JP2003525260A - Method for producing chlorocarboxylic acid chloride - Google Patents

Abstract

(57) Abstract: By reacting a lactone of the formula (II) with a chlorinating agent in the presence of a chlorination catalyst, chlorocarboxylic acid chloride of the formula (I) wherein R ¹ and R ² Independently represents a hydrogen atom, a carbon-containing organic group, a halogen, a nitro- or a cyano group, Y has from 1 to 10 carbon atoms in the chain and is an unsubstituted or carbon-containing organic group, a halogen, a nitro- And / or an alkylene chain substituted by a cyano group, wherein the alkylene chain may be interrupted by one ether-, thioether-, tertiary amino- or keto group, wherein Y and / or Or the carbon-containing organic groups of R ¹ and / or R ² may be linked together to form a non-aromatic system), the reaction being carried out in the presence of a boron compound. Embedded image

Description

Detailed Description of the Invention

[0001]   The present invention provides formula (I):

[0002]

[Chemical 3]

[Wherein R ¹ and R ² independently of one another represent a hydrogen atom, a carbon-containing organic group, a halogen, a nitro or a cyano group, and Y has 1 to 10 carbon atoms in the chain. Represents an alkylene chain which is unsubstituted or substituted by a carbon-containing organic group, a halogen, a nitro- and / or a cyano group, wherein the alkylene chain is one ether-, thioether-, tertiary amino- or keto It may be interrupted by radicals, where Y and / or
Or the carbon-containing organic radicals of R ¹ and / or R ² may be bonded to each other to form a non-aromatic system] for the preparation of chlorocarboxylic acid chlorides in the presence of a chlorination catalyst, (II):

[0004]

[Chemical 4]

[0005] The present invention relates to a method carried out by reacting a lactone of [wherein R ¹ , R ² and Y represent the above-mentioned] with a chlorinating agent.

Chlorcarboxylic acid chloride is an important reactive intermediate for the production of medicinal and agrochemical agents.

Chlorocarboxylic acid chlorides can be prepared, for example, by reacting the corresponding lactone with a chlorinating agent in the presence of a catalyst. The chlorinating agent used is typically phosgene or thionyl chloride. This is because they form exclusively gaseous substances (CO ₂ or SO ₂ and HCl) as by-products.

When thionyl chloride is used as the chlorinating agent, zinc chloride is usually used as the catalyst. A suitable method is II Grandberg et al., Izv. Timiryazevsk.
S. -kh. Akad. 1974, (6) p. 198 -204 and OP Goel et al., Synthesis, 19
73, p. 538-539. Yields of 65-80% were reached upon conversion of γ-butyrolactone to 4-chlorobutyric acid chloride.

When phosgene is used as the chlorinating agent, various catalyst systems are usually used. U.S. Pat. No. 2,778,852 lists the following as suitable catalysts: pyridine, tertiary amines, heavy metals and acids such as sulfuric acid, phosphoric acid, phosphorus chloride, phosphorus oxychloride, aluminum chloride, sulfuryl chloride and chlorine. Sulfonic acid. A suitable catalyst is, according to DE-A19753773, a urea compound, EP-A0
413264 and EP-A 0435714 are phosphine oxides and according to EP-A 0253214 and EP-A 0583589 are organic nitrogen compounds such as quaternary ammonium salts, heterocyclic nitrogen compounds, amines or formamides.

US Pat. No. 2,778,852 describes the synthesis of 4-chlorobutyric acid chloride by the reaction of γ-butyrolactone with phosgene in the presence of pyridine.

Hydrogen chloride gas is usually additionally introduced in order to increase the yield. However, the use of hydrogen chloride has drawbacks, especially for environmental and economic reasons. This is because it is used in stoichiometric excess and the excess has to be purified and neutralized, which results in considerable salt accumulation. Furthermore, the use of large amounts of hydrogen chloride gas would require additional technical and administrative costs.

The object of the present invention is therefore no longer the known disadvantages and is a process for obtaining chlorocarboxylic acid chloride in high yield and in high purity, which is obtained by reaction of the corresponding lactone with a chlorinating agent. It is to provide a method for producing carboxylic acid chloride.

[0013]   Correspondingly, formula (I):

[0014]

[Chemical 5]

[Wherein R ¹ and R ² each independently represent a hydrogen atom, a carbon-containing organic group, a halogen, a nitro or a cyano group, and Y has 1 to 10 carbon atoms in the chain. Represents an alkylene chain which is unsubstituted or substituted by a carbon-containing organic group, a halogen, a nitro- and / or a cyano group, wherein the alkylene chain is one ether-, thioether-, tertiary amino- or keto It may be interrupted by radicals, where Y and / or
Or the carbon-containing organic groups of R ¹ and / or R ² may be bonded to each other to form a non-aromatic system], in the presence of a chlorination catalyst in the presence of a chlorination catalyst, II):

[0016]

[Chemical 6]

We have discovered a method of carrying out the reaction of a lactone of [wherein R ¹ , R ² and Y represent the above-mentioned] with a chlorinating agent, and the reaction is carried out in the presence of a boron compound. It is characterized by doing.

[0018]   What is important in the method of the present invention is the presence of the boron compound. Suitable boron compound
Examples of the compounds are the compounds and substance groups described below, where various boron compounds are used.
A mixture of is likewise possible: -Boron oxide, eg B_TwoO_Three; -Boric acid (Borsauerstoffsaeuren), eg boric acid (H_ThreeBO_Three, More positive
To be precise, "orthoboric acid"), metaboric acid (HBO_TwoTypes of, for example, α-HB
O_Two, Β-HBO_TwoOr γ-HBO_Two), Oligoboric acid or polyboric acid; -Salts of boric acid, such as inorganic or organic cations, such as alkali metal ions
(For example Li⁺, Na⁺Or K⁺), Alkaline earth metal ions (eg Mg²⁺ , Ca²⁺Or Sr²⁺), Ammonium ion NH_Four ⁺Or 1st, 2nd, 3rd
Or quaternary amines (eg tetramethylammonium, tetraethylammonium
, Tetrapropylammonium, tetraisopropylammonium, phenyl
Limethylammonium, phenyltriethylammonium, trimeethylammo
Ni, triethylammonium, tripropylammonium, triisopropyl
Lumonium, phenyldimethylammonium, phenyldiethylammonium
Or phenylammonium (“anilinium”) borate ([BO_Three ]^{Three -}, More precisely “orthoborate”), oligoborate (eg [B_ThreeO
_Three(OH)₅]^{Two -}, [B_FourO₅(OH)_Four]^{Two -}, [B₅O₆(OH)₆]^{Three -}   Or [B₆O₇(OH)₆]^{Two -}Alternatively, a polyborate (for example, [BO_Two]^-); -Boronic acid (RB (OH)_Two) And their inorganic or organic salts such as phenyl
Ruboronic acid (dihydroxyphenylborane) or disodium phenylborone
G; -Borate esters, e.g. same or different unbranched or branched alkyl groups (e.g.
For example, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl,
2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-
Methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl
, Hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpe
2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-
Dimethyl butyl, 1,2-dimethyl butyl, 1,3-dimethyl butyl, 2,2-dimethyl
Rubutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl,
2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyi
1-ethyl-1-methylpropyl or 1-ethyl-2-methylpropyl)
Mono-, di- or tri-C₁~ C₆-Alkyl-esters such as trimethyl volley
G., Triethyl borate or tripropyl borate; -Boron halides containing fluorine, chlorine, bromine and / or iodine, eg BF_Three
(Boron trifluoride), BCl_Three(Boron trichloride), BBr_Three(Boron tribromide), B
I_Three(Boron triiodide), BF_TwoCl, BFCl_Two, BF_TwoBr, BFBr_Two, B
F_TwoI, BFI_Two, BFClBr, BFClI, BFBrI, BCl_TwoBr, B
ClBr_Two, BCl_TwoI, BClI_Two, BClBrI, BBr_TwoI, BBrI_Two , B_TwoF_Four, B_TwoCl_Four, B_TwoBr_Four, B_TwoI_FourAnd these, such as oxygen, sulfur
Complexes with yellow or nitrogen compounds such as hydrates, alcoholates, etherates,
Complexes with sulfides, ammonia, amines or pyridines, eg [water / BF_Three]
, [Methanol / BF_Three], [Ethanol / BF_Three], [Dimethyl ether B
F_Three], [Diethyl ether / BF_Three], [N-propyl ether / BF_Three],
[Isopropyl ether / BF_Three], [Tetrahydrofuran / BF_Three], [Jime
Cylsulfide / BF_Three], [Ammonia / BF_Three], [Methylamine / BF_Three ], [Dimethylamine / BF_Three], [Trimethylamine / BF_Three], [Ethyla
Min BF_Three], [Diethylamine / BF_Three], [Triethylamine / BF_Three]
, [Urea / BF_Three], [Pyridine / BF_Three], [2-Methylpyridine / BF_Three]
Or [3-methylpyridine / BF_Three].

It is advantageous to use the following compounds: Boron oxide B ₂ O ₃ ; Boric acid H ₃ BO ₃ ; Boric acid tri-C ₃ -C ₄ -alkyl esters, for example trimethylborate, triethyl Borate, tripropylborate, triisopropylborate or tributylborate; -boron trifluoride, boron trichloride or complexes thereof, such as water, alcohols (especially methanol), ethers (especially diethyl ether), sulphides (especially dimethyl sulphide) or Complexes with amines (especially ethylamine), eg boron trifluoride
-Dihydrate or boron trifluoride-etherate (especially with diethyl ether);
Or a mixture of these.

[0020]   Boron oxide B, a halogen-free boron compound_TwoO_Three, Boric acid H_ThreeBO_ThreeOver
Biboric acid tri-C₁~ C_Four-Alkyl esters are particularly preferably used. Boric acid H _Three BO_ThreeAnd trimethylborate are very advantageous. Such a boron compound
Has the advantage that the reaction mixture has no fluoride ions. This makes the halo
It simplifies the overall equipment technology compared to reactions with boron genide.

In the method of the present invention, the boron compound or the mixture thereof is 0.1 to 20 mol%, preferably 0.1 to 10 mol%, and more preferably 0.1 to 10 mol% based on the lactone (II).
Used at a concentration of 5-5 mol%.

[0022]   The chlorocarboxylic acid chloride produced by the method of the present invention has the formula (I):

[0023]

[Chemical 7]

[Wherein, R ¹ and R ² independently of each other represent a hydrogen atom, a carbon-containing organic group, a halogen, a nitro- or a cyano group].

Here, a carbon-containing organic group means an unsubstituted or substituted, aliphatic, aromatic or araliphatic group having 1 to 20 carbon atoms. This group is one or more heteroatoms in an aliphatic or aromatic system, such as oxygen, nitrogen or sulphur, for example -O-,
May contain --S--, --NR--, --CO-- and / or --N = and / or be substituted with one or more functional groups containing eg oxygen, nitrogen, sulfur and / or halogen. It may be substituted, for example with fluorine, chlorine, bromine, iodine and / or cyano. If the carbon-containing organic radical contains one or more heteroatoms, it can also be bound via the heteroatoms. Thus, for example, ether-, thioether- and tertiary amino groups are included. Advantageous examples of carbon-containing organic groups include: C ₁ -C ₂₀ -alkyl, especially C ₁ -C ₆ -alkyl, C _6- .
C _{10 - aryl,} C 7 -C _{20 -} aralkyl, especially _C 7 -C _{10 -} aralkyl, and _C 7 -C _{20 -} alkaryl, especially _C 7 -C _{10 -} alkaryl.

[0026]   As examples of halogen, mention may be made of fluorine, chlorine, bromine and iodine.

R ¹ and R ² in the formula are independently of each other hydrogen, C ₁ -C ₆ -alkyl, C _6-
Represents C ₁₀ -aryl, C ₇ -C ₁₀ -aralkyl or C ₇ -C ₁₀ -alkaryl, for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1, 1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1
-Methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,
2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1 Represents -methylpropyl, 1-ethyl-2-methylpropyl, phenyl, 2-methylphenyl (o-toluoyl), 3-methylphenyl (m-toluoyl), 4-methylphenyl (p-toluoyl), naphthyl or benzyl Chlorcarboxylic acid chloride (I) is preferred. Hydrogen, C ₁ -C ₄ -alkyl,
Hydrogen is especially preferred.

Y represents an alkylene chain having 1 to 10 carbons in the chain, which may be unsubstituted or substituted with carbon-containing organic groups, halogen, nitro- and / or cyano groups, wherein The alkylene chain may be interrupted by ether (-O-), thioether (-S-), tertiary amino (-NR-) or keto (-CO-) groups. Carbon-containing organic groups and halogens are defined as above.

As examples of the group Y, mention may be made of alkenes (CH ₂ ) _n , where n is 1
-10 and where one or more, optionally all hydrogen atoms are C ₁ -C ₆ -alkyl, C ₆ -C ₁₀ -aryl, C ₇ -C ₁₀ -aralkyl and / or C ₇ -C ₁₀ -alkaryl, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,
2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1- Dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3
1,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1
-Ethyl-2-methylpropyl, phenyl, 2-methylphenyl (o-toluoyl)
3-methylphenyl (m-toluoyl), 4-methylphenyl (p-toluoyl)
, Naphthyl or benzyl.

[0030]   In the formula, Y is an unsubstituted alkene (CH_Two)_n(Where n is 2-8, preferably 2
4), eg CH_TwoCH_Two, CH_TwoCH_TwoCH_TwoAnd CH_TwoCH_TwoCH _Two CH_TwoPreference is given to chlorocarboxylic acid chloride (I)

It is also possible that the organic radicals R ¹ and / or R ² and / or that of Y are linked to one another to form a non-aromatic system. Hexahydrophthalide can be mentioned as an example.

Chlorocarboxylic acid chlorides (I) which are very advantageous as products of the process according to the invention
) Is 4-chlorobutyric acid chloride (4-chlorobutanoic chloride), 5-chlorovaleric acid chloride (5-chloropentanoic chloride) or 6-chlorocaproic acid chloride (6-chlorohexanoic chloride). is there.

[0033]   The lactone to be used has the formula (II):

[0034]

[Chemical 8]

[Wherein R ¹ , R ² and Y represent the above]. Of course, mixtures of different lactones can also be used. γ-butyrolactone, δ-valerolactone or ε-
It is very advantageous to use caprolactone.

Phosgene, diphosgene (trichloromethylchloroformate), triphosgene (bis (trichloromethyl) carbonate) and / or thienyl chloride are advantageously used as chlorinating agents. Preference is given to using phosgene or thienyl chloride, in particular gaseous and / or liquid phosgene.

As chlorination catalysts, in principle all known chlorination catalysts, in particular nitrogen and phosphorus compounds, such as open-chain or cyclic, unsubstituted or substituted urea, di-N, N-substituted Formamide (eg N, N-dimethylformamide), trialkylphosphine oxide, unsubstituted or substituted triarylphosphine oxide, substituted or unsubstituted pyridine, quaternary ammonium salt (eg benzyltrimethylammonium chloride), amidine or hydrochloric acid Preference is given to the salts, including salts, unsubstituted or mono- or poly-N-substituted guanidine or hexaalkylguanidinium salts.

As the chlorination catalyst, urea compounds, phosphine oxides, pyridine compounds or mixtures thereof are advantageously used.

Urea compounds which are preferably used are described, for example, in DE-A 19753773. Formula (III):

[0040]

[Chemical 9]

[0041] [In the formula, X represents oxygen or sulfur, and R^Three~ R⁶Are independently of one another and advantageously C₁~ C ₁₀ -Represents alkyl or here the radical R^ThreeOr R^FourOne of the groups is R⁵Or R⁶
C with one of_Two~ C_Four-Forming an alkylene chain] open chain substitution
It is particularly advantageous to use urea compounds which have been prepared. Liquid under the conditions of this reaction
Urea compounds such as N, N'-dimethylethylene urea (1,3-dimethyl-2-imidazole
Zolidinone), N, N'-dimethylpropyleneurea (1,3-dimethyltetrahydro)
-2 (1H) -pyrimidinone), N, N, N ', N'-tetrabutylurea or N, N
, N ', N'-tetramethylthiourea is very advantageous. The urea compound described is
As such or in the form of their salts with hydrochloric acid, eg as the hydrochloride salt or
Of its Vilsmeier-type as can be obtained by reaction with phosgene
It can be used in the form of a salt, but the hydrochloride salt is preferred.

Phosphine oxides which are preferably used are described, for example, in EP-A 0413264. Formula (IV):

[0043]

[Chemical 10]

Wherein R ^{7 to} R ⁹ independently of one another are preferably C ₁ -C ₁₀ -alkyl or unsubstituted or C ₁ -C ₄ -alkyl-substituted phenyl. Particular preference is given to using alkylphosphine oxides or unsubstituted or substituted triarylphosphine oxides. Phosphine oxide that is liquid under the reaction conditions,
Such as linear or branched trioctyl -, trihexyl - or a mixture of tributyl phosphine oxide and triphenyl phosphine oxide or various phosphine oxide (e.g. Cytec Industries sold by the company Cyanex ^(R)) also highly advantageous is there.

[0045]   Substituted or unsubstituted pyridines that are advantageously used have the formula (V):

[0046]

[Chemical 11]

[Wherein R ^{10 to} R ¹⁴ independently of one another preferably represent hydrogen or C ₁ -C ₄ -alkyl]. It is also possible for two adjacent groups to be joined together to form a non-aromatic or aromatic system. Mono-C ₁ -C ₄ -alkyl-pyridines are particularly preferred, monomethylpyridines, especially 3-methylpyridine (β-picoline), being most preferred.

In the process according to the invention, in particular 3-methylpyridine, triphenylphosphine oxide and / or trialkylphosphine oxide are used.

The use of liquid chlorination catalysts has particular process-technical advantages. This eliminates, for example, the cumbersome handling and weighing of solids and their transport. Moreover, the subsequent distillation work-up results in a bottom product with a substantially lower viscosity, and clogging is avoided.

In the method of the present invention, the chlorination catalyst is contained in an amount of 0.1 to 20 mol%, preferably 0.1 to 10 mol%, more preferably 0.5 to 5 mol% based on the lactone (II). Used in concentration.

In another advantageous embodiment of this method, the catalyst is used in the form of a complex of a boron compound and a chlorination catalyst. It can be produced, for example, upstream of the reactor or by mixing the two components in the reactor. An example of a suitable complex is the BF ₃ -β-picoline complex.

The reactors used for the chlorination are, in principle, those described in the relevant technical literature.
It can be any device for liquid or liquid-liquid reactions. In order to achieve high space-time yields, good mixing between the liquid containing the lactone, the chlorination catalyst and the boron compound and the added chlorinating agent is important. As non-limiting examples, stirred tanks, stirred tank cascades, countercurrent reaction columns, flow tubes (preferably filled with baffles),
Bubble columns and loop reactors are included.

This method is advantageously carried out without the use of solvents. However, it is possible to add solvents which are inert to the chlorinating agent used. Inert solvents are, for example, aromatic hydrocarbons such as toluene, chlorobenzene, o-, m- or p-dichlorobenzene, o-, m- or p-xylene, cyclic carbonates such as ethylene carbonate or propylene carbonate, preparations It is the same chlorocarboxylic acid chloride or mixture thereof as is to be done. If a solvent is used, it is advantageous to use the same chlorocarboxylic acid chloride that is to be prepared. The addition of a solvent is advantageous if, for example, a lactone (II) is used which has a high molecular weight, a high viscosity and is solid under the conditions of the reaction.

The method of the present invention can be carried out at a temperature of 50 to 200 ° C., preferably 80 to 200 ° C., more preferably 110 to 160 ° C. This is generally from 0.01
It is carried out under a pressure of 5 MPa (absolute), preferably 0.5-2 MPa (absolute), and more preferably under atmospheric pressure.

The total amount of phosgene introduced into the process of the present invention is generally 0.8 to 1.5 mol, preferably 0.9 to 1.2 mol, per mol of lactone (II).

The addition of the starting materials (lactone (II) and chlorinating agent) and catalyst (chlorination catalyst and boron compound) can generally be carried out in any order. In one variant, the lactone (II), the chlorination catalyst, the boron compound and optionally the solvent are precharged and then the chlorinating agent is introduced, or in another variant, all components are introduced simultaneously. Is advantageous. Embodiments which exist between these two variants are of course also possible and in some cases also advantageous.

During the addition of the starting materials and the catalyst, the various components can be brought into contact with one another upstream of or in the reactor as desired. Thus, for example, it is possible to pre-form a complex from a boron compound and a chlorinating agent (eg BF ₃ -β-picoline complex). In addition, it is also possible to pre-react between the chlorination catalyst and the chlorinating agent (eg Vilsmeier-salt from N, N-dialkylformamide and phosgene or thionyl chloride).

[0058]   The method of the present invention can be carried out discontinuously or continuously.

A) Discontinuous In the case of discontinuous production, the reaction mixture containing the lactone (II), the chlorination catalyst, the boron compound and optionally the solvent is generally contained in one reactor, for example in a stirred tank. Charge in advance and stir well. The desired amount of liquid or gaseous chlorinating agent is then added at the desired temperature and pressure. After the addition of the chlorinating agent, the reaction solution is continuously reacted for a few minutes to a few hours. This post reaction can also be carried out in this reactor or in a vessel downstream thereof.

In a special variant of the discontinuous process, the liquid chlorinating agent (eg thionyl chloride) can also be precharged, optionally together with a chlorination catalyst and / or a boron compound and / or a solvent. . The lactone (II) is then added, optionally with a chlorination catalyst and / or boron compound and / or solvent, at the desired temperature and pressure over a period of time.

B) Continuous Reactors which are suitable for continuous processes are, for example, stirred tanks, stirred tank cascades or countercurrent reaction columns. At the beginning of the continuous process, the solvent (e.g. the same chlorocarboxylic acid chloride as to be produced), the chlorination catalyst and the boron compound are generally precharged to the reactor, the system is heated to the desired temperature, After that, a liquid or gaseous chlorinating agent is added. Then, in parallel with the continuous feeding of the chlorinating agent, the continuous introduction of the lactone (II), which generally contains a further chlorinating agent and a further boron compound and is optionally dissolved in a solvent, is started. After the reactor contents have been converted to chlorocarboxylic acid chloride, the amounts of lactone (II) and chlorinating agent are adjusted so that both of these components are introduced in substantially equimolar amounts. The reaction mixture is withdrawn from the reactor, for example via a riser or an overflow line, at a rate corresponding to the feed rate. It is advantageous to feed this reaction solution to another vessel for post-reaction.

It is then generally advantageous to strip off the unreacted chlorinating agent from this reaction solution, for example by the passage of a gas which is chemically inert to the reaction solution, for example nitrogen. is there.

It is possible to collect and reuse unreacted chlorinating agent which escapes from the reactor during the synthesis step and / or is expelled by subsequent stripping,
It is advantageous. A suitable collecting device is, for example, a cold trap in which the chlorinating agent solidifies.

The reaction solution resulting from the reaction of the lactone (II) with the chlorinating agent can be worked up in a conventional manner. Work-up by distillation is advantageous, where stripping can optionally be carried out upstream of or in the distillation column.

It is possible and advantageous to partially or completely recycle the bottoms obtained from the purification by distillation and in particular containing the chlorination catalyst and the boron compound. Of course, prior to the recycling operation, other aftertreatments of the bottom product, for example, the chlorination catalyst and / or the boron compound can be separated by distillation. If the process is carried out with recycling of the chlorination catalyst and / or the boron compound, only part of it is recycled and the other part is replaced with fresh catalyst, for example to eliminate possible by-products. Is advantageous.

In one general embodiment of the synthesis for the preparation of the chlorocarboxylic acid chlorides (I) in a discontinuous manner, in one general embodiment, the appropriate amount of the lactone (II), the (preferably liquid) chlorination catalyst, boron The compound and optionally the solvent (eg the same chlorocarboxylic acid chloride as it should be produced) is precharged into the stirred tank. The reaction system is then heated to the desired temperature and liquid and / or gaseous phosgene or liquid thionyl chloride are continuously introduced under atmospheric pressure and with vigorous stirring. The resulting gaseous by-products carbon dioxide or sulfur dioxide and hydrogen chloride are also removed. After the desired amount of chlorinating agent has been supplied, the reaction solution is post-reacted under continuous stirring at a controlled temperature for some time. During this post-reaction, the chlorinating agent still present in the reaction solution reacts with the remaining lactone (II). An inert gas flow is possible under vigorous stirring to remove or strip excess chlorinating agent and its reaction products carbon dioxide or sulfur dioxide and hydrogen chloride from the reaction solution. Then, the resulting reaction solution is subjected to a post-treatment step. Work-up is generally carried out by distillation, optionally in vacuum.
In the case of high molecular weight chlorocarboxylic acid chlorides, other purification methods are possible, for example crystallization.

In a general embodiment for the continuous production of chlorocarboxylic acid chloride (I),
The solvent (e.g. the same chlorocarboxylic acid chloride as to be prepared), the chlorination catalyst and the boron compound are precharged into a reactor, e.g. a stirred tank, and the system is heated to the desired temperature to give a liquid or Gaseous chlorinating agent is added. Then, in parallel with the continuous feeding of the chlorinating agent, the continuous introduction of the lactone (II), which generally contains a further chlorination catalyst and a further boron compound, and which is optionally dissolved in a solvent, is started. . After conversion of the reactor contents to chlorocarboxylic acid chloride, the amounts of lactone (II) and chlorinating agent are adjusted so that both of these components are introduced in substantially equimolar amounts. The reaction quantity corresponding to the feed quantity is withdrawn from the reactor, for example via a riser or an overflow line. The reaction solution withdrawn is collected in a subsequent vessel of the reactor, for example in a stirred tank for post-reactions. Once the subsequent vessel has been filled with the reaction effluent, the overhead product is optionally stripped of the associated products carbon dioxide and hydrogen chloride, as described above, and then subjected to work-up. Work-up can be carried out, for example, by distillation.

The process of the invention makes it possible to produce chlorocarboxylic acid chlorides by reaction of the corresponding lactones with chlorinating agents, and to obtain the chlorocarboxylic acid chlorides in high yield and in high purity, It does not have the disadvantage of the additional introduction of hydrogen chloride gas. During the aftertreatment, the chlorocarboxylic acid chloride can be easily separated from the boron compound added according to the invention.

Examples Experimental apparatus The experimental apparatus consists of a 1 liter double-walled jacket-glass container equipped with a stirrer, a thermostat control device, an inlet tube for gaseous or liquid chlorination catalyst and a 2-piece cooler cascade. Become. The two-piece cooler cascade consists of a high-power cooler maintained at -10 ° C and a carbon dioxide cooler maintained at -78 ° C. The experiment was carried out under atmospheric pressure.

Example 1 (according to the invention) 200 g (2.0 mol) δ-valerolactone, 9.3 g (0.1 mol) β-picoline (3-methylpyridine) in a double-walled jacket-glass container. And boric acid 3.1
g (0.05 mol) was precharged. Phosgene gas total 229g (2.32mol)
Was introduced at 144 ° -148 ° C. under vigorous stirring for 5 hours. Then
The system was held for an additional hour without feeding phosgene for post reaction. After stripping off the remaining unconverted phosgene with nitrogen, 310 g of crude effluent were obtained. The crude effluent was fractionally distilled at 70 ° C. to 75 ° C. and a pressure of 0.7 kPa (absolute) (7 mbar absolute). 255 g of 5-chlorovaleric acid chloride having a purity of> 98 GC-area% were isolated. This corresponds to a yield of 82%.

Example 2 (according to the invention) In a double-walled jacket-glass container, 172 g (2.0 mol) of γ-butyrolactone, 9.3 g (0.1 mol) of β-picoline (3-methylpyridine) and Boric acid 3.1
g (0.05 mol) was precharged and heated to 140 ° C. Phosgene gas total 2
42 g (2.45 mol) at 140 ° C.-147 ° C. under vigorous stirring for 4 hours 15
Introduced in minutes. The system was then held for an additional hour without feeding phosgene for post reaction. After stripping off the remaining unconverted phosgene with nitrogen at 100 ° C., 289 g of crude effluent was obtained. This crude effluent contained 93.6 GC-area% 4-chlorobutyric acid chloride.

Example 3 (according to the invention) 172 g (2 mol) of γ-butyrolactone in a double-walled jacket-glass container,
Cyanex ^(R) 923 (a product sold by Cytec Industries Inc., a mixture of various trialkylphosphine oxide having an average molecular weight 348 g / mol) 34.8 g (0.1 mol) and boric acid 3.1 g ( 0.05 mol) was precharged.
A total of 251 g (2.54 mol) of phosgene gas was introduced at 144 ° C.-148 ° C. under vigorous stirring over 5 hours and 20 minutes. The system is then subjected to a post reaction,
It was held for an additional hour without feeding phosgene. After stripping off the remaining unconverted phosgene with nitrogen at 100 ° C. for 7 hours, 314 g of crude effluent was obtained. The crude effluent was fractionally distilled at a pressure of 51 kPa (absolute) (51 mbar, absolute) and 87 ° C. 242 g of 4-chlorobutyric acid chloride having a purity of> 99 GC-area% were isolated. This corresponds to a yield of 86%.

Example 4 (according to the invention) 200 g (2.0 mol) δ-valerolactone, 9.3 g (0.1 mol) β-picoline (3-methylpyridine) in a double-walled jacket-glass container. And 5.2 g (0.05 mol) of boric acid trimethyl ester were precharged and heated to 140 ° C.
A total of 242 g (2.45 mol) of phosgene gas was introduced at 140 ° C. to 146 ° C. under vigorous stirring. The system was then held for an additional hour without feeding phosgene for post reaction. After stripping off the remaining unconverted phosgene with nitrogen at 100 ° C., 318 g of crude effluent was obtained. The crude effluent was fractionally distilled at 75-77 ° C and 0.9 kPa (absolute) (9 mbar, absolute). 10 g of initial distillate (this is already 5-chlorovaleric chloride 96.6 GC-area%
Containing), 256 g of pure fraction was isolated. It contained 98.2 GC-area% 5-chlorovaleric acid chloride. The total yield after distillation was 85%.

Example 5 (according to the invention) Double-walled jacket-in a glass container 10 g of delta-valerolactone (0.1 mol)
, Benzyltrimethylammonium chloride 1.14 g (0.006 mol) and boric acid 0.31 g (0.05 mol) were precharged. Liquid thionyl chloride total 15.5
g (0.13 mol) were introduced at 120 ° C to 125 ° C under vigorous stirring over 7 hours. The system was then held for an additional hour without feeding thionyl chloride for post reaction. The reaction effluent contained 70 GC-area% 5-chlorovaleric acid chloride and 7 GC-area% unconverted δ-valerolactone.

Example 6 (Comparative Example) 192 g (2.23 mol) of γ-butyrolactone and 2 g (0.025 mol) of pyridine were precharged in a double-walled jacket-glass container and heated to 120 ° C. A total of 60 g (0.61 mol) of phosgene gas was introduced at 120-124 ° C. under vigorous stirring over 8 hours. The crude effluent was fractionally distilled after stripping off the remaining unconverted phosgene with nitrogen. 76 g of the first fraction contains 21.6 GC-area% 4-chlorobutyric acid chloride and 110 g of the second fraction
Of this fraction contained 2.6 GC-area% 4-chlorobutyric acid chloride. This corresponds to a total yield of 6%.

Comparative Example 6 shows that unsatisfactory yields can only be achieved in the absence of boron compounds and without the introduction of hydrogen chloride.

[Procedure for Amendment] Submission for translation of Article 34 Amendment of Patent Cooperation Treaty

[Submission date] December 13, 2001 (2001.12.13)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 1

[Correction method] Change

[Contents of correction]

[Chemical 1] [In the formula, R ¹ and R ² each independently represent a hydrogen atom, a carbon-containing organic group, a halogen, a nitro or a cyano group, and Y has 1 to 10 carbon atoms in the chain and is unsubstituted. Or an alkylene chain substituted by a carbon-containing organic group, a halogen, a nitro- and / or a cyano group, the alkylene chain being interrupted by one ether-, thioether-, tertiary amino- or keto group. It is possible that Y and /
Or the carbon-containing organic groups of R ¹ and / or R ² may be bonded to each other to form a non-aromatic system], in the presence of a chlorination catalyst in the presence of a chlorination catalyst, II):

[Chemical 2] When the lactone of [wherein R ¹ , R ² and Y represent the above] is reacted with a chlorinating agent, this reaction is carried out by using boron oxide, boric acid, a salt of boric acid, or a salt thereof. Process for producing chlorocarboxylic acid chloride, characterized in that it is carried out in the presence of a mixture.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 2

[Correction method] Change

[Contents of correction]

─────────────────────────────────────────────────── ─── Continued front page    (81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, I T, LU, MC, NL, PT, SE, TR), OA (BF , BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, G M, KE, LS, MW, MZ, SD, SL, SZ, TZ , UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AG, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, B Z, CA, CH, CN, CR, CU, CZ, DE, DK , DM, DZ, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, J P, KE, KG, KP, KR, KZ, LC, LK, LR , LS, LT, LU, LV, MA, MD, MG, MK, MN, MW, MX, MZ, NO, NZ, PL, PT, R O, RU, SD, SE, SG, SI, SK, SL, TJ , TM, TR, TT, TZ, UA, UG, US, UZ, VN, YU, ZA, ZW (72) Inventor Johem Henkelmann             Federal Republic of Germany Mannheim Bassar             Manstrasse 25 (72) Inventor Friedrich Cross             Federal Republic of Germany Mannheim Zukkov             Strasse 2 (72) Inventor Heinz-Josef Knoyper             Federal Republic of Germany Lower Kirchen             Buchenweg 24 F-term (reference) 4H006 AA02 AC30 AC47 BA29 BA30                       BA31 BA32 BA37 BA51 BA53                       BC10 BC11 BC34 BE51 BE52                       BM10 BM72 BS10 BS90                 4H039 CA52 CA65 CH70

Claims (10)

[Claims] 1. Formula (I): [In the formula, R ¹ and R ² each independently represent a hydrogen atom, a carbon-containing organic group, a halogen, a nitro or a cyano group, and Y has 1 to 10 carbon atoms in the chain and is unsubstituted. Or an alkylene chain substituted by a carbon-containing organic group, a halogen, a nitro- and / or a cyano group, the alkylene chain being interrupted by one ether-, thioether-, tertiary amino- or keto group. It is possible that Y and /
Or the carbon-containing organic groups of R ¹ and / or R ² may be bonded to each other to form a non-aromatic system], in the presence of a chlorination catalyst in the presence of a chlorination catalyst, II): When the lactone of [wherein R ¹ , R ² and Y represent the above] is reacted with a chlorinating agent, this reaction is carried out in the presence of a boron compound. Process for producing carboxylic acid chloride. 2. Boron trifluoride, boron trichloride or a complex thereof, boron oxide, boric acid, tri (C ₁ -C ₄ -alkyl) borate or a mixture of at least two of these boron compounds is used as the boron compound. The method according to claim 1, which is used. 3. The method according to claim 1, wherein the boron compound is used in a concentration of 0.1 to 20 mol% based on the lactone (II). 4. The process according to claim 1, wherein phosgene, diphosgene, triphosgene and / or thionyl chloride are used as chlorinating agent. 5. The method according to claim 1, wherein a urea compound, a phosphine oxide, a pyridine compound or a mixture thereof is used as a chlorination catalyst. 6. The process according to claim 5, wherein 3-methylpyridine, triphenylphosphine oxide and / or trialkylphosphine oxide is used as chlorination catalyst. 7. The method according to claim 1, wherein the chlorination catalyst is used in a concentration of 0.1 to 20 mol% with respect to the lactone (II). 8. The process according to claim 1, wherein the chlorination catalyst and the boron compound are used in the form of a complex of both components. 9. The method according to claim 1, wherein the reaction is carried out at a temperature of 50 to 200 ° C. and a pressure of 0.01 to 5 MPa (absolute). 10. The lactone (II) is γ-butyrolactone, δ-valerolactone or ε-caprolactone, which is used in any one of claims 1 to 9.
The method described in the section.