Photosensitizer compound, preparation method and application in plants

Abstract

The present invention provides a compound of formula I or an agriculturally acceptable salt thereof. The compound of formula I can be used to improve the health of plants. For example, the compound of formula I can be used to inhibit microbial pathogens of plants, or to improve the resistance of plants to one or more abiotic stresses. Also provided are methods for preparing the compound of formula I and synthetic intermediates.

Description

[0001] Related Applications

[0002] This application claims priority to U.S. Provisional Application No. 62 / 796,981, filed on January 25, 2019, the entire contents of which are incorporated herein by reference for all purposes. Technical Field

[0003] The technical field generally relates to photosensitizer tetrapyrrole compounds and their use for promoting plant health. More specifically, the technical field relates to modified dihydrochlorin e6 compounds and their use for photodynamic inhibition of microbial pathogens (e.g., fungal or bacterial pathogens) in plants. The modified dihydrochlorin e6 compounds can also be used to improve the abiotic stress resistance or tolerance of plants and / or as pesticides to protect plants from plant pests. Background Art

[0004] Photodynamic inhibition of microbial pathogens involves exposing a photosensitizer to light to generate reactive oxygen species (ROS), such as singlet oxygen, which can adversely affect microbial pathogens. Existing photodynamic inhibition techniques and applications have various drawbacks. Summary of the invention

[0005] In one aspect of the present specification, there is provided a compound of formula I or an agriculturally acceptable salt thereof:

[0006]

[0007] It is used to promote plant health,

[0008] in:

[0009] Z 1 , Z 2 and Z 3 Each independently is OR 1 or NR 2 R 3 ;

[0010] R 1 , R 2 and R 3 are each independently H, alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl, or substituted alkynyl, wherein if Z 1 , Z 2 and Z 3 Each is OR 1 , then at least one R 1 Not H, and if Z 1 , Z 2 and Z 3 Each is NR 2 R3 , then at least one R 3 Not H;

[0011] R a , R b , R c , R d , R e and R f are each independently H, alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl, or substituted alkynyl;

[0012] is a single bond or a double bond;

[0013] is a single bond or a double bond; and

[0014] M is 2H or a metal species,

[0015] Wherein, the substituted alkyl, substituted aryl, substituted alkenyl and substituted alkynyl are independently substituted by one or more of the following groups: -X, -R B , -O - ,=O,-OR B 、-SR B , -S - 、-NR B 2. Si(R C )3. -N + R B 3. -NR B -(Alk)-NR B 2. -NR B -(Alk)-N + R B 3. -NR B -(Alk)-OR B 、-NR B -(Alk)-OP(=O)(OR B )(O - ),-NR B -(Alk)-OP(=O)(OR B )2.-NR B -(Alk)-Si(R C )3. -NR B -(Alk)-SR B 、-O-(Alk)-NR B 2. -O-(Alk)-N + R B 3. -O-(Alk)-OR B 、-O-(Alk)-OP(=O)(OR B )(O- )、-O-(Alk)-OP(=O)(OR B )2、-O-(Alk)-Si(R C )3. -O-(Alk)-SR B , =NR B , -CX3, -CN, -OCN, -SCN, -N=C=O, -NCS, -NO, -NO2, =N2, -N3, -NHC(=O)R B 、-OC(=O)R B 、-NHC(=O)NR B 2. -S(=O)2-, -S(=O)2OH, -S(=O)2R B 、-OS(=O)2OR B 、-S(=O)2NR B 2. -S(=O)R B ,-OP(=O)(OR B )(O - ),-OP(=O)(OR B )2.-P(=O)(OR B )2, -P(=O)(O - )2、-P(=O)(OH)2、-P(O)(OR B )(O - ), -C(=O)R B 、-C(=O)X、-C(S)R B 、-C(O)OR B 、-C(O)O - 、-C(S)OR B 、-C(O)SR B 、-C(S)SR B 、-C(O)NR B 2. -C(S)NR B 2 or -C(=NR B )NR B 2;

[0016] X is independently halogen: F, Cl, Br or I;

[0017] R B each is independently H, alkyl, aryl, aralkyl, heterocycle, alkoxy such as poly(ethyleneoxy), PEG, or poly(methyleneoxy), end-capped poly(ethyleneoxy), end-capped PEG, or end-capped polymethyleneoxy, or a protecting group;

[0018] The end-capped poly(ethyleneoxy), end-capped PEG, and end-capped poly(methyleneoxy) groups are each independently end-capped with an alkyl, aryl, aralkyl, alkenyl, alkynyl, CO(alkyl), CO(aryl), CO(aralkyl), CO(alkenyl), or CO(alkynyl);

[0019] R C Each is independently alkyl, aryl, aralkyl, O(alkyl), O(aryl), O(aralkyl), or O(trisubstituted silyl);

[0020] The trisubstituted silyl groups are each independently substituted with three functional groups selected from the group consisting of alkyl, alkenyl, alkynyl, aryl and aralkyl; and

[0021] Each Alk is independently an alkylene group, an alkenylene group, or an alkynylene group.

[0022] In another aspect of the present specification, there is provided a compound of formula I or an agriculturally acceptable salt thereof:

[0023]

[0024] It is used to promote plant health,

[0025] in:

[0026] Z 1 Yes OR 1 ;

[0027] Z 2 and Z 3 One of them is NR 2 R 3 NR 2 -(CH2) n -NR 4 R 5 NR 2 -(CH2) n -N + R 4 R 5 R 6 Y - NR 2 -(CH2) n -O(PO3H) - W + NR 2 -(CH2) n -Si(R 7 )3.NR 2 -(CH2) n -SR 8 NR 2 -(CH2) n -NR 4-(CH2) p -NR 9 R 10 、NR 2 -(CH2) n -NR 4 -(CH2) p -N + R 9 R 10 R 11 Y - 、NR 2 -(CH2) n -NR 4 -(CH2) p -O(PO3H) - W + 、NR 2 -(CH2) n -NR 4 -(CH2) p -Si(R 7 )3、NR 2 -(CH2) n -NR 4 -(CH2) p -SR 8 、OR 3 、O(CH2) n -NR 4 R 5 、O(CH2) n -N + R 4 R 5 R 6 Y - 、O(CH2) n -O(PO3H) - W + 、O(CH2) n -Si(R 7 )3、O(CH2) n -SR 8 、O(CH2) n -NR 4 -(CH2) p -NR 9 R 10 、O(CH2) n -NR 4 -(CH2) p -N + R 9 R 10 R 11 Y - 、O(CH2) n -NR4 -(CH2) p -O(PO3H) - W + or O(CH2) n -NR 4 -(CH2) p -Si(R 7 )3; and

[0028] Z 2 and Z 3 The other one is OR 12 ;

[0029] or

[0030] Z 2 YesNR 2 R 3 NR 2 -(CH2) n -NR 4 R 5 NR 2 -(CH2) n -N + R 4 R 5 R 6 Y - NR 2 -(CH2) n -O(PO3H) - W + NR 2 -(CH2) n -Si(R 7 )3.NR 2 -(CH2) n -SR 8 NR 2 -(CH2) n -NR 4 -(CH2) p -NR 9 R 10 NR 2 -(CH2) n -NR 4 -(CH2) p -N + R 9 R 10 R 11 Y - NR 2 -(CH2) n -NR 4 -(CH2) p -O(PO3H) - W+ 、NR 2 -(CH2) n -NR 4 -(CH2) p -Si(R 7 )3、NR 2 -(CH2) n -NR 4 -(CH2) p -SR 8 、OR 3 、O(CH2) n -NR 4 R 5 、O(CH2) n -N + R 4 R 5 R 6 Y - 、O(CH2) n -O(PO3H) - W + 、O(CH2) n -Si(R 7 )3、O(CH2) n -SR 8 、O(CH2) n -NR 4 -(CH2) p -NR 9 R 10 、O(CH2) n -NR 4 -(CH2) p -N + R 9 R 10 R 11 Y - 、O(CH2) n -NR 4 -(CH2) p -O(PO3H) - W + 或O(CH2) n -NR 4 -(CH2) p -Si(R 7 )3;以及

[0031] Z 3 =Z 2 ;

[0032] R 1 、R 2 、R 4 、R 6 、R8 , R 9 , R 10 , R 11 and R 12 are each independently H, alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, or -(CH2) q -(CH2CH2O) m -R 13 ;

[0033] R 3 and R 5 are each independently alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, or -(CH2) q -(CH2CH2O) m -R 13 ;

[0034] R 7 is alkyl, O(alkyl), or O(trisubstituted silyl);

[0035] R 13 is H, alkyl, substituted alkyl, aryl, substituted aryl, CO(alkyl) or CO(substituted alkyl), alkenyl, substituted alkenyl, CO(alkenyl) or CO(substituted alkenyl), alkynyl, substituted alkynyl, CO(alkynyl) or CO(substituted alkynyl);

[0036] W + It is an agriculturally acceptable cation;

[0037] Y - It is an agriculturally acceptable anion;

[0038] n is an integer selected from 1 to 16;

[0039] p is an integer selected from 1 to 16;

[0040] q is an integer selected from 0 to 16;

[0041] m is an integer selected from 1 to 100;

[0042] R a , R b , R c , R d , R e and R f are each independently H, alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl, or substituted alkynyl;

[0043] is a single bond or a double bond;

[0044] is a single bond or a double bond; and

[0045] M is 2H or a metal species,

[0046] Wherein, the substituted alkyl, substituted aryl, substituted alkenyl and substituted alkynyl are each independently substituted by one or more of F, Cl, Br, I, hydroxyl, CN and N3.

[0047] In yet another aspect of the present specification, there is provided a compound of formula I or an agriculturally acceptable salt thereof:

[0048]

[0049] in:

[0050] Z 1 Yes OR 1 ;

[0051] Z 2 and Z 3 One of them is NR 2 R 3 NR 2 -(CH2) n -NR 4 R 5 NR 2 -(CH2) n -N + R 4 R 5 R 6 Y - NR 2 -(CH2) n -O(PO3H) - W + NR 2 -(CH2) n -Si(R 7 )3.NR 2 -(CH2) n -SR 8 NR 2 -(CH2) n -NR 4 -(CH2) p -NR 9 R 10 NR 2 -(CH2) n -NR 4 -(CH2) p -N + R 9 R 10 R 11 Y -NR 2 -(CH2) n -NR 4 -(CH2) p -O(PO3H) - W + NR 2 -(CH2) n -NR 4 -(CH2) p -Si(R 7 )3.NR 2 -(CH2) n -NR 4 -(CH2) p -SR 8 、O(CH2) n -NR 4 R 5 、O(CH2) n -N + R 4 R 5 R 6 Y - 、O(CH2) n -O(PO3H) - W + 、O(CH2) n -Si(R 7 )3. O(CH2) n -SR 8 、O(CH2) n -NR 4 -(CH2) p -NR 9 R 10 、O(CH2) n -NR 4 -(CH2) p -N + R 9 R 10 R 11 Y - 、O(CH2) n -NR 4 -(CH2) p -O(PO3H) - W + or O(CH2) n -NR 4 -(CH2) p -Si(R 7 )3; and

[0052] Z 2 and Z 3 The other one is OR12 ;

[0053] or

[0054] Z 2 is NR 2 R 3 、NR 2 -(CH2) n -NR 4 R 5 、NR 2 -(CH2) n -N + R 4 R 5 R 6 Y - 、NR 2 -(CH2) n -O(PO3H) - W + 、NR 2 -(CH2) n -Si(R 7 )3、NR 2 -(CH2) n -SR 8 、NR 2 -(CH2) n -NR 4 -(CH2) p -NR 9 R 10 、NR 2 -(CH2) n -NR 4 -(CH2) p -N + R 9 R 10 R 11 Y - 、NR 2 -(CH2) n -NR 4 -(CH2) p -O(PO3H) - W + 、NR 2 -(CH2) n -NR 4 -(CH2) p -Si(R 7 )3、NR 2 -(CH2) n -NR 4 -(CH2) p -SR 8 、O(CH2) n-NR 4 R 5 、O(CH2) n -N + R 4 R 5 R 6 Y - 、O(CH2) n -O(PO3H) - W + 、O(CH2) n -Si(R 7 )3. O(CH2) n -SR 8 、O(CH2) n -NR 4 -(CH2) p -NR 9 R 10 、O(CH2) n -NR 4 -(CH2) p -N + R 9 R 10 R 11 Y - 、O(CH2) n -NR 4 -(CH2) p -O(PO3H) - W + or O(CH2) n -NR 4 -(CH2) p -Si(R 7 )3; and

[0055] Z 3 =Z 2 ;

[0056] R 1 , R 2 and R 12 are each independently H, alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl, or substituted alkynyl;

[0057] R 3 is alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, or substituted alkynyl;

[0058] R 4 , R 6 , R 8 , R 9 , R 10 , and R 11are each independently H, alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, or -(CH2) q -(CH2CH2O) m -R 13 ;

[0059] R 5 is alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, or -(CH2) q -(CH2CH2O) m -R 13 ;

[0060] R 7 is alkyl, O(alkyl), or O(trisubstituted silyl);

[0061] R 13 is H, alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, CO(alkyl), CO(substituted alkyl), CO(alkenyl), CO(substituted alkenyl), CO(alkynyl), or CO(substituted alkynyl);

[0062] W + It is an agriculturally acceptable cation;

[0063] Y - It is an agriculturally acceptable anion;

[0064] n is an integer selected from 1 to 16;

[0065] p is an integer selected from 1 to 16;

[0066] m is an integer selected from 1 to 100;

[0067] q is an integer selected from 0 to 16;

[0068] R a , R b , R c , R d , R e and R f are each independently H, alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl, or substituted alkynyl;

[0069] is a single bond or a double bond;

[0070] is a single bond or a double bond; and

[0071] M is 2H or a metal species,

[0072] Wherein, the substituted alkyl, substituted aryl, substituted alkenyl and substituted alkynyl are each independently substituted by one or more of F, Cl, Br, I, CN and N3.

[0073] In yet another aspect of the present specification, there is provided a compound of formula I-B1 or an agriculturally acceptable salt thereof:

[0074]

[0075] in:

[0076] Z 1 Yes OR 1 ;

[0077] R 2 is H, alkyl or substituted alkyl;

[0078] R 3 is an alkyl group or a substituted alkyl group;

[0079] Z 3 Yes OR 12 or Z 3 =NR 2 R 3 ;

[0080] R 1 and R 12 Each is independently H, alkyl or substituted alkyl;

[0081] R a , R b , R c , R d , R e and R f are each independently H, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, or substituted alkynyl; and

[0082] M is 2H or a metal species,

[0083] Wherein, the substituted alkyl, substituted alkenyl and substituted alkynyl are independently substituted by one or more of F, Cl, Br, I, CN and N3.

[0084] In yet another aspect of the present specification, there is provided a compound of formula I-B2 or an agriculturally acceptable salt thereof:

[0085]

[0086] in:

[0087] Z 1 Yes OR 1 ;

[0088] R 5is alkyl, substituted alkyl, or -(CH2) p -NR 9 R 10 ;

[0089] R 2 , R 4 , R 9 and R 10 Each is independently H, alkyl or substituted alkyl;

[0090] n is an integer selected from 1 to 16;

[0091] p is an integer selected from 1 to 16;

[0092] Z 3 Yes OR 12 or Z 3 =NR 2 -(CH2) n -NR 4 R 5 ;

[0093] R 1 and R 12 Each is independently H, alkyl or substituted alkyl;

[0094] R a , R b , R c , R d , R e and R f are each independently H, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, or substituted alkynyl; and

[0095] M is 2H or a metal species,

[0096] Wherein, the substituted alkyl, substituted alkenyl and substituted alkynyl are independently substituted by one or more of F, Cl, Br, I, hydroxyl, CN and N3.

[0097] In yet another aspect of the present specification, there is provided a compound of formula I-B3 or an agriculturally acceptable salt thereof:

[0098]

[0099] in:

[0100] Z 1 Yes OR 1 ;

[0101] Z 4 Is Si(R 7 )3 or SR 8 ;

[0102] Z3 Yes OR 12 or Z 3 =NR 2 -(CH2) n -Z 4 ;

[0103] R 1 , R 2 and R 12 Each is independently H, alkyl or substituted alkyl;

[0104] R 7 is alkyl, O(alkyl), or O(trisubstituted silyl);

[0105] R 8 is H, alkyl, substituted alkyl, or -(CH2CH2O) m -R 13 ;

[0106] R 13 is H, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, CO(alkyl), CO(substituted alkyl), CO(alkenyl), CO(substituted alkenyl), CO(alkynyl), or CO(substituted alkynyl);

[0107] n is an integer selected from 1 to 16;

[0108] m is an integer selected from 1 to 100;

[0109] R a , R b , R c , R d , R e and R f are each independently H, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl; and

[0110] M is 2H or a metal species,

[0111] Wherein, the substituted alkyl, substituted alkenyl and substituted alkynyl are independently substituted by one or more of F, Cl, Br, I, hydroxyl, CN and N3.

[0112] In yet another aspect of the present specification, there is provided a compound of formula I-B4a or an agriculturally acceptable salt thereof:

[0113]

[0114] in:

[0115] Z 1 Yes OR 1 ;

[0116] Z3 Yes OR 12 or Z 3 =NR2-(CH2) n -O(PO3H) - W + ;

[0117] R 1 , R 2 and R 12 Each is independently H, alkyl or substituted alkyl;

[0118] n is an integer selected from 1 to 16;

[0119] W + It is an agriculturally acceptable cation;

[0120] R a , R b , R c , R d , R e and R f are each independently H, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl; and

[0121] M is 2H or a metal species,

[0122] Wherein, the substituted alkyl, substituted alkenyl and substituted alkynyl are independently substituted by one or more of F, Cl, Br, I, hydroxyl, CN and N3.

[0123] In yet another aspect of the present specification, there is provided a compound of formula I-B4c or an agriculturally acceptable salt thereof:

[0124]

[0125] in:

[0126] Z 1 Yes OR 1 ;

[0127] Z 3 Yes OR 12 or Z 3 =NR2-(CH2) n -NR 4 R 5 R 6+ Y - ;

[0128] R 1 , R 2 and R 12 Each is independently H, alkyl or substituted alkyl;

[0129] R4 , R 5 and R 6 Each is independently an alkyl group or a substituted alkyl group;

[0130] n is an integer selected from 1 to 16;

[0131] Y - It is an agriculturally acceptable anion;

[0132] R a , R b , R c , R d , R e and R f are each independently H, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl; and

[0133] M is 2H or a metal species,

[0134] Wherein, the substituted alkyl, substituted alkenyl and substituted alkynyl are independently substituted by one or more of F, Cl, Br, I, hydroxyl, CN and N3.

[0135] In yet another aspect of the present specification, there is provided a compound of formula IC or an agriculturally acceptable salt thereof:

[0136]

[0137] in:

[0138] Z 1 Yes OR 1 ;

[0139] Z 3 =OR 12 , and m is an integer selected from 1 to 100; or

[0140] Z 3 =O(CH2CH2O) m -R 13 , and m is an integer selected from 5 to 100;

[0141] R 1 and R 12 Each is independently H, alkyl or substituted alkyl;

[0142] R 13 is H, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, CO(alkyl), CO(substituted alkyl), CO(alkenyl), CO(substituted alkenyl), CO(alkynyl), or CO(substituted alkynyl);

[0143] R a , R b , Rc , R d , R e and R f are each independently H, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, or substituted alkynyl;

[0144] is a single bond or a double bond;

[0145] is a single bond or a double bond; and

[0146] M is 2H or a metal species,

[0147] Wherein, the substituted alkyl, substituted alkenyl and substituted alkynyl are independently substituted by one or more of F, Cl, Br, I, hydroxyl, CN and N3.

[0148] The present specification also provides a composition comprising at least one compound as defined herein or an agriculturally acceptable salt thereof, and a carrier liquid.

[0149] The present specification also provides a method for promoting plant health. The method comprises applying a compound as defined herein, or an agriculturally acceptable salt thereof, or a composition as defined herein to a plant; and exposing the plant to light. Promoting plant health may include at least one of: preventing or inhibiting the growth of microbial pathogens (e.g., fungal or bacterial pathogens) of plants, increasing the resistance of plants to one or more abiotic stresses, and controlling pests of plants (e.g., harmful insects or corresponding larvae).

[0150] This specification also provides a method for preparing a compound of formula II-A and / or formula II-B or a salt thereof:

[0151]

[0152] in:

[0153] R 17 is H, alkyl, aryl, or alkoxy;

[0154] R a , R b , R c , R d , R e and R f are each independently H, alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl;

[0155] is a single bond or a double bond;

[0156] is a single bond or a double bond; and

[0157] M is 2H or a metal species,

[0158] wherein the substituted alkyl, substituted aryl, substituted alkenyl and substituted alkynyl are each independently substituted by one or more of F, Cl, Br, I, hydroxyl, CN and N3;

[0159] The method comprises:

[0160] The compound of formula III or its salt is reacted with a compound of general formula (R 17 Anhydride reaction of CO)2O:

[0161] BRIEF DESCRIPTION OF THE DRAWINGS

[0162] Figure 1 It is shown that Ce6-mixed-DMAE 15,17 A graph showing the relative inactivation of the Gram-negative bacterium Erwinia amylovora by amides;

[0163] Figure 2 It is shown that Ce6-mixed-DMAE 15,17 A graph showing the relative inactivation of the Gram-negative bacterium Xanthomonas axonopodis by amides;

[0164] Figure 3 It is shown that Ce6-mixed-DMAE 15,17 A graph showing the relative inactivation of the Gram-negative bacterium Rhodococcus fascians by amides;

[0165] Figure 4 The Ce6-mixed-DMAE in the tobacco wildfire pathogen (Pseudomonas syringae pv.Tabaci) sample under light conditions is shown 15,17 Plot comparing dose responses of amide and Ce6Na3.

[0166] Figure 5 is a graph showing the inhibition of fungal lesion formation of Colletotrichum orbiculare ATC20767 on Nicotiana benthamiana host plants. DETAILED DESCRIPTION

[0167] Some microbial pathogens (such as Gram-negative bacteria and certain types of fungi) have cell membranes that are difficult to penetrate. More specifically, these microbial pathogens sometimes have an impermeable outer cell membrane that contains endotoxins and can block small molecules such as antibiotics, dyes, and detergents, thereby protecting the sensitive inner membrane and cell wall. Therefore, it may be challenging to use photodynamic therapy to inhibit the growth of certain microbial pathogens in plants because photosensitizer compounds often cannot penetrate well into the cell wall. It is also challenging to improve plant resistance to damage caused by abiotic stress.

[0168] In some cases, photodynamic inhibition of microbial pathogens present on plants can be achieved by applying photosensitizer compounds. Photosensitizer compounds react to light by producing reactive oxygen species (ROS). In other cases, photosensitizer compounds can be used to increase the resistance of plants to damage caused by one or more abiotic stresses.

[0169] Some compounds of the present specification are photosensitizer compounds that can be derived from the skeleton of dihydrochlorin e6 (hereinafter referred to as "Ce6"). Compounds derived from Ce6 can also be referred to as "modified Ce6". Some compounds of the present specification are photosensitizer compounds with a skeleton similar to Ce6, but are not necessarily derived from Ce6. In some cases, these compounds can be used to improve plant health. That is, depending on the compound and / or the mode of application, the compounds of the present invention can be used in plants to photodynamically inhibit microbial pathogens on plants, to increase the resistance of plants to damage caused by one or more abiotic stresses and / or as pesticides.

[0170] definition

[0171] Unless otherwise indicated, the following terms and phrases used herein are intended to have the following meanings.

[0172] When a trade name is used herein, it is intended to independently include both the trade name product and the active ingredients of the trade name product.

[0173] As used herein, the phrase "compound of formula I" refers to a compound of formula I or an agriculturally acceptable salt thereof. With respect to isolatable intermediates, the phrase "compound of formula (number)" refers to the compound of that formula and a salt thereof, and optionally an agriculturally acceptable salt.

[0174] As used herein, the term "alkyl" refers to a hydrocarbon containing primary, secondary, tertiary or cyclic carbon atoms. For example, but not limitation, an alkyl group can have 1 to 20 carbon atoms (i.e., C1-C 20The alkyl groups of the present invention include, but are not limited to, methyl (Me, -CH3), ethyl (Et, -CH2CH3), 1-propyl (n-Pr, n-propyl, -CH2CH2CH3), 2-propyl (i-Pr, isopropyl, -CH(CH3)2), 1-butyl (n-Bu, n-butyl, -CH2CH2CH2CH3), 2-methyl-1-propyl (i-Bu, isobutyl, -CH2CH(CH3)2), 2-butyl (s-Bu, sec-butyl, -CH(C H3)CH2CH3), 2-methyl-2-propyl (t-Bu, tert-butyl, -C(CH3)3), 1-pentyl (n-pentyl, -CH2CH2CH2CH2CH3), 2-pentyl (-CH(CH3)CH2CH2CH3), 3-pentyl (-CH(CH2CH3)2), 2-methyl-2-butyl (-C(CH3)2CH2CH3), 3-methyl-2-butyl (-CH(CH3)CH(CH3)2), 3-methyl-1-butyl (-CH 2CH2CH(CH3)2), 2-methyl-1-butyl (-CH2CH(CH3)CH2CH3), 1-hexyl (-CH2CH2CH2CH2CH2CH3), 2-hexyl (-CH(CH3)CH2CH2CH2CH3), 3-hexyl (-CH(CH2CH3)(CH2CH2CH3)), 2-methyl-2-pentyl (-C(CH3)2CH2CH2CH3), 3-methyl-2-pentyl (-CH(CH3)CH(CH 3)CH2CH3), 4-methyl-2-pentyl (-CH(CH3)CH2CH(CH3)2), 3-methyl-3-pentyl (-C(CH3)(CH2CH3)2), 2-methyl-3-pentyl (-CH(CH2CH3)CH(CH3)2), 2,3-dimethyl-2-butyl (-C(CH3)2CH(CH3)2), 3,3-dimethyl-2-butyl (-CH(CH3)C(CH3)3), and octyl (-(CH2)7CH3).

[0175] As used herein, the term "alkenyl" refers to an alkenyl group containing primary, secondary, tertiary or cyclic carbon atoms and having at least one site of unsaturation (ie, carbon-carbon sp 2 For example, but not limitation, an alkenyl group can have 2 to 20 carbon atoms (i.e., C2-C 20The term "alkenyl" refers to a cyclopentenyl group having 2 to 8 carbon atoms (i.e., C2-C8 alkenyl), 2 to 6 carbon atoms (i.e., C2-C6 alkenyl), or 2 to 4 carbon atoms (i.e., C2-C4 alkenyl). Examples of suitable alkenyl groups include, but are not limited to, ethylene or vinyl (-CH=CH2), allyl (-CH2CH=CH2), cyclopentenyl (-C5H7), and 5-hexenyl (-CH2CH2CH2CH2CH=CH2).

[0176] As used herein, the term "alkynyl" refers to a hydrocarbon containing primary, secondary, tertiary or cyclic carbon atoms and having at least one site of unsaturation (i.e., a carbon-carbon sp triple bond). For example, but not limitation, an alkynyl group can have 2 to 20 carbon atoms (i.e., C2-C 20 The term "alkynyl" refers to a group having 2 to 8 carbon atoms (i.e., C2-C8 alkynyl), 2 to 6 carbon atoms (i.e., C2-C6 alkynyl), or 2 to 4 carbon atoms (i.e., C2-C4 alkynyl). Suitable alkynyl groups include, but are not limited to, ethynyl (-C≡CH) and propargyl (-CH2C≡CH).

[0177] As used herein, the term "alkoxy" can be interchanged with the term "O(alkyl)", wherein the "alkyl" group as defined above is attached to the parent molecule via an oxygen atom. For example, but not limitation, the alkyl portion of the O(alkyl) group can have 1 to 20 carbon atoms (i.e., C1-C 20 The term "alkyl" refers to an alkyl radical having 1 to 8 carbon atoms (i.e., C1-C8 alkyl), 1 to 6 carbon atoms (i.e., C1-C6 alkyl), or 1 to 4 carbon atoms (i.e., C1-C4 alkyl). Examples of suitable alkoxy or O(alkyl) groups include, but are not limited to, methoxy (-OCH3 or -OMe), ethoxy (-OCH2CH3 or -OEt), and tert-butoxy (-OC(CH3)3 or -OtBu). Similarly, those skilled in the art will understand "O(alkenyl)", "O(alkynyl)" and the corresponding substituent groups.

[0178] As used herein, the term "acyl" refers to several functional moieties, such as "C=O (alkyl)", "C=O (alkenyl)", "C=O (alkynyl)" and their corresponding substituent groups, wherein the "alkyl", "alkenyl" and "alkynyl" groups are as defined above and are connected to the O, N, S of the parent molecule through the C=O group. For example, but not limitation, the alkyl portion of the C=O (alkyl) group can have 1 to 20 carbon atoms (i.e., C1-C 20The term "alkyl" refers to an alkyl radical having 1 to 8 carbon atoms (i.e., C1-C8 alkyl), 1 to 6 carbon atoms (i.e., C1-C6 alkyl), or 1 to 4 carbon atoms (i.e., C1-C4 alkyl). Examples of suitable acyl groups include, but are not limited to, formyl (i.e., carboxaldehyde group), acetyl, trifluoroacetyl, propionyl, and butyryl. Those skilled in the art will appreciate that corresponding definitions apply to the "C=O(alkenyl)" and "C=O(alkynyl)" moieties. In this specification, "C=O(alkyl)", "C=O(alkenyl)", "C=O(alkynyl)" may also be written as "CO(alkyl)", "CO(alkenyl)" and "CO(alkynyl)", respectively.

[0179] As used herein, the term "alkylene" refers to a saturated, branched or straight chain or cyclic hydrocarbon radical having two monovalent radical centers derived by removing two hydrogen atoms from the same or two different carbon atoms of the parent alkane. For example, but not limited to, the alkylene group can have 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms. Typical alkylene groups include, but are not limited to, methylene (-CH2-), 1,1-ethyl (-CH(CH3)-), 1,2-ethyl (-CH2CH2-), 1,1-propyl (-CH(CH2CH3)-), 1,2-propyl (-CH2CH(CH3)-), 1,3-propyl (-CH2CH2CH2-) and 1,4-butyl (-CH2CH2CH2CH2-).

[0180] As used herein, the term "alkenylene" refers to an unsaturated, branched or straight chain, or cyclic hydrocarbon radical having two monovalent radical centers derived from the same or two different carbon atoms of a parent olefin by removing two hydrogen atoms. For example, but not limitation, alkenylene can have 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms. Typical alkenylene includes, but is not limited to, 1,2-vinyl (-CH=CH-).

[0181] As used herein, the term "alkynylene" refers to an unsaturated, branched or straight chain, or cyclic hydrocarbon radical having two monovalent radical centers derived by removing two hydrogen atoms from the same or two different carbon atoms of the parent alkyne. For example, but not limited to, the alkynylene can have 2 to 20 carbon atoms, 2 to 10 carbon atoms, 2 to 6 carbon atoms, or 2 to 4 carbon atoms. Typical alkynylenes include, but are not limited to, ethynyl (-C≡C-), propargyl (-CH2C≡C-) and 4-pentynyl (-CH2CH2CH2C≡C-).

[0182] As used herein, the term "aryl" refers to an aromatic hydrocarbon group derived by removing a hydrogen atom from a single carbon atom of a parent aromatic ring system. For example, but not limited to, an aryl group can have 6 to 20 carbon atoms, 6 to 14 carbon atoms, or 6 to 10 carbon atoms. Typical aryl groups include, but are not limited to, groups derived from benzene (e.g., phenyl), groups derived from substituted benzenes, naphthalene, anthracene, and biphenyl.

[0183] As used herein, the term "aralkyl" refers to a radical in which the carbon atom (usually a terminal carbon atom or sp 3 A non-cyclic alkyl group in which one of the hydrogen atoms bonded to a carbon atom is replaced by an aryl group. Typical aralkyl groups include, but are not limited to, benzyl, 2-phenylethan-1-yl, naphthylmethyl, 2-naphthyleth-1-yl, naphthylbenzyl, 2-naphthylphenyleth-1-yl, etc. For example, but not limited to, the aralkyl group may include 7 to 20 carbon atoms, such as 1 to 6 carbon atoms in the alkyl portion and 6 to 14 carbon atoms in the aryl portion.

[0184] As used herein, the term "arylalkenyl" refers to a radical in which the carbon atom (usually a terminal carbon atom or sp 3 Carbon atoms, but also sp 2 The non-cyclic alkenyl group that one of the hydrogen atoms bonded to aryl (carbon atom) is replaced by aryl. The aryl moiety of arylalkenyl can include any aryl as described herein, and the alkenyl moiety of arylalkenyl can include any alkenyl as described herein. The arylalkenyl can include 8 to 20 carbon atoms, for example, the alkenyl moiety is 2 to 6 carbon atoms and the aryl moiety is 6 to 14 carbon atoms.

[0185] As used herein, the term "arylalkynyl" refers to a radical in which the carbon atom (usually a terminal carbon atom or sp 3 The term "arylalkynyl" refers to a non-cyclic alkynyl group in which one of the hydrogen atoms bonded to an aryl group is replaced by an aryl group. The aryl moiety of the arylalkynyl group may include, for example, any aryl group disclosed herein, and the alkynyl moiety of the arylalkynyl group may include, for example, any alkynyl group disclosed herein. For example, but not limitation, the arylalkynyl group may include 8 to 20 carbon atoms, for example, the alkynyl moiety may be 2 to 6 carbon atoms and the aryl moiety may be 6 to 14 carbon atoms.

[0186] As used herein, the term "heterocycle" refers to a group comprising a covalently closed ring, wherein at least one atom forming the ring is a heteroatom. For example, but not limited to, a heterocycle can be formed by three, four, five, six, seven, eight, nine or more than nine atoms. Any number of these atoms can be heteroatoms (i.e., a heterocycle can include one, two, three, four, five, six, seven, eight, nine or more than nine heteroatoms). In a heterocycle comprising two or more heteroatoms, these two or more heteroatoms can be the same or different from each other. The heterocycle can be substituted. The combination with the heterocycle can be at a heteroatom or through a carbon atom. It should also be understood that in this specification, the term "heterocycle" also includes a "heteroaryl" group.

[0187] As used herein, the term "protecting group" refers to a portion of a compound that masks or alters the properties of a functional group or the properties of the compound as a whole. The chemical substructures of protecting groups can vary widely. One function of a protecting group is to serve as an intermediate for the synthesis of a parent active substance. Chemical protecting groups and strategies for protection / deprotection are well known in the art. See "Protective Groups in Organic Chemistry", Theodora W. Greene (John Wiley & Sons, Inc., New York, 1991).

[0188] As used herein, the term "substituted" when referring to alkyl, alkylene, alkoxy, alkenyl, alkynyl, alkenylene, aryl, alkynylene and the like, for example, "substituted alkyl", "substituted alkylene", "substituted alkoxy"-"or substituted O(alkyl)", "substituted alkenyl", "substituted alkynyl", "substituted alkenylene", "substituted aryl" and "substituted alkynylene", means that one or more hydrogen atoms in alkyl, alkylene, alkoxy, alkenyl, alkynyl, alkenylene, aryl and alkynylene, respectively, are each independently replaced with a non-hydrogen substituent, unless otherwise indicated.

[0189] Typical non-hydrogen substituents include, but are not limited to: -X, -R B , -O - ,=O,-OR B 、-SR B , -S - 、-NR B 2. Si(R C )3. -N + R B 3. -NR b -(Alk)-NR B 2. -NR B -(Alk)-N + R B 3. -NR B -(Alk)-ORB 、-NR B -(Alk)-OP(=O)(OR B )(O - )、-NR B -(Alk)-OP(=O)(OR B )2、-NR B -(Alk)-Si(R C )3、-NR B -(Alk)-SR B 、-O-(Alk)-NR B 2、-O-(Alk)-N + R B 3、-O-(Alk)-OR B 、-O-(Alk)-OP(=O)(OR B )(O - )、-O-(Alk)-OP(=O)(OR B )2、-O-(Alk)-Si(R C )3、-O-(Alk)-SR B 、=NR B 、-CX3、-CN、-OCN、-SCN、-N=C=O、-NCS、-NO、-NO2、=N2、-N3、-NHC(=O)R B 、-OC(=O)R B 、-NHC(=O)NR B 2、-S(=O)2-、-S(=O)2OH、-S(=O)2R B 、-OS(=O)2OR B 、-S(=O)2NR B 2、-S(=O)R B 、-OP(=O)(OR B )(O - )、-OP(=O)(OR B )2、-P(=O)(OR B )2、-P(=O)(O - )2、-P(=O)(OH)2、-P(O)(OR B )(O - )、-C(=O)R B 、-C(=O)X、-C(S)R B 、-C(O)OR B 、-C(O)O - 、-C(S)OR B 、-C(O)SR B 、-C(S)SR B、-C(O)NR B 2. -C(S)NR B 2 or -C(=NR B )NR B 2; wherein X is independently a halogen: F, Cl, Br or I; R B R is independently H, alkyl, aryl, aralkyl, heterocycle, alkoxy (e.g., poly(ethyleneoxy), PEG, or poly(methyleneoxy)), or a protecting group; C Each is independently alkyl, O(alkyl) or O(trisubstituted silyl); and Alk is each independently alkylene, substituted alkylene, alkenylene, substituted alkenylene, alkynylene or substituted alkynylene. Unless otherwise indicated, when the term "substituted" is used in conjunction with a group having two or more parts capable of substitution (such as aralkyl), the substituent may be attached to the aryl portion, the alkyl portion or both.

[0190] It is also understood that the term "trisubstituted silyl" refers to a silyl group independently substituted with three functional groups selected from alkyl, alkenyl, alkynyl, aryl and aralkyl. Non-limiting examples of trisubstituted silyl groups include trimethylsilyl and dimethylphenylsilyl.

[0191] As used herein, the term "PEG" or "poly(ethylene glycol)" is intended to encompass any water-soluble poly(ethylene oxide). Typically, substantially all or all of the subunits of the monomers are ethylene oxide subunits, although the PEG may contain different end-capping moieties or functional groups. The PEG chains of the present specification may include one of the following structures: -(CH2CH2O) m -or-(CH2CH2O) m-1 CH2CH2-, depending on whether the terminal oxygen is substituted, wherein m is an integer, optionally selected from 1 to 100, 1 to 50, 1 to 30, 5 to 30, 5 to 20, or 5 to 15. PEG can be terminated with an "end-capping group", which is typically a non-reactive carbon-containing group attached to the terminal oxygen or other terminal atom of the PEG. Non-limiting examples of end-capping groups can include alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, CO(alkyl), CO(substituted alkyl), CO(alkenyl), CO(substituted alkenyl)), CO(alkynyl) or CO(substituted alkynyl).

[0192] Those skilled in the art will recognize that the substituents and other parts of the compounds of this specification should be selected to provide agriculturally useful compounds that can be formulated into acceptable agricultural compositions with a stable degree that can be applied to plants. The definitions and substituents of various and subclasses of the compounds of this specification are described and illustrated herein. Those skilled in the art will appreciate that any combination of the definitions and substituents described herein should not produce inoperable substances or compounds. It should also be understood that the phrase "inoperable substances or compounds" refers to compound structures that violate relevant scientific principles (e.g., carbon atoms connected to more than four covalent bonds) or compounds that are too unstable to be separated and formulated into agriculturally acceptable compositions.

[0193] The substituents selected for the compounds of this specification may be present recursively. In this context, a "recursive substituent" means that a substituent can refer to another instance of itself. Due to the recursive nature of such substituents, in theory, a large number of compounds can be present in any given embodiment. For example, R x Including R y Substituent. R y It can be R. R can be W 3 .W 3 It can be W 4 , and W 4 It can be R or include R y Substituents. Those skilled in the art of organic chemistry understand that the total number of such substituents will be subject to reasonable restrictions on the desired properties of the intended compound. For example, these properties include, but are not limited to, physical properties (such as molecular weight, solubility or log P), application properties (such as activity for the intended target, the possibility of being applied to plants), and practical properties (such as ease of synthesis). Typically, in a given embodiment, each recursive substituent can independently occur 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 3, 2, 1 or 0 times. For example, in a given embodiment, each recursive substituent can independently occur 3 times or less times. Recursive substituents are the expected aspects of the compounds of this specification. Those skilled in the art of organic chemistry understand the versatility of this type of substituents.

[0194] As used herein, the term "agriculturally acceptable salt" refers to a salt that shows insecticidal activity (i.e., active to one or more biological stresses) or can improve the resistance of plants to one or more abiotic stresses. The term also refers to a salt that is converted or can be converted into a compound or salt that has insecticidal activity or can improve the resistance of plants to one or more abiotic stresses in plants, water or soil. "Agriculturally acceptable salt" can be an agriculturally acceptable cation or an agriculturally acceptable anion. Non-limiting examples of agriculturally acceptable cations can include cations derived from alkali metals or alkaline earth metals and cations derived from ammonia and amines. For example, agriculturally acceptable cations can include sodium cations, potassium cations, magnesium cations, alkylammonium cations and ammonium cations. Non-limiting examples of agriculturally acceptable anions can include halide anions, phosphate anions, alkyl sulfate anions and carboxylate anions. For example, agriculturally acceptable anions can include chloride anions, bromide anions, methyl sulfate anions, ethyl sulfate anions, acetate anions, lactate anions, dimethyl phosphate anions or polyalkoxylated phosphate anions.

[0195] As used herein, the term "optionally substituted" when referring to a particular moiety of the compounds of the present specification, the term means that all substituents in that moiety are hydrogen, or one or more hydrogens of that moiety may be substituted with substituents such as those listed under the definition of the term "substituted" or otherwise specified.

[0196] It should be understood that all enantiomers, diastereomers and racemic mixtures, tautomers, polymorphs and pseudopolymorphs within the scope of the chemical formulas and compositions described herein and agriculturally acceptable salts thereof are included in this specification. All mixtures of these enantiomers and diastereomers are also within the scope of this specification.

[0197] The compound of this specification and its agriculturally acceptable salt can exist as different polymorphs or pseudopolymorphs.As used herein, crystalline polymorphism refers to the ability of crystalline compounds to exist with different crystal structures.Crystal polymorphism may be due to the difference (stacking polymorphism) of crystal packing or the difference (conformation polymorphism) of packing between different conformers of the same molecule.As used herein, crystalline pseudopolymorphism refers to the ability of hydrates or solvates of compounds to exist with different crystal structures.Due to the difference (stacking pseudopolymorphism) of crystal packing or due to the difference (conformation pseudopolymorphism) of packing between different conformers of the same molecule, the pseudopolymorphism of the compounds of the present invention may exist.The description and explanation of the compound of this specification are intended to include all polymorphs and pseudopolymorphs of the compound and its agriculturally acceptable salt.

[0198] The compounds of the present specification and their agriculturally acceptable salts may also exist as amorphous solids. As used herein, an amorphous solid is a solid in which the positions of atoms in the solid are not in long-range order. The description and illustration of the compounds of the present specification are intended to include all amorphous forms of the compounds and their agriculturally acceptable salts.

[0199] The modifier "about" used in connection with a quantity is inclusive of the stated value and has the meaning dictated by the context. For example, the modifier "about" may include the degree of error associated with the measurement of the quantity.

[0200] For agricultural use (i.e., application to plants), the salts of the compounds of the invention are agriculturally acceptable salts. However, agriculturally unacceptable salts may also be used to prepare or purify agriculturally acceptable compounds, for example. Therefore, all salts are understood to be within the scope of this specification, whether or not they are agriculturally acceptable salts.

[0201] It is understood that the compounds described herein may be in their unionized, ionized, and zwitterionic forms, and may be associated with various amounts of water (eg, stoichiometric amounts of water), such as in the form of hydrates.

[0202] Whenever a compound described herein is represented by more than one identical designated group (e.g., “R 1 ” or “R 2 ”), it will be understood that these groups may be the same or different, i.e., each group is independently selected. For example, in the expression “Si(OR 7 )3 Each R 7 In the phrase "is independently alkyl or aryl", it should be understood that each R 7 can be independently selected from alkyl and aryl. Si(OR 7 )3Thus including all three R 7 are all the same symmetrical groups, and at least one of the R 7 The group and the other two R 7 Different asymmetric groups, or each R 7 It should also be understood that this applies to all R defined herein. q or Z q group (e.g., q is selected from 1 to 17, a to f or A to C). 1 =Z 2 ” When “Z 1 " group will be understood to be necessarily associated with another "Z 2 "The groups are the same.

[0203] In some cases, the compounds described herein may also exist as tautomeric forms. Although only one delocalized resonance structure is usually depicted, all such forms are contemplated within the scope of the present specification. For example, the tetrapyrrole ring system described herein may exist as various tautomers, and all possible tautomeric forms thereof are within the scope of the present specification.

[0204] As used herein, the term "growing medium" refers to any soil (of any composition) or soilless (e.g., hydroponic) substrate suitable for growing and cultivating plants. The growth substrate may further include any naturally occurring and / or synthetic material suitable for growing and cultivating plants. As used herein, the phrase "any surface of the growth substrate" or "surface of the growth substrate" refers to a surface that is directly exposed to natural light and / or simulated light and / or weather.

[0205] As used herein, the term "applying" means contacting the surface of a growth substrate with at least one compound of the invention (e.g., a combination, composition, solution, emulsion comprising at least one compound of the invention) by any means known in the art (e.g., pouring, root bathing, soil drench, drip irrigation, etc.), or contacting an area below the surface of a growth substrate with at least one compound of the invention or any combination thereof (e.g., by soil injection), or directly contacting a plant with at least one compound of the invention (e.g., spraying).

[0206] As used herein, the term "crop plants" refers to non-woody plants that are grown, cared for, and harvested as a source of food and / or energy in a year or less cycle. Non-limiting examples of crop plants include sugar cane, wheat, rice, corn (maize), potatoes, sugar beets, barley, sweet potatoes, cassava, soybeans, tomatoes, and legumes (beans and peas).

[0207] As used herein, the term "woody plant" refers to a perennial woody plant (e.g., a tree) having a single stem or trunk and side branches at a distance from the ground. Woody plants can be deciduous trees, evergreen trees (e.g., conifers), or shrubs. Non-limiting examples of woody plants include maple trees, citrus trees, apple trees, pear trees, oak trees, ash trees, pine trees, and spruce trees.

[0208] As used herein, the term "lawn grass" refers to cultivated grasses that provide ground cover, such as turf or lawns that are mowed or mowed regularly to maintain a consistent height. Grasses belong to the Poaceae family, which is subdivided into six subfamilies, three of which include common lawn grasses: Festucoideae, a cool-season lawn grass; and Panicoideae and Eragrostoideae, a warm-season lawn grass. A limited number of species are widely used as lawn grasses, which generally meet the criteria of forming a uniform soil cover and tolerating mowing and traffic. Typically, lawn grasses have a flattened crown for easy mowing without cutting off the growing point. In this article, the term "lawn grass" includes areas where one or more grass species are cultivated to form a relatively uniform soil cover, including mixed varieties combined by different cultivars of the same species, or mixed products combined by different species and / or different cultivars.

[0209] Non-limiting examples of turf grasses include: bluegrass (e.g., Kentucky bluegrass), bentgrass (e.g., creeping bentgrass), chaff grass, fescue (e.g., red fescue), ryegrass (e.g., annual ryegrass), wheatgrass (e.g., wheatgrass), beach grass, bromegrass (e.g., Arizona Brome), cattail (e.g., sand cattail), alkali grass (Puccinellia distans), foxtail grass (Cynosurus cristatus), bermudagrass (Cynodon spp., e.g., Cynodon dactylon), hybrid bermudagrass (e.g., tifdwarf bermudagrass), zoysia (e.g., Zoysia japonica), St. Augustinegrass (e.g., Bitter Blue St. Augustinegrass), centipede grass (Eremochloa aophiuroides), carpet grass (Axonopus fissifolius), Paspalum notatum, Pennisetum clandestinum, Buchloe dactyloids, Seashore Paspalum (Paspalumvaginatum), Bouteloua gracilis, Bouteloua eriopoda, Sideoats Grama (Bouteloua curtipendula), Crabgrass (e.g., Alkali Field Millet), Gerbil Millet (Sporobolus cryptandrus), Prairie Millet (Sporobolus heterolepis), Hordeum (e.g., California Barley), Common Barley, Meadow Barley, Alopecurus (e.g., Creeping Foxtail and Pasture Foxtail), Stipa (e.g., Needle & Thread), Elymus (e.g.,Blue Wildrye, Cenchrus ciliaris, Briza maxima, Andropogon gerardii, Schizachyruimscoparium, Andropogon hallii, Muhlenbergia rigenss, Tripsacum dactyloides, Hilaria jamesii, Deschampsiacaespitosa, Oryzopsis hymenoides, Sorghastrum nutans, Eragrostis trichodes, Eragrostis mellica, California Melic, Koeleria pyramidata, Prairie Sandreed, Agrostis rubra alba), Phalaris arundinacea, Spartina pectinata, Leptochloa dubia, Sitanion hystrix, virgatum, and Aristida purpurea.

[0210] As used herein, the phrase "promoting plant health" includes at least one of controlling diseases, diseases or damage caused by plant pests and increasing resistance or tolerance of plants to abiotic stresses. In other words, the phrase "promoting plant health" includes at least one of "controlling infection of plants by one or more biotic agents", "controlling infestation of plants by one or more insect pests", and "increasing resistance of plants to one or more abiotic stresses".

[0211] As used herein, the phrase "controlling plant infection by biotic agents" refers to reducing, alleviating or stabilizing infection and / or any other existing undesirable conditions or side effects caused by an infestation of insect pests or the association of microbial pathogens. Microbial pathogens may include fungi, bacteria (Gram-positive or Gram-negative), viruses, viroids, virus-like organisms, phytoplasmas, and the like.

[0212] As used herein, the term "abiotic stress" refers to environmental conditions that negatively affect the growth, development, yield and yield quality of crops and other plants to less than optimal levels. Non-limiting examples of abiotic stress include, for example: photooxidative conditions, drought (water deficit), excessive watering (flooding and submergence), extreme temperatures (cold, freezing and heat), extreme light levels (high and low), radiation (UV-B and UV-A), excess Na + Salinity due to (alkalinity), chemical factors (e.g. pH), mineral (metal and metalloid) toxicity, deficiency or excess of essential nutrients, gaseous pollutants (ozone, sulfur dioxide), wind, mechanical factors and other sources of stress.

[0213] As used herein, the term "increasing stress resistance" (etc.) refers to increasing the ability of plants to survive or thrive under stress conditions. The increased resistance or tolerance can be directed to a specific stressor, such as drought, excess water, nutrient deficiency, salt, low temperature, cool, or high temperature, or multiple stressors. In some cases, increasing resistance to one or more abiotic stresses can be exemplified by a reduction in plant quality degradation compared to untreated plants subjected to the same stress. In other cases, increasing resistance to one or more abiotic stresses can be exemplified by maintaining or improving plant quality compared to untreated plants subjected to the same stress.

[0214] Photosensitizer compounds

[0215] As described above, photosensitizer compounds can be used to achieve photodynamic inhibition of biotic agents (ie, microbial pathogens and / or insect pests) present on plants. Photosensitizer compounds respond to light by producing reactive oxygen species (ROS).

[0216] According to the type of ROS generated, photosensitizers can be divided into two categories, namely type I photosensitizers and type II photosensitizers. On the one hand, type I photosensitizers, when excited at an appropriate wavelength in the presence of oxygen, form short-lived free radicals by extracting or transferring electrons from a substrate. On the other hand, type II photosensitizers form a highly reactive oxygen state called "singlet oxygen", also referred to herein as "reactive singlet oxygen". Singlet oxygen generally has a relatively long lifespan and a large radius of action.

[0217] It should be understood that the photosensitizer compound can be metallized or non-metallized. When metallized, as in the case of various nitrogen-containing macrocyclic compounds complexed with metals, the metal can be selected to produce a Type I or Type II photosensitizer that responds to light exposure. For example, when a chlorin compound is metallized with copper, the ROS produced are generally Type I photosensitizers. When the same chlorin compound is metallized with magnesium, the ROS produced are generally Type II photosensitizers. Both Type I and Type II photosensitizers can be used to achieve photodynamic inhibition of biotic factors present on plants or to protect plants from abiotic stresses.

[0218] It should be understood that the term "singlet oxygen photosensitizer" as used herein refers to a compound that generates a reactive singlet oxygen species when excited by light. In other words, the term "singlet oxygen photosensitizer" refers to a photosensitizer in which the type II process defined above is dominant over the type I process.

[0219] Chlorin e6 (Ce6) is also known as "phytochlorin", as shown below. Ce6 is a tetrapyrrole with a macrocyclic ring of 20 carbon atoms, each pyrrole being connected to two other pyrroles of the macrocyclic ring by a single carbon bridge. It should be understood that "tetrapyrrole" refers to four pyrrole-like rings. As used herein, a "pyrrole-like" ring is a five-atom ring with four carbon atoms and one nitrogen atom. In the following description of Ce6, the carbons of the macrocyclic ring are counted from 1 to 20. In the chemical structure of Ce6, three groups with carboxylic acids are provided at the C13 (COOH), C15 (CH2COOH) and C17 (CH2CH2COOH) positions.

[0220]

[0221] The compounds of this specification include photosensitizer compounds based on or similar to the above-mentioned Ce6 skeleton, which have the general formula I represented below, or its agriculturally acceptable salt. In the following, the term "photosensitizer compound" refers to one or more compounds of formula I. In other words, the term "photosensitizer compound" may refer to a compound of formula I, or a combination or mixture of two or more compounds of formula I.

[0222]

[0223] In one aspect, there is provided a compound of formula I or an agriculturally acceptable salt thereof, wherein:

[0224] Z 1 , Z 2 and Z 3 Each independently is OR 1 or NR 2 R 3 ;

[0225] R 1 , R 2 and R 3 are each independently H, alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl, or substituted alkynyl, wherein if Z 1 , Z 2 and Z 3 Each is OR 1 , then at least one R 1 is not H, and if Z 1, Z 2 and Z 3 Each is NR 2 R 3 , then at least one R 3 Not H;

[0226] R a , R b , R c , R d , R e and R f are each independently H, alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl;

[0227] is a single bond or a double bond;

[0228] is a single bond or a double bond; and

[0229] M is 2H or a metal species,

[0230] Wherein, the substituted alkyl, substituted aryl, substituted alkenyl and substituted alkynyl are independently substituted by one or more of the following groups: -X, -R B , -O - ,=O,-OR B 、-SR B , -S - 、-NR B 2. Si(R C )3. -N + R B 3. -NR B -(Alk)-NR B 2. -NR B -(Alk)-N + R B 3. -NR B -(Alk)-OR B 、-NR B -(Alk)-OP(=O)(OR B )(O - ),-NR B -(Alk)-OP(=O)(OR B )2.-NR B -(Alk)-Si(R C )3. -NR B -(Alk)-SR B 、-O-(Alk)-NR B 2. -O-(Alk)-N + R B 3. -O-(Alk)-ORB 、-O-(Alk)-OP(=O)(OR B )(O - )、-O-(Alk)-OP(=O)(OR B )2、-O-(Alk)-Si(R C )3. -O-(Alk)-SR B , =NR B , -CX3, -CN, -OCN, -SCN, -N=C=O, -NCS, -NO, -NO2, =N2, -N3, -NHC(=O)R B 、-OC(=O)R B 、-NHC(=O)NR B 2. -S(=O)2-, -S(=O)2OH, -S(=O)2R B 、-OS(=O)2OR B 、-S(=O)2NR B 2. -S(=O)R B ,-OP(=O)(OR B )(O - ),-OP(=O)(OR B )2.-P(=O)(OR B )2, -P(=O)(O - )2、-P(=O)(OH)2、-P(O)(OR B )(O - ), -C(=O)R B 、-C(=O)X、-C(S)R B 、-C(O)OR B 、-C(O)O - 、-C(S)OR B 、-C(O)SR B 、-C(S)SR B 、-C(O)NR B 2. -C(S)NR B 2 or -C(=NR B )NR B 2;

[0231] X is independently halogen: F, Cl, Br or I;

[0232] R B each is independently H, alkyl, aryl, aralkyl, heterocycle, alkoxy such as poly(ethyleneoxy), PEG, or poly(methyleneoxy), end-capped poly(ethyleneoxy), end-capped PEG, or end-capped polymethyleneoxy, or a protecting group;

[0233] The end-capped poly(ethyleneoxy), end-capped PEG, and end-capped poly(methyleneoxy) groups are each independently end-capped with an alkyl, alkenyl, alkynyl, CO(alkyl), CO(alkenyl), or CO(alkynyl);

[0234] R C Each is independently alkyl, aryl, aralkyl, O(alkyl), O(aryl), O(aralkyl), or O(trisubstituted silyl);

[0235] The trisubstituted silyl groups are each independently substituted by three functional groups selected from the group consisting of alkyl, alkenyl, alkynyl, aryl and aralkyl; and

[0236] Each Alk is independently an alkylene group, an alkenylene group, or an alkynylene group.

[0237] In some embodiments, Z 1 Yes OR 1 , Z 2 and Z 3 One of them is NR 2 R 3 , and Z 2 and Z 3 The other one is OR 1 In other embodiments, Z 1 Yes OR 1 , Z 2 YesNR 2 R 3 , and Z 3 =Z 2 In some embodiments, R 1 is H, and / or R 2 is H, and / or R 3 It is an alkyl group or a substituted alkyl group.

[0238] In some embodiments:

[0239] Z 1 Yes OR 1 ;

[0240] Z 2 and Z 3 One of them is NR 2 R 3 NR 2 -(CH2) n -NR 4 R 5 NR 2 -(CH2) n -N + R 4 R 5 R 6 Y - NR2 -(CH2) n -O(PO3H) - W + 、NR 2 -(CH2) n -Si(R 7 )3、NR 2 -(CH2) n -SR 8 、NR 2 -(CH2) n -NR 4 -(CH2) p -NR 9 R 10 、NR 2 -(CH2) n -NR 4 -(CH2) p -N + R 9 R 10 R 11 Y - 、NR 2 -(CH2) n -NR 4 -(CH2) p -O(PO3H) - W + 、NR 2 -(CH2) n -NR 4 -(CH2) p -Si(R 7 )3、NR 2 -(CH2) n -NR 4 -(CH2) p -SR 8 、O(CH 2 ) n -NR 4 R 5 、O(CH2) n -N + R 4 R 5 R 6 Y - 、O(CH2) n -O(PO3H) - W + 、O(CH2) n -Si(R 7 )3、O(CH2) n -SR 8 、O(CH2) n-NR 4 -(CH2) p -NR 9 R 10 、O(CH2) n -NR 4 -(CH2) p -N + R 9 R 10 R 11 Y - 、O(CH2) n -NR 4 -(CH2) p -O(PO3H) - W + or O(CH2) n -NR 4 -(CH2) p -Si(R 7 )3; and

[0241] Z 2 and Z 3 The other one is OR 12 ;

[0242] or

[0243] Z 2 YesNR 2 R 3 NR 2 -(CH2) n -NR 4 R 5 NR 2 -(CH2) n -N + R 4 R 5 R 6 Y - NR 2 -(CH2) n -O(PO3H) - W + NR 2 -(CH2) n -Si(R 7 )3.NR 2 -(CH2) n -SR 8 NR 2 -(CH2) n -NR 4 -(CH2) p -NR 9 R 10 NR 2-(CH2) n -NR 4 -(CH2) p -N + R 9 R 10 R 11 Y - 、NR 2 -(CH2) n -NR 4 -(CH2) p -O(PO3H) - W + 、NR 2 -(CH2) n -NR 4 -(CH2) p -Si(R 7 )3、NR 2 -(CH2) n -NR 4 -(CH2) p -SR 8 、O(CH2) n -NR 4 R 5 、O(CH2) n -N + R 4 R 5 R 6 Y - 、O(CH2) n -O(PO3H) - W + 、O(CH2) n -Si(R 7 )3、O(CH2) n -SR 8 、O(CH2) n -NR 4 -(CH2) p -NR 9 R 10 、O(CH2) n -NR 4 -(CH2) p -N + R 9 R 10 R 11 Y - 、O(CH2) n -NR 4 -(CH2) p -O(PO3H) - W + 或O(CH2) n-NR 4 -(CH2) p -Si(R 7 )3; and

[0244] Z 3 =Z 2 ;

[0245] R 1 , R 2 and R 12 are each independently H, alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl;

[0246] R 3 is alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl;

[0247] R 4 , R 6 , R 8 , R 9 , R 10 and R 11 are each independently H, alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, or -(CH2) q -(CH2CH2O) m -R 13 ;

[0248] R 5 is alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, or -(CH2) q -(CH2CH2O) m -R 13 ;

[0249] R 7 is alkyl, O(alkyl), or O(trisubstituted silyl);

[0250] R 13 is H, alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, CO(alkyl), CO(substituted alkyl), CO(alkenyl), CO(substituted alkenyl), CO(alkynyl), or CO(substituted alkynyl);

[0251] W + It is an agriculturally acceptable cation;

[0252] Y - It is an agriculturally acceptable anion;

[0253] n is an integer selected from 1 to 16;

[0254] p is an integer selected from 1 to 16;

[0255] q is an integer selected from 0 to 16;

[0256] m is an integer selected from 1 to 100;

[0257] R a , R b , R c , R d , R e and R f are each independently H, alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl;

[0258] is a single bond or a double bond;

[0259] is a single bond or a double bond; and

[0260] M is 2H or a metal species,

[0261] Wherein, the substituted alkyl, substituted aryl, substituted alkenyl and substituted alkynyl are each independently substituted by one or more of F, Cl, Br, I, CN and N3.

[0262] In some embodiments, is a single bond; and It's a double bond.

[0263] In some embodiments, the compound of Formula I is a compound of Formula I-A1* or an agriculturally acceptable salt thereof:

[0264]

[0265] In some embodiments, R a , R b , R c , R d , R e and R f Each is independently an alkyl or alkenyl group. In a non-limiting example, R a , R c , R e and R f is methyl; R b is vinyl; and R d It is ethyl.

[0266] In some embodiments, M is 2H. In some embodiments, M is a metal species selected from the group consisting of Mg(II), Zn(II), Pd(II), Sn(IV), Al(III), Pt(II), Si(IV), Ge(IV), Ga(III), and In(III).

[0267] In another aspect, there is provided a compound of formula I or an agriculturally acceptable salt thereof, wherein:

[0268] Z 1 Yes OR 1 ;

[0269] Z 2 and Z 3 One of them is NR 2 R 3 NR 2 -(CH2) n -NR 4 R 5 NR 2 -(CH2) n -N + R 4 R 5 R 6 Y - NR 2 -(CH2) n -O(PO3H) - W + NR 2 -(CH2) n -Si(R 7 )3.NR 2 -(CH2) n -SR 8 NR 2 -(CH2) n -NR 4 -(CH2) p -NR 9 R 10 NR 2 -(CH2) n -NR 4 -(CH2) p -N + R 9 R 10 R 11 Y - NR 2 -(CH2) n -NR 4 -(CH2) p -O(PO3H) - W + NR 2 -(CH2) n -NR 4 -(CH2) p -Si(R 7 )3.NR 2-(CH2) n -NR 4 -(CH2) p -SR 8 , OR 3 、O(CH2) n -NR 4 R 5 、O(CH2) n -N + R 4 R 5 R 6 Y - 、O(CH2) n -O(PO3H) - W + 、O(CH2) n -Si(R 7 )3. O(CH2) n -SR 8 、O(CH2) n -NR 4 -(CH2) p -NR 9 R 10 、O(CH2) n -NR 4 -(CH2) p -N + R 9 R 10 R 11 Y - 、O(CH2) n -NR 4 -(CH2) p -O(PO3H) - W + or O(CH2) n -NR 4 -(CH2) p -Si(R 7 )3; and

[0270] Z 2 and Z 3 The other one is OR 12 ;

[0271] or

[0272] Z 2 YesNR 2 R 3 NR 2 -(CH2) n -NR 4 R 5 NR 2 -(CH2)n -N + R 4 R 5 R 6 Y - 、NR 2 -(CH2) n -O(PO3H) - W + 、NR 2 -(CH2) n -Si(R 7 )3、NR 2 -(CH2) n -SR 8 、NR 2 -(CH2) n -NR 4 -(CH2) p -NR 9 R 10 、NR 2 -(CH2) n -NR 4 -(CH2) p -N + R 9 R 10 R 11 Y - 、NR 2 -(CH2) n -NR 4 -(CH2) p -O(PO3H) - W + 、NR 2 -(CH2) n -NR 4 -(CH2) p -Si(R 7 )3、NR 2 -(CH2) n -NR 4 -(CH2) p -SR 8 、OR 3 、O(CH2) n -NR 4 R 5 、O(CH2) n -N + R 4 R 5 R 6 Y - 、O(CH2) n -O(PO3H) - W +、O(CH2) n -Si(R 7 )3. O(CH2) n -SR 8 、O(CH2) n -NR 4 -(CH2) p -NR 9 R 10 、O(CH2) n -NR 4 -(CH2) p -N + R 9 R 10 R 11 Y - 、O(CH2) n -NR 4 -(CH2) p -O(PO3H) - W + or O(CH2) n -NR 4 -(CH2) p -Si(R 7 )3; and

[0273] Z 3 =Z 2 ;

[0274] R 1 , R 2 , R 4 , R 6 , R 8 , R 9 , R 10 , R 11 and R 12 are each independently H, alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, or -(CH2) q -(CH2CH2O) m -R 13 ;

[0275] R 3 and R 5 are each independently alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, or -(CH2) q -(CH2CH2O) m -R 13 ;

[0276] R 7 is alkyl, O(alkyl), or O(trisubstituted silyl);

[0277] R 13 is H, alkyl, substituted alkyl, aryl, substituted aryl, CO(alkyl) or CO(substituted alkyl), alkenyl, substituted alkenyl, CO(alkenyl) or CO(substituted alkenyl), alkynyl, substituted alkynyl, CO(alkynyl) or CO(substituted alkynyl);

[0278] W + It is an agriculturally acceptable cation;

[0279] Y - It is an agriculturally acceptable anion;

[0280] n is an integer selected from 1 to 16;

[0281] p is an integer selected from 1 to 16;

[0282] q is an integer selected from 0 to 16;

[0283] m is an integer selected from 1 to 100;

[0284] R a , R b , R c , R d , R e and R f are each independently H, alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl;

[0285] is a single bond or a double bond;

[0286] is a single bond or a double bond; and

[0287] M is 2H or a metal species,

[0288] Wherein, the substituted alkyl, substituted aryl, substituted alkenyl and substituted alkynyl are each independently substituted by one or more of F, Cl, Br, I, hydroxyl, CN and N3.

[0289] In some embodiments, is a single bond; and It's a double bond.

[0290] In some embodiments, the compound of Formula I is a compound of Formula I-A1* or an agriculturally acceptable salt thereof:

[0291]

[0292] In some embodiments, R a , R b , R c , R d , Re and R f Each is independently an alkyl or alkenyl group. For example, but not limited to, R a , R c , R e and R f It can be methyl; R b may be vinyl; and R d It may be ethyl.

[0293] In some embodiments, M is 2H. In some embodiments, M is a metal species selected from the group consisting of: Mg, Zn, Pd, Sn, Al, Pt, Si, Ge, Ga and In. It should be understood that when the metal species is mentioned without mentioning its degree of oxidation, all suitable oxidation states of the metal species are considered, which is understood by those skilled in the art. In some embodiments, M is a metal species selected from the group consisting of: Mg (II), Zn (II), Pd (II), Sn (IV), Al (III), Pt (II), Si (IV), Ge (IV), Ga (III) and In (III). In yet other embodiments, M is a metal species selected from the group consisting of: Cu (II), Co (II), Fe (II) and Mn (II).

[0294] In some embodiments, R 1 , R 2 , R 4 , R 6 , R 8 , R 9 , R 10 , R 11 and R 12 Each is independently H, alkyl, or substituted alkyl. 3 and R 5 Each is independently alkyl or substituted alkyl. 13 is H, alkyl, substituted alkyl, CO(alkyl), or CO(substituted alkyl).

[0295] In some embodiments, the compounds are selected such that at least one of the following is true: R 1 For H, R 2 For H, R 3 is an alkyl group, R 4 is H or alkyl, R 5 is an alkyl group, R 6 is an alkyl group, R 7 is O(trisubstituted silyl), R 8 -(CH2) q -(CH2CH2O) m -R13 , R 9 is an alkyl group, R 10 is an alkyl group, R 11 is an alkyl group, R 12 For H, R 13 is H, alkyl, alkenyl, CO(alkyl), or CO(alkenyl).

[0296] In some embodiments, W + is selected from the group consisting of sodium, potassium, magnesium and ammonium cations. - Selected from the group consisting of chloride, bromide, phosphate, dimethylphosphate, methylsulfate, ethylsulfate, acetate and lactate.

[0297] In some embodiments, n is an integer selected from 1 to 16, or 1 to 12, or 1 to 8, or 1 to 6, or 1 to 4, or 2 to 4. Similarly, in some embodiments, p is an integer selected from 1 to 16, or 1 to 12, or 1 to 8, or 1 to 6, or 1 to 4, or 2 to 4. With respect to the PEG moiety, m is an integer that may be selected from 1 to 100, or 1 to 80, or 1 to 60, or 1 to 50, or 1 to 30, or 1 to 20, or 1 to 10, or 5 to 30, or 5 to 20, or 5 to 10. Similarly, in some embodiments, q is an integer selected from 0 to 16, or 0 to 12, or 0 to 8, or 0 to 6, or 0 to 4. In some embodiments, q=1. In yet other embodiments, q=0.

[0298] In some embodiments, Z 2 YesNR 2 R 3 NR 2 -(CH2) n -NR 4 R 5 NR 2 -(CH2) n -N + R 4 R 5 R 6 Y - NR 2 -(CH2) n -O(PO3H) - W + NR 2 -(CH2) n -Si(R 7 )3.NR 2 -(CH2) n -SR 8 NR 2 -(CH2) n -NR4 -(CH2) p -NR 9 R 10 、NR 2 -(CH2) n -NR 4 -(CH2) p -N + R 9 R 10 R 11 Y - 、NR 2 -(CH2) n -NR 4 -(CH2) p -O(PO3H) - W + 、NR 2 -(CH2) n -NR 4 -(CH2) p -Si(R 7 )3、NR 2 -(CH2) n -NR 4 -(CH2) p -SR 8 、OR 3 、O(CH2) n -NR 4 R 5 、O(CH2) n -N + R 4 R 5 R 6 Y - 、O(CH2) n -O(PO3H) - W + 、O(CH2) n -Si(R 7 )3、O(CH2) n -SR 8 、O(CH2) n -NR 4 -(CH2) p -NR 9 R 10 、O(CH2) n -NR 4 -(CH2) p -N + R 9 R 10 R 11 Y - 、O(CH2)n -NR 4 -(CH2) p -O(PO3H) - W + or O(CH2) n -NR 4 -(CH2) p -Si(R 7 )3; and Z 3 Yes OR 12 or Z 3 =Z 2 .

[0299] In some embodiments, Z 2 YesNR 2 R 3 NR 2 -(CH2) n -NR 4 R 5 NR 2 -(CH2) n -N + R 4 R 5 R 6 Y - NR 2 -(CH2) n -O(PO3H) - W + NR 2 -(CH2) n -Si(R 7 )3.NR 2 -(CH2) n -SR 8 NR 2 -(CH2) n -NR 4 -(CH2) p -NR 9 R 10 ; and Z 3 Yes OR 12 or Z 3 =Z 2 .

[0300] In some embodiments, Z 3 Yes OR 12 For example, Z 3 It can be OH. In other embodiments, Z 3 =Z 2 .

[0301] In other aspects, provided is a compound of formula I-B1 or an agriculturally acceptable salt thereof:

[0302]

[0303] in:

[0304] Z 1 Yes OR 1 ;

[0305] R 2 is H, alkyl or substituted alkyl;

[0306] R 3 is an alkyl group or a substituted alkyl group;

[0307] Z 3 Yes OR 12， or Z 3 =NR 2 R 3 ;

[0308] R 1 and R 12 Each is independently H, alkyl or substituted alkyl;

[0309] R a , R b , R c , R d , R e and R f are each independently H, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl; and

[0310] M is 2H or a metal species,

[0311] Wherein, the substituted alkyl, substituted alkenyl and substituted alkynyl are independently substituted by one or more of F, Cl, Br, I, CN and N3.

[0312] In some embodiments, the compound of formula I-B1 is a compound of formula I-B1* or an agriculturally acceptable salt thereof:

[0313]

[0314] In some embodiments, R 1 Yes H, R 2 is H, and / or R 3 is an alkyl group. For example, R 3 It can be (C1-C 12 )alkyl, (C1-C8)alkyl, or (C1-C4)alkyl. 3 Yes OR 12 , and R 12 It can be H. In other embodiments, Z 3 =NR2 R 3 .

[0315] In some embodiments, the compound of formula I-B1 is a compound of the following formula or an agriculturally acceptable salt thereof:

[0316]

[0317] In some embodiments, the compound of formula I-B1* is a compound of the following formula or an agriculturally acceptable salt thereof:

[0318]

[0319] In other aspects, provided is a compound of formula I-B2 or an agriculturally acceptable salt thereof:

[0320]

[0321] in:

[0322] Z 1 Yes OR 1 ;

[0323] R 5 is alkyl, substituted alkyl, or -(CH2) p -NR 9 R 10 ;

[0324] R 2 , R 4 , R 9 and R 10 Each is independently H, alkyl or substituted alkyl;

[0325] n is an integer selected from 1 to 16;

[0326] p is an integer selected from 1 to 16;

[0327] Z 3 Yes OR 12， or Z 3 =NR 2 -(CH2) n -NR 4 R 5 ;

[0328] R 1 and R 12 Each is independently H, alkyl or substituted alkyl;

[0329] R a , R b , R c , R d , R e and Rf are each independently H, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl; and

[0330] M is 2H or a metal species,

[0331] Wherein, the substituted alkyl, substituted alkenyl and substituted alkynyl are independently substituted by one or more of F, Cl, Br, I, hydroxyl, CN and N3.

[0332] In some embodiments, the compound of formula I-B2 is a compound of formula I-B2* or an agriculturally acceptable salt thereof:

[0333]

[0334] In some embodiments, R 1 Yes H, R 2 is H, and / or R 4 is H or alkyl. In some embodiments, R 4 is H, and R 5 In some embodiments, R 4 and R 5 is an alkyl group. For example, R 4 and / or R 5 It can be (C1-C 12 )alkyl, (C1-C8)alkyl, or (C1-C4)alkyl. In some embodiments, R 5 Yes - (CH2) p -NR 9 R 10 In some embodiments, R 9 and R 10 is an alkyl group, or R 9 is H and R 10 is an alkyl group. For example, R 9 and / or R 10 It can be (C1-C 12 In some embodiments, n is an integer selected from 1 to 16, or 1 to 12, or 1 to 8, or 1 to 6, or 1 to 4, or 2 to 4.

[0335] In some embodiments, the compound of formula I-B2* is a compound of the formula: or an agriculturally acceptable salt thereof:

[0336]

[0337]

[0338]

[0339]

[0340] In some embodiments, the compound of formula I-B2* is a compound of the formula: or an agriculturally acceptable salt thereof:

[0341]

[0342]

[0343]

[0344] In other aspects, provided is a compound of formula I-B3 or an agriculturally acceptable salt thereof:

[0345]

[0346] in:

[0347] Z 1 Yes OR 1 ;

[0348] Z 4 Is Si(R 7 )3 or SR 8 ;

[0349] Z 3 Yes OR 12 or Z 3 =NR 2 -(CH2) n -Z 4 ;

[0350] R 1 , R 2 and R 12 Each is independently H, alkyl or substituted alkyl;

[0351] R 7 is alkyl, O(alkyl), or O(trisubstituted silyl);

[0352] R 8 is H, alkyl, substituted alkyl, or NR 2 -(CH2) n -NR 4 R 5 ;

[0353] R 13 is H, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, CO(alkyl), CO(substituted alkyl), CO(alkenyl), CO(substituted alkenyl), CO(alkynyl), or CO(substituted alkynyl);

[0354] n is an integer selected from 1 to 16;

[0355] m is an integer selected from 1 to 100;

[0356] R a , R b , R c , R d , R e and R f are each independently H, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl; and

[0357] M is 2H or a metal species,

[0358] Wherein, the substituted alkyl, substituted alkenyl and substituted alkynyl are independently substituted by one or more of F, Cl, Br, I, hydroxyl, CN and N3.

[0359] In some embodiments, the compound of formula I-B3 is a compound of formula I-B3* or an agriculturally acceptable salt thereof:

[0360]

[0361] In some embodiments, R 1 Yes H, R 2 is H, and / or R 12 is H or alkyl. In some embodiments, R 7 is alkyl, O(alkyl) or O(trisubstituted silyl), wherein alkyl is (C1-C 12 )alkyl, (C1-C8)alkyl, or (C1-C4)alkyl. In some embodiments, n is an integer selected from 1 to 16, or 1 to 12, or 1 to 8, or 1 to 6, or 1 to 4, or 2 to 4. In some embodiments, Z 3 Yes OR 12 In other embodiments, Z 3 =NR 2 -(CH2) n -Z 4 .

[0362] In some embodiments, the compound of formula I-B3 is a compound of the formula: or an agriculturally acceptable salt thereof:

[0363]

[0364] wherein m is an integer selected from 4 to 15.

[0365] In some embodiments, the compound of formula I-B3* is a compound of the following formula or an agriculturally acceptable salt thereof:

[0366]

[0367] wherein m is an integer selected from 4 to 15.

[0368] In some embodiments, the compound of formula I-B3 is the following compound or an agriculturally acceptable salt thereof:

[0369]

[0370]

[0371] In some embodiments, the compound of formula I-B3* is a compound of the formula: or an agriculturally acceptable salt thereof:

[0372]

[0373] In some embodiments, the compound of formula I-B3 is the following compound or an agriculturally acceptable salt thereof:

[0374]

[0375] In some embodiments, the compound of formula I-B3* is:

[0376]

[0377] or an agriculturally acceptable salt thereof.

[0378] In other aspects, provided is a compound of formula I-B4a or an agriculturally acceptable salt thereof:

[0379]

[0380] in:

[0381] Z 1 Yes OR 1 ;

[0382] Z 3 Yes OR 12 or Z 3 =NR2-(CH2) n -O(PO3H) - W + ;

[0383] R 1 , R 2 and R 12 Each is independently H, alkyl or substituted alkyl;

[0384] n is an integer selected from 1 to 16;

[0385] W + It is an agriculturally acceptable cation;

[0386] R a, R b , R c , R d , R e and R f are each independently H, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl; and

[0387] M is 2H or a metal species,

[0388] Wherein, the substituted alkyl, substituted alkenyl and substituted alkynyl are independently substituted by one or more of F, Cl, Br, I, hydroxyl, CN and N3.

[0389] In some embodiments, the compound of formula I-B4a is a compound of formula I-B4a* or an agriculturally acceptable salt thereof:

[0390]

[0391] In some embodiments, R 1 Yes H, R 2 is H, and / or R 12 is H or alkyl. In some embodiments, n is an integer selected from 1 to 16, or 1 to 12, or 1 to 8, or 1 to 6, or 1 to 4, or 2 to 4. W + is selected from the group consisting of sodium cations, potassium cations, magnesium cations, and ammonium cations. 3 Yes OR 12 In other embodiments, Z 3 =NR2-(CH2) n -O(PO3H) - W + .

[0392] In some embodiments, the compound of Formula I-B4a is the following compound or an agriculturally acceptable salt thereof:

[0393]

[0394] In some embodiments, the compound of formula I-B4a* is a compound of the formula: or an agriculturally acceptable salt thereof:

[0395]

[0396] In other aspects, provided is a compound of formula I-B4c or an agriculturally acceptable salt thereof:

[0397]

[0398] in:

[0399] Z 1 Yes OR1 ;

[0400] Z 3 Yes OR 12 or Z 3 =NR2-(CH2) n -NR 4 R 5 R 6+ Y - ;

[0401] R 1 , R 2 and R 12 Each is independently H, alkyl or substituted alkyl;

[0402] R 4 , R 5 and R 6 Each is independently an alkyl group or a substituted alkyl group;

[0403] n is an integer selected from 1 to 16;

[0404] Y - It is an agriculturally acceptable anion;

[0405] R a , R b , R c , R d , R e and R f are each independently H, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl; and

[0406] M is 2H or a metal species,

[0407] Wherein, the substituted alkyl, substituted alkenyl and substituted alkynyl are independently substituted by one or more of F, Cl, Br, I, hydroxyl, CN and N3.

[0408] In some embodiments, the compound of formula I-B4c is a compound of formula I-B4c* or an agriculturally acceptable salt thereof:

[0409]

[0410] In some embodiments, R 1 Yes H, R 2 is H, and / or R 12 is H or alkyl. In some embodiments, n is an integer selected from 1 to 16, or 1 to 12, or 1 to 8, or 1 to 6, or 1 to 4, or 2 to 4. In some embodiments, R 4 , R 5 and R 6 is alkyl, and optionally R 4=R 5 =R 6 Y- is selected from the group consisting of chloride, bromide, phosphate, dimethylphosphate, methylsulfate, ethylsulfate, acetate, and lactate. In some embodiments, Z 3 Yes OR 12 In other embodiments, Z 3 =NR2-(CH2) n -NR 4 R 5 R 6+ Y - .

[0411] In some embodiments, the compound of Formula I-B4c is the following compound or an agriculturally acceptable salt thereof:

[0412]

[0413] In some embodiments, the compound of formula I-B4c* is a compound of the formula: or an agriculturally acceptable salt thereof:

[0414]

[0415] In other aspects, provided are compounds of formula IC or agriculturally acceptable salts thereof:

[0416]

[0417] in:

[0418] Z 1 Yes OR 1 ;

[0419] Z 3 =OR 12 , and m is an integer selected from 1 to 100; or

[0420] Z 3 =O(CH2CH2O) m -R 13 , and m is an integer selected from 5 to 100;

[0421] R 1 and R 12 Each is independently H, alkyl or substituted alkyl;

[0422] R 13 is H, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, CO(alkyl), CO(substituted alkyl), CO(alkenyl), CO(substituted alkenyl), CO(alkynyl), or CO(substituted alkynyl);

[0423] R a , Rb , R c , R d , R e and R f are each independently H, alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl;

[0424] is a single bond or a double bond;

[0425] is a single bond or a double bond; and

[0426] M is 2H or a metal species,

[0427] Wherein, the substituted alkyl, substituted alkenyl and substituted alkynyl are independently substituted by one or more of F, Cl, Br, I, hydroxyl, CN and N3.

[0428] In some embodiments, the compound of Formula IC is a compound of Formula IC* or an agriculturally acceptable salt thereof:

[0429]

[0430] In some embodiments, R 1 is H, and / or R 12 is H. In some embodiments, m is an integer selected from 5 to 100, or 5 to 80, or 5 to 50, or 5 to 20, or 5 to 10. In some embodiments, Z 3 Yes OR 12 In other embodiments, Z 3 =O(CH2CH2O) m -R 13 In some embodiments, R 13 is H, alkyl, alkynyl, CO(alkyl), or CO(alkynyl).

[0431] In some embodiments, the compound of Formula IC is the following compound or an agriculturally acceptable salt thereof:

[0432]

[0433] in:

[0434] m is an integer selected from 1 to 100; and

[0435] R 14 It is an aryl group, an alkyl group, a substituted aryl group or a substituted alkyl group.

[0436] In some embodiments, the compound of Formula IC is the following compound or an agriculturally acceptable salt thereof:

[0437]

[0438] in:

[0439] m is an integer selected from 5 to 100; and

[0440] R 14 It is an alkyl group or a substituted alkyl group.

[0441] In some embodiments, the compound of Formula IC is the following compound or an agriculturally acceptable salt thereof:

[0442]

[0443] In some embodiments, the compound of formula IC* is the following compound or an agriculturally acceptable salt thereof:

[0444]

[0445] In some embodiments, the compound of Formula IC is the following compound or an agriculturally acceptable salt thereof:

[0446]

[0447] In some embodiments, the compound of formula IC* is the following compound or an agriculturally acceptable salt thereof:

[0448]

[0449] Synthetic intermediates and manufacturing methods

[0450] In one aspect, compounds of formula II-A and / or formula II-B are provided, which can be used to synthesize compounds of formula I, I-A1, I-B1, I-B2, I-B3, I-B4a, I-B4c and / or IC described herein, or salts thereof:

[0451]

[0452] in:

[0453] R 7 is H, alkyl, aryl, or alkoxy;

[0454] R a , R b , R c , R d , R e and R f are each independently H, alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl;

[0455] is a single bond or a double bond;

[0456] is a single bond or a double bond; and

[0457] M is 2H or a metal species,

[0458] Wherein, the substituted alkyl, substituted aryl, substituted alkenyl and substituted alkynyl are independently substituted by one or more of F, Cl, Br, I, hydroxyl, alkenyl, CN and N3.

[0459] In some embodiments, is a single bond; and It's a double bond.

[0460] In some embodiments, the compound of formula II-A and the compound of formula II-B are compounds of formula II-A1* or compounds of formula II-B1* or salts thereof:

[0461]

[0462] In some embodiments, R a , R b , R c , R d , R e and R f Each is independently an alkyl or alkenyl group. For example, but not limited to, R a , R c , R e and R f It can be methyl; R b may be vinyl; and R d It may be ethyl.

[0463] In some embodiments, M is 2H. In some embodiments, M is a metal species selected from the group consisting of Mg(II), Zn(II), Pd(II), Sn(IV), Al(III), Pt(II), Si(IV), Ge(IV), Ga(III), and In(III).

[0464] For example, the compound of formula II-A may be a compound of the following formula or a salt thereof:

[0465]

[0466] For example, the compound of formula II-A1* may be a compound of the following formula or a salt thereof:

[0467]

[0468] For example, the compound of formula II-B may be the following compound or a salt thereof:

[0469]

[0470] For example, the compound of formula II-B1* may be a compound of the following formula or a salt thereof:

[0471]

[0472] In another aspect, a method for preparing a compound of formula II-A and / or formula II-B or a salt thereof is provided:

[0473]

[0474] in:

[0475] R 17 is H, alkyl, aryl, or alkoxy;

[0476] R a , R b , R c , R d , R e and R f are each independently H, alkyl, substituted alkyl, aryl, substituted aryl, alkenyl, substituted alkenyl, alkynyl or substituted alkynyl;

[0477] is a single bond or a double bond;

[0478] is a single bond or a double bond; and

[0479] M is 2H or a metal species,

[0480] wherein the substituted alkyl, substituted aryl, substituted alkenyl and substituted alkynyl are independently substituted by one or more of F, Cl, Br, I, hydroxyl, alkenyl, CN and N3;

[0481] The method comprises:

[0482] The compound of formula III or its salt is reacted with the general formula (R 17 CO)2O anhydride reaction,

[0483]

[0484] M 1 is 2H or metal species, M 1 Different from or the same as M.

[0485] In some embodiments, M is 2H and M 1 is 2H. In other embodiments, M is a metal species and M 1 =M.

[0486] In other embodiments, M is a metal species and M 1is 2H. In this case, the method may further comprise a metalation reaction of a compound of formula II-A or II-B, wherein M=2H.

[0487] In other embodiments, M is 2H and M 1 is a metal species. In this case, the method may further include a compound of formula II-A or formula II-B or wherein M=M 1 Demetallation reaction of a compound of formula III to obtain the corresponding compound wherein M=2H.

[0488] In other embodiments, M 1 is a first metal species and M is a second metal species. In this case, the method may include a trans-metalation reaction to convert the compound of formula II-A or formula II-B or formula III to replace the first metal species and insert the second metal species.

[0489] In some embodiments, the compound of formula III and the compound of formula (R 17 The reaction of the anhydride of CO)2O is carried out at a temperature of up to 50°C, or up to 40°C, or between about 15°C and about 40°C. In some embodiments, the temperature is ambient temperature. 17 The reaction of the anhydride of (R 17 CO)2O (i.e., the reaction can be carried out under "neat" conditions).

[0490] According to R 17 The molar ratio of II-A:II-B can vary depending on the nature of the groups. For example, when R 17 When R is methyl, a compound of formula II-A is obtained. 17 When it is tert-butoxy, a compound of formula II-B is obtained.

[0491] Synthesis of photosensitizer compounds

[0492] In addition, a method for preparing a compound of formula I, I-A1, I-B1, I-B2, I-B3, I-B4a, I-B4c and / or IC described herein is provided, comprising reacting a compound of formula II-A or II-B or a salt thereof with a corresponding nucleophile (e.g., amine, alcohol, etc.). The reaction can be carried out in the presence or absence of a base (the base is, for example, sodium bicarbonate).

[0493] For example, the compound of formula II-A can be reacted with 2 equivalents or more of a nucleophile RXH (X=O or X=NH) in the presence or absence of a base to give a mixture of mono- and di-substituted (bis) reaction compounds as shown below.

[0494]

[0495] In another example, the compound of Formula II-B can be reacted with a nucleophile RXH (X=O or X=NH) in the presence or absence of a base to give a monosubstituted (mono) compound as shown below.

[0496]

[0497] Examples of such reactions can be found in the Examples section.

[0498] Chelating agents

[0499] In some embodiments, photosensitizer compounds can be applied to plants in combination with chelators (also referred to herein as permeabilizers). In some cases, photosensitizer compounds react with light by producing ROS, while chelators can enhance the overall effect of inhibiting the growth of microbial pathogens, for example, by increasing the permeability of the outer membrane of microbial pathogens to photosensitizers. It should be understood that the term "chelator" used herein generally refers to a compound that can form a variety of chelate bonds with one or more metals or ions.

[0500] In some embodiments, chelating agent can include at least one carboxyl, at least one hydroxyl, at least one phenolic group and / or at least one amino group, or its agriculturally acceptable salt. In some embodiments, chelating agent can include aminocarboxylic acid compound or its agriculturally acceptable salt. The aminocarboxylic acid or its agriculturally acceptable salt can include aminopolycarboxylic acid or its agriculturally acceptable salt. For example, the aminopolycarboxylic acid can include two amino groups and two alkyl carboxyl groups combined with each amino group. The alkyl carboxyl group can be methyl carboxyl.

[0501] In some embodiments, the chelating agent is selected from the group consisting of aminopolycarboxylic acids, aromatic or aliphatic carboxylic acids, amino acids, phosphonic acids, and hydroxycarboxylic acids or agriculturally acceptable salts thereof.

[0502] In some embodiments, the methods and compositions described herein include one or more aminopolycarboxylic acid chelating agents. Examples of aminopolycarboxylic acid chelating agents include, but are not limited to, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylenediaminetriacetic acid (HEDTA) and ethylenediaminedisuccinic acid (EDDS), cyclohexanediaminetetraacetic acid (CDTA), N-(2-hydroxyethyl)ethylenediaminetriacetic acid (EDTA-OH), glycol ether diaminetetraacetic acid (GEDTA), alanine diacetic acid (ADA), alkanoylethylenediaminetriacetic acid (e.g., lauroylethylenediaminetriacetic acid (LED3A)), aspartic acid diacetic acid (ASDA), aspartic acid monoacetic acid, diaminocyclohexanetetraacetic acid (CDTA), 1,2-diaminopropanetetraacetic acid (DPTA), The present invention relates to an aqueous solution of at least one ethylenediamine diacetic acid (ADA-OH), 1,3-diamino-2-propanol tetraacetic acid (DTPA), diethylenetriamine pentaethylenephosphonic acid (DTPMP), diglycolic acid, dipicolinic acid (DPA), ethanolamine diacetic acid, hydroxyethyliminodiacetic acid (EDG), ethylenediamine diglutaric acid (EDDG), ethylenediamine di(hydroxyphenylacetic acid (EDDHA)), ethylenediamine dipropionic acid (EDDP), ethylenediamine disuccinic acid (EDDS), ethylenediamine monosuccinic acid (EDMS), ethylenediaminetetraacetic acid (EDTA), ethylenediamine tetrapropionic acid (EDTP) and ethylene glycol aminoethyl ester tetraacetic acid (EGTA) and agriculturally acceptable salts thereof (e.g., sodium, calcium and / or potassium salts).

[0503] A non-limiting example of a chelating agent is ethylenediaminetetraacetic acid (EDTA) or an agriculturally acceptable salt thereof.The aminocarboxylate may, for example, be a sodium salt or a calcium salt.

[0504] Another non-limiting example of a chelating agent is polyaspartic acid or an agriculturally acceptable salt thereof (ie, polyaspartate), such as sodium polyaspartate. The molecular weight of the polyaspartate may be, for example, 2,000 to 3,000.

[0505] Thus, the chelating agent may be a polymeric compound that may include aspartic acid units, carboxyl groups, and other features found in polyaspartic acid. Polyaspartic acid may be a copolymer having alpha and beta bonds in various ratios (e.g., 30% alpha, 70% beta, randomly distributed along the polymer chain). A non-limiting example of sodium polyaspartate is DS100.

[0506] Other non-limiting examples of chelating agents include EDDS (ethylenediamine-N,N'-disuccinic acid), IDS (iminodisuccinic acid (N-1,2-dicarboxyethyl)-D,L-aspartic acid), isopropylamine, triethanolamine, triethylamine, ammonium hydroxide, tetrabutylammonium hydroxide, hexamine, GLDA (L-glutamic acid N,N-diacetic acid) or agriculturally acceptable salts thereof. Chelating agents can be metallized or non-metallized. In some embodiments, IDS can be used as a tetrasodium salt of IDS (e.g., tetrasodium iminodisuccinate), which can be CX100. In some embodiments, EDDS can be used as the trisodium salt of EDDS. In some embodiments, GLDA can be used as the tetrasodium salt of GLDA.

[0507] In some embodiments, the chelating agent can include one or more amino acid chelating agents. Examples of amino acid chelating agents include, but are not limited to, alanine, arginine, asparagine, aspartic acid, glutamic acid, glutamine, glycine, histidine, isoleucine, leucine, lysine, methionine, proline, serine, threonine, tyrosine, valine, or salts thereof (e.g., sodium salts, calcium salts, and / or potassium salts) and combinations thereof.

[0508] In some embodiments, the chelating agent may include one or more aromatic carboxylic acid chelating agents or aliphatic carboxylic acid chelating agents. Examples of aromatic carboxylic acid chelating agents or aliphatic carboxylic acid chelating agents include, but are not limited to, oxalic acid, succinic acid, pyruvic acid, malic acid, malonic acid, salicylic acid, and anthranilic acid and salts thereof (e.g., sodium salts, calcium salts, and / or potassium salts). In some embodiments, the methods and compositions described herein include one or more polyphenol chelating agents. A non-limiting example of a polyphenol chelating agent is tannic acid, such as tannic acid.

[0509] In some embodiments, the chelating agent may include one or more hydroxycarboxylic acid chelating agents. Examples of hydroxycarboxylic acid-type chelating agents include, but are not limited to, malic acid, citric acid, glycolic acid, heptanoic acid, tartaric acid, and salts thereof (eg, sodium, calcium, and / or potassium salts).

[0510] It should be understood that one or more chelating agents can be applied in the form of free acid, agriculturally acceptable salt or a combination thereof. In some embodiments, each of the one or more chelating agents is applied in the form of free acid. In other embodiments, the chelating agent can be applied in the form of a salt. Exemplary salts include sodium salts, potassium salts, calcium salts, ammonium salts, amine salts, amide salts and combinations thereof. In other embodiments, when there is more than one chelating agent, at least one chelating agent is applied in the form of free acid, and at least one chelating agent is applied in the form of a salt.

[0511] Additives and auxiliaries

[0512] In some embodiments, the photosensitizer compound can be applied to plants in combination with one or more agriculturally suitable adjuvants. Each of the one or more agriculturally suitable adjuvants can be independently selected from the group consisting of: one or more activator adjuvants (e.g., one or more surfactants; for example, one or more oily adjuvants, for example, one or more penetrants) and one or more utility adjuvants (e.g., one or more wetting agents or dispersants; one or more wetting agents; one or more emulsifiers; one or more drift control agents; one or more thickeners; one or more sedimentation agents; one or more water quality improvers; one or more buffers; one or more defoamers; one or more UV blockers; one or more antioxidants; one or more fertilizers, nutrients and / or micronutrients; and / or one or more herbicide safeners). Exemplary adjuvants are provided in Hazen, JL Weed Technology 14: 773-784 (2000), the entire contents of which are incorporated herein by reference.

[0513] In some embodiments, the photosensitizer compound can be applied to plants in combination with an oil. The oil can be selected from the group consisting of mineral oil (e.g., paraffin oil), vegetable oil, essential oil, and mixtures thereof. In some cases, the photosensitizer compound can be combined with an oil to improve the solubility of the photosensitizer compound when it contacts the plant. In the presence of a carrier liquid (e.g., water) or without a carrier liquid, the oil can be added together with the photosensitizer compound or added separately.

[0514] The non-limiting examples of vegetable oils include oils containing medium chain triglycerides (MCT), or oils extracted from nuts. Other non-limiting examples of vegetable oils include coconut oil, canola oil, soybean oil, rapeseed oil, sunflower oil, safflower oil, peanut oil, cottonseed oil, palm oil, rice bran oil and mixtures thereof. The non-limiting examples of mineral oils include paraffin oil, branched paraffin oil, naphthenic oil, aromatic oil and mixtures thereof.

[0515] Non-limiting examples of paraffin oils include various grades of polyalphaolefins (PAO). For example, paraffin oils may include HT60 TM HT100 TM 、High Flash Jet、LSRD TM and N65DW TM The paraffinic oil may include paraffins having a carbon number ranging from about 12 to about 50, or about 16 to 35. In some cases, the average carbon number of the paraffins may be 23. In some embodiments, the oil may have a paraffin content of at least 80%, or at least 90%, or at least 99% by weight.

[0516] Photosensitizer compound and oil can be added sequentially or simultaneously.When adding simultaneously, photosensitizer compound and oil can be used as the part of same composition or as the part of two separate compositions to add.In some embodiments, photosensitizer compound and oil can be combined with oil-in-water emulsion.That is to say, this combination can comprise the nitrogenous macrocyclic compound combined with oil and water, so that composition is mixed with oil-in-water emulsion.Oil-in-water emulsion can also comprise other additives, for example chelating agent, surfactant or its combination.

[0517] As used herein, the term "oil-in-water emulsion" refers to a mixture in which one of oil (e.g., paraffin oil) and water is dispersed in the other (e.g., water) in the form of droplets. In some embodiments, the oil-in-water emulsion is prepared by a method comprising combining the paraffin oil, water, and any other components, and applying shear until an emulsion is obtained. In other embodiments, the oil-in-water emulsion is prepared by a method comprising combining the paraffin oil, water, and any other components in a mixing tank and spraying through the nozzle of a spray gun.

[0518] In some embodiments, the photosensitizer compound is part of a composition that includes a carrier liquid. A suitable carrier liquid can allow a stable solution, suspension, and / or emulsion of the components of the composition to be obtained in the carrier liquid. In some embodiments, the carrier liquid is water. In other embodiments, the carrier liquid is a mixture of water and other solvents or oils that are immiscible or only partially soluble in water.

[0519] In some embodiments, a combination of a photosensitizer compound and an oil can be used to improve plant resistance to abiotic stress. The combination can be an oil-in-water emulsion, wherein the surfactant is selected so that the photosensitizer compound remains dispersed in the oil-in-water emulsion for delivery to the plant.

[0520] The combination can include a surfactant (also referred to as an emulsifier). The surfactant can be selected from the group consisting of ethoxylated alcohols, polymeric surfactants, fatty acid esters, polyethylene glycols, ethoxylated alkyl alcohols, monoglycerides, alkyl monoglycerides, amphipathic glycosides and mixtures thereof. For example, the fatty acid ester can be a sorbitan fatty acid ester. The surfactant can include a glycoside of plant origin, such as saponin. The surfactant can be used as an adjuvant to help cover plant leaves. The surfactant can be an acceptable polysorbate-based surfactant (e.g., Tween 80), a nonionic surfactant blend (e.g., AtloxTM 3273), or other suitable surfactants.

[0521] In some embodiments, the polyethylene glycol may include the formula R 15 -O-(CH2CH2O) f -R 16 of polyethylene glycol, wherein R 15and R 16 Each is independently H, alkyl, substituted alkyl, aryl, substituted aryl, CO(alkyl), or CO(substituted alkyl); f is an integer selected from 1 to 100; wherein the substituted alkyl is independently substituted by one or more of F, Cl, Br, I, hydroxyl, alkenyl, CN and N3.

[0522] Compositions including photosensitizer compounds

[0523] It should also be understood that the photosensitizer compound and other agents (e.g., chelators, oils, surfactants, etc.) can be provided to the plant separately or together as part of the same composition. In some embodiments, the components of the composition can be packaged in a concentrated form without a carrier liquid, and the operator can directly add a carrier liquid (e.g., water) to form the composition, which can then be applied to the plant.

[0524] When the components are provided as part of a single composition, a composition having certain concentrations and relative proportions of the components can be provided. For example, the composition can have about 100 nM to about 50 mM, about 5 μM to about 10 mM, about 1 μM to about 1000 μM, about 5 μM to about 200 μM of a photosensitizer compound, about 10 μM to about 150 μM of a nitrogen-containing macrocyclic compound, about 25 μM to about 100 μM of a nitrogen-containing macrocyclic compound, or about 50 μM to about 75 μM of a photosensitizer compound.

[0525] For example, but not limitation, the composition can also include about 2 μM to about 10,000 μM chelator, about 5 μM to about 5,000 μM chelator, about 10 μM to about 1,000 μM chelator, about 25 μM to about 500 μM chelator, about 50 μM to about 100 μM chelator.

[0526] For example, but not limited to, the relative ratio of the nitrogen-containing macrocyclic compound and the chelating agent in the composition can be about 50:1 to about 1:1000, about 20:1 to about 1:500, about 10:1 to about 1:100, or about 1:1 to about 1:10 by weight.

[0527] For example, but not limitation, the photosensitizer compound and the oil may be applied in relative proportions of about 50:1 to about 1:1000, about 20:1 to about 1:500, about 10:1 to about 1:100, or about 1:1 to about 1:10 by weight.

[0528] Compositions comprising photosensitizer compounds can be applied to plants in a variety of ways. For example, compositions can be prepared to include photosensitizer compounds, chelating agents and delivery fluids (e.g., water or water-oil emulsions). The composition can be applied to plants by spraying, spraying, spraying, pouring or any other suitable method. Antimicrobial compositions can be applied to leaves, seeds, roots and / or stems of plants. Other additives can also be included in the antimicrobial compositions, and other application methods can also be carried out.

[0529] The plants to which the composition is applied can be exposed to natural sunlight outdoors or indoors (e.g., in a greenhouse), or to artificial light indoors. Providing exposure to incident light allows the photosensitizer compound to generate ROS, thereby promoting the destruction of microbial growth.

[0530] In some embodiments, photosensitizer compounds can be used to process seeds or seedlings. In some cases, the processing of seeds or seedlings can stimulate germination and growth, and / or can improve the resistance of plants to abiotic stress. In some embodiments, seeds or seedlings can be treated with photosensitizer compounds before being planted in a growth matrix. In some embodiments, seeds or seedlings can be treated with photosensitizer compounds after being planted in a growth matrix.

[0531] Photosensitizer compounds can be directly surface coated on seeds and applied to seedling roots or seedling leaves (foliar application to seedlings). In some embodiments, solutions or emulsions containing photosensitizer compounds can be directly sprayed onto seeds or seedlings. In some embodiments, seeds or seedlings can be immersed in solutions or emulsions containing photosensitizer compounds. In some embodiments, the roots of seedlings can be immersed in solutions or emulsions containing photosensitizer compounds. In some embodiments, seeds can be placed in containers, and solutions containing photosensitizer compounds can be introduced into containers. The container can then be shaken for an appropriate time (e.g., about 1 minute to several minutes) so that the solution contacts the seeds. The seeds shaken can then be dried (e.g., air-dried) before planting.

[0532] Various modes of application can be used to apply photosensitizer compounds once, twice or more than twice to seeds or seedlings. For example, seeds can be processed after being planted in a growth matrix. In another example, seeds and / or seedlings can be processed before and after planting (for example, in furrows, processing and / or foliar application). In another example, seeds can be processed before and / or after planting, and subsequent seedlings (for example, root treatment and / or leaf treatment) can be further processed.

[0533] Microbial pathogens

[0534] Microbial pathogens to which compositions including photosensitizer compounds may be applied include fungal pathogens and bacterial pathogens. In this case, the composition may be referred to as an "antimicrobial composition".

[0535] Fungal pathogens to which the antimicrobial composition may be applied include Alternaria solani, which can infect plants such as tomatoes and potatoes; Botrytis cinerea, which can infect grapes, berries and bulb crops; or Sclerotinia homoeocarpa, which can commonly infect turfgrass. Other fungal pathogens in the genera Alternaria, Botrytis or Sclerotinia may also be treated with the antimicrobial composition. The antimicrobial composition can be applied to plants affected or susceptible to pathogens that cause a variety of plant diseases, such as Colletotrichum, Fusarium, Puccinia, Erysiphaceae, Cercospora, Rhizoctonia, Bipolaris, Microdochium, Venturia inaequalis, Monilinia fructicola, Gymnosporangium juniperi-virginianae, Plasmodiophora braceicae, Ustilago zeae, Phytophthora, Pythium, Fusarium oxysporum, Phytophthora infestans, Taphrina deformans), Powdery Mildew, Phragmidium spp., or other fungal pathogens.

[0536] Bacterial pathogens to which the antimicrobial composition can be applied include Gram-negative bacteria (e.g., Erwinia amylovora) or other bacterial pathogens in the genus Erwinia that can infect woody plants. Erwinia amylovora causes fire blight on a variety of plants including pears, apples, and other Rosaceae crops. The antimicrobial composition can be applied to plants that are affected or susceptible to pathogens that cause a variety of plant diseases, such as Pseudomonas, Xanthomonas, Agrobacterium, Curtobacterium, Streptomyces, E. Coli, Xylella fastidiosa (causing diseases of olive rapid decline syndrome (OQDS)), or other bacterial pathogens.

[0537] It should also be noted that, depending on the type of plant and pathogen and the state of microbial infection, the antimicrobial compositions described herein can have a variety of inhibitory effects on microbial pathogens. Although it is described herein that the antimicrobial compositions can inhibit the growth of microbial pathogens on plants, this expression should not be restrictive, but should be understood to include inhibiting microbial pathogens, preventing microbial pathogens, destroying microbial pathogens, or generally improving the toxicity to microbial pathogens.

[0538] Abiotic stress

[0539] As described above, in some embodiments, the photosensitizer compounds and compositions of the present invention can be used to increase the resistance of plants to one or more abiotic stresses, such as: photooxidative conditions, drought (water deficit), overwatering (flooding and submersion), extreme temperatures (cold, freezing and heat), extreme light levels (high and low), radiation (UV-B and UV-A), excess Na + Salinity due to (alkalinity), chemical factors (e.g. pH), mineral (metal and metalloid) toxicity, deficiency or excess of essential nutrients, gaseous pollutants (ozone, sulfur dioxide), wind, mechanical factors and other sources of stress.

[0540] cold resistance

[0541] When abiotic stress is low temperature stress, applying photosensitizer compounds alone or in combination with additives (such as oil, surfactant and / or chelating agent) can improve the cold resistance of plants. That is, using photosensitizer compounds can allow plants to withstand colder temperature conditions than the temperature conditions usually experienced under the optimal growth conditions or natural growth conditions of plants. Various types of low temperature stress are possible, such as unexpected frost (for example, early autumn frost when healthy crops, fruits, cereals, seeds or leaves are still on plants, or late spring frost that occurs after spring plant growth has begun), colder seasons than average growing seasons, colder conditions than natural winter conditions, minimum winter snow cover, ice accumulation, etc.

[0542] It should be noted that conditions that constitute cold stress for one plant may not be cold stress conditions for another plant. Referring to the USDA regional map, cold stress conditions for plants in region 9 may actually be natural growing conditions for plants in region 8. Likewise, the thickness of snow cover required for survival of one type of plant may not be required for a second type of plant. Therefore, it should be understood that various types of cold stress are possible depending on the type of plant in question.

[0543] The photosensitizer compounds, compositions or combinations described herein can be used to protect plants (including woody plants, non-woody plants and lawn grasses) from frost damage. Frost can be early frost, such as before harvest, after harvest and before dormancy. Frost can be late frost, such as after budding. Low temperature damage can also be freezing to death caused by winter temperatures, which may bring about the loss of living branches or buds and cause plant death. Plants treated by photosensitizer compounds, compositions or combinations described herein can be frost-sensitive plants or low temperature-sensitive plants because they are naturally susceptible to economically or aesthetically significant amounts of damage or injury from frost, freezing or low temperatures.

[0544] The increase in resistance to low temperature stress can be demonstrated by a delay in the onset of dormancy. Plant dormancy can be triggered by a drop in temperature (e.g., the onset of low temperature stress). By increasing the resistance of plants to low temperature stress, dormancy in plants can be delayed until triggered by a further drop in temperature.

[0545] The photosensitizer compounds, compositions or combinations described herein can be used regularly (e.g., at 2-week or 3-week intervals starting from breaking dormancy in spring) and / or by one or more treatments (e.g., 2 times in autumn) to provide a response that shortens or delays the dormancy period of certain plants.

[0546] As used herein, the term "reduced dormancy period" refers to a plant having a reduced dormancy period or an extended growth period relative to a control (eg, an untreated plant).

[0547] In some embodiments, the harvesting step can be performed one week, one month, two months or more after the last application of a photosensitizer compound, composition or combination described herein, wherein the active agent is still effective in reducing the effects of low temperature stress on the plant during the intervening period.

[0548] In some cases, resistance to low temperature stress includes resistance to early frost or late frost or winter damage. In some cases, the photosensitizer compounds, compositions or combinations described herein can be used to protect early growth during temperature fluctuations (e.g., in early spring) from cold. In some cases, the photosensitizer compounds, compositions or combinations described herein can be used to protect plants from cold in low temperature months (e.g., in winter).

[0549] In some cases, when trees have fully healthy and vigorous leaves, the photosensitizer compounds, compositions or combinations described herein can be applied by soil drench and / or foliar application (e.g., spray until runoff) at the beginning of exposure to low temperatures (e.g., late fall) or before exposure to low temperatures. In some cases, the photosensitizer compounds, compositions or combinations described herein can be applied by soil drench and / or foliar application (e.g., spray until runoff) during late fall and winter (e.g., in warm climates). In some cases, the photosensitizer compounds, compositions or combinations described herein can be applied by soil drench in late fall, followed by foliar application (e.g., spray until runoff) in winter to achieve maximum tolerance.

[0550] In some cases, the photosensitizer compounds, compositions or combinations described herein can be applied 1 to 4 times at intervals of 1 to 6 months (e.g., every 2 to 3 months). Further treatments can be performed during the spring and / or growing season to increase resistance to subsequent low temperature stress conditions.

[0551] Heat resistance

[0552] When abiotic stress is high temperature stress, the use of photosensitizer compounds, compositions or combinations as described herein can improve tolerance to high temperatures during the growing season. That is, the use of photosensitizer compounds, compositions or combinations as described herein can allow plants to be subjected to temperature conditions higher than those usually experienced under the optimal growth conditions or natural growth conditions of plants. High temperature stress can have various reasons, such as plants that usually need shaded growth conditions lack shade, or are higher than normal summer temperatures.

[0553] It should be noted that conditions that constitute heat stress for one plant may not be heat stress conditions for another plant.

[0554] Light oxidation resistance

[0555] When the abiotic stress is photooxidative stress, the use of photosensitizer compounds, compositions or combinations described herein can improve tolerance to stressful light conditions during periods of increased reactive oxygen generation. That is, the use of photosensitizer compounds, compositions or combinations described herein allows plants to be subjected to stronger light exposure conditions (e.g., ultraviolet irradiation conditions) than those typically experienced under optimal growth conditions or natural growth conditions of the plant. Photooxidative stress can have various causes, such as strong light conditions or certain types of illumination that induces free radical formation.

[0556] It should be noted that conditions that constitute photooxidative stress in one plant may not be photooxidative stress conditions in another plant.

[0557] Shade tolerance

[0558] Shade stress or "low light (LL) stress" may become a problem that affects plant growth and quality. When the abiotic stress is shade stress, the application of photosensitizer compounds, compositions or combinations as described herein can improve the shade tolerance of plants. That is, the application of photosensitizer compounds, compositions or combinations as described herein can allow plants that normally require partial sunlight or full sunlight for optimal growth conditions or natural growth conditions to tolerate shade conditions. Various types of shade stress are possible, such as prolonged cloudy weather, excessive growth of adjacent plants or trees casting shadows on the plants, or lack of a sunny planting location.

[0559] Shading may be a periodic problem. For example, in certain months of the year, a building located near a plant may cast a shadow on the plant, resulting in shading stress. As the earth moves in a year, the building may no longer cast a shadow on the plant in another few months, and then the situation may repeat in the next year cycle. In this case, the photosensitizer compound, composition or combination described herein can be applied to the plant before the shading stress period begins, and can also be applied during the shading stress period. The damage to the plant that is usually caused by the shading stress period can be prevented or reduced.

[0560] For many types of plants, shade conditions are not considered abiotic stress conditions, as some plants require shade as part of their optimal growing conditions. It should also be noted that conditions that constitute shade stress for one plant may not be shade stress conditions for another plant.

[0561] Drought tolerance

[0562] Drought can be defined as the absence of rainfall or irrigation for a period of time sufficient to deplete soil moisture and harm plants. Drought stress occurs when water loss from a plant exceeds the ability of the plant's roots to absorb water and / or when the plant's water content decreases enough to interfere with normal growing processes. The severity of the effects of drought conditions can vary from plant to plant, as plant water requirements can vary with plant type, plant age, root depth, soil quality, etc.

[0563] Photosensitizer compounds as herein described, compositions or combinations can be applied to plants before drought begins and / or during drought.Using photosensitizer compounds as herein described, compositions or combinations can improve the resistance of plants to drought stress.Compared with untreated plants subjected to the same drought stress, improving resistance can include maintaining or improving the quality of plants.Compared with untreated plants subjected to the same drought stress, improving resistance can include reducing the degeneration of plant quality.If plants do not obtain enough rainfall or irrigation, the drought stress produced may add more to the slowing down of growth than all other environmental stresses.

[0564] It should also be noted that conditions that constitute drought stress for one plant may not be drought stress conditions for another plant.

[0565] Preventing Salt Damage

[0566] Salt can be naturally present in a plant's growing environment. Salinity stress refers to the osmotic forces exerted on a plant when it is grown in a salt marsh or other conditions where salt levels are too high. For example, plants grown near a body of salt water may be exposed to salt present in the air or in the water used to water the plants. In another example, salt applied to the surfaces of roads, sidewalks, and driveways during the winter to improve driving conditions may migrate and / or seep into the soil of plants growing nearby. This increased salt content in the plant's growing environment can result in salinity stress, which can damage the plant.

[0567] Applying the photosensitizer compounds, compositions or combinations described herein to plants can improve the resistance of plants to salinity stress and prevent or reduce the deterioration of plant quality that would otherwise result. The combination can be applied before or during salinity stress.

[0568] It should also be noted that conditions that constitute salinity stress for one plant may not be salinity stress conditions for another plant.

[0569] Transplant shock resistance

[0570] Plants transplanted from one growth environment to another growth environment (e.g., from a flower pot to a flower bed or garden) may be subject to transplant shock stress due to exposure to new environmental conditions (e.g., wind, direct sunlight, or new soil conditions). Applying a photosensitizer compound, composition, or combination as described herein to the root of a plant can reduce the effects on the plant caused by transplantation. In some cases, plant growth and / or developmental barriers to transplanted plants can be reduced or prevented by applying a photosensitizer compound, composition, or combination as described herein.

[0571] It should be noted that conditions that constitute transplant shock stress for one plant may not be transplant shock stress conditions for another plant.

[0572] Tolerance to excess water or waterlogging

[0573] Although plants need a certain amount of water for healthy plant growth and development, exposure of plants to excessive water ("water stress") can damage plants. Applying photosensitizer compounds, compositions or combinations as described herein to plants before the onset of excess water conditions can increase the resistance of plants to water stress. Photosensitizer compounds, compositions or combinations as described herein can be applied during water stress, however, photosensitizer compounds, compositions or combinations as described herein may be diluted due to excess water. Therefore, pretreatment before the excess water period can be more effective.

[0574] It should be noted that what constitutes an excessive water stress condition for one plant may not be an excessive water stress condition for another plant.

[0575] Insecticidal activity

[0576] In some embodiments, the compounds and combinations of the present specification can be used to protect plants from insect plant pests. It should be understood that as used herein, the term "plant pest" or "pest" refers to insects and / or their larvae that are known or have the potential to cause damage to plants. In some embodiments, the compounds and combinations of the present specification can induce light-induced death in pests.

[0577] In some embodiments, the pests are selected from the order Hemiptera (aphids, whiteflies, scales, mealybugs, stink bugs), Coleoptera (beetles), Lepidoptera (butterflies, moths), Diptera (flies), Thysanoptera (thrips), Orthoptera (grasshoppers, locusts), Hymenoptera (wasps, ants), Blattodea (cockroaches and termites), and acarina pests (spider mites).

[0578] Non-limiting examples of pests include: lepidopteran larvae, such as armyworms (e.g., Spodoptera exigua), sugar moths, loopers (e.g., Trichoplusia ni), and heliothines (e.g., Spodoptera fugiperda JESmith, Spodoptera exigua Hübner, Agrotis ipsilon Hufnagel, and Heliothis virescens Fabricius) from the family Noctuidae; stem borers, boxworms, webworms, coneworms, cabbage worms, and skeleton worms from the family Pyralidae; pink stem borers (e.g., Ostrinia nubilalis Hübner, Amyelois transitella Walker, Crambus caliginosellus Clemens), meadow moths (Pyralidae: Pyralinae) such as Herpetogramma licarsisalis Walker); leaf rollers, aphids, seed and fruit borers from the family Cirrhilabrus (e.g., Cydia pomonella Linnaeus, Endopizaviteana Clemens, Grapholita molesta Busck); and many other economically important Lepidoptera (e.g., Plutella xylostella Linnaeus, Pectinophoragossypiella Saunders, Lymantria dispar Linnaeus);Leaf-feeding coleoptera larvae and adults, including weevils from the families of the family ... virgiferavirgiferaLeConte); beetles and other beetles from the family Scarabaeidae (e.g. Japanese beetle (Popilliajaponica Newman), Oriental beetle (Anomala orientalis Waterhouse), Northern rhinoceros beetle (Cyclocephala borealis Arrow), Southern rhinoceros beetle (Cyclocephala immaculata Olivier or C.lurida Bland)), dung beetle and white grub (Aphodius species), turf beetle (Ataenius spretulus Haldeman), green June beetle (Cotinis nitida Linnaeus), Asian garden beetle (Maladera castanea Arrow), May / June gill beetle (Phyllophaga spp.) and European beetle (Rhizotrogus majalis Razoumowsky); skin beetles from the family Dermestidae; wireworms from the family Elateridae; bark beetles from the family Scolytidae and flour beetles from the family Tenebrionidae;Adults and nymphs of the order Orthoptera include grasshoppers, locusts, and crickets (e.g., migratory grasshoppers (e.g., Melanoplus sanguinipes Fabricius, M. differentialis Thomas), American grasshoppers (e.g., Schistocerca americana Drury, Schistocerca gregaria Forskal, Locusta migratoria Linnaeus, Zonocerus spp.)); adults and nymphs of the order Diptera include leaf miners, midges, fruit flies (Tephritidae), straw flies (e.g., Oscinella frit Linnaeus); adults and nymphs of the order Hemiptera and Homoptera, such as plant insects from the family Miridae, leafhoppers from the family Cicadidae (e.g., Empoasca spp.); wax cicadas from the families Cicadidae and Delphacidae (e.g., Peregrinus maidis); treehoppers from the family Membracidae; wheat bugs from the family Penicidae (e.g., Blissus leucopterus hirtus Montandon and Blissus insularis Barber) and other seed bugs; foam bugs from the family Cicadidae; pumpkin bugs from the family Pseudococcidae; red bugs and cotton red bugs from the family Pseudococcidae; mealybugs from the family Pseudococcidae (e.g., Planicoccus citriRisso); cicadas from the family Cicadidae; psyllids from the family Psyllidae (e.g., Citrus psyllid Diaphorinacitri); whiteflies from the family Aleyrodidae (Bemisia argentifolii);Aphids from the family Aphididae, for example, melon aphid (Aphis gossypii), pea aphid (Acyrthisiphon pisum Harris), cowpea aphid (Aphiscraccivora Koch), black bean aphid (Aphis fabae Scopoli), melon or cotton aphid (Aphis gossypii), apple aphid (Aphis pomi De Geer), spiraea aphid (Aphis spiraecola Patch), foxglove aphid (Aulacorthum solani Kaltenbach), strawberry aphid (Chaetosiphon fragaefolii Cockerell), Russian wheat aphid (Diuraphis noxia Kurdjumov / Plant Paaserini), pink apple aphid (Dysaphis plantaginea Paaserini), woolly apple aphid (Eriosoma lanigerum Hausmann), peach aphid (Hyalopterus pruni Geoffroy), radish aphid (Lipaphis erysimi Kaltenbach), wheat aphid (Metopolophium dirrhodum Walker), potato aphid (Macrosipum euphorbiae Thomas), peach aphid (Myzus persicae Sulzer), lettuce aphid (Nasonovia ribisnigri Mosley), root and gall aphids, corn leaf aphid (Rhopalosiphum maidis Fitch), bird cherry oat aphid (Rhopalosiphum padi Linnaeus), wheat aphid (Schizaphis graminum Rondani), English grain aphid (Sitobion avenae Fabricius), spotted alfalfa aphid (Therioaphis maculata Buckton), black citrus aphid (Toxoptera aurantii Boyerde Fonscolombe), orange aphid (Toxoptera citricidae Kirkaldy and green peach aphid (Myzus persicae); phylloxera from the family Phylloxera; mealybugs from the family Mealycopodidae; scales from the families Coccinellidae, Theridiidae and Magnaporthe; web bugs from the family Myrmecophaga; stink bugs from the family Pentatomidae;Adults and larvae of the order Thysanoptera include onion thrips (Thrips tabaci Lindeman), western flower thrips (Frankliniella spp.), and other leaf-feeding thrips. Agronomic pests also include invertebrate arthropods, such as mites from the family Tetranychidae: two-spotted spider mites (e.g., Tetranychus urticae Koch), flat mites from the family Rutaceae (e.g., Brevipalpus lewisi McGregor; rust mites and bud mites from the family Acaridae and other leaf-feeding mites. Economically important agricultural pest nematodes (e.g., root-knot nematodes of the genus Meloidogyne, lesion nematodes of the genus Pratylenchus, and thick root nematodes of the genus Trichodorus) and members of the classes Nematoda, Ascarida, Enterobius, Rhabditis, Spirulina, and Orthoptera.;

[0579] Types of plants

[0580] Combination of the present invention can be used for various types of plants affected by abiotic stress. The plant can be non-woody crops, woody plants or lawn grass. The plant can be selected from the plant of the following group consisting of: crops, fruit viewing plants, vegetable plants, leguminous plants, cereal plants, fodder plants, oilseed plants, field plants, garden plants, greenhouse plants, indoor plants, flower plants, lawn plants, lawn grass, trees (such as fruit trees) and other plants that may be affected by microbial pathogens and / or one or more abiotic stresses. In the absence of light or with light, some compounds of this specification sheet will show a certain degree of toxicity to various harmful plant pests.

[0581] In some embodiments, the plant is a crop selected from the group consisting of sugarcane, wheat, rice, corn (maize), potato, sugar beet, barley, sweet potato, cassava, soybean, tomato, and legumes (beans and peas).

[0582] In other embodiments, the plant is a tree selected from the group consisting of deciduous trees and evergreen trees. Examples of trees include, but are not limited to, maple trees, fruit trees (such as citrus trees, apple trees, and pear trees), oak trees, ash trees, pine trees, and spruce trees.

[0583] In other embodiments, the plant is a shrub.

[0584] In other embodiments, the plant is a fruit plant or a nut plant. Non-limiting examples of the plant include: acerola (Barbados cherry), atemoya, carambola (star fruit), rambutan, almond, apricot, cherry, nectarine, peach, pistachio, apple, avocado, banana, platain, blueberry, bush berry, cranberry, raspberry, fig, grape, mango, olive, papaya, pear, pineapple, plum, strawberry, grapefruit, lemon, lime, orange (e.g., navel orange and valencia), tangelo, tangerine, mandarin and berry plants and small fruit plants (small fruit plants).

[0585] In other embodiments, the plant is a vegetable plant. Non-limiting examples of the plant include asparagus, beans, beets, broccoli, Chinese broccoli, broccoli raab, Brussels sprouts, cabbage, cauliflower, Chinese cabbage (e.g., pakchoi and napa), Chinese mustard cabbage (juncea), Cavalo broccoli, kale, kale, kohlrabi, mizuna, mustard greens, mustard spinach, rapeseed greens, celery, chayote, Chinese waxgourd, citron melon, cucumber, gherkin, hyotan, cucuzza, loofah, Chinese okra, balsam apple, balsam pear, bitter melon, Chinese cucumber, true cantaloupe, cantaloupe, cantaloupe, casaba, crenshaw melon, golden pershaw melon, honeydew melon, honeydew galls, mango melon, Persian melon, pumpkin, zucchini, winter squash, watermelon, taro (taro), eggplant, ginger, ginseng, herbs and spices (e.g., curly basil, lemon balm, cilantro, Mexican oregano, mint), Japanese radish (daikon), lettuce, okra, peppers, potatoes, radishes, sweet potatoes, Chinese artichokes (Japanese artichokes), corn, and tomatoes.

[0586] In other embodiments, the plant is a flower plant, such as a rose, a flowering shrub, or an ornamental plant. Non-limiting examples of such plants include: flower plants and foliage plants (including roses and other flowering shrubs, foliage plants, and bedding plants), fruit trees (such as apple, cherry, peach, and pear trees), non-fruit trees, shade trees, ornamental trees and shrubs (e.g., conifers, deciduous broad-leaved evergreens, and woody ornamentals).

[0587] In some embodiments, the plant is a houseplant. Non-limiting examples of such plants include: chrysanthemum, dieffenbachia, dracaena, ferns, gardenias, geranium, jade plant, palm, philodendron, and schefflera.

[0588] In some embodiments, the plants are plants grown in a greenhouse. Non-limiting examples of such plants include: ageratum, crown of thorns, dieffenbachia, dogwood, dracaena, ferns, ficus, holly, lisianthus, magnolia, orchids, palms, petunia, poinsettia, schefflera, sunflowers, aglaonema, aster, azaleas, begonias, browallia, camellias, carnations, celosia, chrysanthemum, coleus, cosmos, crepemyrtle, dusty miller, easter lily, lilies, fuchsia, gardenias, gerbera, helichrysum, hibiscus foliage, hydrangea, impatiens, jade plant, marigold, new guinea, impatiens, nicotiana, philodendron, portulaca, rieger begonias, snapdragon and zinnias.

[0589] Combination synergy

[0590] In some embodiments, the combination can show a synergistic response that inhibits the growth of microbial pathogens in plants. It should be understood that the terms "synergistic" or "synergistic" used herein refer to the interaction of two or more components in the combination (or composition) so that their combined effect is greater than the sum of their individual effects. In the context of this specification, this can include two or more effects in nitrogen-containing macrocyclic compounds, oils and chelating agents. In some cases, nitrogen-containing macrocyclic compounds and oils can exist in a synergistically effective amount. In some cases, nitrogen-containing macrocyclic compounds and chelating agents can exist in a synergistically effective amount. In some cases, oil and chelating agents can exist in a synergistically effective amount. In some cases, nitrogen-containing macrocyclic compounds, oils and chelating agents can exist in a synergistically effective amount.

[0591] In some cases, synergy can be evaluated by the method proposed in SR Colby, "Calculating synergistic and antagonistic responses of herbicide combinations", Weeds 15, 20-22 (1967). The expected efficacy (E) can be expressed as: E = X + Y (100-X) / 100, where X is the efficacy of the first component in the combination, expressed as a % of the untreated control, and Y is the efficacy of the second component in the combination, expressed as a % of the untreated control. When the observed efficacy is higher than the expected efficacy, the two components are considered to be present in a synergistically effective amount.

[0592] Example

[0593] In the following description of the experimental procedures and examples, a number of abbreviations and acronyms are used. Although most of these abbreviations and acronyms will be understood by those skilled in the art, Table A contains a list of most of these abbreviations and acronyms.

[0594] Table A: List of abbreviations and acronyms

[0595]

[0596]

[0597] Preparation of compounds

[0598] Chlorin e6 (Ce6) was purchased from Frontier Scientific; acetic anhydride was purchased from Caledon; di-tert-butyl dicarbonate, copper (II) acetate, zinc acetate (99.99%), palladium (II) acetate, trimethylsilyl chloride, MeI, potassium carbonate, sodium bicarbonate, N-(n-butyl)ethylenediamine (97%), N,N-dimethylbutylenediamine (98%), N,N-diethyldiethylenetriamine (98%), n-butylamine, dodecylamine, (2-aminoethyl)trimethylammonium chloride hydrochloride (DMAE·HCl), poly(ethylene glycol) monooleate (MW860), and lanthanum (III) trifluoromethanesulfonate were purchased from Sigma-Aldrich; (3-aminopropyl)tris(trimethylsiloxy)silane was purchased from Gelest; polyethylene glycol monoallyl ether was purchased from Clariant; α-hydroxy-poly(ethylene glycol)-ω-(ethylthio)ethylamine was purchased from Enroute Interfaces. All chemicals were used as received. Solvents used in this study were purchased from Caledon and dried by passing through an activated alumina column under a stream of nitrogen before use. The yields reported are mass balances assuming a 1:1 mixture of monofunctional and difunctional products.

[0599] 1 H and 13 CNMR spectra were recorded at room temperature on a Bruker AV-600 (600.13 MHz for proton and 150.9 MHz for carbon, respectively). Electrospray ionization mass spectrometry (ESI-MS) was performed using an Agilent 6340 ion trap mass spectrometer.

[0600] Compound 1(Ce6-Ac 17 -Cycl 13,15 Dianhydride)

[0601]

[0602] Chlorin e6 (Ce6) (0.261 g, 0.44 mmol) was suspended in anhydrous acetic anhydride (44 mL). The reaction mixture was stirred at room temperature for 20 hours in the absence of ambient light. Acetic acid and volatile organics were removed at 45 ° C and reduced pressure. The residue was suspended in dichloromethane (DCM, 20 mL) and filtered. After removing DCM under reduced pressure, 0.250 g of compound 1 was obtained as a dark purple solid (yield 91%).

[0603] 1H NMR(δ,600.13MHz,CD2Cl2):-0.65(br,1H),-0.53(br,1H),1.24(m,3H),1.57(m,3H),1.66(d,3 H, J=7.0Hz),2.00(s,2H),2.02(m,1H),2.28(m,1H),2.57(m,1H),2.64(m,1H),3.07(s,3H),3.2 8(s,3H),3.56(m,2H),3.59(s,3H),4.10(m,1H),4.32(m,1H),4.45(m,1H),5.27(m,2H),6.06(d ,1H,J=11.6Hz), 6.23(d,1H,J=17.8Hz), 7.85(m,1H), 8.49(s,1H), 9.20(s,1H) and 9.48(s,1H)ppm.

[0604] 13 C NMR (δ, 150.9MHz, CD2Cl2): 11.1, 11.2, 12.1, 17.5, 19.6, 22.4, 23.4, 24.2, 29.4,30.8,32.3,39.2,40.7,49.4,52.3,94.1,99.0,99.1,104.7,117.1,12 2.9, 128.9, 129.1, 129.4, 131.3, 132.8, 125.5, 136.4, 136.5, 137.8, 141.4, 142.7, 146.4, 149.7, 157.6, 160.9, 165.7, 166.3, 166.8, 168.0 and 174.3 ppm.

[0605] MS-ESI(HRMS)m / z,C36H37N4O6(M+H + ), calculated value: 621.2635; measured value: 621.2708.

[0606] Compound 2 (Ce6-Cycl 13,15 Anhydride

[0607]

[0608] A mixture of Ce6 (0.255 g, 0.427 mmol), di-tert-butyl dicarbonate (0.099 g, 0.441 mmol) and 4-dimethylaminopyridine (0.004 g, 0.036 mmol) in DCM (30 mL) was heated at 40° C. for 2 hours. The reaction mixture was filtered, and the solvent and volatiles were removed under reduced pressure at 40° C. The resulting solid was washed with hexane (3×10 mL) and then dried in vacuo to give compound 2, 0.253 g, 89% yield.

[0609] MS-ESI(HRMS)m / z,C34H35N4O5(M+H + ), calculated value: 579.2602; measured value: 579.2600.

[0610] Compound 3a (Ce6-dimethyl 15,17 ester)

[0611]

[0612] Trimethylsilyl chloride (1.185 g, 10.906 mmol) was slowly added to a suspension of Ce6 (1.001 g, 1.678 mmol) in DCM (20 mL) at room temperature, and the mixture was stirred at room temperature for 5 minutes, and then methanol (7 mL) was slowly added. After stirring at room temperature overnight, the mixture was concentrated to about 5 mL under reduced pressure and precipitated in diethyl ether (20 mL). The precipitate was washed with diethyl ether (10 mL×3) and dried in vacuo to obtain compound 3a (Ce6-dimethyl 15，17 Ester) (0.946 g, 90% yield).

[0613] 1 H NMR (δ, 600.13MHz, CDCl3): 1.50 (m, 6H), 2.13 (m, 2H), 2.32 (m, 1H), 3.06-3.32 (m, 12H), 3.38 (m, 2H), 3.57 (m, 3H), 3.66 (s,3H),4.14(m,3H),4.65(br,2H),4.96(br,2H),6.05(m,2H),7.61(m,1H),8.35(s,1H),9.33(s,1H),9.55(s,1H)ppm.

[0614] 13 C NMR (δ, 150.9 MHz, CDCl3): 13C NMR (δ, 150.9MHz, CDCl3): 11.3, 12.3, 13.17, 16.6, 19.6, 23.2, 27.4, 30.4, 39.9, 47.9, 49.8, 51.9, 52.8, 93.1, 101.1, 108 .0,122.1,125.5,128.0,133.1,133.2,133.8,134.4,136.7,139.0,141.3,143.8,168.0,169.6,169.7,172.0,173.3ppm.

[0615] MS-ESI (HRMS) m / z, C36H41N4O6 (M+H+), calculated value: 625.3021; ​​found value: 625.3031.

[0616] Compound 3b (Ce6-trimethyl 13,15,17 ester)

[0617]

[0618] Potassium carbonate (23.070 g, 166.92 mmol) was added to a solution of dihydrochlorin e6 (1.990 g, 3.34 mmol) in DMF (40 mL); MeI (4.739 g, 33.38 mmol) was added dropwise. After the reaction mixture was stirred overnight at room temperature in N2 without ambient light, a saturated aqueous solution of NH4Cl (30 mL) was added. The resulting mixture was then extracted with DCM (20 mL×3), and the combined organic layers were washed with brine (5 mL), dried over Na2SO4, filtered, concentrated in vacuo, and precipitated in MeOH. The resulting precipitate was filtered and dried in vacuo to give pure compound 3b (Ce6-trimethyl ester) (1.753 g, 82% yield).

[0619] 1H NMR (δ, 600.13MHz, CDCl3): -1.56(s,1H),-1.42(s,1H),1.58(m,3H),1.67(m,3H),2.12(m, 2H),2.47(m,1H),3.15(s,3H),3.34(s,3H),3.48(s,3H),3.53(s,3H),3.63(m,2H),3.68(s, 3H),4.16(s,3H),4.33(m,2H),5.15(d,1H,J=18.9Hz),5.26(d,1H,J=19.0Hz),6.00(d,1H, J=14.5Hz), 6.20(d,1H, J=17.9Hz), 7.90(m,1H), 8.64(s,1H), 9.41(s,1H), 9.57(s,1H)ppm.

[0620] 13 C NMR (δ, 150.9MHz, CDCl3): 11.3, 12.2, 12.4, 17.7, 19.7, 23.0, 29.6, 31.1, 49.4, 51.7, 52.2, 53.0, 53.1, 93.6, 102.2, 102.3, 12 1.8,123.6,129.4,130.6,134.8,135.4,135.5,135.9,136.5,139.5,145.0,148.9,154.8,167.0,169.5,169.6,173.1,173.6.

[0621] MS-ESI (HRMS) m / z, C37H43N4O6 (M+H+), calculated value: 639.3177; found value: 639.3169.

[0622] General Step A

[0623]

[0624] According to the synthesis steps of Ce6-dianhydride (Compound 1), after vacuum removal of acetic anhydride and volatile organics, the obtained Ce6-dianhydride (dark solid) was redissolved in DCM and filtered, and the corresponding amine or alcohol compound RXH (X = NH or O, 2.1 equivalents) was added. The mixture was stirred at room temperature overnight in the absence of ambient light. The reaction mixture was filtered, concentrated and precipitated in ether. The precipitation step was repeated twice, and the resulting precipitate was separated by filtration, washed with ether (5mL×2), and then dried in vacuo.

[0625] General Procedure B

[0626]

[0627] According to the synthesis steps of Ce6-monoanhydride (Compound 2), after washing with hexane, the obtained Ce6-monoanhydride was redissolved in DCM (20 mL), and the corresponding amine or alcohol (RXH, X = NH or O, 1 equivalent) was added. The mixture was stirred at room temperature for 4 hours in the absence of ambient light. The reaction mixture was concentrated and precipitated in ether, the precipitate was separated by filtration, washed with ether (5 mL × 2), dissolved in DCM (10 mL), filtered the DCM solution, and washed twice with DCM (5 mL). The combined DCM solution was evaporated under reduced pressure and then dried in vacuo.

[0628] Compound 4-mixed (Ce6-mixed-DMAE 15,17 Amide)

[0629]

[0630] According to the general procedure A, Ce6 (4.9447 g, 8.30 mmol), acetic anhydride (60 mL, 634.7 mmol), N,N-dimethylethylenediamine (3.0712 g, 33.2 mmol) were used as reactants. Compound 4-mixture was prepared by compound 4-mono (Ce6-mono-DMAE 15 Amide) and compound 4-bis(Ce6-di-DMAE 15，17 Amide) (yield 94%) was obtained as a mixture in a ratio of 1.46:1 based on the results of LC-UV-HRMS (ESI).

[0631] 1 H NMR (δ, 600.13 MHz, CDCl3): 1 H NMR(δ,600.13MHz,CDCl3):-2.14(br,1H),-1.90(br,1H),1.67-1.73(m,6H),1 .93-2.11(m,9H),2.25-2.33(m,5H),2.60-2.75(m,5H),3.35(m,3H),3.46(m,3 H),3.60(m,3H),3.82(m,2H),4.47-4.50(m,2H),6.15(d,1H,J=11.6Hz),6.37( d,1H,J=17.8Hz),8.13(m,1H),8.82,8.85(s,1H),9.66,9.67,9.70(s,2H)ppm.

[0632] 13C NMR (δ, 150.9MHz, CDCl3): 11.39, 12.16, 15.29, 17.79, 19.71, 23.03, 23.29, 23.33, 30.76, 31.06, 37.40, 39.2 5,39.83,42.71,43.29,43.88,44.75,45.35,49.05,49.21,53.22,56.55,58.06,93.65,93.66,98.80,100.0,1 00.3,103.4,121.3,129.33,129.5,129.7,131.0,132.5,132.8,133.7,133.8,133.9,134.0,134.3,134.5,13 5.5,136.06,136.13,137.8,137.9,144.1,144.2,149.1,152.9,153.0,168.5,172.8,175.4,177.0,179.2ppm.

[0633] Ce6-mono-DMAE 15 Amide: MS-ESI (HRMS) m / z, C38 H47 N6 O5 (M+H + ), calculated value: 667.3602; measured value: 667.3604.

[0634] Ce6-di-DMAE 15,17 Amide: MS-ESI (HRMS) m / z, C42 H57 N8 O4 (M+H + ), calculated value: 737.4497; measured value: 737.4495.

[0635] Compound 4-mono(Ce6-mono-DMAE 15 Amide)

[0636]

[0637] Following General Procedure B, Ce6 (0.254 g, 0.427 mmol), di-tert-butyl dicarbonate (0.099 g, 0.441 mmol), 4-dimethylaminopyridine (0.004 g, 0.036 mmol) and N,N-dimethylethylenediamine (0.040 g, 0.42 mmol) were used to obtain Ce6-mono-DMAE as a dark green solid. 15 Amide (0.264 g, 93% yield).

[0638] 1H NMR (δ, 600.13MHz, CDCl3): -2.37(s,1H),-1.99(br,1H),1.67(m,6H),1.93-2.11( m,6H),2.22(m,2H),2.37(m,2H),2.51(m,2H),2.74(br,2H),3.30(s,3H),3.50(m, 6H),3.75(s,2H),4.46(br,2H),5.33(br,1H),5.86(br,1H),6.14(d,2H,J=11.2Hz ), 6.35 (d, 2H, J = 17.8Hz), 8.11 (m, 1H), 8.23 ​​(s, 1H), 9.59 (s, 1H), 9.65 (s, 1H) ppm.

[0639] Ce6-mono-DMAE 15 Amide, MS-ESI (HRMS) m / z, C38 H47 N6 O5, (M+H + )Calculated value: 667.3602; Measured value: 667.3600.

[0640] Compound 4-bis(Ce6-di-DMAE 15，17 Amide)

[0641]

[0642] Compound 3Ce6-dimethyl 15,17 A toluene solution (50 mL) of ester (0.200 g, 0.320 mmol), N,N-dimethylethylenediamine (0.0612 g, 0.65 mmol) and lanthanum (III) trifluoromethanesulfonate (0.0192 g, 0.032 mmol) was heated at 100°C for 24 hours. The reaction mixture was concentrated to about 5 mL under reduced pressure and cooled to room temperature. The resulting precipitate was collected by filtration, washed with toluene (2 mL×2), and dried in vacuum at room temperature to obtain a dark green solid Ce6-di-DMAE 15，17 Amide (0.215 g, 91%).

[0643] 1H NMR(δ,600.13MHz,DMSO):-2.30(s,1H),-1.90(s,1H),1.69-1.72(m,6H),2.19(m ,12H),2.23(m,2H),2.45(m,4H),2.67(m,br,2H,),2.88(m,4H),3.34(s,3H),3.52 (s,3H),3.56(s,3H),3.83(m,2H),4.49(m,1H),4.60(m,1H),6.18(d,1H,J=11.6Hz ), 6.47 (d, 1H, J = 17.9Hz), 8.36 (m, 1H), 9.10 (s, 1H), 9.69 (s, 1H), 9.78 (s, 1H) ppm.

[0644] Ce6-di-DMAE 15，17 Amide: MS-ESI (HRMS) m / z, C42 H57 N8 O4 (M+H + )Calculated value: 737.4497. Measured value: 737.4504.

[0645] Compound 5-mixed (Ce6-mixed-BAE 15,17 Amide)

[0646]

[0647] Following general procedure A, compound 1 (0.300 g, 0.484 mmol) was dissolved in DCM (20 mL) and N-(n-butyl)ethylenediamine (0.115 g, 0.967 mmol) was added. Compound 5-was mixed with 5-mono(Ce6-mono-BAE 15 Amide) and 5-bis(Ce6-di-BAE 15，17 A mixture of 2-(4-(2-(4-(2-amino-1-yl)-2-nitropropene)-4-nitropropene (4-(2-amino-1-yl)-2-nitropropene) (4-(2-amino-1-yl)-2-nitropropene) (2-(2-amino-1-yl)-2-nitropropene) (4 ...

[0648] 1 H NMR(δ,600.13MHz,CDCl3):-2.26(br,1H),-1.95(br,1H),0.76(m,3H),1.2 0-1.37(m,4H),1.64(m,6H),2.07-2.30(m,2H),2.40-2.77(m,6H),3.22(m,3 H),3.39(m,3H),3.48(m,3H),3.71(m,2H),4.41(m,br,2H),5.52(br,2H),6. 01(d,1H,J=10.7),6.24(m,1H),8.00(m,1H),8.85(s,1H),9.60(br,2H)ppm.

[0649] 13 C NMR (δ, 150.9MHz, CDCl3): 11.4, 12.1, 12.2, 13.4, 13.7, 17.8, 19.8, 20.2, 22.7, 23.2, 23 .5,27.6,27.8,30.9,31.3,34.2,36.5,39.6,39.9,45.0,46.8,47.0,47.5,48.1,48.8,5 3.5,94.1,99.0,100.4,102.3,121.3,129.4,129.7,131.2,132.5,133.9,134.0,134.2, 135.2,136.2,138.1,144.2,149.3,153.1,168.7,169.4,175.8,176.0,177.4,180.7ppm.

[0650] Ce6-mono-BAE 15 Amide, MS-ESI (HRMS) m / z, C40 H51 N6 O5 (M+H + ), calculated value: 695.3915; measured value: 695.3916.

[0651] Ce6-Bis-BAE 15,17 Amide, MS-ESI (HRMS) m / z, C46 H65 N8 O4 (M+H + ), calculated value: 793.5123; measured value: 793.5121.

[0652] Compound 5-mono(Ce6-mono-BAE 15 Amide)

[0653]

[0654] Following General Procedure B, Ce6 (0.318 g, 0.533 mmol), di-tert-butyl dicarbonate (0.118 g, 0.540 mmol), 4-dimethylaminopyridine (0.003 g, 0.025 mmol) and N-(n-butyl)ethylenediamine (0.064 g, 0.533 mmol) were used to obtain Ce6-mono-BAE as a dark green solid. 15 Amide (0.322 g, 87% yield).

[0655] 1H NMR(δ,600.13MHz,CDCl3):-2.33(s,1H),-1.99(br,1H),0.68(m,3H),1.20(br,2H) ,1.37(br,2H),1.61(br,6H),2.19(m,2H),2.41(m,2H),2.76(m,4H),3.22(m,3H),3 .38(m,3H),3.48(m,3H),3.70(m,2H),4.37(br,1H),4.44(br,1H),5.49(br,2H),6. 01(d,1H,J=10.7),6.23(m,1H,J=17.4),8.01(m,1H),8.78(s,1H),9.59(br,2H)ppm.

[0656] 13 C NMR (δ, 150.9MHz, CDCl3): 11.4, 12.0, 12.2, 13.2, 13.7, 17.7, 19.5, 19.7, 20.1 ,23.5,27.5,30.4,32.9,36.6,39.6,44.7,46.7,47.6,48.8,53.3,94.0,99.0,1 00.3,102.4,121.2,128.6,129.3,129.7,131.4,132.5,133.7,133.9,134.3,13 5.3,136.1,137.9,144.1,149.4,153.0,168.2,169.0,175.5,175.9,180.2ppm.

[0657] Ce6-mono-BAE 15 Amide, MS-ESI (HRMS) m / z, C40 H51 N6 O5 (M+H + ), calculated value: 695.3915; measured value: 695.3916.

[0658] Compound 6-mixed (Ce6-mixed-DMAB 15,17 Amide)

[0659]

[0660] Following general procedure A, Ce6-bis-anhydride (0.306 g, 0.493 mmol) was dissolved in DCM (20 mL) and N,N-dimethylbutaneethylenediamine (0.117 g, 0.988 mmol) was added. Compound 6-was prepared by 6-mono(Ce6-mono-DMAB 15 Amide) and 6-bis(Ce6-di-DMAB 15，17A mixture of 2-(4 ...

[0661] 1 H NMR (δ, 600.13MHz, CDCl3): 1.533-1.82(m,18H),1.91(m,4H),2.15(m,2H),2.28(m,3H),2.25-3.02(m,5H),3.21(s,3H),3.37-3.52(m,6H) ),3.66(m,2H),4.32-4.53(m,2H),6.05(d,1H,J=11.6Hz),6.25(d,1H,J=17.6Hz),8.02(m,1H),8.79(s,1H),9.55(s,1H),9.59(s,1H)ppm.

[0662] 13 C NMR (δ, 150.9MHz, CDCl3): 11.2, 12.1, 17.7, 19.5, 21.5, 21.7, 22.2, 22.3, 23.4, 23.5, 23.6, 24.5, 2 6.0,26.3,31.2,34.6,38.3,38.7,39.2,41.8,42.2,42.7,42.8,48.5,49.2,53.3,55.8,56.6,57.0, 94.1,98.7,99.6,99.9,103.5,121.3,129.2,129.5,131.0,132.6,132.8,133.4,133.5,133.7,133 .8,134.9,135.2,136.2,137.5,144.0,149.0,152.6,152.8,168.3,173.8,175.3,177.5,179.5ppm.

[0663] Ce6-mono-DMAB 15 Amide, MS-ESI (HRMS) m / z, C40 H51 N6 O5 (M+H + ), calculated value: 695.3915; measured value: 695.3913.

[0664] Ce6-Bis-DMAB 15,17 Amide, MS-ESI (HRMS) m / z, C46 H65 N8 O4 (M+H + ), calculated value: 793.5123; measured value: 793.5125.

[0665] Compound 7-mono(Ce6-mono-DEAEAE 15 Amide)

[0666]

[0667] According to general procedure A, a solution of compound 1 (0.578 g, 0.932 mmol) in DCM (20 mL) and N,N-diethyldiethylenetriamine (98%) (0.303 g, 1.865 mmol) were used to obtain crude compound 7-mixed (Ce6-mono-DEAEAE 15 Amide and Ce6-bis-DEAEAE 15，17 Compound 7-mono(Ce6-mono-DEAEAE 15 Amide) was the only product isolated after work-up. Compound 7-mono was isolated as a dark green solid (0.422 g, 56% yield).

[0668] 1 H NMR (δ, 600.13MHz, CDCl3): -2.36(br,1H),-2.02(br,1H),1.04(m,6H),1.64-1.73(m,6H),1.98-2.27(m,2H),2.37-2.80(m,6H),2.53(m,2H), 3.09-3.55(13H),3.66(br,4H),4.38(m,2H),5.30(br,2H),6.01(m,2H ),6.23(m,2H),7.61(m,1H),8.01(m,1H),8.76(s,1H),9.56(s,1H)ppm.

[0669] 13 C NMR (δ, 150.9MHz, CDCl3): 10.2, 11.4, 11.8, 12.2, 17.8, 19.7, 23.4, 31.2, 34.2, 36.8, 39.7, 45.5, 46.6, 48.6, 49.0, 51.8, 53.5, 94.0 ,100.1,121.3,129.3,131.2,132.6,133.6,133.9,135.5,136.1,137.8,144.1,149.2,152.8,168.6,171.1,175.5,176.8,179.5ppm.

[0670] Ce6-mono-DEAEAE 15 Amide, MS-ESI (HRMS) m / z, C42 H56 N7 O5 (M+H + ), calculated value: 738.4337; measured value: 738.4350.

[0671] Compound 8-Mixed (Ce6-Mixed-C4 15,17 Amide)

[0672]

[0673] According to the general procedure A, compound 1 (0.301 g, 0.486 mmol), n-butylamine (0.0746 g, 0.102 mmol) and NaHCO3, 0.2024 g (2.528 mmol) were used to obtain compound 8-mono(Ce6-mono-C4 15 Amide) and compound 8-bis(Ce6-bis-C4 15,17 A mixture of 2-(4-( ...

[0674] 1 H NMR(δ,600.13MHz,CDCl3):-1.92(br,1H),-2.14(s,1H),0.93-1.25(m,9H),1.57-1 .63(m,5H),1.71-1.75(m,5H),2.17-2.26(m,2H),2.69-2.79(m,2H),2.79-2.98(m, 4H),3.36(m,3H),3.53(m,3H),3.66(m,3H),3.83(m,2H),4.51(m,2H),6.16(d,2H,J =11.6),6.38(d,2H,J=17.8),8.15(m,1H),8.87,8.88(s,1H),9.74,9.75(s,1H)ppm.

[0675] 13 C NMR (δ, 150.9MHz, CDCl3): 11.3, 11.4, 12.2, 12.3, 13.3, 13.5, 17.7, 19.55, 19.64, 19.7, 19.8, 19.9, 23. 5,23.7,30.1,30.8,31.0,33.2(m),38.7,39.6,39.7,40.3,40.4,49.0,53.1,93.4,94.2,99.2,99.3,10 0.6,100.7,101.6,102.4,121.3,121.4,129.3,129.5,129.6,129.7,131.3,133.2,133.8,133.9,134.1 ,134.3,135.0,135.1,136.2,138.0,144.3,144.4,149.4,153.1,167.3,172.1,174.6,175.8,179.3ppm.

[0676] Ce6-mono-C4 15 Amide, MS-ESI (HRMS) m / z, C38 H46 N5 O5 (M+H + ), calculated value: 652.3493; measured value: 652.3491.

[0677] Ce6-Bi-C4 15,17 Amide, MS-ESI (HRMS) m / z, C42 H55 N6 O4 (M+H + ), calculated value: 707.4279; measured value: 707.4277.

[0678] Compound 9-Mixed (Ce6-Mixed-C 12 15,17 Amide)

[0679]

[0680] General procedure A was followed using compound 1 (0.301 g, 0.486 mmol), dodecylamine (0.1886 g, 1.018 mmol) and NaHCO3 (0.2054 g, 2.445 mmol). The concentrated DCM solution was precipitated in cold hexanes (in an ice bath) and repeated twice to give compound 9-mono(Ce6-mono-C12 15 Amide) and 9-bis(Ce6-bis-C12 15,17 A mixture of 9-aminobenzoic acid and benzoic acid amide) was mixed to give a dark green solid (0.339 g, 82% yield). The product was formed in a ratio of about 1:1.25.

[0681] 1 H NMR (δ, 600.13MHz, CDCl3): -1.82(brs,2H),0.7-0.8(m,23H),0.8-1.2(m,25H),1.2-1.4(24H),1.6(bs,9H),2.2,2.4,2.8(bs,3x 1H)_3.1-3.3(m,9H),3.40(m,5H),3.58(m,5H),3.69(m,5H),3.43(bs,3H),5.4(bs ,2H),6.16(d,2H,J=11.6),6.38(d,2H,J=17.8),7.98(m,1H),8.74(s,1H),9.54(bs 1H),9.68(s,1H)ppm.

[0682] 13C NMR (δ, 150.9 MHz, CDCl3): 17.7, 19.7, 22.6, 23.3, 23.4, 26.7, 26.8 26.9, 30.0 (complex m), 31.8 (m), 39.5, 39.7, 40.3, 49.2, 53.3, 94.1, 99.0 (x2), 101.8, 121.9, 129.3 (x2), 130.2, 130.4, 135.0, 136.0, 139.3, 144.8, 169.5, 170.1, 172.9, 174.5 ppm.

[0683] Ce6-mono-C12 15 Amide, MS-ESI (HRMS) m / z, C46 H62 N5 O5 (M+H + ), calculated value: 764.4745; measured value: 764.4750.

[0684] Ce6-Bis-C12 15,17 Amide, MS-ESI (HRMS) m / z, C58 H87 N6 O4 (M+H + ), calculated value: 931.6783; measured value: 931.6788.

[0685] Compound 10-mixed (Ce6-mixed-TMEA 15,17 Amide acetate)

[0686]

[0687] Compound 1 (0.300 g, 0.486 mmol), (2-aminoethyl)trimethylammonium chloride hydrochloride (0.1712 g, 0.978 mmol) and NaHCO (0.206 g, 2.447 mmol) in anhydrous CH3CN (20 mL) were used. Acetic acid (1 mL) was added to the reaction mixture, and the reaction mixture was stirred for 30 minutes. After removing the solvent and volatiles, the residue was washed with DCM (10 mL×3), and the combined DCM solution was concentrated, precipitated in ether, and dried in vacuo. Compound 10-mono(Ce6-mono-TMEA) was used as the catalyst. 15 Amide) and compound 10-bis(Ce6-bis-TMEA 15，17 A mixture of 1,2-diaminobenzamide) was added to give 10-mixture as a dark green solid (0.295 g, 90% yield).

[0688] 1H NMR (δ, 600.13MHz, CDCl3): -1.52(br,2H),1.53(m,5H),1.77(m,br,6H),2.03(m,br,9H),2.44-2.52(m,12H),2.72(br,2H),3.01-3.55(m,15 H),4.29(m,br,2H),6.04(d,1H,J=11.6Hz),6.23(d,1H,J=17.8Hz),7.97(m,1H),8.21(m,1H),8.21(br,1H),9.48(br,1H),9.54(br,1H)ppm.

[0689] 13 C NMR (δ, 150.9MHz, CDCl3): 11.2, 12.0, 12.1, 17.6, 19.5, 22.2, 22.3, 23.3, 2 3.4,33.0,33.9,38.5,40.9,48.6,48.7,52.2,52.7,52.9,53.0,53.6,63.4 ,63.9,64.6,98.7,99.6,121.4,129.4,130.6,133.4,133.8,135.2,136.2, 137.5,144.1,148.9,152.6,168.2,171.7,174.2,174.9,176.0,178.0ppm.

[0690] Ce6-mono-TMEA 15 Amide, MS-ESI (HRMS) m / z, C39 H50 N6 O5 (M+H + ), calculated value: 681.3759; measured value: 681.3755.

[0691] Ce6-Bis-TMEA 15,17 Amide, MS-ESI (HRMS) m / z, C44 H62 N8 O4 (M+H + ), calculated value: 765.4810; measured value: 765.4815.

[0692] Compound 11-mono(Ce6-mono-EP OA 15 )

[0693]

[0694] 0.186 g (1.29 mmol) of 2-aminoethyl dihydrogen phosphate and 0.542 g (6.545 mmol) of NaHCO3 in anhydrous DMSO (20 mL) were stirred at room temperature for 30 minutes, and a DCM solution of compound 2 (0.400 g, 0.645 mmol in 10 mL DCM) was added dropwise. The mixture was stirred at room temperature overnight in the absence of ambient light. The reaction mixture was evaporated under vacuum (80 ° C, 0.1 mmHg). A DCM (20 mL) solution of octylamine was added to the obtained solid and stirred at room temperature for 30 minutes. The mixture was filtered, concentrated and precipitated in ether. The precipitation step was repeated twice, and the obtained precipitate was separated by filtration, washed with ether (5 mL × 2), and then dried in vacuo. Compound 11-mono (Ce6-mono-EP 15 Amide) as a dark green solid (0.205 g, 44%).

[0695] MS-ESI (HRMS) m / z, C36 H43 N5 O9 P (M+H+), calculated: 720.2793; found: 720.2799; (M+Na+): 742.2612; found: 742.2612. Octylamine (M+H+) at M / z 130.1592.

[0696] Compound 12-mixed (Ce6-mixed-PEG 600 -Oleic acid 15,17 ester)

[0697]

[0698] To a solution of compound 1 (0.501 g, 0.810 mmol) in DCM (20 mL) was added NaHCO3 (2 g, 23.8 mmol) and polyethylene glycol monooleate, MW 860 (1.385 g, 1.610 mmol). After stirring overnight at room temperature in the dark, the reaction mixture was filtered, concentrated and precipitated in ether. The precipitation step was repeated twice and the combined precipitate was dried in vacuo. 12-mono(Ce6-mono-PEG 600 15 -oleate) and 12-bis(Ce6-bis-PEG 600 15,17 -oleate) to obtain 12-mixture (0.720 g, 80% yield).

[0699] 1H NMR (δ, 600.13MHz, CDCl3): -2.3(bs,1H),-1.9(br,1H),0.80(s,1H),1.22(m,7H),1.4- 1.7(m,9H),1.8-2.3(m,7H),2.3-3.8(m,77H),3.8-4.4(m,5H),5.27(bs,1H),5.4-5.9(m 2H), 6.01 (d, 2H, J = 11.6), 6.24 (d, 2H, J = 17.8), 8.00 (m, 1H), 8.70 (m, 1H), 9.56 (s, 2H) ppm.

[0700] 13 C NMR (δ, 150.9 MHz, CDCl3): 11.4, 12.2, 14.1, 17.8, 19.7, 22.7, 23.3, 24.9, 27.1, 29.1, 29.5 (many signals), 34.2, 49.0, 63.5, 69 (many signals), 93.7, 98.7, 102.7, 121.0, 125.7, 129.7, 130.1, 133.7, 135.9, 136.2, 143.9, 149.2, 173.8 ppm.

[0701] Ce6-mono-PEG 600 15 -Oleate: MS-ESI m / z, a series of peaks with 6 EO units as the central peak at (M+H+) m / z 1169.3, with a mass increase or decrease of 44 Da between peaks.

[0702] Ce6-bis-PEG 600 15,17 -Oleate: MS-ESI m / z, a series of peaks with 6 EO units as the central peak at (M+H+) m / z 1521.5, with a mass increase or decrease of 44 Da between peaks.

[0703] Compound 13-mixed (Ce6-mixed-PEG 400 -Allyl 15,17 ester)

[0704]

[0705] To a solution of compound 1 (0.417 g, 0.672 mmol) in DCM (20 mL) were added NaHCO3 (1.035 g, 11.9 mmol) and polyethylene glycol monooleate, based on 1H NMR, MW is 388 (0.521 g, 1.344 mmol). After stirring overnight at room temperature in the dark, the reaction mixture was filtered, concentrated and precipitated in ether. The precipitation step was repeated twice. The combined precipitates were dried in vacuo. 400 15 -allyl ester) and 13-bis(Ce6-bis-PEG 400 15,17 -allyl esters) to give 13-(0.780 g, 80% yield).

[0706] Ce6-mono-PEG 400 15 -Allyl ester: MS-ESI m / z, a series of peaks with 8 EO units as the central peak at (M+H+) m / z 1033.3, with a mass increase or decrease of 44 Da between peaks.

[0707] Ce6-bis-PEG 400 15,17 -Allyl ester: MS-ESI m / z, a series of peaks with 8 EO units as the central peak at (M+H+) m / z 1161.4, with a mass increase or decrease of 44 Da between peaks.

[0708] Compound 14-Mixed (Ce6-Mixed-T (TMS) SP 15,17 Amide)

[0709]

[0710] To a solution of compound 1 (0.201 g, 0.323 mmol) in DCM (20 mL) was added (3-aminopropyl)tris(trimethylsiloxy)silane (0.228 g, 0.645 mmol). After stirring overnight at room temperature in the dark, the solvent and volatiles were removed in vacuo, and the residue was dissolved in hexane (20 mL), filtered, evaporated and dried in vacuo. Compound 14-mono(Ce6-mono-T(TMS)SP 15 Amide) and 14-bis(Ce6-bis-T(TMS)SP 15，17 A mixture of 1,2-diaminobenzamide) was obtained to give 14 (0.3081 g, 87% yield).

[0711] Ce6-mono-T(TMS)SP 15 Amide, MS-ESI (HRMS) m / z, C46 H70 N5 O8 Si4 (M+H + ), calculated value: 932.4296; measured value: 932.4288.

[0712] Ce6-Bi-T(TMS)SP15,17 Amide, MS-ESI (HRMS) m / z, C58 H103 N6 O10 Si8 (M+H + ), calculated value: 1267.5884; measured value: 1267.5876.

[0713] Compound 15-mono(Ce6-mono-3TP-PEG 400 15 Amide)

[0714]

[0715] Ce6-mono-3TP-PEG was obtained by following the general procedure B using compound 2 (0.243 g, 0.420 mmol) and α-hydroxy-poly(ethylene glycol)-ω-(ethylthio)ethylamine (0.195 g, 0.420 mmol). 400 15 Amide as a dark green solid (0.394 g, 90% yield).

[0716] MS-ESI m / z, a series of peaks with 8 EO units as the central peak at (M+H+) m / z 1066.6, with a mass increase or decrease of 44 Da between peaks.

[0717] General Procedure C–Synthesis of Ce6-Copper Complexes

[0718] The Ce6 compound (1 equivalent) prepared by general procedure A or B was dissolved in a solvent mixture of dichloromethane and methanol in a ratio of 1:2. Copper (II) acetate (1.2 equivalents) was added, and the reaction mixture was heated at 45 ° C in N2 in the absence of ambient light for 2 hours. The solvent was removed under reduced pressure. The residue was extracted with DCM (10 mL×3). The combined DCM extracts were concentrated, precipitated in ethyl acetate and dried in vacuo.

[0719] Compound Ce6-Mixed-DMAE 15,17 Copper amide

[0720] Follow general procedure C using Ce6-mixed-DMAE 15,17 Amide (0.102 g, 0.151 mmol) and Cu(OAc)2 (0.033 g, 0.181 mmol). 15 Amide and Cu Ce6-bis-DMAE 15,17 The mixture of amides was used to obtain Cu Ce6-mixed-DMAE 15,17 Amide as a green solid (0.1273 g, 95% yield).

[0721] Cu Ce6-mono-DMAE 15 Amide: MS-ESI (HRMS) m / z, C38 H45 Cu N6 O5 (M+H+), calculated value: 728.2742; found value: 728.2705.

[0722] Cu Ce6-bis-DMAE 15,17 Amide: MS-ESI (HRMS) m / z, C42 H55 Cu N8 O4 (M+H + ), calculated value: 798.3637; measured value: 798.3648.

[0723] Compound Cu Ce6-Mixed-C4 15,17 Amide

[0724] Follow general procedure C using Ce6-mixed-C4 15,17 Amide (0.100 g, 0.153 mmol) and Cu(OAc)2 (0.034 g, 0.184 mmol). 15 Amide and Cu Ce6-bis-C4 15,17 A mixture of amides was obtained to obtain CuCe6-mixed-C4 15,17 Amide as a green solid (0.114 g, 89% yield).

[0725] Cu Ce6-mono-C4 15 Amide: MS-ESI (HRMS) m / z, C38 H44 Cu N5 O5 (M+H+), calculated: 713.2638; found: 713.2625.

[0726] Cu Ce6-Bis-C4 15,17 Amide: MS-ESI (HRMS) m / z, C42 H53 Cu N6 O4 (M+H + ), calculated value: 768.3419; measured value: 768.3416.

[0727] Compound Cu Ce6-Mixed-C12 15,17 Amide

[0728] Follow general procedure C using Ce6-mixed-C12 15,17 Amide (0.101 g, 0.130 mmol) and Cu(OAc)2 (0.029 g, 0.156 mmol). 15 Amide and Cu Ce6-bis-C12 15,17 A mixture of amides was obtained by CuCe6-mixed-C12 15,17Amide as a green solid (0.108 g, 86% yield).

[0729] Cu Ce6-mono-C12 15 Amide: MS-ESI (HRMS) m / z, C46 H60 Cu N5 O5 (M+H+), calculated value: 825.3885; found value: 825.3866.

[0730] Cu Ce6-Bis-C12 15,17 Amide: MS-ESI (HRMS) m / z, C58 H85 Cu N6 O4 (M+H+), calculated value: 992.5923; found value: 992.5926.

[0731] Compound Cu Ce6-mono-DMAE 15 Amide

[0732] Follow general procedure C using Ce6-mono-DMAE 15 Amide (0.207 g, 0.311 mmol) and Cu(OAc)2 (0.069 g, 0.373 mmol). Obtain Cu Ce6-mono-DMAE 15 Amide as a green solid (0.253 g, 92% yield).

[0733] Cu Ce6-mono-DMAE 15 Amide: MS-ESI (HRMS) m / z, C38 H45 Cu N6 O5 (M+H+), calculated value: 728.2742; found value: 728.2690.

[0734] Compound Cu Ce6-mono-DEAEAE 15 Amide

[0735] Following general procedure C, Ce6-mono-DEAEAE was used. 15 Amide (0.220 g, 0.298 mmol) and Cu(OAc)2 (0.067 g, 0.358 mmol). Obtain Cu Ce6-mono-DEAEAE 15 Amide as a green solid (0.257 g, 90% yield).

[0736] Cu Ce6-mono-DMAE 15 Amide: MS-ESI (HRMS) m / z, C42 H54 Cu N7 O5 (M+H + ), calculated value: 799.3477; measured value: 799.3440.

[0737] Compound Cu Ce6-Mixed-BAE15,17 Amide

[0738] Follow general procedure C using Ce6-mixed-BAE 15,17 Amide (0.136 g, 0.196 mmol) and Cu(OAc)2 (0.044 g, 0.235 mmol). 15 Amide and Cu Ce6-bis-BAE 15,17 A mixture of amides was obtained to obtain CuCe6-mixed-BAE 15,17 Amide as a green solid (0.146 g, 84% yield).

[0739] CuCe6-mono-BAE 15 Amide: MS-ESI (HRMS) m / z, C40 H49 Cu N6 O5 (M+H + ), calculated value: 756.3055; measured value: 756.3056.

[0740] Cu Ce6-Bis-BAE 15,17 Amide: MS-ESI (HRMS) m / z, C42 H55 Cu N8 O4 (M+H + ), calculated value: 854.4268; measured value: 854.4269.

[0741] Compound Cu Ce6-Mixed-TMEA 15,17 Amide acetate

[0742] Following general procedure C, use Ce6-mixed-TMEA 15,17 Amide (0.102 g, 0.138 mmol) and Cu(OAc)2 (0.031 g, 0.171 mmol). 15 Amide and Cu Ce6-bis-TMEA 15,17 A mixture of amides was used to obtain Cu Ce6-mixed-TMEA 15,17 The amide was obtained as a dark green solid (0.117 g, 88% yield).

[0743] Cu Ce6-mono-TMEA 15 Amide: MS-ESI (HRMS) m / z, C39 H47 Cu N6 O5 (M+H+), calculated value: 742.2898; found value: 742.2878.

[0744] Cu Ce6-Bis-TMEA 15,17 Amide: MS-ESI (HRMS) m / z, C44 H59 Cu N8 O4 (M+H +), calculated value: 826.3955; found value: 826.3960. (M+H2 + ):413.7017; measured value:413.7019.

[0745] Compound Cu Ce6-mixed-DMAB 15,17 Amide

[0746] Following general procedure C, use Ce6-mixed-DMAB 15,17 Amide (0.105 g, 0.152 mmol) and Cu(OAc)2 (0.0340 g, 0.187 mmol). 15 Amide and Cu Ce6-bis-DMAB 15,17 The mixture of amides obtained Cu Ce6-mixed-DMAB 15,17 Amide as a green solid (0.105 g, 79% yield).

[0747] Cu Ce6-mono-DMAB 15 Amide: MS-ESI (HRMS) m / z, C40 H49 Cu N6 O5 (M+H+) calcd: 756.3055. Found: 756.3040.

[0748] Cu Ce6-bis-DMAB 15,17 Amide: MS-ESI (HRMS) m / z, C46 H63 Cu N8 O4 (M+H+) calcd: 854.4263. Found: 854.4254.

[0749] Compound Cu Ce6-mono-3TP-PEG 400 15 Amide

[0750] Follow general procedure C using Ce6-mono-3TP-PEG 400 15 Amide (0.702 g, 0.657 mmol) and Cu(OAc)2 (0.184 g, 0.986 mmol). Obtain Cu Ce6-mono-3TP-PEG 400 15 Amide as a dark blue-green solid (0.529 g, 72% yield).

[0751] Cu Ce6-mono-3TP-PEG 400 15 Amide: MS-ESI (HRMS) m / z, C55 H78 Cu N5 O14 S (M+H+), calculated value: 1127.4557; found value: 1127.4585.

[0752] Compound Zn Ce6-mixed-DMAE 15,17 Amide

[0753] Ce6-mixed-DMAE in MeOH (20 mL) 15,17 A mixture of amide (0.903 g, 1.295 mmol) and zinc acetate (0.364 g, 1.943 mmol) was heated at 60 °C for 3 h under N2 and in the dark, and the solvent was removed under reduced pressure. The residue was extracted 3 times with DCM (10 mL). The combined DCM extracts were concentrated and precipitated in ethyl acetate / ether (1:1), and this was repeated twice to give ZnCe6-mixed-DMAE 15,17 Amide as a dark blue solid (0.688 g, 70% yield).

[0754] 1 H NMR(δ,500.25MHz,d6-DMSO): 1.64-1.72(m,6H),1.85(m,9H),2.35(s,br,5H),2.60(s,br.2H),2.76(m,br,3H),3.33-3.35(m,6H),3.38(m, 3H),3.45(m,2H),3.82(m,3H),4.37-4.55(m,2H),6.00(m,1H),6.23(m ,1H),8.24(m,1H),8.8.62-8.75(m,1H),9.45(m,1H),9.54(m,1H)ppm.

[0755] ZnCe6-mono-DMAE 15 Amide: MS-ESI (HRMS) m / z, C38 H45 N6 O5 Zn (M+H + ), calculated value: 729.2737; measured value: 729.2714.

[0756] ZnCe6-di-DMAE 15,17 Amide: MS-ESI (HRMS) m / z, C42 H55 N8 O4 Zn (M+H + ), calculated value: 799.3632; measured value: 799.3618.

[0757] Compound Zn Ce6-mono-3TP-PEG 400 15 Amide

[0758] Ce6-mono-3TP-PEG in MeOH (20 mL) 400 15A mixture of amide (0.501 g, 0.469 mmol) and zinc acetate (0.129 g, 0.704 mmol) was heated at 60 °C for 3 h in N2 and darkness, and the solvent was removed under reduced pressure. The residue was extracted 3 times with DCM (10 mL). The combined DCM extracts were concentrated and precipitated in ethyl acetate / ether (1:3), repeated twice, and dried under vacuum to obtain Zn Ce6-mono-3TP-PEG 400 15 The amide was obtained as a dark blue solid (0.489 g, 92% yield).

[0759] ZnCe6-mono-3TP-PEG 400 15 Amide: MS-ESI (HRMS) m / z, calculated for C55 H78 N5 O14 S Zn (EO unit n=8) (M+H+): 1128.4552. Found: 1128.4573.

[0760] Compound Pd Ce6-mixed-DMAE 15,17 Amide

[0761] Ce6-mixed-DMAE in a solvent mixture of THF (20 mL) and MeOH (20 mL) 15,17 A mixture of amide (0.8002 g, 1.151 mmol) and palladium (II) acetate (0.3879 g, 1.727 mmol) was heated at 60 °C for 20 h under N2 and in the dark, and the solvent was removed under reduced pressure. The residue was extracted three times with DCM (20 mL). The combined DCM extracts were concentrated and precipitated in ethyl acetate / ether (1:1), repeated twice, and dried under vacuum to give Pd Ce6-mixed-DMAE 15,17 The amide was obtained as a dark green solid (0.515 g, 56% yield).

[0762] PdCe6-mono-DMAE 15 Amide: MS-ESI (HRMS) m / z, C38 H45 N6 O5 Pd (M+H + ), calculated value: 771.2486; measured value: 771.2493.

[0763] PdCe6-di-DMAE 15，17 Amide: MS-ESI (HRMS) m / z, C42 H55 N8 O4 Pd (M+H + ), calculated value: 841.3381; measured value: 841.3362.

[0764] Biological Activity

[0765] Example 1

[0766] E. amylovora was grown in liquid culture. The samples were treated with 1 μM to 100 μM photosensitizer Ce6-mixed-DMAE 15,17 The cells were incubated with amide (PS) for 5 or 30 minutes, and then illuminated with 395 nm (14.8 mW / cm 2 ) for 30 minutes. The colony forming units (CFU) of bacteria were counted on the plates. The results are summarized in Figure 1 middle.

[0767] Figure 1 Description: Use Ce6-Mixed-DMAE 15,17 The samples were incubated for 5 or 30 minutes and then illuminated with 395 nm light (14.8 mW / cm 2 ) were irradiated for 30 min. Data represent mean ± standard deviation (n ≥ 3 replicates).

[0768] Example 2

[0769] Xanthomonas aegypti was grown in liquid culture. Samples were treated with 1 μM to 100 μM photosensitizer Ce6-mixed-DMAE 15,17 The cells were incubated with amide (PS) for 5 or 10 minutes, and then illuminated with 395 nm (14.8 mW / cm 2 ) for 30 minutes or 5 minutes. The colony forming units (CFU) of bacteria were counted on the plates. The results are summarized in Figure 2 middle.

[0770] Figure 2 Description: Use Ce6-Mixed-DMAE 15,17 The samples were incubated for 5 or 30 minutes and then illuminated with 395 nm light (14.8 mW / cm 2 ) were irradiated for 30 min. Data represent mean ± standard deviation (n = 4 replicates).

[0771] Example 3

[0772] R. fascians was cultured in DSMZ 53 medium supplemented with glucose. The bacterial suspension was cultured in 20 mL of bacterial suspension in a 100 mL glass flask in a shaking incubator at 26°C for two days. The samples were treated with 1 μM to 100 μM photosensitizer Ce6-mixed-DMAE 15,17 The cells were incubated with amide (PS) for 5 or 10 minutes, and then illuminated with 395 nm (14.8 mW / cm 2) for 30 minutes or 5 minutes. The colony forming units (CFU) of bacteria were counted on the plates 120 hours after irradiation. The results are summarized in Figure 3 middle.

[0773] Figure 3 Description: Use Ce6-Mixed-DMAE 15,17 The samples were incubated for 5 or 30 minutes and then illuminated with 395 nm light (14.8 mW / cm 2 ) were irradiated for 30 min. Data represent mean ± standard deviation (n = 3 replicates).

[0774] Example 4

[0775] Obtain the effect of tobacco syringa samples on Ce6-mixed-DMAE under light conditions 15,17 Comparative dose response of Ce6Na3 and Ce6Na3. Pseudomonas syringae samples were incubated with the corresponding photosensitizers in a shaking incubator for 30 min and then subjected to 1000 μmol / m 2 / s photosynthetically active radiation for 1 hour. The results are summarized in Figure 4 middle.

[0776] Example 5

[0777] Alternaria solani hyphae were grown in liquid culture for 24 h. Mycelial spheroids (average diameter 2 mm) were treated with 1 μM to 100 μM Ce6-mixed-DMAE. 15,17 The samples were incubated with amide for 100 minutes. 2 ) for 120 minutes, and the radial growth of hyphae on agar medium was measured 7 days later. If no growth on the agar plate was observed after 7 days, the sample was considered dead. The results are shown in Table 1:

[0778] Table 1: Ce6-Mixed-DMAE 15,17 Effect of PS on Alternaria solani

[0779]

[0780] Example 6

[0781] Botrytis cinerea hyphae were grown in liquid culture for 48 hours. Mycelial spheroids (average diameter 2 mm) were treated with 1 μM to 100 μM Ce6-mixed-DMAE. 15,17 The samples were incubated with amide for 100 minutes. 2) for 120 minutes, and the radial growth of hyphae on the agar medium was measured 7 days later. If no growth on the agar plate was observed after 7 days, the sample was considered dead. The results are shown in Table 2:

[0782] Table 2: Ce6-Mixed-DMAE 15,17 Effect of PS against Botrytis cinerea

[0783]

[0784] Example 7

[0785] The Ce6-mixed-DMAE 15,17 The control of Psoralea coli by amide and Ce6Na3 (comparative) was performed on Psoralea coli. The treatments were changed to potato dextrose agar (PDA) at the desired concentrations. Then, a 5 mm diameter plug of Psoralea coli isolates (a total of 3 isolates were tested) was inoculated into the center of the treated Petri-dish and incubated in the dark at 21°C for 24 hours. After 24 hours, one set of Petri-dishes (triplicate) was placed in the dark (no light) and the other set was placed under illumination (light) for the remainder of the experiment (all at 21°C). The radial growth of the fungus was monitored daily until the growth of Psoralea coli on the untreated PDA reached the edge of the Petri-dish. The light emitted was approximately 180 μmol / m 2 / s photosynthetically active radiation (PAR) of fluorescent lamps. The results are shown in Table 3:

[0786] Table 3: Effect of Ce6-Mix-DMAE in the Psoralea coli agar plate test under light and dark conditions 15,17 Comparative dose response of amide and Ce6Na3.

[0787]

[0788]

[0789] Example 8

[0790] The Ce6-mixed-DMAE 15,17 Control of the fungal plant pathogen Colletotrichum orbiculare ATC20767 (Cgm) in host plants Nicotiana benthamiana treated with amides combined with surfactants. N. benthamiana plants were treated approximately 2 hours prior to inoculation with a spore suspension of Cgm. Plants were then exposed to light for 24 hours and then incubated in the dark until disease symptoms were evident in water-treated control plants. Once disease symptoms were evident, lesions were counted and leaf area was measured to determine the number of lesions / cm2 Leaf area. Four replicates were used for each treatment and the plants were randomly placed under the light source. The light emitted by 2 / s photosynthetically active radiation (PAR) provided by LED lamps. Figure 5 shown.

[0791] Figure 5 Description: The formation of fungal lesions of Colletotrichum ATC20767 on the host plants of Nicotiana benthamiana was inhibited. Ce6-Mixed-DMAE 15,17 The amide was applied 2 h before inoculation with fungal spores, followed by 24 h of light exposure.

[0792] Example 9

[0793] To evaluate Ce6-mixed-DMAE 15,17 The effects of amide on insect pests were applied to poinsettia plants infested with whiteflies (Benmisia tabaci) and compared to untreated controls. For each treatment, five replicates were arranged in an RCB design in a greenhouse environment. Plants were placed on wire mesh benches. Treatments were applied using a CO2 powered backpack sprayer with a single solid cone nozzle (TG1) at 60 psi. During application, all plants were treated individually and then placed outdoors in direct sunlight for 8 hours before returning to the greenhouse plot area. The second application was made 7 days after the first application.

[0794] Two disks (d = 5.47 cm) were taken from each plant / plot. 2 ) and observed under a stereoscope. Whitefly nymphs were counted on both discs 1 day before application and 6, 13, 20 and 28 days after application (DAA). At the beginning of the trial, the number of whiteflies was considered uniform in all plants / plots, with an average of 48 nymphs / sample. The number of whiteflies after application is summarized in Table 4A. Compared with the untreated control, Ce6-mixed-DMAE 15,17 Amide reduced the number of whitefly nymphs.

[0795] Plants were rated for phytotoxicity at 6 DAA and 13 DAA (0-10, where 0 = healthy plants and 10 = dead plants) by visually observing symptoms such as chlorosis, necrosis, deformation, and stunted growth, and compared with untreated control plants. The results are shown in Table 4B. Ce6-Mixed-DMAE 15,17 The amide treatment did not result in phytotoxicity in the plants.

[0796] Table 4A: Ce6-Mixed-DMAE 15,17Number of live whitefly nymphs / sample before and after amide treatment

[0797]

[0798] Table 4B: Phytotoxicity of Treated Poinsettia Plants

[0799]

[0800] Example 10

[0801] Experiments were performed to evaluate the antifungal activity of several Ce6 derivatives synthesized herein. The following methods were used and the results are summarized in Tables 5 and 6.

[0802] Agar protocol: The modified Ce6 was evaluated for control of P. spp. Treatments were changed to potato dextrose agar (PDA) at the desired concentrations. A 5 mm diameter plug of P. spp. isolate (a total of 3 isolates were tested) was then inoculated into the center of the treated Petri dishes and incubated in the dark at 21 °C for 24 h. After 24 h, one set of Petri dishes (triplicate) was placed in the dark and the other set was placed in the light for the remainder of the experiment (all at 21 °C). Radial growth of the fungus was monitored daily until the growth of P. spp. on untreated PDA reached the edges of the Petri dishes. Light was emitted by a luminescent lamp emitting approximately 180 μmol / m 2 / s photosynthetically active radiation (PAR) provided by fluorescent lamps.

[0803] Broth protocol: The modified chlorins were evaluated for control of P. spp. The treatments were prepared at the desired concentrations in phosphate buffered saline (PBS) in 24-well plates (incubations in light and dark were performed in duplicate). Then, plugs of 5 mm in diameter of P. spp. isolates (a total of 3 isolates were tested) were inoculated into PBS and incubated in the dark at 21°C for 2 h. After 2 h, one 24-well plate (triplicate isolates) was left in the dark and the other 24-well plate was placed in the light for 1 h (all at 21°C). After illumination, the fungal plugs were removed from PBS, blotted on sterile filter paper, and transferred to untreated potato dextrose agar (PDA). The radial growth of the fungus was monitored daily until the growth of P. spp. reached the edge of the covered petri dish. The illumination consisted of a luminescent light source emitting approximately 1000 μmol / m 2 / s photosynthetically active radiation (PAR) provided by LED lights.

[0804] Table 5: Effects of Ce6 derivatives on pathogenic bacteria

[0805]

[0806] Table 6: Effects of Ce6 derivatives on pathogenic bacteria

[0807]

[0808] Embodiment 11

[0809] Experiments were conducted to evaluate the modified Ce6 against the Gram-negative plant pathogen Pseudomonas syringae pv. tabaci. Treatments were prepared at the desired concentrations in phosphate buffered saline (PBS) in 96-well plates. The bacterial suspension was inoculated into PBS and incubated in the dark at 28°C for 30 min. After 30 min, the 96-well plates were placed under illumination for 1 h (21°C). Another plate prepared at the same time was kept in the dark without illumination and used as a dark control. After illumination, the bacterial suspension was serially diluted and 10 μL of each dilution was evenly spread on a tryptic soy agar (TSA) plate and incubated in the dark at 28°C for 48 h. After 48 h, bacterial colonies were counted and the results were logarithmically transformed (log colony forming units (CFU) / mL). Relative inactivation was determined by taking the difference between logCFU (PBS control) and logCFU (treatment). The sample is illuminated by emitting about 1000 μmol / m 2 / s photosynthetically active radiation (PAR) LED lamp (Heliospectra RX30) provided.

[0810] The modified Ce6 evaluated was Ce6-mixed-DMAE 15,17 Amide, Ce6-bis-DMAE 15,17 Amide and Ce6-mono-DMAE 15 The results are shown in Table 7.

[0811] Table 7: Effects of Ce6 derivatives on pathogenic bacteria

[0812]

[0813]

[0814] It can be seen that all forms of Ce6 DMAE amide (i.e. Ce6-mixed-DMAE 15,17 Amide, Ce6-bis-DMAE 15,17 Ce6-mono-DMAE 15The same relative inactivation was obtained for all forms of Ce6DMAE amide. This is due to the fact that the data are expressed as relative inactivation (i.e., log ratio between PBS control and treatment). Because treatment with all forms of Ce6 DMAE amide killed all bacteria and left no colony forming units, this value was set to 1 CFU / mL to avoid mathematical errors. Therefore, the degree of inactivation depends on the control counts, so the values ​​between treatments are the same. Nevertheless, these experiments show that all forms of Ce6DMAE amide are active against Gram-negative bacteria.

[0815] Example 12

[0816] Effects of treatments on salt stress tolerance in strawberry plants (Fragaria x ananassa)

[0817] In this example, the effect of modified chlorin compounds on strawberry plants (Fragaria xananassa) cv Delizz was tested. The experiment was conducted in a greenhouse. The test was designed to determine the activity of the compounds on salt stress tolerance of strawberry plants.

[0818] In the experiment, seedlings of strawberry plants were grown in 5-inch plastic pots filled with a professional soil mixture (LC 1 Sunshine, SungroHorticulture, Canada) and irrigated regularly with fertilizer water. When the strawberry plants were in the 4-5 leaf stage, 3 foliar application treatments were carried out with different formulations, using a handheld spray bottle to provide uniform coverage. The plants were sprayed at intervals of 7 days. 24 hours after the first spraying, the plants were exposed to salt stress by soaking the roots in a 15mM sodium chloride solution. The salinity level was gradually increased to 20mM NaCl, and salt soaking was arranged at intervals of 5 to 7 days. Plants were harvested 3 weeks after the last foliar spray. Surfactants were added to each treatment. The experiment was carried out in a completely randomized design, with 5 replicates for each treatment.

[0819] Table 8: Effect of treatments on salt stress tolerance of strawberry plants (Fragaria x ananassa).

[0820]

[0821] Treatment of strawberry plants with the tested chlorin compounds enhanced the plants' tolerance to salt stress.

[0822] Example 13

[0823] Effects of treatments on drought stress tolerance of strawberry plants.

[0824] In this example, the effect of modified chlorin compounds was tested on strawberry plants (Fragaria x ananassa) cv Delizz. The experiments were conducted in a greenhouse. The test was designed to determine the activity of the compounds on drought stress tolerance of strawberry plants.

[0825] In the experiment, seedlings of strawberry plants were grown in 5-inch plastic pots filled with a professional soil mix (LC 1 Sunshine, SungroHorticulture, Canada) and irrigated regularly with fertilizer water. When the strawberry plants were in the 4-5 leaf stage, foliar application treatments were carried out 3 times with different Suncor formulations, using a handheld spray bottle to provide uniform coverage. The plants were sprayed at intervals of 7 days. After the first foliar treatment and during the experiment, the strawberry plants were exposed to reduced water conditions (drought stress) until the wilting point (20% to 30% of the soil moisture capacity-SMC), and watered to 50% SMC. Plants were harvested 3 weeks after the last foliar spray. Surfactants were added to each treatment. The experiment was carried out in a completely randomized design with 7 replicates for each treatment.

[0826] Table 9: Effects of treatments on drought stress tolerance of strawberry plants.

[0827]

[0828] Treatment of strawberry plants with the tested chlorin compounds enhanced the plants' tolerance to drought stress.

[0829] Embodiment 14

[0830] Effects of treatments on heat stress tolerance of tomato plants (Solanum lycopersicum) cv. Tiny Tim

[0831] The experiments were conducted in a growth chamber under controlled conditions. The test was designed to determine the activity of the compounds on high temperature stress tolerance in tomato plants.

[0832] In the experiment, tomato plants cv. Tiny Tim were grown in a greenhouse at a temperature of 24°C-26°C. Tomato seedlings were transplanted into 5-inch plastic pots filled with industrial soil mixture (LC 1 Sunshine, Sungro Horticulture, Canada). At the 5-6 leaf stage, plants were treated with the test solution (foliar spray to runoff) using a handheld spray bottle to provide uniform coverage. After 48 hours of spraying, the plants were moved into a growth chamber and exposed to high temperature stress for 10 days. Tomato plants were watered regularly to avoid water shortage. Ten days later, the tomato plants were transferred back to the greenhouse and treated with the test solution for the second time. Forty-eight hours after the second spraying, the plants were placed in a growth chamber and exposed to high temperature stress for another 10 days. Growth chamber conditions: 16 hours / 8 hours of light / dark photoperiod; temperature in the dark: 19°C; temperature during light: the temperature gradually increased from 19°C to 37°C in 4 hours, and continued for 8 hours, and the temperature gradually decreased from 37°C to 19°C. Foliar treatment (spraying) was performed 2 times. Surfactants were added to each treatment. The experiment was conducted in a completely randomized design with 6 replicates for each treatment.

[0833] Table 10: Effects of chlorin formulations on high temperature stress tolerance of strawberry plants.

[0834]

[0835] The novel chlorin formulation improved the tolerance of tomato plants to heat stress and increased plant biomass compared to untreated controls.

[0836] Embodiment 15

[0837] Effects of treatments on salt stress tolerance of Poa pratensis

[0838] Kentucky bluegrass (Poa pratensis) was grown under greenhouse conditions for about 3 weeks. After 3 weeks, the plants were sprayed with the formulation and left to stand for 24 hours, and then the pots were placed in a 170 mM NaCl solution until the soil was saturated. The salt application was repeated again 7 days later, for a total of 2 salt applications. Salt stress was assessed based on a turf quality scale of 1–9; where 1 = dead, brown turf; 6 = minimally acceptable turf quality (based on standards for golf courses or sports fields); and 9 = dense, dark green turf (healthy). Data are the average of 5 replicates.

[0839] Table 11: Effects of salt stress on turf quality

[0840]

[0841]

[0842] Example 16

[0843] Effects of treatment on silkworms

[0844] Experiments were performed to evaluate the toxicity of photosensitizer compounds to silkworm (Bombyx mori (L.)) larvae.

[0845] Colonies of third instar larvae of Bombyx mori were purchased from distributor Recorp Inc. (Ontario, Canada) and maintained on fresh mulberry leaves (Morus rubra) for 2 days before treatment.

[0846] Mulberry buds are harvested from trees grown outside and are not treated with any pesticides. Fresh mulberry buds are washed with tap water and then air-dried.

[0847] Small mulberry buds (8-10 leaves) were cut from mature healthy branches and inserted into 50 ml plastic vials filled with water. The vials were covered with lead and plastic mesh to prevent water evaporation and larvae from drowning. Host plant cuttings were sprayed with the test solution until runoff, and the vials with the sprayed branches were placed in a 1 L transparent plastic container lined with filter paper.

[0848] Homogeneous silkworm larvae (3rd instar) were sprayed separately and placed on the treated mulberry buds in containers. A soft fine paintbrush was used to deal with the insects. The container containing the plant buds and insects was covered with white mesh wire.

[0849] All treatments were finely sprayed using a 2 oz handheld sprayer bottle (ULINE, Canada). A water treatment was used as a control.

[0850] The containers containing the buds and insects were randomly placed on a metal rack equipped with LED lights and immediately treated with 450 μmol m - 2 s -1 of light. The experiment was conducted in a plant growth chamber at a temperature of 24°C-26°C and a photoperiod of 12 hours of LED light and 12 hours of darkness. The silkworms were allowed to feed on the treated mulberry leaves for 48 hours. The food source was changed once a day. The experiment used a completely randomized design with 4 replicates per treatment and 10 insects per replicate. If no movement was detected after mechanical stimulation with a paintbrush, the larvae were considered dead. The number of live and dead insects was recorded. The insect mortality was evaluated until 72 hours after treatment (HAT-hours after treatment). The phytotoxicity symptoms of mulberry leaves were evaluated.

[0851] Zn-Ce6-mixed-DMAE 15,17 Amide and Pd-Ce6-mixed-DMAE 15,17 The amide is formulated with propylene glycol and Pluronic F-127 surfactant to enhance solubility in water.

[0852] Table 12: Effects of photosensitizers on mortality of silkworm larvae.

[0853]

[0854] *Surfactant (0.5% propylene glycol + 0.1% Pluronic F-127)

[0855] 0.1% Ce6-Mixed-DMAE 15,17 Amide and 0.1% Pd-Ce6-mixed-DMAE 15,17 The treatment of amide + 0.5% propylene glycol + 0.1% Pluronic F127 resulted in larval mortality of 57.5% and 35%, respectively, and significantly reduced larval weight.

[0856] Treated mulberry buds did not show any visible symptoms of phytotoxicity. None of the formulations tested caused phytotoxicity to the leaves of the plants.

[0857] Embodiment 17

[0858] Control of the Fungal Pathogen Cgm on Nicotiana benthamiana

[0859] The control of the fungal plant pathogen Colletotrichum spp. ATC20767 (Cgm) by host plants N. benthamiana after treatment with modified chlorin e6 compounds was evaluated. N. benthamiana plants were treated approximately 2 hours prior to inoculation with a spore suspension of Cgm. Plants were then exposed to light for 24 hours and then incubated in the dark until disease symptoms were evident in water-treated control plants. Once disease symptoms were evident, lesions were counted and leaf area was measured to determine the number of lesions / cm 2 Leaf area. Four replicates were used for each treatment and the plants were randomly placed under the light source. The light emitted by 2 The results are shown in Tables 13 and 14.

[0860] Table 13: Effects of modified Ce6 compounds on anthrax bacteria

[0861] deal with Disease suppression % <![CDATA[0.05% Ce6 - mixed - DMAE 15,17 amide]]> 87 <![CDATA[0.05% Zn-Ce6-Mixed-DMAE 15,17 Amide]]> 35 <![CDATA[0.05% Pd-Ce6 - Hybrid - DMAE 15,17 Amide]]> 1 <![CDATA[0.05% Cu - Ce6 - mixed - DMAE 15,17 amide]]> 69 Untreated control 0

[0862] Surfactants may be added to the solution to increase the solubility of the compound and spread it on the leaf surface.

[0863] Table 14: Effects of modified Ce6 compounds on anthrax bacteria

[0864] deal with Disease suppression % Untreated control 0 <![CDATA[0.05% Ce6 - mixed - DMAE 15,17 amide + surfactant]]> 72 <![CDATA[0.05% Zn-Ce6-Mixed-DMAE 15,17 Amide + Surfactant]]> 97 <![CDATA[0.05% Pd-Ce6 - mixed - DMAE 15,17 amide + surfactant]]> 87 <![CDATA[0.05% Cu-Ce6-Mixed-DMAE 15,17 Amide + Surfactant]]> 96 <![CDATA[0.05% Ce6 - mono - DMAE 15 amide + surfactant]]> 94 Surfactants -29

[0865] *Surfactant (0.5% propylene glycol + 0.1% Pluronic F-127)

[0866] In another experiment, the effect of PEG-modified Ce6 compounds on Cgm was tested.

[0867] Table 15: Effects of modified Ce6 compounds on anthrax bacteria

[0868]

[0869]

[0870] *Surfactant (0.5% propylene glycol + 0.1% Pluronic F-127)

[0871] Embodiment 18

[0872] Control of the bacterial pathogen Pst in Arabidopsis thaliana

[0873] In LED lamps (PAR 24 μmol m -2 s -1 ) at a temperature of 25°C ± 3°C and a relative humidity of 65%, Arabidopsis plants were grown under a 12-hour light: 12-hour dark photoperiod. After 3 weeks, the plants were sprayed with the formulation (50% diluted in water), allowed to dry for 2 hours, and then sprayed with tobacco wildfire pathogen (Pseudomonas syringae pv. tabaci) (diluted in 10mM MgCl2 at OD0.08). Plants were kept under a plastic dome until symptoms appeared. Disease severity was assessed by counting the number of yellow leaves / plant. Data are the average of 3 replicates.

[0874] Table 16: Effects of modified Ce6 compounds on bacterial pathogen Pst on Arabidopsis

[0875] deal with Disease suppression % Untreated control 0 <![CDATA[0.05% Ce6 - mixed - DMAE 15,17 amide + surfactant]]> 48 <![CDATA[0.05% Zn - Ce6 - Hybrid - DMAE 15,17 Amide + Surfactant]]> 45 <![CDATA[0.05% Pd-Ce6-Mixed-DMAE 15,17 Amide + Surfactant]]> 52 <![CDATA[0.05% Cu-Ce6-Mixed-DMAE 15,17 Amide + Surfactant]]> 34 <![CDATA[0.05% Ce6 - mono - DMAE 15 amide + surfactant]]> 56 <![CDATA[0.05% Ce6 - mono - 3TP - PEG 400 15 amide + surfactant]]> 22 <![CDATA[0.05% Zn-Ce6-monoclonal-3TP-PEG 400 15 amide + 0.05% surfactant]]> 34 Surfactants 0

[0876] *Surfactant (0.5% propylene glycol + 0.1% Pluronic F-127)

[0877] Embodiment 19

[0878] Control of P. stylosa (Pst) on Nicotiana benthamiana

[0879] The control of the bacterial plant pathogen Pseudomonas syringae psoriasiformis (Pst) by host plants N. benthamiana after treatment with modified chlorin e6 compounds was evaluated. N. benthamiana plants were treated approximately 2 hours prior to inoculation with a spore suspension of Cgm. Plants were then exposed to light for 24 hours and then incubated in the dark until disease symptoms were evident in water-treated control plants. Once disease symptoms were evident, lesions were counted and leaf area was measured to determine the number of lesions / cm 2 Leaf area. Four replicates were used for each treatment and the plants were randomly placed under the light source. The light emitted by 2 The results are shown in Table 17.

[0880] Table 17: Effects of modified Ce6 on Pseudomonas syringae psoriasii (Pst) on Nicotiana benthamiana

[0881] Disease suppression % Untreated control 0 <![CDATA[0.1% Zn-Ce6-mono-3TP-PEG 400 15 amide]]> 47 <![CDATA[0.1% Ce6 - mono - 3TP - PEG 400 15 amide]]> 63 <![CDATA[0.1% Pd-Ce6 - Hybrid - DMAE 15,17 Amide + Surfactant]]> 65 Surfactants 34

[0882] *Surfactant (0.5% propylene glycol + 0.1% Pluronic F-127)

[0883] Embodiment 20

[0884] Control of rose aphids using modified Ce6 compounds

[0885] Experiments were conducted to evaluate the toxicity of chlorin derivatives to the pest rose aphid (Marcosiphum rosae). The experiments were conducted on rose bushes (cv Knockout, Double red) infested with aphids. The experiments were conducted in a plant nursery (Crop Inspection Service, California, Valley center, USA). The experimental plants were not exposed to insecticide treatments before testing.

[0886] The experimental rose plants were grown outdoors in 3-gallon black plastic pots filled with Sunshine #4 soil mix. The plants were irrigated daily and fertilized twice weekly with 200 ppm of a soluble fertilizer 20-20-20.

[0887] The experiment used the tops of rose plants newly infested with aphid nymphs. The number of rose aphid colonies gathered at the top of the shoots was counted before treatment, and the treated shoots were covered with white 4×6” mesh organza bags (ULINE, USA) to avoid infestation by natural enemies. The bags were placed on the shoots during the experiment. At the beginning of the experiment, the aphid number (on the shoots) was considered uniform, with 25-28 aphids per shoot. A completely randomized design was performed on 6 replicates (one bud per plant).

[0888] Treatments were applied using a 2 oz plastic handheld spray bottle (Natural Cylinder Spray Bottle, ULINE, Canada) to provide a uniform fine spray on the plant buds. Rose buds were sprayed thoroughly with the tested treatments and exposed to direct sunlight. A second treatment was applied 7 days after the first application using the same method.

[0889] The effect of the treatments on insects was determined by counting live insects 7 days after the first treatment and 14 days after the second treatment.

[0890] Plants were evaluated for phytotoxicity 6 days after each foliar spray.

[0891] Table 18: Effects of chlorin derivatives on rose aphids

[0892]

[0893] Compared with water-treated controls, 0.1% Ce6-mono-3TP-PEG400 15 Amide and 0.1% Ce6-mixed-DMAE 15,17 The amide treatment showed good effects against rose aphids and suppressing insect numbers.

[0894] Treated rose bush buds did not show any visible symptoms of phytotoxicity.

[0895] Embodiment 21

[0896] Control of Cucumber Mosaic Virus on Sweet Pepper Plants

[0897] Dwarf bell pepper 'Golden baby belle hybrid' seedlings were transplanted into pots filled with pro-mix at the 3-4 leaf stage and placed in a temperature of 26 / 23°C (day / night), 70% relative humidity, and a light intensity of 270 μmol m -2 s -1 , 12 h photoperiod in a growth chamber. On days 7, 14, 21, and 28 after transplantation, 0.1 wt% Ce6-mixed-DMAE was sprayed with a handheld sprayer. 15,17 The formulation of amide and surfactant was applied as a foliar application until the leaves were completely covered with the solution (approximately 2.5 ml / pot). The plants were watered abundantly by hand irrigation and fertilized every 2 weeks with a 28-8-18 complete fertilizer at 0.73 g nitrogen m -2Fertilization. Cucumber mosaic virus (CMV) inoculation was performed 2 hours after the third application. For inoculation, leaves (about 1 g) of tobacco plants infected with CMV virus were ground in about 1 mL of PBS buffer (50 mM, pH 7) using a mortar and pestle, and a small amount of corundum was added to the mixture. Q-tip was used to apply to the upper surface of the top three newly grown leaves of the pepper leaves. A randomized block design was used with 4 replicates. The pots were randomly rearranged in the growth chamber twice a week. The severity of CMV disease development in the leaves was measured on days 19, 21, 28, 35 and at the end of the experiment. Disease severity was calculated as follows: Disease severity = number of infected leaves / 3 inoculated leaves + number of infected young leaves / total number of young leaves.

[0898] Table 19: Disease severity of cucumber mosaic virus (CMV)

[0899]

[0900] *Surfactant: 0.1% APG325N

[0901] All publications, patents and patent documents cited above are incorporated herein by reference as if individually incorporated by reference. The compounds, compositions, methods and uses described herein have been described with reference to various embodiments and techniques. However, it will be appreciated by those skilled in the art that many variations and modifications may be made while remaining within the spirit and scope of the appended claims.

Claims

1. A compound of formula I or an agriculturally acceptable salt thereof: in: Z 1 is OR 1 ; Z 2 YesNR 2 -(CH2) n -NR 4 R 5 NR 2 -(CH2) n -N + R 4 R 5 R 6 Y - NR 2 -(CH2) n -O(PO3H) - W + NR 2 -(CH2) n -Si(R 7 )3.NR 2 -(CH2) n -SR 8 , or NR 2 -(CH2) n -NR 4 -(CH2) p -NR 9 R 10 ;as well as Z 3 Yes OR 12 ;or WITH 3 =Z 2 ; R 1 is H; R 2 is H; R 4 is H or an alkyl group having 1 to 20 carbon atoms; R 5 is an alkyl group having 1 to 20 carbon atoms; R 6 is an alkyl group having 1 to 20 carbon atoms; R 7 is O(trisubstituted silyl); R 8 is H or an alkyl group having 1 to 20 carbon atoms; R 9 is an alkyl group having 1 to 20 carbon atoms; R 10 is an alkyl group having 1 to 20 carbon atoms; R 12 is H; R 13 is H, alkyl having 1-20 carbon atoms, alkenyl having 2-20 carbon atoms, or CO(alkenyl) wherein the alkenyl has 2-20 carbon atoms; W + It is an agriculturally acceptable cation; Y - It is an agriculturally acceptable anion; n is an integer selected from 2 to 4; p is an integer selected from 2 to 4; q is an integer selected from 0 to 16; m is an integer selected from 1 to 20; R a , R c , R e and R f is methyl; R b For vinyl; R d Ethyl; is a single bond or a double bond; is a single bond or a double bond; and M is 2H or a metal species.

2. The compound according to claim 1 or an agriculturally acceptable salt thereof, wherein: is a single bond; and It's a double bond.

3. The compound according to claim 1 or its agriculturally acceptable salt, wherein the compound is: and / or 4. The compound according to claim 1 or 2 or an agriculturally acceptable salt thereof, wherein M is 2H.

5. The compound according to claim 1 or 2 or an agriculturally acceptable salt thereof, wherein M is a metal species selected from the group consisting of Cu(II), Co(II), Fe(II), Mn(II), Mg(II), Zn(II), Pd(II), Sn(IV), Al(III), Pt(II), Si(IV), Ge(IV), Ga(III) and In(III).

6. The compound according to claim 5 or an agriculturally acceptable salt thereof, wherein M is a metal species selected from the group consisting of Cu(II), Pd(II) and Zn(II).

7. The compound according to claim 5 or an agriculturally acceptable salt thereof, wherein M is Cu(II).

8. The compound according to claim 1 or 2 or an agriculturally acceptable salt thereof, wherein W + Selected from the group consisting of sodium, potassium, magnesium and ammonium cations.

9. The compound according to claim 1 or 2 or an agriculturally acceptable salt thereof, wherein Y - Selected from the group consisting of chloride, bromide, phosphate, dimethylphosphate, methylsulfate, ethylsulfate, acetate and lactate.

10. The compound according to claim 1 or 2 or an agriculturally acceptable salt thereof, wherein Z 3 =Z 2 .

11. A composition comprising: At least one compound as defined in any one of claims 1 to 10 or an agriculturally acceptable salt thereof; and Carrier liquid.

12. The composition of claim 11, further comprising a chelating agent.

13. The composition according to claim 12, wherein The chelating agent comprises at least one carboxylic acid group or an agriculturally acceptable salt thereof.

14. The composition according to claim 12 or 13, wherein The chelating agent comprises at least two carboxylic acid groups or agriculturally acceptable salts thereof.

15. The composition according to claim 12 or 13, wherein The chelating agent contains at least one amino group or an agriculturally acceptable salt thereof.

16. The composition according to claim 12 or 13, wherein The chelating agent includes an amino-carboxylic acid compound or an agriculturally acceptable salt thereof.

17. The composition according to claim 16, wherein The amino-carboxylic acid compound includes an aminopolycarboxylic acid compound or an agriculturally acceptable salt thereof.

18. The composition according to claim 12 or 13, wherein The chelating agent is selected from the group consisting of ethylenediaminetetraacetic acid (EDTA) or its agriculturally acceptable salt, ethylenediamine-N,N'-disuccinic acid (EDDS) or its agriculturally acceptable salt, iminodisuccinic acid (IDS) or its agriculturally acceptable salt, and mixtures thereof.

19. The composition according to claim 12 or 13, wherein The chelating agent includes polyaspartic acid or an agriculturally acceptable salt thereof.

20. The composition according to claim 12 or 13, wherein The chelating agent is metallated.

21. The composition according to claim 12 or 13, wherein The chelating agent is metal-free.

22. The composition of any one of claims 11 to 13, further comprising a surfactant.

23. The composition according to claim 22, wherein The surfactant is selected from the group consisting of ethoxylated alcohols, polymeric surfactants, fatty acid esters, poly(ethylene glycol), ethoxylated alkyl alcohols, monoglycerides, alkyl monoglycerides, and mixtures thereof.

24. The composition according to claim 22, wherein The surfactant comprises formula R 15 -O-(CH2CH2O) f -R 16 of poly(ethylene glycol), in: R 15 and R 16 are each independently H, alkyl, substituted alkyl, aryl, substituted aryl, CO(alkyl) or CO(substituted alkyl); and f is an integer selected from 1 to 100; wherein the substituted alkyl is independently substituted by one or more of F, Cl, Br, I, hydroxyl, alkenyl, CN and N3.

25. The composition according to claim 24, wherein The substituted alkyl group is methyl, vinyl or CO(methyl).

26. The composition according to any one of claims 11 to 13, further comprising an oil selected from the group consisting of mineral oil, essential oil, vegetable oil and mixtures thereof.

27. The composition according to claim 26, wherein The oil comprises a vegetable oil selected from the group consisting of coconut oil, canola oil, soybean oil, rapeseed oil, sunflower oil, safflower oil, peanut oil, cottonseed oil, palm oil, rice bran oil, and mixtures thereof.

28. The composition according to claim 26, wherein The oil includes a mineral oil selected from the group consisting of paraffinic oil, branched paraffinic oil, naphthenic oil, aromatic oil and mixtures thereof.

29. The composition according to claim 26, wherein The oil comprises a poly-alpha-olefin (PAO).

30. The composition according to any one of claims 11 to 13, wherein The carrier liquid comprises water.

31. A composition according to any one of claims 11 to 13, wherein The carrier liquid comprises an oil-in-water emulsion.

32. A method for promoting plant health, comprising: applying a compound as defined in any one of claims 1 to 10 or an agriculturally acceptable salt thereof, or a composition as defined in any one of claims 11 to 31 to a plant; and The plants are exposed to light.

33. The method of claim 32, wherein: Promoting plant health includes preventing or inhibiting the growth of microbial pathogens of said plants.

34. The method of claim 32, wherein: Promoting plant health includes inhibiting the growth of microbial pathogens of said plants.

35. The method according to claim 33 or 34, wherein: The microbial pathogens include fungal pathogens.

36. The method of claim 35, wherein: The fungal pathogen includes at least one of Botrytis cinerea, Alternaria solani and Sclerotinia homoeocarpa.

37. The method according to claim 33 or 34, wherein: The microbial pathogens include bacterial pathogens.

38. The method of claim 37, wherein: The bacterial pathogens include Gram-negative bacteria.

39. The method of claim 38, wherein: The bacterial pathogens include at least one of Erwinia amylovora, Xanthomonas axonopodis and Escherichia coli.

40. The method of claim 33 or 34, wherein: The microbial pathogens include viruses, viroids, viro-like organisms, or phytoplasmas.

41. The method of claim 40, wherein: The microbial pathogens include viruses.

42. The method according to claim 41, wherein: The virus is cucumber mosaic virus (CMV).

43. The method of claim 32, wherein: Promoting plant health includes increasing the plant's resistance to one or more abiotic stresses.

44. The method of claim 43, wherein: The one or more abiotic stresses are selected from the group consisting of low temperature stress, high temperature stress, water stress, transplant shock stress, low light stress, photooxidative stress, drought stress and salt stress.

45. The method according to claim 43 or 44, wherein: The compound is applied to the plant at or before the onset of one or more of the abiotic stresses.

46. ​​The method of claim 43 or 44, wherein: The compound is applied to the plant after the onset of the abiotic stress.

47. The method of claim 32, wherein: Promoting plant health includes controlling pests of said plants.

48. The method of claim 47, wherein: The pests of the plants are selected from the group consisting of insects and insect larvae.

49. The method according to claim 47 or 48, wherein: The compound is applied to the plants at or before the time when the plants are infested by the pests.

50. The method of claim 47 or 48, wherein: The compound is applied to the plants after the plants have been infested by the pests.

51. The method according to any one of claims 32 to 34, wherein: The plants are non-woody crops, woody plants or turf grasses.

52. The method of claim 51, wherein: The plant is a woody plant.

53. The method of claim 52, wherein: The woody plant is a tree.

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