EP0442973A1 - Process for the acylation of thiazolidines - Google Patents

Process for the acylation of thiazolidines

Info

Publication number
EP0442973A1
EP0442973A1 EP90901137A EP90901137A EP0442973A1 EP 0442973 A1 EP0442973 A1 EP 0442973A1 EP 90901137 A EP90901137 A EP 90901137A EP 90901137 A EP90901137 A EP 90901137A EP 0442973 A1 EP0442973 A1 EP 0442973A1
Authority
EP
European Patent Office
Prior art keywords
process according
hydrogen
formula
buffer
lower alkyl
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.)
Withdrawn
Application number
EP90901137A
Other languages
German (de)
English (en)
French (fr)
Inventor
Nancy Kerlinger
Richard D. Gless
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.)
Zeneca Inc
Original Assignee
ICI Americas Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by ICI Americas Inc filed Critical ICI Americas Inc
Publication of EP0442973A1 publication Critical patent/EP0442973A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/04—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members

Definitions

  • the present invention is related to the acylation of thiazolidines using acyl halide ⁇ in the presence of certain bases.
  • R is haloalkyl
  • each of R 1 and R 2 is hydrogen or lower alkyl
  • R 1 and R 2 are useful as antidotes against crop injury when used with various herbicides.
  • Such compounds are disclosed, for example, in U.S. Patent 4,319,031. Desirous plants such as crop plants can be protected against injury by
  • thiocarbamate-type herbicides alone or mixed with other herbicides, by adding to the soil a non-phytotoxic antidotally effective amount of a compound of the above formula.
  • reaction a the yield is about 65% or less.
  • reaction b the yield is below 50%.
  • a method for synthesizing other dichloroacetamides by treatment with chloral and sodium cyanide in aqueous sodium carbonate is known (British Patent 692,165 (1953); Chem. Abstracts (1954) 48. 8260g). However, when this method is attempted to produce the above
  • the process of the present invention provides acylated substituted thiazolidines in surprisingly increased yields by reaction of the starting material with an acyl halide in the presence of a buffer compound.
  • the product is further purified by washing it with a. strong base.
  • this invention is directed to a process for the manufacture of a compound having the formula
  • R is haloalkyl
  • R 1 is hydrogen or lower alkyl
  • R 2 is hydrogen or lower alkyl
  • R 1 and R 2 are as defined above,
  • any material which will function as a buffer, giving resistance to a change in the pH of the reaction mixture and keeping the pH within the desired range, may be used in the present invention.
  • buffer substances are normally selected from the salts of weak acids or bases, such as the phosphates, the carbonates, the borates, the acetates and ammonium salts.
  • the buffers useful in the present invention may include, but are not limited to, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium phosphate, sodium orthophosphate, potassium phosphate, calcium hydroxide, borax and the like. Since the preferable pH range for the reaction of the invention is basic, the buffer will preferably be selected from the base buffers.
  • the buffer is present in the reaction in an amount that serves to keep the reaction within the desired pH range.
  • the quantity used in any particular application will be determined in large part by the individual needs of the manufacturing facility. Factors which enter into such a determination include the cost of the buffer, recovery costs, pH range desired, and system capacity. Aside from these considerations, the buffer quantity is not a critical feature of the invention and can vary over a wide range. It will be most convenient to use an amount of buffer which comprises from about 50 to about 250 mole percent, preferably from about 80 to about 200 mole percent based on the starting
  • the preferred range of pH is from about 2 to about 12, more preferably from about 5 to about 11, and most preferably from about 7 to about 10.
  • the process may successfully be run over a wide range of temperatures.
  • the operating temperature may range from about -10°C to about 80°C.
  • temperature control is often desirable since higher yields of product tend to be obtained at temperatures below about 25°C.
  • the preferable temperature range of the reaction is from about 0°C to about 15°C and more preferably from about 2°C to about 10°C.
  • Temperature control can be achieved by external cooling supplied by any conventional means known in the art, including ice baths, coils, jackets, and the like.
  • the process does not have a critical operating pressure, but is operable over a wide pressure range, subject only to considerations of economy and materials of
  • the reaction is preferably run using an excess of the acyl halide. While the amount of excess is purely a question of process economy, such as raw material costs and recovery expenses, the reaction is most conveniently run at an acyl halide excess of up to about 35%.
  • reaction will proceed with no additional water other than that which may be present with the starting thiazolidine of formula II, it is generally preferred to run the reaction in the presence of water for ease of handling and improved reactant contact, with resulting higher yields and use of less starting acyl halide.
  • the amount of water present in the reaction is not critical and can be in the range of from about 0.1 to about 20.0 grams per gram of starting thiazolidine and is preferably from about 1.0 to about 5.0 grams per gram of starting thiazolidine.
  • solvents can be used in the practice of the present invention. Any inert solvent can be used,
  • aliphatic compounds for example hexane or octane
  • aromatic compounds for example benzene, toluene, xylene or mesitylene
  • chlorinated aliphatic or aromatic compounds for example methylene chloride, ethylene dichloride or chlorobenzene;
  • ethers for example 1,2-dimethoxyethane, diethyl ether, tetrahydrofuran or 1,4-dioxane
  • ketones for example acetone or methyl isobutyl ketone
  • nitriles for example
  • acylated thiazolidines produced by the reaction of the invention can be recovered from the reaction mixture by any conventional technique.
  • the process further comprises washing the product with a strong base as a purification step.
  • a strong base such as sodium hydroxide , ammonium
  • haloalkyl refers to an alkyl group
  • halogen is conveniently selected from bromo, chloro and fluoro.
  • R 2 have the following values: R is haloalkyl of 1 to 10 carbon atoms; R 1 is hydrogen or lower alkyl of 1 to 4 atoms; and R 2 is hydrogen or lower alkyl of 1 to 4 atoms.
  • R a haloalkyl of 1 to 5 carbon atoms, straight or branched, and substituted with 1 to 3 halogens is
  • Such halogens are preferably bromo or chloro.
  • R 1 methyl or ethyl is preferred.
  • R 2 hydrogen, methyl or ethyl is preferred.
  • This example illustrates the preparation of 2,2- dimethyl-N-dichloroacetyl-1,3-thiazolidine according to the invention.
  • reaction mixture was warmed to 25°C by replacing the ice bath with a 35°C water bath.
  • the previously distinct liquid phases formed an emulsion which dispersed when water (300 mL) was added to dissolve the inorganic solids.
  • the phases were separated, and the toluene solution was washed twice with 80 mL portions of 20% aq. NaOH.
  • the area percent of the side-product N,S-bis(dichloroacetyl)- cysteamine was reduced from 10.8% to less than 1% (as measured by HPLC).
  • the toluene solution was then washed with 3N HCl (167 mL).
  • This example illustrates the preparation of 2,2- dimethyl-N-dichloroacetyl-1,3-thiazolidine using various inorganic bases and solvents and, in comparison, using a strong base, NaOH.
  • the base to be examined was added to a mixture of
  • 2,2-dimethyl-1,3-thiazolidine (6.0 g, 0.051 mole), 100 mL of solvent and 70 mL of water.
  • a solution of dichloroacetyl chloride (9.8 g, 0.067 mole) diluted to 10 mL with solvent was then added to the vigorously stirred reaction mixture over 67 min., maintaining an internal reaction temperature of ca. 2- 5°C.
  • the reaction mixture was stirred an additional 10 min. after completion of the addition and then filtered if
  • This example illustrates the preparation of 2,2- dimethyl-N-dichloroacetyl-1, 3-thiazolidine using
  • This example is of the reaction as in Example 3 above but carried out under typical prior art Schotten- Baumann conditions using caustic as the base to prepare 2,2- dimethyl-N-dichloroacetyl-1,3-thiazolidine.
  • This example shows the effect of using a buffer compound, potassium carbonate, versus the prior art sodium hydroxide as the base in the preparation of 2, 2-dimethy1-N- dichloroacetyl-1,3-thiazolidine. This example also shows the effects of temperature and the amount of base (buffer or NaOH).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
EP90901137A 1988-11-14 1989-10-27 Process for the acylation of thiazolidines Withdrawn EP0442973A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US27091388A 1988-11-14 1988-11-14
US270913 1988-11-14

Publications (1)

Publication Number Publication Date
EP0442973A1 true EP0442973A1 (en) 1991-08-28

Family

ID=23033363

Family Applications (2)

Application Number Title Priority Date Filing Date
EP90901137A Withdrawn EP0442973A1 (en) 1988-11-14 1989-10-27 Process for the acylation of thiazolidines
EP89311386A Withdrawn EP0369649A1 (en) 1988-11-14 1989-11-02 Process for the acylation of thiazolidines

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP89311386A Withdrawn EP0369649A1 (en) 1988-11-14 1989-11-02 Process for the acylation of thiazolidines

Country Status (8)

Country Link
EP (2) EP0442973A1 (ja)
JP (1) JPH04501725A (ja)
KR (1) KR900701768A (ja)
BR (1) BR8907771A (ja)
HU (1) HUT56836A (ja)
IL (1) IL92278A0 (ja)
WO (1) WO1990005725A1 (ja)
ZA (1) ZA898637B (ja)

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3959304A (en) * 1974-07-01 1976-05-25 Stauffer Chemical Company Certain 3-haloacyl-2,2,5-trimethyl-oxazolidines
US4278799A (en) * 1980-04-28 1981-07-14 Stauffer Chemical Company Continuous process for the production of dichloroacetamides

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9005725A1 *

Also Published As

Publication number Publication date
HU900508D0 (en) 1991-07-29
JPH04501725A (ja) 1992-03-26
ZA898637B (en) 1991-04-24
IL92278A0 (en) 1990-07-26
KR900701768A (ko) 1990-12-04
HUT56836A (en) 1991-10-28
WO1990005725A1 (en) 1990-05-31
EP0369649A1 (en) 1990-05-23
BR8907771A (pt) 1991-08-27

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