US3857841A - Process for the manufacture of carboxylic acid and sulfonic acid chlorides - Google Patents

Process for the manufacture of carboxylic acid and sulfonic acid chlorides Download PDF

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Publication number
US3857841A
US3857841A US00388883A US38888373A US3857841A US 3857841 A US3857841 A US 3857841A US 00388883 A US00388883 A US 00388883A US 38888373 A US38888373 A US 38888373A US 3857841 A US3857841 A US 3857841A
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acid
parts
phosgene
reaction
carboxylic acid
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US00388883A
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G Keil
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Hoechst AG
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Hoechst AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/81—Amides; Imides
    • C07D213/82—Amides; Imides in position 3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/58—Preparation of carboxylic acid halides
    • C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides

Definitions

  • US. Pat. No. 2,657,233 provides a process for the manufacture of dicarboxylic acid dichlorides from dicarboxylic acids and phosgene under a pressure above atmospheres gage and at temperatures in the range of from 100 to 250C.
  • British Specification No. 540,096 discloses the manufacture of carboxylic acid chlorides from carboxylic acids having at least 10 carbon atoms and phosgene at a temperature of at least 100C in the presence of 5% of tertiary amines.
  • US. Pat. No. 2,848,491 is concerned with the reaction of mono-carboxylic acids with phosgene at a temperature in the range of from room temperature to 200C, preferably 90 to 200C, in the presence of an anion exchanger.
  • chlorides or carboxylic and sulfonic acids can be obtained in simple manner and withhigh purity by reacting the salts of carboxylic acids or sulfonic acids and N,N-dimethyl acetamide, N-methyl-pyrrolidone, or other N,N-dialkyl carboxylic acid amides having at least 4 carbon atoms, optionally dissolved in acetonitrile, or other polar inert solvents, with phosgene at a temperature of from 20 to 0C and completing the reaction by heating at a temperature of at most +30C.
  • the reaction takes place very quickly and with a high yield according to the following equations:
  • N,N-dimethyl acetamide, N-methyl-pyrrolidone, or other N,N-dialkyl carboxylic acid amides having at least 4 carbon atoms can be used, for example tetramethyl-urea, whereas the lowest representative of this class the N,N-dimethyl formamide is unsuitable because of the very low yield obtained therewith.
  • the salt-like compounds from the acids and dimethyl acetamide need not be prepared in a seperate reaction and isolated in substance.
  • equimolecular amounts of the components can be used in the phosgenation.
  • the salts of carboxylic acids or sulfonic acids and dimethyl acetamide, N-methyl-pyrrolidone, or other higher N,N-dialkylcarboxylic acid amides are often sparinglysoluble only in the chosen solvent, but a very low solubility is already sufficient to start the reaction.
  • acetonitrile Besides acetonitrile, other polar solvents or diluents that can be mixed with water or are readily soluble in water can be used, provided that they are inert to the reactants at the reaction temperatures. Solvents of this type are, for example, propionitrile, tetrahydrofurane, glycol dimethyl ether, and diglycol dimethyl ether.
  • the ratio of amide salt to acetonitrile or another polar diluent can vary in the range of from 1 0.8 to l 2.0, preferably 1 1.2 to 1 1.6 parts by weight. It is also possible to operate without a special diluent, provided that an excess of the N-alkyl-pyrrolidone or, N,N-dialkyl-carboxylic acid amide required for the forf' mation of the salt-like addition compounds is used.
  • reaction temperatures should be kept so low that no secondary reactions of the phosgene or the acidchlorides with the nitrogen-containing salt forming agents or the free acid may occur.
  • reaction temperatures are in the range of from 3(i" to +30C,preferably, however from 20 to +20C.
  • phosgene is introduced at low temperature, for example about 15C, and the reaction is then completed by heating, for example to 20C. At temperatures exceeding 30C continuouslydecreasing yields of the desired acid chlorides are obtained.
  • each equivalent of the carboxyl group or sulfonic acid group 1.0 to 1.5 equivalents, preferably 1.1 to 1.2
  • phosgene equivalents of phosgene are used.
  • the phosgene can be added in dosed quantities at atmospheric pressure or at elevated pressure.
  • Sulfonic acids often contain crystal water, but the hydrates may also be used if one mole of phosgene and two moles of the nitrogen containing salt forming agent are additionally used tobind one mole of crystal water.
  • the termination of the reaction can be perceived by the end of the CO separation.
  • a suspension is used for phosgenation
  • the formation of a clear solution likewise indicates the end of the reation.
  • the reaction time is in the range of from 1 to about hours.
  • the reaction mixture Prior to working up the reaction mixture by distillation it is necessary to remove the formed hydrochlorides of the nitrogen containing compounds, for example of dimethyl acetamide, as these substances react with the acid chlorides at elevated temperature.
  • the reaction mixture can be diluted with a non polar solvent for example benzene, whereupon the hydrochloride crystallizes out and can be filtred off.
  • a non polar solvent for example benzene
  • reaction solutions obtained in the process of the invention can be directly used for further reactions without further treatment or purification of the acid chlorides. It is thus possible to produce unsaturated and/or temperature sensitive acid chlorides and directly to use the reaction solutions obtained for further reactions.
  • the reaction solutions can be reacted, for example, with amines, alcohols or phenols. They are also suitable for the manufacture of polyamides, for example by the process disclosed in German Pat. No. 1,420,681, without isolating the acid chlorides obtained.
  • aliphatic, cycloaliphatic, aromatic and heterocyclic mono-, diand polycarboxylic acids possibly carrying substituents which do not react at the chosen reaction temperatures with the acid chlorides or phosgene, such as, for exammple, acetic acid, chloroacetic acid, propionic acid, acrylic 5 acid, butyric acid, crotonic acid, cyclohexanecarboxylic acid, adipic acid, sebacic acid, cyclohexane-l,4 dicarboxylic acid, benzoic acid, toluylic acid, naphthalene-carboxylic acids, halogenated benzoic acids, isophthalic acid, tereph- 0 thalic acid, trimellitic acid, nicotinic acid, quinoline-carboxylic acid, indole-3-carboxylic acid, pyrazine-2,3-dicarboxylic acid;
  • aliphatic, cycloaliphatic and aromatic monoand disulfonic acids possibly containing further substituents which sre inert to sulfonic acid chlorides and phosgene at low temperatures, for example methane-sulfonic acid, ethane-disulfonic acid, butane-sulfonic acid, B-chlorethane-sulfonic acid, cyclohexane-sulfonic acid, benzene-sulfonic acids, toluene-sulfonic acids, p-chloro-benzene-sulfonic acids,- naphthalene-sulfonic acids, benzene-1,3-disulfonic acid, naphthalenedisulfonic acids, pyridine-3-sulfonic acid.
  • EXAMPLE 1 61 Parts of benzoic acid were dissolved in a mixture of 49.5 parts of N-methyl-pyrrolidone and 200 parts by volume of aceto-nitrile. The solution was cooled to 15C with the exclusion of moisture and at a temperature in a range of from to l5C 60 parts of phosgene were introduced within about 30 minutes. When the introduction was terminated, the solution was stirred for about minutes at 15C. Next, the reaction mixture was heated to about +C within the course of 2 hours. During this period of time considerable amounts of CO were split off. The reaction mixture was stirred for a further hour at 20C and diluted with 2,000 parts by volume of benzene or toluene.
  • EXAMPLE 2 166 parts of isophthalic acid were mixed with 174 parts of N,N-dimethyl acetamide and 500 parts by volume of acetonitrile. By heating at about C a homogeneous solution was obtained. On cooling the salt of 1 mole isophthalic acid and 2 moles of dimethyl acetamide crystallized out. At -10C 220 parts of phosgene were introduced into the mixture with the exclusion of moisture within the course of 1 hour. The mixture was then heated to +20C during the course of 1 hour. A yellowish solution formed with splitting off of CO Stirring of the solution was continued for 2 hours at +20C, whereupon it was diluted with 4,000 parts by volume of benzene.
  • EXAMPLE 8 95.1 Parts of p-toluene-sulfonic acid monohydrate were dissolved in a mixture of 130.5 parts of N,N- dimethyl acetamide and 300 parts by volume of acetonitrile, the solution was cooled to 10C and at that temperature 110 parts of phosgene were introduced 2 moles of dimethyl acetamide having the summation formula C H N O were obtained. The decomposition point of the compound was found to be 82C.
  • EXAMPLE 6 1n the manner described above a mixture of 83 parts of terephthalic acid, 87 parts of dimethyl acetamide and 300 parts by volume of acetonitrile was reacted with 110 parts of phosgene. After termination of the reaction a solution of 87 parts of dimethyl acetamide in 100 parts of methanol was dropped into the reaction mixture. The temperature rose to C. After having been allowed to stand for 1 hour at about 25C, the reaction mixture was poured on ice. The crystalline pre cipitate was filtred off with suction, washed and dried. 63 Parts (65 of the 'theory) of terephthalic acid dimethyl ester melting at 141C were obtained.
  • EXAMPLE 7 118 Grams of phosgene were introduced at 13C into a mixture of 128 parts of cyclohexane-carboxylic during the course of about 1 hour. The mixture was stirred for 30 minutes at 10C, the temperature was rised to +20C within 2 hours and the mixture kept at that temperature for another 2 hours. Considerable amounts of CO separated. The mixture was diluted with benzene, the dimethyl acetamide hydrochloride was filtred off, the filtrate was rapidly washed with a small amount of icewater and concentrated. The residue was distilled under reduced pressure. 88.6 Parts (93 of the theory) of p-toluene-sulfonic acid chloride melting at 69C distilled over at 135 136C under 10 mm Hg.
  • EXAMPLE 9 25 Parts of p-toluene-sulfonic acid monohydrate were dissolved in 100 parts by volume of N,N-dimethyl acetamide and benzene was added to the solution until it became turbid. The separating crystals were filtred off with suction, washed with benzene and dried. 22.5 Parts (62 of the theory) of colorless crystals were obtained which started to decompose at 73C. It was the p-toluene-sulfonic acid dimethyl acetamide salt of the summation formula C H NO S.
  • EXAMPLE 1 1 73 Parts of adipic acid, 87 parts of N,N-dimethyl acetamide and 200 parts by volume of acetonitrile were reacted at 12C with 1 12 grams of phosgene. The reaction mixture was allowed to warm up to +21C whereby CO was split off. The mixture was diluted with 2,000 parts by volume of benzene and the dimethyl acetamidehydrochloride was filtred off with suction. The filtrate was concentrated in a thin layer evaporator. From themes-Hue a further portion of dimethyl acetamide hydrochloride separated, which was filtred off. The filtrate was distilled and 52.1 parts (57 of the theory) of adipic acid dichloride were obtained at a boiling pointof 97C under 2 mm Hg.
  • EXAMPLE 13 72 Parts of acrylic acid were dissolved in 87 parts of EXAMPLE 14 During the course of 90 minutes a solution of 123 grams of pyridine-3-carboxylic acid (nicotinic acid) in 600 milliliters of dimethyl acetamide was reacted at l0C with 120 grams of phosgene. The reaction was completed by heating the reaction mixture to +20C for a short while. The reaction solution was againcooled to l0C and 219 grams of diethyl amine were dropped in at that temperature within 20 minutes. The reaction mixture was heated at +20C and allowed to stand for some hours at that temperature. The dark brown reaction solution was poured into water, sodium hydroxide was added and the mixture extracted with benzene. The benzene phase was dried and concentrated. By fractional distillation 125.5 grams of nicotinic acid diethyl amide were obtained in the form of a yellowish oil at a temperature of 126C under 0.8 mm Hg.
  • a process for the manufacture of a carboxylic acid chloride from the corresponding carboxylic acid and phosgene which comprises reacting the salt-like addition compound of an aliphatic, cycloaliphatic, aromatic or heterocyclic carboxylic acid having 1 or 2 hetero nitrogen atoms with an N-alkyl-pyrrolidone or an N,N-dialkyl-carboxylic acid amide having at least 4 carbon atoms in the molecule, in a polar, inert solvent present in weight ratio of 0.8:1 to 20:1 to said salt like addition compound, with 1.0 to 1.5 molar equivalents of phosgene based upon said carboxylic acid at a temperature from 30C to +30C, at atmospheric pressure or elevated pressure and completing the reaction by heating the reaction mixture to at most +30C.
  • reaction temperature is in the range of from 20 to +20C.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US00388883A 1972-08-19 1973-08-16 Process for the manufacture of carboxylic acid and sulfonic acid chlorides Expired - Lifetime US3857841A (en)

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Application Number Priority Date Filing Date Title
DE2240883A DE2240883A1 (de) 1972-08-19 1972-08-19 Verfahren zur herstellung von carbonsaeure- und sulfonsaeurechloriden

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US (1) US3857841A (enrdf_load_stackoverflow)
DE (1) DE2240883A1 (enrdf_load_stackoverflow)
FR (1) FR2196305B1 (enrdf_load_stackoverflow)
GB (1) GB1434400A (enrdf_load_stackoverflow)
NL (1) NL7311194A (enrdf_load_stackoverflow)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4101571A (en) * 1975-03-29 1978-07-18 Basf Aktiengesellschaft Manufacture of sulfamic acid halides
US4104298A (en) * 1975-04-05 1978-08-01 Basf Aktiengesellschaft Manufacture of sulfamic acid halides
US4211723A (en) * 1975-06-11 1980-07-08 Ihara Chemical Industry Co., Ltd. Process for producing chlorosulfonylbenzoylchloride
US4213919A (en) * 1978-11-13 1980-07-22 Basf Aktiengesellschaft Manufacture of β-chlorocarboxylic acid chlorides
US4297301A (en) * 1978-11-29 1981-10-27 Societe Nationale Des Poudres Et Explosifs Process for the manufacture of organic acid chlorides
US4393009A (en) * 1979-07-03 1983-07-12 Bayer Aktiengesellschaft Process for the preparation of aromatic dicarboxylic acid dichlorides
US5166427A (en) * 1988-10-31 1992-11-24 Basf Aktiengesellschaft Preparation of acyl chlorides
US5200560A (en) * 1990-04-21 1993-04-06 Basf Aktiengesellschaft Preparation of carboxylic chlorides
US5245063A (en) * 1990-09-11 1993-09-14 Basf Aktiengesellschaft Preparation of carbonyl chlorides
US5792888A (en) * 1995-05-01 1998-08-11 Zeneca Limited Process for phosgenation in the presence of acetonitrile

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2743542A1 (de) * 1977-09-28 1979-04-05 Bayer Ag Verfahren zur herstellung von sulfonsaeurechloriden
FR2464244A1 (fr) * 1979-08-30 1981-03-06 Poudres & Explosifs Ste Nale Procede de fabrication de chlorures d'acides organiques
DE19838516A1 (de) * 1998-08-25 2000-03-09 Degussa Verfahren zur Herstellung von Sulfonylhalogeniden
WO2005030696A1 (en) * 2003-09-26 2005-04-07 Huntsman Advanced Materials (Switzerland) Gmbh Process for the production of acrylic acid esters containing carboxyl groups

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2888486A (en) * 1953-11-20 1959-05-26 Du Pont Process for producing aromatic sulfonyl halides
US3706794A (en) * 1966-02-28 1972-12-19 Ici Ltd Production of sulphonyl chlorides

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1140185B (de) * 1958-06-03 1962-11-29 Basf Ag Verfahren zur Herstellung von gesaettigten ª‰-Chlorfettsaeurechloriden mit 3 bis 4 Kohlenstoffatomen
US3318950A (en) * 1963-12-10 1967-05-09 Du Pont Process for preparing carboxylic acid chlorides

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2888486A (en) * 1953-11-20 1959-05-26 Du Pont Process for producing aromatic sulfonyl halides
US3706794A (en) * 1966-02-28 1972-12-19 Ici Ltd Production of sulphonyl chlorides

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4101571A (en) * 1975-03-29 1978-07-18 Basf Aktiengesellschaft Manufacture of sulfamic acid halides
US4104298A (en) * 1975-04-05 1978-08-01 Basf Aktiengesellschaft Manufacture of sulfamic acid halides
US4211723A (en) * 1975-06-11 1980-07-08 Ihara Chemical Industry Co., Ltd. Process for producing chlorosulfonylbenzoylchloride
US4213919A (en) * 1978-11-13 1980-07-22 Basf Aktiengesellschaft Manufacture of β-chlorocarboxylic acid chlorides
US4297301A (en) * 1978-11-29 1981-10-27 Societe Nationale Des Poudres Et Explosifs Process for the manufacture of organic acid chlorides
US4393009A (en) * 1979-07-03 1983-07-12 Bayer Aktiengesellschaft Process for the preparation of aromatic dicarboxylic acid dichlorides
US5166427A (en) * 1988-10-31 1992-11-24 Basf Aktiengesellschaft Preparation of acyl chlorides
US5200560A (en) * 1990-04-21 1993-04-06 Basf Aktiengesellschaft Preparation of carboxylic chlorides
US5245063A (en) * 1990-09-11 1993-09-14 Basf Aktiengesellschaft Preparation of carbonyl chlorides
US5792888A (en) * 1995-05-01 1998-08-11 Zeneca Limited Process for phosgenation in the presence of acetonitrile

Also Published As

Publication number Publication date
DE2240883A1 (de) 1974-02-28
FR2196305B1 (enrdf_load_stackoverflow) 1979-03-02
GB1434400A (en) 1976-05-05
NL7311194A (enrdf_load_stackoverflow) 1974-02-21
FR2196305A1 (enrdf_load_stackoverflow) 1974-03-15

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