US3890392A - Preparation of methyl vinyl ketone from 3-ketobutan-1-ol - Google Patents

Preparation of methyl vinyl ketone from 3-ketobutan-1-ol Download PDF

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Publication number
US3890392A
US3890392A US373071A US37307173A US3890392A US 3890392 A US3890392 A US 3890392A US 373071 A US373071 A US 373071A US 37307173 A US37307173 A US 37307173A US 3890392 A US3890392 A US 3890392A
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US
United States
Prior art keywords
weight percent
methyl vinyl
vinyl ketone
acid
ketobutan
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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
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US373071A
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English (en)
Inventor
George Ember
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
F Hoffmann La Roche AG
Hoffmann La Roche Inc
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F Hoffmann La Roche AG
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Filing date
Publication date
Application filed by F Hoffmann La Roche AG filed Critical F Hoffmann La Roche AG
Priority to US373071A priority Critical patent/US3890392A/en
Priority to DE19742426039 priority patent/DE2426039A1/de
Priority to IT23757/74A priority patent/IT1014884B/it
Priority to NL7408057A priority patent/NL7408057A/xx
Priority to FR7421632A priority patent/FR2234263B1/fr
Priority to CS4444A priority patent/CS176279B2/cs
Priority to GB2790374A priority patent/GB1412928A/en
Priority to JP49072207A priority patent/JPS5036411A/ja
Application granted granted Critical
Publication of US3890392A publication Critical patent/US3890392A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
    • C07C45/66—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups by dehydration

Definitions

  • ABSTRACT A process for obtaining methyl vinyl ketone by heating a solution comprising about 1 to 30 weight percent 3-ketobutan-l-ol, about 0.005 to 0.50 weight percent of a strong acid, and one or more inert solvents.
  • Methyl vinyl ketone has heretofore been obtained by dehydrating 3-ketobutan-1-ol in the presence of a relatively concentrated, strong acid. See German Pat. No. 730,117, wherein N-sulfuric acid or N-hydrochloric acid utilized (about 5% by wt.), and White et al., Journal of the Chemical Society 1943: pp. 25-31 (1943), wherein 110% by weight of hydrochloric acid or phosphoric acid utilized.
  • methyl vinyl ketone is obtained by heating a solution comprising about 1 to 30 weight percent 3-ketobutanl-ol, about 0.005 to 0.50 weight percent of a strong acid and about 70 to 99 weight percent of an inert solvent.
  • a solution comprising about 1 to 30 weight percent 3-ketobutanl-ol, about 0.005 to 0.50 weight percent of a strong acid and about 70 to 99 weight percent of an inert solvent.
  • methyl vinyl ketone is obtained byheating a solution comprising 1 to 30 weight percent 3-ketobutan-l-ol, 0.005 to 0.50 weight percent of a strong acid and 70 to 99 weight percent of an inert solvent.
  • the weight percents of the acid, the 3-ketobutan-l-ol and the inert solvent are based on the entire solution containing these materials.
  • the solution containing the 3-ketobutan-l-ol and the strong acid also contains one or more inert solvents as diluents.
  • any conventional, inert solvent in which the 3- ketobutan-l-ol and the strong acid are soluble can be utilized.
  • inert solvents which can be utilized, either individually or in a mixture of solvents, are water; the lower alkanols, such as methanol, ethanol and isopropanol; ketones such as acetone, methyl ethyl ketone, tetrahydrofuran and dioxane; and the chlorinated hydrocarbons, such as tetrachloroethane, trichloroethylene and chlorobenzene.
  • a mixture of inert solvents comprising about 0 to about'60% water and 40 to 100% of one or more inert, water soluble, or-
  • ganic solvents is utilized, particularly a mixture of inert solvents which contains about to 45% water. Especially preferred is a mixture of inert solvents consisting essentially of about 55 to 90% acetone and about 10 to 45% water.
  • the inert solvent can also contain trace or larger amounts of various other diluents, such as diacetone alcohol and mesityl oxide, as well as traces of materials, such as formaldehyde, which do not significantly affect the acid dehydration of 3-ketobutan-l-ol to methyl vinyl ketone.
  • the inert solvent of the process of this invention comprises about to 99%.
  • the inert solvent comprises about to of the solution containing the 3-ketobutan-l-ol and the acid.
  • any conventional strong acid having a dissociation constant (in water at 25C.) of greater than about 10* can be utilized.
  • the preferred strong acids which can be utilized are the mineral acids, such as sulfuric acid, sulfurous acid, hydrochloric acid, perchloric acid, hydrobromic acid and phosphoric acid, and the strong organic acids, such as formic acid, oxalic acid, trichloroacetic acid and the sulfonic acids, such as the toluene sulfonic acids, particularly paratoluene sulfonic acid, the lower alkyl sulfonic acids, particularly methyl sulfonic acid, and the nitrophenyl sulfonic acids, particularly p-nitrophenyl sulfonic acid.
  • the foregoing strong acids especially preferred for use in the process of this invention are sulfuric acid, phosphoric acid and the sulfonic acids, particularly paratoluene sulfonic acid.
  • the amounts of strong acid and 3- ketobutan-l-ol utilized respectively comprise between about 0.005 and 0.50% and l to 30% of the solution containing these reactants. It is preferred that the acid be present in an amount between about 0.02 and 0.20% of the reaction mixture. A particular preferred amount of acid is between about 0.05 and 0.1%. It is also preferred that the 3-ketobutan-l-ol be present in an amount greater than 5%, particularly in an amount between about 10 to 20%.
  • temperatures of about C, to about 300C. can be utilized, with temperatures of C. to 260C. being preferred, particularly temperatures of C. to 220C.
  • any pressure at or above the vapor pressure of the reaction mixture at the temperature of the reaction mixture can be utilized.
  • pressures of about 300 p.s.i.a. to about 800 p.s.i.a. are generally utilized.
  • greater pressures can also be utilized, such as a pressure of up to approximately 7000 p.s.i.a., as well as lower pressures of down to approximately 30 p.s.i.a.
  • the methyl vinyl ketone produced by the process of this invention can be suitably isolated from the reaction mixture in a conventional manner. It can be isolated by fractional distillation and/0r extraction of the reaction mixture which results when the process of this invention is carried out in a homogeneous system, i.e., with one liquid phase.
  • the methyl vinyl ketone can be isolated by heating the solution, containing the methyl vinyl ketone, to its boiling point to produce a distillate containing principally water and methyl vinyl ketone.
  • the methyl vinyl ketone can then be conveniently extracted from the water in a conventional manner, such as by treating the distillate with pentane.
  • liquid phase process of this invention yields of up to about 98% methyl vinyl ketone, based on ketobutanol, can be expeditiously obtained with virtually complete consumption of ketobutanol.
  • reaction rate of this process is relatively high, resulting in relatively large outputs of methyl vinyl ketone with conventional, liquid phase processing equipment. In fact, reaction times of less than one hour, preferably to minutes, can be utilized for the reaction to go to completion.
  • acetone is utilized as in inert solvent in this process
  • the mixture of 3- ketobutan-l-ol and acetone which is conventionally produced by the reaction of acetone and formaldehyde, can be utilized directly as the starting material in this process, without having to remove the acetone therefrom.
  • EXAMPLE 5 Utilizing the procedure of Example 1, test mixtures containing 3-ketobutan-l -ol and acetone were formulated with and without phosphoric acid. Each test was charged into a bomb, and the bomb was immersed in an oil bath at 200C. for 15 minutes. The results, as analyzed by gas chromatography, are summarized below in Table 5.
  • the yield of methyl vinyl ketone was about 95
  • the yield of methyl vinyl ketone was about i 3% with about 50% conversion of ketobutanol. ketobutanol.
  • the yield of methyl vinyl ketone was about 89.8%, with about 81.6% conversion of ketobutanol.
  • a process for obtaining methyl vinyl ketone comprising heating, at a temperature of 100C. to 300C. and at a pressure at or above the vapor pressure of the reaction mixture, a solution comprising about 1 to 30 65% with about 25% conversion of weight percent 3-ketobutan-l-ol, about 0.005 to 0.50 weight percent of sulfuric acid, and about to 99 weight percent of an inert solvent.
  • said inert solvent comprises about 0 to 60 weight percent water and about 40 to 100 weight percent of an inert organic solvent.
  • said inert solvent comprises about 55 to weight percent acetone and about 10 to 45 weight percent water.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
US373071A 1973-06-25 1973-06-25 Preparation of methyl vinyl ketone from 3-ketobutan-1-ol Expired - Lifetime US3890392A (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
US373071A US3890392A (en) 1973-06-25 1973-06-25 Preparation of methyl vinyl ketone from 3-ketobutan-1-ol
DE19742426039 DE2426039A1 (de) 1973-06-25 1974-05-30 Verfahren zur herstellung von methylvinylketon
IT23757/74A IT1014884B (it) 1973-06-25 1974-06-07 Procedimento per la preparazione di metil vinil chetone
NL7408057A NL7408057A (enrdf_load_stackoverflow) 1973-06-25 1974-06-17
FR7421632A FR2234263B1 (enrdf_load_stackoverflow) 1973-06-25 1974-06-21
CS4444A CS176279B2 (enrdf_load_stackoverflow) 1973-06-25 1974-06-24
GB2790374A GB1412928A (en) 1973-06-25 1974-06-24 Process for the manufacture of methyl vinyl ketone
JP49072207A JPS5036411A (enrdf_load_stackoverflow) 1973-06-25 1974-06-24

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US373071A US3890392A (en) 1973-06-25 1973-06-25 Preparation of methyl vinyl ketone from 3-ketobutan-1-ol

Publications (1)

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US3890392A true US3890392A (en) 1975-06-17

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US373071A Expired - Lifetime US3890392A (en) 1973-06-25 1973-06-25 Preparation of methyl vinyl ketone from 3-ketobutan-1-ol

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US (1) US3890392A (enrdf_load_stackoverflow)
JP (1) JPS5036411A (enrdf_load_stackoverflow)
CS (1) CS176279B2 (enrdf_load_stackoverflow)
DE (1) DE2426039A1 (enrdf_load_stackoverflow)
FR (1) FR2234263B1 (enrdf_load_stackoverflow)
GB (1) GB1412928A (enrdf_load_stackoverflow)
IT (1) IT1014884B (enrdf_load_stackoverflow)
NL (1) NL7408057A (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4866210A (en) * 1987-01-28 1989-09-12 Basf Aktiengesellschaft Preparation of ketones
US4885395A (en) * 1986-09-25 1989-12-05 Basf Aktiengsellschaft Preparation of alpha, beta-unsaturated ketones

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH058469Y2 (enrdf_load_stackoverflow) * 1986-06-09 1993-03-03

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB576480A (en) * 1942-10-31 1946-04-05 Universal Oil Prod Co Process for producing olefinic hydrocarbons

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE730117C (de) * 1937-02-25 1943-01-09 Consortium Elektrochem Ind Verfahren zur Herstellung von Buten-1-on-3
FR1298957A (fr) * 1961-05-19 1962-07-20 Melle Usines Sa Procédé de déshydratation catalytique de composés hydroxy-carbonyliques
DE2052782B2 (de) * 1970-10-28 1979-06-13 Basf Ag, 6700 Ludwigshafen Verfahren zur Herstellung von olefinisch ungesättigten Verbindungen durch Dehydratisierung von Alkoholen
DE2111723C3 (de) * 1971-03-11 1978-03-16 Basf Ag, 6700 Ludwigshafen Verfahren zur Herstellung von Methylvinylketon

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB576480A (en) * 1942-10-31 1946-04-05 Universal Oil Prod Co Process for producing olefinic hydrocarbons

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
White et al., "Journal of the Chemical Society", 1943, pp. 25-31 (1943). *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4885395A (en) * 1986-09-25 1989-12-05 Basf Aktiengsellschaft Preparation of alpha, beta-unsaturated ketones
US4866210A (en) * 1987-01-28 1989-09-12 Basf Aktiengesellschaft Preparation of ketones

Also Published As

Publication number Publication date
JPS5036411A (enrdf_load_stackoverflow) 1975-04-05
FR2234263A1 (enrdf_load_stackoverflow) 1975-01-17
FR2234263B1 (enrdf_load_stackoverflow) 1978-01-13
GB1412928A (en) 1975-11-05
NL7408057A (enrdf_load_stackoverflow) 1974-12-30
DE2426039A1 (de) 1975-01-30
CS176279B2 (enrdf_load_stackoverflow) 1977-06-30
IT1014884B (it) 1977-04-30

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