JPH0710838B2 - Method for producing 3,4,5,6-tetrahydrophthalimide - Google Patents
Method for producing 3,4,5,6-tetrahydrophthalimideInfo
- Publication number
- JPH0710838B2 JPH0710838B2 JP1123500A JP12350089A JPH0710838B2 JP H0710838 B2 JPH0710838 B2 JP H0710838B2 JP 1123500 A JP1123500 A JP 1123500A JP 12350089 A JP12350089 A JP 12350089A JP H0710838 B2 JPH0710838 B2 JP H0710838B2
- Authority
- JP
- Japan
- Prior art keywords
- anhydride
- group
- thpi
- producing
- reaction
- 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.)
- Expired - Fee Related
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- AFJWMGOTLUUGHF-UHFFFAOYSA-N 4,5,6,7-tetrahydroisoindole-1,3-dione Chemical compound C1CCCC2=C1C(=O)NC2=O AFJWMGOTLUUGHF-UHFFFAOYSA-N 0.000 title claims description 5
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- 229930195733 hydrocarbon Natural products 0.000 claims description 15
- -1 alicyclic hydrocarbons Chemical class 0.000 claims description 12
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000012429 reaction media Substances 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- HMMBJOWWRLZEMI-UHFFFAOYSA-N 4,5,6,7-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CCCC2=C1C(=O)OC2=O HMMBJOWWRLZEMI-UHFFFAOYSA-N 0.000 claims description 6
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 claims description 5
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 19
- 150000002430 hydrocarbons Chemical class 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 238000009835 boiling Methods 0.000 description 10
- 230000005484 gravity Effects 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 5
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- 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 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KMOUUZVZFBCRAM-UHFFFAOYSA-N 1,2,3,6-tetrahydrophthalic anhydride Chemical compound C1C=CCC2C(=O)OC(=O)C21 KMOUUZVZFBCRAM-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- QDTDKYHPHANITQ-UHFFFAOYSA-N 7-methyloctan-1-ol Chemical compound CC(C)CCCCCCO QDTDKYHPHANITQ-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004439 Isononyl alcohol Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Indole Compounds (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、工業的に優れた3,4,5,6−テトラヒドロフタ
ルイミド（以下「Δ１−THPI」という。）の製造方法に
関する。TECHNICAL FIELD The present invention relates to an industrially excellent method for producing 3,4,5,6-tetrahydrophthalimide (hereinafter referred to as “Δ 1 -THPI”).
［従来の技術］ Δ１−THPIは、殺虫剤、除草剤等の農薬の中間体として
有用な工業材料である。[Prior Art] [Delta] 1- THPI is an industrial material useful as an intermediate for agricultural chemicals such as insecticides and herbicides.
このものの製造方法として、これまでに、例えば以下の
方法が知られている。For example, the following method has been known as a method for manufacturing this product.
（１）3,4,5,6−テトラヒドロフタル酸無水物（以下
「Δ１−THPA」という。）と尿素とを155〜160℃に加熱
して得られるΔ１−THPIをベンゼンで再結晶して分離す
る方法（J.Chem.Soc.,4846,（1952））。(1) Recrystallization of Δ 1 -THPI obtained by heating 3,4,5,6-tetrahydrophthalic anhydride (hereinafter referred to as “Δ 1 -THPA”) and urea to 155 to 160 ° C. with benzene. Separation method (J. Chem. Soc., 4846, (1952)).
（２）Δ１−THPAとアンモニア水とを110〜160℃の温度
条件下で反応させる方法（USSR.化学薬学ジャーナル，
［３］,28（1969））。(2) A method of reacting Δ 1 -THPA with aqueous ammonia under the temperature condition of 110 to 160 ° C. (USSR.
[3], 28 (1969)).
（３）Δ１−THPAとアンモニアガスとを145〜152℃の温
度条件下で反応させる方法（ソ連国発明者証第859,363
号）。(3) Method of reacting Δ 1 -THPA and ammonia gas under a temperature condition of 145 to 152 ° C. (Soviet inventor certificate No. 859,363
issue).
しかしながら、上記の各製造方法において高純度、高収
率でΔ１−THPIを得るためには、高純度のΔ１−THPAを
原料として用いなければならない。However, in order to obtain Δ 1 -THPI with high purity and high yield in each of the above production methods, high purity Δ 1 -THPA must be used as a raw material.
一方、本発明者らは、先に1,2,3,6−テトラヒドロ無水
フタル酸（以下「Δ４−THPA」という。）を異性化する
方法を提案した（特公昭58−54144号、特公昭58−54148
号）。On the other hand, the present inventors have previously 1,2,3,6-tetrahydrophthalic anhydride (hereinafter referred to as "Δ 4 -THPA".) The proposed method of isomerization (JP-B-58-54144, JP Kosho 58-54148
issue).
これらの方法は、工業的に優れたΔ１−THPAの製造方法
ではあるが、通常、生成物中にはヘキサヒドロ無水フタ
ル酸、無水フタル酸及びΔ４−THPA等のΔ１−THPAの構
造異性体等（以下、総称して「混在無水フタル酸類」と
いう。）が約１〜10％程度混在する。Although these methods are industrially excellent methods for producing Δ 1 -THPA, the products are usually structural isomers of Δ 1 -THPA such as hexahydrophthalic anhydride, phthalic anhydride and Δ 4 -THPA. Body etc. (hereinafter collectively referred to as "mixed phthalic anhydrides") are mixed in about 1 to 10%.
斯かるΔ１−THPAを主成分とし、混在無水フタル酸類を
含有するカルボン酸無水物に対し、従来の方法に従って
アンモニアを作用させた場合、上記の混在無水フタル酸
類も同時にイミド化される。これらのイミド化物は容易
に分離することができないため、別途、精製工程をとら
なくてはならず、結果として高純度のΔ１−THPIを収率
よく得ることができない。When ammonia is allowed to act on a carboxylic acid anhydride containing Δ 1 -THPA as a main component and containing mixed phthalic anhydrides according to a conventional method, the mixed phthalic anhydrides are simultaneously imidized. Since these imidized products cannot be easily separated, a separate purification step must be taken, and as a result, highly pure Δ 1 -THPI cannot be obtained in good yield.
［発明が解決しようとする課題］ 本発明者らは、従来の方法の如く、原料としてΔ１−TH
PAの精製物を用いなくとも高純度のΔ１−THPIを収率よ
く得ることができる工業的に優れた方法を提案すべく鋭
意検討の結果、 （１）アンモニアによるイミド化の条件下において、混
在無水フタル酸類は、酸無水物よりもモノエステル化物
が安定であるためイミド化されにくく、他方、Δ１−TH
PAでは、酸無水物のみならずそのモノエステル化物であ
っても容易にイミド化されること、 （２）そのため、原料がΔ１−THPA粗物であっても、こ
れをイミド化に先立ってモノエステル化工程を経ること
により原料中、Δ１−THPAのみが選択的にイミド化され
ること、 （３）更に、反応媒体として反応基質及びΔ１−THPIに
不活性な特定の炭化水素を適用することにより、生成し
たΔ１−THPIは、特別に再結晶等の精製工程を経ること
なく混在する上記モノエステル化物と容易に分離でき、
高純度のΔ１−THPIを収率よく回収できること、 を見い出し、斯かる知見に基づいて本発明を完成するに
至った。[Problems to be Solved by the Invention] The present inventors use Δ 1 -TH as a raw material as in the conventional method.
As a result of diligent studies to propose an industrially excellent method capable of obtaining highly purified Δ 1 -THPI in a high yield without using a purified product of PA, (1) under conditions of imidization with ammonia, The mixed phthalic anhydrides are less likely to be imidized because the monoester compound is more stable than the acid anhydride, while Δ 1 -TH
In PA, not only the acid anhydride but also its monoester compound can be easily imidized. (2) Therefore, even if the raw material is a Δ 1 -THPA crude product, it can be imidized prior to imidization. Only Δ 1 -THPA is selectively imidized in the raw material through the monoesterification step. (3) Furthermore, a reaction substrate and a specific hydrocarbon inert to Δ 1 -THPI are used as a reaction medium. By applying it, the produced Δ 1 -THPI can be easily separated from the mixed monoester compound without undergoing a purification step such as recrystallization.
It was found that high-purity Δ 1 -THPI can be recovered in good yield, and the present invention has been completed based on such findings.
即ち、本発明は、工業的に優れた高純度のΔ１−THPIの
製造方法を提供することを目的とする。That is, an object of the present invention is to provide an industrially excellent method for producing highly pure Δ 1 -THPI.
［課題を解決するための手段］ 本発明に係るΔ１−THPIの製造方法は、 （１）無水フタル酸、ヘキサヒドロ無水フタル酸及び3,
4,5,6−テトラヒドロ無水フタル酸の構造異性体からな
る群より選ばれる１種又は２種以上のカルボン酸無水物
（Ａ）を含有する3,4,5,6−テトラヒドロ無水フタル酸
粗物を原料とし、 （２）一般式（Ｉ）で表わされるアルコールにより少な
くとも上記カルボン酸無水物（Ａ）をモノエステル化
し、 Ｒ（OH）ｎ （Ｉ） ［式中、Ｒは炭素数１〜22のアルキル基、アルケニル
基、アリール基、アラルキル基又は脂環式炭化水素基を
表わし、ｎは１〜３の整数を表わす。］ （３）次いで3,4,5,6−テトラヒドロ無水フタル酸及び
／又はそのモノエステル化物をアンモニアでイミド化す
ることを特徴とする。[Means for Solving the Problems] The method for producing Δ 1 -THPI according to the present invention includes (1) phthalic anhydride, hexahydrophthalic anhydride, and 3,
Crude 3,4,5,6-tetrahydrophthalic anhydride containing one or more carboxylic acid anhydrides (A) selected from the group consisting of structural isomers of 4,5,6-tetrahydrophthalic anhydride (2) at least the above carboxylic acid anhydride (A) is monoesterified with an alcohol represented by the general formula (I) to obtain R (OH) n (I) [wherein R represents a carbon number of 1 to 1; 22 represents an alkyl group, an alkenyl group, an aryl group, an aralkyl group or an alicyclic hydrocarbon group, and n represents an integer of 1 to 3. ] (3) Then, 3,4,5,6-tetrahydrophthalic anhydride and / or its monoester product is imidized with ammonia.
本発明において許容される混在無水フタル酸類の量は、
所定の効果を奏する限り特に限定されるものではない
が、通常、Δ１−THPAと混在無水フタル酸（以下、総称
して「原料無水フタル酸類」という。）に対し１〜20重
量％程度、より工業的な原料組成としては３〜15重量％
程度である。The amount of mixed phthalic anhydrides allowable in the present invention is
It is not particularly limited as long as it has a predetermined effect, but is usually about 1 to 20% by weight based on Δ 1 -THPA and phthalic anhydride mixed (hereinafter collectively referred to as “raw material phthalic anhydrides”), 3 to 15% by weight for a more industrial raw material composition
It is a degree.
一般式（Ｉ）で表わされるアルコールの種類は、少なく
とも混在無水フタル酸類と反応して相当するモノエステ
ルを形成し得、当該モノエステル化物がイミド化反応中
においてその構造を保持することにより所定の効果を奏
するものである限り特に限定されるものではない。具体
的には、以下のアルコールが例示され、これらは単独で
又は２種以上の混合物で用いられる。The type of alcohol represented by the general formula (I) is capable of reacting with at least mixed phthalic anhydrides to form a corresponding monoester, and the monoester product retains its structure during the imidization reaction, so that a predetermined monoester can be obtained. It is not particularly limited as long as it has an effect. Specifically, the following alcohols are exemplified, and these are used alone or in a mixture of two or more kinds.
（１）炭素数１〜22の直鎖状又は分岐鎖状の脂肪族飽和
若しくは脂肪族不飽和アルコール、 斯かるアルコールとしては、一般式（Ｉ）におけるＲと
して、メチル、エチル、プロピル、ｎ−ブチル、イソブ
チル、アミル、ヘキシル、ヘプチル、ｎ−オクチル、２
−エチルヘキシル、イソオクチル、イソノニル、ｎ−デ
シル、イソデシル、ウンデシル、ドデシル、トリデシ
ル、ミリスチル、セチル、ステアリル、ベヘニル、アリ
ル、オレイル等の各基を有する各種のアルコール、 （２）ベンジルアルコール等の芳香族アルコール、 （３）シクロヘキシルアルコール等の脂環式アルコー
ル、 （４）エチレングリコール、プロピレングリコール、グ
リセリン等の多価アルコール。(1) a straight-chain or branched-chain aliphatic saturated or aliphatic unsaturated alcohol having 1 to 22 carbon atoms, and as such an alcohol, R in the general formula (I) is methyl, ethyl, propyl, n- Butyl, isobutyl, amyl, hexyl, heptyl, n-octyl, 2
-Ethylhexyl, isooctyl, isononyl, n-decyl, isodecyl, undecyl, dodecyl, tridecyl, myristyl, cetyl, various alcohols having groups such as stearyl, behenyl, allyl, oleyl, and (2) aromatic alcohols such as benzyl alcohol (3) Alicyclic alcohols such as cyclohexyl alcohol, (4) Polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin.
なかでも、沸点が120℃以上のアルコールが、後のイミ
ド反応の進行上好ましい。Of these, alcohols having a boiling point of 120 ° C. or higher are preferable in terms of the progress of the subsequent imide reaction.
当該アルコールの適用量は、少なくとも混在無水フタル
酸類をモノエステル化するに足る量であればよく、より
工業的な面で好ましくは原料無水フタル酸類１モルに対
して0.1〜20モル程度、好ましくは0.5〜10モルである。The applied amount of the alcohol may be at least an amount enough to monoesterify the mixed phthalic anhydrides, and from a more industrial viewpoint, it is preferably about 0.1 to 20 mols, preferably 1 mol of the phthalic anhydrides. It is 0.5 to 10 mol.
原料無水フタル酸類は、上記アルコールの存在下、好ま
しくは窒素ガス等の不活性ガスの雰囲気下で、通常、60
〜140℃程度に加熱することにより溶解し、少なくとも
混在無水フタル酸類は容易に相当するモノエステルとな
る。The raw material phthalic anhydride is usually 60% in the presence of the above alcohol, preferably in an atmosphere of an inert gas such as nitrogen gas.
It dissolves when heated to about 140 ° C, and at least the mixed phthalic anhydride easily becomes the corresponding monoester.
上記モノエステル化反応に引続いて行なわれるイミド化
反応は、好ましくは反応基質及びΔ１−THPIに不活性な
特定の炭化水素類を反応媒体とし、アンモニアを徐々に
添加しながら、攪拌下、加熱することにより効率よく進
行する。The imidization reaction carried out subsequent to the above monoesterification reaction is preferably carried out by using a reaction substrate and a specific hydrocarbon inert to Δ 1 -THPI as a reaction medium, while gradually adding ammonia, while stirring, By heating, it progresses efficiently.
上記反応において推奨される炭化水素類としては、炭素
数６〜16の脂肪族炭化水素、脂環式炭化水素及び芳香族
炭化水素等の炭化水素類が挙げられ、これらは単独で又
は２種以上混合して用いられる。The hydrocarbons recommended in the above reaction include hydrocarbons such as aliphatic hydrocarbons having 6 to 16 carbon atoms, alicyclic hydrocarbons and aromatic hydrocarbons, which may be used alone or in combination of two or more. Used as a mixture.
当該化合物として、具体的にはヘキサン、ヘプタン、オ
クタン、デカン、ドデカン、シクロヘキサン、デカリ
ン、テトラリン、トルエン、キシレン及び石油精製の際
に得られる混合炭化水素等が例示される。特にイミド化
反応の進行上、140℃以上の沸点を有する化合物が好ま
しく、なかでもドデカン、デカリン、パラフィン−ナフ
テン系混合炭化水素が好ましい。Specific examples of the compound include hexane, heptane, octane, decane, dodecane, cyclohexane, decalin, tetralin, toluene, xylene, and mixed hydrocarbons obtained during petroleum refining. In particular, a compound having a boiling point of 140 ° C. or higher is preferable, and dodecane, decalin, and a paraffin-naphthene mixed hydrocarbon are particularly preferable in terms of the progress of imidization reaction.
反応媒体の添加量は、所定のイミド化反応が進行する限
り特に限定されるものではないが、通常、当該炭化水素
類と上記アルコール類の総量が、原料無水フタル酸類に
対して25〜250重量％の範囲内、好ましくは50〜200重量
％で用いられる。The addition amount of the reaction medium is not particularly limited as long as the predetermined imidization reaction proceeds, but usually the total amount of the hydrocarbons and the alcohols is 25 to 250 wt% relative to the raw material phthalic anhydride. %, Preferably 50 to 200% by weight.
この炭化水素類は、原料無水フタル酸類の前記モノエス
テル化の段階で存在せしめても差し支えない。The hydrocarbons may be present in the stage of the monoesterification of the raw material phthalic anhydride.
イミド化反応に供されるアンモニア源の形態としては、
気体状又は水溶液のいずれも採用できるが、取扱い上簡
便なアンモニア水を用いることが、工業上好ましい。As the form of the ammonia source used for the imidization reaction,
Although either gaseous or aqueous solution can be adopted, it is industrially preferable to use ammonia water which is easy to handle.
このアンモニア水は、10〜35重量％程度、好ましくは20
〜30重量％の濃度で用いられる。This ammonia water is about 10 to 35% by weight, preferably 20
Used at a concentration of ~ 30% by weight.
又、アンモニアの適用量は、Δ１−THPAに対し、1.01〜
2.5倍モル程度であり、これ以上添加しても特に有意差
は認められない。Also, application of ammonia, relative to Δ 1 -THPA, 1.01~
It is about 2.5 times the molar amount, and no significant difference is observed even if added more than this.
アンモニア水の添加方法としては、所定量を一括して添
加するよりも反応中において徐々に添加する方が目的物
の収率向上を図る上で好ましい。As a method of adding ammonia water, it is preferable to gradually add it during the reaction rather than to add a predetermined amount all at once, in order to improve the yield of the target product.
反応温度としては、100〜160℃程度、好ましくは120〜1
40℃が適用される。The reaction temperature is about 100 to 160 ° C, preferably 120 to 1
40 ° C is applied.
イミド化反応は、通常、常圧下で行なわれるが、反応系
より水を留去し得る限りは減圧下でも加圧下でも差し支
えない。The imidization reaction is usually carried out under normal pressure, but it may be under reduced pressure or under pressure as long as water can be distilled off from the reaction system.
斯かるイミド化反応は、通常２〜10時間程度で完結す
る。Such imidization reaction is usually completed in about 2 to 10 hours.
尚、イミド化反応は、窒素ガス等の不活性ガス雰囲気下
で行なうのが好ましい。The imidization reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen gas.
本発明に係るΔ１−THPIの製造方法は、回分式のみなら
ず、連続的製造方法としても適用できる。The manufacturing method of Δ 1 -THPI according to the present invention can be applied not only as a batch method but also as a continuous manufacturing method.
［実施例］ 以下に実施例を掲げ、本発明を詳しく説明する。[Examples] The present invention will be described in detail below with reference to Examples.
実施例１ 攪拌機、冷却器付きデカンター、温度計、窒素ガス導入
管及びアンモニア水添加装置を備えた１４ツ口フラス
コに、次の組成（GLCによる）を有する原料無水フタル
酸類152g（１モル）、 Δ１−THPA 90重量％ ヘキサヒドロ無水フタル酸 3 無水フタル酸 1 Δ１−THPA構造異性体 2 その他 4 ２−エチルヘキサノール（沸点:184℃、比重:0.834［20
℃］）200ml及びパラフィン−ナフテン系混合物（沸点:
163〜194℃、比重:0.770［15℃］、以下「石油系混合炭
化水素」という。）200mlを仕込み、攪拌下に加熱溶解
した後、120℃で28重量％のアンモニア水121g（2.0モ
ル）を3.5時間にわたって添加しながら水を系外に留去
し、イミド化を行なった。反応終了後、冷却し、濾過、
乾燥して純度99.9％のΔ１−THPIを96％の対理論収率で
得た。Example 1 In a 14-necked flask equipped with a stirrer, a decanter with a cooler, a thermometer, a nitrogen gas introduction tube and an ammonia water addition device, 152 g (1 mol) of a raw material phthalic anhydride having the following composition (according to GLC), Δ 1- THPA 90 wt% Hexahydrophthalic anhydride 3 Phthalic anhydride 1 Δ 1- THPA structural isomer 2 Other 4 2-Ethylhexanol (boiling point: 184 ° C, specific gravity: 0.834 [20
200 ml) and a paraffin-naphthene mixture (boiling point:
163-194 ℃, specific gravity: 0.770 [15 ℃], hereinafter referred to as "petroleum-based mixed hydrocarbons". ) 200 ml was charged and dissolved by heating under stirring, and then 121 g (2.0 mol) of 28% by weight ammonia water was added at 120 ° C. over 3.5 hours to distill the water out of the system for imidization. After completion of the reaction, cooling, filtration,
After drying, Δ 1 -THPI having a purity of 99.9% was obtained with a theoretical yield of 96%.
実施例２ アルコールとしてイソノニルアルコール（沸点:198〜20
5℃、比重:0.834［20℃］）200mlを、反応媒体としてデ
カリン（沸点:196℃、比重:0.897［20℃］）200mlを使
用し、反応温度として130℃を適用した以外は実施例１
に準じてΔ１−THPIを調製したところ、純度99.8％の目
的物が対理論収率95％で得られた。Example 2 Isononyl alcohol (boiling point: 198-20 as alcohol)
Example 1 except that 200 ml of 5 ° C., specific gravity: 0.834 [20 ° C.]), 200 ml of decalin (boiling point: 196 ° C., specific gravity: 0.897 [20 ° C.]) were used as the reaction medium, and 130 ° C. was applied as the reaction temperature.
When Δ 1 -THPI was prepared according to the above procedure, the desired product with a purity of 99.8% was obtained with a theoretical yield of 95%.
実施例３ アルコールとしてｎ−ブチルアルコール（沸点:117℃、
比重:0.810［20℃］）50mlを、反応媒体として石油系混
合炭化水素250mlを使用した以外は実施例１に準じてΔ
１−THPIを調製したところ、純度99.7％の目的物が対理
論収率95％で得られた。Example 3 As an alcohol, n-butyl alcohol (boiling point: 117 ° C.,
(Specific gravity: 0.810 [20 ° C.]) 50 ml and Δ in accordance with Example 1 except that 250 ml of petroleum mixed hydrocarbon was used as the reaction medium.
When 1- THPI was prepared, the target product with a purity of 99.7% was obtained with a theoretical yield of 95%.
実施例４ アルコールとしてデシルアルコール（沸点:232℃、比
重:0.830［20℃］）200mlを、反応媒体としてドデカン
（沸点:214℃、比重:0.751［20℃］）200mlを使用した
以外は実施例１に準じてΔ１−THPIを調製したところ、
準度99.8％の目的物が対理論収率96％で得られた。Example 4 Example except that 200 ml of decyl alcohol (boiling point: 232 ° C., specific gravity: 0.830 [20 ° C.]) was used as alcohol, and 200 ml of dodecane (boiling point: 214 ° C., specific gravity: 0.751 [20 ° C.]) was used as a reaction medium. When Δ 1 -THPI was prepared according to 1 ,
The target product with a degree of substandard of 99.8% was obtained with a theoretical yield of 96%.
実施例５ アルコールとしてプロピレングリコール（沸点:187℃、
比重:1.038［20℃］）100mlを、反応媒体として石油系
混合炭化水素300mlを使用した以外は実施例１に準じて
Δ１−THPIを調製したところ、純度99.9％の目的物が対
理論収率96％で得られた。Example 5 Propylene glycol as an alcohol (boiling point: 187 ° C.,
(Specific gravity: 1.038 [20 ° C]) 100 ml and Δ 1 -THPI was prepared according to Example 1 except that 300 ml of petroleum mixed hydrocarbon was used as the reaction medium. It was obtained at a rate of 96%.
実施例６ 石油系混合炭化水素を用いずに２−エチルヘキサノール
300mlを使用した以外は実施例１に準じてΔ１−THPIを
調製したところ、純度99.8％の目的物が対理論収率86％
で得られた。Example 6 2-Ethylhexanol Without Using Petroleum Mixed Hydrocarbon
When Δ 1 -THPI was prepared according to Example 1 except that 300 ml was used, the target product with a purity of 99.8% was 86% based on the theoretical yield.
Obtained in.
実施例７ 原料無水フタル酸類を次の組成（GLCによる）に代えた
以外は実施例１に準じてΔ１−THPIを調製したところ、
純度99.9％の目的物が対理論収率96％で得られた。Example 7 When Δ 1 -THPI was prepared according to Example 1 except that the raw material phthalic anhydride was changed to the following composition (according to GLC),
The target product with a purity of 99.9% was obtained with a theoretical yield of 96%.
Δ１−THPA 87重量％ ヘキサヒドロ無水フタル酸 6 無水フタル酸 3 Δ１−THPA構造異性体 1 その他 3 比較例１ アルコールを用いずに、反応媒体としての石油系混合炭
化水素を400ml使用した以外は実施例１に準じてΔ１−T
HPIを調製したところ、純度92.1％の目的物が対理論収
率108％で得られた。Δ 1 -THPA 87 wt% Hexahydrophthalic anhydride 6 Phthalic anhydride 3 Δ 1 -THPA structural isomer 1 Other 3 Comparative example 1 Except that 400 ml of petroleum mixed hydrocarbon was used as a reaction medium without using alcohol. Δ 1 −T according to Example 1
When HPI was prepared, the target compound with a purity of 92.1% was obtained with a theoretical yield of 108%.
［発明の効果］ 本発明に係る製造方法を適用することにより、反応基
質、反応生成物に対し何らの精製手段をとることなく、
簡便に、高純度のΔ１−THPIを高収率で調製することが
できる。[Effects of the Invention] By applying the production method according to the present invention, without taking any purification means for the reaction substrate and the reaction product,
High-purity Δ 1 -THPI can be easily prepared in high yield.
Claims (2)
ンモニアでイミド化して3,4,5,6−テトラヒドロフタル
イミドを製造するに際し、 （１）無水フタル酸、ヘキサヒドロ無水フタル酸及び3,
4,5,6−テトラヒドロ無水フタル酸の構造異性体からな
る群より選ばれる１種又は２種以上のカルボン酸無水物
（Ａ）を含有する3,4,5,6−テトラヒドロ無水フタル酸
粗物を原料とし、 （２）一般式（Ｉ）で表わされるアルコールにより少な
くとも上記カルボン酸無水物（Ａ）をモノエステル化
し、 Ｒ（OH）ｎ （Ｉ） ［式中、Ｒは炭素数１〜22のアルキル基、アルケニル
基、アリール基、アラルキル基又は脂環式炭化水素基を
表わし、ｎは１〜３の整数を表わす。］ （３）次いで3,4,5,6−テトラヒドロ無水フタル酸及び
／又はそのモノエステル化物をアンモニアでイミド化す
ることを特徴とする3,4,5,6−テトラヒドロフタルイミ
ドの製造方法。1. When producing 3,4,5,6-tetrahydrophthalimide by imidizing 3,4,5,6-tetrahydrophthalic anhydride with ammonia, (1) phthalic anhydride, hexahydrophthalic anhydride and 3,
Crude 3,4,5,6-tetrahydrophthalic anhydride containing one or more carboxylic acid anhydrides (A) selected from the group consisting of structural isomers of 4,5,6-tetrahydrophthalic anhydride (2) at least the above carboxylic acid anhydride (A) is monoesterified with an alcohol represented by the general formula (I) to obtain R (OH) n (I) [wherein R represents a carbon number of 1 to 1; 22 represents an alkyl group, an alkenyl group, an aryl group, an aralkyl group or an alicyclic hydrocarbon group, and n represents an integer of 1 to 3. (3) Next, a method for producing 3,4,5,6-tetrahydrophthalimide, which comprises imidizing 3,4,5,6-tetrahydrophthalic anhydride and / or its monoester product with ammonia.
化水素、脂環式炭化水素及び芳香族炭化水素からなる群
より選ばれる１種又は２種以上の化合物を適用すること
を特徴とする請求項１記載の3,4,5,6−テトラヒドロフ
タルイミドの製造方法。2. A reaction medium comprising one or more compounds selected from the group consisting of aliphatic hydrocarbons having 6 to 16 carbon atoms, alicyclic hydrocarbons and aromatic hydrocarbons. The method for producing 3,4,5,6-tetrahydrophthalimide according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1123500A JPH0710838B2 (en) | 1989-05-17 | 1989-05-17 | Method for producing 3,4,5,6-tetrahydrophthalimide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1123500A JPH0710838B2 (en) | 1989-05-17 | 1989-05-17 | Method for producing 3,4,5,6-tetrahydrophthalimide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02304062A JPH02304062A (en) | 1990-12-17 |
| JPH0710838B2 true JPH0710838B2 (en) | 1995-02-08 |
Family
ID=14862159
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1123500A Expired - Fee Related JPH0710838B2 (en) | 1989-05-17 | 1989-05-17 | Method for producing 3,4,5,6-tetrahydrophthalimide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0710838B2 (en) |
-
1989
- 1989-05-17 JP JP1123500A patent/JPH0710838B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02304062A (en) | 1990-12-17 |
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