US20010029305A1 - Method of producing cyclopentanone nitriles - Google Patents

Method of producing cyclopentanone nitriles Download PDF

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US20010029305A1
US20010029305A1 US09/811,485 US81148501A US2001029305A1 US 20010029305 A1 US20010029305 A1 US 20010029305A1 US 81148501 A US81148501 A US 81148501A US 2001029305 A1 US2001029305 A1 US 2001029305A1
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formula
base
compound
producing
general formula
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US6414177B2 (en
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Johny De Schrijver
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Evonik Operations GmbH
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Degussa Huels AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/08—Preparation of carboxylic acid nitriles by addition of hydrogen cyanide or salts thereof to unsaturated compounds
    • C07C253/10—Preparation of carboxylic acid nitriles by addition of hydrogen cyanide or salts thereof to unsaturated compounds to compounds containing carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/08—Preparation of carboxylic acids or their salts, halides or anhydrides from nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated

Definitions

  • the present invention relates to a method of producing compounds of the general formula (I).
  • the present method therefore has the object of providing another method of producing the compounds of general formula (I) that in particular permits the production of the compounds of formula (I) in a more economical manner.
  • R is a linear or any branched (C 1 -C 18 ) alkyl group
  • a start is made from compounds of the general formula (II)
  • R has the significance indicated above, reacts the compounds in the presence of hydrogen cyanide or a precursor producing hydrogen cyanide in situ and in the presence of catalytic amounts of base, it is totally surprisingly possible to carry out the reaction in the absence of any added organic solvent.
  • the amount of base to be used is a function of its effectiveness in the reaction medium and the possibility of minimizing the expense of feed substances.
  • the base is preferably used in an amount of 0.01 to 10 molar %, preferably 0.1 to 5 molar %, especially preferably 0.5 to 5 molar % relative to the enone (II).
  • the temperature can be selected as desired in the reaction under consideration. It should be regulated in such a manner that the reaction takes place as rapidly as possible but that, on the other hand, as few byproducts as possible are formed.
  • the reaction is advantageously carried out at a temperature of 10°-120° C., preferably 30°-80° C.
  • the present invention is concerned in a further embodiment with the use of the nitrile (I) produced in accordance with the invention in a method of producing perfumes with the general formula (III)
  • the nitrile (I) is preferably not isolated in an intermediate manner but rather the conversion of the nitrile function immediately follows its production. This only becomes possible as a result of the fact that the nitrile (I) can be produced in extremely pure form based on the method of the invention and that any other byproducts created do not contaminate the perfume that is finally obtained.
  • the further processing of (I) to (III) can take place analogously with U.S. Pat. No. 4,016,109.
  • a (C 1 -C 18 ) alkyl group that is linear or branched in any way denotes an alkyl group with 1 to 18 C atoms that comprises all theoretically possible bonding isomers such as, e.g., methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert.-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, etc.
  • Lithium hydroxide (4.07 g; 0.17 mole) is dosed at 40° C. to 2-n-hexylcyclopentenone (1402.8 g; 8.435 mole).
  • Hydrogen cyanide (251.6 g; 9.28 moles, 1.1 eq.) is dosed in at 40° C. in 30 minutes, during which the temperature rises to 62° C. The mixture is additionally heated 2 hours longer at 55° C.
  • the yield of 2-n-hexyl-3-cyanocyclopentanone is 94.3 % (1534.3 g).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A method for producing compounds of the general formula (I)
Figure US20010029305A1-20011011-C00001
in which R is a linear or any branched (C1-C18) alkyl group, from compounds of the general formula (II)
Figure US20010029305A1-20011011-C00002
that are reacted in the presence of hydrogen cyanide or a precursor producing hydrogen cyanide in situ and of catalytic amounts of base. The presence of another polar solvent is not necessary. Compounds of formula (I) are important intermediates for perfumes and aromatic substances.

Description

    CROSS-REFERENCE TO RELATED APPLICATION
  • This application is based on German Application DE 10015 063.2, filed Mar. 25, 2000, which disclosure is incorporated herein by reference. [0001]
    • FIELD OF THE INVENTION
  • The present invention relates to a method of producing compounds of the general formula (I). [0002]
    Figure US20010029305A1-20011011-C00003
  • These nitriles are valuable intermediates for the production of perfumes and aromatic substances. [0003]
    • BACKGROUND OF THE INVENTION
  • According to U.S. Pat. No. 4,016,109, such compounds are obtained either under acidic conditions by the Michael addition of cyanide ions or by the base-catalyzed addition of hydrogen cyanide released from acetone cyanohydrin in situ to the corresponding cyclopentenone. That method has the disadvantage that the hydrogen cyanide must first be converted into the cyanohydrin and must subsequently be released again from the latter. Moreover, an organic solvent is present in this reaction. It is advantageous in large-scale methods for the methods to be carried out economically, which means, among other things, that as little feed material as possible is used in the methods. [0004]
    • SUMMARY OF THE INVENTION
  • The present method therefore has the object of providing another method of producing the compounds of general formula (I) that in particular permits the production of the compounds of formula (I) in a more economical manner. [0005]
  • In order to produce compounds of the general formula (I) [0006]
    Figure US20010029305A1-20011011-C00004
  • in which R is a linear or any branched (C[0007] 1-C18) alkyl group, a start is made from compounds of the general formula (II)
    Figure US20010029305A1-20011011-C00005
  • in which R has the significance indicated above, reacts the compounds in the presence of hydrogen cyanide or a precursor producing hydrogen cyanide in situ and in the presence of catalytic amounts of base, it is totally surprisingly possible to carry out the reaction in the absence of any added organic solvent. [0008]
  • This is surprising since the bases used are also salt-like compounds that are normally only soluble in very polar, organic solvents such as, e.g., methanol, and there was the danger of these substances being withdrawn from the reaction by precipitation and not being able to develop any action any longer. Thus, by way of example, in DE 39 42 371 (corresponding to U.S. Pat. No. 5,091,554) and DE 1 00 85 871, the presence of polar, organic solvents (DMF or an excess of isophorone) is preferred in a comparable reaction. Under the given circumstances it is therefore surprising that under these conditions no significant side reactions such as, e.g., aldol or Michael addition of enone (II) and nitrile (I) or polymerization of hydrogen cyanide take place. Totally surprisingly, a yield of >94 % nitrile (I), that is better than that obtained with the state of the art, is achieved with the reaction conditions in accordance with the invention. [0009]
  • In principle, all organic and inorganic bases familiar to an expert in the art for this purpose can be considered as bases to be used, in as far as they display a sufficient effect for the catalysis of the Michael addition. This can be readily explained in routine experiments. Note, by way of example, the experiments cited in DE 39 42 371. It is preferable to use advantageous, inorganic substances such as, e.g., NaOH, Na[0010] 2CO3, Ca(OH)2, etc. as bases. LiOH is preferably used.
  • The amount of base to be used is a function of its effectiveness in the reaction medium and the possibility of minimizing the expense of feed substances. The base is preferably used in an amount of 0.01 to 10 molar %, preferably 0.1 to 5 molar %, especially preferably 0.5 to 5 molar % relative to the enone (II). [0011]
  • The temperature can be selected as desired in the reaction under consideration. It should be regulated in such a manner that the reaction takes place as rapidly as possible but that, on the other hand, as few byproducts as possible are formed. The reaction is advantageously carried out at a temperature of 10°-120° C., preferably 30°-80° C. [0012]
  • The present invention is concerned in a further embodiment with the use of the nitrile (I) produced in accordance with the invention in a method of producing perfumes with the general formula (III) [0013]
    Figure US20010029305A1-20011011-C00006
  • in which R has the significance indicated above and R′=H, Na, K, Li, Ca[0014] 1/2, Mg1/2, or a linear or branched (C1-C18)-alkyl group. The nitrile (I) is preferably not isolated in an intermediate manner but rather the conversion of the nitrile function immediately follows its production. This only becomes possible as a result of the fact that the nitrile (I) can be produced in extremely pure form based on the method of the invention and that any other byproducts created do not contaminate the perfume that is finally obtained. The further processing of (I) to (III) can take place analogously with U.S. Pat. No. 4,016,109.
  • In the framework of the invention a (C[0015] 1-C18) alkyl group that is linear or branched in any way denotes an alkyl group with 1 to 18 C atoms that comprises all theoretically possible bonding isomers such as, e.g., methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert.-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, etc.
  • Likewise, in the framework of the invention the indication of the general formulas also comprises all possible enantiomers and diastereomers as well as mixtures of them.[0016]
    • DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • Example: [0017]
  • Laboratory procedure for the production of 2-n-hexyl-3-cyanocyclopentanone [0018]
    Figure US20010029305A1-20011011-C00007
  • Lithium hydroxide (4.07 g; 0.17 mole) is dosed at 40° C. to 2-n-hexylcyclopentenone (1402.8 g; 8.435 mole). Hydrogen cyanide (251.6 g; 9.28 moles, 1.1 eq.) is dosed in at 40° C. in 30 minutes, during which the temperature rises to 62° C. The mixture is additionally heated 2 hours longer at 55° C. The yield of 2-n-hexyl-3-cyanocyclopentanone is 94.3 % (1534.3 g). [0019]

Claims (10)

What is claimed is:
1. A method for producing a compound of general formula (I)
Figure US20010029305A1-20011011-C00008
in which R is a linear or branched (C1-C18) alkyl group, from a compound of general formula (II)
Figure US20010029305A1-20011011-C00009
in which R has the significance indicated above, in the presence of hydrogen cyanide or a precursor producing the hydrogen cyanide in situ and in the presence of catalytic amounts of base, comprising:
carrying out the method in the absence of any added organic solvent.
2. The method according to
claim 1
, comprising using LiOH as the base.
3. The method according to
claim 1
, wherein the base is used in an amount of 0.01 to 10 molar %, relative to the compound of formula (II).
4. The method according to
claim 3
, wherein the base is used in an amount of 0.1 to 5 molar % relative to the compound of formula (II).
5. The method according to
claim 3
, wherein the base is used in an amount of 0.5 to 5 molar % relative to the compound of formula (II).
6. The method according to
claim 1
, comprising carrying out the method at a temperature of 10°-120° C.
7. The method according to
claim 6
, comprising carrying out the method at a temperature of 20°-100° C.
8. The method according to
claim 6
, comprising carrying out the method at a temperature of 30°-80° C.
9. A method of using a nitrite of formula (I) produced according to
claim 1
, comprising:
adding the nitrile of formula (I) in a method of producing perfumes of the general formula (III)
Figure US20010029305A1-20011011-C00010
In which R has the significance indicated in
claim 1
, and R′ is H, Na, K, Li, Ca1/2, Mg1/2, or a linear or branched (C1-C18)-alkyl group.
10. The method according to
claim 9
, wherein the nitrite (I) is not isolated as an intermediate compound.
US09/811,485 2000-03-25 2001-03-20 Method of producing cyclopentanone nitriles Expired - Fee Related US6414177B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10015063 2000-03-25
DE10015063.2 2000-03-25
DE10015063A DE10015063A1 (en) 2000-03-25 2000-03-25 Process for the preparation of 1,3-cyclopentanonitriles

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US6414177B2 US6414177B2 (en) 2002-07-02

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Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4016109A (en) * 1970-11-04 1977-04-05 Polak's Frutal Works N.V. Alicyclic ketoester perfume compositions
DE3942371A1 (en) * 1989-12-21 1991-06-27 Degussa METHOD FOR PRODUCING 1,3,3-TRIMETHYL-5-OXO-CYCLOHEXANE-CARBONITRIL

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