Method for preparing monophosphite

Abstract

To provide processes for preparing monophosphites that dispense with laborious purification of the monophosphites after synthesis, and compounds used for the preparation.SOLUTION: A method for preparing a monophosphite (5) includes reacting, for example, a tetrazole (1) with a compound (2), followed by a reaction with a phenolic compound (4).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for preparing monophosphite and a compound used in the preparation thereof.

Background Art

[0002] Classically, monophosphite is prepared using a Cl-containing compound or via a Cl-containing intermediate.

[0003] As described in WO 2015 / 176929 pamphlet, when a chlorine residue remains in an organophosphorus compound by synthesis, problems occur when using the organophosphorus compound. For example, the steel of a nuclear reactor can be attacked by chlorine.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] Monophosphite prepared using a Cl-containing compound needs to be laboriously purified after synthesis in order to reduce the Cl content. However, even after laborious purification, Cl residues still remain in the monophosphite, causing problems when this compound is further used.

[0006] The technical object of the present invention is to provide a method for reducing or eliminating problems arising in relation to the prior art.

Means for Solving the Problems

[0007] This object is achieved by the method according to claim 1.

[0008] (a) First, filling a compound Y which is a 5-membered ring in which at least one carbon atom is substituted by a nitrogen atom; (b) Adding P(NX2)3 (wherein X is -(C1-C6)-alkyl); (c) Adding a compound of formula (I):

[0009]

Chemical formula

[0010] (wherein R 1 , R 2 , R 3 are each independently selected from -H, -(C1-C 12 )-alkyl, -O-(C1-C 12 )-alkyl, -(C6-C 10 )-aryl, -CN, -NO2).) ; and a method comprising .

[0011] Examples of 5-membered rings in which a carbon atom is substituted by a nitrogen atom include pyrrolidine, 2-pyrroline, 3-pyrroline, and azole.

[0012] Examples of 5-membered rings in which two carbon atoms are substituted by nitrogen atoms include diazolidine, 1,2-diazole, and 1,3-diazole.

[0013] Examples of 5-membered rings in which three carbon atoms are substituted by nitrogen atoms include 1,2,3-triazolidine, 1,2,4-triazolidine, 1,2,3-triazole, and 1,2,4-triazole.

[0014] Examples of 5-membered rings in which four carbon atoms are substituted by nitrogen atoms include tetrazolidine, 5H-tetrazole, and 2,5-dihydro-1H-tetrazole.

[0015] Examples of 5-membered rings in which five carbon atoms are substituted by nitrogen atoms include 1H-pentazole.

[0016] In a variant of this method, the 5-membered ring (Y) has at least one double bond.

[0017] In a variant of this method, the 5-membered ring (Y) has two double bonds.

[0018] In a variant of this method, the 5-membered ring (Y) has at least one N-H bond.

[0019] In a variant of this method, the 5-membered ring (Y) has at least two nitrogen atoms.

[0020] In a variant of this method, the 5-membered ring (Y) has at least three nitrogen atoms.

[0021] In a variant of this method, the 5-membered ring (Y) has four nitrogen atoms.

[0022] In a variant of this method, Y is the following compound.

[0023]

Chemical formula

[0024] In a variant of this method, X is -(C1-C2)-alkyl.

[0025] In a variant of this method, X is -CH3.

[0026] In a variant of this method, R 1 , R 2 , R 3 are selected from -H, -(C1-C 12 )-alkyl, -O-(C1-C 12 )-alkyl, -(C6-C 10 )-aryl.

[0027] In a variant of this method, R 1 , R 2 , R 3 are selected from -H, -(C1-C 12)-alkyl, -O-(C1-C 12 )-alkyl selected from the group consisting of.

[0028] In one variation of this method, R 1 , R 2 , R 3 is selected from -H, -(C1-C 12 )-alkyl.

[0029] In one variation of this method, R 1 , R 2 , R 3 is selected from -H, -CH3, -O-CH3, - tert Bu.

[0030] In one variation of this method, the compound of formula (I) has the following structure (4).

[0031]

Chemical formula

[0032] In one variation of this method, the method includes an additional step (d) of adding a solvent.

[0033] In one variation of this method, the solvent is selected from acetonitrile (ACN), toluene, xylene, THF, heptane.

[0034] In one variation of this method, the solvent is acetonitrile (ACN).

[0035] In one variation of this method, the synthesis is carried out in the absence of Cl.

[0036] In addition to the method itself, the compounds used in the method are also claimed. The compound according to formula (3).

[0037]

Chemical formula

[0038] Hereinafter, the present invention will be described in more detail with reference to examples.

Example

[0039] Synthesis of Alkanox

[0040]

Chemical formula

[0041] To generate tris(1H-tetrazol-1-yl)phosphine (3), HMPT (2) (163 mg, 1 mmol) was added to a 0.45 M acetonitrile solution of tetrazole (1) (13.4 mL, 6 mmol), and the mixture was stirred under argon at room temperature for 5 minutes. Subsequently, 3 equivalents of 2,4-di-tert-butylphenol (4) (619 mg, 3 mmol) were added to the solution. The reaction mixture was further stirred under argon at 60 °C for about 20 hours. After 15 - 30 minutes, a white precipitate gradually formed in the solution. As a post-treatment, the precipitate was filtered off under anaerobic conditions, washed once with acetonitrile (2 mL), and dried under vacuum. Yield (5): 0.50 g of white solid (= 77%).

[0042] 31 P NMR (CD2Cl2): 129.9 ppm. 1 H NMR (CD2Cl2): 7.40 (3H, d, J 2.5 Hz, 3xH ar )、7.40 (3H, dd, J 8.5, 2.1 Hz, 3xH ar )、7.12 (3H, dd, J 8.5, 2.5 Hz, 3xH ar )、1.41 (27H, s, 3xC(CH3)3), 1.30 (27H, s, 3xC(CH3)3). 13 C NMR (CD2Cl2): 149.5 (d, J 4.0 Hz, 3xC ar -O), 146.2 (3xC ar )、139.4 (d, J 2.6 Hz, C ar )、125.0 (3xC arH), 124.0 (3xC ar H), 119.2 (d, J 18.2 Hz, 3xC ar H), 35.4 (3x t C), 34.8 (3x t C), 31.7 (9xCH3), 30.4 (9xCH3).

[0043] The novel synthetic route makes it possible to remove Cl-containing compounds. First, this omits the time-consuming purification of the monophosphite after synthesis, and second, it also avoids the introduction of residual chlorine into the reactor.

Claims

1. (a) a step of first filling a compound Y which is a 5-membered ring in which at least one carbon atom is substituted with a nitrogen atom; (b) P(NX ２ ) ３ (wherein X is -(C １ -C ６ )-alkyl).) and the step of adding (c) a step of adding a compound represented by formula (I): 【Chemical 1】 (wherein, R １ , R ２ , R ３ is selected from -H, -(C １ -C １２ )-alkyl, -O-(C １ -C １２ )-alkyl, -(C ６ -C １０ )-aryl, -CN, -NO ２ ).) ; A method comprising the steps of.

2. The method according to claim 1, wherein the 5-membered ring (Y) has at least one double bond.

3. The method according to claim 1 or claim 2, wherein the 5-membered ring (Y) has two double bonds.

4. The method according to claim 1, wherein the 5-membered ring (Y) has at least one N-H bond.

5. The method according to claim 1, wherein the 5-membered ring (Y) has at least two nitrogen atoms.

6. The method according to claim 1, wherein the 5-membered ring (Y) has at least three nitrogen atoms.

7. The method according to claim 1, wherein the 5-membered ring (Y) has four nitrogen atoms.

8. Y is the following: [Chemical Formula 2] The method according to claim 1, which is a compound of.

9. X is -(C １ -C ２ )-alkyl, the method according to claim 1.

10. X is -CH ３ The method according to claim 1, wherein

11. R １ 、R ２ 、R ３ is selected from -H, -(C １ -C １２ )-alkyl, -O-(C １ -C １２ )-alkyl, -(C ６ -C １０ )-aryl, and the method according to claim 1.

12. R １ 、R ２ 、R ３ is selected from -H, -(C １ -C １２ )-alkyl, -O-(C １ -C １２ )-alkyl, the method according to claim 1.

13. The method according to claim 1, further comprising an additional step (d) of adding a solvent.

14. The method according to claim 13, wherein the solvent is selected from acetonitrile (ACN), toluene, xylene, THF, and heptane.

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