TWI250985B - Method for preparing sterically hindered phosphoramidates - Google Patents

Abstract

Sterically hindered phosphoramidates such as N,N'-bis[di-(2,6-xylenoxy)phosphinyl]piperazine are prepared by the reaction of a sterically hindered diaryl chlorophosphate, such as di-(2,6-xylyl) chlorophosphate, with a basic nitrogen compound containing at least two basic N-H groups, preferably a heterocyclic compound such as piperazine, in the presence of calcium oxide as an acid acceptor. The reaction is conducted in the presence of at least one dipolar aprotic solvent.

Description

1250985 A7 __ B7 V. INSTRUCTIONS (1) Reference to the relevant application This case claims the priority of the provisional application number 6 0 / 1 3 5 7 5 5. BACKGROUND OF THE INVENTION This invention relates to the preparation of sterically hindered aminophosphates, particularly from nitrogen bases and diaryl chlorophosphates. A sterically hindered amino phosphate such as N,N > bis[2-(2'6-xyloxy)phosphino]hexahydropyrazine (hereinafter sometimes referred to as XPP) as a synthetic resin Flammable additives (especially thermoplastic resins such as polycarbonate 'ABS resins and blends thereof) have been found to have particular advantages, including improved blending of the high temperature stability. For example, reference is made to U S 5 9 7 3 0 4 1 and the same applicant's application numbers 09/235679 and 0 9/364915. XP P and its homologues are diaryl chlorophosphates (such as bis(2'6-xylylene) chlorophosphate) and heterocyclic compounds containing two basic N-indenyl groups (such as hexahydropyrazine). It is conveniently prepared by reaction. According to the prior art of Talley, J. Chem. Eng. Data, 33, 22 1 -222 (1 983), the reaction is carried out in the presence of chloroform as a solvent and triethylamine as an acid acceptor. The amount of triethylamine used is stoichiometric or excessive, which reacts with the by-product hydrogen chloride to complete the reaction.

Talley's literature describes the preparation of several homologous compounds, including those derived from benzylamine, cyclohexylamine, aniline, ethylenediamine, p-phenylenediamine and hexahydrogen hydrazine-nitrogen compounds. The reported yield can reach 90% (this is the same as the Chinese National Standard (CNS) A4 specification (21〇x 297 mm). (Please read the back note and fill out this page) F-Install -----r---订----------" Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing -4- 250985 A7 _____B7__ V. Invention description (2) Aniline responders), and As low as 61% (reactive with p-phenylenediamine). Hexahydropyrazine produces X P p in a yield of only 68%, which is the lowest number. To make X P P an industrially available flame retardant additive, it is necessary to significantly improve its yield. At the same time, the use of the relatively toxic solvent chloroform and the stoichiometric amount of triethylamine is also reduced in the industrial scale. Therefore, it is of interest to develop high yield methods for the preparation of XPP and its homologues with less harmful materials. BRIEF SUMMARY OF THE INVENTION The present invention has found that less expensive alkaline mineralization in the preparation of XPP and its homologues as an acid to reduce a dipolar aprotic solvent, with high or high partial or rapid reaction. Therefore, in one embodiment of the present invention, the preparation of the steric hindrance comprises contacting the sterly hindered chlorophosphate diaryl ester with at least two basic nitrogen-based compounds and when present in the presence of at least one dipolar aprotic solvent as the acid. A specific example is the preparation of a hindered amine comprising diaryl chlorophosphate in contact with at least two basic compounds and in the presence of a dipolar aprotic solvent as an acid acceptor having an amine temperature of at least about 0 °. C, preferably at least about 1 2 〇t:. Please read the note on the back first.

The Intellectual Property Office of the Ministry of Economic Affairs, the employee consumption cooperative, prints a compound, calcium dioxide, an acceptable agent, and uses it at the same time. The method of producing amino phosphate by a method, a method of treating a calcium oxide and a phosphite of a basic N-fluorene group, and a basic nitrogen-containing calcium dioxide of a ruthenium-hydrazine group At least one phosphatidyl phosphate glass transfer 〇 ° C, preferably at least about the size of the paper, applicable to China National Standard (CNS) A4 specification (210 X 297 mm) -5 - 1250985 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative Α7 Β7 V. DESCRIPTION OF THE INVENTION (3) Detailed Description; Preferred Embodiments In the present invention, a hindered amino phosphate is a compound in which at least one aryl substituent is attached to a phosphorus hetero atom, and At least one substituent on the aromatic ring is ortho to the aryl-phosphorus heteroatom. The hindered bisphosphochlorophosphate used in the method of the present invention has the following formula:

Wherein Ar is an aryl group, each R1 is a deutero group, an aryl group or a halogen, Q1 is oxygen or sulfur, Q2 is oxygen, sulfur or NR1, and η is 1 to the number of free valence positions on the aromatic ring, and At least one R 1 on the aromatic ring is ortho to the phosphorus heteroatom bond. Preferably, Ar is a phenyl group and η is from 1 to 5. Preferably, each R 1 is a primary or secondary C i - 4 alkyl group; more preferably a methyl group, and η is 2, and each substituent is ortho to the phosphorus hetero atom bond. Therefore, the preferred amino phosphate is bis(2,4,6-trimethyl chlorophosphate) and bis(2,6-xylylene chlorophosphate). Any acyclic or cyclic compound containing at least two basic hydrazine-hydrazine groups can be used. Suitable compounds include those having the formula: (II) R2NH-CH2CH2-NHR2 wherein each R 2 is a primary or secondary C i -4 alkyl group, or two / R 2 oximes are an exoethyl group. Examples of the acyclic compound are N,N>-dimethylethylenediamine and hydrazine, N >-diethylethylenediamine. It is preferred to use a heterocyclic compound, examples of which are hexahydropyrrole and 1,2,3,4 tetrahydroquinoxaline. The paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ΤβΤ "

1250985

V. Description of the invention (4 Both = can be unsubstituted or substituted. The best is hexahydropyrazine. In the specific case of h ^ bauxite, the method of the invention can be used to prepare glass transfer "degree is at least about 〇c ' Preferably, it is at least about 丄〇, more preferably at least about 20 C' of the amino-pure acid ester. The process of the invention is particularly useful for the preparation of the fe-based pity ester of formula III: Q1 (III) A2 Q1 , 11 , Np — a4 A3 Ministry of Economic Affairs Intellectual Property Office Staff Consumer Cooperatives prints that each Q 1 is oxygen or sulfur; each A 1 - 4 is alkoxy, alkylthio 'aryloxy or arylthio, or a aryloxy or arylthio group substituted with at least one alkyl or halogen, or a mixture thereof; or an amine residue. In a more preferred embodiment of the invention, each Q: is oxygen; each A ^ - 4 is 2, 4,6-trisyloxy or 2,6-xyleneoxy. These amino phosphates are hexahydropyrrole-type amino phosphates. In the above formula, each Q 1 is oxygen; each A i - 4 is The glass transition temperature of the 2,6-xylylene amino phosphate is about 62 ° C and the melting point is about 192 t: In another preferred embodiment, the present invention The process can be used to prepare an amino phosphate having a glass transition temperature of at least about 0 ° C, preferably at least about 1 Torr, more preferably at least about 20 ° C, having the formula I V :

Each of Q 1 is oxygen or sulfur; each A 5 - 9 is alkoxy, and the alkane paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 public ^^ "

1250985 A7 - B7 V. INSTRUCTIONS (5) Thio, aryloxy or arylthio' or an aryloxy or arylthio group substituted with at least one alkyl or halogen, or a mixture thereof; or an amine residue , η is from 0 to about 5. In a more preferred embodiment, each Q 1 is oxygen; each A 5 9 is phenoxy, 2,6-xylyleneoxy or 2,4,6-trimethylphenyloxy, and η is from 0 to about 5. In another preferred embodiment, the process of the invention can be used to prepare an amino phosphate having a glass transition temperature of at least about 0 ° C, preferably at least about 1 ° C, more preferably at least about 20 t, It has the formula V: Q1

Each of the Q 1 is oxygen or sulfur, and each of the A 1 13 - 15 is an alkoxy group, an alkylthio group, an aryloxy group or an arylthio group, or at least one An alkyl or halogen substituted aryloxy or arylthio group, or a mixture thereof; or an amine residue. In a more preferred embodiment, each Q1 is oxygen; each A1()-15 is a phenoxy group, a 2,6-xylyleneoxy group or a 2,4,6-trimethyloxy group. In another preferred embodiment, the process of the present invention can be used to prepare an amino phosphate having a glass transition temperature of at least about 0 ° C, preferably at least about 1 ° C, more preferably at least about 20 t. It has the formula VI: This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -8 - 1250985

Wherein each Q is oxygen or sulfur; each A 1 6 1 9 is an alkoxy group, a k-thio group, a aryloxy group or an arylthio group, or a aryloxy group or an aromatic sulfur substituted with at least one alkyl group or a halogen. a group, or a mixture thereof; or an amine residue; each R 3 is an alkyl group, or two R 3 conjugates are an alkylene group or an alkyl-substituted alkylene group. In a more preferred embodiment, each Q 1 is oxygen; two R 3 combined oximes are unsubstituted (c H 2 ) m alkylene, m is 2 to oxime; and each A i 6 — i 9 is benzene Oxy ' 2 ' 6 -monomethyloxy or 2,4,6-trimethyloxy. In a more preferred embodiment, each Q1 is oxygen; each R3 is a methyl group; and each of eight: 6 is phenoxy, 2,6-xyleneoxy or 2,4,6-trimethylphenoxy, respectively. In another preferred embodiment, the process of the present invention can be used to prepare an amino phosphate having a glass transition temperature of at least about 〇 ° C, preferably at least about 1 ° C, more preferably at least about 20 ° C. , which has the formula v I j : (Please read the notes on the back and fill out this page)

Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed νπ R4 R6 burR5 γ type such as 4 R sulfur or oxygen is Q. The paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 1250985 A7 B7 V. INSTRUCTIONS (7) (VIII)

N—X1 —N

N-乂一

A22 Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed in which each Q 1 is oxygen or sulfur; each A 2 . 2 2 is alkoxy, thiol, aryloxy or arylthio, or an aryloxy or arylthio group substituted with at least one alkyl or halogen, or a mixture thereof; or an amine residue; Each Z 1 is an alkyl group, an aryl group or an aryl group substituted with at least one alkyl group or a halogen group, or a mixture thereof; each X 1 is an alkylene group, an aryl group or an aryl group substituted with at least one alkyl group or halogen. Or a mixture thereof; η is 〇 to about 5; R 5 and R 6 are respectively an oxy group, a thiol group, an aryloxy group or an arylthio group, or a aryloxy group or a group containing at least one of a substituent or a halogen. a thio group, or a mixture thereof; or an amine residue. In a more preferred embodiment, each Q 1 is oxygen; each A 2 Q - 2 2 is phenoxy, 2,6-monomethyloxy or 2,4,6-trimethyloxy; each Z1 is A Or benzyl; each X1 is c2 - C24 alkyl; n is 〇 to about 5, R and R are phenoxy, 2,6-xyleneoxy or 2,4,6-trimethyloxo, respectively base. In another preferred embodiment, the process of the present invention can be used to prepare an amino phosphate having a glass transition temperature of at least about 0 C', preferably at least about 1 Torr, more preferably at least about 20 ° C. Having the formula; [x : Q1II (IX) R7—P-R9 R8 where Q1 is oxygen or sulfur, and R7 is as shown in formula X. The paper size is applicable to the National Standards (CNS) A4 specification (210 X 297 mm). ) -10 (Please read the note on the back 咅 3 items and then fill out this page) P-装-----r---订---------Line 1250985

V. Invention Description &

The Intellectual Property Office of the Ministry of Economic Affairs, the Consumers' Cooperatives, prints that each Q 1 is oxygen or sulfur; each x 2 is an alkylene or alkyl substituted alkyl aryl or alkaryl; each z 2 is an alkylene group Or an alkyl substituted pendant, R 1 . , R i : and R i 2 are each an alkoxy group, an alkylthio group, an aryloxy group or an arylthio group 'or an aryloxy group or an arylthio group substituted with at least one alkyl group or a halogen or a mixture thereof; or Is an amine residue; η is from 0 to about 5; R 8 and R 9 are respectively an alkoxy group, an alkylthio group, an aryloxy group or an arylthio group, or an aryloxy group having at least one of a substituent or a phenyl group substituted Or an arylthio group, or a mixture thereof; or an amine residue. In a more preferred embodiment, each Q 1 is oxygen; each X 2 is an alkylene group or a substituted alkyl group; each ζ 2 is an alkylene group or an alkyl substituted alkyl group; R8, R9, R1Q, Rii And Ri2 are phenoxy, 2,6-xylyleneoxy or 2,4,6-trimethyloxy, respectively; η is 〇 to about 5. In a more preferred embodiment, each Q i is oxygen; each of χ 2 and Ζ 2 is an unsubstituted (C Η 2 ) m alkylene group, m is from 2 to 10; R 8, R 9, R 1 0, R11 and R12 are each a phenoxy group, a 2,6-xylyleneoxy group or a 2,4,6-trimethyloxy group; and η is from 〇 to about 5. In a particularly preferred embodiment, the amino phosphate is derived from hexahydropyrazine (i.e., X 2 and Ζ 2 are each -C Η 2 - C Η 2 -). In another preferred embodiment, the method of the present invention can be used to prepare a glass transition temperature of at least about 0 ° C, preferably at least about 10 ° C, more preferably at least (please read the phonetic transcription on the back side; This page) t· F»binding---------line" This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) -11 - 1250985 A7 B7

i. Description of the invention 6) A cyclic amino phosphate of about 2 〇 t, having the formula X I R16 (XI)

〇

Q1 II p —A23 (Please read the notes on the back and fill out this page.) The Ministry of Economic Affairs, Intellectual Property Office, and the Consumer Cooperatives, print that each of R 1 3 — 16 is hydrogen or alkyl, and X 3 is alkyl. Q 1 is oxygen or sulfur, and A 2 3 is a group derived from a primary or secondary amine having the same or different groups of aliphatic, alicyclic, aromatic or alkane aromatic groups, or A 2 3 It is a group derived from a heterocyclic amine, or A 2 3 is an anthracene compound. Preferably, Q 1 is oxygen. It should be noted that when η is 〇, there are two aromatic rings at this position which are linked by a single bond (i.e., X 3 does not exist) and are adjacent to the phosphonium bond, adjacent > position. In another preferred embodiment, the process of the invention can be used to prepare bicyclic amine groups having a glass transition temperature of at least about 0 ° C, preferably at least about 10 ° C, more preferably at least about 20 ° C. Phosphate ester, which has the formula XII: line "This paper scale applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) _ 12 _ 1250985

, invention description (10

ο where Q1 is oxygen or sulfur; each R is an alkylene group; m and η are each 0 or 1 - 2

Please read the back of the note first Μ this page

A Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed G1—n — Z3 where G is the sulphur 'extension base' hospital base instead of the extension base 'square base or courtyard aryl; each Z 3 is alkyl, aryl or Is an aryl group substituted with at least one alkyl group or halogen, or a mixture thereof; or A 2 4 is G2 / \ a Y2 wherein G 2 is an alkylene group, an aryl group or an alkylaryl group; Y 2 is an alkylene group or an alkyl group The base replaces the base. A preferred amine based vinegar is that Q 1 is oxygen, A is a residue of hexahydropyridin, and the amino phosphate has a plane of symmetry through A 2 4 . A better amino phosphate is Q 1 is oxygen; A 2 4 is a residue of hexahydropyrroline, and the amino phosphate has a plane of symmetry through A 2 4, and each aromatic paper scale is applicable to the Chinese country. Standard (CNS) A4 size (210 X 297 mm) -13- A7

1250985 V. Inventive Note (n) & at least one R substituent is methyl and adjacent to an oxygen substituent; η and m are each 1; Χ4 is chr25, wherein R25 is hydrogen or ci 6 alkyl When g η is 〇, there are two aromatic rings at this position which are linked by a single bond (ie, 'X4 does not exist) and are adjacent to, adjacent to, the position of the phosphonium bond. The process can also be used to prepare an aminophosphorus having a moderate glass transition temperature, i.e., using various substituted or unsubstituted aryl moieties. According to the invention, the acid acceptor and solvent which can be used for preparing the amino phosphate are calcium oxide and a dipolar aprotic solvent, such as dimethylformamide, dimethylethylamine, dimethyl sulfoxide, and hydrazine. (sulfolane), hexamethylphosphonium and N-methylpyrrolidone. Dimethylformamide is generally a preferred dipolar aprotic solvent because it is less expensive. Other solvents, including but not limited to, chloroform 'methylene chloride or toluene, can be used in admixture with dipolar aprotic solvents, which are sometimes useful for yield. It is preferred to exclude water from the reaction mixture. The process of the present invention is generally carried out at about 20 - 1 Torr ° C, preferably about 20 - 60 ° C. It is preferred to use an inert atmosphere such as nitrogen or argon. Various methods can be used to blend the reagents. A preferred acid acceptor, a solvent and a basic nitrogen compound are added sequentially or three at the same time. The molar ratio of the diaryl chlorophosphate to the basic nitrogen compound is about 2.0 to 2.5:1; preferably 2. 0 5 to 2.2:1. Calcium dioxide is at least stoichiometric as an acid acceptor, i.e., the molar ratio of calcium dioxide to diaryl chlorophosphate is about 0.5 to 1.0: 0 because calcium dioxide is divalent. The dipolar aprotic solvent typically accounts for about 1 5 - 1 0% by volume of the total solvent. The progress of the reaction can be monitored by industry-recognized analytical methods. Usually please read the notes first. This page is printed by the Intellectual Property Office of the Ministry of Economic Affairs. Employees' Consumption Cooperatives Print this paper scale Applicable to China National Standard (CNS) A4 specification (210 X 297 mm) -14- 1250985 A7 ----- B7 V. DESCRIPTION OF THE INVENTION (12) 〇, 5 - 1 5 hours is required for the reaction to be completed efficiently. The amino phosphate is then isolated by conventional procedures. The yield of the present invention is comparable to that obtained with triethylamine as the acid acceptor. The invention is illustrated by the following examples. Example 1 Take a 5 OmL three-necked flask, install a mechanical stirrer and a condenser connected to a nitrogen source, and add 86 〇 mg (10 mm 〇 1) of hexahydropyrazine under nitrogen, 560 mg (1 0 mm ο 1) Anhydrous calcium dioxide, 5 〇 mg of o-triphenyl (internal standard) and 2 OmL of anhydrous dimethylformamide. Stirring was started and 6·20 g (20 m m ο 1 ) of bis(2,6-xylylene chlorophosphate) was added in one portion. The reaction mixture was periodically sampled until the product composition no longer changed. The yield of X P P was 7 0 · 3 %. The XPP yield of the control group using triethylamine was 7 0 · 2 %. Example 2 In the flask of Example 1, 860 mg (1 〇mmo 1) of hexahydropyrazine, 56 〇mg was added under nitrogen ( lOmmo 1) anhydrous calcium dioxide, 50 mg of o-triphenyl (internal standard) and 20 m of anhydrous chloroform. Stirring was started and 6·20 g (20 m m ο 1 ) chlorophosphor-6-xyl ester was added in one portion. After stirring the reaction mixture for an hour, it was found to have a conversion of X P p of 16%. Then join, please read the back of the note. This page is written by the Ministry of Economic Affairs, Intellectual Property Bureau, Staff Consumer Cooperative, Printing Acid II.

L The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -15- 1250985 V. Description of the invention (13-methylformamide, stirring for another 30 minutes. Analysis of X pp yield The present invention is intended to be illustrative, and is not intended to limit the scope of the invention.

Read the back of the note. Filled with · f loaded this _ page I

I I Order • I I Line Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Print This paper scale applies to China National Standard (CNS) A4 specification (210 X 297 mm) -16-

Claims (1)

1250985 A8 B8 C8 D8 Patent application scope Annex 3A: Patent application No. 89 1 1 926 1 Chinese patent application scope replacement method 93 methods for preparing hindered amino phosphate The beta chlorohydric acid diaryl ester is contacted with a basic nitrogen compound containing at least two basic N-indenyl groups, and is carried out in the presence of calcium dioxide as an acid acceptor and at least one dipolar aprotic solvent. Among them, the diaryl chlorophosphate has the following formula: Q1/ , Λ II (1) ί ρ· • ci , (please read the notes on the back and fill out this page) where A r is aryl, each R1 is hospital a group, an aryl group or a halogen, Q 1 is oxygen or sulfur, Q 2 is oxygen, sulfur or NR 1, η is 1 to the number of free valence positions on the aromatic ring, and at least one R 1 on the aromatic ring Phosphorus heteroatoms are ortho-bonded; and basic nitrogen compounds have the following formula: R 2 Ν Η - C Η 2 C Η NHR Order «! Printed by the Ministry of Economic Intelligence, the Intellectual Property Bureau, the consumer cooperatives, each of which is Level 1 Or the secondary C 1 -R 2 combined is an extended ethyl group. 2. The method of claim 1, wherein Q2 is oxygen, η is 2 or 3, and each R1 is methyl 3. The method of claim 1 is a heterocyclic compound. Alkyl, or two of which A is a phenyl group, the basic nitrogen of which is applicable to the Chinese National Standard (CNS) A4 specification (210X297 public director) · 1 _ 5 · The method of claim 1 The subsolvent is monomethylformamide, dimethylacetamide, and methylpyrrolidone. Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printed 1250985 A8 B8 C8 ______D8 VI. Application for patent scope-" ^-- 4. For example, the method of applying for patent scope item 3, wherein the test nitrogen compound is hexahydropyrazine . Among them, the dipole is non-quality = 甲亚硕 or N-6. As in the method of claim 5, there is another solvent. 7 · If the method of claim 6 is applied, the other solvent is chloroform. 8 · If the method of claim 1 is applied, it is about 2 〇 1 0 0. Contact is made in the temperature range of C and in an inert atmosphere. 9. The method of claim i, wherein the molar ratio of the diaryl chlorophosphate to the basic nitrogen compound is about 2 · 〇 - 2 · 5 : 1. 1 0. The method of claim 1, wherein the molar ratio of the dioxide to the diaryl chlorophosphate is about 〇 5 · i : 丄. 1 1 The method of claim 1, wherein the amount of the dipolar non-protic solvent is about 15 - 1 〇 〇 % of the total volume of the solvent. The method of claim 1, wherein the aminophosphate has a glass transition temperature of at least about 〇t; The method of claim 12, wherein the amino phosphate has a glass transition temperature of at least about 1 〇 °C. The method of claim 12, wherein the aminophosphate has a glass transition temperature of at least about 20 °C. 1 5 ·If the method of claim 6 is applied, the Amino Phosphorus ¥ paper scale applies to the Chinese National Standard (〇凡5) Six 4 Specifications (210\297 mm) One ~ (Please read the back note first) Fill in this page again) 1250985 C8 D8 VI. The patent application range is N,-bis[di(2,6-xylylene)phosphino]hexa-argon batch, and the chloro-disc diaryl vinegar is chlorodisic acid (2) '6-xylylene ester), and the dipolar aprotic solvent is dimethylformamide. The method of claim 6, wherein the amino phosphate is N,-bis[di-(2,6-dimethylphenyl)phosphino]hexahydropyrazine, the diaryl chlorophosphate The ester is bis(2'6-xylylene chlorophosphate), and the dipolar aprotic solvent is a mixture of dimethylformamide and chloroform. (Please read the notes on the back and fill out this page.) Order f Ministry of Economic Affairs Intellectual Property Office Employees Consumption Cooperative Print This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) -3 -