METHOD FOR THE PRODUCTION OF A PHOSPHORAMIDITE AND ITS FURTHER CONVERSION TO MONOPHOSPHITE

Description

[0001] The invention relates to a process for the preparation of a phosphoramidite and its further conversion to monophosphite.

[0002] Monophosphites are classically produced using Cl-containing compounds or via CI-containing intermediates.

[0003] As described in WO 2015 / 176929 A1, chlorine residues from the synthesis remain in the organophosphorus compound, which leads to problems when used. For example, the steel of the reactor can be attacked by the chlorine. A process for the preparation of phosphite derivatives is disclosed in Journal of Applied Polymer Science, 14, 2002, 2984-2992.

[0004] WO 2015 / 176927 A1 discloses a process for the preparation of phosphite derivatives.

[0005] Monophosphites produced using Cl-containing compounds require extensive purification after synthesis to reduce the Cl content. However, even after extensive purification, Cl residues still remain in the monophosphite, which pose problems for the further use of the compound.

[0006] The technical object of the invention is to provide a method in which the problems associated with the prior art are reduced or eliminated.

[0007] The object is achieved by a method according to claim 1.

[0008] Procedure comprising the following steps: a) Presentation of a compound according to the formula ( I ): where R 1< , R 2< , R 3< are selected from: -H, -(C 1 -C 12 )-alkyl, -O-(C 1 -C 12 )-alkyl, -(C 6 -C 10 )-aryl, -CN, - NO 2 ; b) adding P(NX 2 ) 3 , where X is -(C 1 -C 6 )-alkyl; c) reacting the compound from a) and b) to give a compound according to the formula ( II ): d) Addition of the compound according to the formula ( I ): e) adding a compound Y, where Y is a five-membered ring in which at least one C atom is replaced by an N atom; f) reacting the compounds from c) to e) to form a compound according to the formula ( III ):

[0009] Examples of five-membered rings in which one C atom is replaced by one N atom are: pyrrolidine, 2-pyrroline, 3-pyrroline, azole.

[0010] Examples of five-membered rings in which two C atoms have been replaced by N atoms are: diazolidine, 1,2-diazole, 1,3-diazole.

[0011] Examples of five-membered rings in which three C atoms have been replaced by N atoms are: 1,2,3-triazolidine, 1,2,4-triazolidine, 1,2,3-triazole, 1,2,4-triazole.

[0012] Examples of five-membered rings in which four C atoms have been replaced by N atoms are: tetrazolidine, 5H-terazole, 2,5-dihydro-1H-tetrazole.

[0013] Examples of five-membered rings in which five C atoms have been replaced by N atoms are: 1H-pentazole.

[0014] In a variant of the process, R 1< , R 2< , R 3< are selected from: -H, -(C 1 -C 12 )-alkyl, -O-(C 1 -C 12 )-alkyl, -(C 6 -C 10 )-aryl.

[0015] In a variant of the process, R 1< , R 2< , R 3< are selected from: -H, -(C 1 -C 12 )-alkyl, -O-(C 1 -C 12 )-alkyl.

[0016] In a variant of the process, R 1< , R 2< , R 3< are selected from: -H, -(C 1 -C 12 )-alkyl.

[0017] In a variant of the process, R 1< , R 2< , R 3< are selected from: -H, -CH 3 , -O-CH 3 , - tert< Bu.

[0018] In a variant of the process, the compound according to formula (I) has the structure (1):

[0019] In a variant of the process, X is -(C 1 -C 2 )-alkyl.

[0020] In one variant of the process, X stands for -CH 3 .

[0021] In one variant of the process, the five-membered ring (Y) has at least one double bond.

[0022] In one variant of the process, the five-membered ring (Y) has two double bonds.

[0023] In one variant of the process, the five-membered ring (Y) has at least one NH bond.

[0024] In one variant of the process, the five-membered ring (Y) has at least two N atoms.

[0025] In one variant of the process, the five-membered ring (Y) has at least three N atoms.

[0026] In one variant of the process, the five-membered ring (Y) has four N atoms.

[0027] In a variant of the procedure, Y stands for the following compound:

[0028] In a variant of the process, this comprises the additional process step c'): c') addition of a solvent.

[0029] In one variant of the process, the solvent is selected from: acetonitrile, toluene, xylene, THF, heptane.

[0030] In one variant of the process, the solvent is toluene.

[0031] In a variant of the process, the synthesis takes place in the absence of Cl.

[0032] In the following, the invention will be explained in more detail using an exemplary embodiment. Syntheses of Alkanox

[0033]

[0034] In a Schlenk vessel, 2,4-di- tert .-butylphenol (1) (413 mg, 2 mmol) and HMPT (2)(82 mg, 0.5 mmol) in toluene (5 ml) and stirred at 100 °C under a gentle stream of argon. After about 3 days, the maximum formation of the intermediate (bis(2,4-di-tert-butylphenyl)dimethylphosphoramidite (3) (δ p = +137.7 ppm in toluene) and the solution is concentrated under vacuum. The residue containing the excess phenol derivative is then treated with a tetrazole solution (6.4 ml, 0.45M tetrazole in acetonitrile) and stirred at room temperature overnight. After about half an hour, a white precipitate begins to form. After filtration and washing with acetonitrile (3 ml), Alkanox is obtained. (4) in a yield of 56%.

[0035] The new synthesis route makes it possible to dispense with Cl-containing compounds. This not only eliminates the need for time-consuming purification of the diphosphite after synthesis, but also prevents the introduction of residual Cl into the reactor.

Claims

1. Process comprising the process steps of: a) initially charging a compound of the formula (I): wherein R1, R2, R3 are selected from: -H, - (C1-C12) -alkyl, -O- (C1-C12) -alkyl, - (C6-C10) -aryl, -CN, -NO2; b) adding P(NX2)3, wherein X is -(C1-C6)-alkyl; c) reacting the compound from a) and b) to give a compound of the formula (II): d) adding the compound of the formula (I): e) adding a compound Y, wherein Y is a five-membered ring in which at least one carbon atom has been replaced by a nitrogen atom; f) reacting the compounds from c) to e) to give a compound of the formula (III):

2. Process according to Claim 1, wherein R1, R2, R3 are selected from: -H, - (C1-C12) -alkyl, -O-(C1-C12) -alkyl, - (C6-C10) -aryl.

3. Process according to either of Claims 1 and 2, wherein R1, R2, R3 are selected from: -H, -(C1-C12) -alkyl, -O-(C1-C12)-alkyl.

4. Process according to any of Claims 1 to 3, wherein X is -(C1-C2)-alkyl.

5. Process according to any of Claims 1 to 4, wherein X is -CH3.

6. Process according to any of Claims 1 to 5, wherein the five-membered ring (Y) has at least one double bond.

7. Process according to any of Claims 1 to 6, wherein the five-membered ring (Y) has two double bonds.

8. Process according to any of Claims 1 to 7, wherein the five-membered ring (Y) has at least one N-H bond.

9. Process according to any of Claims 1 to 8, wherein the five-membered ring (Y) has at least two nitrogen atoms.

10. Process according to any of Claims 1 to 9, wherein the five-membered ring (Y) has at least three nitrogen atoms.

11. Process according to any of Claims 1 to 10, wherein the five-membered ring (Y) has four nitrogen atoms.

12. Process according to any of Claims 1 to 11, wherein Y is the following compound:

13. Process according to any of Claims 1 to 12, comprising the additional process step of c'): c') adding a solvent.

14. Process according to Claim 13, where the solvent is selected from: acetonitrile, toluene, xylene, THF, heptane.