US 11,718,584 B2
Process for the synthesis anthranilic diamide compounds and intermediates thereof
Phaneendrasai Karri, Guntur-Andhra Pradesh (IN); Jagadish Pabba, Udaipur-Rajasthan (IN); Bharat Uttamrao Shinde, Dist-A.Nagar-Maharashtra (IN); Amol Dnyaneshwar Kalwaghe, Dist-A.Nagar-Maharashtra (IN); Kamble Maruti Madhavrao, Dist: Latur-Maharashtra (IN); Alexander G. M. Klausener, Pulheim (DE); and Deepak Shankar Panmand, Ahmednagar-Maharashtra (IN)
Assigned to PI INDUSTRIES LTD., Udaipur-Rajasthan (IN)
Appl. No. 17/310,712
Filed by PI INDUSTRIES LTD., Udaipur-Rajasthan (IN)
PCT Filed Feb. 20, 2020, PCT No. PCT/IB2020/051410
§ 371(c)(1), (2) Date Aug. 19, 2021,
PCT Pub. No. WO2020/170178, PCT Pub. Date Aug. 27, 2020.
Claims priority of application No. 201911007091 (IN), filed on Feb. 22, 2019.
Prior Publication US 2022/0185782 A1, Jun. 16, 2022
Int. Cl. C07D 231/10 (2006.01); C07C 227/18 (2006.01)
CPC C07D 231/10 (2013.01) [C07C 227/18 (2013.01)] 19 Claims
 
1. A process for the synthesis of a compound of formula (I),

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wherein,
R1 is C1-C4 alkyl or halogen;
R2 is hydrogen, halogen or cyano;
R3a and R3b are independently hydrogen, C1-C4 alkyl or C3-C6 cycloalkyl-C1-C4 alkyl;
R3c are independently hydrogen or C1-C4 alkyl;
R4 is halogen, CF3, OCF2H, OCH2CF3, or

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R5 is halogen;
R6 is hydrogen, halogen;
Z is CR7 or N; and
R7 is hydrogen or halogen,
comprising the steps of:
a) reacting a N-substituted anthranilic amide compound of formula (VI) with a pyrazole acid compound of formula (VII) to obtain the compound of formula (I),

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wherein, R8 is OH, Cl, or O—C1-C4 alkyl;
b) converting an anthranilic amide compound of formula (Va) into the N-substituted anthranilic amide compound of formula (VI) by either of the following steps:
i. in the presence of a suitable base or a suitable acid and a suitable alkylating reagent,
ii. by using suitable transamidation process,
according to the reaction scheme as depicted below:

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or
converting an anthranilic acid compound of formula (V) into the N-substituted anthranilic amide compound of formula (VI) using a suitable amine of formula HN(R3a)(R3b) and a suitable coupling agent according to the reaction scheme as depicted below:

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c) converting a mono- or dicyano substituted aniline compound of formula (IV) into the anthranilic acid compound of formula (V) or the anthranilic amide compound of formula (Va) optionally in the presence of a suitable base or a suitable acid according to the reaction scheme as depicted below:

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or
converting a mono- or dicyano substituted aniline compound of formula (IV) into the N-substituted anthranilic amide compound of formula (VI) by either of the following reaction steps:
i) in the presence of a suitable base or a suitable acid and a suitable alkylating reagent,
ii) aminolysis using a suitable amine of formula HN(R3a)(R3b) according to the reaction scheme as depicted below:

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d) optionally, halogenating a mono- or dicyano substituted aniline compound of formula (IV), wherein R1 and/or R2 are hydrogen in the presence of a suitable halogenating agent to obtain a mono- or dicyano substituted aniline compound of formula (IV), wherein R1 and/or R2 are halogen;
e) converting a mono-, di-, or tri-halogenated aniline compound of formula (III) wherein X is halogen, into the mono- or dicyano substituted aniline compound of formula (IV) using a suitable cyanation reagent according to the reaction scheme as depicted below:

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f) converting a substituted aniline compound of formula (II) into the mono-, di-, or tri-halogenated aniline compound of formula (III) wherein X is halogen, using a suitable halogenating agent, according to the reaction scheme as depicted below:

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