US3519674A - Hydrodimerization of acrylic acid derivatives - Google Patents

Hydrodimerization of acrylic acid derivatives Download PDF

Info

Publication number
US3519674A
US3519674A US655008A US3519674DA US3519674A US 3519674 A US3519674 A US 3519674A US 655008 A US655008 A US 655008A US 3519674D A US3519674D A US 3519674DA US 3519674 A US3519674 A US 3519674A
Authority
US
United States
Prior art keywords
ammonia
acrylic acid
acrylonitrile
reaction
amalgam
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US655008A
Other languages
English (en)
Inventor
Yael Arad
Haim Rosen
David Vofsi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
UCB SA
Original Assignee
UCB SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from IL2634366A external-priority patent/IL26343A/en
Application filed by UCB SA filed Critical UCB SA
Application granted granted Critical
Publication of US3519674A publication Critical patent/US3519674A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • 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 concerns the hydrodimerization of functional derivatives of acrylic acid selected from the group consisting of acrylonitrile, lower-alkyl acrylonitrile and lower alkyl acrylates, to form corresponding adipic acid derivatives.
  • the adipic acid derivatives prepared in accordance with the present invention are useful as reactants in the manufacture of polyamide fibres and polyamide plastics in general.
  • the hydrodimerization of acrylic acid derivatives is known.
  • the processes used, or proposed for use, up to now are classifiable in two groups: (a) electrolytic hydrogenation, (b) reduction by alkali metal amalgam or, in some cases, alkaline earth metal amalgam.
  • the present invention concerns a process of the second group.
  • the present invention is based on the surprising observation that acrylic acid derivatives may be hydrodimerized with the use of an alkali metal amalgam within a reaction medium comprising ammonia.
  • the invention consists in a process for the hydrodimerization of acrylic acid derivatives, selected from the group consisting of acrylonitrile, lower alkyl acrylonitrile and lower alkyl acrylates, using an alkali metal amalgam as reducing agent, wherein the reaction medium comprises ammonia.
  • the ammoniacal reaction medium is aqueous, provided the relative proportions of Water and ammonia on one hand and that of the acrylic acid derivative on the other hand, are kept within certain limits.
  • This embodiment thus consists in a process for the hydrodimerization of an acrylic acid derivative using an alkali metal amalgam as reducing agent, wherein the reaction medium is aqueous ammonia in which the ammonia: water ratio is within the range of from 15 :l to 0.3 1, preferably of from 3:1 to 1:1, and the amount of the acrylic 3,519,674 Patented July 7, 1970 ice acid derivative in the reaction mixture is within the range of from 2 to 30% by weight, preferably from 5 to 10% by weight.
  • the temperature at which the process may be carried out may range from 40 C. to +30 C. where the reaction is carried out within the range of from -40 C. to -10 C. it is a rule possible to work with open vessels under atmospheric pressure. Against this, at higher temperatures, it is necessary to work in closed vessels.
  • the ammoniacal reaction medium is anhydrous consisting of liquid ammonia in which an ammonium or amine salt is dissolved.
  • ammonium and amine salts can be used for this embodiment, the cheap inorganic salts, especially ammonium chloride and ammonium sulfate, are preferred in the performance of the process of the present embodiment on a technical scale. Also, it has been found that the use, of, for example, ammonium chloride makes for a smaller by-production of propionic acid derivatives than the use of, for example, triethylamine hydrocholoride.
  • liquid ammonia provides great advantages from the engineering point of view, since after the termination of the reaction the liquid ammonia can simply be allowed to evaporate, leaving as a residue merely the reaction products and any unconverted starting material in admixture with a solid salt sediment from which the reaction products can readily be separated mechanically.
  • the reaction itself will have to be carried out at so low a temperature that no appreciable evaporation of the ammonia takes place during the reaction itself. Since the boiling point of ammonia under atmospheric pressure is 33 C., a reaction temperature in the neighborhood of 30 C. is a preferred one.
  • the evaporated ammonia can, of course, be recovered.
  • This embodiment therefore, requires simpler and more compact apparatus than does the process according to the first embodiment.
  • the process according to the invention has the great advantage that it uses a cheap reaction medium while at the same time producing very satisfactory yields.
  • a further advantage of the process according to the present invention is that no pH control is required and no neutralizing agent need to be added since the reaction medium is alkaline from the outset and any additional amount of free alkali formed in the course of the reaction is insignificant.
  • the sodium and potassium amalgams are preferred on account of their ready availability.
  • concentration of the alkali metal in the amalgam is not critical and may vary within wide limits. The preferred range is within the limit of 0.01 to 0.5% by weight.
  • EXAMPLE 1 A solution of 10 g. of acrylonitrile and g. of ammonia in 30 g. of water was cooled to 30 C. in a Dry Ice-isopropanol bath. In another flask 2 kg. of sodium amalgam (0.3% by weight of sodium content) were cooled to the same temperature. The solution was poured onto the amalgam and the reaction mixture was maintained at 30 C. under slow swirling for 5 minutes. The amalgam was then separated, ammonia was distilled off, the solution diluted with water and extracted with methylene chloride. The methylene chloride extract contained the reaction product. Gas chromatographic analysis showed that it consisted of 85% of adiponitrile and 5% of propionitrile calculated on the acrylonitrile feed.
  • adiponitrile and propionitrile were separately recovered by fractional distillation. Methylene chloride and propionitrile distilled under atmospheric pressure. The adiponitrile was then distilled at a reduced pressure BP 182 C./20 mm. Hg.
  • EXAMPLE 2 A solution of 10 g. of acrylonitrile and 100 g. of ammonia in 50 g. of water was treated with sodium amalgam at 20 C. as described in Example 1. The products obtained consisted of 72% of adiponitrile and 11% of propionitrile calculated on the acrylonitrile feed, determined as described in Example 1.
  • the metal conversion yield was 89.
  • EXAMPLE 3 2.5 kg. of sodium amalgam containing 0.3% by weight of sodium was introduced into a thick walled flask and 10 g. of acrylonitrile and 50 g. of Water into another flask communicating with the former.
  • the second flask was connected to a vacuum system and also through a control valve to a source of ammonia.
  • the flask with the acrylonitrile and water was cooled in liquid air and evacuated. Thereafter the control valve leading to the ammonia source was opened and 50 gr. of ammonia were distilled into the cold flask. Thereafter the flask was sealed off from the vacuum system and also from the ammonia source.
  • the two communicating flasks were introduced into an ice bath and when the temperature reached C.
  • EXAMPLE 4 A solution of g. of l-methyl acrylonitrile and 90 g. of ammonia in 30 g. of water was reacted for minutes with 2 kg. of amalgam containing 0.3% by weight of sodium. A sample of reaction solution, separated from amalgam, was extracted with methylene chloride and analysed by gas chromatography which showed that the product contained 70% of dimethyl adiponitrile and 10% of isobutyronitrile calculated on the l-methyl acrylonitrile feed.
  • EXAMPLE 5 A solution of 10 g. of acrylonitrile and 100 g. of ammonia in 30 g. of water was reacted with 2.5 kg. of potassium amalgam containing 0.5% by weight of potassium. Procedure in the working up was analogous to that described in Example 1. The product consisted of 83% of adiponitrile and 5% of propionitrile calculated on the acrylonitrile feed.
  • the metal conversion yield was 87%.
  • the products thus obtained consisted of 9 g. of adiponitrile and 0.5 g. of propionitrile and the yields amounted to adiponitrile and 5% propionitrile based on the weight of the acrylonitrile feed.
  • the metal conversion yield of the combined adiponitrile and propionitrile was 90%.
  • EXAMPLE 7 A solution of 10 g. of acrylonitrile and 30 g. of triethylamine hydrochloride in 200 cc. of liquid ammonia was treated with sodium amalgam in the manner described in Example 6. The products, were separated similarly as described in Example 6. The yields amounted to 85% adiponitrile and 9% propionitrile, calculated on the weight of the acrylonitrile feed. The metal conversion yield was EXAMPLE 8 A mixture of 10 g. of ethyl acrylate, 6 g. of ammonium chloride and 200 cc. of liquid ammonia was reacted with sodium amalgam in the manner described in Example 6. The products were separated similarly as in Example 6. The yields ammounted to 72% of diethyl adipate and 6% of ethyl propionate, calculated on the weight of the ethyl acrylate feed. The metal conversion yield was 94%.
  • the reaction medium is aqueous ammonia in which the ammonia:water ratio is within the range of from 15:1 to 03:1 and the amount of acrylic acid derivative in said reaction medium is within the range of from 2 to 30% by weight, said reaction medium being maintained at a temperature of from 40 C. to +30 C.
  • ammonia:water ratio in the reaction medium is within the range of from 3:1 to 1:1.
  • a process as claimed in claim 1, wherein the amount of acrylic acid derivative in thereaction medium is within the range of from 5 to 10% by weight.
  • reaction medium is maintained at a temperature of from 40 C. to 10 C.
  • reaction medium is anhydrous liquid ammonia in which an ammonium or triethylamine salt of an inorganic acid is dissolved and the amount of acrylic acid derivative in said reaction medium is within the range of from about 2 to 30% by weight, said reaction medium being maintained at a temperature at which no substantial evaporation of liquid ammonia takes place.
  • ammonium salt is ammonium chloride.
  • ammonium salt is ammonium sulfate.
  • reaction medium is maintained at a temperature of about 30 C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US655008A 1966-08-16 1967-07-21 Hydrodimerization of acrylic acid derivatives Expired - Lifetime US3519674A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IL2634366A IL26343A (en) 1966-08-16 1966-08-16 Process for the hydrodimerization of acrylic acid derivatives
IL2708966 1966-12-19

Publications (1)

Publication Number Publication Date
US3519674A true US3519674A (en) 1970-07-07

Family

ID=26320427

Family Applications (1)

Application Number Title Priority Date Filing Date
US655008A Expired - Lifetime US3519674A (en) 1966-08-16 1967-07-21 Hydrodimerization of acrylic acid derivatives

Country Status (12)

Country Link
US (1) US3519674A (enrdf_load_stackoverflow)
AT (1) AT272300B (enrdf_load_stackoverflow)
BE (1) BE702635A (enrdf_load_stackoverflow)
CH (1) CH468960A (enrdf_load_stackoverflow)
CS (1) CS149414B2 (enrdf_load_stackoverflow)
DE (1) DE1668767C3 (enrdf_load_stackoverflow)
ES (1) ES344061A1 (enrdf_load_stackoverflow)
GB (1) GB1152104A (enrdf_load_stackoverflow)
LU (1) LU54297A1 (enrdf_load_stackoverflow)
NL (1) NL6710958A (enrdf_load_stackoverflow)
NO (1) NO120521B (enrdf_load_stackoverflow)
SE (1) SE326699B (enrdf_load_stackoverflow)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060183834A1 (en) * 2003-01-23 2006-08-17 Teijin Limited Polymer for carbon fiber precursor

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3193574A (en) * 1960-05-08 1965-07-06 Katchalsky Aharon Process for the preparation of adiponitrile by dimerization of acrylonitrile
US3356708A (en) * 1964-06-02 1967-12-05 Ici Ltd Process for the reductive dimerization of acrylonitrile

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3193574A (en) * 1960-05-08 1965-07-06 Katchalsky Aharon Process for the preparation of adiponitrile by dimerization of acrylonitrile
US3356708A (en) * 1964-06-02 1967-12-05 Ici Ltd Process for the reductive dimerization of acrylonitrile

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060183834A1 (en) * 2003-01-23 2006-08-17 Teijin Limited Polymer for carbon fiber precursor
US7338997B2 (en) * 2003-01-23 2008-03-04 Teijin Limited Polymer for carbon fiber precursor

Also Published As

Publication number Publication date
NL6710958A (enrdf_load_stackoverflow) 1968-02-19
SE326699B (enrdf_load_stackoverflow) 1970-08-03
NO120521B (enrdf_load_stackoverflow) 1970-11-02
AT272300B (de) 1969-07-10
CH468960A (fr) 1969-02-28
ES344061A1 (es) 1968-11-01
DE1668767A1 (de) 1971-01-28
CS149414B2 (enrdf_load_stackoverflow) 1973-07-05
LU54297A1 (enrdf_load_stackoverflow) 1968-03-25
DE1668767B2 (de) 1974-05-30
DE1668767C3 (de) 1975-01-30
BE702635A (enrdf_load_stackoverflow) 1968-02-14
GB1152104A (en) 1969-05-14

Similar Documents

Publication Publication Date Title
DE69105752T2 (de) Verfahren zur herstellung von florfenicol, seine analoga und oxazolinzwischenprodukte.
US3338967A (en) Process for preparing secondary-alkyl primary amines from olefins
US3519674A (en) Hydrodimerization of acrylic acid derivatives
US5455377A (en) Process to prepare alkansulphonamides
FR2470758A1 (fr) Procede pour la fixation de groupes alkyles sur une chaine carbonee portant un groupe fonctionnel
JPS638937B2 (enrdf_load_stackoverflow)
JP2568084B2 (ja) モノ−若しくはジヒドロキシフルオルアルカンの合成方法
US2735850A (en) Preparation of guanamines
DE69828777T2 (de) Verfahren zur herstellung von buttersäureester-derivaten
US2662095A (en) Dimethyl-phosphoric acid amide and its production
US2373800A (en) Preparation of alkali metal azides
DE60027056T2 (de) Verfahren zur Herstellung aliphatischer Fluoroformiate
DE69903610T2 (de) Verfahren zur Herstellung von 5,5'-bi-1H-Tetrazol-Salz
US2717200A (en) Manufacture of hydrazine
US4178309A (en) Manufacture of symmetrical dialkylureas
US3413349A (en) Process for preparing phenylhydroxylamine and cupferron
US3898282A (en) Method for producing {60 -aminocyclohexanone oxime
US2810754A (en) Synthesis of l-glutamine from l-glutamic acid
US3649666A (en) Process for the hydrodimerization of acrylic acid derivatives
US2737511A (en) Extraction of lactam
JPH039898B2 (enrdf_load_stackoverflow)
CA1094578A (en) Process for preparing a cycloalkanol
US3547975A (en) Process for the hydrodimerization of acrylic acid derivatives
IL26343A (en) Process for the hydrodimerization of acrylic acid derivatives
SU258168A1 (ru) Способ получения адипонитрила