JP2948118B2 - Method for producing 1,3-dicyclohexylcarbodiimide - Google Patents
Method for producing 1,3-dicyclohexylcarbodiimideInfo
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- JP2948118B2 JP2948118B2 JP3737595A JP3737595A JP2948118B2 JP 2948118 B2 JP2948118 B2 JP 2948118B2 JP 3737595 A JP3737595 A JP 3737595A JP 3737595 A JP3737595 A JP 3737595A JP 2948118 B2 JP2948118 B2 JP 2948118B2
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- dcc
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- dcu
- methylene chloride
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Description
【０００１】[0001]
【産業上の利用分野】本発明は１，３−ジシクロヘキシ
ルカルボジイミドの製造方法に関する。更に詳しくは
１，３−ジシクロヘキシル尿素を脱水して１，３−ジシ
クロヘキシルカルボジイミドを製造する方法に関する。The present invention relates to a method for producing 1,3-dicyclohexylcarbodiimide. More specifically, the present invention relates to a method for producing 1,3-dicyclohexylcarbodiimide by dehydrating 1,3-dicyclohexylurea.
【０００２】[0002]
【従来の技術】１，３−ジシクロヘキシルカルボジイミ
ド（以下ＤＣＣと呼ぶ。）は医薬合成の中間体、脱水縮
合剤、反応助剤、樹脂の改質剤等として有用であり、そ
の製造方法を分類すると、次の３つの方法が知られてい
る。 ジシクロヘキシルチオ尿素を脱硫化水素する（特公昭
５０−１３２４８号） ジシクロヘキシルイソシアネートを脱炭酸し縮合する
（特開昭５４−６６６５６号） １，３−ジシクロヘキシル尿素（以下ＤＣＵと呼
ぶ。）を脱水する（特開昭６０−１６６６５２号ほ
か）。2. Description of the Related Art 1,3-Dicyclohexylcarbodiimide (hereinafter referred to as DCC) is useful as an intermediate for pharmaceutical synthesis, a dehydrating condensing agent, a reaction aid, a modifier for resins, and the like. The following three methods are known. Dehydrogenation of dicyclohexylthiourea (Japanese Patent Publication No. 50-13248) Decarboxylation and condensation of dicyclohexyl isocyanate (JP-A-54-66656) Dehydration of 1,3-dicyclohexylurea (hereinafter referred to as DCU) ( JP-A-60-166652 and others).
【０００３】ＤＣＣを脱水縮合剤として使用する場合、
通常副生物としてＤＣＵが回収されるので、これを原料
としてリサイクルするの方法が原料コスト面では有利
な方法と考えられる。When DCC is used as a dehydrating condensing agent,
Since DCU is usually recovered as a by-product, a method of recycling it as a raw material is considered to be an advantageous method in terms of raw material cost.
【０００４】上記の方法、すなわち、ＤＣＵを脱水す
る具体的な方法としては以下の方法が知られている。 ａ）オキシ塩化リンとピリジンで処理する方法（特開昭
６０−１６６６５２号） ｂ）ｐートルエンスルホン酸クロライドとピリジンで処
理する方法（ＵＳＰ−２７９７２４０） ｃ）飽和エーテル中ホスゲンで処理し、ジシクロヘキシ
ルクロルホルムアミジニウムクロライドとして単離した
後にアルカリ分解する方法（特開昭５４−７６５５９
号）[0004] The following method is known as a specific method for dehydrating DCU, ie, the above method. a) A method of treating with phosphorus oxychloride and pyridine (JP-A-60-166652) b) A method of treating with p-toluenesulfonic acid chloride and pyridine (USP-2797240) c) A treatment with phosgene in saturated ether and dicyclohexyl A method in which chloroformamidinium chloride is isolated and then alkali-decomposed (JP-A-54-76559).
issue)
【０００５】[0005]
【発明が解決しようとする課題】上記従来法のうち、
ａ），ｂ）の方法は高価なピリジンを多量に使用し、コ
スト面で不利である上に、ピリジンの臭気及び毒性によ
る作業環境上の問題も有している。又、ｃ）は毒性の強
いホスゲンを使用するため、作業環境上の問題は更に深
刻である。このような事情に鑑み、発明者らはピリジン
やホスゲンのような有害物質を使用せずにＤＣＣを収率
良く合成できる方法について検討した結果、特定の溶媒
中でＤＣＵをオキシ塩化リンと反応させ、ついで反応生
成物をアルカリ水溶液で分解して２段階でＤＣＣを合成
することにより上記問題点が解決でき、ＤＣＣが収率良
く得られることを見出した。SUMMARY OF THE INVENTION Among the above conventional methods,
The methods a) and b) use a large amount of expensive pyridine, are disadvantageous in cost, and have problems in the working environment due to odor and toxicity of pyridine. In the case of c), toxic phosgene is used, so that the work environment is more serious. In view of such circumstances, the present inventors have studied a method capable of synthesizing DCC with high yield without using harmful substances such as pyridine and phosgene, and as a result, reacted DCU with phosphorus oxychloride in a specific solvent. Then, it has been found that the above problem can be solved by decomposing the reaction product with an aqueous alkali solution and synthesizing DCC in two steps, and that DCC can be obtained in good yield.
【０００６】[0006]
【課題を解決するための手段】本発明は１，３−ジシク
ロヘキシル尿素（ＤＣＵ）を非塩基性有機溶媒中でオキ
シ塩化リンと反応させ、ついでアルカリ水溶液で分解す
ることを特徴とする１，３−ジシクロヘキシルカルボジ
イミド（ＤＣＣ）の製造方法である。The present invention is characterized in that 1,3-dicyclohexylurea (DCU) is reacted with phosphorus oxychloride in a non-basic organic solvent and then decomposed with an aqueous alkali solution. -A process for producing dicyclohexylcarbodiimide (DCC).
【０００７】第１の反応は下記式（１）により、非塩基
性有機溶媒中でＤＣＵとオキシ塩化リンとを反応させる
工程であり、ｏ−ジクロロホスフォリル−Ｎ−Ｎ’−ジ
シクロヘキシルウロニウム（ＤＤＵＣ）［Ｉ］と推定さ
れる塩が生成する。第２の反応においてはこの反応生成
物である塩にアルカリ水溶液を加えて分解し、ＤＣＣを
得る。[0007] The first reaction is a step of reacting DCU with phosphorus oxychloride in a non-basic organic solvent according to the following formula (1), wherein o-dichlorophosphoryl-NN'-dicyclohexyluronium is used. A salt presumed to be (DDUC) [I] is formed. In the second reaction, an alkaline aqueous solution is added to the salt, which is the reaction product, to decompose to obtain DCC.
【０００８】[0008]
【化１】 Embedded image
【０００９】第１の反応において使用される非塩基性有
機溶媒は脂肪族炭化水素、脂環式炭化水素、芳香族炭化
水素、エーテル類、ハロゲン化炭化水素等のオキシ塩化
リンと反応性のない溶媒であり、それぞれ単独ないしは
混合物で使用することができる。脂肪族炭化水素として
はヘキサン、ヘプタン、オクタン、デカン等、脂環式炭
化水素としてはシクロヘキサン、メチルシクロヘキサ
ン、デカリン等、芳香族炭化水素としてはベンゼン、ト
ルエン、キシレン、メチルナフタレン等、エーテル類と
してはテトラヒドロフラン、イソプロピルエ−テル、エ
チルエ−テル等、ハロゲン化炭化水素としては塩化メチ
レン、クロロホルム、クロロベンゼン等を挙げることが
できるが、特に塩化メチレン、クロロホルム等を使用す
れば反応生成物が溶解して溶液状で得られ、そのままア
ルカリ分解反応に使用して、反応がスムーズに進行する
ので反応溶媒として好適である。The non-basic organic solvent used in the first reaction has no reactivity with phosphorus oxychloride such as aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, ethers and halogenated hydrocarbon. It is a solvent and can be used alone or in a mixture. Hexane, heptane, octane, decane, etc. as aliphatic hydrocarbons, cyclohexane, methylcyclohexane, decalin, etc. as alicyclic hydrocarbons, benzene, toluene, xylene, methylnaphthalene, etc. as aromatic hydrocarbons, ethers as Examples of halogenated hydrocarbons such as tetrahydrofuran, isopropyl ether, and ethyl ether include methylene chloride, chloroform, and chlorobenzene. It is suitable for use as a reaction solvent because it can be used as it is in an alkali decomposition reaction and the reaction proceeds smoothly.
【００１０】反応に使用する溶媒量はＤＣＵが十分に分
散混合する程度が望ましくＤＣＵに対して２〜１５倍重
量が適当である。オキシ塩化リンの使用量は、通常ＤＣ
Ｕに対し１．０〜１．５倍モルがよい。反応温度は使用
する溶媒により異なるが通常１０〜１００℃の範囲が好
ましい。反応時間は１〜１０時間で十分である。The amount of the solvent used in the reaction is preferably such that DCU is sufficiently dispersed and mixed, and is suitably 2 to 15 times the weight of DCU. The amount of phosphorus oxychloride used is usually DC
The mole is preferably 1.0 to 1.5 times mol of U. The reaction temperature varies depending on the solvent used, but is usually preferably in the range of 10 to 100 ° C. A reaction time of 1 to 10 hours is sufficient.
【００１１】反応後、反応液は溶媒の種類により反応生
成物である塩が溶解し、溶液となる場合と、塩が析出
し、スラリーになる場合がある。溶液となる場合は、溶
液をそのまま、アルカリ分解へ使用することができる。
スラリーとなる場合は、そのままアルカリ分解への使用
も可能であるが、分解をスムーズに行なう為に生成した
塩を分離後、塩が溶解する溶媒、例えば塩化メチレン、
クロロホルムに溶解後、アルカリ分解に使用するのが望
ましい。After the reaction, depending on the type of the solvent, the reaction solution may be in the form of a solution in which a salt as a reaction product is dissolved, or in the form of a solution, or in the case of salt precipitation and slurry. When a solution is obtained, the solution can be used as it is for alkali decomposition.
In the case of a slurry, it can be used for alkali decomposition as it is, but after separating the generated salt to smoothly perform the decomposition, a solvent in which the salt is dissolved, for example, methylene chloride,
After dissolving in chloroform, it is desirable to use for alkali decomposition.
【００１２】塩の分解に使用するアルカリは、ＮａＯ
Ｈ，Ｎａ2 ＣＯ3 ，ＫＯＨ，Ｋ2 ＣＯ3 ，ＬｉＯＨ，Ｃ
ａ（ＯＨ）2 ，アンモニア水等、特に制限はないがコス
ト面からＮａＯＨが望ましい。The alkali used to decompose the salt is NaO
H, Na 2 CO 3 , KOH, K 2 CO 3 , LiOH, C
a (OH) 2 , ammonia water and the like are not particularly limited, but NaOH is desirable from the viewpoint of cost.
【００１３】アルカリは通常水溶液として使用する。水
の量は制限はないが、副生するリン酸塩、塩酸塩が溶解
し、析出しない量であることが望ましい。例えばＮａＯ
Ｈの場合、ＮａＯＨ濃度が２０％以下となる水溶液とし
て使用する。The alkali is usually used as an aqueous solution. Although the amount of water is not limited, it is desirable that the by-produced phosphate or hydrochloride be dissolved and not precipitated. For example, NaO
In the case of H, it is used as an aqueous solution having a NaOH concentration of 20% or less.
【００１４】アルカリ分解は、反応生成物である塩の溶
液、又はスラリーをアルカリ水溶液中に滴下するのが好
ましい。逆に、アルカリ水溶液をＤＤＵＣ溶液又はスラ
リーに滴下すると、逆反応が起こりＤＣＵが多量に生成
し、好ましくない。In the alkali decomposition, it is preferable to drop a solution or a slurry of a salt as a reaction product into an aqueous alkali solution. Conversely, when an alkaline aqueous solution is dropped into the DDUC solution or slurry, a reverse reaction occurs and a large amount of DCU is generated, which is not preferable.
【００１５】アルカリ分解時の温度は、１０〜７０℃が
適当である。７０℃以上になると、生成したＤＣＣが水
と反応しＤＣＵとなる量が増え、収率が低下する。The temperature during the alkali decomposition is suitably from 10 to 70 ° C. When the temperature exceeds 70 ° C., the amount of DCC produced reacts with water to form DCU, and the yield decreases.
【００１６】アルカリ分解終了時には、生成したＤＣＣ
は溶媒層へ、リン酸塩、塩酸塩は水層に溶解し、分液さ
れる。又、若干量のＤＣＵと、Ｃａ（ＯＨ）2 をアルカ
リに使用した場合はＣａＣｌ2 等が不溶分として存在す
るので、分液前後に不溶分を濾別しても良い。分離され
た有機溶媒層は、必要に応じて無水Ｎａ2 ＳＯ4 等で脱
水処理後蒸留しＤＣＣを得る。At the end of the alkaline decomposition, the generated DCC
Is dissolved in the solvent layer, and the phosphate and hydrochloride are dissolved in the aqueous layer and separated. When a small amount of DCU and Ca (OH) 2 are used as an alkali, CaCl 2 and the like are present as insoluble components, so that the insoluble components may be separated before and after liquid separation. The separated organic solvent layer is, if necessary, dehydrated with anhydrous Na 2 SO 4 or the like and then distilled to obtain DCC.
【００１７】本法によるＤＣＣの収率はＤＣＵに対して
７５〜８９ｍｏｌ％でありピリジンを使用する場合より
高率である。The yield of DCC according to this method is 75 to 89 mol% based on DCU, which is higher than when pyridine is used.
【００１８】[0018]
【実施例】以下に実施例を挙げて本発明を具体的に説明
する。なお生成したＤＣＣの分析は、内部標準法ガスク
ロマトグラフィー（カラム：島津製作所製、ＣＢＰ−
１、内部標準物質：ナフタレン）により行なった。EXAMPLES The present invention will be specifically described below with reference to examples. The analysis of the generated DCC was performed by internal standard method gas chromatography (column: Shimadzu Corporation, CBP-
1, internal standard substance: naphthalene).
【００１９】［実施例１］塩化メチレン３２０ｇにＤＣ
Ｕ８０ｇを撹拌分散し、分散液にオキシ塩化リン７１．
２ｇを約３０分で滴下した。滴下終了後４０℃で４時間
反応を行ない２５℃まで冷却した。この反応生成物を含
む塩化メチレン溶液を、１０％のＮａＯＨ水溶液８１６
ｇの中に温度３５℃、２時間で滴下し、滴下後３０分撹
拌した後静置し、下層の塩化メチレンを分離した。水層
を１００ｇの塩化メチレンで洗浄し再度、静置、分離し
た。得られた塩化メチレン層を濃縮し粗ＤＣＣ８５ｇを
得た。粗ＤＣＣを１０ｍｍＨｇの減圧下蒸留し、無色透
明なＤＣＣ６６．２ｇを得た（ｂ．ｐ．１６０〜１６１
℃／１０ｍｍＨｇ）。ＤＣＵに対する収率は８９．２ｍ
ｏｌ％、純度９９．２％であった。Example 1 DC was added to 320 g of methylene chloride.
U80g was stirred and dispersed, and phosphorus oxychloride was added to the dispersion.
2 g were added dropwise in about 30 minutes. After the completion of the dropwise addition, the reaction was carried out at 40 ° C. for 4 hours and cooled to 25 ° C. A methylene chloride solution containing the reaction product was added to a 10% NaOH aqueous solution 816.
g at 35 ° C. for 2 hours. After the dropwise addition, the mixture was stirred for 30 minutes and allowed to stand, thereby separating methylene chloride as a lower layer. The aqueous layer was washed with 100 g of methylene chloride, again allowed to stand and separated. The obtained methylene chloride layer was concentrated to obtain 85 g of crude DCC. The crude DCC was distilled under reduced pressure of 10 mmHg to obtain 66.2 g of colorless and transparent DCC (bp 160 to 161).
° C / 10 mmHg). The yield based on DCU is 89.2 m.
ol% and purity 99.2%.
【００２０】［実施例２］実施例１において塩化メチレ
ンの代わりにクロロホルムを用いた以外は実施例１と同
様にしてＤＣＣを製造した。ＤＣＵに対する収率は８
５．３ｍｏｌ％であった。Example 2 A DCC was produced in the same manner as in Example 1 except that chloroform was used instead of methylene chloride. The yield based on DCU is 8
It was 5.3 mol%.
【００２１】［実施例３］シクロヘキサン４００ｇ、Ｔ
ＨＦ８０ｇにＤＣＵ１００ｇを分散し、分散液にオキシ
塩化リン８９ｇを３０分で滴下した。滴下後２０℃で１
０ｈｒ反応させた後、スラリーを濾過し、ＤＤＵＣと推
定される塩１４３ｇを得た。その全量を塩化メチレン４
００ｇに溶解し、１０％ＮａＯＨ水１０００ｇの中へ温
度３５℃、２ｈｒで滴下した。滴下後３０分撹拌、静置
し下層の塩化メチレン層を分離した。上層の水層を更に
塩化メチレン１００ｇで洗浄し、塩化メチレン層を分離
した。得られた塩化メチレン層から塩化メチレンを濃縮
したのち蒸留し、ＤＣＣ６９ｇ（純度９９．８％）を得
た。ＤＣＵに対する収率は７４．９ｍｏｌ％であった。Example 3 400 g of cyclohexane, T
100 g of DCU was dispersed in 80 g of HF, and 89 g of phosphorus oxychloride was added dropwise to the dispersion over 30 minutes. 1 at 20 ° C after dropping
After reacting for 0 hr, the slurry was filtered to obtain 143 g of a salt estimated to be DDUC. The whole amount is methylene chloride 4
The resulting solution was dropped into 1000 g of 10% aqueous NaOH at 35 ° C. for 2 hours. After dropping, the mixture was stirred for 30 minutes and allowed to stand to separate a lower methylene chloride layer. The upper aqueous layer was further washed with 100 g of methylene chloride, and the methylene chloride layer was separated. After methylene chloride was concentrated from the obtained methylene chloride layer and distilled, 69 g of DCC (purity 99.8%) was obtained. The yield based on DCU was 74.9 mol%.
【００２２】［実施例４］実施例３においてシクロヘキ
サンの代わりにヘキサンを用いた以外は実施例３と同様
にしてＤＣＣを製造した。ＤＣＵに対するＤＣＣの収率
は７７．５ｍｏｌ％であった。Example 4 A DCC was produced in the same manner as in Example 3 except that hexane was used instead of cyclohexane. The yield of DCC based on DCU was 77.5 mol%.
【００２３】［比較例１］ＤＣＵ２２．４ｇをピリジン
４９ｇに分散し、７０℃に加熱後オキシ塩化リン１７．
０ｇを２ｈｒで滴下した。滴下終了後、９０℃に昇温し
２ｈｒ反応後冷却した。反応液を水に注ぎ、塩化メチレ
ン１５０ｇで２回抽出した。塩化メチレン層を濃縮後、
蒸留し、ＤＣＣ１４．５（純度９９．５％）を得た。Ｄ
ＣＵに対する収率は７０ｍｏｌ％であった。COMPARATIVE EXAMPLE 1 22.4 g of DCU was dispersed in 49 g of pyridine, heated to 70 ° C., and then mixed with 17.7 g of phosphorus oxychloride.
0 g was added dropwise over 2 hours. After the completion of the dropwise addition, the temperature was raised to 90 ° C., and the reaction was cooled for 2 hours. The reaction solution was poured into water and extracted twice with 150 g of methylene chloride. After concentrating the methylene chloride layer,
Distillation gave DCC 14.5 (99.5% purity). D
The yield based on CU was 70 mol%.
【発明の効果】本発明は非塩基性溶媒を用い、ＤＣＵと
オキシ塩化リンとの反応及び反応生成物のアルカリ水溶
液による分解の２段反応を行なわせることにより、有害
物質を使用せず、しかもピリジンを使用する場合より高
収率でＤＣＣを得ることができるので工業的に優れた方
法である。According to the present invention, a non-basic solvent is used to carry out a two-stage reaction of the reaction between DCU and phosphorus oxychloride and the decomposition of the reaction product with an aqueous alkali solution, thereby eliminating the use of harmful substances. This is an industrially superior method since DCC can be obtained in higher yield than when pyridine is used.
Claims (4)
性有機溶媒中でオキシ塩化リンと反応させ、ついでアル
カリ水溶液で分解することを特徴とする１，３−ジシク
ロヘキシルカルボジイミドの製造方法。1. A process for producing 1,3-dicyclohexylcarbodiimide, comprising reacting 1,3-dicyclohexylurea with phosphorus oxychloride in a non-basic organic solvent, and decomposing it with an aqueous alkali solution.
環式炭化水素、芳香族炭化水素、エーテル類及びハロゲ
ン化炭化水素よりなる群より選ばれたものであることを
特徴とする請求項１記載の１，３−ジシクロヘキシルカ
ルボジイミドの製造方法。2. The non-basic organic solvent is selected from the group consisting of aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, ethers and halogenated hydrocarbons. Item 1. The method for producing 1,3-dicyclohexylcarbodiimide according to Item 1.
塩化リンとの反応生成物溶液、又はスラリーをアルカリ
水溶液へ滴下することを特徴とする請求項１又は２に記
載の１，３−ジシクロヘキシルカルボジイミドの製造方
法。3. The 1,3-dicyclohexylcarbodiimide according to claim 1 or 2, wherein a solution or a slurry of a reaction product of 1,3-dicyclohexylurea and phosphorus oxychloride is dropped into an aqueous alkali solution. Production method.
塩化リンとの反応生成物を塩化メチレン又はクロロホル
ム溶液として、アルカリ水溶液へ滴下することを特徴と
する請求項３記載の１，３−ジシクロヘキシルカルボジ
イミドの製造方法。4. The method according to claim 3, wherein the reaction product of 1,3-dicyclohexylurea and phosphorus oxychloride is added dropwise as a methylene chloride or chloroform solution to an aqueous alkali solution. Production method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3737595A JP2948118B2 (en) | 1995-02-24 | 1995-02-24 | Method for producing 1,3-dicyclohexylcarbodiimide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3737595A JP2948118B2 (en) | 1995-02-24 | 1995-02-24 | Method for producing 1,3-dicyclohexylcarbodiimide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08231491A JPH08231491A (en) | 1996-09-10 |
| JP2948118B2 true JP2948118B2 (en) | 1999-09-13 |
Family
ID=12495780
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3737595A Expired - Lifetime JP2948118B2 (en) | 1995-02-24 | 1995-02-24 | Method for producing 1,3-dicyclohexylcarbodiimide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2948118B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928237A (en) * | 2010-07-13 | 2010-12-29 | 济南巨业精细化工有限公司 | Process for preparing N,N'-dicyclohexyl carbodiimide by regeneration method |
| CN103922970B (en) * | 2014-04-10 | 2015-07-01 | 柳林县兴星能源科技有限责任公司 | Synthesis method of dicyclohexyl carbodiimide |
| CN104262200B (en) * | 2014-09-02 | 2016-06-29 | 山东巨业精细化工有限公司 | One recycles waste water and prepares N, N ' production method of-dicyclohexylcarbodiimide |
| CN109232319A (en) * | 2018-09-07 | 2019-01-18 | 山东金城柯瑞化学有限公司 | The preparation method of dicyclohexylcarbodiimide |
| CN110903217A (en) * | 2019-12-11 | 2020-03-24 | 山东汇海医药化工有限公司 | Method for reducing waste residues of N, N' -dicyclohexylcarbodiimide product |
| CN112142625A (en) * | 2020-10-20 | 2020-12-29 | 山东汇海医药化工有限公司 | Method for reducing waste residues of N, N' -diisopropylcarbodiimide product |
-
1995
- 1995-02-24 JP JP3737595A patent/JP2948118B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08231491A (en) | 1996-09-10 |
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