 0.01 part of rhodium dicarbonyiacetate

Contents are 500 parts indene and 0.05 parts ao 130 ° C and 700 at with an equimolecular structure

[CgHjjRhClJg 10 hours at 100 ° C with an equi-

molecular mixture of carbon monoxide and water. 567 parts of discharge are obtained. Of this

reacted hydrogen under a pressure of 300 at. The 421 parts are used for distillation, with

Gas uptake is 750 at. After analogous preparation 311 pass over parts. 92% of these contain a

processing as in Example 1, 514 parts of distillate are obtained, as a mixture of 1- and 2-formylindane in the isomer ratio

which consists of 86% 1- and 2-formy jindan. The nisvon70: 30.
Isomer ratio of the two components
according to gas chromatographic analysis 72:28. Example 6

30 As in example! 2, you put 500 pieces

Example 3 Indene and 0.2 part of Rh (PO ₃ ) J (CO) Cl at 80 ° C and

700 at with an equimolecular mixture of carbon

As described in Example 2, 500 parts of lenmonoxide and hydrogen are used for 10 hours.

Indene and 0.1 part of Rh (CO) [P (C _e h _u ) ₃ ] ₂ Cl at 120 ° C. The obtained product is obtained after analogous work-up

and 300 at with carbon monoxide and hydrogen, in the 35 reaction product 537 parts of distillate, which is 86%

Volume ratio 1: 1 implemented. One receives after consists of 1- and 2-formylindan. The isomeric

analogous work-up 491 parts of distillate, the ratio is 87: 13.

Claims (1)

if you have temperatures of 80 to 150 ⁰ C Claim; holds. In addition, the implementation will be carried out at pröcken of 50 performed up to 1000 at. Preferably one turns Process for the production of 1 and 2-FormyUn ·· pressures from 200 to 800 at. dan, characterized in that 5 The reaction is carried out in the presence of carbonyl one carried out indene after the oxo synthesis with carbon complexes of rhodium. In general Monoxide and hydrogen at temperatures of between 0.001 ppm and 0.5 percent by weight are used 80 to 180 ⁰ C and pressures from 100 to 1000 at in 'rhodium, calculated as metal, on the amount of Presence of Rhodiumcarbonylko: nplexen reacted indene. Have special stock puts. ίο amounts of 0.1 to 100 ppm have been found. It is possible to prepare the carbonyl complexes separately before the reaction or the starting materials for the carbonyl complexes, such as halides, oxides, '' Chelate complexes or fatty acid salts of rhodium, 15 to be fed separately to the reaction. The catalyst then forms by itself under the reaction conditions. If necessary, the rhodium car- The invention relates to a process for bonyl complexes by adding complexing agents, Production of 1- and 2-formylindane using hydro such as phosphines, phosphites, arsines, stibines, amiformylation from Inden. ao nen, pyrrolidones, 1,3- or 1,4-dicarbonylverbindun-formylindanes have so far only been modified to be cumbersome. Preference is given to square chemically produced and also only in small planar complexes of the formally positive monovalent Yields receive «. For example, 1- Rhodiums, which are either used as such, Formylindane, usable in yields which cannot be used industrially or which arise under the reaction conditions a are, by reacting l-hydroxy-2-as turns. Manufacture iodotetralin with silver nitrate (see Compt. If the implementation is carried out without using rend. Volume 170, p. 466 and Bulletin de la Socioto of solvents, then this serves as the starting point Chimique [4], vol. 27, p. 789). 2-Formylindan leaves indene used as a solvent. Another- by reacting tetralin-2,3-epoxide with one hand, however, it is also possible under reaction conditions Manufacture methyl magnesium bromide (cf. Compt. 30 inert solvents such as hydrocarbons, rend. Volume 214 [1942], p. 117). After another z. B. benzene, toluene, cyclohexane, xylene, hexane or In the process, 2-formylindane is obtained by means of Behan- octane, and also ethers, such as tetrahydrofuran, as well the use of 2-hydroxymethylindane with chromium-sulfur alkanols, such as methanol or butanol, acid (see Journal of the Chemical Society, Volume den. 105, p. 2694). 35 The method according to the invention can AHe methods mentioned so far have in common wise or in suitable devices in a simple manner the disadvantage that they are technically complex or are carried out continuously. The Ver- start from raw materials that are difficult to access. ratio of 1: 2 Formylindan can be used in certain The technical task was set to vary 1- and limits. So you get z. B. by increasing 2-Formylindan in a simpler way than before 40 the temperature, z. B. to 150 ⁰ C, and / or lower put. Pressure, e.g. B. 200 at, an increased proportion of 2-