US3828092A - Process for producing alkyl esters of omega-cyano-acids - Google Patents

Process for producing alkyl esters of omega-cyano-acids Download PDF

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Publication number
US3828092A
US3828092A US00649033A US64903367A US3828092A US 3828092 A US3828092 A US 3828092A US 00649033 A US00649033 A US 00649033A US 64903367 A US64903367 A US 64903367A US 3828092 A US3828092 A US 3828092A
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acrylonitrile
ruthenium
alkyl
methyl
hydrogen
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P Chabardes
P Gandilhon
C Grard
M Thiers
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Rhone Poulenc SA
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Rhone Poulenc SA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups

Definitions

  • the present invention relates to the production of alkyl esters of w-cyanovaleric acid and of cis and trans 5-cyano penten-4-oic acids.
  • the latter are new compounds.
  • adiponitrile may be obtained by reacting acrylonitrile in aqueous solution with a finely divided dispersion of sodium in an inert organic solvent.
  • the yields of adiponitrile are always low, relative to both the acrylonitrile and the metallic sodium consumed.
  • treating acrylonitrile with magnesium in an aliphatic primary mono-alcohol in the presence of mercuric chloride as an activator only gives low yields.
  • 1,229,702 a process for the dimerisation of olefinic compounds has also been described which consists in heating the compounds in the presence of a noble metal derivative such as ruthenium chloride, working under the autogenous pressure of the reagents.
  • a noble metal derivative such as ruthenium chloride
  • methyl acrylate yields methyl a-dihydromuconate by prolonged heating at 210 C. in the presence of ruthenium chloride and methanol.
  • the invention accordingly provides a process for the production of alkyl w-cyano-valerates and S-cyanopenten-4-oates which comprises heating a mixture of acrylonitrile and an alkyl acrylate under hydrogen pressure in the presence of a ruthenium compound as catalyst.
  • reaction coupling products in particularly alkyl 5-cyano-penten-4-oates and alkyl w-cyanovalerates, and dimerisation products of acrylonitrile and alkyl acrylates such as cis and trans 1,4-dicyano-butene-1 and alkyl a-dihyromuconates, as well as their hydrogenation products, namely adiponitrile and alkyl adipates, are simultaneously formed.
  • the catalysts which can be used in the new process are inorganic or organic derivatives of ruthenium such as the halides, thiocyanates, the salts of inorganic oxygen-containing acids such as the sulphates, nitrates, oxyhalides and hydroxyhalides, and the salts of organic aliphatic, cycloaliphatic or aromatic acids such as the acetate, oxalate, stearate and naphthenate.
  • the alcoholates and the phenate may also be used.
  • ruthenium compounds which can be used include the alkali metal and alkaline earth metal ruthenates, the mixed salts of ruthenium and an alkali metal such as the sodium or potassium halogenoruthenates, and the halogenated and nitrosylated or aminated compounds such as nitrosochlororuthenium or trichlororuthenium hexamine.
  • the chelates such as the acetylacetonates, optionally substituted by, for example, aliphatic or cycloaliphatic groups or by halogen atoms, such as 3-bromo-2,4-pentadionato-ruthenium(III) or 1,1,1 trifluoro 2,4 pentadionato-ruthenium(l1l), the glyoximates, quinolinates, salicylaldehydrates, and the derivatives of ethylene diamine, of a,a'-dipyridyl, and of o-phenanthroline are also suitable.
  • Another especially suitable class of catalyst consists of the complexes which ruthenium derivatives form with electron donors.
  • Such complexes are, for example, obtained by using halogenated, carbonylated or nitrosylated derivatives of ruthenium as the ruthenium derivatives and substances having pairs of lone electrons such as the phosphines, arsines, stibines, amines or substances capable of forming structures having pairs of lone electrons and thus also able to act as electron donors, as the electron donors.
  • the complexes formed with electron donors which are specifically cited in French Patent Specification No. 1,337,558 may be used.
  • an amount of catalyst corresponding to an amount of metallic ruthenium of between 0.04 and 1.2% by weight of the mixture of acrylonitrile and alkyl acrylate which is to be treated is generally suitable.
  • These lirnits are however not rigid and in the case of particularly active ruthenium derivatives, such as ruthenium trichloride or acetylacetonate, smaller amounts, e.g. 0.01% or even 0.001% of ruthenium, may be used.
  • the catalysts may be used in the solid state, in a finely divided form, in suspension or in solution in the monomers, in water or in an organic solvent which is inert under the reaction conditions. The catalysts do not change, or
  • the reaction It is essential for the reaction to be carried out in the presence of hydrogen which can be introduced all at once, or in several stages, or even continuously to maintain a constant pressure of hydrogen.
  • the pressure and temperature may vary within certain limits, most commonly from 1 to 50 bars and from 50 C. to 150 C. respectively. There is no advantage in working outside these limits. Below the lower values the reaction proceeds only slowly while above the upper values excessive amounts of propionitrile and alkyl propionates form, at the expense of the desired products, by direct hydrogenation of acrylonitrile and the acrylates. Similarly, increasing the duration of the reaction at a given hydrogen pressure increases the formation of saturated products.
  • the most advantageous working conditions are generally within the range of to 40 bars pressure and 100 to 130 C.
  • the molar ratio acrylonitrile/acrylate is not critical, and may, for example, be from 1:3 to 3:1.
  • the acrylonitrile and alkyl acrylate used in the reaction may be either commercial products or freshly distilled, and either unstabilised products or distilled products to which very small amounts of a stabiliser such as hydroquinone, pt-butyl-pyrocatechol, p-nitrosodimethylaniline or ammonia have been added.
  • the alkyl acrylate will generally be one in which the alkyl group contains 1 to 4 carbon atoms, especially methyl acrylate.
  • the monomers are introduced all at once into a pressure-resistant apparatus, but it has been observed that introducing part of the monomers into the apparatus and then introducing the remainder progressively during the reaction increases the percentage of coupling products at the expense of the dimerisation products.
  • the reaction is preferably carried out in bulk or in the presence of a diluent which is liquid and inert under the working conditions.
  • the reaction period will usually be from 2 to hours.
  • the unconverted monomers, the solvent (if any) and the hydrogenation products of the monomers, which are the sole volatile by-products formed may be isolated by distilling the reaction mixture.
  • the coupling products and the dimerisation products and their hydrogenation derivatives are then separated by fractional distillation.
  • the alkyl 5-cyano-penten-4-oates and w-cyanovalerates may be converted, by hydrogenation, into alkyl w-aminocaproates which are intermediates for the preparation of polycaprolactam; the dicyanobutenes may 'be converted by hydrogenation into adiponitrile which is a starting material for the preparation of hexamethylene diamine used in the synthesis of polyamides; and the alkyl a-dihydromuconates may be hydrogenated to alkyl adipates, which may be saponified to yield adipic acid or used directly in the synthesis of polyesters by reaction with glycols.
  • EXAMPLE 1 0.1 g. of ruthenium chloride (0.48 millimol), 32 g. of acrylonitrile (0.605 mol), 38.4 g. of methyl acrylate (0.440 mol), and 0.05 g. of hydroquinone are introduced into a 250 cm. stainless steel autoclave fitted with a vibratory stirrer system. The autoclave is purged with hydrogen and a hydrogen pressure of 40 bars is then set up. The contents of the autoclave are kept at 110 C. for 5 hours, with stirring. The pressure rises to 48 bars and is then kept at 40 bars by periodically introducing hydrogen. The reaction mixture is then cooled to ambient temperature. The total hydrogen pressure drop is 58 bars.
  • the apparatus is degassed and the reaction mixture is distilled in vacuo.
  • a volatile fraction containing methyl propionate, propionitrile, acrylonitrile (1 g. determined by vapour phase chromatography) and methyl acrylate (20 g.) is first obtained, followed by 18.3 g. of a less volatile fraction distililng at between 60 and 110 C. in a vacuum of 0.6 mm. Hg.
  • the residue weighs 1.5 g.
  • Vapour phase chromatography shows the less volatile fraction to contain: methyl adipate (0.2 g.), methyl oz-dihydromuconate (l g.), cis and trans 1,4-dicyano-butene-l (9.6 g.), cis methyl 5-cyanopenten-4-oate (2.5 g.) trans methyl 5-cyano-penten-4-oate (3.2 g.), methyl w-cyanovalerate (0.5 g.), and adiponitrile (1.3 g.). This corresponds to 6.5% of dimerisation and hydrodimerisation products of methyl acrylate, 59.5% of dimerisation and hydrodimerisation products of acrylonitrile, and 34% of coupling products.
  • EXAMPLE 2 0.2 g. of ruthenium chloride (0.96 millimol), 16 g. of acrylonitrile (0.302 mol), 57.6 g. of methyl acrylate (0.670 mol), and 0.05 g. of hydroquinone are introduced into a 250 cm. autoclave. Working as in Example 1, a hydrogen pressure of 40 bars is then set up and the contents of the autoclave are heated to 110 C. The pressure is maintained at 40 bars Whilst hydrogen is introduced as in Example 1. These conditions are maintained for 5 hours. After cooling the reaction mixture, it is found that the total pressure drop is 60 bars. By distilling the reaction mixture a more volatile fraction containing 9.5 g. of methyl acrylate (0.11 mol) is first isolated, followed by 14.7 g. of a less volatile fraction boiling at between 60 and C./0.4 mm. Hg. Analysis of the latter fraction by vapour phase chromatography shows it to contain:
  • Example 2 is repeated using 24 g. of acrylonitrile (0.454 mol) in place of 16 g. (0.302 mol). The total pressure drop is 97 bars. Distilling the reaction mixture gives first a more volatile fraction containing 11 g. of methyl acrylate by vapour phase chromatography but no acrylonitrile, followed by 22 g. of a less volatile fraction comprising the following.
  • EXAMPLE 4 0.2 g. of ruthenium chloride (0.96 millimol), 19.7 g. of acrylonitrile (0.372 mol), 23.7 g. of methyl acrylate (0.276 mol), and 0.05 g. of hydroquinone are introduced into a 125 cm. autoclave connected to a source of hydrogen through a pressure-reducing manometer. The autoclave is purged with hydrogen. Hydrogen is then introduced and a constant pressure of bars is maintained at 110 C. for 6 hours whilst hydrogen is continuously introduced through the manometer. 9.25 litres of hydrogen are introduced in this way. At the end of the reaction the autoclave is brought to ambient temperature and degassed. The reaction mass is worked up as in the preceding example. 23.25 g. of a fraction which contains neither acrylonitrile nor methyl acrylate are first obtained, followed by 16.20 g. of a fraction the composition of which is as follows:
  • EXAMPLE 6 0.4 g. of ruthenium acetylacetonate (1 millimol), 47.9 g. of methyl acrylate (0.560 mol), 40.1 g. of acrylonitrile (0.756 mol), and 0.1 g. of hydroquinone are introduced into a 250 cm. stainless steel autoclave connected to a source of hydrogen through a pressure-reducing manometer. The autoclave is purged with hydrogen and hydrogen is then introduced to a pressure of 7 bars. The contents of the autoclave are heated to C., and the pressure rises to 10 bars. These conditions are maintained for 6 hours whilst hydrogen is introduced throughout the operation to keep the pressure at 10 bars. At the end of the operation the autoclave is cooled.
  • the amount of hydrogen consumed is 4.5 l.
  • the reaction mass is worked up as in the preceding examples. 63.3 g. of a more volatile fraction are collected, which is shown by gas chromatography to contain 7.6 g. of acrylonitrile and 33.5 g. of methyl acrylate. 20.8 g. of a less volatile fraction and 1.9 g. of residue are thereafter isolated. Gas chromatography shows the less volatile fraction to have the following composition.
  • EXAMPLE 8 0.4 g. of ruthenium acetylacetonate (1 millimol), 16 g. of acrylonitrile (0.302 mol), 19 g. of methyl acrylate (0.220 mol), 0.04 g. of hydroquinone, and 60 cm. of Z-methoxy-ethanol are introduced into the 250 cm? autoclave used in the preceding examples, and the contents of the autoclave are then kept at 110 C. for 6 hours at a constant hydrogen pressure in the preceding examples 8 EXAMPLES 10 TO 12 A series of experiments is carried out by introducing 16.7 g. of acrylonitrile (0.315 mol),- 27 g.
  • Adiponitrile The dichloro-tetrakisacrylonitrile ruthenium-II used as the catalyst is prepared by heating 64 g. of acrylonitrile (containing 0.08 g. of hydroquinone) with 4 g. of ruthenium trichloride dissolved in 80 cm. of Z-methoxy-ethanol under reflux for 28 hours, and then filtering the unreacted ruthenium chloride and concentrating the filtrate in vacuo.
  • the catalyst is ruthenium chloride, ruthenium acetate, ruthenium oxalate, ruthenium stearate, ruthenium acetylacetonate, 3-bromo- 2,4-pentadionatoruthenium (HI), 1,l,1-trifluoro-2,4-pentadionatoruthenium(1H), ruthenium glyoximate, ruthenium quinolinate, ruthenium salicyaldehydate, a chelate of ruthenium with ethylene diamine, a,a -dipyridyl, or 0-phenanthroline, or a complex of ruthenium chloride with butadiene, isoprene, cyclooctadiene, acrolein, methacrm lein, acrylamide, acetonitrile, propionitrile, acrylonitrile, methacrylonitrile, cyanocyclohex

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US00649033A 1966-07-13 1967-06-26 Process for producing alkyl esters of omega-cyano-acids Expired - Lifetime US3828092A (en)

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FR69417A FR1493068A (fr) 1966-07-13 1966-07-13 Procédé de dimérisation de mélanges de composés alpha-beta éthyléniques

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US (1) US3828092A (enrdf_load_stackoverflow)
AT (1) AT269103B (enrdf_load_stackoverflow)
BE (1) BE701280A (enrdf_load_stackoverflow)
CH (1) CH463479A (enrdf_load_stackoverflow)
DE (1) DE1693175B2 (enrdf_load_stackoverflow)
ES (1) ES342997A1 (enrdf_load_stackoverflow)
FR (1) FR1493068A (enrdf_load_stackoverflow)
GB (1) GB1153814A (enrdf_load_stackoverflow)
LU (1) LU54084A1 (enrdf_load_stackoverflow)
NL (1) NL6709352A (enrdf_load_stackoverflow)

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DE1693175A1 (de) 1972-04-13
NL6709352A (enrdf_load_stackoverflow) 1968-01-15
AT269103B (de) 1969-03-10
FR1493068A (fr) 1967-08-25
LU54084A1 (enrdf_load_stackoverflow) 1968-03-12
CH463479A (fr) 1968-10-15
GB1153814A (en) 1969-05-29
DE1693175B2 (de) 1974-01-10
BE701280A (enrdf_load_stackoverflow) 1968-01-12
ES342997A1 (es) 1968-08-16
DE1693175C3 (enrdf_load_stackoverflow) 1974-08-15

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