CA1173057A - Production of carboxylic acids and esters - Google Patents
Production of carboxylic acids and estersInfo
- Publication number
- CA1173057A CA1173057A CA000404487A CA404487A CA1173057A CA 1173057 A CA1173057 A CA 1173057A CA 000404487 A CA000404487 A CA 000404487A CA 404487 A CA404487 A CA 404487A CA 1173057 A CA1173057 A CA 1173057A
- Authority
- CA
- Canada
- Prior art keywords
- carbon monoxide
- organic compound
- propylene
- hydrogen fluoride
- hundred
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 150000002148 esters Chemical class 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title description 3
- 150000001735 carboxylic acids Chemical class 0.000 title description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 81
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 80
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 50
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 40
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 33
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 33
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 31
- 239000002253 acid Substances 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 150000001450 anions Chemical class 0.000 claims abstract description 21
- 239000012808 vapor phase Substances 0.000 claims abstract description 16
- FSQOYWQCIXSBNP-UHFFFAOYSA-N 2-methylpropanoyl fluoride Chemical compound CC(C)C(F)=O FSQOYWQCIXSBNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 12
- -1 propylene Chemical class 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 150000001336 alkenes Chemical class 0.000 claims description 11
- 239000011541 reaction mixture Substances 0.000 claims description 11
- 239000007791 liquid phase Substances 0.000 claims description 10
- 239000012071 phase Substances 0.000 claims description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- WVRPFQGZHKZCEB-UHFFFAOYSA-N Isopropyl 2-methylpropanoate Chemical compound CC(C)OC(=O)C(C)C WVRPFQGZHKZCEB-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- WDAXFOBOLVPGLV-UHFFFAOYSA-N ethyl isobutyrate Chemical compound CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 claims description 5
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 5
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 4
- 229940024423 isopropyl isobutyrate Drugs 0.000 claims description 4
- IJMWOMHMDSDKGK-UHFFFAOYSA-N Isopropyl propionate Chemical compound CCC(=O)OC(C)C IJMWOMHMDSDKGK-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 claims description 2
- XPYQFIISZQCINN-QVXDJYSKSA-N 4-amino-1-[(2r,3e,4s,5r)-3-(fluoromethylidene)-4-hydroxy-5-(hydroxymethyl)oxolan-2-yl]pyrimidin-2-one;hydrate Chemical compound O.O=C1N=C(N)C=CN1[C@H]1C(=C/F)/[C@H](O)[C@@H](CO)O1 XPYQFIISZQCINN-QVXDJYSKSA-N 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 29
- 229940095050 propylene Drugs 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000005810 carbonylation reaction Methods 0.000 description 4
- 150000001733 carboxylic acid esters Chemical class 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000006315 carbonylation Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000002222 fluorine compounds Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000011260 aqueous acid Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-M isobutyrate Chemical compound CC(C)C([O-])=O KQNPFQTWMSNSAP-UHFFFAOYSA-M 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- BHIWKHZACMWKOJ-UHFFFAOYSA-N methyl isobutyrate Chemical compound COC(=O)C(C)C BHIWKHZACMWKOJ-UHFFFAOYSA-N 0.000 description 2
- 150000002895 organic esters Chemical class 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- ZUXNHFFVQWADJL-UHFFFAOYSA-N 3,4,5-trimethoxy-n-(2-methoxyethyl)-n-(4-phenyl-1,3-thiazol-2-yl)benzamide Chemical compound N=1C(C=2C=CC=CC=2)=CSC=1N(CCOC)C(=O)C1=CC(OC)=C(OC)C(OC)=C1 ZUXNHFFVQWADJL-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 1
- 241000283986 Lepus Species 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- JLNTWVDSQRNWFU-UHFFFAOYSA-N OOOOOOO Chemical compound OOOOOOO JLNTWVDSQRNWFU-UHFFFAOYSA-N 0.000 description 1
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Classifications
-
- 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
-
- 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
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
- C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
ABSTRACT OF THE DISCLOSURE
An acylium anion product, e.g., isobutyryl fluoride, is formed by reacting carbon monoxide, an organic compound, propylene, and anhydrous hydrogen fluoride, in a liquid mixture while feeding the carbon monoxide and organic compound, e.g., propylene, into the liquid mixture's vapor phase which is maintained above the supercritical tempera-ture of the vapor mixture at substantially the same rate as the carbon monoxide, organic compound propylene, and anhy-drous acid (hydrogen fluoride) react, under the conditions described herein.
An acylium anion product, e.g., isobutyryl fluoride, is formed by reacting carbon monoxide, an organic compound, propylene, and anhydrous hydrogen fluoride, in a liquid mixture while feeding the carbon monoxide and organic compound, e.g., propylene, into the liquid mixture's vapor phase which is maintained above the supercritical tempera-ture of the vapor mixture at substantially the same rate as the carbon monoxide, organic compound propylene, and anhy-drous acid (hydrogen fluoride) react, under the conditions described herein.
Description
1~73~57 The invention relates to the production of an acylium anion product (acylium fluoride), e.g~, isobutryryl fluoride, from cabon monoxide, anhydrous hydrogen fluoride acid and an organic compound capable of adding carbon monoxide thereto.
The prior art such as U.S. 3,167,585 and 3,703,549 as a whole stresses the requirement of an aqueous acid catalyst reaction medium for production of carboxylic acid from compounds having one or more double bonds. In these processes, serious irreversible polymerization occurs and the aqueous acid medium is corrosive so that expensive equipment is required.
For example, in the prior art, such as in Koch U.S. Patent No. 2,831,877, poor yields of acid fluorides are formed by reacting an olefin with carbon monoxide and anhydrous hydrogen fluoride in a dual phase reaction. The carbon monoxide being in the gaseous state and the olefin and hydrogen fluoride remaining in the liquid state. This frequently causes the olefin to dimerize or polymerize thus being taken out of the reaction, and requires separation from the products.
The prior art problems are overcome by following the reaction conditions described herein to form the acylium anion products and their corresponding carboxylic acids or esters by the process described herein in substantially high yields.
~r, ~`
~73~)57 SUMM~RY OF THE INVENTION
Acylium anion products (acylium fluorides) (e.g., isobutyryl fluoride) arè formed by reacting carbon monoxide, an anhydrous hydrogen fluoride acid described herein (e.g., hydrogen fluoride), and an organic compound capable oE adding carbon monoxide thereto described herein (e.g., propylene) in the liquid phase while feeding the carbon monoxide and the organic compound (e.g., propylene) into the vapor phase over the liquid reaction mixture at substantially the same rate as the carbon monoxide, organic compound and anhydrous hydrogen fluoride acid form the acylium anion product, while maintaining the temperature and pressure of the mixture's vapor phase above the liquid such that the carbon monoxide is in a supercritical fluid phase and dissolves the organic compound, e.g., propylene, therein. The reaction is conducted under conditions whereby the acylium anion products form in substantial yields. The acylium anion product can be separated and reacted with water to form carboxylic acid, e.g., isobutyric acid, or with an alcohol to form a carboxylic ester, e.g., methyl isobutyrate, or the product mixture itself can be reacted with water to form carboxylic acid or with an alcohol to form the carboxylic ester.
DESCRIPTION OF THE INVENTION
The invention concerns a novel process for producing acylium anion products (acylium fluorides) from carbon monoxide, an organic compound capable of adding carbon monoxide thereto described herein and an anhydrous acid described herein.
The carbon monoxide, anhydrous acid, and organic compound are reacted in a liquid mixture under conditions whereby acylium anion product forms in substantial yields;
that is, with less than 10 percent formation of ?olymeric products or other undesirable side products. .~fter the ~173057 -- 3 ~
reaction has started, the carbon monoxide and the organic compound are fed into the vapor phase over the liquid reac-tion mixture at substantially the same rate (that is, fifteen (15), pre~erably ten (10) mole percent) as the carbon monoxide, organic compound, and anhydrous acid react to form the acylium anion product, e.g., isobutyryl fluoride.
The temperatllre and pressure of the mixture's vapor phase above the liGuid mixture is maintained so that the carbon monoxide in ~he mixture's vapor phase is in a supercritical fluid phase and the organic compound, e.g., propylene, dissolves therein. Preferably, the temperature and pressure is maintained at the point where the organic compound dissolves in the carbon monoxide supercritical fluid phase and both the carbon monoxide and organic compound e.g., propylene, transfers into the reaction mixture at the rate at which carbon monoxide, anhydrous acid, and organic com-pound ~eact to form the acylium anion product, thereby preventing side reactions such as polymerization from occurring.
In one embodiment of the invention, the acylium anion product is separated from the reaction mixture, and then further reacted with water or an alcohol under condi-tions whereby the corresponding carboxyLic acid or carboxylic ester forms.
In another embodiment of the invention, the product mixture which has the formed acylium anion product therein is further reac~ed with water or an alcohol under conditions whereby the corresponding carboxylic acid or carboxylic ester forms.
REACTANTS
The carbon monoxide may be from any source, but must be substantiallv free from water so that an anhydrous reactlon mixture is maintained. The carbon monoxide may be diluted with other substances such as hydrogen, propane, or ~73~)57 nonreactive hydrocarbon which do not interfere with the reaction. For example, dry synthesis gas may be used as the source of carbon monoxide. It is preferred, however, that dry carbon monoxide itself be used.
Examples of organic compounds capable of reacting with carbon monoxide are organic esters described herein or ole~ins having at least one unsaturated bond capable of addin~ carbon monoxide thereto as described herein.
The organic esters are represented by the general o ormula R - C - O - R'. R is an alkyl of up to twenty carbon atoms, such as methyl, ethyl, dodecyl, eicosanyl.
Preferably the alkyl is methyl, ethyl, propyl, isopropyl, with isopropyl being the most preferred. ~' is an alkyl of from two to twenty carbon atoms, such as ethyl, propyl, t-butyl, dodecyl eicosanyl. Preferably R' is ethyl or isopropyl, with isopropyl being the most preferred.
When an ester is used in the process described herein, any one of the esters mentioned herein may be used.
It is however, preferable to use isopropyl isobutyrate (2-propanol 2-methylpropionate), ethyl isobutyrate (ethanol
The prior art such as U.S. 3,167,585 and 3,703,549 as a whole stresses the requirement of an aqueous acid catalyst reaction medium for production of carboxylic acid from compounds having one or more double bonds. In these processes, serious irreversible polymerization occurs and the aqueous acid medium is corrosive so that expensive equipment is required.
For example, in the prior art, such as in Koch U.S. Patent No. 2,831,877, poor yields of acid fluorides are formed by reacting an olefin with carbon monoxide and anhydrous hydrogen fluoride in a dual phase reaction. The carbon monoxide being in the gaseous state and the olefin and hydrogen fluoride remaining in the liquid state. This frequently causes the olefin to dimerize or polymerize thus being taken out of the reaction, and requires separation from the products.
The prior art problems are overcome by following the reaction conditions described herein to form the acylium anion products and their corresponding carboxylic acids or esters by the process described herein in substantially high yields.
~r, ~`
~73~)57 SUMM~RY OF THE INVENTION
Acylium anion products (acylium fluorides) (e.g., isobutyryl fluoride) arè formed by reacting carbon monoxide, an anhydrous hydrogen fluoride acid described herein (e.g., hydrogen fluoride), and an organic compound capable oE adding carbon monoxide thereto described herein (e.g., propylene) in the liquid phase while feeding the carbon monoxide and the organic compound (e.g., propylene) into the vapor phase over the liquid reaction mixture at substantially the same rate as the carbon monoxide, organic compound and anhydrous hydrogen fluoride acid form the acylium anion product, while maintaining the temperature and pressure of the mixture's vapor phase above the liquid such that the carbon monoxide is in a supercritical fluid phase and dissolves the organic compound, e.g., propylene, therein. The reaction is conducted under conditions whereby the acylium anion products form in substantial yields. The acylium anion product can be separated and reacted with water to form carboxylic acid, e.g., isobutyric acid, or with an alcohol to form a carboxylic ester, e.g., methyl isobutyrate, or the product mixture itself can be reacted with water to form carboxylic acid or with an alcohol to form the carboxylic ester.
DESCRIPTION OF THE INVENTION
The invention concerns a novel process for producing acylium anion products (acylium fluorides) from carbon monoxide, an organic compound capable of adding carbon monoxide thereto described herein and an anhydrous acid described herein.
The carbon monoxide, anhydrous acid, and organic compound are reacted in a liquid mixture under conditions whereby acylium anion product forms in substantial yields;
that is, with less than 10 percent formation of ?olymeric products or other undesirable side products. .~fter the ~173057 -- 3 ~
reaction has started, the carbon monoxide and the organic compound are fed into the vapor phase over the liquid reac-tion mixture at substantially the same rate (that is, fifteen (15), pre~erably ten (10) mole percent) as the carbon monoxide, organic compound, and anhydrous acid react to form the acylium anion product, e.g., isobutyryl fluoride.
The temperatllre and pressure of the mixture's vapor phase above the liGuid mixture is maintained so that the carbon monoxide in ~he mixture's vapor phase is in a supercritical fluid phase and the organic compound, e.g., propylene, dissolves therein. Preferably, the temperature and pressure is maintained at the point where the organic compound dissolves in the carbon monoxide supercritical fluid phase and both the carbon monoxide and organic compound e.g., propylene, transfers into the reaction mixture at the rate at which carbon monoxide, anhydrous acid, and organic com-pound ~eact to form the acylium anion product, thereby preventing side reactions such as polymerization from occurring.
In one embodiment of the invention, the acylium anion product is separated from the reaction mixture, and then further reacted with water or an alcohol under condi-tions whereby the corresponding carboxyLic acid or carboxylic ester forms.
In another embodiment of the invention, the product mixture which has the formed acylium anion product therein is further reac~ed with water or an alcohol under conditions whereby the corresponding carboxylic acid or carboxylic ester forms.
REACTANTS
The carbon monoxide may be from any source, but must be substantiallv free from water so that an anhydrous reactlon mixture is maintained. The carbon monoxide may be diluted with other substances such as hydrogen, propane, or ~73~)57 nonreactive hydrocarbon which do not interfere with the reaction. For example, dry synthesis gas may be used as the source of carbon monoxide. It is preferred, however, that dry carbon monoxide itself be used.
Examples of organic compounds capable of reacting with carbon monoxide are organic esters described herein or ole~ins having at least one unsaturated bond capable of addin~ carbon monoxide thereto as described herein.
The organic esters are represented by the general o ormula R - C - O - R'. R is an alkyl of up to twenty carbon atoms, such as methyl, ethyl, dodecyl, eicosanyl.
Preferably the alkyl is methyl, ethyl, propyl, isopropyl, with isopropyl being the most preferred. ~' is an alkyl of from two to twenty carbon atoms, such as ethyl, propyl, t-butyl, dodecyl eicosanyl. Preferably R' is ethyl or isopropyl, with isopropyl being the most preferred.
When an ester is used in the process described herein, any one of the esters mentioned herein may be used.
It is however, preferable to use isopropyl isobutyrate (2-propanol 2-methylpropionate), ethyl isobutyrate (ethanol
2-methylpropionate), isopropyl propionate (2-propanol propionate) or ethyl propionate (ethanol propionate) and it is especially preferred to use isopropyl isobutyrate (2-propanG1 2-methylpropionate).
Preferred examples of organic compounds having at least one unsaturated bond capable of adding carbon monoxide thereto which may be used in the process described herein are: olefins having at least one double bond capable of adding carbon monoxide thereto and having up to twenty carbon atoms, examples of which are ethylene, propylene, butenes, 1,3-butadiene, dodecene, l-hexylpropylene. The olefins may be substituted with substituents which do not interfere in the process described herein. Ethylene, propylene, isobutene, l-butene, 2-butene, and 1,3-butadiene are preferred olefins;
Preferred examples of organic compounds having at least one unsaturated bond capable of adding carbon monoxide thereto which may be used in the process described herein are: olefins having at least one double bond capable of adding carbon monoxide thereto and having up to twenty carbon atoms, examples of which are ethylene, propylene, butenes, 1,3-butadiene, dodecene, l-hexylpropylene. The olefins may be substituted with substituents which do not interfere in the process described herein. Ethylene, propylene, isobutene, l-butene, 2-butene, and 1,3-butadiene are preferred olefins;
3~57 ethylene and propylene are highly preferred, and propylene is especially preferred.
When the olefin has additional double bonds, such as 1,3-butadiene, 1,4-pentadiene additional reaction capa-bility exists to form di- or multi-acylium anion products.
O O
~or example, 1,3-bu~adiene can form F - C - (CH2)4 - C - F, which reacts with water to form 1,6-hexandioic acid, O O
HO - C - (C~2)4 - COH, or an alcohol, such as methanol to O O
form dimethyl 1,6-hexanediate, CH30 - C - ~CH2)4 - COC~3.
Although all of the organic compounds described herein may be used in the process described herein; however, it is especially preferred that propylene be used.
The anhydrous acid for the process described is anhydrous hydrogen fluoride. It is possible to use anhydrous hydrogen fluoride acids which have small amounts of water therein, less than 0.02 weight percent, provided an anhydrous acid system is maintained.
REACTION CONDITION_ The reaction of carbon monoxide, with an organic compound described herein and an anhydrous hy~roqen fluoride acid described herein, can occur at temperatures from forty degrees Centigrade (40C) to se~enty degrees Centigrade (70C), but preferably it is at about fifty degrees Centigrade ~50C).
The pressure at which the reaction is conducted can vary from 109 bars (1,600 psia) to 340 bars (5,000 psia), and prefer-ably it is from 169 bars (2,500 psia) to 197 bars (~,900 psia). The pressure and temperature being increased as required for th~ solubility of carbon monoxide in the anhy-drous acid as well as maintaining a supercritical luid phase of carbon monoxide in which the organic compound is dissolved 11~73C:~S7 above the liquid ~hase o~ the reacting medium. Note the term "vapor" as used herein and in the claims is equivalent to "gaseous" or "gas".
The final mole ratio of anhydrous acid to the organic compound described herein in the reacting mixture should be from 1:1 to 100:1, but generally it is from 10:1 to 20:1 and preferablv about 12:1 to 16:1. The mole ratio of carbon monoxlde to the organic compound is from 1:1 to 25:1 or higher, but preferably it is from 15:1 to 25:1.
The carbon monoxide and anhydrous acid, e.g., anhydrous hydrogen fluoride should be thoroughly mixed to form a single liquid phase, prior to the feeding of the organic compound described herein, e~g., propylene and - carbon monoxide as required into the reactor. The organic compound itself can be mixed and diluted with carbon monoxide or inert diluents, e.g., propane, 2rior to addition to the reactor.
It is very important that the addition of carbon monoxide and the or~anic compound to the reactor be at substantially the same rate as carbon monoxide, organic compound and anhydrous acid react; that is, the addition rate should be within fifteen (15) but preferably ten (10) mole percent of the rate at which they are reacting to form the acylium anion product. If the rate of addition of carbon monoxide is faster or greater than that of the organic compound, no adverse effect will generally occur; but if it is slower than the organic compound, then the yield of acylium anion product, e.g., isobutyryl fluoride, will decrease, generally because of adverse side reactions such as polymerization of the double bond of the unsaturated com-pound, and/or carbonylation of oligomers. Thus, it is very important that the organic compound be added at substantially the same rate as it is being used up, or if the carbon monoxide addition rate slows, then the organic compound addition rate must also slow.
1~73~ 7 The proper rate of addition is readil~ controlled by sampling the amount of the acylium anlon product, e.g., isobutyryl fluoride, being formed under the given reaction conditions, or the amount of carbon monoxide being used, and then increasing or decreasing the addition rate in accordance with the rate of formation of the acylium anion, or rate at which carbon monoxide is used.
It is important that the liquid phase reaction mixture be stirred or agitated as rapidly as possible to insure adequate mixing, dilution of the organic compound being added, and transfer of the carbon monoxide and organic compound from ~le vapor or gas phase into the liquid phase.
The reaction of the acylium anion product, e.g., isobutyryl fluoride, with water or alcohol can occur at temperatures from zero degree Centigrade (0C) to one hundred fifty degrees Centigrade (150C) and at pressures from 14.7 psia to 5,000 psia, but normally it occurs at temperatures from forty degrees Centigrade (40C) to seventy degrees Centigrade (70C) and pressures at 500 psia to 3,000 psia.
The temperature and pressure being set to avoid the decomposi-tion of the intended products.
In one embodiment, the reaction mixture itself after the carbonylation is complete is reacted with water or an alcohol. The total amount of water or alcohol may be injected into the reaction mixture after the carbonvlation reaction is complete. Since the hydrolysis or esterifica-tion is exothermic, cooling may be required. Then the carboxylic acid or esters are separated.
In another embodiment, after the carbonylation reaction is complete, from one (1) to one hundred (100) percent of the stable acylium anion product formed is separated from the product mixture. Preferably, from eighty (80) to one hundred (100) percent of the stable acylium anion product is separated, and the remaining product mixture is recvcled for reacting as in Stess ta) and (b) described herein.
1~7~3~5~7 In another embodiment, from one (1) to one hundred (100) percent (preferably from eighty (80) to one hundred (100) ~ercent), of the anhydrous acid is separated from the product mixture and recycled back for further mixing with carbon monoxide in the liuqid phase.
The separations described herein can be by any of the ~nown methods of separation, such as distillation or extraction.
_E ~EACTOR
The process described herein can be carried out in any suitable reactor, such as a continuous stirred tank reactor ~CSTR).
It is extremely important in the present invention to maintain the proper amount of carbon monoxide in solution.
The amount of carbon monoxide which can be dissolved in anhydrous acid, e.g., hydrogen fluoride, or the reaction mixture, can be empirically determined by one of ordinary skill in the art at a particular temperature and a particular pressure. For example, at 3,000 psig and 80C, 9 lbs of carbon monoxide would be dissolved in 100 lbs of hydrogen fluoride. Based on the molar amount of the organic compound which is intended to be reacted, the amount of carbon monoxide needed for the reaction can be determined. For example, as stated above, the desired range of molar ratios of organic compound to carbon monoxide to acid is 1:1-25:1-100 and the preferred ratio is 1:25:14, particularly for propy-lene, carbon monoxide, and anhydrous hydrogen fluoride.
Other information required are the reaction condi-tions desired, i.e., the pressure and the temperature of the reactor. From this, the molar percentage of carbon monoxide dissolved in the acid hydrogen fluoride, can be determ ned.
From this, the amount of acid hydro~en fluoride solution required to supply sufficient carbon monoxide to react with the organic compound can also be determined.
The following examples will illustrate the orocess as described herein.
The carbonylation reactor was a 300 cc Autoclave Engineers Magnedrive Hastelloy C equi~ped with a turbine blade stirrer, a carbon monoxide inlet, a propylene inlet, an outlet for depressurizing the reactor, and an external heater.
The reactor was initially flushed with carbon monoxide and then about 150 grams (7.5 moles) of anhydrous hydrogen fluoride were charged into the reactor. Carbon monoxide was then charged to the preselected pressure into the reactor while the hydrogen fluoride was stirred and the reactor was allowed to equilibrate to the preselected temperature.
lS After the carbon monoxide pressure had stabilized, propvlene was fed into the vapor phase of the liquid mixture (the vapor phase was a mixture of carbon monoxide and hydrogen fluoride) which was above the liquid phase, so as to form a supercritical mixture of propylene and carbon monoxide which transferred into the liquid phase. The propylene was fed through a metering pump while the carbon monoxide was added by maintaining the reactor's pressure at the preselected pressure.
After the reaction was comolete; that is, the predetermined amount of propylene and carbon monoxide had been added, the reactor was stirred for an additional time, from fifteen to thirty minutes, then the reactor was cooled to about -20C with an acetone/dry ice mi~ture, and then 38.5 grams of water waspumped into the reactor over a five-to-ten-minute period, while cooling. The reactor was then vented, opened, and the product mixture was further diluted with ice water, until the hydrogen fluoride was about lO wt.
percent of the mixture. Then 400 grams of sodium sulfate (Na2SO4) was added, and the isobutyric acid and oligomers extracted with 4 separate volumes of cyclohexane (400, 300, 3~S7 200, 200). The cyclohexane extracts were combined and analyzed bv gas chromatography, as well as separating the products by distillation. The percentage yield of isobutyric acid formed is based on the amount o~ propylene added.
Table I shows the results of controlling the feed of propylene and carbon monoxide at various temperatures and pressures. Column 1 gives the example number; ~o].umn 2, the pressure range of the reaction in pounds per square inch gauge (psig); ~olumn 3, the temperature ra~ge of the reaction in degrees Centigrade (C); Column 4 gives the time of complete addition of propylene; Column 5 gives the moles of propylene added per hour; Column 6 gives the apparent reac-tion time, based on the sum of the time of propene addition and additional time for carbon monoxide pressure to stabilize;
Column 7 aives the percent (~) yield of isobutyric added based on the total amount of propylene added. The examples given in Table I were run at a hydrogen fluoride-to propylene mole ratio of 15 moles of hydrogen fluoride to one mole of propylene, and the carbon monoxide/propylene ratio being fed to the reaction mixture was 1.1 moles of carbon monoxide to one mole of propvlene.
It is readily seen from Examples 3, 4 ! 5, 6, ~, 9, and 13 that substantially theoretical yields about 90 per-cent) of isobutyryl fluoride form when the rate of addition of propylene is at substantially the rate it is being used.
The other examples illustrate that i the rate is too rapid, or the pressure too low, or the vapor phase is not above the critical point, or the carbon monoxide solubility in hydrogen fluoride is too low, then below substantial yields of isobutyryl fluoride are obtained.
While the invention has been descri'oed with refer-ence to specific details of certain illustrative embodiments, it is not intended that it shall be limited therebv except insofar as such details appear in the accompanving claims.
11 7 3 ~ 57 .,.j h ~:1 ` ,1 Lr ":1 Cl O
,~
E
C ~ Ul a) o~ u~
h ~ ~J
O ~ o o _t ~ r o o~ ~ o er ~ ~ o ~: ~ r e C ~:
_1 O
~ X ~ ~
O ~ ~ _t ~ u~ U~ .n ~1 0 O ~ ~ ~ ~ ~ ~ o o o _I O ~ O _I ~ O ~ _~ N ~ --~ ~ ~ O ----I O L~ 01 03 ~ ~ O
O
C o~
.:;
E~ ~ O-r o ~ x c~
s~ ~a o o ~ u~ r o o u u~
.C O O ~ ~ ~ co ~ r-- ~ co r~ o ~o o ~D U~ CO
q; ~ ~-r~
~ _1 8 E ~ E
O t~
O ~
O ~ ' ~1 ~ Q~ O ~ o ~ a~ r o o O nl ~ ~O ~.D Cr~ &O ~ O ~ O a~ ~ ~ o ~o ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ N ~ ~I
o ~ E
.,, ~\
V ~
r ~u~Oou~OOOOOOO
O :~-,1 ~ ~ o o ~ _~ ~ ~ o U7 ~ o 3~
o u~ ~ ~ co m co ~ co ~ ~D
~ ~ ~ ~ u~ ~o r ~ ~ O --I ~ ~
a~
CL J- ~ ~ ~ ~
h h h x ~
e;' -, _ O C~ , - r~
.
When the olefin has additional double bonds, such as 1,3-butadiene, 1,4-pentadiene additional reaction capa-bility exists to form di- or multi-acylium anion products.
O O
~or example, 1,3-bu~adiene can form F - C - (CH2)4 - C - F, which reacts with water to form 1,6-hexandioic acid, O O
HO - C - (C~2)4 - COH, or an alcohol, such as methanol to O O
form dimethyl 1,6-hexanediate, CH30 - C - ~CH2)4 - COC~3.
Although all of the organic compounds described herein may be used in the process described herein; however, it is especially preferred that propylene be used.
The anhydrous acid for the process described is anhydrous hydrogen fluoride. It is possible to use anhydrous hydrogen fluoride acids which have small amounts of water therein, less than 0.02 weight percent, provided an anhydrous acid system is maintained.
REACTION CONDITION_ The reaction of carbon monoxide, with an organic compound described herein and an anhydrous hy~roqen fluoride acid described herein, can occur at temperatures from forty degrees Centigrade (40C) to se~enty degrees Centigrade (70C), but preferably it is at about fifty degrees Centigrade ~50C).
The pressure at which the reaction is conducted can vary from 109 bars (1,600 psia) to 340 bars (5,000 psia), and prefer-ably it is from 169 bars (2,500 psia) to 197 bars (~,900 psia). The pressure and temperature being increased as required for th~ solubility of carbon monoxide in the anhy-drous acid as well as maintaining a supercritical luid phase of carbon monoxide in which the organic compound is dissolved 11~73C:~S7 above the liquid ~hase o~ the reacting medium. Note the term "vapor" as used herein and in the claims is equivalent to "gaseous" or "gas".
The final mole ratio of anhydrous acid to the organic compound described herein in the reacting mixture should be from 1:1 to 100:1, but generally it is from 10:1 to 20:1 and preferablv about 12:1 to 16:1. The mole ratio of carbon monoxlde to the organic compound is from 1:1 to 25:1 or higher, but preferably it is from 15:1 to 25:1.
The carbon monoxide and anhydrous acid, e.g., anhydrous hydrogen fluoride should be thoroughly mixed to form a single liquid phase, prior to the feeding of the organic compound described herein, e~g., propylene and - carbon monoxide as required into the reactor. The organic compound itself can be mixed and diluted with carbon monoxide or inert diluents, e.g., propane, 2rior to addition to the reactor.
It is very important that the addition of carbon monoxide and the or~anic compound to the reactor be at substantially the same rate as carbon monoxide, organic compound and anhydrous acid react; that is, the addition rate should be within fifteen (15) but preferably ten (10) mole percent of the rate at which they are reacting to form the acylium anion product. If the rate of addition of carbon monoxide is faster or greater than that of the organic compound, no adverse effect will generally occur; but if it is slower than the organic compound, then the yield of acylium anion product, e.g., isobutyryl fluoride, will decrease, generally because of adverse side reactions such as polymerization of the double bond of the unsaturated com-pound, and/or carbonylation of oligomers. Thus, it is very important that the organic compound be added at substantially the same rate as it is being used up, or if the carbon monoxide addition rate slows, then the organic compound addition rate must also slow.
1~73~ 7 The proper rate of addition is readil~ controlled by sampling the amount of the acylium anlon product, e.g., isobutyryl fluoride, being formed under the given reaction conditions, or the amount of carbon monoxide being used, and then increasing or decreasing the addition rate in accordance with the rate of formation of the acylium anion, or rate at which carbon monoxide is used.
It is important that the liquid phase reaction mixture be stirred or agitated as rapidly as possible to insure adequate mixing, dilution of the organic compound being added, and transfer of the carbon monoxide and organic compound from ~le vapor or gas phase into the liquid phase.
The reaction of the acylium anion product, e.g., isobutyryl fluoride, with water or alcohol can occur at temperatures from zero degree Centigrade (0C) to one hundred fifty degrees Centigrade (150C) and at pressures from 14.7 psia to 5,000 psia, but normally it occurs at temperatures from forty degrees Centigrade (40C) to seventy degrees Centigrade (70C) and pressures at 500 psia to 3,000 psia.
The temperature and pressure being set to avoid the decomposi-tion of the intended products.
In one embodiment, the reaction mixture itself after the carbonylation is complete is reacted with water or an alcohol. The total amount of water or alcohol may be injected into the reaction mixture after the carbonvlation reaction is complete. Since the hydrolysis or esterifica-tion is exothermic, cooling may be required. Then the carboxylic acid or esters are separated.
In another embodiment, after the carbonylation reaction is complete, from one (1) to one hundred (100) percent of the stable acylium anion product formed is separated from the product mixture. Preferably, from eighty (80) to one hundred (100) percent of the stable acylium anion product is separated, and the remaining product mixture is recvcled for reacting as in Stess ta) and (b) described herein.
1~7~3~5~7 In another embodiment, from one (1) to one hundred (100) percent (preferably from eighty (80) to one hundred (100) ~ercent), of the anhydrous acid is separated from the product mixture and recycled back for further mixing with carbon monoxide in the liuqid phase.
The separations described herein can be by any of the ~nown methods of separation, such as distillation or extraction.
_E ~EACTOR
The process described herein can be carried out in any suitable reactor, such as a continuous stirred tank reactor ~CSTR).
It is extremely important in the present invention to maintain the proper amount of carbon monoxide in solution.
The amount of carbon monoxide which can be dissolved in anhydrous acid, e.g., hydrogen fluoride, or the reaction mixture, can be empirically determined by one of ordinary skill in the art at a particular temperature and a particular pressure. For example, at 3,000 psig and 80C, 9 lbs of carbon monoxide would be dissolved in 100 lbs of hydrogen fluoride. Based on the molar amount of the organic compound which is intended to be reacted, the amount of carbon monoxide needed for the reaction can be determined. For example, as stated above, the desired range of molar ratios of organic compound to carbon monoxide to acid is 1:1-25:1-100 and the preferred ratio is 1:25:14, particularly for propy-lene, carbon monoxide, and anhydrous hydrogen fluoride.
Other information required are the reaction condi-tions desired, i.e., the pressure and the temperature of the reactor. From this, the molar percentage of carbon monoxide dissolved in the acid hydrogen fluoride, can be determ ned.
From this, the amount of acid hydro~en fluoride solution required to supply sufficient carbon monoxide to react with the organic compound can also be determined.
The following examples will illustrate the orocess as described herein.
The carbonylation reactor was a 300 cc Autoclave Engineers Magnedrive Hastelloy C equi~ped with a turbine blade stirrer, a carbon monoxide inlet, a propylene inlet, an outlet for depressurizing the reactor, and an external heater.
The reactor was initially flushed with carbon monoxide and then about 150 grams (7.5 moles) of anhydrous hydrogen fluoride were charged into the reactor. Carbon monoxide was then charged to the preselected pressure into the reactor while the hydrogen fluoride was stirred and the reactor was allowed to equilibrate to the preselected temperature.
lS After the carbon monoxide pressure had stabilized, propvlene was fed into the vapor phase of the liquid mixture (the vapor phase was a mixture of carbon monoxide and hydrogen fluoride) which was above the liquid phase, so as to form a supercritical mixture of propylene and carbon monoxide which transferred into the liquid phase. The propylene was fed through a metering pump while the carbon monoxide was added by maintaining the reactor's pressure at the preselected pressure.
After the reaction was comolete; that is, the predetermined amount of propylene and carbon monoxide had been added, the reactor was stirred for an additional time, from fifteen to thirty minutes, then the reactor was cooled to about -20C with an acetone/dry ice mi~ture, and then 38.5 grams of water waspumped into the reactor over a five-to-ten-minute period, while cooling. The reactor was then vented, opened, and the product mixture was further diluted with ice water, until the hydrogen fluoride was about lO wt.
percent of the mixture. Then 400 grams of sodium sulfate (Na2SO4) was added, and the isobutyric acid and oligomers extracted with 4 separate volumes of cyclohexane (400, 300, 3~S7 200, 200). The cyclohexane extracts were combined and analyzed bv gas chromatography, as well as separating the products by distillation. The percentage yield of isobutyric acid formed is based on the amount o~ propylene added.
Table I shows the results of controlling the feed of propylene and carbon monoxide at various temperatures and pressures. Column 1 gives the example number; ~o].umn 2, the pressure range of the reaction in pounds per square inch gauge (psig); ~olumn 3, the temperature ra~ge of the reaction in degrees Centigrade (C); Column 4 gives the time of complete addition of propylene; Column 5 gives the moles of propylene added per hour; Column 6 gives the apparent reac-tion time, based on the sum of the time of propene addition and additional time for carbon monoxide pressure to stabilize;
Column 7 aives the percent (~) yield of isobutyric added based on the total amount of propylene added. The examples given in Table I were run at a hydrogen fluoride-to propylene mole ratio of 15 moles of hydrogen fluoride to one mole of propylene, and the carbon monoxide/propylene ratio being fed to the reaction mixture was 1.1 moles of carbon monoxide to one mole of propvlene.
It is readily seen from Examples 3, 4 ! 5, 6, ~, 9, and 13 that substantially theoretical yields about 90 per-cent) of isobutyryl fluoride form when the rate of addition of propylene is at substantially the rate it is being used.
The other examples illustrate that i the rate is too rapid, or the pressure too low, or the vapor phase is not above the critical point, or the carbon monoxide solubility in hydrogen fluoride is too low, then below substantial yields of isobutyryl fluoride are obtained.
While the invention has been descri'oed with refer-ence to specific details of certain illustrative embodiments, it is not intended that it shall be limited therebv except insofar as such details appear in the accompanving claims.
11 7 3 ~ 57 .,.j h ~:1 ` ,1 Lr ":1 Cl O
,~
E
C ~ Ul a) o~ u~
h ~ ~J
O ~ o o _t ~ r o o~ ~ o er ~ ~ o ~: ~ r e C ~:
_1 O
~ X ~ ~
O ~ ~ _t ~ u~ U~ .n ~1 0 O ~ ~ ~ ~ ~ ~ o o o _I O ~ O _I ~ O ~ _~ N ~ --~ ~ ~ O ----I O L~ 01 03 ~ ~ O
O
C o~
.:;
E~ ~ O-r o ~ x c~
s~ ~a o o ~ u~ r o o u u~
.C O O ~ ~ ~ co ~ r-- ~ co r~ o ~o o ~D U~ CO
q; ~ ~-r~
~ _1 8 E ~ E
O t~
O ~
O ~ ' ~1 ~ Q~ O ~ o ~ a~ r o o O nl ~ ~O ~.D Cr~ &O ~ O ~ O a~ ~ ~ o ~o ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ N ~ ~I
o ~ E
.,, ~\
V ~
r ~u~Oou~OOOOOOO
O :~-,1 ~ ~ o o ~ _~ ~ ~ o U7 ~ o 3~
o u~ ~ ~ co m co ~ co ~ ~D
~ ~ ~ ~ u~ ~o r ~ ~ O --I ~ ~
a~
CL J- ~ ~ ~ ~
h h h x ~
e;' -, _ O C~ , - r~
.
Claims (12)
1. A process for producing acylium fluoride from carbon monoxide, anhydrous hydrogen fluoride acid, and an organic compound capable of adding carbon monoxide thereto, which comprises:
reacting in the liquid phase under conditions whereby acylium fluoride forms in substantial yields, carbon monoxide, anhydrous hydrogen fluoride acid, and an organic compound capable of adding carbon monoxide thereto while feeding carbon monoxide and the organic compound into the vapor phase over the liquid reaction mixture at substantially the same rate as the carbon monoxide organic compound and anhydrous hydrogen fluoride acid react to form the acylium fluoride; the vapor phase over the liquid being maintained at a temperature and pressure whereby the carbon monoxide in the mixture's vapor phase is in a supercritical fluid phase and the organic compound is dissolved therein;
said organic compound being selected from the group consisting of (a) esters of the general formula R - ? - OR', wherein R is an alkyl of up to twenty carbon atoms, and R' is an alkyl from two to twenty carbon atoms, and (b) olefins having at least one double bond capable of adding carbon monoxide thereto and having up to twenty carbon atoms, said temperature being within the range of from forty (40) degrees Centigrade to ninety (90) degrees Centigrade and the pressure is from one hundred and nine (109) bars (1,600 psia) to three hundred and forty (340) bars (5,000 psia);
the final mole ratio of anhydrous hydrogen fluoride acid to organic compound in the reacting mixture being within the range of from one (l) to one hundred (100) moles of anhydrous hydrogen fluoride acid to one (1) mole of organic compound, and the mole ratio of carbon monoxide to organic compound being within the range of from one (1) to twenty-five (25) moles of carbon monoxide to one (1) mole of organic compound.
reacting in the liquid phase under conditions whereby acylium fluoride forms in substantial yields, carbon monoxide, anhydrous hydrogen fluoride acid, and an organic compound capable of adding carbon monoxide thereto while feeding carbon monoxide and the organic compound into the vapor phase over the liquid reaction mixture at substantially the same rate as the carbon monoxide organic compound and anhydrous hydrogen fluoride acid react to form the acylium fluoride; the vapor phase over the liquid being maintained at a temperature and pressure whereby the carbon monoxide in the mixture's vapor phase is in a supercritical fluid phase and the organic compound is dissolved therein;
said organic compound being selected from the group consisting of (a) esters of the general formula R - ? - OR', wherein R is an alkyl of up to twenty carbon atoms, and R' is an alkyl from two to twenty carbon atoms, and (b) olefins having at least one double bond capable of adding carbon monoxide thereto and having up to twenty carbon atoms, said temperature being within the range of from forty (40) degrees Centigrade to ninety (90) degrees Centigrade and the pressure is from one hundred and nine (109) bars (1,600 psia) to three hundred and forty (340) bars (5,000 psia);
the final mole ratio of anhydrous hydrogen fluoride acid to organic compound in the reacting mixture being within the range of from one (l) to one hundred (100) moles of anhydrous hydrogen fluoride acid to one (1) mole of organic compound, and the mole ratio of carbon monoxide to organic compound being within the range of from one (1) to twenty-five (25) moles of carbon monoxide to one (1) mole of organic compound.
2. The process as recited in Claim 1 wherein the organic compound is an ester selected from the group consisting of isopropyl isobutyrate, ethyl isobutyrate, isopropyl propionate, and ethyl propionate.
3. The process as recited in Claim 1. wherein the organic compound is the ester, isopropyl isobutyrate.
4. The process as recited in Claim 1 wherein the organic compound is an olefin selected from the group consisting of ethylene, propylene, isobutene, l-butene, 2-butene and l,3-butadiene.
5. The process as recited in Claim 1 wherein the olefin is selected from the group consisting of ethylene and propylene.
6. The process as recited in Claim 1 wherein the olefin is propylene.
7. The process as recited in claim 1 wherein the temperature is within the range of forty (40) degrees Centigrade to seventy (70) degrees Centigrade and the pressure is within the range of from one hundred sixty-nine (169) bars (2,500 psia) to one hundred ninety-seven (197) bars (2,900 psia), the final mole ratio of anhydrous hydrogen fluoride acid to organic compound in the reacting mixture being within the range of from ten (10) to twenty (20) moles of anhydrous hydrogen fluoride acid to one (1) mole of organic compound, and the mole ratio of carbon monoxide to organic compound being within the range of from fifteen (15) to twenty-five (25) moles of carbon monoxide to one (1) mole of organic compound.
8. The process as recited in Claim 7 wherein the acylium anion product is separated from the reaction mixture.
9. A process for producing isobutyryl fluoride from carbon monoxide, hydrogen fluoride, and propylene, which comprises:
reacting in a substantially anhydrous liquid phase, while mixing the liquid phase, carbon monoxide, hydrogen fluoride, and propylene under conditions whereby isobutyryl fluoride forms, while feeding carbon monoxide and propylene into the vapor phase over the reacting liquid phase at substantially the same rate as the carbon monoxide, propylene and hydrogen fluoride react to form the isobutyryl fluoride;
the vapor phase over the liquid being maintained at a temperature and pressure whereby the carbon monoxide in the vapor phase is a supercritical fluid and propylene is dissolved therein; said reaction temperature being within the range of from forty (40) degrees Centigrade to ninety (90) degrees Centigrade, the pressure being within the range of one hundred and nine (109) bars (1600 psia) to three hundred and forty (340) bars (5000 psia); and the final mole ratio of hydrogen fluoride to propylene being from ten (10) to one hundred (100).
reacting in a substantially anhydrous liquid phase, while mixing the liquid phase, carbon monoxide, hydrogen fluoride, and propylene under conditions whereby isobutyryl fluoride forms, while feeding carbon monoxide and propylene into the vapor phase over the reacting liquid phase at substantially the same rate as the carbon monoxide, propylene and hydrogen fluoride react to form the isobutyryl fluoride;
the vapor phase over the liquid being maintained at a temperature and pressure whereby the carbon monoxide in the vapor phase is a supercritical fluid and propylene is dissolved therein; said reaction temperature being within the range of from forty (40) degrees Centigrade to ninety (90) degrees Centigrade, the pressure being within the range of one hundred and nine (109) bars (1600 psia) to three hundred and forty (340) bars (5000 psia); and the final mole ratio of hydrogen fluoride to propylene being from ten (10) to one hundred (100).
10. The process as recited in claim 9, wherein the temperature is within the range of from forty (40) to seventy (70) degrees Centigrade.
11. The process as recited in claim 10, wherein the pressure is within the range of from two thousand five hundred (2500) psia, (170 bars) to two thousand nine hundred (2900) psia, (190 bars);
12. The process as recited in claim 11, wherein the rate of addition of propylene and carbon monoxide to the vapor phase is within ten (10) mole percent of the rate at which isobutyryl fluoride forms.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US27876481A | 1981-06-29 | 1981-06-29 | |
| US278,764 | 1981-06-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1173057A true CA1173057A (en) | 1984-08-21 |
Family
ID=23066263
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000404487A Expired CA1173057A (en) | 1981-06-29 | 1982-06-04 | Production of carboxylic acids and esters |
Country Status (12)
| Country | Link |
|---|---|
| JP (1) | JPS6024088B2 (en) |
| KR (1) | KR850001914B1 (en) |
| AT (1) | AT388160B (en) |
| AU (1) | AU532639B2 (en) |
| BE (1) | BE893419A (en) |
| CA (1) | CA1173057A (en) |
| CH (1) | CH660180A5 (en) |
| DE (1) | DE3221172C2 (en) |
| FR (1) | FR2508441B1 (en) |
| GB (1) | GB2100729B (en) |
| IT (1) | IT1195930B (en) |
| NL (1) | NL187013C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NZ195559A (en) * | 1979-11-29 | 1984-03-16 | Ris Irrigation Syst | Butterfly sprinkler with dust protection for bearing |
| US4499029A (en) * | 1983-06-15 | 1985-02-12 | Ashland Oil, Inc. | Isobutyryl fluoride manufacture |
| DE3725428A1 (en) * | 1987-07-31 | 1989-02-09 | Basf Ag | METHOD FOR PRODUCING CARBONIC ACID HALOGENIDES |
| FR2691965A1 (en) * | 1992-06-04 | 1993-12-10 | Atochem Elf Sa | Iso-butyryl fluoride prodn. by two=stage process - comprising reacting propylene@ with hydrogen fluoride in gas phase until before pt where oligomers form, then reacting with carbon mon:oxide in liq. hydrogen |
| GB9917429D0 (en) * | 1999-07-23 | 1999-09-22 | Swan Thomas & Co Ltd | Carbonylation reactions |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE972291C (en) * | 1954-05-16 | 1959-07-02 | Studiengesellschaft Kohle Mbh | Process for the production of monocarboxylic acids from olefins, carbon monoxide and water |
| DE973077C (en) * | 1954-07-30 | 1959-11-26 | Studiengesellschaft Kohle Mbh | Process for the production of carboxylic acids from olefins and carbon oxide |
| DE1064941B (en) * | 1957-04-24 | 1959-09-10 | Studiengesellschaft Kohle Mbh | Process for the preparation of mixtures of saturated aliphatic or cycloaliphatic monocarboxylic acid alkyl esters |
| US3065242A (en) * | 1960-02-23 | 1962-11-20 | Du Pont | Production of acyl halides, carboxylic acids and lactones |
| US3167585A (en) * | 1960-08-25 | 1965-01-26 | Gulf Research Development Co | Process for carboxylation of iso-olefins |
| GB942367A (en) * | 1961-04-29 | 1963-11-20 | Basf Ag | Continuous production of carboxylic acids from olefines, carbon monoxide and water |
| NL6816940A (en) * | 1967-11-28 | 1969-05-30 | ||
| GB1232317A (en) * | 1968-12-30 | 1971-05-19 | ||
| BE755997A (en) * | 1969-09-11 | 1971-03-10 | Bp Chem Int Ltd | PRODUCTION OF DICARBOXYLIC ACIDS |
| DE2750719A1 (en) * | 1977-11-12 | 1979-05-17 | Roehm Gmbh | Isobutyric acid prepn. by boron tri:fluoride-catalysed carbonylation - of propylene, isopropanol, ether and/or ester deriv. in aliphatic carboxylic acid medium |
| US4224232A (en) * | 1978-12-21 | 1980-09-23 | Gulf Research & Development Company | Production of carboxylic acids from olefins and mixtures of olefins |
| DE3064472D1 (en) * | 1979-04-09 | 1983-09-08 | Chem Systems | Preparation of acids and esters |
-
1982
- 1982-06-03 AT AT0215082A patent/AT388160B/en not_active IP Right Cessation
- 1982-06-04 BE BE0/208271A patent/BE893419A/en not_active IP Right Cessation
- 1982-06-04 AU AU84609/82A patent/AU532639B2/en not_active Ceased
- 1982-06-04 DE DE3221172A patent/DE3221172C2/en not_active Expired
- 1982-06-04 CH CH3476/82A patent/CH660180A5/en not_active IP Right Cessation
- 1982-06-04 IT IT21707/82A patent/IT1195930B/en active
- 1982-06-04 NL NLAANVRAGE8202268,A patent/NL187013C/en not_active IP Right Cessation
- 1982-06-04 KR KR8202507A patent/KR850001914B1/en active
- 1982-06-04 FR FR8209809A patent/FR2508441B1/en not_active Expired
- 1982-06-04 GB GB08216304A patent/GB2100729B/en not_active Expired
- 1982-06-04 CA CA000404487A patent/CA1173057A/en not_active Expired
- 1982-06-04 JP JP57096065A patent/JPS6024088B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| IT8221707A0 (en) | 1982-06-04 |
| BE893419A (en) | 1982-10-01 |
| NL187013B (en) | 1990-12-03 |
| JPS588036A (en) | 1983-01-18 |
| GB2100729A (en) | 1983-01-06 |
| DE3221172A1 (en) | 1983-01-05 |
| DE3221172C2 (en) | 1984-08-02 |
| ATA215082A (en) | 1988-10-15 |
| FR2508441B1 (en) | 1987-04-30 |
| IT1195930B (en) | 1988-11-03 |
| AU8460982A (en) | 1983-03-10 |
| GB2100729B (en) | 1985-10-30 |
| AU532639B2 (en) | 1983-10-06 |
| KR840000461A (en) | 1984-02-22 |
| KR850001914B1 (en) | 1985-12-31 |
| NL8202268A (en) | 1983-01-17 |
| FR2508441A1 (en) | 1982-12-31 |
| AT388160B (en) | 1989-05-10 |
| JPS6024088B2 (en) | 1985-06-11 |
| CH660180A5 (en) | 1987-03-31 |
| NL187013C (en) | 1991-05-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1114397A (en) | Preparation of formic acid by hydrolysis of methyl formate | |
| US3349107A (en) | Process for preparing carboxylic acids and their alkyl-esters | |
| US4647696A (en) | Method for making isobutyric acid | |
| US2650245A (en) | Synthesis of acetic acid from co and methanol | |
| US4256913A (en) | Preparation of carboxylic acids using a BF3 catalyst complex | |
| US3527779A (en) | Carboxylic acid preparation | |
| CA1173057A (en) | Production of carboxylic acids and esters | |
| US2135459A (en) | Preparation of organic acids from olefines and carbon monoxide | |
| US6111148A (en) | Process for producing tertiary butyl alcohol | |
| US4158100A (en) | Process for the preparation of β-phenylethyl alcohol via homologation | |
| US4360406A (en) | Process for the preparation of tertiary butyl alcohol | |
| US7034189B1 (en) | Preparation of dialkyl peroxides | |
| CA1105060A (en) | Hydrocarbonylation of methanol to ethanol in the presence of added compounds | |
| JPS5839134B2 (en) | Method for producing tertiary-butanol from mixed butylene | |
| JPH0131496B2 (en) | ||
| CA1192576A (en) | Production of an acylium anion product and carboxylic acids and esters therefrom | |
| CA2093749C (en) | Process for preparing ethylidene diacetate using iodine catalysts | |
| US4166189A (en) | Production of methyl esters by contacting methanol or dimethyl ether with carbon monoxide and zinc iodide | |
| US2217650A (en) | Preparation of organic acids | |
| US5227521A (en) | Preparation of trialkylacetic acids, particularly of pivalic acid, using lewis acid catalysts | |
| EP0101719B1 (en) | Formation of isobutyric acid or methyl isobutyrate | |
| US1924768A (en) | Process for the production of carboxylic acids | |
| US2210316A (en) | Method of reacting olefins with sulphuric acid | |
| KR850001915B1 (en) | Process for the preparation of carboxylic esters from isobutyryl fluoride formed by carbonylation | |
| US4721819A (en) | Process for the preparation of higher allylic ethers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEC | Expiry (correction) | ||
| MKEX | Expiry |