阅读说明：本技术 硝化抑制剂的延迟释放配制剂 (Delayed release formulations of nitrification inhibitors ) 是由 B·纳韦 K-H·施奈德 U·米勒 L·卡尔瓦茨基 L·阿诺德 A-N·帕伏列斯库 于 2019-03-06 设计创作，主要内容包括：本发明涉及一种组合物,其包含a)沸石咪唑骨架结构ZIF-8；和b)式(I)化合物或其立体异构体、盐、互变异构体或N-氧化物,其中变量具有如本文主体中所定义的含义。还涉及一种施肥方法,包括用所述组合物进行处理。其他目的是ZIF-8用于降低式(I)化合物的蒸发速率的用途；一种制备所定义的组合物的方法,包括步骤a)将式(I)化合物吸附在ZIF-8上；以及所述组合物用于制备包含式(I)化合物和肥料的颗粒的用途。<Image he="187" wi="349" file="DDA0002677333740000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The present invention relates to a composition comprising a) a zeolitic imidazolate framework ZIF-8; and b) a compound of formula (I) or a stereoisomer, salt, tautomer or N-oxide thereof, wherein the variables have the meanings as defined in the body herein. Also relates to a method for fertilizing, comprising the treatment with said composition. Further objects are the use of ZIF-8 for reducing the evaporation rate of a compound of formula (I); a process for preparing a composition as defined comprising the steps of a) adsorbing a compound of formula (I) on ZIF-8; and the use of said composition for the preparation of granules comprising a compound of formula (I) and a fertilizer.)

1. A composition comprising:

a) zeolitic imidazole framework structure ZIF-8, and

b) a compound of formula (I) or a stereoisomer, salt, tautomer or N-oxide thereof,

wherein the variables have the following meanings:

R¹，R²independently is H;

C₁-C₆alkyl radical, C₂-C₆Alkenyl radical, C₂-C₆Alkynyl, C₁-C₆Haloalkyl, C₁-C₄alkoxy-C₁-C₄Alkyl radical, C₁-C₆Alkoxy radical, C₂-C₆Alkenyloxy radical, C₂-C₆Alkynyloxy, unsubstituted or substituted by one or more R, the same or different^eSubstitution; or

C₃-C₈Cycloalkyl radical, C₃-C₈Cycloalkenyl, heterocyclyl, aryl, heteroaryl, C₃-C₈cycloalkyl-C₁-C₆Alkyl radical, C₃-C₈Cycloalkenyl radical-C₁-C₆Alkyl, heterocyclyl-C₁-C₆Alkyl, aryl-C₁-C₆Alkyl, heteroaryl-C₁-C₆Alkyl, phenoxy or benzyloxy, wherein the cyclic moiety is unsubstituted or substituted by one or more R which may be the same or different^aSubstitution;

a is phenyl which is unsubstituted or substituted by one or more identical or different R^ASubstitution;

R^Ais CN, halogen, NO₂、OR^b、NR^cR^d、C(Y)R^b、C(Y)OR^b、C(Y)NR^cR^d、S(Y)_mR^b、S(Y)_mOR^b；

C₁-C₆Alkyl radical, C₂-C₆Alkenyl radical, C₂-C₆Alkynyl, C₁-C₆Haloalkyl, C₁-C₆Alkoxy radical, C₁-C₆Alkylthio, which is unsubstituted or substituted by one or more identical or different radicals R^eSubstitution; or

C₃-C₈Cycloalkyl radical, C₃-C₈Cycloalkenyl, heterocyclyl, aryl, heteroaryl, C ₃-C₈cycloalkyl-C₁-C₆Alkyl radical, C₃-C₈Cycloalkenyl radical-C₁-C₆Alkyl, heterocyclyl-C₁-C₆Alkyl, aryl-C₁-C₆Alkyl, heteroaryl-C₁-C₆Alkyl, phenoxy, benzyloxy, wherein the cyclic moiety is unsubstituted or substituted by one or more R which may be the same or different^aSubstitution;

R^ais CN, halogen, NO₂、C₁-C₄Alkyl radical, C₁-C₄Haloalkyl or C₁-C₄An alkoxy group;

or two substituents R on adjacent C atoms^aForm a bridge CH₂CH₂CH₂CH₂、OCH₂CH₂CH₂、CH₂OCH₂CH₂、OCH₂CH₂O、OCH₂OCH₂、CH₂CH₂CH₂、CH₂CH₂O、CH₂OCH₂、O(CH₂)O、SCH₂CH₂CH₂、CH₂SCH₂CH₂、SCH₂CH₂S、SCH₂SCH₂、CH₂CH₂S、CH₂SCH₂、S(CH₂) S, and two R^aThe bonded C atoms together form a 5-or 6-membered saturated carbocyclic or heterocyclic ring;

R^bis H, C₁-C₆Alkyl radical, C₂-C₄Alkenyl radical, C₂-C₄Alkynyl, C₁-C₄Haloalkyl, phenyl or benzyl;

R^c、R^dindependently of one another is H, C₁-C₄Alkyl or C₁-C₄A haloalkyl group; or

R^cAnd R^dTogether with the N atom to which they are bonded form a 5-or 6-membered saturated or unsaturated heterocyclic ring, wherein the heterocyclic ring is unsubstituted or substituted by one or more identical or different halogen atoms;

R^eis CN, halogen, C₁-C₄Alkyl radical, C₁-C₄Haloalkyl, C₁-C₄Alkoxy or C₁-C₄A haloalkoxy group;

y is O or S; and is

M is 0, 1 or 2.

2. The composition according to claim 1, wherein the variables of the compound of formula (I) have the following meanings:

R^ais halogen, C₁-C₂Alkyl radical, C₁-C₂An alkoxy group;

or two substituents R on adjacent C atoms^aIs OCH₂CH₂O bridge or O (CH)₂) An O bridge;

R^bis H, C ₁-C₆Alkyl, phenyl and benzyl;

R^c、R^dindependently H, C₁-C₄Alkyl or C₁-C₄A haloalkyl group; and is

R^eIs halogen and C₁-C₄An alkyl group.

3. The composition according to claim 1 or 2, wherein the variables of the compound of formula (I) have the following meanings:

R¹，R²independently is H, C₂-C₆Alkynyl, C₂-C₆Alkynyloxy, aryl-C₁-C₆Alkyl or heteroaryl-C₁-C₆An alkyl group;

wherein R is¹And R²Is H.

4. A composition according to any one of claims 1 to 3, wherein the variables of the compound of formula (I) have the following meanings:

a is phenyl which is unsubstituted or substituted by one or more identical or different R^ASubstitution; and is

R^AIs halogen, NO₂、NR^cR^d、C₁-C₆Alkyl radical, C₁-C₆Haloalkyl, C₁-C₆Alkoxy radical, C₁-C₆Alkylthio, phenoxy or benzyloxy, in which the cyclic moiety is unsubstituted or substituted by one or more identical or different R^aAnd (4) substitution.

5. The composition according to any one of claims 1 to 4, wherein the variables of the compound of formula (I) have the following meanings:

R¹，R²is H; and is

A is phenyl substituted with Cl.

6. The composition of any one of claims 1-5, wherein the weight ratio of compound of formula (I) to ZIF-8 is from 1:10 to 2: 1.

7. The composition of any one of claims 1-6, comprising a fertilizer.

8. The composition of claim 7, wherein the fertilizer is an organic or inorganic amino-containing fertilizer, or a urea-containing fertilizer.

9. A method of fertilizing comprising treating a plant propagation material, a plant growing on soil or a soil substitute and/or a locus where a plant is growing or is intended to grow or a soil substitute with a composition as defined in any one of claims 1 to 8.

10. The method according to claim 10, wherein the plant propagation material, the plant and/or the locus where the plant is growing or is intended to grow or the soil substitute is additionally treated with a fertilizer.

Use of ZIF-8 to reduce the evaporation rate of a compound of formula (I).

12. A process for the preparation of a composition as defined in any one of claims 1 to 8, comprising the step a) of adsorbing a compound of formula (I) as defined in any one of claims 1 to 6 onto the metal organic framework ZIF-8.

13. The process according to claim 12, comprising the step of b) co-granulating the compound of formula (I) adsorbed on ZIF-8 with a fertilizer as defined in claim 7 or 8, wherein the composition is in the form of granules.

14. The process according to claim 13, wherein the temperature in step b) is 50-150 ℃.

15. Use of a composition as defined in any one of claims 1 to 6 for the preparation of a granule comprising a compound of formula (I) and a fertilizer, each as defined in any one of claims 1 to 8.

Example (b):

ZIF-8 asZ1200 was purchased from sigma aldrich.

Zeolite beta was purchased from Alfa Aesar.

A compound A: 1-chloro-4- (prop-2-ynyloxymethyl) benzene (corresponding to compounds 1-15 in Table A).

Working example 1: compound A on ZIF-8

ZIF-8 powder (10g) was placed in a porcelain plate. The ZIF-8 powder is in the activation stage and hardly any substances are adsorbed in the pores of the material. Compound a (3g, with an impurity content below 2%) was slowly added to the manually stirred ZIF-8 powder over 15 minutes at 20-25 ℃ to give sample a, which contained 23 wt% compound a based on the total weight of sample a.

Working example 2: compound A on ZIF-8 with different loading amounts

ZIF-8 was loaded with compound A as described in working example 1, with varying amounts of compound A, to give samples B-H of Table 1.

Table 1: varying amounts of Compound A loaded ZIF-8, [ wt. ]

Comparative working example 1: compound A on zeolite beta

Zeolite beta powder (10g) was placed in a porcelain dish. The zeolite beta powder is in the activation stage and hardly any substances are adsorbed in the pores of the material. Compound a (3g, with an impurity content below 2%) was slowly added to the manually stirred zeolite beta powder over 15 minutes at 20-25 ℃ to give sample K, which contained 23 wt% of compound a based on the total weight of sample K.