US3369043A - Process for the preparation of unsaturated carboxylic acids - Google Patents
Process for the preparation of unsaturated carboxylic acids Download PDFInfo
- Publication number
- US3369043A US3369043A US634774A US63477467A US3369043A US 3369043 A US3369043 A US 3369043A US 634774 A US634774 A US 634774A US 63477467 A US63477467 A US 63477467A US 3369043 A US3369043 A US 3369043A
- Authority
- US
- United States
- Prior art keywords
- acid
- acrolein
- range
- methacrolein
- hydroperoxide
- 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 - Lifetime
Links
- 238000000034 method Methods 0.000 title description 40
- 150000001735 carboxylic acids Chemical class 0.000 title description 8
- 238000002360 preparation method Methods 0.000 title description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 54
- 150000001299 aldehydes Chemical class 0.000 description 17
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 17
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 17
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 16
- 239000002253 acid Substances 0.000 description 13
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical group CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000007800 oxidant agent Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 150000002432 hydroperoxides Chemical class 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 7
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical group CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 2
- JLIDVCMBCGBIEY-UHFFFAOYSA-N 1-penten-3-one Chemical compound CCC(=O)C=C JLIDVCMBCGBIEY-UHFFFAOYSA-N 0.000 description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 2
- CMXNFXBFNYHFAL-UHFFFAOYSA-N 5-methylhex-1-en-3-one Chemical compound CC(C)CC(=O)C=C CMXNFXBFNYHFAL-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 150000001253 acrylic acids Chemical class 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- -1 alkynl Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- SZTBMYHIYNGYIA-UHFFFAOYSA-N 2-chloroacrylic acid Chemical compound OC(=O)C(Cl)=C SZTBMYHIYNGYIA-UHFFFAOYSA-N 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- WFRBDWRZVBPBDO-UHFFFAOYSA-N 2-methyl-2-pentanol Chemical compound CCCC(C)(C)O WFRBDWRZVBPBDO-UHFFFAOYSA-N 0.000 description 1
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 1
- LANHEKZGKDEWLK-UHFFFAOYSA-N 2-methylideneheptanoic acid Chemical compound CCCCCC(=C)C(O)=O LANHEKZGKDEWLK-UHFFFAOYSA-N 0.000 description 1
- BDCFWIDZNLCTMF-UHFFFAOYSA-N 2-phenylpropan-2-ol Chemical compound CC(C)(O)C1=CC=CC=C1 BDCFWIDZNLCTMF-UHFFFAOYSA-N 0.000 description 1
- PMZIOYPAJRJYSI-UHFFFAOYSA-N 3-hydroperoxycyclohexene Chemical compound OOC1CCCC=C1 PMZIOYPAJRJYSI-UHFFFAOYSA-N 0.000 description 1
- FRDAATYAJDYRNW-UHFFFAOYSA-N 3-methyl-3-pentanol Chemical compound CCC(C)(O)CC FRDAATYAJDYRNW-UHFFFAOYSA-N 0.000 description 1
- XQIHFGYUMFFCFG-UHFFFAOYSA-N 4-methyl-2-methylidenepentanoic acid Chemical compound CC(C)CC(=C)C(O)=O XQIHFGYUMFFCFG-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 241001292396 Cirrhitidae Species 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 229930194542 Keto Chemical group 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical class CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- DBCPMEYOKPTIFQ-UHFFFAOYSA-N [Cr](=O)(=O)([O-])[O-].[Cr](=O)(=O)([O-])[O-].[Na+].[Na+].[Na+].[Na+] Chemical compound [Cr](=O)(=O)([O-])[O-].[Cr](=O)(=O)([O-])[O-].[Na+].[Na+].[Na+].[Na+] DBCPMEYOKPTIFQ-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001733 carboxylic acid esters Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical class CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 1
- FGGJBCRKSVGDPO-UHFFFAOYSA-N hydroperoxycyclohexane Chemical compound OOC1CCCCC1 FGGJBCRKSVGDPO-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical group OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Classifications
-
- 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
- C07C53/02—Formic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
- C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
Definitions
- the monomeric acrylic acid is separated by distillation, avoiding local overheating, and bubbling gaseous nitrogen through the mixture in order to inhibit polymerization.
- Example 3 The procedure of Example 2 is repeated using a mixture of methacrolein (10.5 grams), t-butanol (35 grams), chromic acid (1 gram), and cumene hydroperoxide (34 grams), at room temperature for 24 hours.
- the reaction mixture contains 2.7% methacrylic acid, the methacrolein conversion is 77% and the methacrylic acid selectivity based on reacted methacrolein is 21%.
- Example 8 The procedure of Example 3 is repeated with alphaamylacrolein as the aldehyde, for producing alpha-amylacrylic acid, and similar results are obtained.
- Example 9 The procedure of Example 3 is repeated using cyclohexanone peroxide as the hydroperoxide and similar good results are obtained.
Landscapes
- 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)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BE645825D BE645825A (en)) | 1963-04-12 | 1964-03-27 | |
| LU45783D LU45783A1 (en)) | 1963-04-12 | 1964-03-31 | |
| NL6403597A NL6403597A (en)) | 1963-04-12 | 1964-04-03 | |
| GB14482/64A GB1060777A (en) | 1963-04-12 | 1964-04-08 | Production of acrylic acid and substituted derivatives thereof |
| FR970444A FR1395951A (fr) | 1963-04-12 | 1964-04-10 | Procédé chimique pour la préparation d'acide acrylique |
| CH458864A CH431497A (fr) | 1963-04-12 | 1964-04-10 | Procédé de préparation d'un acide carboxylique non saturé |
| DE19641468028 DE1468028A1 (de) | 1963-04-12 | 1964-04-13 | Verfahren zur Herstellung von Acrylsaeure |
| US634774A US3369043A (en) | 1963-04-12 | 1967-04-28 | Process for the preparation of unsaturated carboxylic acids |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US27253663A | 1963-04-12 | 1963-04-12 | |
| US634774A US3369043A (en) | 1963-04-12 | 1967-04-28 | Process for the preparation of unsaturated carboxylic acids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3369043A true US3369043A (en) | 1968-02-13 |
Family
ID=26955586
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US634774A Expired - Lifetime US3369043A (en) | 1963-04-12 | 1967-04-28 | Process for the preparation of unsaturated carboxylic acids |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US3369043A (en)) |
| BE (1) | BE645825A (en)) |
| CH (1) | CH431497A (en)) |
| DE (1) | DE1468028A1 (en)) |
| GB (1) | GB1060777A (en)) |
| LU (1) | LU45783A1 (en)) |
| NL (1) | NL6403597A (en)) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4324331A (en) * | 1980-08-08 | 1982-04-13 | Zimmer, Inc. | Packaging for surgical implements |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2744928A (en) * | 1952-11-28 | 1956-05-08 | Shell Dev | Oxidation of unsaturated aldehydes to acids |
-
1964
- 1964-03-27 BE BE645825D patent/BE645825A/xx unknown
- 1964-03-31 LU LU45783D patent/LU45783A1/xx unknown
- 1964-04-03 NL NL6403597A patent/NL6403597A/xx unknown
- 1964-04-08 GB GB14482/64A patent/GB1060777A/en not_active Expired
- 1964-04-10 CH CH458864A patent/CH431497A/fr unknown
- 1964-04-13 DE DE19641468028 patent/DE1468028A1/de active Pending
-
1967
- 1967-04-28 US US634774A patent/US3369043A/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2744928A (en) * | 1952-11-28 | 1956-05-08 | Shell Dev | Oxidation of unsaturated aldehydes to acids |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4324331A (en) * | 1980-08-08 | 1982-04-13 | Zimmer, Inc. | Packaging for surgical implements |
Also Published As
| Publication number | Publication date |
|---|---|
| BE645825A (en)) | 1964-09-28 |
| LU45783A1 (en)) | 1965-10-01 |
| DE1468028A1 (de) | 1969-01-23 |
| NL6403597A (en)) | 1964-10-13 |
| GB1060777A (en) | 1967-03-08 |
| CH431497A (fr) | 1967-03-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: ATLANTIC RICHFIELD COMPANY, 1500 MARKET STREET, PH Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:HALCON RESEARCH AND DEVELOPMENT CORPORATION, A CORP. OF DE;REEL/FRAME:003845/0048 Effective date: 19810304 |