US2941011A - Process of manufacturing 2, 2, 4-trimethyl-3-penten-1-ol and 2, 2, 4-trimethyl-pentanol - Google Patents
Process of manufacturing 2, 2, 4-trimethyl-3-penten-1-ol and 2, 2, 4-trimethyl-pentanol Download PDFInfo
- Publication number
- US2941011A US2941011A US750288A US75028858A US2941011A US 2941011 A US2941011 A US 2941011A US 750288 A US750288 A US 750288A US 75028858 A US75028858 A US 75028858A US 2941011 A US2941011 A US 2941011A
- Authority
- US
- United States
- Prior art keywords
- trimethyl
- penten
- pentanol
- pentanediol
- manufacturing
- 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
- BIIWBYUXAOCDCC-UHFFFAOYSA-N 2,2,4-trimethylpent-3-en-1-ol Chemical compound CC(C)=CC(C)(C)CO BIIWBYUXAOCDCC-UHFFFAOYSA-N 0.000 title claims description 8
- 238000000034 method Methods 0.000 title claims description 8
- CWPPDTVYIJETDF-UHFFFAOYSA-N 2,2,4-trimethylpentan-1-ol Chemical compound CC(C)CC(C)(C)CO CWPPDTVYIJETDF-UHFFFAOYSA-N 0.000 title description 6
- 238000004519 manufacturing process Methods 0.000 title description 2
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims 2
- -1 aliphatic monocarboxylic acid diester Chemical class 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- KESQFSZFUCZCEI-UHFFFAOYSA-N 2-(5-nitropyridin-2-yl)oxyethanol Chemical compound OCCOC1=CC=C([N+]([O-])=O)C=N1 KESQFSZFUCZCEI-UHFFFAOYSA-N 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000005297 pyrex Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- AVQIDJASTVSUMQ-UHFFFAOYSA-N (3-acetyloxy-2,2,4-trimethylpentyl) acetate Chemical compound CC(=O)OC(C(C)C)C(C)(C)COC(C)=O AVQIDJASTVSUMQ-UHFFFAOYSA-N 0.000 description 1
- FPNGEELBRIGMQJ-UHFFFAOYSA-N 2,2,4-trimethylpent-3-enyl acetate Chemical compound CC(C)=CC(C)(C)COC(C)=O FPNGEELBRIGMQJ-UHFFFAOYSA-N 0.000 description 1
- GLVYLTSKTCWWJR-UHFFFAOYSA-N 2-carbonoperoxoylbenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1C(O)=O GLVYLTSKTCWWJR-UHFFFAOYSA-N 0.000 description 1
- AASALDYTBAOTNM-UHFFFAOYSA-N 5,5-dimethylhex-1-en-1-ol Chemical compound CC(CCC=CO)(C)C AASALDYTBAOTNM-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- OREAFAJWWJHCOT-UHFFFAOYSA-N dimethylmalonic acid Chemical compound OC(=O)C(C)(C)C(O)=O OREAFAJWWJHCOT-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/172—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with the obtention of a fully saturated alcohol
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/095—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of organic acids
Definitions
- This invention relates to a new compound, 2,2,4- trimethyl-3-penten-l-ol, and to a process of making it. It also relates to a process of making 2,2,4-trimethylpentanol. It also relates to esters of 2,2,4-trimethylpenten-l-ol which are new compounds.
- 2,2,4-trimethyl-3-penten-1-01 can be prepared by pyrolysis of a lower aliphatic monocarboxylic acid diester of 2,2,4-trimethyl-1,3-pentanediol, followed by hydrolysis of the product.
- the esters of 2,2,4-trimethyl-1,3-pentanediol can be prepared by esterification of the diol by ordinary methods, such as are shown, for example, in US. Patent 2,625,563.
- Pyrolysis of the diesters of 2,2,4-trimethyl-1,3-pentanediol is carried out at temperatures in the range of 300- 600 C., using contact times varying from 0.01 second to 10 seconds.
- the pyrolysis can he carried out in an empty tube or over suitable refractory materials such as Pyrex chips, alundum, zirconium oxide, titanium oxide, or other inert material.
- carboxylic acid esters of 2,2,4-trimethyl-l-pentanol are useful as oxidation-resistant plasticizers.
- a process of preparing 2,2,4-trimethyl-3-penteml- 01 which comprises pyrolyzing a lower aliphatic monocarboxylic acid diester of 2,2,4-trimethyl-L3-pentanediol and hydrolyzing the resulting lower aliphatic monocarboxylic acid ester of 2,2,4-trimethy1-3-penten-l-ol.
- a process of preparing 2,2,4-trimethyl-pentanol which comprises pyrolyzing a lower aliphatic monocar boxylic acid diester of 2,2,4-trimethyl-1,3-pentanediol, hy-
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
PROCESS OF MANUFACTURING 2,2,4-TRIMETH- gkggENTEN-l-OL AND 2,2,4-TRIMETHYL-PEN- Filed July 23, 1958, Ser. No. 750,288
2 Claims. (Cl. 260-638) No Drawing.
This invention relates to a new compound, 2,2,4- trimethyl-3-penten-l-ol, and to a process of making it. It also relates to a process of making 2,2,4-trimethylpentanol. It also relates to esters of 2,2,4-trimethylpenten-l-ol which are new compounds.
We have found that 2,2,4-trimethyl-3-penten-1-01 can be prepared by pyrolysis of a lower aliphatic monocarboxylic acid diester of 2,2,4-trimethyl-1,3-pentanediol, followed by hydrolysis of the product. The esters of 2,2,4-trimethyl-1,3-pentanediol can be prepared by esterification of the diol by ordinary methods, such as are shown, for example, in US. Patent 2,625,563.
Pyrolysis of the diesters of 2,2,4-trimethyl-1,3-pentanediol is carried out at temperatures in the range of 300- 600 C., using contact times varying from 0.01 second to 10 seconds. The pyrolysis can he carried out in an empty tube or over suitable refractory materials such as Pyrex chips, alundum, zirconium oxide, titanium oxide, or other inert material.
Example 1.-466 grams of 2,2,4-trimethy1-1,3-pentanediol diacetate was pyrolyzed over porcelain Berl saddles using a contact time of 1.5 seconds at 500 C. Distillation of the product on a 30-plate column. at 10 to 1 reflux showed a 48% conversion to 2,2,4-trimethyl-3-penten-l-ol acetate, boiling point 187 C. The yield, based on the 2,2,4-trimethyl-1,3-pentanediol diacetate consumed, was 89%. Saponir'ication of this 2,2,4-trimethyl-3-penten- 1-01 acetate gave a quantitative yield of 2,2,4-trimethyl- 3-penten-l-ol, boiling point 170 C. Percent hydroxyl (phthalate) 100.6; Calc. C=75, H=12.5, =12.5; Found C=75.02, H=12.46, 0:12.52. Unsaturation was 99.86% as trimethylpentenol. Hydrogenation over Raney nickel gave 2,2,4-trimethylpentanol, B.P. 166 C. Oxidation gave acetone and dimethylmalonic acid.
CH: 00 C.OH:
7 nited States Patent 0 Ha acetic acid 6 2,2,4-m'imethyl-8-penten-wl acetate 1 NeOH CH: CH3 CH1. =CH--CHI-OH HI azetrlmethyl-epenten-l-ol 2,2,4-trimethyl-1-pentanol Example 2.572 grams of 2,2,4-trimethyl-1,3-pentanediol diisobutyrate was pyrolyzed over Pyrex chips at 500 C., employing a l-second contact time. Distillation of the product on a 30-plate column at 10 to 1 reflux ratio gave 165 g. of isobutyric acid and 327 g. of 2,2,4-trimethy1-3-penten-1-ol isobutyrate, boiling point 212 C. The remainder of the 2,2,4-trimethyl-1,3-pentanediol diisobutyrate was recovered unchanged. Saponification of the 2,2,4-trimethyl-3-pentene-1-ol acetate isobutyrate gave 2,2,4-trimethyl-3-pentene-l-ol.
The carboxylic acid esters of 2,2,4-trimethyl-l-pentanol are useful as oxidation-resistant plasticizers.
What we claim as our invention and desire to be accured by Letters Patent of the United States is:
1. A process of preparing 2,2,4-trimethyl-3-penteml- 01 which comprises pyrolyzing a lower aliphatic monocarboxylic acid diester of 2,2,4-trimethyl-L3-pentanediol and hydrolyzing the resulting lower aliphatic monocarboxylic acid ester of 2,2,4-trimethy1-3-penten-l-ol.
2. A process of preparing 2,2,4-trimethyl-pentanol which comprises pyrolyzing a lower aliphatic monocar boxylic acid diester of 2,2,4-trimethyl-1,3-pentanediol, hy-
drolyzing the resulting lower aliphatic monocarboxylic acid ester of 2,2,4-trimethy1-3-penten-l-ol to 2,2,4-trimethyl-3-penten-1-ol, and hydrogenating the 2,2,4-trimethyl-3-penten-l-ol.
References Cited in the file of this patent UNITED STATES PATENTS 2,042,221 Groll et a1. May 26, 1936 2,246,285 Arundale et a1 June 17, 1941 2,251,983 Chitwood Aug. 12, 1941 OTHER REFERENCES Courtot: Bull. Soc. Chem., France (3) 35, 222 (1906). Van Aerde: Rec. Trav. Chem. 28, 171-179 (1909).
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No, 2,941,011 June 14 1960 Hugh Jo I-lagenracyer 313, et a1,
It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.
Column 2, line 29 strike out "acetate.
Signed and sealed this 6th day of December 1960,
(SEAL) Attest:
KARL Hr AXLINE ROBERT C. WATSGN Attesting Officer Commissioner of Patents
Claims (1)
1. A PROCESS OF PREPARING 2,2,4-TRIMETHYL-3-PENTEN-1OL WHICH COMPRISES PYROLYZING A LOWER ALIPHATIC MONOCARBOXYLIC ACID DIESTER OF 2,2,4-TRIMETHYL-1,3-PENTANEDIOL AND HYDROLYZING THE RESULTING LOWER ALIPHATIC MONOCARBOXYLIC ACID ESTER OF 2,.2,4-TRIMETHYL-3-PENTEN-1-OL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US750288A US2941011A (en) | 1958-07-23 | 1958-07-23 | Process of manufacturing 2, 2, 4-trimethyl-3-penten-1-ol and 2, 2, 4-trimethyl-pentanol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US750288A US2941011A (en) | 1958-07-23 | 1958-07-23 | Process of manufacturing 2, 2, 4-trimethyl-3-penten-1-ol and 2, 2, 4-trimethyl-pentanol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2941011A true US2941011A (en) | 1960-06-14 |
Family
ID=25017239
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US750288A Expired - Lifetime US2941011A (en) | 1958-07-23 | 1958-07-23 | Process of manufacturing 2, 2, 4-trimethyl-3-penten-1-ol and 2, 2, 4-trimethyl-pentanol |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2941011A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3050551A (en) * | 1960-08-11 | 1962-08-21 | Jacobson Martin | 12-acetoxy-1-hydroxy-9-octadecene and method for producing the same |
| US3201478A (en) * | 1960-06-02 | 1965-08-17 | Texaco Inc | Method of producing a tertiary monohydric alcohol |
| US3329713A (en) * | 1965-06-14 | 1967-07-04 | Eastman Kodak Co | Pyrolysis of 2, 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate |
| US4886919A (en) * | 1987-11-25 | 1989-12-12 | Union Carbide Chemicals And Plastics Company Inc. | Process for the production of saturated neo-alcohols |
| US5196571A (en) * | 1987-10-22 | 1993-03-23 | Basf Aktiengesellschaft | Preparation of unsaturated monoesters |
| WO1995021606A1 (en) * | 1994-02-08 | 1995-08-17 | Union Camp Corporation | 2,2,4-trimethyl-penten-1-yl compounds, fragrance and flavor compositions |
| WO2010074703A3 (en) * | 2008-12-15 | 2010-10-14 | Eastman Chemical Company | Method for producing 2,2,4-trimethyl-1,3-pentanediol di-2-ethylhexanoate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2042221A (en) * | 1934-06-05 | 1936-05-26 | Shell Dev | Production of unsaturated esters and products thereof |
| US2246285A (en) * | 1939-12-01 | 1941-06-17 | Standard Oil Dev Co | Unsaturated esters |
| US2251983A (en) * | 1940-04-25 | 1941-08-12 | Carbide & Carbon Chem Corp | Process for making vinyl esters and other esters of unsaturated alcohols |
-
1958
- 1958-07-23 US US750288A patent/US2941011A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2042221A (en) * | 1934-06-05 | 1936-05-26 | Shell Dev | Production of unsaturated esters and products thereof |
| US2246285A (en) * | 1939-12-01 | 1941-06-17 | Standard Oil Dev Co | Unsaturated esters |
| US2251983A (en) * | 1940-04-25 | 1941-08-12 | Carbide & Carbon Chem Corp | Process for making vinyl esters and other esters of unsaturated alcohols |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3201478A (en) * | 1960-06-02 | 1965-08-17 | Texaco Inc | Method of producing a tertiary monohydric alcohol |
| US3050551A (en) * | 1960-08-11 | 1962-08-21 | Jacobson Martin | 12-acetoxy-1-hydroxy-9-octadecene and method for producing the same |
| US3329713A (en) * | 1965-06-14 | 1967-07-04 | Eastman Kodak Co | Pyrolysis of 2, 2, 4-trimethyl-1, 3-pentanediol monoisobutyrate |
| US5196571A (en) * | 1987-10-22 | 1993-03-23 | Basf Aktiengesellschaft | Preparation of unsaturated monoesters |
| US4886919A (en) * | 1987-11-25 | 1989-12-12 | Union Carbide Chemicals And Plastics Company Inc. | Process for the production of saturated neo-alcohols |
| WO1995021606A1 (en) * | 1994-02-08 | 1995-08-17 | Union Camp Corporation | 2,2,4-trimethyl-penten-1-yl compounds, fragrance and flavor compositions |
| WO2010074703A3 (en) * | 2008-12-15 | 2010-10-14 | Eastman Chemical Company | Method for producing 2,2,4-trimethyl-1,3-pentanediol di-2-ethylhexanoate |
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