阅读说明：本技术 制备多氟化合物的方法 (Process for preparing polyfluoro compounds ) 是由 C·R·皮特 N·桑奇 A·托格尼 于 2019-05-29 设计创作，主要内容包括：本发明涉及制备式Ar-R-1(I)的多氟化合物的方法,其中Ar-R-1(I)是芳族环系,其中R-1选自SF-4Cl、SF-3、SF-2CF-3、TeF-5、TeF-4CF-3、SeF-3、IF-2、SeF-2CF-3和IF-4,X-2为N或CR-2,X-3为N或CR-3,X-4为N或CR-4,X-5为N或CR-5,X-6为N或CR-6,并且所述芳族环系中氮原子的总数为0至3,并且如果X-5为CR-5且X-6为CR-6,则R-5和R-6可一起形成包含一个或多个氮的饱和或不饱和的五或六元环系,其中所述五或六元环系可被一个或多个残基R-7取代,所述方法包括以下反应步骤：使选自Ar-2S-2、Ar-2Te-2、Ar-2Se-2、ArSCF-3、ArI、ArTeCF-3、ArSeCF-3、ArSCF-3和ArSCl的起始材料,其中Ar具有与上述相同的定义,与式(III)的三氯异氰脲酸(TCICA)在碱金属氟化物(MF)的存在下反应。(The invention relates to the preparation of Ar-R 1 (I) The polyfluoro compound of (1), wherein Ar-R 1 (I) Is an aromatic ring system in which R 1 Selected from SF 4 Cl、SF 3 、SF 2 CF 3 、TeF 5 、TeF 4 CF 3 、SeF 3 、IF 2 、SeF 2 CF 3 And IF 4 ，X 2 Is N or CR 2 ，X 3 Is N or CR 3 ，X 4 Is N or CR 4 ，X 5 Is N or CR 5 ，X 6 Is N or CR 6 And the total number of nitrogen atoms in the aromatic ring system is from 0 to 3, and if X is 5 Is CR 5 And X 6 Is CR 6 Then R is 5 And R 6 May together form a saturated or unsaturated five-or six-membered ring system containing one or more nitrogen, wherein the five-or six-membered ring system may be interrupted by one or more residues R 7 Substitution, the process comprising the reaction steps of: is selected from Ar 2 S 2 、Ar 2 Te 2 、Ar 2 Se 2 、ArSCF 3 、ArI、ArTeCF 3 、ArSeCF 3 、ArSCF 3 And ArSCl, wherein Ar has the same definition as above, with trichloroisocyanuric acid (TCICA) of formula (III) in the presence of an alkali Metal Fluoride (MF).)

1. Preparation of formula Ar-R₁(I) The method for producing a polyfluoro compound of (1),

wherein Ar-R₁(I) Is an aromatic ring system which is,

wherein

R₁Selected from SF₄Cl、SF₃、SF₂CF₃、TeF₅、TeF₄CF₃、SeF₃、IF₂、SeF₂CF₃And IF₄，

X₂Is N or CR₂，

X₃Is N or CR₃，

X₄Is N or CR₄，

X₅Is N or CR₅，

X₆Is N or CR₆And is and

the total number of nitrogen atoms in the aromatic ring system is from 0 to 3,

wherein R is₂、R₃、R₄、R₅And R₆Independently selected from hydrogen, fluorine, chlorine, bromine, nitro, trisFluoromethyl, 2,2, 2-trifluoroethyl, pentafluorosulfanyl, phthalimido, azido, benzyloxy, trifluoromethoxy, 2,2, 2-trifluoroethoxy, methoxycarbonyl, ethoxycarbonyl, methylcarbonyl, ethylcarbonyl, acetoxy, t-butyl, phenylcarbonyl, benzylcarbonyl, 3-trifluoromethylphenyl, phenylsulfonyl, methylsulfonyl, chlorophenyl, methyloxonyl, methyl, isopropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, fluoromethyl, fluoroethyl and phenyl,

or if X₅Is CR₅And X₆Is CR₆Then R is₅And R₆May together form a saturated or unsaturated five-or six-membered ring system containing one or more nitrogens, wherein said five-or six-membered ring system may be substituted by one or more groups having a group with R₂To R₆Identically defined residues R₇Is substituted and

provided that

If R is₁Is SF₃Then R is₂And R₆Is neither hydrogen nor fluorine, and

if R is₁Is not SF₃Then R is₂And R₆Independently of one another are hydrogen or fluorine, and

if X is₂、X₃、X₄、X₅And X₆At least one of which is nitrogen, then R₂、R₃、R₄、R₅And R₆At least one of which is not hydrogen,

the method comprises the following reaction steps:

is selected from Ar₂S₂、Ar₂Te₂、Ar₂Se₂、ArSCF₃、ArTeCF₃、ArI、ArSeCF₃、ArSCH₃And the starting material of ArSCl, and,

wherein Ar has the same meaning as defined above,

with trichloroisocyanuric acid (TCICA)

In the presence of an alkali Metal Fluoride (MF), preferably potassium fluoride (KF).

2. The method for producing a polyfluoro compound according to claim 1,

wherein Ar-R₁(I) Is an aromatic ring system which is,

wherein

R₁Selected from SF₄Cl、SF₃、SF₂CF₃、TeF₅、TeF₄CF₃、SeF₃And IF₂，

X₂Is N or CR₂，

X₃Is N or CR₃，

X₄Is N or CR₄，

X₅Is N or CR₅，

X₆Is N or CR₆And is and

the total number of nitrogen atoms in the aromatic ring system is from 0 to 3,

wherein R is₂、R₃、R₄、R₅And R₆Independently selected from the group consisting of hydrogen, fluorine, chlorine, bromine, nitro, trifluoromethyl, 2,2, 2-trifluoroethyl, pentafluorosulfanyl, phthalimido, azido, benzyloxy, trifluoromethoxy, 2,2, 2-trifluoroethoxy, methoxycarbonyl, ethoxycarbonyl, acetoxy, tert-butyl and phenyl, and

provided that

If R is₁Is SF₃Then R is₂And R₆Is neither hydrogen nor fluorine, and

if R is₁Is not SF₃Then R is₂And R₆Independently of one another are hydrogen or fluorine, and

if X is₂、X₃、X₄、X₅And X₆At least one of which is nitrogen, then R₂、R₃、R₄、R₅And R₆At least one of which is not hydrogen,

the method comprises the following reaction steps:

is selected from Ar₂S₂、Ar₂Te₂、Ar₂Se₂、Ar-SCF₃And ArI, the starting materials for the composition,

wherein Ar has the same meaning as defined above,

with trichloroisocyanuric acid (TCICA)

In the presence of an alkali Metal Fluoride (MF), preferably potassium fluoride (KF).

3. The process according to any one of the preceding claims, wherein the process is carried out in the presence of a catalytic amount of a bronsted or lewis acid, and wherein the bronsted or lewis acid is preferably selected from trifluoroacetic acid (TFA), aluminum chloride (aici)₃) Aluminum bromide (AlBr)₃) Boron trifluoride (BF)₃) Tin dichloride (SnCl)₂) Zinc chloride (ZnCl)₂) And titanium tetrachloride (TiCl)₄) Or mixtures thereof, preferably ZnCl₂And TFA, most preferably TFA.

4. The method according to claim 3, wherein the catalytic amount of the Bronsted or Lewis acid is from 5 to 15 mol%, preferably 10 mol%.

5. The process according to any of the preceding claims, wherein the molar ratio of TCICA: MF, preferably TCICA: KF is from 1:1 to 1:10, preferably from 1:1 to 1:5, and most preferably is 1: 2.

6. The method of any one of the preceding claimsFor the preparation of formula Ar-R₁ (I) The polyfluoro compound of (1).

7. The method of any one of the preceding claims, wherein R₁Is SF₄Cl or SF₃Preferably SF₄Cl。

8. A method according to any preceding claim, wherein the aromatic ring system is a substituted or unsubstituted benzene ring, and R is₁To R₆Have the same definitions as in claim 1.

9. The method of any one of claims 1 to 6, wherein X₂、X₃、X₄、X₅And X₆At least one of which is nitrogen, preferably X₂、X₃、X₄、X₅And X₆Wherein exactly one is nitrogen, preferably X₂Is nitrogen.

10. The method of claim 8, wherein X₂、X₃、X₄、X₅And X₆Exactly two of which are nitrogen, preferably X₂And X₆Is nitrogen, or wherein X₂、X₃、X₄、X₅And X₆Exactly three of which are nitrogen, preferably X₂、X₃And X₆Is nitrogen.

11. The method of any one of the preceding claims, wherein R₂、R₃、R₄、R₅And R₆At least one of which is fluorine, chlorine, bromine, methoxycarbonyl, ethoxycarbonyl or acetoxy, preferably chlorine or bromine.

12. The method of any one of claims 1 to 10, wherein the starting material is selected from Ar₂S₂、Ar₂Te₂And Ar₂Se₂Is a diaryl dichalcogenide or diheteroaryl diChalcogenide, preferably Ar₂S₂。

13. The method of any one of claims 1 to 10, wherein the starting material is Ar-SCF₃Or ArI.

14. The process according to any one of the preceding claims, wherein the reaction is carried out by reacting Ar-SF in a second reaction step₄Cl to obtain a compound of formula (V) or (VI)

Wherein

X₂Is N or CR₂，

X₃Is N or CR₃，

X₄Is N or CR₄，

X₅Is N or CR₅，

X₆Is N or CR₆And is and

the total number of nitrogen atoms in the aromatic ring system is from 0 to 3,

R₂and R₆Independently of one another are hydrogen or fluorine, and

R₃、R₄and R₅Independently selected from the group consisting of hydrogen, fluorine, chlorine, bromine, nitro, trifluoromethyl, 2,2, 2-trifluoroethyl, pentafluorosulfanyl, phthalimido, azido, benzyloxy, trifluoromethoxy, 2,2, 2-trifluoroethoxy, methoxycarbonyl, ethoxycarbonyl, acetoxy, tert-butyl and phenyl, and

R₁₀is a linear or branched, substituted or unsubstituted alkyl, alpha-alkenyl or alpha-alkynyl group having 2 to 10 carbon atoms.

15. A compound of formula (I)

Selected from

。