AU650495B2 - Crystallisation process - Google Patents
Crystallisation process Download PDFInfo
- Publication number
- AU650495B2 AU650495B2 AU88249/91A AU8824991A AU650495B2 AU 650495 B2 AU650495 B2 AU 650495B2 AU 88249/91 A AU88249/91 A AU 88249/91A AU 8824991 A AU8824991 A AU 8824991A AU 650495 B2 AU650495 B2 AU 650495B2
- Authority
- AU
- Australia
- Prior art keywords
- butyryl
- hydroxy
- trimethylphenyl
- cyclohex
- compound
- 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
- 238000000034 method Methods 0.000 title claims description 17
- 238000002425 crystallisation Methods 0.000 title description 5
- 239000002904 solvent Substances 0.000 claims description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohex-2-enone Chemical compound O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- CCKSEFYKQOSRRF-UHFFFAOYSA-N CCCC(=O)C1=C(C)C=C(C)C(C2CC(=O)C(C(=O)CC)=C(O)C2)=C1C Chemical compound CCCC(=O)C1=C(C)C=C(C)C(C2CC(=O)C(C(=O)CC)=C(O)C2)=C1C CCKSEFYKQOSRRF-UHFFFAOYSA-N 0.000 claims description 2
- DVECBJCOGJRVPX-UHFFFAOYSA-N butyryl chloride Chemical compound CCCC(Cl)=O DVECBJCOGJRVPX-UHFFFAOYSA-N 0.000 claims description 2
- AQFWNELGMODZGC-UHFFFAOYSA-N o-ethylhydroxylamine Chemical compound CCON AQFWNELGMODZGC-UHFFFAOYSA-N 0.000 claims description 2
- XTKDAFGWCDAMPY-UHFFFAOYSA-N azaperone Chemical compound C1=CC(F)=CC=C1C(=O)CCCN1CCN(C=2N=CC=CC=2)CC1 XTKDAFGWCDAMPY-UHFFFAOYSA-N 0.000 claims 1
- -1 ethoxyimino Chemical group 0.000 claims 1
- ZOGDSYNXUXQGHF-UHFFFAOYSA-N 5-(3-butanoyl-2,4,6-trimethylphenyl)-2-(N-ethoxy-C-ethylcarbonimidoyl)-3-hydroxycyclohex-2-en-1-one Chemical compound CCCC(=O)C1=C(C)C=C(C)C(C2CC(=O)C(C(CC)=NOCC)=C(O)C2)=C1C ZOGDSYNXUXQGHF-UHFFFAOYSA-N 0.000 description 17
- 239000007787 solid Substances 0.000 description 5
- 230000002363 herbicidal effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OILAIQUEIWYQPH-UHFFFAOYSA-N cyclohexane-1,2-dione Chemical class O=C1CCCCC1=O OILAIQUEIWYQPH-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000004682 monohydrates Chemical group 0.000 description 3
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VOYADQIFGGIKAT-UHFFFAOYSA-N 1,3-dibutyl-4-hydroxy-2,6-dioxopyrimidine-5-carboximidamide Chemical compound CCCCn1c(O)c(C(N)=N)c(=O)n(CCCC)c1=O VOYADQIFGGIKAT-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
P/00/11.
Regulation 3.2
AUSTRALIA
Patents Act 1990 6504
ORIGINAL
COMPLETE SPECIFICATION STAN~DARD PATENT **..nvention Title: "CRYSTALLISATION PROCESS"
ICSO
00 following statement is a full description of this invention, 0 *including the best method of performing it known to me:- 0 C 00 I, I I AUS 1488/RLE 0 5555 2 S" CRYSTALLISATION PROCESS 5 This invention relates to cyclohexanedione derivatives and to a method of manufacture.
Certain cyclohexanedione derivatives have been found to have outstanding herbicidal properties. As a result, an extensive patent literature has developed on this subject and typical examples include Australian patents 464555, 555884, 556148 and 566671.
10 Research by the applicants has resulted in a particularly promising herbicidal cyclohexanedione derivative having the chemical name 2-E1-(ethoxyimino)propy13-3-hydroxy-5-(3-butyryl- 2,4,6-trimethylphenyl)cyclohex-2-en-l-one, which will hereinafter be referred to by its proposed common name "fenoxydim". This promise has, however, not yet been commercially realised because it has hitherto not proved possible to make fenoxydim in a 3 physical form which is suitable for formulation as a commercial herbicide. The applicants have so far been able to isolate fenoxydim in two forms, the monohydrate form and the anhydrous form. The monohydrate form is a crystalline off-white solid which is easy to manipulate. It is, however, difficult to formulate, it melts at 30oC (which makes storage in hot countries difficult) and it can dehydrate.
In view of these unfavourable physical properties of the monohydrate, it would be preferable to formulate herbicidal compositions from fenoxydim in its anhydrous form. However, anhydrous fenoxydim has so far only been obtained as a 15 red-brown toffee-like or glass-like substance which is very inconvenient to store and use. Moreover, it is transportable as a solution of less than *purity and in some countries a substance of such purity is regarded as a formulated product rather than a raw material and attracts a higher import duty. Attempts to produce anhydrous fenoxydim in S* any form other than the toffee- or glass-like solid o l' have hitherto failed.
It has now been found that it is possible to 25 make a more easily useable form of fenoxydim. There is therefore provided, according to the present invention, anhydrous fenoxydim in the form of a crystalline powder.
The crystalline powder can easily be formulated into products. It has a melting-point of 82-85 0 C. It is storage-stable, even in hot climates, and it is not hygroscopic. Being pure active ingredient, it occupies less space ard r easily be transported. Most importantly, it makes available to the herbicides formulator the high activity of the substance.
I I, 4 The invention also provides a process for the preparation of anhydrous fenoxydim in the form of a crystalline powder comprising the steps of preparing a solution of fenoxydim in a low-boiling hydrocarbon solvent; cooling the solution to at least O°C; and filtering off the crystals thus formed.
The choice of low boiling (100C maximum) hydrocarbon solvent can be made from a wide range of 10 such materials. There are, naturally, restrictions on the choice of material depending on circumstances and the skilled person will readily appreciate these restrictions. For example, one route to fenoxydim is via the corresponding trione by using a Friedel-Crafts reaction to provide the butyryl group. Such a process is described in Australian Patent Application No. 34225/84. If it is desired S" not to have a preparative stage followed by solution in fresh hydrocarbon solvent but to use the same hydrocarbon solvent throughout, the hydrocarbon solvent must obviously be one which is unaffected by Friedel-Craft reactions. Typical solvents for use in this invention are cyclohexane, alkanes, and petroleum spirits (boiling ranges 40 0 -60 0 C, 60°-40 C, 25 80 0 -100C).
The anhydrous crystals are formed by cooling the solution of fenoxydim to at least 0°C, more preferably to at least -5°C and most preferably to at least -10 0 C. This causes the fenoxydim to crystallise as anhydrous crystals which can then be recovered and dried.
There are a number of variations on the process which make it more efficient. For example, prior to cooling to at least -5 C, it is preferred to cool the solution to 0 0 C with ice and then seed with a crystal of fenoxydim. This results in a greater yield.
The invention is further described with reference to the following examples.
Example 1 A crude 2-[1-(ethyoxyimino)propyll-3-hydroxy- 5-(3-butyryl-2,4,6-trimethylphenyl)cyclohex-2-en-1one used in the crystallization process of the invention may be prepared, for example, by reaction of 3-hydroxy-5-(2,4,6-trimethylphenyl)-2-propionyl- 15 cyclohex-2-en-l-one with n-butyryl chloride in accordance with the process of Example 1 of Australian Patent Application No. 34225/84 and treating the 3-hydroxy-5-(3-butyryl-2,4,6trimethylphenyl)-2-propionylcyclohex-2-en-l-one so 20 obtained with ethoxyamine.
A crude cyclohexane solution of 2-C1-(ethoxyimino)propyll-3-hydroxy-5-(3-butyryl- 2,4,6-trimethylphenyl) cyclohex-2-en-l-one was washed with a solution bicarbonate solution, separated and evaporated with azeotropic removal of water. The residual brown gel was dissolved in petroleum spirit bp 80-100 C (120 ml) and evaporated to dryness again to remove traces of cyclohexane.
The residue was dissolved in hot petroleum spirit bp 80-100 0 C (150 ml) and cooled to less than The solution was seeded with a crystal of anhydrous fenoxydim and further cooled to 0 C until crystallization was observed. The mixture was then cooled to -10°C and stirred rapidly. The -6precipitate was filtered off, washed twice with petroleum spirit and air dried to give fenoxydim (71.2 g, 89%) as a fine white anhydrous solid.
NMR analysis of the brown gel and the final white powder showed the compounds to be the same but infra-red analysis of the solid compounds showed substantial d.ifforences. The brown gel showed significant peaks at 3206, 2968, 2934, 2876, 2578, 1701, 1595 and 1392 cm 1 whereas the anhydrous solid showed peaks at 3386, 2970, 2937, 2878, 1702, -1 1642, 1606, 1553, 1395 and 1045 cm 1 This indicates the presence of a different isomeric form of fenoxydim.
4 s U UU
Claims (4)
- 2. A process for the preparation of anhydrous crystalline form of the compound 2-[(1-(ethoxyimino)-propyl]-3-hydroxy-5-(3-butyryl-2,4,6- trimiethylphenyl)cyclohex-2-en-1 -one comprising the steps of: preparing a solution of said compound in a low-boiling hydrocarbon solvent; cooling the solution to at least 0OC, and collecting the crystals thus formed.
- 3. A process according to claim 2 wherein the compound 2-f[1- (ethioxyirnino)propyl)-3-hydroxy-5-(3-butyryl-2,4,6-trimethylphenyl)cyclohiex-2-en. 1- one is pre-pared by reacting 3-hydroxy-5-(2,4,8-trimethylphenyl)-2- propionyl- cyclohex-2-en-1 -one with n-butyryl chloride and treating the 3-hydroxy-5-(3- butyryl-2,4,6-trimethylphenyl)-2-propionylcyclohex-2-en-1 -one so formed with ethoxyamine.
- 4. A process according to claim 2 wherein the hydrocarbon solvent has a boiling point less than 10000. :6 A process according to claim- 2 wherein the hydrocarbon solvent is chosen 20 from the group which includes cyclohexane, allsanes and petroleum spirit. SI V -t ft ft.
- 8- 6. A process according to claim 2 wherein the solution of the compound 2-[1-(ethoxyimino)pi'opyl]-3 -hydroxy-5-(3-butyryl-2,4,6-trimethylphenyl)- cyclohex-2-en-1-one is cooled to at least -10 0 C. 7. A process for preparation of 2-El- (ethoxyimino) propyll-3-hydroxy-5-(3-butyryl -2,4,6-trimethylphenyl)-cyclohex-2-en-1 one substantially as hereinabove described with reference to the example. 0 0 0 S 0 4@ 0 a.0 004 271 day of k a- 19 Dated this ICI AUSTRALIA OPERATIONS PROPRIETARY LIMITED By its Patent Attorney P3 0 2 CLPR ABSTRACT The invention relates to the compound 2-El- (ethoxyimino)propyl)-3-hydroxy-5-(3-butyryl-2,4 ,6- trimethylphenyl)-cyclohex-2-en-.-one in the form of an anhydrous crystalline powder and a process for the preparation of said anhydrous crystalline powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU88249/91A AU650495B2 (en) | 1990-11-27 | 1991-11-27 | Crystallisation process |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AUPK356990 | 1990-11-27 | ||
| AUPK3569 | 1990-11-27 | ||
| AU88249/91A AU650495B2 (en) | 1990-11-27 | 1991-11-27 | Crystallisation process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU8824991A AU8824991A (en) | 1992-05-28 |
| AU650495B2 true AU650495B2 (en) | 1994-06-23 |
Family
ID=25641025
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU88249/91A Expired AU650495B2 (en) | 1990-11-27 | 1991-11-27 | Crystallisation process |
Country Status (1)
| Country | Link |
|---|---|
| AU (1) | AU650495B2 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU3422584A (en) * | 1983-11-04 | 1985-05-09 | Ici Australia Limited | Preparation of 2-acyl-5-acyl substituted aryl-3- hydroxycyclohex--2-en-1-ones |
| AU556148B2 (en) * | 1982-01-29 | 1986-10-23 | Ici Australia Limited | Cyclohexane -1,3- dione derivatives |
| AU566671B2 (en) * | 1983-07-18 | 1987-10-29 | Ici Australia Limited | Cyclohexene-1,3-dione derivatives |
-
1991
- 1991-11-27 AU AU88249/91A patent/AU650495B2/en not_active Expired
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU556148B2 (en) * | 1982-01-29 | 1986-10-23 | Ici Australia Limited | Cyclohexane -1,3- dione derivatives |
| AU566671B2 (en) * | 1983-07-18 | 1987-10-29 | Ici Australia Limited | Cyclohexene-1,3-dione derivatives |
| AU3422584A (en) * | 1983-11-04 | 1985-05-09 | Ici Australia Limited | Preparation of 2-acyl-5-acyl substituted aryl-3- hydroxycyclohex--2-en-1-ones |
Also Published As
| Publication number | Publication date |
|---|---|
| AU8824991A (en) | 1992-05-28 |
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