US3557186A - Reductive dimerization of acrylonitrile - Google Patents

Reductive dimerization of acrylonitrile Download PDF

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Publication number
US3557186A
US3557186A US737393A US3557186DA US3557186A US 3557186 A US3557186 A US 3557186A US 737393 A US737393 A US 737393A US 3557186D A US3557186D A US 3557186DA US 3557186 A US3557186 A US 3557186A
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Prior art keywords
acrylonitrile
reaction
weight
amalgam
amalgams
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Expired - Lifetime
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US737393A
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English (en)
Inventor
Hans Leitner
Karl Wintersberger
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BASF SE
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BASF SE
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Priority claimed from DE19671618180 external-priority patent/DE1618180A1/de
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B31/00—Reduction in general

Definitions

  • This invention relates to the reductive dimerization of a,fi-olefinic nitriles, carboxylic amides and carboxylic esters, particularly of acrylonitrile.
  • Particularly suitable a,fl-olefinic nitriles, amides or esters which are susceptible to the Michael reaction are acrylonitrile, acrylamide and acrylic esters of low molec ular weight alcohols, for example those having one to four carbon atoms, and also alkyl derivatives of the said compounds, for example those having one to three carbon atoms in the alkyl radical such as methyl, ethyl, propyl or isopropyl derivatives.
  • alkyl derivatives of the said compounds for example those having one to three carbon atoms in the alkyl radical such as methyl, ethyl, propyl or isopropyl derivatives.
  • suitable olefinically unsaturated compounds apart from those already specified are for example crotononitrile, crotonamide, and the corresponding methacrylic derivatives, such as methacrylonitrile, methacrylamide or methacrylic esters.
  • Alkali metal amalgams such as sodium, potassium, lithium, rubidium or caesium amalgams are generally used, but the process may be carried out just as well with alkaline earth metal amalgams such as magnesium, calcium 0r barium amalgams. Easily accessible sodium amalgams is preferred.
  • the content of alkali metal or alkaline earth metal in the amalgam may vary within wide limits: it is preferred to use amalgams having a content of up to 0.8%, particularly from 0.01 to 0.4%, by weight of alkali metal or alkaline earth metal, it is however possible to use amalgams having a higher content than 0.8% by weight.
  • Water is particularly suitable for use as the proton donor. It is also possible however to use lower alcohols, alone or mixed with water, provided they do not react appreciably with acrylonitrile under the reaction conditions, for example lower alcohols having one to three carbon atoms such as methanol, ethanol or isopropanol.
  • the process is generally carried out by placing in a vessel the 0:,[3-Ol6fiIliC compound, the hexamethylenetetramine (which may also be prepared in situ from ammonia and formaldehyde) and the proton donor and then slowly adding the amalgam. Since reaction of the ama1- garn takes place very rapidly, large amounts of amalgam do not accumulate.
  • the a,fl-olefinic compound and the proton donor are as a rule used in the molar ratios which lie within the limits 5:1 to 1:6, particularly 2:1 to 1:3.
  • Hexamethylenetetramine is advantageously used in an amount of from 0.05 to 1.2 moles, preferably from 0.1
  • the amalgam is usually supplied in an amount of from 0.01 to 0.8, preferably from 0.07 to 0.3, gram-equivalent of alkali metal or alkaline earth metal in the amalgam, with reference to 1 mole of a,[i-olefinic compound.
  • solvents acting as promoters are ethers which are miscible with water, such as dioxane or tetrahydrofuran, or polyhydric alcohols such as glycol or alkyl nitriles (cf. US. patent specification No. 3,356,708), sulphones or ,sulphoxides (cf. French patent specification No. 1,467,091), or N alkyl substituted alkane carboxylic acid amides such as dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone (cf. the published papers of Dutch patent applications Nos.
  • suitable solvents are ethers which are miscible with water, such as dioxane or tetrahydrofuran, or polyhydric alcohols such as glycol or alkyl nitriles (cf. US. patent specification No. 3,356,708), sulphones or ,sulphoxides (cf. French patent specification No. 1,467,091)
  • a conventional stabilizer for the a,;8-olefinically unsaturated compound against undesired polymerization for example hydroquinone or p-nitrosodimethylaniline. Amounts of from 0.1 to 1 p.p.m. with reference to the reaction mixture are generally used.
  • the reaction mixture may be worked up for example by separating mercury, filtering off any bicarbonate precipitated or dissolving it by adding water and then recovering the dimerization product. Since the process is preferably carried out in a two-phase system, it is sufficient to separate the organic phase and to fractionate it. The aqueous phase may be immediately reused.
  • a nonpolar organic solvent such as methylene chloride or toluene
  • the invention is illustrated by the following examples.
  • the parts are parts by weight unless othrewise stated.
  • EXAMPLE 1 5000 parts of sodium amalgam (with 0.28% by weight of sodium) is added within twenty minutes to 400 parts of a solution (consisting of 40% by weight of acrylonitrile, by weight of hexamethylenetetramine, 20% by weight of water and 20% by weight of isopropanol) laced in a container provided with a thermometer, cooler, glass electrode for pH measurement, inlet pipe for carbon dioxide and a stirrer, while cooling with ice water and with vigorous mixing.
  • the pH value in the reaction mixture is kept at 8.5 to 9.5 by passing in carbon dioxide and the temperature is regulated at to C.
  • Example 3 The procedure of Example 2 is followed but a mixture is used which consists of 40% by weight of acrylonitrile, 30% by weight of hexamethylenetetramine and 30% by weight of water. 3500 parts of sodium amalgam with 0.4% by weight of sodium is added to this emulsion within twenty-five minutes. The pH value is kept at from 8.5 to 9 by means of carbon dioxide and the temperature. is kept at 35 C. When the reaction is over, mercury is separated and precipitated bicarbonate is filtered 01f and washed with a little water. The aqueous phase is separated from the organic phase and the latter is washed with a little water to remove hexamethylenetetramine and is then distilled. Adiponitrile is obtained in a yield of 84% with reference to acrylonitrile and of with reference to amalgam.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US737393A 1967-06-20 1968-06-17 Reductive dimerization of acrylonitrile Expired - Lifetime US3557186A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19671618180 DE1618180A1 (de) 1967-06-20 1967-06-20 Verfahren zur reduktiven Dimerisierung,alpha,ss-olefinischer Nitrile,Amide oder Ester

Publications (1)

Publication Number Publication Date
US3557186A true US3557186A (en) 1971-01-19

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Family Applications (1)

Application Number Title Priority Date Filing Date
US737393A Expired - Lifetime US3557186A (en) 1967-06-20 1968-06-17 Reductive dimerization of acrylonitrile

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US (1) US3557186A (cs)
FR (1) FR1569389A (cs)
GB (1) GB1220957A (cs)

Also Published As

Publication number Publication date
GB1220957A (en) 1971-01-27
FR1569389A (cs) 1969-05-30

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