TW387891B - Process to prepare a multidentate phosphite compound - Google Patents

Description

Printed by the Central Government Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative «. Α7 Β7 The present invention relates to a method for preparing a multidentate phosphite compound represented by the general formula (1)

Where η is 2-6, R is an η-valent organic group, and R1 and R2 are fused aromatic ring systems having two or more rings. If the substitution reaction is feasible, the rings of R1 and R2 can only Replaced by hydrogen in the ortho position (relative to the oxygen atom). In the preparation of phosphite compounds, a phosphorous azo compound is first prepared, which is obtained by using the alcohols R1- 0Η and R2-0Η with phosphorus chloride as starting materials. The compound is then contacted with the intoxicant R- (0Η) to produce a phosphite. BACKGROUND OF THE INVENTION U.S.P.tent N. 0.5, 2 3 5, 1 1 3 is disclosed to be dissolved in triethylamine 3, 6 -Di-tert-butyl-2-pyrophenol is reacted with PC 1 3 dissolved in toluene to produce bisphosphonium chloride. Then, bisphosphonate and triethylamine are used in 2,2 > The preparation of bidentate phosphonates by contact. The disadvantage of this conventional method is that when using alcohols (R1—0 Η and R 2-_0 Η) as starting materials, the steric hindrance around the hydroxyl group is not suitable for this paper. China National Standard (CNS > Α4 Specification (210X297mm) --------- (¾ ------ tr ------ ^ (Please read the precautions on the back before filling (This page) Printed on the A7 _ _ B7 _ Description of the May 2nd Invention (2) is large enough so that it is extremely difficult to produce the intermediate phosphorus carbides at a high yield. In this case Next, the main production It will be a triorganophosphite compound in which the organic group is equivalent to the initial alcoholate One mole of PC 1 3 reaction. Therefore, it is necessary to find a method for producing phosphorous phosgene in high yield. For the multidentate phosphite compound represented by formula (1), it is still difficult to prepare at present And it must be prepared via phosphorochloride * Summary and purpose of the invention The present invention can meet this demand, wherein the phosphorochloride is prepared by a two-step reaction in the following solvents: a) A compound of the following formula: R3 α \ /

N-P / \ (2)

R4 CI wherein R3 and RigCi—C4 alkyl are contacted with compounds of R1 — 0H and R2 — 0H, and b) the product obtained in step (a), that is, the compound represented by general formula (3): Applicable «« Home Rubbing Standard (CNS) Α4 Specification (210X297mm) --------- Λ 衮 ------- 1T ------ "(Please read the note on the back first Please fill in this page again for the matter) Ministry of Economic Affairs-6- Central Government Quasi Bureau K Industrial Consumer Cooperatives printed A7 __; _B7 _ V. Description of the invention (3) R3 OR1 \ /

N-P / \ ⑶ R4 OR2 is in contact with HY, where Y represents a halogen atom * The present invention makes it possible to obtain phosphorous azo compounds and phosphite compounds of formula (1) in high yield. In Synthesis, 1988, 2, 142., a method for directly preparing a phosphite compound from a dialkyl-N, -dialkylphosphamide compound and a monohydric alcohol in a single step is described. Phosphate ester compounds are monodentate phosphite compounds. • If you want to use a compound R (0H) n (n &n; 1) with more than one alcohol functionality as a starting material and directly make a multidentate phosphite in a similar way Ester compounds do not seem to be easy. Detailed description of the invention The alcohol compounds R1-0Η and R2-0Η as starting materials preferably have 10 to 30 carbon atoms and preferably contain 2 to 4 fused aromatic rings. Examples are phenol, "phenol And phenanthrene. If the substitution reaction is feasible, all carbon atoms ortho to the carbon atom substituted with a hydroxyl group can only be substituted with hydrogen. Other carbon atoms of the fused ring can be substituted with other groups as needed, such as alkoxy, alkyl , Amine and halo. Preferably, R1 and R2 are the same base plaque. R1 and R.2 are preferably 9-Phoenicia or 1-based. · This paper size uses China National Kneading Rate (CNS) Α4 size (210X297 mm) " (Please read the precautions on the back before filling in this Page) Λν. Order

C • LI1 · A7 _ B7_ printed by the Ministry of Economic Affairs, China ’s Associated Bureau of Labor and Workers ’Cooperatives. V. Description of Invention (4) Step (a) can be substantially equivalent to Synthesis · 1 9 8 8, 2, 142 — 144 It is implemented in the manner described above and its entire disclosure is incorporated herein by reference. This work describes the preparation of bis-third butyl alkyl phosphate and aryl esters using bis-third butyl N, N-di.ethylphosphonium amine as an intermediate. This intermediate is similar to the formula ( 3) a compound represented by The compound of formula (2) can be prepared by a method known to those skilled in the art. For example, "R 3 and R 4 can be prepared by a method substantially similar to that described in Synthesis, 1988, 2, 142-144. They are independent of each other and are CX-C4 alkyl groups, such as methyl, ethyl, A propyl group, a butyl group, or a third butyl group. Preferably, R 3 and R 4 are the same group. In step (a), the compound of formula (2) is contacted with RiOH and R2OH in a suitable solvent and preferably in the presence of rhenium. Examples of the base include organic bases, for example, a trialkylamine having 2 to 12 carbon atoms. Examples of suitable solvents include ethers, for example, diethyl ether, dioxane or tetrahydrofuran, and aromatic solvents, for example, benzene or toluene. Step (a) is preferably at a temperature between about 80 and about 60 ° C. Implementation is preferred, and implementation at room temperature is preferred. The concentration of the compound represented by the formula (2) is preferably between about 0.01 and about 5 moles / liter. The molar ratios of RiOH and R2OH to compound (2) are preferably in accordance with chemical calculations. Other ratios are also feasible, but generally speaking, it takes more effort to purify the product. In step (b), Y in HY can be F, Ci, Br, or I. * HY which is more broken is HC1. ΗΥ can exist in gaseous state or dissolved in paper. Applicable to China National Standard (CNS) A4 specification (210 × 297). (Mm) _ -------- Λ equipment— (Please read the notes on the back before filling in the book I) Order A7 — B7 printed by the Male Workers Consumer Cooperative of the Central Procurement Bureau of the Ministry of Economic Affairs 5) Dissolve in solvents such as ethers such as diethyl ether, dioxane or tetrahydrofuran or aromatic solvents such as benzene or toluene. The temperature of step (b) is preferably between 80 ° C and 60 ° C. The molar ratio of HY to compound (3) is preferably between about 0.8 and about 5. The product of step (b) of the phosphorochloride reaction (for example, a compound of the general formula (3)) is usually dissolved in the reaction mixture and the precipitated R3R4NH. HC1 salt is present. In the further use of phosphorochloride Previously, it was best to separate the salts from the phosphorous chloride. The time to perform this separation is most suitable when the reactivity of the R-(〇H) „compound is not very high. The separation can be achieved by, for example, applying the reaction mixture. This is carried out by filtration. The phosphorochloride obtained from is then contacted with the alcohol compound R— (OH) n, where R is an η-valent organic group of the formula (1) and η is 2 to Θ. The conditions for such contacting to make phosphite compounds are well known and are described in, for example, the aforementioned US Patent No. 5, 2 3 5, 1 1 3, which are shown and incorporated in Reference is made herein. In general, the contact is carried out in a suitable solvent, for example, the solvent of step (a) is preferably carried out in the presence of rhenium, for example, organic rhenium (for example, with triethylamine as Example of an alkylamine). The temperature is preferably between about 80 and about 100. Between C. The η-valent group R may be any conventional bridging bridge group used for polydentate phosphite compounds, for example, described in US Patent No. 5, 2, 3, 5, 113, EP-A-2 14 622 And WO-A- This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) ------ 1 ---- Q ------ tr ------ `` (( Read the notes on the back of the poem before filling in this page.) Duanzhuang A7 ___B7 _ Duozhuang A7 ___B7 _ The Group of the Invention in the Note of the Invention (6) 9 5 1 8 0 8 9 Revealed and incorporated herein by reference. The n-valent group preferably has at least two and less than 40 carbon atoms. The n-valent group may be an alkylene group or a divalent aromatic group. Suitable alkylene groups Examples include ethylene, propyl, butyl, or pentyl. Examples of alcohols R — (0 only) „alcohols (which are building elements of η-valent organic groups) include 2, 5 — 2nd Tributylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,5-dimethyl-hydroquinone, 4,6-di-tert-butylresorcinol, 4, 4 > monoisopropylidene bisphenol, 4,4 ^ methylidene Bis (2-methyl-6-third butylphenol), 4,4 > _Oxobis (2-methyl-6-isopropylphenol), 4,6 butylene bis (3-methyl-1 6 —Third butylphenol), 2,2> —Biphenyldiase '3,3', 5,5 -tetramethyl-2,2 '—Biphenyldiase, 3,3-' 5, 5 " —tetrakis tertiary butyl-2, 2-biphenyldiol, 3,3 dimethanyl-5,5-dimethyl-2,2′-biphenyldiol, 3 , 3 < -di-third-butyl-5,5 dimethoxy-2,2 biphenyldiol, 3,3 > -di-third-butyl-5, 5 dimethyl-2, 2- —Biphenyldiol, 2,2-Methylene bis (4-methyl-6-third butylphenol), 2,2> —Methylene bis (4-ethyl-6-third butyl) Phenol), 2, 2 /-thiobis (4-methyl-6-third butyl phenol), 2, 2 ^-thiobis (4- third butyl-6-methylphenol), 2 ——- thiobis (4,6-di-tert-butylphenol), 1, 1 / _thiobis (2-pyrophenol), catechol, 2, dihydroxyfluorene, 1, 8-dihydroxy Some, 1, 4 or 2 paper sizes China B Jialiang Zhun (CNS) A4 specification (210X297 mm)-.. * S1, --------- Λinstallation ------ ir ------, η (please first阖 Read the notes on the reverse side and fill in this 肓) B7 Hydroxyl 棻 2-a phenol) 5. Inhalation instructions (7) One methyl bis (0110 " -1, 2-butyl 2, 2-cyclohexane 2 3, 5 —Trihydroxybenzene, 1, 1 1, 1 one one two one two one phenol, two one nine one phenanthrene, ethylene glycol, J, 3 propylene glycol fermentation, 1, 4-butanediol, pentaerythritol 'Trans-alcohol, cis-1,2-cyclohexanediol, cis-i, 2-cyclohexanedimethanol, cis-1,2-cyclododecanedionase, etc. A preferred and novel bidentate phosphite compound represented by the formula (1) has a group R of the following formula (4):

(Please read the note $ on the back before filling out this page) (4) The Central Consumers ’Bureau of the Ministry of Economic Affairs printed the cooperative consumer cooperative where X is hydrogen or an organic group, and it is fluorenyl, aryl, tris, carbonyl The bidentate phosphite ligand alkyl group for which alkoxy, carbonyl aryloxy aryl carbonyl, amidine, or pyrenyl is preferably C C1, isopropyl, butyl, or third arylsilyl There are three examples. Trimethylsilyl has 6 to 20 carbon atoms, phenanthryl. The more aromatic aryl groups have -10-1 and preferably both X substituents are organic arylsilyl, trialkylsilyl, aryloxy, alkoxy, alkylcarbonyl, more preferably i. The present invention also relates to this brand new β. Alkyl 1 is, for example, methyl, ethyl, propylbutyl, isobutyl, pentyl or hexyl. Triphenylsilyl and trialkylsilyl and triethylsilyl. Preferred aryl groups, for example, benzyl, tolyl, fluorenyl or 6 to 12 carbon atoms which include, for example, benzene paper 0UA Using China National Standards (CNS > A4 Specification (2 丨 0 > < 297mm) Printed by the Central Standards Bureau of the Ministry of Economic Affairs and Consumer Cooperatives A7 B7 V. Description of the Invention (8) Oxygen • Better An alkoxy group has 1 to 10 carbon atoms, which includes, for example, methoxy, ethoxy, third butoxy, or isopropoxy. * Preferred alkoxy groups have 2 to 12 carbon atoms, which include, for example, methylcarbonyl and Third butyl carbonyl group. Preferred arylcarbonyl groups have 7 to 13 carbon atoms such as phenylcarbonyl group. X is most preferably a carbonyl alkoxy group or a carbonyl aryloxy group, a C0-0-R3, where R3 is 1 Alkyl to 20 carbon atoms or aryl with 6 to 2 carbon atomsSuitable R groups include methyl, ethyl, propyl, isopropyl, n-butyl, third Butyl, isobutyl, phenyl, tolyl. It is more preferred if the two X substituents are the same carbonylalkoxy group. The phosphite compound of the orange group R can be conveniently used as part of a homogeneous catalyst system that also contains germanium. This catalyst system is very suitable for the use of unsaturated organic compounds, especially internally unsaturated organic compounds. It is converted into terminal aldehyde organic compound through hydromethylation reaction. Using this catalyst system can produce high reaction rate and high selectivity to produce linear or terminal aldehyde products. For example, it was found that when using this catalyst system The reaction of 3-pentenoic acid Ci-(^ alkyl esters to 5-methylpentanoic acid Ci-Ce alkyl esters can be compared with the method described in the art (for example, described in WO_A -9 5 1 8 0 8 9 Method * Its entirety is shown and incorporated herein by reference) for high selectivity, yield, and reaction rate. The present invention also relates to a method for preparing Ci-Ce alkyl 5-methylvalerate. The alkyl group is the best. It is methyl or ethyl. The multi-tooth type paper size produced by the method of Feng Feng invention and expressed by formula (1), using China National Standard (CNS) A4 (210X297 mm) ---- ----------. IIΛ.benzene ------ tF ------ C (Please read the notes on the back first (Fill in this page again.) A7 B7 printed by the Real Industrial Consumer Cooperative of the Central Standards Bureau of the Ministry of Economics. 5. Description of the invention (9) The phosphite compound is best used as a polymer stabilizer. It is prepared by the method of the present invention and expressed by the formula The polydentate type phosphite compound represented by (1) is preferably used as a flame retardant additive or filler. The polydentate type phosphonium phosphate compound prepared by the method of the present invention is preferably used as a compound that also contains a group VIII metal. Part of a homogeneous catalyst system • This homogeneous catalyst system can be used for the isomerization of olefins • This homogeneous catalyst system is particularly suitable for the hydromethylation reaction of the conversion of ethylenically unsaturated organic compounds into terminal aldehyde compounds . The unsaturated compound is preferably pentenoic acid * or its corresponding ester or eye, and the Group VIII gold tincture is preferably germanium. The formed 5-methylvaleric acid, or its corresponding ester or eye, is an important intermediate in the production of the precursors of nylon-6 and nylon-6,6. The present invention will use the following non-limiting examples Explain

Example I 3.88 g (20 millimoles) of 9-phenanthrene was dissolved in 250 ml of toluene and water was removed by azeotropic distillation. Next, 2.3 g of triethylamine was stirred at room temperature with stirring. And 1.74 g (10 mmol) of diethylaminophosphonium dichloride were added thereto. Diethylamine diphenanthrophosphite (31P NMR 瞋 138. 7ppm) was prepared in this way. · Adding 2 ml of 1MHC 1 ether solution to prepare diphenanthroline phosphorus (31 P NMR 唭 16 1.4 ppm) · The reaction mixture was filtered and 3 g (30 mmol) of triethylamine and 1. 98 g of 2, 2 dihydroxy-1, 1, 1-dihydro-3, 3-dicarboxylic acid Dimethyl acid is added to the mash. After stirring for 10 minutes, anti-friction is completed and the paper is Stxit (CNS) A4 size (210X297 mm) --------- -广)-(Please read the notes on the back before filling this page)

C -12-

A7 ___B7 V. Description of the invention (10) NEt3, HC1 are removed by filtration (Et = ethyl), the solvent is removed, and the product is crystallized from acetonitrile / toluene to purify it (31P NMR5 12 6. 6ppm) * The following formula is expressed The product, Compound 1, has a yield of 90%. (Compound 1)

Comparative Example A Compound 1 can also be prepared using 9-phenanthrol as a starting material according to the synthesis route described in Example 5.? 3 ± 61 ^ 1 < 0.5,235,1135 and Example 10. However, it is not possible to produce the intermediate phosphorochloride in a rhenium yield (about 5%). The main product is tris (9-phenanthrene) phosphite. The yield of the desired product is only 5% and it is difficult to separate. ”This experiment shows that the synthetic route using the previous technology (such as EP— Α- 5 1 8 2 4 1 (Narrator) It is difficult to obtain compound 1.

Example II: 5 · 8 mg of Rh (acac) (CO) 2 (acac = ethyl sugar acetone) (4.8x10-5 moles), 14. 0X10-5 moles as the ligand for compound 1 (complex Base-to-germanium ratio (L / Rh) = 2. 9 mol / oligolar) and 60 ml of toluene were added to the paper block size under nitrogen pressure. Using China Standard Sample (CNS) A4 (210X297 mm) ) (Please read the notes on the back before filling out this page)

C Printed by the Central Economic and Trade Standard Bureau of the Ministry of Economic Affairs βί 工 consuming cooperatives -13-

Du Yin, employee consumption cooperation of the Central Bureau of Economic Affairs of the Ministry of Economic Affairs «. A7 ____ ^ _ B7 _ V. Description of the invention (11) 150 ml 1 ^ 316 11〇7- (: stainless steel autoclave (? &Amp; 1 ^) Afterwards, the autoclave was sealed and purged with nitrogen. Then the pressure of the autoclave was brought to 1 MPa with carbon monoxide / hydrogen (1: 1) and heated to 90 ° C in about 30 minutes. Then Into the autoclave, 7,44 g (65 mmol) of freshly distilled methyl 3-pentenoate and 1.2 g of nonane (filled with toluene to 15 ml) were injected into the autoclave. Gaseous Chromatography Measurement • The conversion rate of 90.1% was measured after 7 hours of reaction. The selectivity for the formation of methyl 5-methylvalerate was 75. 4 The molar ratio (n / b ratio) of the sum of the two methyl mevalonate was 9.3, and the ratio of hydrogenation to methyl valerate was 5.7%.

Example III The ligands of the following formula are repeated in Example II where the ratio of L / R h is (compound 2). The conversion rate is 81.8% and the selectivity to 5-methylvalerate methyl ester is 84.6. % · Example IV * This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) --------- ο ------ iT ------ η < Please Read the precautions on the back before filling out this page) -14-381 (891 A7 B7 V. Send! Speak 2 Ming (strict) _ two-diameter group 1,1'-Liandi Mou_3,3'-dicarboxylic acid The procedure of Example I was repeated with diisopropyl ester as the R1- (0Η) η compound and 9-phenanthrol as RiCOH) starting compound. A compound of the following formula is obtained:

COiiPr. (Compound 3) It was a light yellow powder and the yield was 85%. Example V Using pentaerythritol as R — (〇Η) „compound and 1 phenol as RiCOH) starting compound and repeating the procedure of Example I to prepare a compound of the following formula: (Please read the precautions on the back before filling this page ) Printed by Shellfish Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs

(Compound 4 as a yellow oil with a yield of 80%

Example V The paper size is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) -15-A7 B7 387891 V. Description of the invention (I3) With 2,2 one-dihydroxy-1,1 one-linked two The procedure of Example I was repeated with di-3,3-diethyl dicarboxylate as the R- (OH) n compound and 4-chloro-1-l-phenol as the RUOH starting compound. The yield is about 90%. The present invention has been described in detail and its specific embodiments have been mentioned. Those skilled in the art should understand that many changes and modifications are possible without departing from the spirit and scope of the present invention. (Please read the notes on the back before filling out this page) Printed by the Central Consumers' Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperatives, the size of this paper method is applicable to China National Standard (CNS) A4 (210X297 mm)

Claims (1)

Announcement Private 387891 C8 D8 The Central Bureau of Economic Affairs of the Ministry of Economic Affairs printed for industrial and consumer cooperatives-• 丨 _Hi ·· I. J-— 々, Shenhui 1. Preparation of multi-dentate sub-types represented by the general formula (1) Method for phosphate compound Where η is 2-6, R is an η-valent organic group, and R1 and R2 are fused aromatic ring systems having 2 'or more rings, and the ring can only be hydrogen ortho with respect to the oxygen atom. Position replacement, its if sign is that the phosphorous azo gas is made from the alcohols R1- 0H and R 2- 0H and the vaporized phosphorus, and then the phosphorous azo gas is contacted with the alcohol R- (OH) n, where Phosphorous bicarbonate is prepared in a solvent in two steps: a) Compound of the following formula: R3 CI \ / NP (2) / \ R4 CI where R 3 and R 4 are CC 4 alkyl groups, .接触 and R.20Η compound are contacted, and b) the product obtained in step (a), namely the compound represented by the general formula (3): R3 OR1 \ / N-P (3) / \ R4 OR2 and HY Contact, where Y represents F, Ci, Br, or I · 2. As for the method of the first patent application, where R 3 and R 4 are in Chinese paper size (CNS) A4 (210XW7) %) _ 17--------- πλ— (please read the notes on the back before filling in this page)-order ir. A8 387891 | VI. The scope of patent application is the same alkyl group "(Please (Please read the precautions on the back before filling this page) 3. If the method of the scope of patent application No. 1, where 'the HY is HC 1 and the HC 1 is dissolved in the solvent when contacted with the compound represented by the general formula (3) in. 4. The method according to item 1 of the scope of patent application, wherein the contact of rhenium with the compound represented by the general formula (3) is performed in a solvent, and ΗΥ is a gaseous HC 1 · 5_ The method according to the first scope of patent application Wherein, the temperature of steps (a) and (b) is between about 80 eC and about 60 ° C. 6. The method according to item 1 of the scope of the patent application, wherein the gasification of the plate is separated from the precipitated R3R4NH.HC 1 salt, which is formed simultaneously with the phosphorous chloride. 7. The method according to item 1 of the scope of patent application, wherein R1-OH and R2-OH are catechol, phenol, or phenanthrene. 8 The method according to item 1 of the patent application, wherein the group g R has 2 to 40 carbon atoms. 9. A multidentate phosphite compound represented by the following formula: Printed by the Machining Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs *. This paper uses China National Standards (CNS > A4 size (h〇x297 mm) -18-387891 Sixth, the scope of the application for a patent includes X 疋 bell or test organic group and R1 and R2 are thick mouth aromatic ring systems having two or more rings, and the ring can only be hydrogen ortho with respect to the oxygen atom. Was replaced. 1Q For example, the bidentate phosphite compound of item 9 of the patent application, where 'X' is an alkyl group, an aryl group, a triarylsilyl group, a trialkylmethanyl group, a sulfanyloxy group, and a carbonyl aryloxy group Aryl, aryloxy, alkoxy, alkylcarbonyl, arylcarbonyl, pyrido, or amido. 1 1 · As for the bidentate phosphite compound 'wherein 10' in the scope of the patent application, 'x' is a carbonylalkoxy group or a mineral aryloxy group such as -C0-0-R3 where R3 is a compound having 1 to An alkyl group of 20 carbon atoms or an aryl group having 6-12 carbon atoms · 1 2. As the bidentate type phosphite compound of item 9 of the patent application 'wherein: R1 and r2 are 1- Base or 9 — Fiki. 1 3. The method according to item 1 of the scope of patent application is used to prepare a bidentate phosphite compound as described in item 9 of the scope of patent application. 14 A homogeneous catalyst system, characterized in that the catalyst system comprises a Group VI VIII metal and a bidentate phosphite compound prepared by a method such as the first item in the scope of patent application. 15. A method for preparing an aldehyde compound, characterized in that the method comprises a step of hydroformating an ethylenically unsaturated organic compound into an aldehyde compound in the presence of a homogeneous catalyst system as described in item 14 of the scope of patent application. 16. The method according to item 15 of the scope of patent application, wherein the ethylenically unsaturated organic compound is 3-pentenoic acid Ci-Ce alkyl ester. The paper size is applicable to Chinese national standards (CNSM4 specification (210 X 297 mm) i I --- III I ----- * Line-(Please read the notes on the back before filling out this page) Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -19-