Process for preparation of diphosphites
Through the new synthesis method, the chlorine-free compound and five-membered ring compound are used to solve the difficulties in the formation and purification of hydrogen chloride caused by chlorine residues in the prior art, and the high purity and safe production of diphosphites are achieved.
Patent Information
- Application Number
- CN202410826929.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Priority Date
- 2023-06-27
- Filing Date
- 2024-06-25
- Publication Date
- 2024-12-27
AI Technical Summary
When preparing diphosphite in the prior art, the residue of chlorine-containing compounds leads to difficulty in the formation and purification of hydrogen chloride, affecting the further use of the compound.
Through a new synthetic method, chlorine-free compounds and five-membered ring compounds are used to avoid the use of chlorine through specific reaction steps and solvent selection, thereby reducing the chlorine residue problem.
This method effectively reduces the difficulty of purification of diphosphite, avoids chlorine residues, and improves the purity and safety of the product.
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Abstract
Description
Technical Field
[0001] The present invention relates to a process for preparing diphosphites and to compounds useful in the preparation. Background Art
[0002] Diphosphites are usually prepared using chlorine-containing compounds or via Cl-containing intermediates.
[0003] As described in WO 2012 / 095255 A, from the synthetic chlorine residues remain in the diphosphite, which causes problems when using the diphosphite, for example, forms hydrogen chloride in the reactor.This causes the diphosphite prepared by using the compound of chlorine-containing Cl to be purified with great effort to reduce the Cl content after synthesis.Yet, even after the purification with great effort, the Cl residues will still remain in the diphosphite, which causes problems when the further use of the compound. Summary of the invention
[0004] The technical purpose of the present invention is to provide a method for reducing or eliminating the problems occurring in the prior art.
[0005] This object is achieved by a method according to claim 1 .
[0006] The method comprises the following method steps:
[0007] a)
[0008]
[0009] Where R 1 , R 2 , R 3 , R 4 Selected from: -H, -(C1-C 12 )-alkyl, -O-(C1-C 12 )-alkyl, -(C6-C 10 )-aryl, -CN, -NO2 and X 1 is -(C1-C6)-alkyl;
[0010] b)
[0011]
[0012] where Y 1 is a five-membered ring, wherein at least one C atom is substituted by a N atom;
[0013] c)
[0014]
[0015] Where R 5 , R 6 , R7 , R 8 Selected from -H, -(C1-C 12 )-alkyl, -O-(C1-C 12 )-alkyl, -(C6-C 10 )-aryl, -CN, -NO2.
[0016] Examples of five-membered rings in which a C atom is replaced by a N atom are:
[0017] Pyrrolidine, 2-pyrroline, 3-pyrroline, pyrrole (Azol).
[0018] Examples of five-membered rings in which two C atoms are replaced by N atoms are:
[0019] Oxazoline, 1,2-oxadiazole, 1,3-oxadiazole.
[0020] Examples of five-membered rings in which three C atoms are replaced by N atoms are:
[0021] 1,2,3-Triazolidine, 1,2,4-triazolidine, 1,2,3-triazole, 1,2,4-triazole.
[0022] Examples of five-membered rings in which four C atoms are replaced by N atoms are:
[0023] Tetrazolidinyl, 5H-tetrazolidinyl, 2,5-dihydro-1H-tetrazolidinyl.
[0024] Examples of five-membered rings in which five C atoms are replaced by N atoms are:
[0025] 1H-pentazole.
[0026] In one variation of this method, the five-membered ring (Y 1 ) has at least one double bond.
[0027] In one variation of this method, the five-membered ring (Y 1 ) has two double bonds.
[0028] In one variation of this method, the five-membered ring (Y 1 ) has at least one NH bond.
[0029] In one variation of this method, the five-membered ring (Y 1 ) has at least two N atoms.
[0030] In one variation of this method, the five-membered ring (Y 1 ) has at least three N atoms.
[0031] In one variation of this method, the five-membered ring (Y 1 ) has four N atoms.
[0032] In one variation of this approach, Y 1 For the following compounds:
[0033]
[0034] In one variation of this method, X 1 It is -(C1-C2)-alkyl.
[0035] In one variation of this method, X 1 It is -CH2-CH3.
[0036] In one variation of this method, X 1 It is -CH3.
[0037] In one variation of this method, R 1 , R 2 , R 3 , R 4 Selected from: -H, -(C1-C 12 )-alkyl, -O-(C1-C 12 )-alkyl, -(C6-C 10 )-aryl.
[0038] In one variation of this method, R 1 , R 2 , R 3 , R 4 Selected from: -(C1-C 12 )-alkyl, -O-(C1-C 12 )-alkyl.
[0039] In one variation of this method, R 1 , R 2 , R 3 , R 4 Selected from: -CH3, -O-CH3, - t Bu.
[0040] In one variation of this method, R 5 , R 6 , R 7 , R 8 Selected from: -H, -(C1-C 12 )-alkyl, -O-(C1-C 12 )-alkyl, -(C6-C 10 )-aryl.
[0041] In one variation of this method, R 5 , R 6 , R 7 , R 8 Selected from: -(C1-C12 )-alkyl, -O-(C1-C 12 )-alkyl.
[0042] In one variation of this method, R 5 , R 6 , R 7 , R 8 Selected from: -CH3, -O-CH3, - t Bu.
[0043] In a variant of the method, the method comprises an additional method step d):
[0044] d) Adding solvent.
[0045] In one variation of the process, the solvent is selected from the group consisting of: acetonitrile (ACN), toluene, xylene, THF, heptane.
[0046] In one variation of the process, the solvent is acetonitrile (ACN).
[0047] In one variation of this method, the synthesis is performed in the absence of Cl.
[0048] In addition to the process itself, protection is also claimed for compounds used in the process.
[0049] Compounds according to formula (I):
[0050]
[0051] Where R 10 , R 20 , R 30 , R 40 Selected from: -(C1-C 12 )-alkyl, -O-(C1-C 12 )-alkyl, -(C6-C 10 )-aryl, -CN, -NO2 and X 2 It is -(C1-C6)-alkyl.
[0052] In one embodiment, R 10 , R 20 , R 30 , R 40 Selected from: -(C1-C 12 )-alkyl, -O-(C1-C 12 )-alkyl.
[0053] In one embodiment, R 10 , R 20 , R 30 , R 40Selected from: -CH3, -O-CH3, - t Bu.
[0054] In one embodiment, X 2 It is -(C1-C2)-alkyl.
[0055] In one embodiment, X 2 It is -CH2-CH3.
[0056] In one embodiment, X 2 It is -CH3.
[0057] Compounds according to formula (II):
[0058]
[0059] Where R 11 , R 22 , R 33 , R 44 Selected from: -H, -(C1-C 12 )-alkyl, -O-(C1-C 12 )-alkyl, -(C6-C 10 )-aryl, -CN, -NO2 and Y 2 It is a five-membered ring in which at least one C atom is replaced by a N atom.
[0060] In one embodiment, R 11 , R 22 , R 33 , R 44 Selected from: -H, -(C1-C 12 )-alkyl, -O-(C1-C 12 )-alkyl, -(C6-C 10 )-aryl.
[0061] In one embodiment, R 11 , R 22 , R 33 , R 44 Selected from: -(C1-C 12 )-alkyl, -O-(C1-C 12 )-alkyl.
[0062] In one embodiment, R 11 , R 22 , R 33 , R 44 Selected from: -CH3, -O-CH3, - t Bu.
[0063] In one embodiment, the five-membered ring (Y 2) has at least one double bond.
[0064] In one embodiment, the five-membered ring (Y 2 ) has two double bonds.
[0065] In one embodiment, the five-membered ring (Y 2 ) has at least one NH bond.
[0066] In one embodiment, the five-membered ring (Y 2 ) has at least two N atoms.
[0067] In one embodiment, the five-membered ring (Y 2 ) has at least three N atoms.
[0068] In one embodiment, the five-membered ring (Y 2 ) has four N atoms.
[0069] In one embodiment, Y 2 For the following groups:
[0070] DETAILED DESCRIPTION
[0071] Hereinafter, the present invention will be described in more detail with reference to Examples.
[0072] synthesis
[0073] A) The first stage with -CH2-CH3
[0074]
[0075] 24.3 g (0.099 mol) of 3,3,5,5-tetramethyl-1,1-biphenol was weighed into a 1000 ml Schlenk flask and dried by oil pump vacuum for 15 h. The next morning, the Schlenk flask was filled with argon and the biphenol was dissolved in 400 ml of dry acetonitrile and 25 g (0.096 mol, 27.8 ml) of hexaethylphosphoramidite (tris(diethylamino)phosphine). The solution was then heated to 65 ° C. After 4.5 hours, the reaction was completely converted. The reaction solution was cooled to room temperature for 15 h. The reaction solution was concentrated to dryness at 40 ° C by oil pump vacuum. Purity of the target product: 95%.
[0076] 31 P NMR result: 145.7 ppm.
[0077] B) The first stage with -CH3
[0078]
[0079] 4.38 g (0.018 mol) of 3,3,5,5-tetramethyl-1,1-biphenol was weighed into a 250 ml Schlenk flask and dried under oil pump vacuum for 15 h. The next morning, the Schlenk flask was filled with argon and the biphenol was dissolved in 35 ml of dry acetonitrile and 3.12 g (0.018 mol, 3.5 ml) of hexamethylphosphorotriamide (tris(dimethylamino)phosphine). During the reaction, a gentle stream of argon was introduced to remove the formed dimethylamine. The reaction was stirred at room temperature. After 5 hours, the reaction was completely converted. The reaction solution was left at room temperature for 15 h. The reaction solution was concentrated to dryness at 40 ° C using an oil pump vacuum. Purity of the target product: 96%.
[0080] 31 P NMR result: 145.2 ppm.
[0081] C) Conversion into diphosphite
[0082] Embodiment 1:
[0083]
[0084] In a glove box, 5.7 g (0.018 mol) of the starting compound was weighed into a 250 ml container, taken out, and 52 ml (1.64 g, 0.0234 mol) of a 0.45 M tetrazole-ACN solution was added using an argon-flushed syringe. This gave a suspension. Subsequently, the reaction solution was heated to 60 ° C under a gentle argon flow. After 2 hours, the reaction solution was cooled to room temperature and the reaction was continued for 15 h under a gentle argon flow. Subsequently, 20 ml of dry ACN was added again.
[0085] NMR results: 31 P NMR 135.8ppm.
[0086] 2.4 g (0.010 mol) of 2,2'-bis(3,5-dimethylphenol) was weighed into a 50 ml Schlenk flask, dried for 15 h, and then filled with argon. Subsequently, the biphenol was added portionwise to the 0.022 molar concentration (7.4 g) of ACN-tetrazolyl ligand reaction solution at room temperature under a reverse flow of argon and stirred at 60°C for 15 h. The next morning, the reaction solution was cooled to 0°C, filtered on a glass frit, washed twice more with 10 ml of dry cold ACN, and then the glass frit was dried. Target product purity: 93%.
[0087] 31 P NMR 142.9ppm.
[0088] Embodiment 2:
[0089]
[0090] In a glove box, 5.7 g (0.018 mol) of the starting compound was weighed into a 250 ml container, taken out, and 52 ml (1.64 g, 0.0234 mol) of a 0.45 M tetrazole-ACN solution was added using an argon-flushed syringe. This gave a suspension. Subsequently, the reaction solution was heated to 60 ° C under a gentle flow of argon. After 1 hour, 3.46 g (0.010 mol) of 5,5'-dimethoxy-3,3'-di-tert-butyl-2,2'-biphenol was weighed in, taken out, and poured into the current (0.018 mol) ACN-tetrazole ligand reaction solution in portions at 0 ° C under a reverse flow of argon. Thereafter, the reaction solution was slowly returned to room temperature and allowed to react for 15 h. Subsequently, the solid was filtered on a glass frit, washed twice more with 10 ml of dry ACN, and then dried. Purity of the target product: 83%.
[0091] 31 P NMR 142.0, 141.1 ppm.
[0092] The novel synthesis route can save the use of Cl-containing compounds. This saves the laborious purification of the diphosphite after synthesis and avoids the introduction of residual Cl into the reactor.
Claims
1. A method comprising the following steps: a) Where R 1 , R 2 , R 3 , R 4 Selected from: -H, -(C1-C 12 )-alkyl, -O-(C1-C 12 )-alkyl, -(C6-C 10 )-aryl, -CN, -NO2 and X 1 is -(C1-C6)-alkyl; b) where Y 1 is a five-membered ring, wherein at least one C atom is substituted by a N atom; c) Where R 5 , R 6 , R 7 , R 8 Selected from -H, -(C1-C 12 )-alkyl, -O-(C1-C 12 )-alkyl, -(C6-C 10 )-aryl, -CN, -NO2.
2. The method according to claim 1, The five-membered ring has at least one double bond.
3. The method according to any one of claims 1 or 2, The five-membered ring has at least one NH bond.
4. The method according to any one of claims 1 to 3, where Y 1 For the following compounds:
5. The method according to any one of claims 1 to 4, Where X 1 It is -(C1-C2)-alkyl.
6. The method according to any one of claims 1 to 5, Where R 1 , R 2 , R 3 , R 4 Selected from: -H, -(C1-C 12 )-alkyl, -O-(C1-C 12 )-alkyl, -(C6-C 10 )-aryl.
7. The method according to any one of claims 1 to 6, Where R 1 , R 2 , R 3 , R 4 Selected from: -(C1-C 12 )-alkyl, -O-(C1-C 12 )-alkyl.
8. The method according to any one of claims 1 to 7, Where R 5 , R 6 , R 7 , R 8 Selected from: -H, -(C1-C 12 )-alkyl, -O-(C1-C 12 )-alkyl, -(C6-C 10 )-aryl.
9. The method according to any one of claims 1 to 8, Where R 5 , R 6 , R 7 , R 8 Selected from: -(C1-C 12 )-alkyl, -O-(C1-C 12 )-alkyl.
10. The method according to any one of claims 1 to 9, It comprises the additional method step d): d) Adding solvent.
11. The method according to claim 10, The solvent is selected from: acetonitrile (ACN), toluene, xylene, THF, heptane.
12. A compound according to formula (I): Where R 10 , R 20 , R 30 , R 40 Selected from: -(C1-C 12 )-alkyl, -O-(C1-C 12 )-alkyl, -(C6-C 10 )-aryl, -CN, -NO2 and X 2 It is -(C1-C6)-alkyl.
13. The compound according to claim 12, Where R 10 , R 20 , R 30 , R 40 Selected from: -(C1-C 12 )-alkyl, -O-(C1-C 12 )-alkyl.
14. A compound according to formula (II): Where R 11 , R 22 , R 33 , R 44 Selected from: -H, -(C1-C 12 )-alkyl, -O-(C1-C 12 )-alkyl, -(C6-C 10 )-aryl, -CN, -NO2 and Y 2 It is a five-membered ring in which at least one C atom is replaced by a N atom.
15. The compound according to claim 14, where Y 2 The following groups:
Citation Information
Patent Citations
Method for the purification of biphephos
WO2012095255A1