TW201004969A

TW201004969A - Phosphorous containing compound having side-chain functional group

Info

Publication number: TW201004969A
Application number: TW97128417A
Authority: TW
Inventors: Qing-Xuan Lin; yu-ting Fang
Original assignee: Univ Nat Chunghsing
Priority date: 2008-07-25
Filing date: 2008-07-25
Publication date: 2010-02-01
Also published as: TWI351406B

Abstract

The invention relates to a phosphorous containing compound having side-chain functional group which has a structure illustrated in equation (I). The functional groups in equation (I) are respectively defined in the specification and the claims. The phosphorous containing compound has side-chain reactive function group which facilitates the preparation of polyetherimide or polyamide.

Description

201004969 九、發明說明：【發明所屬之技術領域】本發明是有關於一種含構化合物，特別是指一種具有側鏈反應官能基（如酚基、胺基或羧酸基）的含磷化合物。【先前技術】201004969 IX. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD The present invention relates to a structural compound, and more particularly to a phosphorus-containing compound having a side chain reactive functional group such as a phenol group, an amine group or a carboxylic acid group. [Prior Art]

近年來，有機磷化合物被發現具備良好的難燃特性，且相較於含i素之難燃劑，有機磷化合物不會產生有毒氣體，.且添加量較少，發煙量較低。鑑於上述優點，目前有機磷化合物已被嘗試添加至高分子中，以使高分子具備難燃性。除了難燃性質之外，含有聯苯基亞膦酸酯側基團 (biphenylene phosphinate pendant group)的高分子更具備高玻璃轉移溫度、低介電性質、良好的溶解度及機械性質，其用途更為廣泛。然而，在眾多有機磷化合物中，又以 9,10-二氫-9-氧雜-10-磷雜菲-10氧化物（9,10-<11117(11*〇-9-〇乂&-10-phosphaphenanthrene 1 Ο-oxide，簡稱為 DOPO)最常被廣泛使用。 TW 572954揭示一種如下式所示之含磷化合物：In recent years, organophosphorus compounds have been found to have good flame retardant properties, and organophosphorus compounds do not produce toxic gases compared to i-containing flame retardants, and the amount of addition is small, and the amount of smoke is low. In view of the above advantages, organic phosphorus compounds have been attempted to be added to polymers to make them difficult to ignite. In addition to its flame retardant properties, polymers containing a biphenylene phosphinate pendant group have high glass transition temperature, low dielectric properties, good solubility and mechanical properties, and their use is even more widely. However, among the many organophosphorus compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 oxide (9,10-<11117 (11*〇-9-〇乂&amp ;-10-phosphaphenanthrene 1 Ο-oxide, abbreviated as DOPO, is most commonly used. TW 572954 discloses a phosphorus-containing compound as shown in the following formula:

5 2010049695 201004969

~a5~\ n)~Q' N一~^\r29 ; R21 〜R28 分別為 ft 七 m p 刀⑺馮虱或Cl〜C4之烷基；Q'為 X1為Q，或氫、硝基、胺基、羥基、曱基等基團；八5為_〇_、_c〇〇_~a5~\ n)~Q' N_~^\r29 ; R21 to R28 are respectively ft seven mp knives (7) von 虱 or Cl~C4 alkyl; Q' is X1 is Q, or hydrogen, nitro, amine a group such as a base, a hydroxyl group, a thiol group; the eighth group is _〇_, _c〇〇_

由於需要使用較多量之DOPO ’所以整個製備成本較高，此外，由於結構對稱’造成衍生之聚醯亞胺與聚醯胺的玻璃轉移偏低。此外，當Y1為羥基時，由於三級醇易受酸或高溫作用而脫水’故在酸中或高溫下的環境下不安定。由於上述含磷化合物仍有需要改進之處，特別是提昇含磷化合物的反應性’以利於後續與其他化合物或高分子進行反應，如能成功克服此問題，應有助於讓高分子的應用更臻完善。【發明内容】不同於以往專利僅限於DOPO的加成反應，本專利中則在DOPO與羰基（carbonyl)進行加成反應後，在酸催化下，再與酚、苯胺等具有推電子基團（如〇H，OR，NH2， NHR與NR2)的苯環化合物進行縮合反應，將官能基OH， 201004969 OR，NH2 ’ NHR與NR2基團導入以利後續改質。本專利應有祕讓磷“分子的應収臻完善。因此’本發明之目的’即在提供一種適合與高分子反應結合或與高分子組合使用之具有側鏈官能基的含磷化合物0 於疋本發明具有側鍵官能基的含鱗化合物，是由下式（I)所示：Due to the need to use a larger amount of DOPO', the overall preparation cost is higher, and in addition, the glass transition of the derivatized polyimine and polyamide is lower due to structural symmetry. Further, when Y1 is a hydroxyl group, since the tertiary alcohol is easily dehydrated by an acid or a high temperature, it is unstable in an acid or high temperature environment. Since the above phosphorus-containing compounds still need improvement, especially to improve the reactivity of the phosphorus-containing compound, in order to facilitate subsequent reaction with other compounds or polymers, if the problem can be successfully overcome, it should be helpful for the application of the polymer. More perfect. SUMMARY OF THE INVENTION Unlike the prior patents, which are limited to the addition reaction of DOPO, in this patent, after the addition reaction of DOPO with a carbonyl group, under the acid catalysis, it has an electron-withdrawing group with phenol, aniline or the like ( For example, a benzene ring compound of H, OR, NH2, NHR and NR2) is subjected to a condensation reaction, and a functional group OH, 201004969 OR, NH2 'NHR and NR2 groups are introduced to facilitate subsequent modification. This patent should have a secret to the phosphorus "molecular acceptance". Therefore, the 'object of the present invention' is to provide a phosphorus-containing compound having a side chain functional group suitable for use in combination with a polymer or in combination with a polymer. The scaly compound having a side bond functional group of the present invention is represented by the following formula (I):

於式（I)中，R1〜R10分別表示氫、C1〜C6烷基、C1〜C6烷氧基、C3〜C7環烷基、苯基、硝基、笨氧基、ci〜C10鹵烷基、二IL甲基、三氟曱氧基或鹵素原子；〇 A 表示一〇—或—〇_c—; Q表不硝基或胺基； D表示羥基、胺基、C1-C6烷基、C1〜C6烧氧基、C3〜C7 環烷基、Cl〜CIO鹵烷基、三氟甲基、三 —Ν 原子、-OCN、一、一氟甲氧基、鹵素 0 Η Η II N-R，、—N-C-R，、In the formula (I), R1 to R10 represent hydrogen, C1 to C6 alkyl, C1 to C6 alkoxy, C3 to C7 cycloalkyl, phenyl, nitro, phenyloxy, ci~C10 haloalkyl, respectively. , di-IL methyl, trifluoromethoxy or halogen atom; 〇A represents a 〇- or -〇_c-; Q represents no nitro or amine group; D represents a hydroxyl group, an amine group, a C1-C6 alkyl group, C1-C6 alkoxy, C3~C7 cycloalkyl, Cl~CIO haloalkyl, trifluoromethyl, tri-anthracene, -OCN, monofluorofluoro, halogen 0 Η II NR, -NCR,,

Ο ΟΟ Ο

Η II •Ν—fc_〇—R’ 201004969Η II •Ν—fc_〇—R’ 201004969

基、C3〜C7環烷基或ci〜CIO鹵烷基；X表示—〇一或 —Ν— ;Υ表示氫、硝基、羥基、胺基、羧酸基' ci〜C6 烷基、C1〜C6烷氧基、C3〜C7環烷基、三氟f基、三氟曱氧基或鹵素原子；及R"及R12分別表示氫' C1〜C6烷基、C1〜C6烷氧基、C3〜C7環烷基、苯基、硝基、苯氧基、C1〜C10鹵烧基、三私曱基、三氟甲氧基或鹵素原子本發明之具有侧鏈官能基的含磷化合物由於在侧鏈處（即「Dj )具有反應性官能基（如胺基、羥基、羧酸基等），因此後續可利於與其他化合物或高分子進行反應，或者與高分子組合使用。於式⑴中’以q為胺基，D為羥基為例，可以此單體，與一般市售二酸酐反應，形成側鏈具有酚基的聚醯亞胺。利用重複單元上的酚基，可以對聚醯亞胺進行如交聯，變性，再反應等改質。【實施方式】於式⑴中’較佳地’ D表示羥基或胺基。較佳地，R1〜R10分別表示氳，即如下式（11)所示： 201004969a C3~C7 cycloalkyl group or a ci~CIO haloalkyl group; X represents - hydrazine or hydrazine; hydrazine represents hydrogen, nitro, hydroxy, amine, carboxylic acid group 'ci~C6 alkyl, C1~ a C6 alkoxy group, a C3~C7 cycloalkyl group, a trifluorof group, a trifluorodecyloxy group or a halogen atom; and R" and R12 each represent a hydrogen 'C1 to C6 alkyl group, a C1 to C6 alkoxy group, C3~ C7 cycloalkyl, phenyl, nitro, phenoxy, C1~C10 haloalkyl, tripentyl, trifluoromethoxy or halogen atom. The phosphorus-containing compound having a side chain functional group of the present invention is on the side The chain (ie, "Dj" has a reactive functional group (such as an amine group, a hydroxyl group, a carboxylic acid group, etc.), so that it can be subsequently reacted with other compounds or polymers, or used in combination with a polymer. In the formula (1) Taking q as an amine group and D as a hydroxyl group, the monomer can be reacted with a commercially available dianhydride to form a polyimine having a phenol group in a side chain. By using a phenol group on a repeating unit, The amine is subjected to modification such as crosslinking, denaturation, re-reaction, etc. [Embodiment] In the formula (1), 'preferably' D represents a hydroxyl group or an amine group. Preferably, R1 ~R10 denotes 氲, which is as shown in the following formula (11): 201004969

Q (Π) 〇Q (Π) 〇

與上述式（I)相同] 在本發明之. 合物如上式（II；)所下：具體例中’該具有側鏈官能基的含磷化下’其中，D、A、Q與化合物編號對應如The same as the above formula (I)] The compound of the present invention is as defined above in the formula (II;): In the specific example, 'the phosphating of the side chain functional group', wherein D, A, Q and the compound number Corresponding

[A、Q及D的定義本發月之式(1)所示之化合物的製法可依據—般產學界可知之方法進行製備’較佳地，可利用以下兩種方法進二製備（在以下說明書中，取代基編號是依據式⑴化合物中: 相同界定範圍之取代基編號來表示）：方法（一）： 9 201004969 (al)提供一種由下式（〇所示化合物： «3[Definition of A, Q and D The preparation method of the compound represented by the formula (1) of the present month can be carried out according to a method known in the artisan industry.] Preferably, the following two methods can be used for the preparation (below In the specification, the substituent number is expressed in the compound of the formula (1): the substituent number of the same defined range): Method (I): 9 201004969 (al) provides a compound of the formula: «3

(a2)使該式⑴所示化合物與下式（H)所示化合物進行反應，以製得Q為硝基之該式（I)所示化合物： Z^-A1(a2) reacting the compound of the formula (1) with a compound of the following formula (H) to obtain a compound of the formula (I) wherein Q is a nitro group: Z^-A1

(Η) ，及選擇性地進行以下步驟（a3)， (a3)使該Q為硝基之該式（I)所示化合物進行還原反應，以製得Q為胺基之該式⑴所示化合物，於該式（丨丨）中〇 Z 表示齒素原子。 A 1表示單鍵或一較佳地，該式（i)所示化合物是由下式（iv)所示化合物Ο 、下式（V)所示化合物與下式（vi)所示化合物進行反應所製. 得：(Η), and optionally performing the following step (a3), (a3) subjecting the compound represented by the formula (I) wherein the Q is a nitro group to a reduction reaction, to obtain a formula wherein the Q is an amine group (1) In the formula (丨丨), 〇Z represents a dentate atom. A 1 represents a single bond or preferably, the compound of the formula (i) is reacted with a compound represented by the following formula (iv), a compound represented by the following formula (V), and a compound represented by the following formula (vi). Made by:

10 20100496910 201004969

而於本發明之一具體例中，該式（iv)為苯酚（phenol)或苯胺（aniline)，該式（v)所示化合物為D0P0，該式（vi)所示化合物為4,4-二經基二苯甲酮（4,4-(1丨11}^<1!>0父>^61120卩116110116 ，DHBP)。在方法（一）中，較佳地，該步驟（a2)之反應是於一觸媒存在下進行，該觸媒是選自於三乙基胺、氟化鉋、氟化斜、氣化絶、氯化卸、碳酸鉀、碳酸納、氫氧化奸或氫氧 I化納。於本發明之一具體例中，該步驟（a2)之式（ii)所示化合物選自於1-氣-4-石肖基苯（l-chloro-4-nitrobenzene)或4-石肖基苯醯氯（4-nitrobenzoyl chloride)。較佳地，該步驟（a3)之還原反應是在一還原劑存在下進行，該還原劑是選自於氫氣與鈀/碳之組合、聯胺 (hydrazine)與1巴/碳之組合或删氫化納。方法（二）： (bl)提供一種由下式（iii)所示之化合物： (iii) (b2)使該式（iii)所示化合物、下式（iv)所示化合物與下式 (v)所示化合物進行反應，以製得Q為硝基之該式（I) 所示化合物： D (iv) .10 地進行以下步驟（b3)In one embodiment of the present invention, the formula (iv) is phenol or aniline, the compound represented by the formula (v) is D0P0, and the compound represented by the formula (vi) is 4,4-. Di-based benzophenone (4,4-(1丨11}^<1!>0 parent>^61120卩116110116, DHBP). In the method (I), preferably, the step ( The reaction of a2) is carried out in the presence of a catalyst selected from the group consisting of triethylamine, fluorinated planing, fluoridation, gasification, chlorination, potassium carbonate, sodium carbonate, and sulphur Or a hydrogen oxyhydroxide. In one embodiment of the present invention, the compound of the formula (ii) of the step (a2) is selected from 1-chloro-4-nitrobenzene or 4-nitrobenzoyl chloride. Preferably, the reduction reaction of the step (a3) is carried out in the presence of a reducing agent selected from the group consisting of hydrogen and palladium/carbon. Combination of hydrazine with 1 bar/carbon or sodium hydride. Method (2): (bl) provides a compound represented by the following formula (iii): (iii) (b2) to give the formula (iii) a compound represented by the following formula (iv) With a compound of formula (v), the Q is nitro to produce the formula of (I), the compound: D (iv) .10 to perform the steps of (b3)

1 w 〇—ρ—ο λ 及選擇性 π 201004969 (b3)使該Q為硝基之該式⑴所示化合物進行還原反應，以製得Q為胺基之該式（I)所示化合物。較佳地，該式（iii)所示化合物是由上述式（vi)所示化合物與上述式（ii)所示化合物進行反應所製得。而於本發明之 -具體例中’該式(vi)所示化合物為4,4_二羥基二苯甲酮以及該式⑻所示化合物選自於！氣·4_靖基苯或4•硝基苯酿氣本發月之八有侧鍵g能基的含鱗化合物由於在側鍵處（ ❹ 即「D」）具有反應性官能基（如胺基、經基、幾酸基等），因此’後續可與具有至少-個反應性官能基團之其他化合物（二酸或二肝#)或高分子（環氧樹脂等）進行反應，以利於與高分子併用及提昇高分子的難燃性。本發明將就以下實施例來作 F ^ 步說明，但應瞭解的是’ S亥實施例僅為例示說明夕田硯月之用，而不應被解釋為本發實施之限制。而為了使本發明之構成特徵、操作方法、目的及優點更加容易瞭解’將本發明實施例之製作方式整理反應流程，此流程僅作為說明 ^ 之用而非用於侷限本發明的範圍· 12 2010049691 w 〇-ρ-ο λ and selectivity π 201004969 (b3) The compound represented by the formula (1) wherein Q is a nitro group is subjected to a reduction reaction to obtain a compound of the formula (I) wherein Q is an amine group. Preferably, the compound of the formula (iii) is obtained by reacting a compound of the above formula (vi) with a compound of the above formula (ii). In the specific example of the present invention, the compound represented by the formula (vi) is 4,4-dihydroxybenzophenone, and the compound represented by the formula (8) is selected from! Gas·4_Jingji Benzene or 4•Nitrobenzene Brewing Gas The scaly compound having a side bond g energy group has a reactive functional group (such as an amine group) at the side bond (❹, ie, “D”). , a trans group, a few acid groups, etc.), so that 'subsequent reaction with other compounds having at least one reactive functional group (diacid or di-hepatide #) or a polymer (epoxy resin, etc.) to facilitate Polymers are used together to enhance the flame retardancy of polymers. The invention will be described with reference to the following examples, but it should be understood that the embodiment of the invention is merely illustrative of the use of the present invention and should not be construed as limiting the implementation. In order to make the constituent features, operation methods, objects and advantages of the present invention easier to understand, the process of the embodiment of the present invention is used to organize the reaction flow, and the flow is only for the purpose of description and is not intended to limit the scope of the present invention. 201004969

<實施例> 以下實施例所製得之化合物分別以1H-NMR進行結構 ® 分析。 [實施例1]利用方法（二）進行化合物（B)及（C)之合成實施例1是依據以下反應式進行反應： 13 201004969<Examples> The compounds obtained in the following examples were each subjected to structural ® analysis by 1H-NMR. [Example 1] Synthesis of Compounds (B) and (C) by Method (2) Example 1 was carried out in accordance with the following reaction formula: 13 201004969

H〇-^ /~c~\ ^OH DHBP α-Η〇κΝ〇2H〇-^ /~c~\ ^OH DHBP α-Η〇κΝ〇2

P OHP OH

(B) (C) 將 38.56 克（0.18 莫耳）的 DHBP、62.39 克（0.396 莫耳） ❿ 的1-氣-4-硝基苯、52.24克的碳酸鉀及30毫升的氮，氮-二甲基乙酿胺（Ν,Ν-dimethylacetamide，DMAc)放置於反應器中，於攪拌下將反應溫度升高至120°C，持續反應12小時後停止攪拌。待反應器冷卻至室溫後，將反應液滴入1〇〇〇毫升之食鹽水中，即可析出呈黃色固體的DHBP-A。利用過濾方式將DHBP-A取出，再以大量去離子水清洗並於110°C 之真空烘箱下進行烘乾，以製得73.53克的DHBP-A (產率為90%)，進一步利用醋酸酐進行再結晶的純化步驟，可獲 ❹ 得66.85克的DHBP-A(產率為81°/。，熔點為154°C)，其 NMR圖譜如圖1所示。化合物（B>之製備：將上述所製得之24克（0.0526莫耳）的DHBP-A、11.37 克（0.0526莫耳）的DOPO、0.96克（DOPO重量的4 wt%)的硫酸及49.50克（0.526莫耳）的苯酚放置於反應器中。接著於攪拌下將反應溫度升高至130°C，持續反應12小時後停止攪拌。待反應器冷卻至室溫後，將反應液滴入500毫升 14 201004969 之熱水中，即可析出呈黃色固體的化合物（B)。利用過濾方式將化合物（B)取出，再以大量熱水清洗並於110°C之真空烘箱下進行烘乾，以製得36.4克的化合物（B)(產率為92°/〇) ，進一步利用醋酸進行再結晶的純化步驟，可獲得26.1克的化合物（B)(產率為66%，熔點為227°C)，其NMR圖譜如圖2所示。化合物（C)之製備： • 將4克上述所製得的化合物（B)、0.2克的Pd/C及40克 ® 的氮，氮-二曱基甲醢胺（N，N-dimethylformamide，DMF)放置於反應器中，接著於氫氣下（壓力控制在3.5公斤/平方公分）反應24小時。待反應結束後，將反應液進行過濾，再滴入 500毫升的飽和食鹽水中，即可析出化合物（C)。利用過濾方式將化合物（C)取出，再以大量去離子水清洗並於80°C之真空烘箱下進行烘乾，以製得3.35克的化合物（C)(產率為 91%)，進一步利用丙酮將上述產物溶解，接著再倒入去離子水中析出，可獲得2.3克呈白色的化合物（C)(產率為63% ，熔點為115°C)，其NMR圖譜如圖3所示。 ‘ [實施例2]利用方法（二）進行化合物（D)及（E)之合成實施例2是依據以下反應式進行反應： 15 201004969(B) (C) 38.56 g (0.18 mol) of DHBP, 62.39 g (0.396 mol) of 1-nitro-4-nitrobenzene, 52.24 g of potassium carbonate and 30 ml of nitrogen, nitrogen-two Methyl etheneamine (DMAc) was placed in the reactor, and the reaction temperature was raised to 120 ° C with stirring. After the reaction was continued for 12 hours, the stirring was stopped. After the reactor was cooled to room temperature, the reaction was dropped into 1 mL of brine to precipitate DHBP-A as a yellow solid. DHBP-A was taken out by filtration, washed with a large amount of deionized water and dried in a vacuum oven at 110 ° C to obtain 73.53 g of DHBP-A (yield 90%), further utilizing acetic anhydride The purification step of recrystallization was carried out to obtain 66.85 g of DHBP-A (yield 81 ° /., melting point: 154 ° C), and the NMR spectrum thereof is shown in Fig. 1. Preparation of Compound (B>: 24 g (0.0526 mol) of DHBP-A, 11.37 g (0.0526 mol) of DOPO, 0.96 g (4 wt% of DOPO weight) of sulfuric acid and 49.50 g of the above-obtained (0.526 mol) of phenol was placed in the reactor. The reaction temperature was then raised to 130 ° C with stirring, and stirring was stopped after 12 hours of reaction. After the reactor was cooled to room temperature, the reaction was dropped into 500. In the hot water of ML 14 201004969, the compound (B) is precipitated as a yellow solid. The compound (B) is taken out by filtration, washed with a large amount of hot water and dried in a vacuum oven at 110 ° C. 36.4 g of the compound (B) (yield 92 ° / 〇) was obtained, and further purification step using acetic acid for recrystallization was carried out to obtain 26.1 g of the compound (B) (yield 66%, melting point: 227 ° C). The NMR spectrum is shown in Figure 2. Preparation of Compound (C): • 4 g of the above-prepared compound (B), 0.2 g of Pd/C and 40 g of nitrogen, nitrogen-didecyl N, N-dimethylformamide (DMF) was placed in the reactor followed by hydrogen (pressure controlled at 3.5) Kg/cm 2 ) Reaction for 24 hours. After the reaction is completed, the reaction solution is filtered, and then dropped into 500 ml of saturated brine to precipitate the compound (C). The compound (C) is taken out by filtration, and then It was washed with a large amount of deionized water and dried in a vacuum oven at 80 ° C to obtain 3.35 g of the compound (C) (yield 91%), which was further dissolved by acetone, and then poured into deionized water. When precipitated in water, 2.3 g of a white compound (C) (yield 63%, melting point 115 ° C) was obtained, and the NMR spectrum thereof is shown in Fig. 3. 'Example 2> Compound (2) Synthesis of Example (D) and (E) Example 2 was carried out in accordance with the following reaction formula: 15 201004969

化合物（D)之製備：除了將苯酚置換為48.99克的苯胺以及將熱水置換為甲醇之外，其餘製備及純化步驟皆與上述實施例1之化合物 (B)的方法相同，最後製得34.1克的化合物（D)(產率為87% ，熔點為243°C)，其NMR圖譜如圖4所示。化合物（E)之製備：依據上述實施例1之化合物（C)的還原方法，使上述化合物（D)進行同樣還原步驟，最後製得4.98克的化合物（E)( 產率為90%)，進一步利用乙醇將上述產物溶解，接著再倒入去離子水中析出，可獲得3.91克呈白色的化合物（E)(產率為71%，熔點為120°C)，其NMR圖譜如圖5所示。 [實施例3]利用方法（二）進行化合物（G)及（H)之合成實施例3是依據以下反應式進行反應： 201004969Preparation of Compound (D): The preparation and purification steps were the same as those of the above-mentioned Compound (B) of Example 1, except that the phenol was replaced with 48.99 g of aniline and the hot water was replaced with methanol, and finally 34.1 was obtained. The gram of the compound (D) (yield 87%, melting point 243 ° C), and the NMR spectrum thereof is shown in Fig. 4. Preparation of Compound (E): According to the reduction method of the compound (C) of the above Example 1, the above compound (D) was subjected to the same reduction step, and finally 4.98 g of the compound (E) (yield: 90%) was obtained. Further, the above product was dissolved by ethanol, and then poured into deionized water to obtain 3.91 g of a white compound (E) (yield 71%, melting point: 120 ° C), and the NMR spectrum is shown in FIG. . [Example 3] Synthesis of Compounds (G) and (H) by Method (2) Example 3 was carried out in accordance with the following reaction formula: 201004969

OH (Η)OH (Η)

除了將1-氣-4-硝基苯置換為73 48克（〇 396莫耳）的4_ 硝基苯醯氣之外，其餘製備及純化步驟皆與實施例丨中之 DHBP-A相同，最後製得83 93克的DHBp_F (產率91%)。化合物（G)之匍措：The preparation and purification steps were the same as those of DHBP-A in Example 除了 except that 1-gas-4-nitrobenzene was replaced by 73 48 g (〇396 mol) of 4-nitrobenzene gas. 83 93 g of DHBp_F (yield 91%) was obtained. Compound (G) measures:

除了將DHBP-A置換為3〇·75克（〇〇6莫耳）的DHBp_F DOPO用量改變為12 97克（〇〇6莫耳）、硫酸用量改為 1.23克以及苯酚用量改為56.47克（〇 6莫耳）之外，其餘製備及純化步驟皆與上述實施例j之化合物（B)的方法相同，最後製得43·35克的化合物（G)(產率為90%)。 1匕_合物（ΒΠ之: 將2克上述所製得的化合物（〇)、克的pd/c及2〇克的DMF放置於反應器中，同樣依據上述實施例丨之化合物（C)的方法進行還原步驟，最後製得1.65克的化合物（H)( 產率為89。/。），進一步利用乙醇將上述產物溶解，接著再倒入去離子水中析出，可獲得1.2克呈白色的化合物（H)(產率為 65%) 〇 17 201004969 [實施例4】利用方法（二）進行化合物（L)及（J)之合成實施例4是依據以下反應式進行反應：In addition to replacing DHBP-A with 3〇·75 g (〇〇6 mol), the amount of DHBp_F DOPO was changed to 12 97 g (〇〇6 mol), the amount of sulfuric acid was changed to 1.23 g, and the amount of phenol was changed to 56.47 g ( The preparation and purification steps were the same as those of the compound (B) of the above Example j except that 〇6 moles, and finally 43.35 g of the compound (G) (yield: 90%) was obtained. 1 匕合物 (ΒΠ: 2 g of the above-prepared compound (〇), gram of pd / c and 2 g of DMF were placed in the reactor, also according to the above examples of the compound (C) The reduction step was carried out, and finally 1.65 g of the compound (H) (yield 89%) was obtained, and the above product was further dissolved by ethanol, followed by pouring into deionized water to obtain 1.2 g of white. Compound (H) (yield 65%) 〇17 201004969 [Example 4] Synthesis of Compound (L) and (J) by Method (2) Example 4 was carried out in accordance with the following reaction formula:

nh2 (J) 化合物（L)之製備：除了將DHBP-A置換為26.95克（0.0526莫耳）的DHBP-F、硫酸用量改為1.078克、將苯酚置換為48.99克（0.526 莫耳）的苯胺以及將熱水置換為甲醇之外，其餘製備及純化步驟皆與上述實施例1之化合物（B)的方法相同，最後製得 34.67克的化合物（L)(產率為82%)。化合物（J)之製備：將3克上述所製得的化合物（L)、0.0495克的Pd/C及 30克的DMF放置於反應器中，同樣依據上述實施例1之化合物（C)的方法進行還原步驟，最後製得2.36克的化合物（J) (產率為85%)，進一步利用乙醇將上述產物溶解，接著再倒入去離子水中析出，可獲得2.082克呈白色的化合物（J)(產率為75%)。 [實施例5】利用方法（一）進行化合物（D)之合成 18 201004969 實施例5是依據以下反應式進行反應：Nh2 (J) Preparation of compound (L): except DHBP-A was replaced with 26.95 g (0.0526 mol) of DHBP-F, sulfuric acid was changed to 1.078 g, and phenol was replaced with 48.99 g (0.526 mol) of aniline. The preparation and purification steps were the same as those of the compound (B) of the above Example 1, except that the hot water was replaced by methanol, and finally 34.67 g of the compound (L) (yield: 82%) was obtained. Preparation of Compound (J): 3 g of the above-prepared compound (L), 0.0595 g of Pd/C and 30 g of DMF were placed in a reactor, also in accordance with the method of the compound (C) of the above Example 1. The reduction step was carried out, and finally 2.36 g of the compound (J) (yield 85%) was obtained, and the above product was further dissolved by ethanol, followed by pouring into deionized water to obtain 2.082 g of a white compound (J). (Yield 75%). [Example 5] Synthesis of Compound (D) by Method (1) 18 201004969 Example 5 was carried out in accordance with the following reaction formula:

將21.42克（0.1莫耳）的DHBP、21.62克（0.1莫耳）的 DOPO、100克的苯胺及 4·30克的對曱苯磺酸（？-toluenesulfonic acid，P-TSA)放置於一反應器中，接著於攪拌下將反應溫度升高至130°C，並反應12小時後再停止攪拌。待反應器冷卻至室溫後，將反應液滴入100毫升之乙腈（acetonitrile)中，即可析出呈黃色固體的DHBP-K。利用過濾方式將DHBP-A取出，再以大量乙腈清洗並於100°C 之真空烘箱下進行烘乾，以製得32.9克的DHBP-K (產率為 65%，熔點為 300°C)。化合物（D)之製備：將 45.5 克（0·09 莫耳）的 DHBP-K、31.51 克（0.20 莫耳）的1-氣-4-硝基苯、26.26克（0.19莫耳）的碳酸鉀及300克的 DMAc放置於反應器中，接著依據上述實施例1之化合物 (B)的製備及純化步驟進行，最後獲得65.94克的化合物（D)( 產率為98%)，再利用醋酸酐進行再結晶步驟，而獲得53.83 克經純化之化合物（D)(產率為80%)。由以上實施例1〜5結果，證明本發明之具有側鏈官能基的含磷化合物確實可成功地被製備，且產率都在60%以上。本發明具有側鏈官能基的含磷化合物因為在側鏈具有 19 201004969 反應性官能基，更有利於後續與其他化合物或高分子進行反應，或與高分子組合使用，進而提昇高分子的難燃性或其他各項性質。惟以上所述者，僅為本發明之較佳實施例而已，當不能以此限定本發明實施之範圍，即大凡依本發明申請專利範圍及發明說明内容所作之簡單的等效變化與修飾，皆仍屬本發明專利涵蓋之範圍内。【圖式簡單說明】圖1是一 NMR圖，說明DHBP-Α的結構分析；圖2是一 NMR圖，說明化合物（B)的結構分析；圖3是一 NMR圖，說明化合物（C)的結構分析；圖4是一 NMR圖，說明化合物（D)的結構分析；及圖5是一 NMR圖，說明化合物（E)的結構分析。【主要元件符號說明】21.42 g (0.1 mol) of DHBP, 21.62 g (0.1 mol) of DOPO, 100 g of aniline and 4.30 g of p-toluenesulfonic acid (P-TSA) were placed in a reaction. The reaction temperature was then raised to 130 ° C with stirring, and the reaction was stopped after 12 hours of reaction. After the reactor was cooled to room temperature, the reaction was dropped into 100 ml of acetonitrile to precipitate DHBP-K as a yellow solid. DHBP-A was taken out by filtration, washed with a large amount of acetonitrile and dried in a vacuum oven at 100 ° C to obtain 32.9 g of DHBP-K (yield 65%, melting point: 300 ° C). Preparation of Compound (D): 45.5 g (0·09 mol) of DHBP-K, 31.51 g (0.20 mol) of 1-gas-4-nitrobenzene, 26.26 g (0.19 mol) of potassium carbonate And 300 g of DMAc was placed in the reactor, followed by the preparation and purification steps of the compound (B) of the above Example 1, to finally obtain 65.94 g of the compound (D) (yield 98%), and then acetic anhydride was used. The recrystallization step was carried out to obtain 53.83 g of the purified compound (D) (yield: 80%). From the results of the above Examples 1 to 5, it was confirmed that the phosphorus-containing compound having a side chain functional group of the present invention can be successfully produced, and the yield is over 60%. The phosphorus-containing compound having a side chain functional group of the present invention has a reactive functional group of 19 201004969 in the side chain, which is more advantageous for subsequent reaction with other compounds or polymers, or in combination with a polymer, thereby improving the flame retardancy of the polymer. Sex or other properties. The above is only the preferred embodiment of the present invention, and the scope of the invention is not limited thereto, that is, the simple equivalent changes and modifications made by the scope of the invention and the description of the invention are All remain within the scope of the invention patent. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an NMR chart illustrating structural analysis of DHBP-Α; FIG. 2 is an NMR chart illustrating structural analysis of compound (B); and FIG. 3 is an NMR chart illustrating compound (C) Structural Analysis; Fig. 4 is an NMR chart illustrating the structural analysis of the compound (D); and Fig. 5 is an NMR chart illustrating the structural analysis of the compound (E). [Main component symbol description]

Claims

201004969 、申請專利範圍：201004969, the scope of application for patents:

Q 式（I)所 (I) 示Q (I) (I)

Cl〜C6烷、C1 〜C10 於式（I)中，R1〜Ri〇分別表示氫、C1〜C6烷基、氧基、C3〜C7環烷基、苯基、硝基、苯氧基 _烷基、三氟曱，、三氟甲氧基或齒素原子 A 表示一〇—或一〇—c—; Q表示硝基或胺基； D表示羥基、胺基、C1〜C6烷基、C1〜C6烷氧基、 C3〜C7環烧基、C1〜C10 _烧基、三I曱基、三氟甲 /-A —N 氧基、鹵素原子、一OCN、一、 Ο ο Η Η II Η II N-R' 、 —N-C-R' 、 —N-C-0-R'Cl~C6 alkane, C1 to C10 In the formula (I), R1 to Ri, respectively, represent hydrogen, C1 to C6 alkyl, oxy, C3 to C7 cycloalkyl, phenyl, nitro, phenoxy-alkane A group, a trifluoroantimony, a trifluoromethoxy group or a dentate atom A represents a fluorene- or a hydrazine-c-; Q represents a nitro group or an amine group; D represents a hydroxyl group, an amine group, a C1 to C6 alkyl group, C1 ~C6 alkoxy group, C3~C7 cycloalkyl group, C1~C10 _alkyl group, trianthylene group, trifluoromethyl/-A-N-oxy group, halogen atom, one OCN, one, ο ο Η Η II Η II NR', —NCR', —NC-0-R'

Η ? Η , —Ν一C""N —R 、jQ^CH3 其中，Rf表示C1~C6烷基、Cl〜C6烷氧基、C3~C7環 21 201004969 院基或Cl〜C 10鹵烧基；X表示一〇—或一S3— ; γ表示氫、硝基、羥基、胺基、羧酸基、C1-C6烷基、 C1-C6烧氧基、C3〜C7環燒基、三氟甲基、三乳甲氧基或鹵素原子；及Rn及R12分別表示氫、C1〜C6烷基、C1〜C6烷氧基、C3〜C7環烷基、苯基、硝基、苯氧基、C1〜CIO鹵烷基、三氟甲基、三氟甲氧基或鹵素原子。Η ? Η , —Ν一C""N —R , jQ^CH3 where Rf denotes C1~C6 alkyl, Cl~C6 alkoxy, C3~C7 ring 21 201004969 Courtyard or Cl~C 10 halogen X represents a hydrazine - or a S3 -; γ represents hydrogen, nitro, hydroxy, amine, carboxylic acid, C1-C6 alkyl, C1-C6 alkoxy, C3~C7 cycloalkyl, trifluoro a methyl group, a trimethoxymethoxy group or a halogen atom; and Rn and R12 each represent hydrogen, C1 to C6 alkyl, C1 to C6 alkoxy, C3 to C7 cycloalkyl, phenyl, nitro, phenoxy, C1 to CIO haloalkyl, trifluoromethyl, trifluoromethoxy or halogen atom.

2 ·依據申清專利範圍第丨項所述之具有側鏈官能基的含磷化合物，其中，該R!〜RlO分別表示氫。 3.依據申請專利範圍第丨項所述之具有側鏈官能基的含磷化合物，其中，D表示羥基或胺基。 4. 依據申 4匕合物 5. 依據申彳匕合物 6. 依據申化合物 7. 依據申化合物 8. 依據申化合物 9. 依據申化合物2. A phosphorus-containing compound having a side chain functional group according to the scope of the invention, wherein R! to R10 represent hydrogen, respectively. 3. A phosphorus-containing compound having a side chain functional group according to the scope of the invention, wherein D represents a hydroxyl group or an amine group. 4. According to the application of the compound 5. According to the application of the compound 6. According to the application of the compound 7. According to the application of the compound 8. According to the application of the compound

6月專利範圍第2項所述之具有側鏈官能基的含』，其中D表示羥基、人為一〇—，以及Q為硝基 "月專利範圍第2項所述之具有側鏈官能基的含^ ，其中D表不羥基、A為一〇—，以及q為胺基请專利範圍第2項所述之具有側鏈官能基的含^ >，其中D表示羥基、八為_〇-^—，及Q為硝基 °月專利範圍第2項所述之具有側鏈官能基的含>1 J其中D表示羥基、A為—“―，及。為胺基吻專利範圍第2項所述之具有侧鏈官能基的含其中，D表不胺基、A為一〇—以及Q為硝基t 月專利範圍第2項所述之具有側鏈官能基的含) 其中，D表不胺基、A為一Ο—以及q為胺基£ 22 201004969 1 〇.依據申請專利範圍第2項所述之具有側鏈官能基的含磷〇化合物，其中，D表示胺基、A為—〇_c—及Q為硝基。 11.依據申請專利範圍第2項所述之具有侧鏈官能基的含峨〇 —一II 化合物，其中D表示胺基、A為0一C—以及Q為胺基。 12·—種由下式（I)所示之具有側鏈官能基的含磷化合物的製法 ❷The side chain functional group described in item 2 of the June patent range, wherein D represents a hydroxyl group, an artificial one, and Q is a nitro group; Containing ^, wherein D is not a hydroxyl group, A is a fluorene-, and q is an amine group. The compound having a side chain functional group as described in the second item of the patent scope, wherein D represents a hydroxyl group, and eight is a 〇 -^-, and Q is a nitro group having a side chain functional group as described in item 2 of the patent range, wherein D represents a hydroxyl group, and A is - "-, and is an amine-based patent range. The above-mentioned one having a side chain functional group, wherein D is a non-amino group, A is a fluorene-, and Q is a nitro group having a side chain functional group as described in the second aspect of the patent range) D is a non-amino group, A is a hydrazine - and q is an amine group. The hydrogen-containing fluorene compound having a side chain functional group according to claim 2, wherein D represents an amine group, A is -〇_c- and Q is a nitro group. 11. A ruthenium-II compound having a side chain functional group according to the scope of claim 2, wherein D The amine group, A is 0-C-, and Q is an amine group. 12) A method for preparing a phosphorus-containing compound having a side chain functional group represented by the following formula (I)

(I) 於式（I)中’ R1〜R10分別表示氫、C1〜C6烷基、C1〜C6 烷氧基、C3〜C7環烷基、笨基、硝基、苯氧基、 C1〜C10鹵烷基、三〇氟曱基、三氟曱氧基或函素原子； ❷ a表示—〇—或—0一c—，Q表示硝基或胺基；及D表示羥基、胺基、C1〜C6烧基、C1〜C6烷氧基、C3〜C7 環院基、Cl〜CIO鹵烧基、二氟^曱基、三氟曱氧基、(I) In the formula (I), R1 to R10 represent hydrogen, C1 to C6 alkyl, C1 to C6 alkoxy, C3 to C7 cycloalkyl, phenyl, nitro, phenoxy, C1 to C10, respectively. a haloalkyl group, a trifluorofluorenyl group, a trifluorodecyloxy group or a functional atom; ❷ a represents -〇- or -0-c-, Q represents a nitro group or an amine group; and D represents a hydroxyl group, an amine group, C1 ~C6 alkyl, C1~C6 alkoxy, C3~C7 ring-based, Cl~CIO haloalkyl, difluoro-fluorenyl, trifluoromethoxy,

〇 Ά 素原子、-OCN、一、〇 Η II —N-C-R' Ο Ο Η II Η II Μ -Ν—C—Ο—R' λ ——Ν—C—Ν—、 23 201004969〇素原子, -OCN, I, 〇 Η II —N-C-R' Ο Ο Η II Η II Μ -Ν—C—Ο—R′ λ ——Ν—C—Ν—, 23 201004969

C3〜C7環貌其中，R'表示C1~C6烷基、Cl〜C6院氧基基或Cl〜CIO鹵烷基；X表示一0—或—g— . __ 一 ,y表示氫、石肖基、經基、胺基、缓酸基、C1〜C6烧某、^C3~C7 ring shape, wherein R' represents C1~C6 alkyl group, Cl~C6 alkoxy group or Cl~CIO haloalkyl group; X represents a 0- or -g-. __, y represents hydrogen, stone Schottky, Base group, amine group, slow acid group, C1~C6 burned, ^

C 1〜C6燒氧基、C3〜C7環烷基、三氟甲基、三氟甲氧 ,, 12 氣基或鹵素原子，及R及R分別表示氫、C1〜C6烷基巫 L1〜C6惊n 基、C3〜C7環烷基、苯基、硝基、疋軋 β甘-在 +乳暴、C1〜C10鹵烷基、二氟甲基、三氟甲氧基或鹵素原子，該製法包含之步驟為：提供一種由下式⑴所示化合物：C 1~C6 alkoxy, C3~C7 cycloalkyl, trifluoromethyl, trifluoromethoxy, 12 gas or halogen atom, and R and R respectively represent hydrogen, C1~C6 alkyl witch L1~C6 a n-group, a C3~C7 cycloalkyl group, a phenyl group, a nitro group, a ruthenium-beta-glycolate, a C1 to C10 haloalkyl group, a difluoromethyl group, a trifluoromethoxy group or a halogen atom. The steps involved are: providing a compound represented by the following formula (1):

0) 〇 1¾. /1 ，以製得Q為硝：與下式(Η)所示化合物途父：基之該式(1)所示化合物： γ») R* ，選擇性地進及下步驟：使該Q為硝基之驾 24 201004969 示化合物進行還原反應1製得Q為胺基之該式⑴所示化合物，於式⑴及（Π)中^〜R1。及D的定義與該式⑴ 相同；表示單鍵或—. 早^ ，以及Z1表示豳素原子。 13.依據申請專利_ 12項所述之具有側鏈官能基的含磷，合物的製法，其中，該式⑴中之r1〜r6H r1。為氫’ D為羥基。 ❹ ❿ 14·依據中請專利範圍帛12項所述之具有側鏈官能基的含磷，合物的製法，其中，該式⑴中之r1〜r0、Μ及r1〇為鼠’ D為胺基。 ’ 15. 依據申請專利麵12項所述之具有側鏈官能基的含磷化合物的製法，其中，該式⑴）中，該V為單鍵。 16. 依據中請專利範圍第12項所述之具有側鏈官^基的含碟化合物的製法，其中，該式（ii)中，該…為―@一。 17·依據中請專利範圍帛12項所述之具有側鏈官能基的含碟化。物的製法，其中，該式⑴所示化合物與式⑴)所示化 0物之反應疋於一觸媒存在下進行，該觸媒是選自於三乙基胺、氟化鉋、氟化鉀、氣化鎚、氣化鉀、碳酸鉀、碳酸鈉、氫氧化鉀或氫氧化鈉。 18·依據中請專利範圍帛12項所述之具有側鏈官能基的含碟化^物的製法，其中，該還原反應是在—還原劑存在下進订，該還原劑是選自於氫氣與把/碳之組合、聯胺與把 /碳之組合或硼氫化鈉。 &依據中請專利範圍帛12項所述之具有側鏈官能基的含碟化合物的製法，其中，該式⑴所示化合物是由下式（iv) 25 201004969 所示化合物、下或,v 一 200) 〇13⁄4. /1 to obtain Q as nitrate: a compound shown by the following formula (Η): a compound of the formula (1): γ») R* , selectively enters and lowers Step: The compound represented by the formula (1) is obtained by formulating the compound of the formula (1), wherein the Q is a nitro group, and the compound is subjected to a reduction reaction 1 to obtain an amine group in the formula (1) and (Π). And D has the same definition as the formula (1); represents a single bond or -. early ^, and Z1 represents a halogen atom. 13. The method for producing a phosphorus-containing compound having a side chain functional group according to claim 12, wherein r1 to r6H r1 in the formula (1). It is hydrogen and D is a hydroxyl group. ❹ · 14. The method for preparing a phosphorus-containing compound having a side chain functional group according to the scope of Patent Application 帛12, wherein r1~r0, Μ and r1〇 in the formula (1) are the mouse 'D is an amine base. 15. The method for producing a phosphorus-containing compound having a side chain functional group according to claim 12, wherein in the formula (1)), the V is a single bond. 16. A process for the preparation of a dish-containing compound having a side chain group according to the scope of claim 12, wherein in the formula (ii), the ... is "@". 17. The inclusion of a side chain functional group as described in the scope of patent application 帛12. The method for producing a substance, wherein the reaction of the compound represented by the formula (1) with the compound represented by the formula (1)) is carried out in the presence of a catalyst selected from the group consisting of triethylamine, fluorinated planing, and fluorination. Potassium, gasification hammer, potassium carbonate, potassium carbonate, sodium carbonate, potassium hydroxide or sodium hydroxide. 18. The method according to claim 12, wherein the reduction reaction is carried out in the presence of a reducing agent selected from the group consisting of hydrogen-containing compounds having a side chain functional group, wherein the reducing agent is selected from the group consisting of hydrogen. Combination with / carbon, hydrazine and / carbon or sodium borohydride. & The method for preparing a dish-containing compound having a side chain functional group according to the scope of the patent application, wherein the compound represented by the formula (1) is a compound represented by the following formula (iv) 25 201004969, lower or v. One 20

法飞（V)所不化合物與下★. 進行反應所製得：、式（Vl)所示化合物該式（iv)、（v)及（vi)中相同。The compound represented by the formula (Vl) is obtained by reacting the compound of the compound (V) with the compound of the following formula: (iv), (v) and (vi).

種由下式⑴所示之具有側鏈官能基的含碟化合物的製Preparation of a dish containing compound having a side chain functional group represented by the following formula (1)

於式⑴中’ R1〜R1。分別表示氫、C1〜C6燒基、Ο,燒氧基、C3〜c7環烷基、笨基、硝基、苯氧基、Ci〜cw 齒燒基、三氟甲基、三氟曱氧基或鹵素原子； 0 八衣不或一0-C—，Q表示硝基或胺基；及D表示羥基、胺基、C1〜C6烷基、C1〜C6烷氧基、C3〜C7環烷基、C1〜C10齒烷基、三氟甲基、三氟曱氧基、齒素原= -〇· -N ~〇CN、 T7 -N-R' Ο II 'C~R，、 26 201004969In the formula (1), 'R1 to R1. Respectively represent hydrogen, C1~C6 alkyl, hydrazine, alkoxy, C3~c7 cycloalkyl, phenyl, nitro, phenoxy, Ci~cw dentate, trifluoromethyl, trifluoromethoxy Or a halogen atom; 0 octagonal or a 0-C-, Q represents a nitro or amine group; and D represents a hydroxyl group, an amine group, a C1 to C6 alkyl group, a C1 to C6 alkoxy group, a C3 to C7 cycloalkyl group , C1~C10 dentate alkyl, trifluoromethyl, trifluoromethoxy, dentinogen = -〇· -N ~〇CN, T7 -NR' Ο II 'C~R,, 26 201004969

Ο 其中，R’表示Cl〜C6烷基、Cl〜C6烷惫I 氣基、C3〜C7環烷基或Cl〜CIO鹵烷基；χ表示一〇—或〜g〜. ，γ表示氫、硝基、羥基、胺基、羧酸基、C1〜C6焓其^ 也基、C1〜C6烷氧基、C3〜C7環烷基、三氟甲基、三敦 . ,, 甲氧基或鹵素原子 ’及R及Ri2分別表示氫、C1〜C6烷基、院氧基、C3〜C7環烷基、苯基、硝基、苯氧基、ci〜c;鹵院基、三氟曱基、三氟甲氧基或鹵素原子，該製法包含之步驟為：提供一種由下式（iii)所示化合物：使該式（iii)所示化合物、下式（v)所示化合物與下式 (iv)所示化合物進行反應，以製得q為硝基之該式（I)所示化合物：Wherein R' represents a Cl~C6 alkyl group, a Cl~C6 alkane I gas group, a C3~C7 cycloalkyl group or a Cl~CIO haloalkyl group; χ represents a 〇- or ~g~. , γ represents hydrogen, Nitro, hydroxy, amine, carboxylic acid, C1 to C6, aryl, C1 to C6 alkoxy, C3 to C7 cycloalkyl, trifluoromethyl, ternary, methoxy or halogen Atoms 'and R and Ri2 respectively represent hydrogen, C1 to C6 alkyl, alkoxy, C3 to C7 cycloalkyl, phenyl, nitro, phenoxy, ci~c; halogen-based, trifluoromethyl, a trifluoromethoxy group or a halogen atom, the process comprising the steps of: providing a compound represented by the following formula (iii): a compound represented by the formula (iii), a compound represented by the following formula (v), and the following formula ( Iv) The compound shown is reacted to produce a compound of formula (I) wherein q is a nitro group:

27 201004969 」擇性地進行以下步驟：使該q為硝基之該式⑴所示化CF物進行還原反應，以製 ^ 裂付Q為胺基之該式⑴所示化合物’於式⑽、⑺及㈣中的定義與該式（I)相同。 21. 依據中請專利範㈣2G項所述之具有㈣官能基的含磷化合物的製法’其中，該式㈤)之R5〜R8為氫。 22. 依射請專圍第2Q項所述之具有側鏈官能基的含碟化合物的製法，其中，該式⑴的ri〜r4為氫。27 201004969 </ RTI> selectively performing the following steps: subjecting the CF compound represented by the formula (1) wherein q is a nitro group to a reduction reaction, to produce a compound represented by the formula (1) in which Q is an amine group, in the formula (10), The definitions in (7) and (4) are the same as in the formula (I). 21. A process for producing a phosphorus-containing compound having a (iv) functional group as described in the 2G term of the patent application, wherein R5 to R8 of the formula (5)) are hydrogen. 22. According to the method of preparing a dish-containing compound having a side chain functional group as described in the item 2Q, wherein ri to r4 of the formula (1) are hydrogen.

23. 依射請專利範圍第2Q項所述之具有㈣官能基的含碟化0物的製法，其中，該式（iv)的R9及R1❶為氫，D為羥基。依據巾請專利範圍第2Q項所述之具有㈣官能基的含碟化。物的製法，其中，該式（iv)的R9及R10為氫，D為胺基。 …23. A process for the preparation of a disk-containing compound having a (iv) functional group as described in the second aspect of the patent, wherein R9 and R1 of the formula (iv) are hydrogen and D is a hydroxyl group. According to the towel, the discarding of the (four) functional group described in the second item of the patent scope is described. The method for producing a substance wherein R9 and R10 in the formula (iv) are hydrogen and D is an amine group. ...

2 5 ·依據中請專利範圍第2 G項所述之具有鬚官能基的含鱗化合物的製法，其中，該式（iii)所示化合物、該式（v)所不化合物與該式（iv)所示化合物之反應是於一觸媒存在下進仃，該觸媒是選自於有機酸、無機酸或此兩者之一組合。 26 .依據申請專利範圍第25項所述之具有侧鏈官能基的含磷化合物的製法，其中，該觸媒是選自於醋酸、對-甲基笨續酸、甲基磺酸、硫酸、2_胺基苯磺酸、3_吡啶磺酸、對胺基苯磺酸、氣化氫、溴化氫、碘化氫、氟化氫、三氟乙酸、硝酸、磷酸或此等之一組合。 28 201004969 27.依據申清專利範圍第20項所述之具有侧鏈官能基的含磷化合物的製法，其中，該式（iii)所示化合物是由下式所示化合物與下式（ii)所示化合物進行反應所製得：2 5 . The method for preparing a scaly compound having a functional group according to the second aspect of the patent application, wherein the compound represented by the formula (iii), the compound of the formula (v) and the formula (iv) The reaction of the indicated compound is carried out in the presence of a catalyst selected from the group consisting of organic acids, inorganic acids or a combination of the two. The method for producing a phosphorus-containing compound having a side chain functional group according to claim 25, wherein the catalyst is selected from the group consisting of acetic acid, p-methylphenyl acid, methanesulfonic acid, sulfuric acid, 2_Aminobenzenesulfonic acid, 3-pyridinesulfonic acid, p-aminobenzenesulfonic acid, hydrogenated hydrogen, hydrogen bromide, hydrogen iodide, hydrogen fluoride, trifluoroacetic acid, nitric acid, phosphoric acid or a combination thereof. 28 201004969 27. The method for producing a phosphorus-containing compound having a side chain functional group according to claim 20, wherein the compound represented by the formula (iii) is a compound represented by the following formula and (ii) The compound shown is reacted to obtain:

式（vi)及（ii)中，Z1表示齒素原子，Al表示單鍵或卜 —II —C—以及R5〜R8與該式（iii)的定義相同。 ® 28.依據申請專利範圍第20項所述之具有侧鏈官能基的含磷化合物的製法，其中，該還原反應是在一還原劑存在下進行，該還原劑是選自於氫氣與鈀/碳之組合、聯胺與鈀 /碳之組合或硼氫化鈉。In the formulae (vi) and (ii), Z1 represents a dentate atom, and Al represents a single bond or a -II-C- and R5 to R8 are the same as defined in the formula (iii). ® 28. The method for producing a phosphorus-containing compound having a side chain functional group according to claim 20, wherein the reducing reaction is carried out in the presence of a reducing agent selected from the group consisting of hydrogen and palladium/ A combination of carbon, a combination of hydrazine and palladium on carbon or sodium borohydride.

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