JP2016040231A - Plant circadian rhythm regulating agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a plant circadian rhythm regulating agent, and a more simple and convenient plant circadian rhythm regulating method.SOLUTION: A plant circadian rhythm regulating agent contains a heterocycle-containing compound represented by the general formula (1) or an agriculturally acceptable salt, hydrate or solvate thereof as an active ingredient.SELECTED DRAWING: None

Description

  The present invention relates to a plant circadian rhythm adjusting agent and a method of using the same.

  Plant circadian rhythm is a variety of plant activities such as flower formation (Non-Patent Documents 1 to 3), growth (Non-Patent Document 4), accumulation of primary metabolites (starch, sugar, etc.) (Non-Patent Document 5), Accumulation of secondary metabolites (such as anthocyanins) (Non-patent document 6), low-temperature stress response (Non-patent document 7), drought stress response (Non-patent document 7), expression of resistance to pathogenic bacteria (Non-patent document) 8), nitrogen metabolism (Non-patent document 9), iron metabolism (Non-patent document 10), opening and closing of pores (Non-patent document 11), leaf greening (Non-patent document 12), water absorption (Non-patent document 13) It is known to affect seed dormancy (Non-Patent Document 14), stem turning motion (Non-Patent Document 15), and the like. Therefore, it is expected that these activities can be adjusted by adjusting the circadian rhythm.

  As a method of adjusting the plant circadian rhythm, for example, a method of mutating a circadian clock-related gene or introducing an artificially designed circadian clock-related gene is known (Patent Document 1).

  However, these technologies require genetic recombination of plants, making it difficult to apply to plant species for which genetic recombination systems have not been established, and to some extent rejection reactions to genetically modified crops. Development of a method for adjusting the plant circadian rhythm without recombination is required.

International Publication No. 2011/049243

Current Opinion in Plant Biology 2010, 13: 594-603. TRENDS in Plant Science 2006, Vol.11 No.11 550-558. Mol Plant, May 2013; 6: 635-649. Nature, Vol 448 | 19 July 2007 358-363. The Plant Cell, Vol. 17, 3257-3281, December 2005. Science 290, 2110-2113 (2000). Plant Cell Physiol. 50 (3): 447-462 (2009). Nature Vol 470 3 February 2011 110-115. Current Opinion in Genetics & Development 2010, 20: 588-598. Plant Physiology, February 2013, Vol. 161, pp. 893-903. Development 125, 485-494 (1998). Biosci. Biotechnol. Biochem, 71 (3), 834-839, 2007. Plant Cell Physiol. 52 (2): 373-383 (2011). The Plant Cell, Vol. 21: 1722-1732, June 2009. Plant Cell Physiol. 46 (8): 1423-1427 (2005).

  It is an object of the present invention to provide a plant circadian rhythm adjusting agent and a simpler method for adjusting a plant circadian rhythm.

  As a result of intensive studies in view of the above problems, the present inventors have found that the above problems can be solved by using a heterocyclic-containing compound represented by the following general formula (1). The present invention has been completed as a result of further research based on this finding. That is, the present invention includes the following configurations.

  Item 1. General formula (1):

[Wherein, Q ¹ and Q ² are the same or different and each represents a heterocycle; X ¹ represents a single bond or a divalent group; Z represents a single bond or a double bond; X ² represents Z When is a single bond, it represents a single bond or a divalent group, and when Z is a double bond, it represents a trivalent group; R ^a and R ^b are the same or different and each represents a hydrogen atom, a lower alkyl group, A lower cycloalkyl group, a lower alkylthio group, a lower alkylcarboxyl group, a hydroxyl group, an oxo group, a carboxyl group, an amino group, or a nitrile group; ^Rc is the same or different and each represents a halogen atom or an optionally substituted lower group; An alkyl group, an optionally substituted lower alkoxy group, an optionally substituted lower heteroalkyl group, or an amide group; ma and mb are the same or different and each represents an integer of 0 or 1 to 5; And mc are the same or different and each represents 0 or an integer of 1 to 5; R ^d is a hydrogen atom or the general formula (2):

{Wherein X ³ represents a single bond or a divalent group; R ^e is the same or different and each represents a halogen atom, an optionally substituted lower alkyl group, an optionally substituted lower alkoxy group, or a substituted group. The lower heteroalkyl group which may be made, or an amino group is shown; me shows the integer of 0 or 1-3. }
P represents 0 or 1; q represents 0 or an integer of 1 to 3; However, if p is 0 and Q ¹ is the nitrogen-free, q is an integer of 1 to 3, X ² is a divalent group containing a nitrogen atom. ]
Or a plant circadian rhythm adjusting agent comprising an agriculturally acceptable salt, hydrate or solvate thereof as an active ingredient.

  Item 2. Compounds represented by general formula (1) are represented by general formulas (1-1) to (1-5):

[Wherein R ^{1-1 to} R ^1-4 are the same or different and each represents a hydrogen atom, a lower alkyl group, a lower cycloalkyl group, a lower alkylthio group, a lower alkyl carboxyl group, a hydroxyl group, an oxo group, a carboxyl group, an amino group. A group, a nitrile group, or a phenylalkyl group; R ^{1-5 to} R ^1-9 are the same or different and each is a hydrogen atom, a halogen atom, an optionally substituted lower alkyl group, or an optionally substituted group; A lower alkoxy group or an optionally substituted lower heteroalkyl group; R ^1-10 represents a lower alkyl group or a general formula (3):

{Wherein R ^{1-11 to} R ^1-15 are the same or different, and each represents a hydrogen atom, a halogen atom, an optionally substituted lower alkyl group, an optionally substituted lower alkoxy group, or a substituted group. Or a lower heteroalkyl group or an amide group. }
Y represents a nitrogen atom or a carbon atom; a dotted line and a solid line parallel thereto indicate a single bond when Y is a nitrogen atom, and a double bond when Y is a carbon atom. ]

[Wherein, R ^{2-1 to} R ^2-2 are the same or different and each represents a hydrogen atom, a lower alkyl group, a lower cycloalkyl group, a lower alkylthio group, a lower alkyl carboxyl group, a hydroxyl group, an oxo group, a carboxyl group, an amino group. R ^{2-3 to} R ^2-11 are the same or different and each represents a hydrogen atom, a halogen atom, an optionally substituted lower alkyl group, an optionally substituted lower alkoxy group, Or the lower heteroalkyl group which may be substituted is shown. ]

Wherein, R ^3-1 is a hydrogen atom, a lower alkyl group, lower cycloalkyl group, a lower alkylthio group, a lower alkyl carboxyl group, a hydroxyl group, an oxo group, a carboxyl group, an amino group, or a nitrile group; R ^{3- 2 to} R ^3-11 are the same or different and are each a hydrogen atom, a halogen atom, an optionally substituted lower alkyl group, an optionally substituted lower alkoxy group, or an optionally substituted lower heteroalkyl group. Indicates. ]

Wherein, R ^4-1 is a hydrogen atom, a lower alkyl group, lower cycloalkyl group, a lower alkylthio group, a lower alkyl carboxyl group, a hydroxyl group, an oxo group, a carboxyl group, an amino group, or a nitrile group; R ^{4- 2 to} R ^4-6 are the same or different and are each a hydrogen atom, a halogen atom, an optionally substituted lower alkyl group, an optionally substituted lower alkoxy group, or an optionally substituted lower heteroalkyl group. Indicates. ]

[Wherein, R ^{5-1 to} R ^5-10 are the same or different and each represents a hydrogen atom, a lower alkyl group, a lower cycloalkyl group, a lower alkylthio group, a lower alkyl carboxyl group, a hydroxyl group, an oxo group, a carboxyl group, an amino group. Group or nitrile group. ]
Item 2. The plant circadian rhythm modifier according to Item 1, which is a compound represented by any one of:

  Item 3. Item 3. The plant circadian rhythm modifier according to Item 2, wherein the compound represented by the general formula (1) is a compound represented by the general formula (1-1).

Item 4. Item 4. The plant circadian rhythm modifier according to Item 3, wherein R ^{1-5 to} R ^1-9 are the same or different and each is a hydrogen atom or a halogen atom.

Item 5. Item 5. The plant circadian rhythm modifier according to Item 3 or 4, wherein at least one of R ^{1-5 to} R ^1-9 is a halogen atom.

Item 6. Item 6. The plant circadian rhythm modifier according to any one of Items 3 to 5, wherein R ^1-10 is a group represented by General Formula (3).

Item 7. Item 7. The plant circadian rhythm modifier according to Item 6, wherein R ^{1-11 to} R ^1-15 are the same or different and each is a hydrogen atom or a halogen atom.

  Item 8. Item 8. The plant circadian rhythm modifier according to any one of Items 3 to 7, wherein Y is a nitrogen atom.

Item 9. Item 9. The plant circadian rhythm modifier according to any one of Items 3 to 8, wherein R ^{1-1 to} R ^1-4 are the same or different and each is a hydrogen atom or an oxo group.

  Item 10. Item 3. The plant circadian rhythm regulator according to Item 2, wherein the compound represented by the general formula (1) is a compound represented by the general formula (1-2).

Item 11. Item 11. The plant circadian rhythm modifier according to Item 10, wherein R ^{2-3 to} R ^2-11 are the same or different and each is a hydrogen atom or a halogen atom.

Item 12. At least one or more of R ^2-3 to R ^2-7 is a halogen atom, plant circadian rhythm regulator according to claim 10 or 11.

Item 13. R ^2-1 is a carboxyl group or a lower alkyl carboxyl group, a plant circadian rhythm regulator according to any one of Items 10 to 12.

Item 14. R ^2-2 is a lower alkyl group, a plant circadian rhythm regulator according to any one of Items 10 to 13.

  Item 15. Item 15. A method for adjusting a plant circadian rhythm, wherein the plant circadian rhythm adjusting agent according to any one of items 1 to 14 is applied to a plant or a soil in which the plant grows.

  ADVANTAGE OF THE INVENTION According to this invention, the simple plant circadian rhythm adjustment method which does not require a gene recombination technique, and the plant circadian rhythm regulator used for it can be provided. In addition, according to the present invention, adjustment of plant activity affected by circadian rhythm, for example, flowering time adjustment, growth adjustment, primary metabolite (starch, sugar, etc.) accumulation adjustment, secondary metabolite (anthocyanin etc.) accumulation adjustment Adjustment of low temperature stress response, adjustment of drought stress response, adjustment of resistance to pathogenic bacteria, adjustment of nitrogen metabolism, adjustment of iron metabolism, adjustment of stomatal opening and closing, adjustment of leaf greening, adjustment of water absorption, It is possible to adjust the dormancy of seeds and the swivel movement of stems.

The plant circadian rhythm adjustment action of the typical compounds (1a, 1h, 1j, 1u, 1v, and 1x) is shown (Example 8).

1. Definitions of Terms In the foregoing and following description of this specification, suitable examples of various definitions that fall within the scope of the present invention are described below.

  Although it does not restrict | limit especially as a heterocyclic ring, A monocyclic, bicyclic, or tricyclic is preferable, and monocyclic (especially 5 or 6 membered ring) or bicyclic (especially 5 membered ring and 6 membered ring) Fused ring) is more preferred, and bicyclic (particularly 5- and 6-membered fused rings) is even more preferred. As the hetero atom contained in the heterocyclic ring, one or more of a nitrogen atom, a sulfur atom and an oxygen atom are preferable, and a nitrogen atom is more preferable. Specifically, pyrazolopyrimidine (especially pyrazolo [3,4-d] pyrimidine), triazole (especially 1,2,3-triazole), isoxazole, thiadiazole (especially 1,3,4-thiazole), pyrrolopyrimidine (Especially pyrrolo [3,2-c] pyrimidine), pyridine, pyrazole, oxadiazole (especially 1,2,4-oxadiazole), furan, triazine (especially 1,2,4-triazine), pyrimidine, Thienopyrimidine (especially thieno [2,3-d] pyrimidine), piperazine, thiophene, thiochromenopyridine (especially thiochromeno [4,3-b] pyridine, benzo [d] imidazo [2,1-b] thiazole), etc. Pyrazolopyrimidine (especially pyrazolo [3,4-d] pyrimidine), triazole (especially 1,2,3-triazole), isoxazole, thiadiazole (especially 1,3,4-thiazole), pyrrolopyrimidine (Particularly pyrrolo [3,2-c] pyrimidine), pyridine, pyrazole and the like, more preferably pyrazolopyrimidine (particularly pyrazolo [3,4-d] pyrimidine), triazole (particularly 1,2,3- Triazole) and the like, and more preferably pyrazolopyrimidine (particularly pyrazolo [3,4-d] pyrimidine).

  Although it does not restrict | limit especially as a bivalent group, Preferably the number of atoms of a main chain is 1-5, More preferably, it is 1-3, More preferably, the bivalent group which is 1 or 2 is mentioned. As the atoms constituting the main chain, a nitrogen atom, a sulfur atom, an oxygen atom, a carbon atom or the like is preferable, and a nitrogen atom, a sulfur atom, an oxygen atom or the like is more preferable. The divalent group may be substituted, and the substituent is preferably an oxo group, a lower alkyl group, a nitrile group or the like. Specifically, the following groups:

Etc.

  Although it does not restrict | limit especially as a trivalent group, Preferably the number of atoms of a main chain is 1-3, More preferably, the trivalent group which is 1 or 2 is mentioned. As the atoms constituting the main chain, a carbon atom, a nitrogen atom, a sulfur atom, an oxygen atom and the like are preferable, and a carbon atom is more preferable. Specifically, the following groups:

Etc.

  Although it does not restrict | limit especially as a lower alkyl group, For example, a C1-C6 linear or branched C1-C4 alkyl group, More preferably, a C1-C2 alkyl group is mentioned. Specific examples of such a lower alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group.

  The lower cycloalkyl group is not particularly limited, and examples thereof include a cycloalkyl group having 3 to 6 carbon atoms, preferably 3 to 5 carbon atoms, and more preferably 3 or 4 carbon atoms. Specific examples of such lower cycloalkyl groups include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

  The lower alkylthio group is not particularly limited, and examples thereof include linear or branched alkylthio groups having 1 to 6, preferably 1 to 4, and more preferably 1 or 2 carbon atoms. Specific examples of such a lower alkylthio group include a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, an isobutylthio group, a sec-butylthio group, and a t-butylthio group. .

  Although it does not restrict | limit especially as a lower alkyl carboxyl group, For example, a linear or branched C1-C6, Preferably it is C1-C4, More preferably, it is C1-C2 alkylcarboxyl group. . Specific examples of such lower alkyl carboxyl groups include methyl carboxyl group, ethyl carboxyl group, n-propyl carboxyl group, isopropyl carboxyl group, n-butyl carboxyl group, isobutyl carboxyl group, sec-butyl carboxyl group, t- A butyl carboxyl group etc. are mentioned.

  Although it does not restrict | limit especially as a halogen atom, Preferably a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., More preferably, a chlorine atom, a bromine atom, etc., More preferably, a chlorine atom is mentioned.

  The lower alkyl group which may be substituted is not particularly limited. For example, the lower alkyl group may be substituted with an oxo group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom) or the like (preferably a halogen atom). Examples thereof may include linear or branched alkyl groups having 1 to 6, preferably 1 to 4 carbon atoms. There is no restriction | limiting in particular in the number of substituents, 0-6 pieces are preferable and 0-3 are more preferable. Specific examples of the optionally substituted lower alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. And a methyl fluoride group.

  The lower alkoxy group which may be substituted is not particularly limited. For example, the lower alkoxy group may be substituted with an oxo group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom) or the like (preferably a halogen atom). Examples thereof may include linear or branched alkyl groups having 1 to 6, preferably 1 to 4 carbon atoms. There is no restriction | limiting in particular in the number of substituents, 0-6 pieces are preferable and 0-3 are more preferable. Specific examples of the optionally substituted lower alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. And a methyl fluoride group.

  The lower heteroalkyl group which may be substituted is not particularly limited, but for example, an oxo group, a straight chain which may be substituted with a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.) or Examples include branched heteroalkyl groups having 1 to 6 atoms in the main chain. There is no restriction | limiting in particular in the number of substituents, 0-4 pieces are preferable and 0-2 are more preferable. Specific examples of the optionally substituted lower heteroalkyl group include the following groups:

Etc.

  The phenylalkyl group is not particularly limited, and examples thereof include a phenylalkyl group having 7 to 9 carbon atoms, preferably 7 or 8 carbon atoms, and more preferably 7 carbon atoms. Specific examples of such a phenylalkyl group include a benzyl group and a phenylethyl group.

2. Plant circadian rhythm modifier The plant circadian rhythm modifier of the present invention is:
General formula (1):

[Wherein, Q ¹ and Q ² are the same or different and each represents a heterocycle; X ¹ represents a single bond or a divalent group; Z represents a single bond or a double bond; X ² represents Z When is a single bond, it represents a single bond or a divalent group, and when Z is a double bond, it represents a trivalent group; R ^a and R ^b are the same or different and each represents a hydrogen atom, a lower alkyl group, A lower cycloalkyl group, a lower alkylthio group, a lower alkylcarboxyl group, a hydroxyl group, an oxo group, a carboxyl group, an amino group, or a nitrile group; ^Rc is the same or different and each represents a halogen atom or an optionally substituted lower group; An alkyl group, an optionally substituted lower alkoxy group, an optionally substituted lower heteroalkyl group, or an amide group; ma and mb are the same or different and each represents an integer of 0 or 1 to 5; mc are the same or different and each represents 0 or an integer of 1 to 5; R ^d is a hydrogen atom or general formula (2):

{Wherein X ³ represents a single bond or a divalent group; R ^e is the same or different and each represents a halogen atom, an optionally substituted lower alkyl group, an optionally substituted lower alkoxy group, or An optionally substituted lower heteroalkyl group or an amino group; me represents an integer of 0 or 1 to 3; }
P represents 0 or 1; q represents 0 or an integer of 1 to 3; However, if p is 0 and Q ¹ is the nitrogen-free, q is an integer of 1 to 3, X ² is a divalent group containing a nitrogen atom. ]
Or an agriculturally acceptable salt, hydrate or solvate thereof as an active ingredient.

  The agriculturally acceptable salt is not particularly limited, and either an acidic salt or a basic salt can be employed. Examples of acid salts include inorganic acid salts such as hydrochloride, hydrobromide, sulfate, nitrate, and phosphate, acetate, propionate, tartrate, fumarate, maleate, apple And acid salts, citrates, methanesulfonates, paratoluenesulfonates, and the like. Examples of the basic salt include alkali metal salts such as sodium and potassium, and alkaline earth metal salts such as calcium salt and magnesium salt.

  The solvate is not particularly limited as long as it is a solvate of the compound represented by the general formula (1) or a salt thereof and an agriculturally acceptable solvent. Examples of the agriculturally acceptable solvent include ethanol, glycerol, acetic acid and the like.

  Preferred embodiments of the compound represented by the general formula (1) are as follows.

X ¹ is preferably a single bond.

  Z is preferably a single bond.

X ² is preferably a single bond.

R ^a or R ^b is preferably hydrogen, a lower alkyl group, a lower cycloalkyl group, an oxo group, or a carboxyl group.

R ^c or R ^e is preferably a halogen atom, a lower alkyl group, a lower alkyl group substituted with a halogen atom, a lower alkoxy group, or a lower alkoxy group substituted with a halogen atom.

  As ma or mb, an integer of 0 or 1 to 3 is preferable.

  As mc, 0 or an integer of 1-3 is preferably mentioned, More preferably, an integer of 1-3 is mentioned, More preferably, 2 is mentioned.

R ^d is preferably a hydrogen atom. In addition, when q is 1, R ^d is preferably a group represented by the general formula (2).

X ³ is preferably a divalent group, more preferably an oxo group.

  As me, an integer of 1 to 3 is more preferable, and 2 is more preferable.

  p is preferably 0.

  As q, Preferably the integer of 0 or 1-2 is mentioned, More preferably, the integer of 1-2 is mentioned, More preferably, 2 is mentioned.

  Preferred examples of the compound represented by the general formula (1) include compounds represented by the general formulas (1-1) to (1-15).

[Wherein R ^{1-1 to} R ^1-4 are the same or different and each represents a hydrogen atom, a lower alkyl group, a lower cycloalkyl group, a lower alkylthio group, a lower alkyl carboxyl group, a hydroxyl group, an oxo group, a carboxyl group, an amino group. A group, a nitrile group, or a phenylalkyl group; R ^{1-5 to} R ^1-9 are the same or different and each is a hydrogen atom, a halogen atom, an optionally substituted lower alkyl group, or an optionally substituted group; A lower alkoxy group or an optionally substituted lower heteroalkyl group; R ^1-10 represents a lower alkyl group or a general formula (3):

{Wherein R ^{1-11 to} R ^1-15 are the same or different, and each represents a hydrogen atom, a halogen atom, an optionally substituted lower alkyl group, an optionally substituted lower alkoxy group, or a substituted group. Or a lower heteroalkyl group or an amide group. }
Y represents a nitrogen atom or a carbon atom; a dotted line and a solid line parallel thereto indicate a single bond when Y is a nitrogen atom, and a double bond when Y is a carbon atom. ]

[Wherein, R ^{2-1 to} R ^2-2 are the same or different and each represents a hydrogen atom, a lower alkyl group, a lower cycloalkyl group, a lower alkylthio group, a lower alkyl carboxyl group, a hydroxyl group, an oxo group, a carboxyl group, an amino group. R ^{2-3 to} R ^2-11 are the same or different and each represents a hydrogen atom, a halogen atom, an optionally substituted lower alkyl group, an optionally substituted lower alkoxy group, Or the lower heteroalkyl group which may be substituted is shown. ]

Wherein, R ^3-1 is a hydrogen atom, a lower alkyl group, lower cycloalkyl group, a lower alkylthio group, a lower alkyl carboxyl group, a hydroxyl group, an oxo group, a carboxyl group, an amino group, or a nitrile group; R ^{3- 2 to} R ^3-11 are the same or different and are each a hydrogen atom, a halogen atom, an optionally substituted lower alkyl group, an optionally substituted lower alkoxy group, or an optionally substituted lower heteroalkyl group. Indicates. ]

Wherein, R ^4-1 is a hydrogen atom, a lower alkyl group, lower cycloalkyl group, a lower alkylthio group, a lower alkyl carboxyl group, a hydroxyl group, an oxo group, a carboxyl group, an amino group, or a nitrile group; R ^{4- 2 to} R ^4-6 are the same or different and are each a hydrogen atom, a halogen atom, an optionally substituted lower alkyl group, an optionally substituted lower alkoxy group, or an optionally substituted lower heteroalkyl group. Indicates. ]

[Wherein, R ^{5-1 to} R ^5-10 are the same or different and each represents a hydrogen atom, a lower alkyl group, a lower cycloalkyl group, a lower alkylthio group, a lower alkyl carboxyl group, a hydroxyl group, an oxo group, a carboxyl group, an amino group. Group or nitrile group. ]

[Wherein R ^{6-1 to} R ^6-3 are the same or different and each represents a hydrogen atom, a lower alkyl group, a lower cycloalkyl group, a lower alkylthio group, a lower alkyl carboxyl group, a hydroxyl group, an oxo group, a carboxyl group, an amino group. R ^{6-4 to} R ^6-8 are the same or different and each represents a hydrogen atom, a halogen atom, an optionally substituted lower alkyl group, an optionally substituted lower alkoxy group, Or the lower heteroalkyl group which may be substituted is shown. ]

[Wherein R ^{7-1 to} R ^7-3 are the same or different and each represents a hydrogen atom, a lower alkyl group, a lower cycloalkyl group, a lower alkylthio group, a lower alkyl carboxyl group, a hydroxyl group, an oxo group, a carboxyl group, an amino group. R ^{7-4 to} R ^7-18 are the same or different and each represents a hydrogen atom, a halogen atom, an optionally substituted lower alkyl group, an optionally substituted lower alkoxy group, Or the lower heteroalkyl group which may be substituted is shown. ]

[Wherein R ^{8-1 to} R ^8-3 are the same or different and are each a hydrogen atom, a lower alkyl group, a lower cycloalkyl group, a lower alkylthio group, a lower alkyl carboxyl group, a hydroxyl group, an oxo group, a carboxyl group, an amino group. R ^{8-4 to} R ^8-8 are the same or different and each represents a hydrogen atom, a halogen atom, an optionally substituted lower alkyl group, an optionally substituted lower alkoxy group, Or the lower heteroalkyl group which may be substituted is shown. ]

[Wherein, R ^{9-1 to} R ^9-6 are the same or different and each represents a hydrogen atom, a lower alkyl group, a lower cycloalkyl group, a lower alkylthio group, a lower alkyl carboxyl group, a hydroxyl group, an oxo group, a carboxyl group, an amino group. Group or nitrile group. ]

[Wherein, R ^{10-1 to} R ^10-3 are the same or different and each represents a hydrogen atom, a lower alkyl group, a lower cycloalkyl group, a lower alkylthio group, a lower alkyl carboxyl group, a hydroxyl group, an oxo group, a carboxyl group, an amino group. R ^{10-4 to} R ^10-8 are the same or different and each represents a hydrogen atom, a halogen atom, an optionally substituted lower alkyl group, an optionally substituted lower alkoxy group, Or the lower heteroalkyl group which may be substituted is shown. ]

[Wherein R ^{11-1 to} R ^11-4 are the same or different and each represents a hydrogen atom, a lower alkyl group, a lower cycloalkyl group, a lower alkylthio group, a lower alkyl carboxyl group, a hydroxyl group, an oxo group, a carboxyl group, an amino group. R ^{11-5 to} R ^11-14 are the same or different and each represents a hydrogen atom, a halogen atom, an optionally substituted lower alkyl group, an optionally substituted lower alkoxy group, Or the lower heteroalkyl group which may be substituted is shown. ]

[Wherein R ^{12-1 to} R ^12-7 are the same or different and each represents a hydrogen atom, a lower alkyl group, a lower cycloalkyl group, a lower alkylthio group, a lower alkylcarboxyl group, a hydroxyl group, an oxo group, a carboxyl group, an amino group. R ^{12-8 to} R ^12-12 are the same or different and each represents a hydrogen atom, a halogen atom, an optionally substituted lower alkyl group, an optionally substituted lower alkoxy group, Or the lower heteroalkyl group which may be substituted is shown. ]

[Wherein, R ^{13-1 to} R ^13-7 are the same or different and each represents a hydrogen atom, a lower alkyl group, a lower cycloalkyl group, a lower alkylthio group, a lower alkyl carboxyl group, a hydroxyl group, an oxo group, a carboxyl group, an amino group. Group or nitrile group. ]

[Wherein, R ^{14-1 to} R ^14-12 are the same or different and each represents a hydrogen atom, a lower alkyl group, a lower cycloalkyl group, a lower alkylthio group, a lower alkyl carboxyl group, a hydroxyl group, an oxo group, a carboxyl group, an amino group. Group or nitrile group. ]

[Wherein, R ^{15-1 to} R ^15-6 are the same or different and each represents a hydrogen atom, a lower alkyl group, a lower cycloalkyl group, a lower alkylthio group, a lower alkyl carboxyl group, a hydroxyl group, an oxo group, a carboxyl group, an amino group. Group or nitrile group. ]
Preferred embodiments of the compound represented by the general formula (1-1) are as follows.

R ^{1-1 to} R ^1-4 are preferably a hydrogen atom, a lower alkyl group, a phenylalkyl group, an oxo group, and more preferably a hydrogen atom, an oxo group, and the like. In a more preferred embodiment, R ^1-1 and R ^1-4 are oxo groups, R ^1-3 is a hydrogen atom, R ^1-2 is a hydrogen atom, a lower alkyl group, a phenylalkyl group, etc. (especially hydrogen Atom) is an example.

R ^{1-5 to} R ^1-9 are preferably a hydrogen atom, a halogen atom, a lower alkyl group (carbon number is preferably 1 to 2, more preferably 1), or a lower alkyl group substituted with a halogen atom (carbon The number is preferably 1 to 2, more preferably 1), a lower alkoxy group (the carbon number is preferably 1 to 2, more preferably 1), a lower alkoxy group substituted with a halogen atom (the carbon number is preferably 1 to 1). 2, more preferably 1), more preferably a hydrogen atom, a halogen atom, a lower alkyl group, or a lower alkyl group substituted with a halogen atom. More preferable embodiments include an embodiment in which at least one of R ^{1-5 to} R ^1-9 (preferably 1 to 3) is the above group other than a hydrogen atom, and the other is a hydrogen atom.

R ^1-10 is preferably a group represented by the general formula (3).

R ^{1-11 to} R ^1-15 preferably include a hydrogen atom and a halogen atom, and more preferably a hydrogen atom.

  Y is preferably a nitrogen atom.

  Specific examples of the compound represented by the general formula (1-1) include compound 1 (1a), 1b to 1z, 1aa to 1hh and the like described in Examples described later. Among these, from the viewpoint of higher activity to prolong the plant circadian rhythm, compounds 1a, 1m, 1n, 1o, 1p, 1q, 1s, 1t, 1u, 1v, 1w, 1x, 1z, 1cc Is preferred, compounds 1a, 1m, 1p, 1s, 1t, 1u, 1v, 1w, 1x, 1z, 1cc are more preferred, compounds 1a, 1u, 1v, 1x, 1z are more preferred, and compounds 1a, 1u are more preferred Further preferred. Further, from the viewpoint of higher activity of shortening the plant circadian rhythm, compounds 1c, 1d, 1h, 1i, 1j, 1k are preferred, compounds 1h, 1j are more preferred, and compound 1j is even more preferred. .

  Preferred embodiments of the compound represented by the general formula (1-2) are as follows.

R ^{2-1 to} R ^2-2 preferably include a hydrogen atom, a lower alkyl group, a carboxyl group, a lower alkyl carboxyl group, and the like. As a more preferred embodiment, an embodiment in which R ^2-1 is a carboxyl group or a lower alkyl carboxyl group (even more preferably, an embodiment in which R ^2-2 is a hydrogen atom or a lower alkyl group (particularly a lower alkyl group)). Can be mentioned.

R ^{2-3 to} R ^2-11 are preferably a hydrogen atom, a halogen atom, or the like. A more preferable embodiment includes an embodiment in which 1 to 3 (particularly 2) of R ^{2-3 to} R ^2-7 are halogen atoms, and the others are hydrogen atoms.

  Specific examples of the compound represented by the general formula (1-2) include compound 2 and compounds 2d1 to 2d3 described in Examples described later. Among these, the compound 2 and the compound 2d3 are preferable, and the compound 2d3 is more preferable from the viewpoint that the activity of shortening the plant circadian rhythm is higher.

  Preferred embodiments of the compound represented by the general formula (1-3) are as follows.

As R ^<3-1> , Preferably a hydrogen atom is mentioned.

R ^{3-2 to} R ^3-11 are preferably a hydrogen atom, a halogen atom, or an optionally substituted lower heteroalkyl group. In a more preferred embodiment, in the group of R ^{3-2 to} R ^3-6 or the group of R ^{3-2 to} R ^3-11 , in one group, 1 to 3 (particularly 2) are halogen atoms and Is a hydrogen atom, and in the other group, all are hydrogen atoms, or 1 or 2 (especially 1) may be substituted lower heteroalkyl groups, and the others are hydrogen atoms An embodiment is mentioned. In this more preferred embodiment, the position of the ^optionally substituted lower heteroalkyl group is preferably R ^3-5 or R ^3-8 .

  Specific examples of the compound represented by the general formula (1-3) include the compound 3 described in Examples described later.

  Preferred embodiments of the compound represented by formula (1-4) are as follows.

^R4-1 preferably includes a hydrogen atom, a lower alkyl group, a lower cycloalkyl group, and more preferably a lower cycloalkyl group.

R ^{4-2 to} R ^4-6 are preferably a hydrogen atom, a halogen atom or the like.

  Specific examples of the compound represented by the general formula (1-4) include the compound 4 described in Examples described later.

  Preferred embodiments of the compound represented by the general formula (1-5) are as follows.

As R ^<5-1 > -R <^5-10> , a hydrogen atom, an oxo group, etc. are mentioned preferably. More preferable embodiments include an embodiment in which R ^5-2 , R ^5-3 , R ^5-5 , or R ^5-6 (particularly R ^5-5 ) is an oxo group, and the other is a hydrogen atom. .

  Specific examples of the compound represented by the general formula (1-5) include compound 5 described in Examples described later.

  Preferred embodiments of the compound represented by the general formula (1-6) are as follows.

R ^{6-1 to} R ^6-3 are preferably a hydrogen atom, a lower alkylthio group, an amino group, a nitrile group, and more preferably a lower alkylthio group, an amino group, a nitrile group, and the like.

R ^{6-4 to} R ^6-8 preferably include a hydrogen atom, a halogen atom, an optionally substituted lower alkyl group (particularly a lower alkyl group substituted with a halogen atom), and the like. A more preferable embodiment includes an embodiment in which 1 to 3 of R ^{6-4 to} R ^6-8 are a halogen atom or an optionally substituted lower alkyl group, and the others are hydrogen atoms.

  Specific examples of the compound represented by the general formula (1-6) include compound 6 described in Examples described later.

  Preferred embodiments of the compound represented by the general formula (1-7) are as follows.

As R ^<7-1 > -R <^7-3> , Preferably a hydrogen atom, a lower alkyl group, a hydroxyl group, an oxo group, etc. are mentioned, More preferably, a lower alkyl group, a hydroxyl group, an oxo group, etc. are mentioned.

R ^{7-4 to} R ^7-18 preferably include a hydrogen atom, a halogen atom, and the like.

  Specific examples of the compound represented by the general formula (1-7) include compound 7 described in Examples described later.

  Preferred embodiments of the compound represented by the general formula (1-8) are as follows.

As R ^<8-1 > -R <^8-3> , Preferably a hydrogen atom is mentioned.

R ^{8-4 to} R ^8-8 are preferably a hydrogen atom, a halogen atom or the like. As a more preferable aspect, the aspect whose 1-3 among R ^{< 8-4} > -R ^{< 8-8} > is a halogen atom and the other is a hydrogen atom is mentioned.

  Specific examples of the compound represented by the general formula (1-8) include compound 8 described in Examples described later.

  Preferred embodiments of the compound represented by the general formula (1-9) are as follows.

R ^{9-1 to} R ^9-6 are preferably a hydrogen atom, a lower alkyl group, a hydroxyl group and the like. As a more preferable embodiment, an embodiment in which R ^9-5 and / or R ^9-6 is a lower alkyl group, a hydroxyl group or the like, and the other is a hydrogen atom can be mentioned.

  Specific examples of the compound represented by the general formula (1-9) include compound 9 described in Examples described later.

  Preferred embodiments of the compound represented by the general formula (1-10) are as follows.

As R ^<10-1 > -R <^10-3> , Preferably a hydrogen atom is mentioned.

R ^{10-4 to} R ^10-8 preferably include a hydrogen atom, a halogen atom, an optionally substituted lower alkyl group, and the like. A more preferable embodiment includes an embodiment in which 1 to 3 (particularly 1) of R ^{10-4 to} R ^10-8 are optionally substituted lower alkyl groups, and the others are hydrogen.

  Specific examples of the compound represented by the general formula (1-10) include the compound 10 described in Examples described later.

  Preferred embodiments of the compound represented by the general formula (1-11) are as follows.

R ^{11-1 to} R ^11-4 are preferably a hydrogen atom, an oxo group, or the like. A more preferred embodiment includes an embodiment in which R ^11-2 is hydrogen and the others are oxo groups.

R ^{11-5 to} R ^11-14 preferably include a hydrogen atom, a halogen atom, an optionally substituted lower heteroalkyl group, and the like. As a more preferred ^embodiment, the group or groups ^R 11-5 ^{to R 11-9} of R ^{11-5 to R 11-9,} 1 to 3 one in one group but a halogen atom and the other represents a hydrogen atom In the other group, there are embodiments in which all are hydrogen atoms, or 1 or 2 (especially 1) are optionally substituted lower heteroalkyl groups and the others are hydrogen atoms. . In this more preferred embodiment, the position of the ^optionally substituted lower heteroalkyl group is preferably R ^11-7 or R ^11-12 .

  Specific examples of the compound represented by the general formula (1-11) include compound 11 described in Examples described later.

  Preferred embodiments of the compound represented by the general formula (1-12) are as follows.

R ^{12-1 to} R ^12-7 are preferably a hydrogen atom.

R ^{12-8 to} R ^12-12 preferably include a hydrogen atom, a halogen atom, an optionally substituted lower alkyl group, and the like. As a more preferable embodiment, an embodiment in which 1 to 3 (particularly 1) of R ^{12-8 to} R ^12-12 is a lower alkyl group which may be substituted, and the other is a hydrogen atom. .

  Specific examples of the compound represented by the general formula (1-12) include the compound 12 described in Examples below.

  Preferred embodiments of the compound represented by the general formula (1-13) are as follows.

R ^{13-1 to} R ^13-7 are preferably a hydrogen atom.

  Specific examples of the compound represented by the general formula (1-13) include compound 13 described in Examples described later.

  Preferred embodiments of the compound represented by the general formula (1-14) are as follows.

R ^{14-1 to} R ^14-12 preferably include a hydrogen atom, an oxo group, a nitrile group, and the like. More preferable embodiments include embodiments in which 1 to 3 (especially 2) of R ^{14-5 to} R ^14-12 are oxo groups, nitrile groups, and the like, and the other is a hydrogen atom, and more preferable embodiments. As an example, R ^14-5 and R ^14-6 are an oxo group, a nitrile group, and the like, and the others are hydrogen atoms.

  Specific examples of the compound represented by the general formula (1-14) include compound 14 described in Examples described later.

  Preferred embodiments of the compound represented by the general formula (1-15) are as follows.

R ^{15-1 to} R ^15-6 are preferably a hydrogen atom, an amino group, or the like. As a more preferable aspect, the aspect whose 1-3 (especially 2) of R ^{< 15-1>} -R ^<14-6> is an amino group etc., and other than that is a hydrogen atom is mentioned.

  Specific examples of the compound represented by the general formula (1-15) include compound 15 described in Examples described later.

  Among the compounds represented by the general formulas (1-1) to (1-15), from the viewpoint that the plant circadian rhythm adjusting action is higher, the general formulas (1-1) to (1-5) are preferable. The compound shown, More preferably, the compound shown by general formula (1-1) or (1-2), More preferably, the compound shown by general formula (1-1) is mentioned. In addition, from the viewpoint that the activity of prolonging the plant circadian rhythm is higher, the compounds represented by the general formula (1-1) or (1-3) to (1-5) are preferable. From the viewpoint that the activity of shortening the circadian rhythm is higher, a compound represented by the general formula (1-1) or (1-2) is preferable.

For the compound represented by the general formula (1-1), by adjusting the substitution position of the hydrogen atom and the halogen atom in R ^{1-5 to} R ^1-9, the activity of making the cycle longer and the activity of making the cycle shorter Any activity can be exhibited highly. For example, from the viewpoint of higher activity to prolong the plant circadian rhythm, compounds 1a, 1m, 1n, 1o, 1p, 1q, 1s, 1t, 1u, 1v, 1w, 1x, 1z, 1cc are preferred. , Compounds 1a, 1m, 1p, 1s, 1t, 1u, 1v, 1w, 1x, 1z, 1cc are more preferable, compounds 1a, 1u, 1v, 1x, 1z are more preferable, and compounds 1a, 1u are still more preferable . Further, from the viewpoint of higher activity of shortening the plant circadian rhythm, compounds 1c, 1d, 1h, 1i, 1j, 1k are preferred, compounds 1h, 1j are more preferred, and compound 1j is even more preferred. .

  Examples of the compound represented by the general formula (1) include compounds 1 to 15 (all known compounds), 1b to 1z, 1aa to 1hh, 2d1 to 2d3, and other commercially available known compounds described in Examples below. These may be used as starting materials, or those synthesized by combining known substitution reactions, addition reactions, etc. alone or in combination.

  The compound represented by the general formula (1-1) can be synthesized by the following scheme as an example, and can be synthesized by a method in which a known substitution reaction, addition reaction, or the like is combined with this scheme.

  The reaction between compound 11-1 and compound 12-1 (hereinafter abbreviated as “reaction 1”) may be carried out in a solvent, but is preferably carried out under solvent-free conditions. When a solvent is used, for example, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, chlorobenzene, dichlorobenzene, xylene, trichlorobenzene, anisole and the like can be used.

  The molar ratio of compound 11-1 to compound 12-1 in Reaction 1 is not particularly limited, but compound 12-1 is, for example, 0.1 to 5 mol, preferably 0.25 to 3 with respect to 1 mol of compound 11-1. Mol, more preferably about 0.5 to 2 mol.

  Although the temperature of reaction 1 is not specifically limited, For example, it is 50-150 degreeC, Preferably it can be about 80-150 degreeC.

  Although the time of reaction 1 is not particularly limited, it can be, for example, about 0.5 to 4 hours, preferably about 1 to 2 hours.

  After reaction 1, it is desirable to filter and wash with an appropriate solvent (for example, a mixed solvent of hexane and ethyl acetate).

  After reaction 1, an appropriate solvent (for example, DMF) and NaH are added, and the mixture is stirred at 0 to 40 ° C. (preferably 0 ° C. to room temperature) to obtain the compound represented by the general formula (1-1). . The stirring time at this time is not particularly limited, but can be, for example, about 0.5 to 4 hours, preferably about 1 to 3 hours.

  Among the compounds represented by the general formula (1), the compound represented by the general formula (1-2) is exemplified by the following scheme, or a known substitution reaction, addition reaction, saponification reaction and the like are combined in this scheme. It can also be synthesized by the method.

Reaction a is performed by extracting a proton from the hydroxyl group of compound 11-2 with sodium hydride to produce phenoxide (reaction a1), and then condensing this with compound 12-2 (reaction a2). Reaction a is preferably performed in a suitable solvent such as dimethylformamide. The temperature, time, and the like of reaction a1 and reaction a2 can be appropriately selected based on known information. For example, the reaction a1 is performed by stirring at a low temperature of about 0 degree for 0.5 to 2 hours,
Reaction a2 is performed by stirring at about 40 to 60 degrees for about 8 to 16 hours.

  The molar ratio of compound 11-2 to compound 12-2 in reaction a is not particularly limited, but compound 11-2 is, for example, 0.1 to 5 mol, preferably 0.5 to 3 with respect to 1 mol of compound 12-2. Mol, more preferably about 1 to 2 mol.

  Reactions b and c are reactions for producing a compound (compound 13-2) in which the nitro group of the condensate is converted to an azide group from the condensate obtained by reaction a2. In the above reaction scheme, an example of a catalyst, a solvent, and the like to be used is shown. However, the present invention is not limited to this, and other catalysts, solvents, and the like that can be employed in the reactions b and c may be used. In the reactions b and c, the reaction temperature, reaction time, and the like can be appropriately selected based on known information.

Reactions d and e are reactions in which the azide group of compound 13-2 forms a triazole ring by the Huisgen reaction. Reactions d and e are preferably carried out in the presence of a catalyst such as copper (II) sulfate pentahydrate and a reducing agent such as sodium ascorbate. Moreover, reaction temperature, reaction time, etc. can be suitably selected based on well-known information according to conditions, such as the presence or absence of a catalyst.

The compound represented by the general formula (1) can adjust the circadian rhythm of the plant (long period or short period). Here, the longer period means that the time from peak to peak in the expression cycle of a plant clock-related gene (such as CCA1 gene) becomes longer, and the shorter period means that this time becomes shorter. means.

The presence or absence of plant circadian rhythm-regulating activity can be determined by, for example, introducing a DNA linking a luminescent enzyme gene such as a fluorescent gene or luciferase gene downstream of the promoter of a clock-related gene into a plant and measuring the increase / decrease cycle of luminescence derived from the transgene. It can be determined by evaluating whether or not the time from peak to peak in the luminescence cycle is affected by the addition of the test compound. A high-sensitivity bioluminescence measuring device (CL96, manufactured by Neutral Electric Co., Ltd.) is suitable for measuring the luminescence cycle. According to this apparatus, the luminescence cycle of a maximum of 1536 types of samples can be simultaneously measured while adjusting the culture conditions (temperature, light and dark, CO ₂ concentration, etc.). By adopting the determination method and the apparatus, it is possible to determine the plant circadian rhythm-regulating activity of 1000 or more test compounds in about one week.

  Since circadian rhythm is known to affect various activities of plants (Non-Patent Documents 1 to 15), according to the compound represented by the general formula (1), the regulation of these activities, for example, flowers Adjustment of growth period, adjustment of growth, adjustment of accumulation of primary metabolites (starch, sugar, etc.), adjustment of accumulation of secondary metabolites (anthocyanin, etc.), adjustment of low temperature stress response, adjustment of drought stress response, resistance to pathogenic bacteria Expression adjustment, nitrogen metabolism adjustment, iron metabolism adjustment, stomatal opening / closing adjustment, leaf greening adjustment, water absorption adjustment, seed dormancy adjustment, stem turning movement adjustment, etc. are possible.

  More specifically, for example, regarding the adjustment of the flower formation time, in the case of a long-day plant, the circadian rhythm becomes late blooming due to a long period, while the circadian rhythm becomes short blooming. It is known to be. In the case of short-day plants, the reverse is considered. For this reason, for example, for long-day plants whose tissues other than flowers (for example, leaves, stems, roots, etc.) are harvested organs, the circadian rhythm is long-perioded so that they bloom late, and the yield of harvested organs is reduced. Increase can be achieved. As another example of use, when a flower or an organ (fruit, seed, etc.) that accompanies flower formation is the target of harvesting, the circadian rhythm is adjusted to advance (or delay) the flower formation time. , Climates unfavorable for flower formation (rainy season (season), dry season (season), etc.) can be avoided. The target plant of the plant circadian rhythm adjusting agent of the present invention is not particularly limited. For example, it can be widely applied to plants such as angiosperms (dicotyledonous plants, monocotyledonous plants, etc.), gymnosperms, moss plants, and fern plants. Specific examples include eggplants such as tomatoes, peppers, peppers, eggplants, cucumbers, pumpkins, melons, watermelons and other cucumbers, cabbage, broccoli, Chinese cabbage and other vegetables, celery, parsley, lettuce, etc. , Leek such as leek, onion, garlic, soybeans, peanuts, beans such as green beans, peas, azuki bean, other fruit vegetables such as strawberries, straight roots such as radish, turnip, carrot, burdock, taro, cassava, potato Potatoes such as sweet potatoes and potatoes, soft vegetables such as asparagus, spinach and honey bees, flower buds such as eustoma, stock, carnation and chrysanthemum, cereals such as rice and corn, turf such as bentgrass and corn, rape , Oil crops such as peanuts, sugar crops such as sugar cane and sugar beet, cotton Textile crops such as rush, feed crops such as clover, sorghum and dent corn, deciduous fruit trees such as apples, pears, grapes and peaches, citrus fruits such as Satsuma mandarin, lemon and grapefruit, satsuki, azalea and cedar And the like.

  The target organ of the plant circadian rhythm adjusting agent of the present invention is not particularly limited as long as it is an organ constituting a plant body. Examples of target organs include stems, buds, roots, ovaries, and fruits.

  The plant circadian rhythm adjusting agent of the present invention may be the compound of the present invention itself, but may contain various additives in addition to the compound of the present invention depending on the dosage form, application mode, and the like. The content rate of the compound of this invention in a plant circadian rhythm regulator is not specifically limited. Specifically, 0.0001 to 100% by weight, preferably about 0.01 to 50% by weight is exemplified.

  The dosage form of the plant circadian rhythm adjusting agent of the present invention is not particularly limited as long as it is an agriculturally acceptable dosage form. For example, liquid agent, solid agent, powder agent, granule, granule, wettable powder, flowable agent, emulsion, paste agent, dispersant and the like can be mentioned.

  The additive is not particularly limited as long as it is an agriculturally acceptable additive. Examples include carriers, surfactants, thickeners, extenders, binders, vitamins, antioxidants, pH adjusters, volatilization inhibitors, and dyes.

  The application mode of the plant circadian rhythm adjusting agent of the present invention is not particularly limited as long as it is a known mode (or a mode developed in the future) as a usage mode of agricultural chemicals. Examples thereof include spraying, dripping, coating, mixing and dissolution in a plant growth environment (in soil, water, solid medium, liquid medium, etc.).

  EXAMPLES The present invention will be described in detail below based on examples, but the present invention is not limited to these examples.

Example 1. Screening for compounds that regulate plant circadian rhythm
For each of 10,000 test compounds, the presence / absence of a plant circadian rhythm adjustment effect, its nature (longer or shorter cycle), and the strength of the effect were evaluated. Specifically, it was performed as follows.

  The promoter of the CCA1 gene, which is a clock-related gene (from Arabidopsis thaliana, -506 to +891 when the translation start point is 0, Nakamichi et al., Plant Cell Physiol. 45 (1): 57-67 (2004) DNA in which the coding sequence of the luciferase protein was arranged downstream of the sequence of Figure 1-Ac was introduced into the Arabidopsis genome according to a known method. The seeds of the obtained genetically modified strain (Nakamichi et al., Plant Cell Physiol. 50 (3): 447-462 (2009)) were collected and sterilized by treatment with 2.5% sodium hypochlorite. Sterilized seeds were sown on MS agar medium (1 × MS salt mixture, 0.3% gellan gum, ph5.7) and cultured under conditions of constant temperature of 22 ° C. and switching between light / dark every 12 hours. On the 4th day after germination, the plant body was transferred to a 96-well plate with MS agar medium, and 20 μL of MS liquid containing test compound (final concentration 25 μM) and luciferin (Wako Pure Chemicals, 120-05114) (final concentration 250 μM) (1 × MS salt mixture, 2% sucrose, ph 5.7) was added to the culture plate, and the culture was further continued. The day after the addition, the culture plate was set in a luminescence measuring device (manufactured by Neutral Electric Co., Ltd., CL96), and the amount of luminescence from Arabidopsis thaliana was measured for 3 days or more while culturing under constant light conditions at 22 ° C. Using the CL96 software, a sine curve was drawn based on the obtained light emission data, and the cycle of the light emission rhythm was obtained. The circadian rhythm waveform data was obtained by processing the maximum luminescence value of the sample to be “1” (Nakamichi et al., Plant Cell Physiol. 45: 57-67 (2004)).

  As a result of the above screening, 15 compounds (compounds 1 to 15) were found as compounds having a plant circadian rhythm adjusting action. Table 1 shows the structural formulas of these compounds, the nature of the plant circadian rhythm-regulating action (long period or short period), and their strength. In Table 1, “++” indicates that the cycle changed by 3 hours or more compared to DMSO control, and “++” indicates that the cycle changed by 1 hour or more and less than 3 hours compared with DMSO control. "+" Indicates that the cycle has changed by more than 0.5 hour but less than 1 hour compared to DMSO control.

Example 2 Synthesis of Compound 1 (1a) and its derivatives (1b-1z)
Compounds in which Ar is a group shown below (Compound 1 (1a) and its derivatives (1b to 1z)) were synthesized.

  Details of the synthesis method of the representative compound (1a) are shown below.

  Ethyl-5-amino-1-phenyl-1H-pyrazole-4-carboxylate (2a: 233 mg, 1.0 mmol) and 1,2-dichloro-4-isocyanatobenzene (3a: 188 mg, 1.0 mmol) were added to 110 Heated at <RTIgt; C </ RTI> for 1-2 hours. The temperature of the reaction solution was returned to room temperature, filtered, and washed with a solvent (hexane: ethyl acetate = 4: 1). Thereto, DMF (1 mL) and NaH (60% dispersion in mineral oil, 12 mg, 0.3 mmol, 1.2 equiv) were added at 0 ° C., and the mixture was stirred at room temperature. The reaction was quenched by the addition of methanol. The reaction was extracted with ethyl acetate, washed with brine, dried over Na2SO4 and concentrated. The obtained mixture was purified by PTLC (hexane / EtOAc = 1: 1) to obtain the desired product (1a) as a white solid (yield 70%). 1H NMR (600 MHz, CDCl3) δ 7.04 (d, J = 9.0 Hz, 1H), 7.20-7.32 (m, 4H), 7.41 (d, J = 6.1 Hz, 2H), 7.59 (d, J = 7.8 Hz , 1H), 8.09 (s, 1H).

  The other derivatives (1b to 1z) were synthesized in the same manner as the synthesis of compound 1a, using an appropriate material compound instead of compound 3a. The appearance, yield, and NMR data of the obtained derivative are shown below.

  1b: White solid (yield 50%). 1H NMR (600 MHz, CDCl3) δ 7.05-7.36 (m, 5H), 7.44 (d, J = 8.4 Hz, 2H), 7.49-7.57 (m, 3H), 7.81 (d, J = 8.2 Hz, 1H) .

  1c: white solid (yield 12%). 1H NMR (400 MHz, CDCl3) δ 3.90 (s, 3H), 7.03 (d, J = 9.2 Hz, 2H), 7.12 (d, J = 9.2 Hz, 2H), 7.23 (d, J = 7.2 Hz, 1H ), 7.29 (t, J = 7.2 Hz, 1H), 7.45 (d, J = 7.2 Hz, 2H), 8.09 (s, 1H) 10.2 (brs, 1H).

  1d: white solid (yield 81%). 1H NMR (400 MHz, CDCl3) [delta] 7.11 (d, J = 8.8 Hz, 2H), 7.21-7.37 (m, 2H), 7.40-7.50 (m, 4H), 7.86 (s, 1H).

  1e: White solid (61% yield). 1H NMR (400 MHz, CDCl3) δ 7.14-7.26 (m, 4H), 7.27-7.39 (m, 3H), 7.47 (dt, J = 6.8, 1.6 Hz, 2H), 8.10 (s, 1H).

  1f: white solid (yield 13%). 1H NMR (400 MHz, CDCl3) δ 7.11 (d, J = 8.0 Hz, 1H), 7.16-7.25 (m, 3H), 7.30 (t, J = 7.8 Hz, 1H), 7.39-7.45 (m, 2H) , 7.48 (d, J = 7.8 Hz, 1H), 7.51 (d, 8.4 Hz, 1H), 8.09 (s, 1H).

  1 g: white solid (41% yield). 1H NMR (400 MHz, CDCl3) δ 7.16-7.30 (m, 4H), 7.37 (d, J = 8.4 Hz, 2H), 7.43 (d, J = 7.8 Hz, 2H), 8.09 (s, 1H).

  1h: white solid (73% yield). 1H NMR (400 MHz, CDCl3) δ 7.27 (d, J = 2.4 Hz, 1H), 7.30-7.37 (m, 3H), 7.42-7.50 (m, 3H), 7.53 (d, J = 8.8 Hz, 1H) , 8.11 (s, 1H).

  1i: White solid (25% yield). 1H NMR (400 MHz, CDCl3) δ 7.22 (dd, J = 8.0, 1.6 Hz, 1H), 7.37 (t, J = 8.0 Hz, 1H), 7.38-7.46 (m, 3H), 7.47-7.54 (m, 2H), 7.63 (dd, J = 8.0, 1.6 Hz, 1H), 8.12 (s, 1H).

  1j: White solid (57% yield). 1H NMR (400 MHz, CDCl3) δ 7.16 (d, J = 8.0 Hz, 1H), 7.21-7.29 (m, 2H), 7.32 (t, 8.0 Hz, 1H), 7.39 (dd, 8.0, 2.4 Hz, 1H ), 7.44 (d, J = 7.8 Hz, 2H)), 8.10 (s, 1H).

  1k: white solid (yield 48%). 1H NMR (400 MHz, CDCl3) [delta] 7.29-7.38 (m, 3H), 7.43 (d, J = 8.4 Hz, 2H), 7.48-7.57 (m, 4H), 8.12 (s, 1H).

  1l: white solid (41% yield). 1H NMR (400 MHz, CDCl3) δ 6.98 (d, J = 8.0 Hz, 1H), 7.03-7.10 (m, 1H), 7.32 (t, J = 8.4 Hz, 1H), 7.38-7.44 (m, 3H) , 7.46-7.52 (m, 2H), 8.12 (s, 1H).

  1m: white solid (yield 30%). 1H NMR (400 MHz, CDCl3) [delta] 7.26-7.34 (m, 1H), 7.39-7.53 (m, 7H), 7.60 (dd, J = 7.2, 2.0 Hz, 1H), 8.12 (s, 1H).

  1n: White solid (yield 60%). 1H NMR (400 MHz, CDCl3) δ 6.96-7.10 (m, 2H), 7.23 (t, J = 8.4 Hz, 2H), 7.32-7.43 (m, 3H), 7.44-7.52 (m, 2H), 8.11 ( s, 1H).

  1o: White solid (42% yield). 1H NMR (400 MHz, CDCl3) δ 7.04-7.10 (m, 1H), 7.18-7.36 (m, 5H), 7.42 (d, J = 7.2 Hz, 2H), 7.44-7.52 (m, 2H), 8.09 ( s, 1H).

  1p: White solid (41% yield). 1H NMR (400 MHz, CDCl3) [delta] 7.16-7.37 (m, 6H), 7.40-7.58 (m, 3H), 8.09 (s, 1H).

  1q: White solid (90% yield). 1H NMR (400 MHz, CDCl3) [delta] 7.35-7.42 (m, 3H), 7.45-7.55 (m, 4H), 8.12 (s, 1H).

  1r: white solid (yield 28%). 1H NMR (400 MHz, CDCl3) δ 7.17 (d, J = 8.0 Hz, 1H), 7.24-7.40 (m, 5H), 7.41 (s, 1H), 7.44 (d, J = 8.0 Hz, 2H), 7.66 (d, J = 8.0 Hz, 1H), 8.10 (s, 1H).

  1s: white solid (yield 15%). 1H NMR (400 MHz, CDCl3) δ 6.95 (dt, J = 8.8, 2.0 Hz, 1H), 7.03 (d, J = 8.0 Hz, 1H), 7.20-7.38 (m, 4H), 7.45 (d, J = 7.2 Hz, 2H), 7.50 (dd, J = 8.0, 2.0 Hz, 1H), 8.10 (s, 1H).

  1t: white solid (yield 42%). 1H NMR (400 MHz, CDCl3) δ 7.05 (d, J = 8.4 Hz, 2H), 7.19 (d, J = 7.6 Hz, 2H), 7.33 (t, J = 7.6 Hz, 1H), 7.41 (d, J = 7.6 Hz, 2H), 7.65 (d, J = 8.4 Hz, 2H), 8.10 (s, 1H).

  1u: White solid (14% yield). 1H NMR (400 MHz, CDCl3) δ 2.49 (s, 3H), 7.01 (d, J = 8.4 Hz, 1H), 7.20 (s, 1H), 7.22-7.32 (m, 3H), 7.38 (d, J = 8.4 Hz, 1H), 7.43 (d, J = 7.6 Hz, 2H), 8.09 (s, 1H).

  1v: white solid (33% yield). 1H NMR (600 MHz, CDCl3) δ 6.99 (d, J = 8.4 Hz, 2H), 7.36-7.52 (m, 5H), 7.85 (d, J = 8.4 Hz, 2H), 8.12 (s, 1H).

  1w: white solid (42% yield). 1H NMR (600 MHz, CDCl3) δ 7.11 (t, J = 7.8 Hz, 2H), 7.24-7.29 (m, 1H), 7.34 (t, J = 7.8 Hz, 2H), 7.41-7.47 (m, 4H) , 8.09 (s, 1H).

  1x: white solid (yield 26%). 1H NMR (400 MHz, CDCl3) δ 7.30-7.38 (m, 5H), 7.46 (dd, J = 8.0, 2.0 Hz, 2H), 7.80 (d, J = 8.0 Hz, 2H), 8.12 (s, 1H) .

  1y: white solid (yield 12%). 1H NMR (400 MHz, CDCl3) δ 7.00 (t, J = 8.0 Hz, 1H), 7.29-7.60 (m, 7H), 7.76 (d, J = 8.0 Hz, 1H), 8.13 (s, 1H).

  1z: white solid (57% yield). 1H NMR (400 MHz, CDCl3) δ 2.48 (s, 3H), 7.08 (d, 8.4 Hz, 2H), 7.12-7.28 (m, 3H), 7.33 (d, J = 8.0 Hz, 2H), 7.42 (d , J = 7.6 Hz, 2H), 8.08 (s, 1H).

Example 3 Synthesis of Compound 1 Derivatives (1aa to 1ee) The following derivatives (1aa to 1ee) were synthesized. The synthesis was performed in the same manner as the synthesis of compound 1a, using an appropriate material compound instead of compound 2a. The appearance, yield, and NMR data of the derivatives (1aa to 1ee) are shown below.

  1aa: White solid (yield 26%). 1H NMR (600 MHz, CD3OD) δ 3.86 (s, 3H), 7.24 (dd, J = 8.4, 1.8 Hz, 1H), 7.54 (d, J = 1.8 Hz, 1H), 7.66 (d, J = 8.4 Hz , 1H), 7.87 (s, 1H).

  1bb: white solid (yield 18%). 1H NMR (400 MHz, CDCl3) δ 2.40 (s, 3H), 7.08-7.18 (m, 3H), 7.32-7.40 (m, 3H), 7.59 (d, J = 8.4 Hz, 1H), 8.09 (s, 1H).

  1cc: white solid (yield 62%). 1H NMR (400 MHz, CDCl3) δ 2.40 (s, 3H), 7.08-7.18 (m, 3H), 7.32-7.40 (m, 3H), 7.59 (d, J = 8.4 Hz, 1H), 8.09 (s, 1H).

  1dd: white solid (45% yield). 1H NMR (400 MHz, CDCl3) δ 7.02 (dd, J = 8.8, 2.0 Hz, 1H), 7.13 (t, J = 8.0 Hz, 1H), 7.22-7.31 (m, 1H), 7.35 (dd, J = 8.0, 1.2 Hz, 1H), 7.38 (d, J = 8.0 Hz, 1H), 7.53 (dd, J = 6.0, 3.2 Hz, 1H), 7.62 (d, J = 8.8 Hz, 1H), 7.71 (dd, J = 6.0, 3.2 Hz, 1H), 8.09 (s, 1H), 11.5 (brs, 1H).

  1ee: white solid (39% yield). 1H NMR (400 MHz, CDCl3) δ 6.97-7.11 (m, 2H), 7.34-7.42 (m, 2H), 7.55 (dd, J = 8.8, 2.8 Hz, 1H), 7.65 (t, J = 2.0 Hz, 1H), 8.07 (s, 1H).

Example 4 Synthesis of Derivative (1ff) of Compound 1 Derivative (1ff) was synthesized according to the following reaction scheme.

  NaH (60% dispersion in mineral oil, 8.0 mg, 0.2 mmol, 2.0 equiv) was added to a DMF solution (0.4 mL) of compound 1a (37.2 mg, 0.1 mmol) at 0 ° C. The resulting dispersion was warmed at room temperature for 20 minutes and then cooled to 0 ° C. Iodomethane (12.5 μL, 0.2 mmol, 2.0 equiv) was added and stirred at room temperature overnight. The resulting reaction solution was quenched by adding methanol. The reaction was extracted with ethyl acetate, washed with brine, dried over Na2SO4 and concentrated. The resulting mixture was purified by PTLC (hexane / EtOAc = 1: 1) to obtain the desired product (1ff) as a white solid (yield 8%). 1H NMR (400 MHz, CDCl3) δ 4.02 (s, 3H), 7.11 (dd, J = 8.4, 2.0 Hz, 1H), 7.35-7.40 (m, H), 7.52 (t, J = 8.4 Hz, 2H) 7.60 (d, J = 8.4 Hz, 1H), 8.09 (d, J = 8.4 Hz, 2H), 8.20 (s, 1H).

Example 5 FIG. Synthesis of Derivative (1gg) of Compound 1 A derivative (1gg) was synthesized according to the following reaction scheme.

  To a DMF solution (0.4 mL) of Compound 1a (37.2 mg, 0.1 mmol), NaH (60% dispersion in mineral oil, 6.0 mg, 0.15 mmol, 1.5 equiv) and NaI ((3.7 mg, 0.003) at 0 ° C. The resulting dispersion was warmed at room temperature for 20 minutes and then cooled to 0 ° C. Bromomethylbenzene (17.8 μL, 0.15 mmol, 1.5 equiv) was added and stirred at room temperature overnight. The resulting reaction solution was quenched by the addition of methanol, extracted with ethyl acetate, washed with brine, dried over Na 2 SO 4 and concentrated, and the resulting mixture was PTLC (hexane / EtOAc = 2: 2). The product (1gg) was obtained as a white solid (yield 21%) 1H NMR (600 MHz, CDCl3) δ 5.02 (s, 2H), 6.64 (d, J = 6.6 Hz, 2H ), 7.12-7.24 (m, 6H), 7.35 (t, J = 7.2 Hz, 2H), 7.38 (d, J = 3.0 Hz, 1H), 7.49 (t, J = 7.2 Hz, 1H), 7.59 (d , J = 7.8 Hz, 1H), 8.14 (s, 1H).

Example 6 Synthesis of Derivative (1hh) of Compound 1 A derivative (1hh) was synthesized according to the following reaction scheme.

  In a 200 mL three-necked flask containing a magnetic stirrer, CuI (57.0 mg, 0.3 mmol, 10 mol%), (1S, 2S) -cyclohexane-1,2-diamine (0.41 mL, 0.3 mmol, 10 mol%) , Iodobenzene (3.6 mmol, 1.2 equiv), 5-bromo-1H-indazole (7: 3.0 mmol, 1.0 equiv), and 1.4-dioxane (30 mL) were added. The vessel was sealed under a nitrogen atmosphere and stirred for 24 hours while refluxing. The resulting reaction solution was cooled to room temperature and then passed through a short silica gel pad (ethyl acetate). The filtrate was evaporated and purified by flash column chromatography (hexane / EtOAc = 20: 1) to give 5-bromo-1-phenyl-1H-indazole (8) and 5-bromo-1-phenyl-1H- A mixture of indazole (9) was obtained. A 30 mL two-necked flask containing a magnetic stirrer was charged with Pd (PPh3) 2Cl2 (35.0 mg, 0.05 mmol, 10 mol%), 2M Na2CO3 solution (2 mL), ethanol (0.4 mL), a mixture of 8 and 9 ( 8 + 9: 148.3 mg, 0.5 mmol, 1.0 equiv) and toluene (2.0 mL) were added. The vessel was sealed under a nitrogen atmosphere and stirred for 1 hour while refluxing. The resulting reaction solution was cooled to room temperature and then passed through a short silica gel pad (ethyl acetate). Filtration after drying over Na2SO4. The filtrate was evaporated and then purified by PTLC (hexane / EtOAc = 10: 1, then CHCl3) to obtain the desired product (6) as a yellow solid (yield 51%). 1H NMR (600 MHz, CDCl3) δ 7.39 (t, J = 7.8 Hz, 1H), 7.45 (dt, J = 8.4, 2.0 Hz, 1H), 7.17 (d, J = 7.6 Hz, 2H), 7.24 (t , J = 7.6 Hz, 1H), 7.30 (t, J = 7.6 Hz, 2H), 7.45 (d, J = 3.5 Hz, 1H).

Example 7 Synthesis of Compound 2 Derivatives (2d1-2d3) Derivatives (compounds 2d1-2d3) were synthesized according to the following reaction scheme.

To a DMF solution (15 mL) of sodium hydride ((60% dispersion in mineral oil, 0.60 g, 15 mmol) in a DMF solution (5 mL of 2,4-dichlorophenol (2.60 g, 16 mmol) at 0 ° C) mL) was added dropwise over 2 minutes, and after stirring at 0 ° C. for 1 hour, 2-fluoronitrobenzene (1.0 mL, 10 mmol) was added dropwise, and the reaction vessel was stirred for 12 hours while heating in an oil bath at 50 ° C. The resulting reaction solution was cooled to 0 ° C. and quenched by addition of 1N hydrochloric acid, extracted with diethyl ether, washed with saturated brine, dried over Na ₂ SO ₄ and concentrated. The resulting mixture was purified by silica gel column chromatography (hexane / ethyl acetate = 6/1) to obtain 2,4-dichloro-1- (2-nitrophenoxy) benzene (2.80 g). -Dichloro-1- (2-nitrophenoxy) benzene, iron (3.35 g, 60 mmol), and ammonium hydrochloride (3.21 g, 60 mmol) was suspended in a mixed solvent of ethanol (40 mL) and water (40 mL), and heated for 2 hours at 100 ° C. The resulting reaction solution was cooled to room temperature, and then celite pad (ethyl acetate). After concentrating and concentrating, the residue was purified by silica gel column chromatography (hexane / ethyl acetate = 10/1) to obtain 2- (2,4-dichlorophenoxy) aniline (2.51 g). -Dichlorophenoxy) aniline and 6N hydrochloric acid (40 mL) were mixed, and sodium nitrite (0.69 g, 10 mmol) was added at 0 ° C. After stirring at 0 ° C. for 30 minutes, sodium azide ( 0.78 g, 12 mmol) was added, and the mixture was warmed to room temperature and stirred for 2 hours, and then the reaction mixture was diluted with water (50 mL) .The reaction mixture was extracted with ethyl acetate and washed with saturated brine. , dried over Na ₂ SO _4, and concentrated. the resulting mixture was purified by silica gel column chromatography (hexane Purification by down), to give compound (2c) (2.38 g) as a viscous liquid brown.

Compound (2c) (0.28 g, 1 mmol), copper sulfate (0.25 g, 1 mmol), sodium ascorbate (0.20 g, 1 mmol), and ethyl propionate (0.1 mL, 0.1 mmol) in acetonitrile (3 mL) Was added. The reaction was heated at 100 ° C. for 30 minutes under microwave irradiation. The resulting reaction solution was cooled to room temperature, passed through a celite pad (ethyl acetate), and quenched by adding 1N hydrochloric acid. The mixture was extracted with ethyl acetate, washed with saturated aqueous sodium hydrogen carbonate solution, dried over Na ₂ SO ₄ and concentrated. The obtained mixture was washed with ethanol to obtain compound (2d3) (0.27 g) as a white solid. 1H NMR (400 MHz, CDCl3) δ 8.78 (s, 1H), 7.96 (dd, J = 7.8, 0.9 Hz, 1H), 7.50 (d, J = 1.8 Hz, 1H), 7.42 (tdd, J = 8.2, 1.8, 0.9 Hz, 1H), 7.31 (t, J = 7.8 Hz, 1H), 7.23-7.25 (m, 1H), 6.99 (dd, J = 8.7, 0.9 Hz, 1H), 6.86 (d, J = 8.2 Hz), 4.46 (q, J = 7.3 Hz, 2H), 1.43 (t, J = 7.3 Hz, 3H).

DMSO (3 mL) was added to compound (2c) (0.42 g, 1.5 mmol), ethyl acetoacetate (0.13 mL, 1 mmol), and diethylamine (0.1 mL, 1 mmol). The reaction was heated at 150 ° C. for 1 hour under microwave irradiation. The resulting reaction solution was cooled to room temperature and then quenched by adding 1N hydrochloric acid. The mixture was extracted with ethyl acetate, washed with saturated aqueous sodium hydrogen carbonate solution, dried over Na ₂ SO ₄ and concentrated. The obtained mixture was purified by silica gel column chromatography (hexane / ethyl acetate = 2/1) to obtain compound (2d2) (0.08 g) as a white solid. 1H NMR (400 MHz, CDCl3) δ 7.48-7.52 (m, 2H), 7.44 (d, J = 2.3 Hz, 1H), 7.31 (td, J = 7.8, 1.4 Hz, 1H), 7.20 (dd, J = 9.1, 2.3 Hz, 1H), 6.91 (d, J = 9.1 Hz, 1H), 6.86 (dd, J = 9.1, 1.4 Hz, 1H), 4.46 (q, J = 7.3 Hz, 2H), 2.61 (s, 3H), 1.44 (t, J = 7.3 Hz, 3H).

The compound (2d2) (7.84 mg, 0.2 mmol) was dissolved in a mixed solvent of 1,4-dioxane (4 mL) and ethylene glycol (4 mL), and 2N aqueous potassium hydroxide solution (1 mL) was added. The reaction was heated at 150 ° C. for 1 hour under microwave irradiation. After cooling to room temperature, the mixture was extracted with 1N aqueous sodium hydride solution and washed with diethyl ether. Concentrated hydrochloric acid was added to the obtained aqueous solution to adjust the pH to 5-6, and the mixture was extracted with ethyl acetate, washed with saturated brine, dried over Na ₂ SO ₄ , and concentrated to give compound (2d1) ( 0.06 g) was obtained as a white solid. 1H NMR (400 MHz, CDCl3) δ 7.51-7.55 (m, 2H), 7.45 (d, J = 2.3 Hz, 1H), 7.32 (td, J = 7.8, 1.4 Hz, 1H), 7.20 (dd, J = 8.7, 2.3 Hz, 1H), 6.93 (d, J = 9.1 Hz, 1H), 6.88 (dd, J = 9.1, 1.4 Hz, 1H), 2.64 (s, 3H).

Example 8 FIG. Evaluation of Plant Circadian Rhythm Adjusting Action of Derivatives About the compounds synthesized in Examples 2 to 7 described above, the properties of plant circadian rhythm adjusting action (long period or short period) and the same by the same method as in Example 1 Strength was evaluated. As a result, it has been clarified that all compounds have a plant circadian rhythm adjustment effect.

  As the strength of the long-periodic activity, in order from the strong compound group, group A (1a, 1u), group B (1v, 1x, 1z), group C (1m, 1p, 1s, 1t, 1w, 1cc), Group D (1n, 1o, 1q) and Group E (1b, 1aa, 1ff, 1gg, 1hh). As the strength of the short-periodic activity, group a (1j), group b (1h), group c (1c, 1d, 1i, 1k, 2d3), group d (1e, 1f, 1l, 2d1, 2d2).

  Data for representative compounds (1a, 1h, 1j, 1u, 1v, and 1x) are shown in FIG.

Claims (15)

General formula (1):
[Wherein, Q ¹ and Q ² are the same or different and each represents a heterocycle; X ¹ represents a single bond or a divalent group; Z represents a single bond or a double bond; X ² represents Z When is a single bond, it represents a single bond or a divalent group, and when Z is a double bond, it represents a trivalent group; R ^a and R ^b are the same or different and each represents a hydrogen atom, a lower alkyl group, A lower cycloalkyl group, a lower alkylthio group, a lower alkylcarboxyl group, a hydroxyl group, an oxo group, a carboxyl group, an amino group, or a nitrile group; ^Rc is the same or different and each represents a halogen atom or an optionally substituted lower group; An alkyl group, an optionally substituted lower alkoxy group, an optionally substituted lower heteroalkyl group, or an amide group; ma and mb are the same or different and each represents an integer of 0 or 1 to 5; And mc are the same or different and each represents 0 or an integer of 1 to 5; R ^d is a hydrogen atom or the general formula (2):
{Wherein X ³ represents a single bond or a divalent group; R ^e is the same or different and each represents a halogen atom, an optionally substituted lower alkyl group, an optionally substituted lower alkoxy group, or a substituted group. The lower heteroalkyl group which may be made, or an amino group is shown; me shows the integer of 0 or 1-3. }
P represents 0 or 1; q represents 0 or an integer of 1 to 3; However, if p is 0 and Q ¹ is the nitrogen-free, q is an integer of 1 to 3, X ² is a divalent group containing a nitrogen atom. ]
Or a plant circadian rhythm adjusting agent comprising an agriculturally acceptable salt, hydrate or solvate thereof as an active ingredient. Compounds represented by general formula (1) are represented by general formulas (1-1) to (1-5):
[Wherein R ^{1-1 to} R ^1-4 are the same or different and each represents a hydrogen atom, a lower alkyl group, a lower cycloalkyl group, a lower alkylthio group, a lower alkyl carboxyl group, a hydroxyl group, an oxo group, a carboxyl group, an amino group. A group, a nitrile group, or a phenylalkyl group; R ^{1-5 to} R ^1-9 are the same or different and each is a hydrogen atom, a halogen atom, an optionally substituted lower alkyl group, or an optionally substituted group; A lower alkoxy group or an optionally substituted lower heteroalkyl group; R ^1-10 represents a lower alkyl group or a general formula (3):
{Wherein R ^{1-11 to} R ^1-15 are the same or different and are each a hydrogen atom, a halogen atom, an optionally substituted lower alkyl group, an optionally substituted lower alkoxy group, or a substituted atom. And may represent a lower heteroalkyl group or an amide group. }
Y represents a nitrogen atom or a carbon atom; a dotted line and a solid line parallel thereto indicate a single bond when Y is a nitrogen atom, and a double bond when Y is a carbon atom. ]
[Wherein, R ^{2-1 to} R ^2-2 are the same or different and each represents a hydrogen atom, a lower alkyl group, a lower cycloalkyl group, a lower alkylthio group, a lower alkyl carboxyl group, a hydroxyl group, an oxo group, a carboxyl group, an amino group. R ^{2-3 to} R ^2-11 are the same or different and each represents a hydrogen atom, a halogen atom, an optionally substituted lower alkyl group, an optionally substituted lower alkoxy group, Or the lower heteroalkyl group which may be substituted is shown. ]
Wherein, R ^3-1 is a hydrogen atom, a lower alkyl group, lower cycloalkyl group, a lower alkylthio group, a lower alkyl carboxyl group, a hydroxyl group, an oxo group, a carboxyl group, an amino group, or a nitrile group; R ^{3- 2 to} R ^3-11 are the same or different and are each a hydrogen atom, a halogen atom, an optionally substituted lower alkyl group, an optionally substituted lower alkoxy group, or an optionally substituted lower heteroalkyl group. Indicates. ]
Wherein, R ^4-1 is a hydrogen atom, a lower alkyl group, lower cycloalkyl group, a lower alkylthio group, a lower alkyl carboxyl group, a hydroxyl group, an oxo group, a carboxyl group, an amino group, or a nitrile group; R ^{4- 2 to} R ^4-6 are the same or different and are each a hydrogen atom, a halogen atom, an optionally substituted lower alkyl group, an optionally substituted lower alkoxy group, or an optionally substituted lower heteroalkyl group. Indicates. ]
[Wherein, R ^{5-1 to} R ^5-10 are the same or different and each represents a hydrogen atom, a lower alkyl group, a lower cycloalkyl group, a lower alkylthio group, a lower alkyl carboxyl group, a hydroxyl group, an oxo group, a carboxyl group, an amino group. Group or nitrile group. ]
The plant circadian rhythm regulator of Claim 1 which is a compound shown by either. The plant circadian rhythm regulator of Claim 2 whose compound shown by General formula (1) is a compound shown by General formula (1-1). The plant circadian rhythm regulator according to claim 3, wherein R ^{1-5 to} R ^1-9 are the same or different and each is a hydrogen atom or a halogen atom. The plant circadian rhythm regulator according to claim 3 or 4, wherein at least one of R ^{1-5 to} R ^1-9 is a halogen atom. The plant circadian rhythm regulator according to any one of claims 3 to 5, wherein R ^1-10 is a group represented by the general formula (3). The plant circadian rhythm regulator according to claim 6, wherein R ^{1-11 to} R ^1-15 are the same or different and each is a hydrogen atom or a halogen atom. The plant circadian rhythm regulator according to any one of claims 3 to 7, wherein Y is a nitrogen atom. The plant circadian rhythm regulator according to any one of claims 3 to 8, wherein R ^{1-1 to} R ^1-4 are the same or different and each is a hydrogen atom or an oxo group. The plant circadian rhythm regulator of Claim 2 whose compound shown by General formula (1) is a compound shown by General formula (1-2). R ^2-3 to R ^2-11 are the same or different and are each a hydrogen atom or a halogen atom, plant circadian rhythm regulator of claim 10. At least one or more of R ^2-3 to R ^2-7 is a halogen atom, plant circadian rhythm regulator according to claim 10 or 11. R ^2-1 is a carboxyl group or a lower alkyl carboxyl group, a plant circadian rhythm regulator according to any one of claims 10 to 12. R ^2-2 is a lower alkyl group, a plant circadian rhythm regulator according to any one of claims 10 to 13. The adjustment method of a plant circadian rhythm which applies the plant circadian rhythm regulator in any one of Claims 1-14 to the soil which a plant or a plant grows.