JPH01180864A - Production of isocyanate compound - Google Patents
Production of isocyanate compoundInfo
- Publication number
- JPH01180864A JPH01180864A JP444288A JP444288A JPH01180864A JP H01180864 A JPH01180864 A JP H01180864A JP 444288 A JP444288 A JP 444288A JP 444288 A JP444288 A JP 444288A JP H01180864 A JPH01180864 A JP H01180864A
- Authority
- JP
- Japan
- Prior art keywords
- adamantane
- compound
- formula
- isocyanate compound
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 isocyanate compound Chemical class 0.000 title claims abstract description 18
- 239000012948 isocyanate Substances 0.000 title claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- ORILYTVJVMAKLC-UHFFFAOYSA-N Adamantane Natural products C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 abstract description 12
- 150000001875 compounds Chemical class 0.000 abstract description 9
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000292 calcium oxide Substances 0.000 abstract description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 239000000835 fiber Substances 0.000 abstract description 2
- 239000003973 paint Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011787 zinc oxide Substances 0.000 abstract description 2
- 150000002513 isocyanates Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000004821 distillation Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- MLXLDKWQJYBKOH-UHFFFAOYSA-N 1,3-diisocyanatoadamantane Chemical compound C1C(C2)CC3CC1(N=C=O)CC2(N=C=O)C3 MLXLDKWQJYBKOH-UHFFFAOYSA-N 0.000 description 3
- AYKPBQKKIQUHAF-UHFFFAOYSA-N 1-n,3-n-dimethyladamantane-1,3-dicarboxamide Chemical compound C1C(C2)CC3CC1(C(=O)NC)CC2(C(=O)NC)C3 AYKPBQKKIQUHAF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- XMJHPCRAQCTCFT-UHFFFAOYSA-N methyl chloroformate Chemical compound COC(Cl)=O XMJHPCRAQCTCFT-UHFFFAOYSA-N 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- MPAQPXALASKCOX-UHFFFAOYSA-N N=C=O.C1C(C2)CC3CC1CC2C3 Chemical class N=C=O.C1C(C2)CC3CC1CC2C3 MPAQPXALASKCOX-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GHVZOJONCUEWAV-UHFFFAOYSA-N [K].CCO Chemical compound [K].CCO GHVZOJONCUEWAV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- JMWOVPMZIVGXGQ-UHFFFAOYSA-N adamantane-1,3-diamine;hydrochloride Chemical compound Cl.C1C(C2)CC3CC1(N)CC2(N)C3 JMWOVPMZIVGXGQ-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
- 125000003262 carboxylic acid ester group Chemical class [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- OQNGCCWBHLEQFN-UHFFFAOYSA-N chloroform;hexane Chemical compound ClC(Cl)Cl.CCCCCC OQNGCCWBHLEQFN-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 150000001913 cyanates Chemical class 0.000 description 1
- QIGYDSTVZKNHEY-UHFFFAOYSA-L dipotassium;dichloromethane;carbonate Chemical compound [K+].[K+].ClCCl.[O-]C([O-])=O QIGYDSTVZKNHEY-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、イソシアネート化合物の製造方法に関し、さ
らに詳しくは、アダマンタンのインシアネート化合物の
製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing an isocyanate compound, and more particularly to a method for producing an adamantane incyanate compound.
［従来の技術およびその問題点］
アダマンタンのイソシアネート誘導体を製造する方法と
しては、例えば、酸アジドを経由する方法（米国特許第
３，３０１，８２７号）、アミンにホスゲンを反応させ
る方法［Ｚｈ、Ｖｓｅｓ−Ｋｈｉｍ−０−ｖａｙ ２４
（１） 、９５（１９７５）あるいはフランス特許第１
，５４１，３５９号］、臭化物にシアン酸塩を反応させ
る方法（特公昭５０−８８０６０号）が知られているが
、上記方法はいずれも毒性の高い原料を使用するので安
全面で問題があり、改良が望まれている。[Prior art and its problems] Methods for producing isocyanate derivatives of adamantane include, for example, a method via acid azide (US Pat. No. 3,301,827), a method of reacting amine with phosgene [Zh, Vses-Khim-0-vay 24
(1), 95 (1975) or French Patent No.
, 541, 359], and a method of reacting bromide with cyanate (Japanese Patent Publication No. 50-88060), but all of the above methods use highly toxic raw materials and therefore have safety problems. , improvements are desired.
また、一般的なインシアネート化合物を製造する方法と
して、熱分解する方法（米国特許第２．４０９，７１２
号）や触媒を用いて熱分解する方法［Ｊ、Ａ−Ｇ、Ｓ、
互、４３５８（１１５６月が知られているが、これらの
方法がアダマンタンのイソシアネート化合物に適用され
た例はない。In addition, as a general method for producing incyanate compounds, a thermal decomposition method (U.S. Pat. No. 2,409,712
method of thermal decomposition using a catalyst [J, A-G, S,
4358 (1156) are known, but there are no examples of these methods being applied to adamantane isocyanate compounds.
本発明は上記従来技術の欠点を改良したインシアネート
化合物の製造方法、特にアダマンタンのインシアネート
化合物の製造方法を提供することを目的とするものであ
る。The object of the present invention is to provide a method for producing an incyanate compound, in particular a method for producing an adamantane incyanate compound, which improves the drawbacks of the prior art.
［問題点を解決するための手段］
本発明者らは、上記目的を達成すべく鋭意研究した結果
、アダマンタンのウレタン化合物を特別な塩基性触媒を
用いて加熱、減圧蒸留することによってアダマンタンの
インシアネート化合物を得られることができることを見
出し、本発明を完成するに至った。[Means for Solving the Problems] As a result of intensive research to achieve the above object, the present inventors have discovered that adamantane is inorganic by heating and vacuum distilling an adamantane urethane compound using a special basic catalyst. The inventors have discovered that cyanate compounds can be obtained, and have completed the present invention.
すなわち、本発明の構成は、次式（１）：％式％（１）
（式中、Ｒは炭素数１〜３のアルキル基であり、ｎはＯ
〜３の整数であり、ｍは１〜４の整数であり、Ａｄはア
ダマンタン骨格を表わし、該骨格は炭素数１〜３の低級
アルキル基、アリル基、アラルキル基、アルキルアリル
基、低級アルコキシ基で置換されていてもよい。）
で表されるアダマンタン化合物を、塩基性触媒の存在下
で加熱、減圧蒸留して、式（２）：％式％（２）
（式中、ｎ、ｍおよびＡｄは前記と同じ意味を有する。That is, the structure of the present invention is the following formula (1): % formula % (1) (wherein, R is an alkyl group having 1 to 3 carbon atoms, and n is O
m is an integer of 1 to 4, Ad represents an adamantane skeleton, and the skeleton is a lower alkyl group having 1 to 3 carbon atoms, an allyl group, an aralkyl group, an alkylaryl group, or a lower alkoxy group. may be replaced with . ) is heated and distilled under reduced pressure in the presence of a basic catalyst to obtain formula (2): % formula % (2) (where n, m and Ad have the same meanings as above) .
）
で表わされるイソシアネート化合物を得ることを特徴と
するインシアネート化合物の製造方法である。) This is a method for producing an incyanate compound, which is characterized by obtaining an isocyanate compound represented by the following.
本発明の方法において、式（１）で表されると共に出発
物質であるアダマンタンのウレタン化合物の具体例とし
ては、例えば、１．３−ジ（メチルカルバミル）−アダ
マンタン、ｌ−メチルカルバミルアダマンタン、１．３
−ジメチル−５−メチルカルバミルアダマンタン、１，
３−ジメチル−５，７−ジ（メチルカルバミル）アダマ
ンタン、１．３−ジ（メチルカルバミルメチル）アダマ
ンタン、１．３−ジ（エチルカルバミル）アダマンタン
等が挙げられる。In the method of the present invention, specific examples of the adamantane urethane compound represented by formula (1) and serving as a starting material include 1,3-di(methylcarbamyl)-adamantane, l-methylcarbamyladamantane, , 1.3
-dimethyl-5-methylcarbamyladamantane, 1,
Examples include 3-dimethyl-5,7-di(methylcarbamyl)adamantane, 1,3-di(methylcarbamylmethyl)adamantane, and 1,3-di(ethylcarbamyl)adamantane.
上記のアダマンタンのウレタン化合物の中で、特に好ま
しいものは、ｎがＯまたは１で、ｍが１または２のもの
である。この具体例としては、■−インシアナトアダマ
ンタン、１，３−ジメチル−５−インシアナトアダマン
タン、１，３−ジイソシアナトアダマンタン、１．３−
ジメチル−５゜７−ジイソシアナトアダマンタン等があ
る。Among the above adamantane urethane compounds, particularly preferred are those in which n is O or 1 and m is 1 or 2. Specific examples include ■-incyanatoadamantane, 1,3-dimethyl-5-incyanatoadamantane, 1,3-diisocyanatoadamantane, 1.3-
Examples include dimethyl-5°7-diisocyanatoadamantane.
また、アダマンタン骨格の置換基の具体例としては、例
えばメチル基、エチル基、プロピル基などの低級アルキ
ル基、アリル基、ベンジル基などのアラルキル基、メチ
ルアリル基、エチルアリル基などのアルキルアリル基、
メトキシ基、エトキシ基などの低級アルコキシ基が挙げ
られるが、低級アルキル基が好ましい。Specific examples of substituents on the adamantane skeleton include lower alkyl groups such as methyl, ethyl, and propyl; aralkyl groups such as allyl and benzyl; alkylaryl groups such as methylallyl and ethylallyl;
Examples include lower alkoxy groups such as methoxy and ethoxy groups, with lower alkyl groups being preferred.
この出発物質は例えば、アダマンタンのアミン化合物の
塩酸塩を溶剤に溶解し、ハロゲン置換カルボン酸エステ
ル等と反応させることによって得ることができる。その
−例として、１，３−ジアミノアダマンタンの塩酸塩を
炭酸カリウム−塩化メチレン溶液に溶解し、クロロ蟻酸
メチルを添加して反応させ、得られた反応混合物をｎ−
ヘキサン−クロロホルムで再結晶することによって得る
ことができる。This starting material can be obtained, for example, by dissolving the hydrochloride of an amine compound of adamantane in a solvent and reacting it with a halogen-substituted carboxylic acid ester. As an example, 1,3-diaminoadamantane hydrochloride is dissolved in a potassium carbonate-methylene chloride solution, methyl chloroformate is added and reacted, and the resulting reaction mixture is n-
It can be obtained by recrystallizing from hexane-chloroform.
本発明の方法に用いられる塩基性触媒としては、例えば
酸化カルシウム、酸化カドミウム、酸化亜鉛、酸化セリ
ウム、二酸化マンガン、−酸化鋼、酸化ニッケル等の金
属酸化物、ナトリウムメチラート、カリウムメチラート
、ナトリウムエチラート、カリウムエチラート等のアル
コラード、酢酸ナトリウム、酢酸カリウム等の酢酸塩等
を用いることができる。これらの触媒の中でも金属酸化
物が好ましく、特に、周期律表第１Ｉａ族の金属の酸化
物、中でも酸化カルシウムが好ましい。これらの触媒の
量は通常、式（１）で表される化合物に対し、１〜３０
重量％、好ましくは、５〜２０重量％用いられる。触媒
の量が１重量％未満では、インシアネート化合物の生成
効率が低く、３０重量％を超えると反応物の加熱攪拌が
難しくなり、縮合反応したと思われるゲル状反応生成物
が増加する。Basic catalysts used in the method of the present invention include, for example, metal oxides such as calcium oxide, cadmium oxide, zinc oxide, cerium oxide, manganese dioxide, steel oxide, nickel oxide, sodium methylate, potassium methylate, sodium oxide, etc. Alcoholades such as ethylate and potassium ethylate, acetates such as sodium acetate and potassium acetate, and the like can be used. Among these catalysts, metal oxides are preferred, and oxides of metals in Group 1Ia of the periodic table, especially calcium oxide, are preferred. The amount of these catalysts is usually 1 to 30% relative to the compound represented by formula (1).
% by weight, preferably from 5 to 20% by weight. When the amount of the catalyst is less than 1% by weight, the production efficiency of the incyanate compound is low, and when it exceeds 30% by weight, it becomes difficult to heat and stir the reactants, and the amount of gel-like reaction products that are considered to have undergone a condensation reaction increases.
本発明の方法の第一段階である加熱工程において、加熱
温度は１５０〜３００℃、好ましくは、２００〜２５０
℃である。加熱温度が１５０ ℃以下であると、反応が
進行せず、３ｏｏ℃を超えると、副反応が起こり、ゲル
状物質となることがある。In the heating step, which is the first step of the method of the present invention, the heating temperature is 150 to 300°C, preferably 200 to 250°C.
It is ℃. If the heating temperature is below 150° C., the reaction will not proceed, and if it exceeds 30° C., side reactions may occur, resulting in a gel-like substance.
また、加熱時間は、０．５〜３時間、好ましくは、０．
５〜１．５時間である。加熱時間が０．５時間未満であ
ると、反応が進行せず、３時間を超えると副反応が起こ
り、ゲル状物質となることがある。The heating time is 0.5 to 3 hours, preferably 0.5 to 3 hours.
It is 5 to 1.5 hours. If the heating time is less than 0.5 hours, the reaction will not proceed, and if it exceeds 3 hours, side reactions may occur, resulting in a gel-like substance.
本発明の方法の第二段階である減圧蒸留工程において、
減圧度は１０−０．０１ｍｍＨｇ、好ましくは０、１−
トｍ＋＋＋Ｈｇテあり、減圧度カニ０ＩＩＩＩＨ８未
満であると、留出温度が上るため釜の温度をあげねばな
らず、このため原料がゲル化しゃすくなるという弊害が
生じ、０．０１ｍ＋ｍＨｇを超えると、蒸留生成物であ
るイソシアネート化合物に原料が混じり込むようになる
。In the vacuum distillation step, which is the second step of the method of the present invention,
The degree of reduced pressure is 10-0.01 mmHg, preferably 0, 1-
If the degree of vacuum is less than 0IIIH8, the distillation temperature will rise and the temperature of the pot will have to be raised, which will cause the disadvantage that the raw material will be more likely to gel.If it exceeds 0.01m+mHg, Raw materials become mixed into the isocyanate compound, which is a distillation product.
また、この工程では、加熱温度は１００〜２００℃、好
ましくは、１３０〜１７０ ℃であり、加熱温度が１０
０℃未満であると、反応物が留出せず、２００℃を超え
ると、重合物が生成して収率が低下する。In addition, in this step, the heating temperature is 100 to 200°C, preferably 130 to 170°C, and the heating temperature is 100 to 200°C, preferably 130 to 170°C.
If the temperature is less than 0°C, the reactant will not be distilled out, and if it exceeds 200°C, a polymer will be produced and the yield will be reduced.
尚、この工程の時間は１．０〜４．０時間である。Note that the time for this step is 1.0 to 4.0 hours.
本発明の方法は、通常、無溶媒で行なわれるが、反応に
不活性な溶媒を用いても良く、例えば、トルエン、キシ
レン、シクロヘキサン、デカリンを用いることができる
。The method of the present invention is usually carried out without a solvent, but a solvent inert to the reaction may be used, such as toluene, xylene, cyclohexane, and decalin.
本発明の方法において、上記操作を１回行なうことによ
って、目的物を得ることができるのであるが、１回目の
操作によって得られた留分を用いて上記操作を２回以上
繰り返すことによって、さらに高収率で高純度の目的物
を得ることができる。In the method of the present invention, the desired product can be obtained by performing the above operation once, but by repeating the above operation two or more times using the fraction obtained in the first operation, the desired product can be obtained. The desired product can be obtained in high yield and with high purity.
本発明の方法によって得られる式（２）で示されるアダ
マンタンのインシアネート化合物は、２゜４−ジイソシ
アナトトルエン、１．６−ジイソシアナトヘキサンと比
較して耐水性、耐薬品性、耐溶剤性及び耐光性等の優れ
た特性を有し、例えば、繊維、塗料、接着剤等に好適に
用いることができる。The adamantane incyanate compound represented by formula (2) obtained by the method of the present invention has better water resistance, chemical resistance, and resistance compared to 2゜4-diisocyanatotoluene and 1,6-diisocyanatohexane. It has excellent properties such as solvent resistance and light resistance, and can be suitably used for, for example, fibers, paints, adhesives, etc.
Ｕ実施例コ 以下、実施例を掲げて本発明をさらに詳細に説明する。U example Hereinafter, the present invention will be explained in more detail with reference to Examples.
（調製例）
１．３−ジ（メチルカルバミル）アダマンタンの合成
特公昭４４−２０３３８号に準じて合成した５０ｇの１
゜３−ジアミノアダマンタンの塩酸塩を１５％炭酸カリ
ウム水溶液５００＋Ｊｊ−塩化メチレン５００＋＋１に
溶解し、６５ｇのクロロ蟻酸メチルを滴下し３０”Ｃで
５時間攪拌した。得られた反応混合物の塩化メチレン層
を再結晶して、１，３−ジ（メチルカルバミル）アダマ
ンタン５１ｇを得た。融点は１４７〜１４８℃であった
。第１図に得られた１、３−ジ（メチルカルバミル）ア
ダマンタンの ＩＨ−ＮＭＲスペクトルを示す。尚、ス
ペクトルのピークの帰属は以下の通りである。(Preparation example) 1. Synthesis of 3-di(methylcarbamyl)adamantane 50g of 1 synthesized according to Japanese Patent Publication No. 20338/1973
゜3-Diaminoadamantane hydrochloride was dissolved in 15% potassium carbonate aqueous solution 500+Jj-methylene chloride 500++1, 65g of methyl chloroformate was added dropwise and stirred at 30"C for 5 hours. The methylene chloride layer of the resulting reaction mixture was dissolved. Recrystallization yielded 51 g of 1,3-di(methylcarbamyl)adamantane.The melting point was 147-148°C. An IH-NMR spectrum is shown.The peak assignments of the spectrum are as follows.
■ ３．６ｐｐ＋ｗ
■ ４．６８ｐｐｍ
■ ２．２４ｐｐｍ
尚、１．３ｐｐｍのピークはＣＤＣｌ３中の不純物によ
るものである。■ 3.6pp+w ■ 4.68ppm ■ 2.24ppm Note that the peak at 1.3ppm is due to impurities in CDCl3.
（実施例１）
調製例１で得られた１、３−ジ（メチルカルバミル）ア
ダマンタン５１ｇに１０ｇの酸化カルシウムを添加し、
アルゴンガス雰囲気下、２５０℃で加熱し、１．５時間
攪拌した。次いで、圧力０．５＋ｓｍＨｇ、反応容器の
温度１５０℃で３時間減圧蒸留を行なって、留分３５ｇ
を得た後、その留分に再度酸化カルシウム７ｇを加え、
２５０℃で１時間加熱後、圧力０．５ ＋ｕ＋Ｈｇ、反
応容器の温度１５０℃で３時間減圧蒸留を行なって、純
度９８％の１，３−ジイソシアナトアダマンタン２０ｇ
（収率４９％）を得た。(Example 1) 10 g of calcium oxide was added to 51 g of 1,3-di(methylcarbamyl)adamantane obtained in Preparation Example 1,
The mixture was heated at 250° C. and stirred for 1.5 hours under an argon gas atmosphere. Next, vacuum distillation was carried out for 3 hours at a pressure of 0.5+smHg and a reaction vessel temperature of 150°C to obtain 35g of distillate.
After obtaining, 7g of calcium oxide was added to the fraction again,
After heating at 250°C for 1 hour, vacuum distillation was performed for 3 hours at a pressure of 0.5 + U + Hg and a reaction vessel temperature of 150°C to obtain 20 g of 1,3-diisocyanatoadamantane with a purity of 98%.
(yield 49%).
尚、得られた蒸留物の沸点は０．５ｍｍＨｇで１０８℃
であった。第２図に１，３−ジイソシアナトアダマンタ
ンの ＩＨ−ＮＭＲスペクトルを示す。尚、ＩＨ−ＮＭ
Ｒスペクトルのピークの帰属は以下の通りである。The boiling point of the obtained distillate was 108°C at 0.5 mmHg.
Met. FIG. 2 shows the IH-NMR spectrum of 1,3-diisocyanatoadamantane. Furthermore, IH-NM
The peak assignments of the R spectrum are as follows.
■
■ １．５５ｐｐｍ
尚、ＣＤＣｌ ３中の不純物のピークが２．２５１１Ｐ
票に、微量に残存しているジイソシアネート化合物原料
のピークが３．７０ｐｐｍに認められる。また、ＫＢｒ
板上にサンプルを塗布して赤外吸収スペクトルを測定し
たところ、２，２５０ｃｍ−１にインシアネート基によ
る強い吸収が認められた。■ ■ 1.55ppm In addition, the peak of impurities in CDCl 3 is 2.2511P
In the chart, a peak of a trace amount of remaining diisocyanate compound raw material is observed at 3.70 ppm. Also, KBr
When a sample was applied on a plate and an infrared absorption spectrum was measured, strong absorption due to incyanate groups was observed at 2,250 cm-1.
（実施例２）
１．３−ジ（メチルカルバミル）アダマンタン２５ｇに
５．０ｇの酸化カルシウムを加え、アルゴンガス雰囲気
下２５０℃で１時間攪拌した。その後、直チニ圧力０．
５ｍｍＨｇ、反応容器の温度１５０”ｃ −１？ ３時
間減圧蒸留を行なって、１８．０ｇの留分を得た。その
留分をガスクロマトグラフィーで分析したところ１．３
−ジイソシアナトアダマンタン（６５薦ｏ１１）と１−
イソシアナト−３−（メチルカルバミル）アダマンタン
（３５ｍｏｌりとの混合物であった。(Example 2) 5.0 g of calcium oxide was added to 25 g of 1.3-di(methylcarbamyl)adamantane, and the mixture was stirred at 250° C. for 1 hour under an argon gas atmosphere. After that, the straight chini pressure is 0.
5 mmHg, reaction vessel temperature 150"c -1? Distillation under reduced pressure was carried out for 3 hours to obtain a fraction of 18.0 g. Analysis of the fraction by gas chromatography revealed that it was 1.3
-Diisocyanatoadamantane (65 recommendation o11) and 1-
It was a mixture with isocyanato-3-(methylcarbamyl)adamantane (35 mol).
比較例１
１．３−ジ（メチルカルバミル）アダマンタン１．６ｇ
を、触媒を用いることなく、アルゴンガス雰囲気下２５
０℃で１．５時間加熱攪拌後、圧力０．５厘畦ｇ、反応
容器の温度１５０℃で３時間減圧蒸留を行なったが、留
出成分は得られず、蒸留釜中には原料が残っているだけ
であった。Comparative Example 1 1.6 g of 1.3-di(methylcarbamyl)adamantane
under an argon gas atmosphere without using a catalyst for 25 minutes.
After heating and stirring at 0°C for 1.5 hours, vacuum distillation was carried out for 3 hours at a pressure of 0.5 mm and a reaction vessel temperature of 150°C, but no distillate components were obtained, and there was no raw material in the distillation vessel. There was only one left.
［発明の効果］
本発明の方法によれば、毒性のある原料を用いる必要が
ないので極めて安全であり、また特定の溶媒を用いて加
熱、減圧蒸留という簡単な操作によって、高収率で目的
物を得ることができ、その操作を繰り返すことによって
、ざらに高収率の目的物を得ることができる。[Effects of the Invention] The method of the present invention is extremely safe because it does not require the use of toxic raw materials, and can achieve the desired purpose in high yield by using a specific solvent, heating, and distillation under reduced pressure. By repeating the operation, the desired product can be obtained in a relatively high yield.
第１図は、本発明の１実施例である方法に用いられた原
料物質の ＩＨ−ＮＭＲスペクトルを示し、第２図は、
本発明の１実施例である方法によって得られた１、３−
ジイソシアナトアダマンタンの ＩＨ−ＮＭＲスペクト
ルを示すものである。
特許出願人 出光興産株式会社FIG. 1 shows an IH-NMR spectrum of a raw material used in a method that is an example of the present invention, and FIG.
1,3- obtained by a method that is an embodiment of the present invention
This shows an IH-NMR spectrum of diisocyanatoadamantane. Patent applicant Idemitsu Kosan Co., Ltd.
Claims (1)
〜３の整数であり、ｍは１〜４の整数であり、Ａｄはア
ダマンタン骨格を表わし、該骨格は炭素数１〜３の低級
アルキル基、アリル基、アラルキル基、アルキルアリル
基、低級アルコキシ基で置換されていてもよい。） で表されるアダマンタン化合物を、塩基性触媒の存在下
で加熱、減圧蒸留して、 式（２）： Ａｄ［（ＣＨ＿２）＿ｎＮＣＯ］＿ｍ（２） （式中、ｎ、ｍおよびＡｄは前記と同じ意味を有する。 ） で表わされるイソシアネート化合物を製造することを特
徴とするイソシアネート化合物の製造方法。(1) Following formula (1): Ad[(CH_2)_nNHCOOR]_m(1) (wherein, R is an alkyl group having 1 to 3 carbon atoms, and n is 0
m is an integer of 1 to 4, Ad represents an adamantane skeleton, and the skeleton is a lower alkyl group having 1 to 3 carbon atoms, an allyl group, an aralkyl group, an alkylaryl group, or a lower alkoxy group. may be replaced with . ) is heated and distilled under reduced pressure in the presence of a basic catalyst to obtain the formula (2): Ad[(CH_2)_nNCO]_m(2) (where n, m and Ad are the above-mentioned 1. A method for producing an isocyanate compound, the method comprising producing an isocyanate compound represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63004442A JP2796714B2 (en) | 1988-01-12 | 1988-01-12 | Method for producing isocyanate compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63004442A JP2796714B2 (en) | 1988-01-12 | 1988-01-12 | Method for producing isocyanate compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01180864A true JPH01180864A (en) | 1989-07-18 |
| JP2796714B2 JP2796714B2 (en) | 1998-09-10 |
Family
ID=11584320
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63004442A Expired - Fee Related JP2796714B2 (en) | 1988-01-12 | 1988-01-12 | Method for producing isocyanate compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2796714B2 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5446761A (en) * | 1977-09-21 | 1979-04-12 | Idemitsu Kosan Co Ltd | Preparation of n-adamantylcarbamate ester analog |
| JPS5488201A (en) * | 1977-12-22 | 1979-07-13 | Mitsubishi Chem Ind Ltd | Preparation of isocyanate from carbamic acid esters |
-
1988
- 1988-01-12 JP JP63004442A patent/JP2796714B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5446761A (en) * | 1977-09-21 | 1979-04-12 | Idemitsu Kosan Co Ltd | Preparation of n-adamantylcarbamate ester analog |
| JPS5488201A (en) * | 1977-12-22 | 1979-07-13 | Mitsubishi Chem Ind Ltd | Preparation of isocyanate from carbamic acid esters |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2796714B2 (en) | 1998-09-10 |
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