OA19375A - New catalytic system for scalable preparation of indoxacarb. - Google Patents

New catalytic system for scalable preparation of indoxacarb. Download PDF

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OA19375A
OA19375A OA1201900384 OA19375A OA 19375 A OA19375 A OA 19375A OA 1201900384 OA1201900384 OA 1201900384 OA 19375 A OA19375 A OA 19375A
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process according
solvent mixture
group
indoxacarb
mixtures
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OA1201900384
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Rajuri VENKATARAMANA
Jayapal Reddy BICIDI
Bijukumar Gopinathan Pillai
Sreedevi MANNAM
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Adama Makhteshim Ltd.
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Abstract

It is an object of the present invention to provide a novel and advantageous process for commercially preparing of indoxacarb which is racemic or enantiomerically enriched at chiral center from its amide precursor using a new catalytic system. More particularly, it relates to an efficient method of preparationofindoxacarb which is racemic or enantiomerically enriched at chiral center from methyl-7-chloro-2.5-dihydro-2-[[[(4trif1uoromethoxy)phenyl]amino]carbonyi]indeno[l,2-e][1.3.4]oxadiazine-4a(3H) carboxylate represented as formula (I) using methoxycarbonylation agent and metal salt of methylsulfinyimethylide in hydrocarbon solvent in the presence of organic base and phase transfer catalyst.

Description

The présent invention concerns an improved scalable process for préparation of arthropodicidal oxadiazine indoxacarb which is racemic or enantiomerically enriched at chiral center from its amide precursor methyl-7-chloro-2,5-dihydro-2-[[[(4trifluoromethoxy)phenyl]amino]carbonyl]-indeno[1,2-e][1,3,4]oxadiazine-4a(3H) carboxylate represented as formula (I) using methoxycarbonylation agent and a new catalytic system.
BACKGROUND OF THE INVENTION:
Arthropodicidal oxadiazines and the corresponding synthetic methods for the préparation of biologically activeoxadiazines are previously disclosed in PCT patent applications WO
9211249 and WO 9319045. However, these préparative methods still must be improved for safe économie commercial operation. In particular, acylation of amide precursorin the presence of sodium hydride baseby methylchloroformate has been disclosed as an efficient way to préparé the insecticide indoxacarb represented as compound of general formula (I).
In general, sodium hydride is a common base for substrate activation in nucleophilic substitution reactions. Sodium hydride is a commonly used base for deprotonation of alcohols, phénols, amides, ketones, esters and other functional groups for the promotion of their nucleophilic substitution. Sodium hydride can behave both as a base and as a source of hydride. This dual ability in the presence of an electrophile such as methylchloroformate results in the formation of byproducts when dimethylformamide or acetonitrile are used as solvents for these reactions.
PCT patent application WO9211249 discloses in a general way the acylation of amide precursor of active oxadiazine using sodium hydride in DMF and methyl chloroformate without any experimental data on yield and enantiomer of final active oxadiazine.
This type of conversion includes side reactions, in particular, a disproportionation reaction of métal hydride with DMF, resulting in dimethylamine and carbon monoxide, which has been reported long ago by Neumeyer JL, Cannon JG. J Org Chem. 1961; 26: 4681 —4682; Armarego DD, Perrin WLF. Purification of Laboratory Chemicals. Butterworth Heinemann; 1997. p. 192.
Indian patent application 140/MUM/2013 assigned to Cheminova India Ltd., discloses the acylation of amide precursor of indoxacarb using methyl chloroformate and sodium hydride in acetonitrile or, preferably, in a solvent system of methylene dichloride and acetonitrile.
It is known that acetonitrile is a hygroscopic solvent readily absorbing water from air. In case of industrial processes which should be kept in dry conditions, like the aforementioned acylation process, it is unfavorable. In addition, it appears that acetonitrile is not inevitably inert toward this process. It is known that acetonitrile undergoes deprotonation reaction with strong bases, in particular, with métal hydrides, affording the nitrile-stabilized anion, which can participate in side reactions producing the trimer 4-amino-2,6-dimethylpyrimidine as reported by Anthony R. Ronzio and William B. Cook in Org. Synth. 1944, 24, 6.
Methylene dichloride is a highly volatile halogenated solvent having environmental and health hazards and its open applications in commercial scale is unfavorable.
Indian patent IN241255 assigned to Gharda Chemicals Ltd., discloses the aforementioned acylation of amide precursor of indoxacarb using sodium hydride and methylchloroformate in the solvent mixture consisting of aliphatic hydrocarbons, aromatic hydrocarbons and ether solvents like dioxane, monoglyme, diglyme and any other open chain or cyclic ethers.
Ether solvents tend to absorb and react with oxygen from the air to form unstable peroxides which may detonate with extreme violence when they become concentrated by évaporation or distillation during recovery processes, when combined with other compounds that give a detonatable mixture, or when disturbed by unusual heat, shock, or friction. Therefore, the use of large volumes of ether solvents in a commercial scale is unfavorable.
In addition, former methods lack reproducibility and should be finely elaborated before to be desired in the commercial scale.
In view ofthe above, there is still a need for an improved process for large scale preparing of indoxacarb from its amide precursor, which process is suitable for industrial use, highly efficient, low-cost, environmentally friendly, and provides a high yield, reproducibility and easy workup, thereby overcoming the deficiencies of the prior art.
It has been surprisingly found that reacting of amide precursor of indoxacarb with methoxycarbonylation agent and métal sait of methylsulfinylmethylide in hydrocarbon solvent in the presence of organic base and phase transfer catalyst results in formation of higher indoxacarb yields and reproducibility avoiding the use of toxic and explosive solvent Systems.
SUMMARY OF THE INVENTION
The présent invention providesa process for préparation ofmdoxacarb represented as formula (II) which is racemic or enantiomerically enriched at chiral center which process comprises reacting of compound represented by the following formula (I) which is racemic or enantiomerically enriched at chiral center;
with methoxycarbonylation agent and métal sait of methylsulfinylmethylide in hydrocarbon solvent in the presence of organic base and phase transfer catalyst. In addition the invention provides the process of isolation of indoxacarb which is racemic or enantiomerically enriched at chiral center comprising recrystallization of crude semisolid reaction product using nheptane/toluene solvent mixture, n-heptane/ethyl acetatesolvent mixture and/or methyl cyclohexane/methanol solvent mixture.
DETAILED DESCRIPTION OF THE INVENTION:
Définitions:
Prior to setting forth the présent subject matter in detail, it may be helpful to provide définitions of certain terms to be used herein. Unless defined otherwise, ail technical and scientific terms used herein hâve the same meaning as is commonly understood by one of skill in the art to which this subject matter pertains.
The term “a” or “an” as used herein includes the singular and the plural, unless specifically stated otherwise. Therefore, the terms “a,” “an,” or “at least one” can be used interchangeably in this application.
Throughout the application, descriptions of various embodiments use the term “comprising”; however, it will be understood by one skilled in the art, that in some spécifie instances, an embodiment can altematively be described using the language “consisting essentially of” or “consisting of’.
For purposes of better understanding the présent teachings and in no way limiting the scope of the teachings, unless otherwise indicated, ail numbers expressing quantities, percentages, or proportions, and other numerical values used in the spécification and claims, are to be understood as being modified in ail instances by the term “about.”
Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following spécification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. In this regard, use of the term “about” herein specifically includes ±10% from the indicated values in the range. In addition, the endpoints of ail ranges directed to the same component or property herein are inclusive of the endpoints, are independently combinable, and include ail intermediate points and ranges.
Préparation ofMethyl 7-chloro-2,5-dihydro-2-[[(methoxycarbonyl)[4(trifluoromethoxy)phenyl]amino]carbonyl]-indeno[l,2-e][l,3,4]oxadiazine-4a(3H)-carboxylate (Indoxacarb):
The présent invention provides a process for préparation ofmdoxacarb represented as formula (II) which is racemic or enantiomerically enriched at chiral center
CHS
which process comprises reacting of compound represented by the following formula (I) which 15 is racemic or enantiomerically enriched at chiral center:
with methoxycarbonylation agent and métal sait of methylsulfmylmethylide in hydrocarbon solvent in the presence of organic base and phase transfer catalyst.
According to an embodiment, the methoxycarbonylation agent is selected from the group consisting of methyl chloroformate, dimethyl dicarbonate and the mixture thereof.
According to one aspect of the invention, the molar ratio of amide precursor of formula (I) to methoxycarbonylation agent is from about 1:1 to about 1:5.
According to an embodiment, the hydrocarbon solvent is selected from the group consisting of paraffinic solvents, aromatic solvents and the mixtures thereof.
According to preferred embodiment, the hydrocarbon solvent is selected from the group consisting of hexane, petroleum ether, toluene, chlorobenzene, xylene, mesitylene, and the mixtures thereof.
According to another embodiment, the process of préparation of compound represented as formula (II) may be carried out at a température of from about -5 to + 20°C; preferably, from about-5 to +5°C.
According to an embodiment of the invention, métal salts of methylsulfmylmethylide are selected from the group consisting of alkali metals salts and mixtures thereof; preferably from sodium methylsulfmylmethylide, potassium methylsulfmylmethylide and/or the mixtures thereof.
In another embodiment of the invention, the organic base is selected from the group consisting of secondary and/or tertiary amines and/or the mixture thereof.
In another preferred embodiment the organic base is selected from the group consisting of Nmethyl imidazole, 4-dimeÎhylaminopyridine, l,4-diazabicyclo[2.2.2]octane (DABCO), 1,8diazabicyclo[5.4.0]undec-7-ene (DBU) and/or the mixtures thereof.
According to an embodiment, the phase transfer catalyst is selected from the group consisting of tetra-butyl ammonium iodide, tetra-ethyl ammonium bromide, tetra-methyl ammonium bromide, tetra-propyl ammonium bromide, tetra-butyl ammonium bromide and/or the mixtures thereof.
In a preferred embodiment, the phase transfer catalyst is tetra-butyl ammonium bromide (TBAB).
According to an embodiment, the métal sait of methylsulfmylmethylide is prepared using métal hydride and dimethyl sulfoxide.
In an embodiment, the métal hydride is selected from the group consisting of sodium hydride, potassium hydride and/or the mixtures thereof.
In another embodiment, the reaction of préparation of métal sait of methylsulfïnylmethylide may be carried out at a température of from about -5 to + 20°C; preferably, of from about -5 to +5°C.
According to a preferred embodiment, indoxacarb is recrystallized from final crude semisolid product using n-heptane/toluene solvent mixture. Especially preferred ratio of nheptane/toluene solvent mixture is from about 10: 0.1 to about 10:1.
According to a preferred embodiment the molar ratio of amide precursor of formula (I) to methyl chloroformate is from about 1:2 to about 1: 3.3.
According to another preferred embodiment, the molar ratio of amide precursor of formula (I) to dimethyl dicarbonate is from about 1:2 to about 1:3.
In another embodiment, the molar ratio of amide precursor of formula (I) to the organic base is from about 1: 0.1 to about 1:1, preferably from about 1: 0.25 to 1:1.
According to an embodiment, the molar ratio of amide precursor of formula (I) to the phase transfer catalyst is from about 1: 0.1 to about 1:1, preferably from about 1: 0.25 to 1:1.
According to another embodiment, the molar ratio of amide precursor of formula (I) to the métal hydride is from about 1:1 to about 1:3; preferably from about 1:1.5 to about 1:2.
According to another embodiment, the molar ratio of amide precursor of formula (I) to dimethyl sulfoxide is from about 1:1 to about 1:3; preferably from about 1:1.3 to about 1: 1.7.
According to another preferred embodiment, indoxacarb is recrystallized from final crude semisolid product using n-heptane/toluene solvent mixture.
According to an embodiment, the n-heptane/toluene solvent mixture comprising from about 10: 0.1 to about 10:2 of n-heptane/toluene, preferably, from about 10: 0.1 to about 10:0.5, more preferably, from about 10: 0.1 to about 10:1.
According to another preferred embodiment, indoxacarb is recrystallized from final crude semisolid product using n-heptane/ethyl acetate solvent mixture. Preferred ratio of nheptane/ethyl acetate solvent mixture is from about 10: 0.1 to about 10:2, more preferably, from about 10: 0.1 to about 10:0.5, especially préférable, from about 10: 0.1 to about 10:1.
According to additional preferred embodiment, indoxacarb is recrystallized from final crude semisolid product using methyl cyclohexane/methanol solvent mixture. Especially preferred ratio of methyl cyclohexane/methanol solvent mixture is from about 10: 0.1 to about 10:2, more preferably, from about 10: 0.1 to about 10:0.5, especially préférable, from about 10: 0.1 to about 10:1.
According to another embodiment, the métal sait of methylsulfmylmethylide is prepared in-situ without isolation.
The progress of the reactions involved in the processes enclosed by the invention can be monitored using any suitable method, which can include, for example, chromatographie methods such as, e.g., high performance liquid chromatography (HPLC), thin layer chromatography (TLC), and the like.
In yet another embodiment, the compound of formula (II), can be isolated from the reaction mixture by any conventional techniques well-known in the art. Such isolation techniques can be selected, without limitation, from the group consisting of concentration, extraction, précipitation, cooling, filtration, crystallization, centrifugation, and a combination thereof, followed by drying.
According to an embodiment, the résultant compound of formula (II) is présent at a purity of at least 80%, at least 85%, at least 88%, at least 89%, at least 90%, at least 91%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98%, or at least 99%.
Without further élaboration, it is believed that one skilled in the art using the preceding description can utilize the présent invention to its fullest extent. The following examples are presented in order to illustrate certain embodiments of the invention. The following examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever.
EXAMPLE 1 (One-pot synthesis):
250.0 g (1.0 eq.) of methyl-7-chloro-2,5-dihydro-2-[[[(4 trifluoromethoxy)phenyl] amino] carbonyl] -indeno [ 1,2-e] [ 1,3,4] oxadiazine-4a(3 H) carboxylate having chiral ratio (88(S): 12(R)) was mixed with 2450 mL of toluene and with 55.0 g (1.32 eq.) of DMSO at -5°C to 0°C. Then 42.6 g (2.0 eq.) of NaH (60% in minerai oil) was charged and the resulting mixture was stirred for 30 minutes at -5°C to 0°C. Then 16.1 g (0.25 eq.) of DMAP and 43.5 g (0.25 eq) of tetra-bulyl ammonium bromide (TBAB) were added at -5°C to 0°C. Then 164.4 g (3.3 eq.) of methyl chloroformate in 125 mL toluene was added dropwise to the reaction mixture at -5°C to 0°C. The reaction was held for additional 30 minutes and then quenched with methanol and final semisolid was recrystallized from n-heptane/toluene (10/1 V/V) to get 92 % of indoxacarb with chiral ratio rétention of 99%.
EXAMPLE 2(One-pot synthesis):
250.0 (1.0 eq.) ofmethyl-7-chloro-2,5-dihydro-2-[[[(4- trifluoromethoxy) phenyl] amino] carbonyl]-indeno [l,2-e][ 1,3,4] oxadiazine-4a(3 H) carboxylate having chiral ratio (75(S): 25(R)) was mixed with 2450 mL of toluene and with 55.0 g (1.32 eq) of DMSO at -5°C to 0°C. Then 42.6 g (2.0 eq.) of NaH (60% in minerai oil) was charged and the resulting mixture was stirred for 30 minutes at -5°C to 0°C. Then 164.4 g (3.3 eq.) of methyl chloroformate in 125 mL toluene was added dropwise to the reaction mixture at -5°C to 0°C. The reaction was held for additional 30 minutes and then quenched with methanol and final semisolid was recrystallized from n-heptane/toluene (10/0.5 V/V) to get 92 % of Indoxacarb with chiral ratio rétention of 99%.
EXAMPLE 3 (two-pot synthesis):
250.0 g (1.0 eq.) Methyl-7-chloro-2,5-dihydro-2-[[[(4trifluoromethoxy)phenyl] amino] carbonyl] -indeno [ 1,2-e] [ 1,3,4] oxadiazine-4a(3 H) carboxylate having chiral ratio (88(S): 12(R)) and 1960 mL (7.8 Vol.) Toluene and 44.0 g (1.06 eq) DMSO were mixed in flask A. 11.0 ml of DMSO (0.14 eq) and 42.6 g (2.0 eq) ofNaH (60% in minerai oil) were mixed at -5°C to 0°C in flask B. The content of flaskA was addeddropwise to the content of flaskB at -5°C to +5°C and stirred for 30 minutes. Then 16.1 g (0.25 eq) of N,Ndimethylaminopyridineand 43.5 g (0.25 eq) of TBAB at -5 C to 0 C were added. After that, 164.4 g (3.3 eq) of methyl chloroformate in 125 mL (0.5 Vol.) of toluene were added dropwise to the reaction at -5°C to 0°C. After 30 minutes of stirring, the reaction was quenched with methanol at -5°C to +5°C and brought to 30°C. and concentrated to get semisolid. Then obtained semisolid was recrystallized from n-heptane/toluene (10/1 V/V) to get final99% of indoxacarbwith chiral ratio rétention of 99%.

Claims (28)

1. A process for préparation of Indoxacarb represented as formula (II) which is racemic or enantiomerically enriched at chiral center
which process comprises reacting of compound represented by the following formula (I) which is racemic or enantiomerically enriched at chiral center:
with the methoxycarbonylation agent and métal sait of methylsulfinylmethylide in hydrocarbon solvent in the presence of organic base and phase transfer catalyst.
15
2. The process according to claim 1, wherein the methoxycarbonylation agent is selected from the group consisting of methyl chloro formate, dimethyl dicarbonate and the mixture thereof.
3. The process according to claim 1, wherein the métal salts of methylsulfinylmethylide is selected from the group consisting of alkali metals salts and/or the mixtures thereof.
4. The process according to claim 3, wherein the métal sait of methylsulfinylmethylide is selected from sodium methylsulfinylmethylide, potassium methylsulfinylmethylide and/or the mixtures thereof.
5. The process according to claim 1, wherein the hydrocarbon solvent is selected fromthe group consisting of paraffinic solvents, aromatic solvents and the mixtures thereof.
6. The process according to claim 5, wherein the hydrocarbon solvent is selected from the group consisting of hexane, petroleum ether, toluene, chlorobenzene, xylene, mesitylene, and the mixtures thereof.
7. The process according to claim 1, wherein the organic base is selected from the group consisting of secondary and/or tertiary amines and/or the mixture thereof.
8. The process according to claim 7, wherein the organic base is selected from the group consisting ofN-methyl imidazole, 4-dimethylaminopyridine, l,4-diazabicyclo[2.2.2]octane (DABCO), l,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and/or the mixtures thereof.
9. The process according to claim 8, wherein the organic base is 4-dimethylaminopyridine.
10. The process according to claim 1, wherein the phase transfer catalyst is selected from the group consisting of tetra-butyl ammonium iodide, tetra-ethyl ammonium bromide, tetra-methyl ammonium bromide, tetra-propyl ammonium bromide, tetra-butyl ammonium bromide and/or the mixtures thereof.
11. The process according to claim 10, wherein the phase transfer catalyst is tetra-butyl ammonium bromide (TBAB).
12. The process according to claim 1, which comprises in-situ préparation ofthe métal sait of methylsulfinylmethylide.
13. The process according to claim 1, wherein the métal sait of methylsulfinylmethylide is prepared using métal hydride and dimethyl sulfoxide.
14. The process according to claim 13, wherein the métal hydride is selected from the group consisting of sodium hydride, potassium hydride and/or the mixtures thereof.
15. The process according to claim 1, wherein the reaction is carried out at a température of from about -5 to + 20°C.
16. The process according to claim 13, wherein the reaction is carried out at a température of from about -5 to + 20°C.
17. The process of isolation of indoxacarb which is racemic or enantiomerically enriched at chiral center comprising recrystallization of crude semisolid reaction product using nheptane/toluene solvent mixture.
18. The process according to claim 17, wherein the solvent mixture comprises from about 10: 0.1 to about 10:2 of n-heptane/toluene.
19. The process according to claim 18, wherein the solvent mixture comprises from 10: 0.1 to about 10:0.5 of n-heptane/toluene.
20. The process according to claim 18, wherein the solvent mixture comprises from 10: 0.1 to about 10:1 of n-heptane/toluene.
21. The process of isolation of indoxacarb which is racemic or enantiomerically enriched at chiral center comprising recrystallization of crude semisolid reaction product using nheptane/ethyl acetate solvent mixture.
22. The process according to claim 21, wherein the solvent mixture comprises from about 10: 0.1 to about 10:2 of n-heptane/ethyl acetate.
23. The process according to claim 21, wherein the solvent mixture comprises from 10: 0.1 to about 10:0.5 of n-heptane/ethyl acetate.
24. The process according to claim 21, wherein the solvent mixture comprises from 10: 0.1 to about 10:1 of n-heptane/ethyl acetate.
25. The process of isolation of indoxacarb which is racemic or enantiomerically enriched at chiral center comprising recrystallization of crude semisolid reaction product using methyl cyclohexane/methanol solvent mixture.
26. The process according to claim 21, wherein the solvent mixture comprises from about 10: 0.1 to about 10:2 of methyl cyclohexane/methanol.
27. The process according to claim 25, wherein the solvent mixture comprises from 10: 0.1 to about 10:0.5 of methyl cyclohexane/methanol.
28. The process according to claim 25, wherein the solvent mixture comprises from 10: 0.1 to about 10:1 of methyl cyclohexane/methanol.
OA1201900384 2017-03-29 2018-03-27 New catalytic system for scalable preparation of indoxacarb. OA19375A (en)

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