US3032583A - Process for obtaining alpha-beta, deltaepsilon unsaturated esters - Google Patents

Process for obtaining alpha-beta, deltaepsilon unsaturated esters Download PDF

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Publication number
US3032583A
US3032583A US76144A US7614460A US3032583A US 3032583 A US3032583 A US 3032583A US 76144 A US76144 A US 76144A US 7614460 A US7614460 A US 7614460A US 3032583 A US3032583 A US 3032583A
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Prior art keywords
nickel
thiourea
reaction
chloride
iron
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US76144A
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English (en)
Inventor
Chiusoli Gian Paolo
Merzoni Sergio
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Montedison SpA
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Montedison SpA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
    • C07C51/14—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on a carbon-to-carbon unsaturated bond in organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds

Definitions

  • This invention is an improvement in processes for reacting allyl derivatives with acetylene, carbon monoxide,
  • R is hydrogen or a methyl or its homologues, and R is H or an alkyl radical.
  • R is phenyl. It also holds with primary chloroderivatives that are substituted at the double bond with alkyls, secondary chloroderivatives,
  • the present invention relates to a new method of execution of the reaction of allyl chloroderivatives with acetylene and carbon monoxide without need for recourse to use of nickel-carbonyl. Instead, subdivided nickel is employed in the presence of thiourea.
  • Nickel with acetylene probably forms complexes of the following type:
  • Thiourea is not used in stoichiometric amounts. Suitable proportions are readily determined experimentally. The preferred range is 0.1 to 0.5 mol per mole of chloroderivative.
  • the amount of thiourea required from the reaction with Raney nickel is higher than with nickel from the system iron-nickel chloride for the reason that Raney nickel contains active hydrogen which is eliminated by reactivation with thiuorea.
  • R R and R are hydrogen, or methyl, or higher homologues, such as ethyl, propyl, butyl, hexyl.
  • the aliphatic alcohols used preferably contain 1 to 5 carbon atoms.
  • the most convenient temperature range is between 10 and +50 C., and preferably between 10 and 30 C.
  • a dilution in the reaction solution higher than 8 parts of solvent per part of chloroderivative is preferable.
  • the products obtained belong to the same class of 2,5-dienic esters of the aforementioned main applications. It should however be noted that the increase in the amount of thiourea and depending on the nature of the chloroderivative, and on the reaction conditions, and in the thermal treatment during the separation of the products, can result in the formation (due to the isomerizing activity of the thiourea), not only of compounds containing the double bond conjugated with the carboxy group in the cis form, but also of a small amount of product in the trans form and with conjugated double bonds.
  • Tautomerism is a typical property of these products.
  • 2,5 heptadienoic ester is easily accompanied by the tautomer 3,5 to an extent of l0 15%.
  • the reactor is washed with nitrogen while agitating. Nickel or iron are added in amounts higher than that consumed by the reaction. The excess is filtered off at the end of the reaction. A stream of carbon monoxide and acetylene is passed through the solution while the latter is brought to the desired temperature of reaction by heating or cooling.
  • the ratios of acetylene to carbon monoxide vary depending on the needs of the reaction, i.e. depending on the more or less catalytic character connected with the reactivity of each chloroderivative.
  • the acetylene/carbon monoxide ratio is adjusted, on the basis of the analysis of the gases, depending on the reaction consumption.
  • the Examples 1-7 reported below were carried out without recycling the gases, while maintaining a 1:1 ratio, which generally avoids the stopping of the reaction due to defect of acetylene, or any excessive formation of side products due to the excess of acetylene.
  • the process can be carried out also (see Example 9 below) with recycling otthe reaction gases, so as to maintain a concentration more suitable for the reaction.
  • a mixture of chloroderivative and thiourea in alcohol is introduced slowly into the reaction vessel while controlling the temperature.
  • Thiourea can be introduced first. The duration of the addition depends on the reactivity of the chloroderivative.
  • the reaction is generally complete within a few hours.
  • the gas is then removed by a stream of nitrogen, the nickel and iron excess being then filtered off and the alcohol distilled together with the non-converted product, with duplication products of the allyl radical of the chloroderivative and with small amounts of esters which in some cases distill easily with water, if this is present in the alcohol.
  • the recovery can be carried out by salting out the distillate with a saturated calcium chloride solution.
  • the oily layer is taken up again with a little water, decanted or collected in ether, washed with water, dried and distilled.
  • the distillation is preferably carried out under vacuum, which facilitates obtaining the esters,
  • the products are treated to refiux with alkali, e.g. aqueous NaOH, following the known art.
  • alkali e.g. aqueous NaOH
  • the products are cataly-tically hydrogenated at room temperature over Raney nickel or Pd catalysts by known methods.
  • Example 1 400 ml. of methanol and 30 ml. of wet Raney nickel are placed in a 1-liter S-necked glass flask provided with thermometenagitator, inlet tube for the gases, reflux condenser and separatory funnel.
  • the apparatus is flushed with nitrogen, the suspension is agitated and bubbling of carbon monoxide and acetylene (CO flowrate 3 liters per hour; C H flow-rate 31 liters per hour) is started; the temperature of the suspension is adjusted to C. by a cooling bath, which also maintains this temperature during the reaction.
  • CO flowrate 3 liters per hour CO flowrate 3 liters per hour
  • C H flow-rate 31 liters per hour carbon monoxide and acetylene
  • the two mixed ether extracts are distilled on an oil bath by first separating the distillation heads up to C. and then, at 6366 C. (34 mm. Hg), a fraction of 25 g. containing the methyl ester of 2,5-hexadienoic acid separates.
  • Example 2 400 ml. of methanol and 30 ml. of wet Raney nickel are placed in a IOOO-ml. glass flask provided with thermometer, agitator, inlet pipe for the gases, reflux condenser and separating funnel. The apparatus is flushed with nitrogen, the suspension is agitated, and bubbling of carbon monoxide and acetylene (CO flow rate 3 liters per hour, C H flow rate 3 l./h.) is started.
  • CO flow rate 3 liters per hour C H flow rate 3 l./h.
  • Example 3 400 ml. of methanol, 15 g. of subdivided iron and 5 g. of NiCl .H O are placed in a 1000 ml. glass flask provided with thermometer, agitator, reflux condenser and separating funnel. After flushing with nitrogen, the suspension is agitated, and bubbling of CO and C H (CO'fiow rate 3 liters per hour; C H flow rate 3 l./h.) is started. While keeping the suspension at 30 C., a solution consisting of:
  • Example 4 A 14 g. of thiourea and 20 ml. of wet Raney nickel are placed in a 1000 ml. flask provided with thermometer, agitator, gas inlet tube, reflux condenser and separating tunnel, containing400 ml. of methyl alcohol; a temperature increase of 10? C. takes place. After flushing with nitrogen, the suspension is agitated, and bubbling of CO and C H (CO flow rate of 3 liters per hour; C H flow rate 3 l./h.) is started. The suspension iskept at 10 C. and a solution containing 40 g. of crotyl chloride, and ml. methanol is dropped from the separating funnel within 5 hours.
  • CO and C H CO flow rate of 3 liters per hour
  • Example 5 400 ml. of methanol, 15 g. of divided iron and 5 g. of NiCl .6H O are placed in the flask of the preceding examples. After flushing with nitrogen, the suspension is agitated, and bubbling of CO and C H (CO flow rate 3 liters per hour, C H flow rate 3 l/h.) is started. The suspension is kept at 20 C. and a solution consisting of 40 g. of crotyl chloride 16 g. of thiourea 180 ml. of methanol is dropped from the separating funnel Within 5 hours. After 6 hours the gases are removed by a stream of nitrogen. By proceeding as in the preceding examples, 31 g. containing the methyl ester of 2,5-heptadienoic acid (boiling point 72-75 C./ 20 mm. Hg) are obtained.
  • CO and C H CO flow rate 3 liters per hour, C H flow rate 3 l/h.
  • Example 6 400 ml. of methanol and 30 ml. of wet nickel obtained by reducing nickel hydroxide in aqueous phase at 100- 120 C. under 50 atms. are introduced into the flask of the preceding examples. After flushing with nitrogen, the suspension is agitated, and bubbling of CO and C H (CO flow rate 3 liters per hour, C H flow rate 3 l./h.) is started. Temperature is kept at 30 C. and a solution consisting of 30 g. of crotyl chloride g. of thiourea, and 180 ml. of methanol is dropped from the separating funnel within 5 hours. After 6 hours the gases are removed by a stream of nitrogen. By operating as in the preceding examples, 16 g. containing the methyl ester of 2,5-heptadienoic acid (boiling point 7275 C./20 mm. Hg) are obtained. 4 g. nickel have been transformed into the chloride.
  • Example 7 100 ml. of methanol and 7 ml. of wet Raney nickel are placed in a 500 ml. flask provided with a thermometer, agitator, gas inlet tube, reflux condenser and separating funnel. After flushing with nitrogen, the suspension is agitated, and bubbling of CO and C H (CO flow rate 2 liters per hour, C H flow rate 2 l./h.) is started. The suspension is kept at 20 C. while a solution consisting of:
  • Example 8 800 ml. of methanol, 10 g. of NiCl .6H O, 7 g. of iron, pulverized and sieved under carbon dioxide on a 16,000- mesh sieve, 4 g. of thiourea and g. of basic magnesium carbonate (MgCO .Mg(OH) .5H O, are placed in a flask provided with a mechanical agitator, a reflux condenser, a separating funnel and a gas inlet tube. After flushing with nitrogen and carbon monoxide, a stream of 4 l./h. CO and of 4 l./h. C H is introduced at 30 C. for 6 hours. At the same time from the separating funnel 40 g. of 98% commercial methallyl chloride mixed with 100 ml. of methanol are dropped from the separating funnel for 5 hours.
  • MgCO .Mg(OH) .5H O basic magnesium carbonate
  • the mixture is discharged and filtered.
  • the filtrate is distilled, the residue is treated wtih water acidified with sulfuric acid and collected in ether. After drying on sodium sulfate and distilling, 39.2 g. of distillate at 65-69" C./ 18 mm. Hg, containing 5-methyl-2,5-hexadienoic acid methyl ester are obtained, the residue amounting to 3.2 g.
  • Example 9 800 ml. of methanol, 10 g. of NiCl .6H O, 7 g. of
  • Example 10 800 ml. of methyl alcohol, 7 g. iron pulverized and sieved on a 16,000-mesh sieve, 10 g. of nickel chloride hexahydrate, 4 g. of thiourea and 21 g. of
  • Example 8 4 l./h. of CO and 4 l./h. of C H are then introduced at 30 C. for 6 hours, and 40 g. of crotyl chloride in ml. of methanol are dropped from the separating funnel within 5 hours.
  • the 5-methy1-2,5-hexadienoic acid and its esters are isomerized to 5-methyl2,4-hexadienoic acid upon heating or by saponification with sodium hydroxide.
  • the corresponding S-phenyl compounds are similarly isomerized to 3,5-dienes.
  • 2,4-acid esters undergo characteristics Diels-Alder condensation reactions. For instance, they can be utilized in the manner described in British Patent 569,113, namely by condensation with castor oil, to make modified drying oils.
  • US. Patents 2,420,694 and 2,382,297 (Example 7) are also in point.
  • esters of fatty acids are known, as evidenced by the text, Kirt-Othmer, Encyclopedia of Chemical Technology.
  • a process for preparing an alpha-beta, delta-epsilon, diene carboxylic acid ester comprising reacting an allyl chloroderivative containing up to 20 carbon atoms, of the formula:
  • R, R and R groups are taken from the class consisting of hydrogen, methyl, and homologues of methyl; with acetylene, carbon monoxide, and an aliphatic alcohol containing up to five carbon atoms, at 10 to +50 C., in the presence of metallic nickel and thiourea.
  • a process of making an alkyl ester of 2,5-hexadienoic acid comprising reacting allyl chloride with an alkanol having up to five carbon atoms, acetylene, and carbon monoxide in the presence of finely divided nickel and thiourea.
  • a process of making an alkyl ester of 5-methyl-2-,5- hexadienoic acid comprising reacting methallyl chloride with an alkanol having up to five carbon atoms, acetylene, and carbon monoxide in the presence of finely divided nickel and thiourea.
  • a process of making an alkyl ester of 2,5-heptadienoic acid comprising reacting crotyl chloride with an alkanol having up to five carbon atoms, acetylene, and carbon monoxide in the presence, of finely divided nickel and thiourea.
  • a process of making an alkyl ester of 8,8-dimethyl- 2,5-nonandienoic acid comprising reacting 5,5-dimethyl- 2-hexenyl chloride with an alkanol having up to five carbon atoms, acetylene, and carbon monoxide in the presence of finely divided nickel and thiourea.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US76144A 1959-12-18 1960-12-16 Process for obtaining alpha-beta, deltaepsilon unsaturated esters Expired - Lifetime US3032583A (en)

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IT2111259 1959-12-18
IT1681460 1960-09-29

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BE (1) BE598237R (en(2012))
DE (1) DE1274575B (en(2012))
DK (1) DK107804C (en(2012))
FR (1) FR1212892A (en(2012))
GB (1) GB952477A (en(2012))
NL (1) NL124913C (en(2012))

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3203978A (en) * 1961-06-06 1965-08-31 Montedison Spa Process for preparing the methyl ester of 2, 5-hexadienoic acid
US3299111A (en) * 1963-01-02 1967-01-17 Diamond Alkali Co Unsaturated acids derived from polyacetylenic compounds
US3547981A (en) * 1966-07-27 1970-12-15 Montedison Spa Process for preparing alkyl muconates and maleates
US4465634A (en) * 1980-12-23 1984-08-14 Istituto Donegani S.P.A. Process for preparing dienoic acids

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1212892A (fr) * 1959-12-18 1960-03-28 Montedison Spa Procédé pour la préparation de dérivés carboxyliques alpha-beta, delta-epsilon-non saturés, et produits obtenus
DE1280850B (de) * 1963-07-27 1968-10-24 Hoechst Ag Verfahren zur Herstellung von Dien-(1, 4)-carbonsaeuren-(1) und deren Estern
NL8103411A (nl) * 1981-07-17 1983-02-16 Multinorm Bv Maaier.

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE859617C (de) * 1937-07-24 1952-12-15 Bayer Ag Verfahren zur Herstellung von tetracyclischen Derivaten der Sterinreihe
DE854948C (de) * 1939-10-08 1952-11-10 Basf Ag Verfahren zur Herstellung von Acrylsaeure, ihren Estern und Substitutionserzeugnissen
DE868149C (de) * 1942-08-09 1953-02-23 Basf Ag Verfahren zur Herstellung von Gemischen aus Carbonsaeureamiden oder -estern
DE881650C (de) * 1943-02-12 1953-07-02 Basf Ag Verfahren zur Herstellung von Acrylsaeure, ihren Estern und Substitutionserzeugnissen
DE944789C (de) * 1953-11-15 1956-06-21 Basf Ag Verfahren zur Herstellung von Acrylsaeureestern
DE1000806C2 (de) * 1954-10-26 1957-06-19 Basf Ag Verfahren zur Herstellung von Acrylsaeure oder deren Derivaten
DE1046030B (de) * 1956-04-18 1958-12-11 Basf Ag Verfahren zur Herstellung von Acrylsaeureverbindungen
FR1212892A (fr) * 1959-12-18 1960-03-28 Montedison Spa Procédé pour la préparation de dérivés carboxyliques alpha-beta, delta-epsilon-non saturés, et produits obtenus

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3203978A (en) * 1961-06-06 1965-08-31 Montedison Spa Process for preparing the methyl ester of 2, 5-hexadienoic acid
US3299111A (en) * 1963-01-02 1967-01-17 Diamond Alkali Co Unsaturated acids derived from polyacetylenic compounds
US3547981A (en) * 1966-07-27 1970-12-15 Montedison Spa Process for preparing alkyl muconates and maleates
US4465634A (en) * 1980-12-23 1984-08-14 Istituto Donegani S.P.A. Process for preparing dienoic acids

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NL124913C (en(2012)) 1968-09-16
DK107804C (da) 1967-07-10
NL258646A (en(2012)) 1964-04-27
DE1274575B (de) 1968-08-08
BE598237R (fr) 1961-06-16
GB952477A (en) 1964-03-18
FR1212892A (fr) 1960-03-28

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