JPS6332063B2 - - Google Patents
Info
- Publication number
- JPS6332063B2 JPS6332063B2 JP15786880A JP15786880A JPS6332063B2 JP S6332063 B2 JPS6332063 B2 JP S6332063B2 JP 15786880 A JP15786880 A JP 15786880A JP 15786880 A JP15786880 A JP 15786880A JP S6332063 B2 JPS6332063 B2 JP S6332063B2
- Authority
- JP
- Japan
- Prior art keywords
- bis
- group
- aminobenzoic acid
- present
- general formula
- 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
Links
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 14
- 229960004050 aminobenzoic acid Drugs 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 4
- -1 phenylenedioxy group Chemical group 0.000 claims description 4
- 229940064734 aminobenzoate Drugs 0.000 claims description 3
- 238000000034 method Methods 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical class NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000005277 alkyl imino group Chemical group 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 125000004434 sulfur atom Chemical group 0.000 description 3
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 2
- ZNSMNVMLTJELDZ-UHFFFAOYSA-N Bis(2-chloroethyl)ether Chemical compound ClCCOCCCl ZNSMNVMLTJELDZ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 235000002597 Solanum melongena Nutrition 0.000 description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 description 2
- 150000005415 aminobenzoic acids Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 239000012454 non-polar solvent Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- KYXVBVSREIBNDA-UHFFFAOYSA-N 1,2-bis(2-chloroethoxy)benzene Chemical compound ClCCOC1=CC=CC=C1OCCCl KYXVBVSREIBNDA-UHFFFAOYSA-N 0.000 description 1
- AGYUOJIYYGGHKV-UHFFFAOYSA-N 1,2-bis(2-chloroethoxy)ethane Chemical compound ClCCOCCOCCCl AGYUOJIYYGGHKV-UHFFFAOYSA-N 0.000 description 1
- FMGGHNGKHRCJLL-UHFFFAOYSA-N 1,2-bis(chloromethyl)benzene Chemical compound ClCC1=CC=CC=C1CCl FMGGHNGKHRCJLL-UHFFFAOYSA-N 0.000 description 1
- VVQCLPAXTIKHQZ-UHFFFAOYSA-N 1,3-bis(2-chloroethoxy)benzene Chemical compound ClCCOC1=CC=CC(OCCCl)=C1 VVQCLPAXTIKHQZ-UHFFFAOYSA-N 0.000 description 1
- GRJWOKACBGZOKT-UHFFFAOYSA-N 1,3-bis(chloromethyl)benzene Chemical compound ClCC1=CC=CC(CCl)=C1 GRJWOKACBGZOKT-UHFFFAOYSA-N 0.000 description 1
- DKPKDJGAQOVXJC-UHFFFAOYSA-N 1,4-bis(2-chloroethoxy)benzene Chemical compound ClCCOC1=CC=C(OCCCl)C=C1 DKPKDJGAQOVXJC-UHFFFAOYSA-N 0.000 description 1
- ZZHIDJWUJRKHGX-UHFFFAOYSA-N 1,4-bis(chloromethyl)benzene Chemical compound ClCC1=CC=C(CCl)C=C1 ZZHIDJWUJRKHGX-UHFFFAOYSA-N 0.000 description 1
- ZCFRYTWBXNQVOW-UHFFFAOYSA-N 1-(2-chloroethoxy)-2-[2-(2-chloroethoxy)ethoxy]ethane Chemical compound ClCCOCCOCCOCCCl ZCFRYTWBXNQVOW-UHFFFAOYSA-N 0.000 description 1
- FOZVXADQAHVUSV-UHFFFAOYSA-N 1-bromo-2-(2-bromoethoxy)ethane Chemical compound BrCCOCCBr FOZVXADQAHVUSV-UHFFFAOYSA-N 0.000 description 1
- IBSQPLPBRSHTTG-UHFFFAOYSA-N 1-chloro-2-methylbenzene Chemical compound CC1=CC=CC=C1Cl IBSQPLPBRSHTTG-UHFFFAOYSA-N 0.000 description 1
- OSOUNOBYRMOXQQ-UHFFFAOYSA-N 1-chloro-3-methylbenzene Chemical compound CC1=CC=CC(Cl)=C1 OSOUNOBYRMOXQQ-UHFFFAOYSA-N 0.000 description 1
- ZBUIOKOKFSYRFY-UHFFFAOYSA-N 2-[2-(4-aminobenzoyl)oxyethoxy]ethyl 4-aminobenzoate Chemical compound C1=CC(N)=CC=C1C(=O)OCCOCCOC(=O)C1=CC=C(N)C=C1 ZBUIOKOKFSYRFY-UHFFFAOYSA-N 0.000 description 1
- AJHPGXZOIAYYDW-UHFFFAOYSA-N 3-(2-cyanophenyl)-2-[(2-methylpropan-2-yl)oxycarbonylamino]propanoic acid Chemical compound CC(C)(C)OC(=O)NC(C(O)=O)CC1=CC=CC=C1C#N AJHPGXZOIAYYDW-UHFFFAOYSA-N 0.000 description 1
- ALYNCZNDIQEVRV-PZFLKRBQSA-N 4-amino-3,5-ditritiobenzoic acid Chemical compound [3H]c1cc(cc([3H])c1N)C(O)=O ALYNCZNDIQEVRV-PZFLKRBQSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- QKSKPIVNLNLAAV-UHFFFAOYSA-N bis(2-chloroethyl) sulfide Chemical compound ClCCSCCCl QKSKPIVNLNLAAV-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- HAWPXGHAZFHHAD-UHFFFAOYSA-N mechlorethamine Chemical compound ClCCN(C)CCCl HAWPXGHAZFHHAD-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- SFMJNHNUOVADRW-UHFFFAOYSA-N n-[5-[9-[4-(methanesulfonamido)phenyl]-2-oxobenzo[h][1,6]naphthyridin-1-yl]-2-methylphenyl]prop-2-enamide Chemical compound C1=C(NC(=O)C=C)C(C)=CC=C1N1C(=O)C=CC2=C1C1=CC(C=3C=CC(NS(C)(=O)=O)=CC=3)=CC=C1N=C2 SFMJNHNUOVADRW-UHFFFAOYSA-N 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyurethanes Or Polyureas (AREA)
Description
本発明は一般式
〔式中、R1は低級アルカン基を示し、Ａはイオ
ウ原子、低級アルキルイミノ基、フエニレン基、
フエニレンジオキシ基または―Ｏ―
（CH2CH2O）o―（ｎは０〜２の整数を示す。）を
示す。〕で表わされるビス（アミノベンゾエート）
類の製造法に関するものである。
本発明の方法により製造されるビス（アミノベ
ンゾエート）類は、ポリウレタンの硬化剤として
有用な化合物である。
従来、ビス（アミノベンゾエート）類の製造法
としては、英国特許第1182377号に開示されてい
るように、
(1)(2)(3)の方法がある。(1)(2)の方法は２工程であり
しかも接触還元といつた危険な操作が必要であつ
た。また(3)の方法についても２工程でありしかも
純度および収率が悪いなどの欠点があつた。以上
述べた様に(1)(2)(3)の方法は、工程数が２工程であ
りしかも操作が煩雑であるなどの欠点があつた。
また(1)(2)(3)の方法のうちでは高収率で得られる(1)
の方法について本発明者が追試したところ２工程
のトータル収率は、低いなどの欠点もあつた。
本発明者らは、従来の方法の欠点を解決すべく
創意工夫を行つたところ、意外にも一般式、
Ｘ―R1―Ａ―R1―Ｙで表わされるジハロゲン化
物とアミノ安息香酸および塩基を反応せしめたと
ころ、一般式
The present invention is based on the general formula [In the formula, R 1 represents a lower alkane group, A is a sulfur atom, a lower alkylimino group, a phenylene group,
Phenylenedioxy group or -O-
(CH 2 CH 2 O) o - (n represents an integer of 0 to 2). ] Bis(aminobenzoate)
This relates to the manufacturing method of the following types. The bis(aminobenzoates) produced by the method of the present invention are useful compounds as curing agents for polyurethanes. Conventionally, as a method for producing bis(aminobenzoates), as disclosed in British Patent No. 1182377, There are methods (1), (2), and (3). Methods (1) and (2) involve two steps and require dangerous operations such as catalytic reduction. Furthermore, method (3) also had drawbacks such as being a two-step process and having poor purity and yield. As mentioned above, the methods (1), (2), and (3) had drawbacks such as requiring two steps and complicated operations.
Also, among methods (1), (2), and (3), (1) can be obtained in high yield.
When the present inventor conducted a follow-up test on the method described above, it also had drawbacks such as a low total yield in the two steps. The present inventors made creative efforts to solve the shortcomings of conventional methods, and unexpectedly found that a dihalide represented by the general formula, X-R 1 -A-R 1 -Y, an aminobenzoic acid, and a base When reacted, the general formula
【式】で
表わされるビス（アミノベンゾエート）類が一工
程で、しかも高収率で製造でき、従来の欠点を解
決し得ることを認め本発明をなしたものである。
すなわち本発明は、一般式
Ｘ―R1―Ａ―R1―Ｙ
〔式中、ＸおよびＹはハロゲン原子を示し、R1
は低級アルカン基を示し、Ａはイオウ原子、低級
アルキルイミノ基、フエニレン基、フエニレンジ
オキシ基または―Ｏ―（CH2CH2O）o―（ｎは０
〜２の整数を示す。）を示す。〕で表わされるジハ
ロゲン化物（以下ジハロゲン化物は同意とする。）
とアミノ安息香酸類および塩基を反応せしめるこ
とを特徴とする、一般式
（式中、R1とＡは上記と同様の意味を示す。）で
表わされるビス（アミノベンゾエート）類〔以下
ビス（アミノベンゾエート）類は同意とする。〕
の製造方法を提供するものである。
本発明において使用する一般式
Ｘ―R1―Ａ―R1―Ｙ
で示されるジハロゲン化物としては、ＸとＹは塩
素原子、臭素原子、ヨウ素原子などのハロゲン原
子であり、R1は低級アルカン基であり、Ａはイ
オウ原子、低級アルキルイミノ基、フエニレン
基、フエニレンジオキシ基または―Ｏ―
（CH2CH2O）o―（ｎは０〜２の整数である）で
あるような化合物であつて、たとえば、ビス（２
―クロロエチル）エーテル．ビス（２―ブロモエ
チル）エーテル、１，８―ジクロロ―３，６―ジ
オキサオクタン、１，11―ジクロロ―３，６，９
―トリオキサウンデカン、ビス（２―クロロエチ
ル）スルフイド、Ｎ，Ｎ―ビス（２―クロロエチ
ル）Ｎ―メチルアミン、１，４―ビス クロロメ
チル ベンゼン、１，３―ビス クロロメチル
ベンゼン、１，２―ビス クロロメチル ベンゼ
ン、１，４―ビス（２―クロロエトキシ）ベンゼ
ン、１，３―ビス（２―クロロエトキシ）ベンゼ
ン、１，２―ビス（２―クロロエトキシ）ベンゼ
ン等があげられる。
またアミノ安息香酸としては、たとえば、２―
アミノ安息香酸、３―アミノ安息香酸、４―アミ
ノ安息香酸等があげられる。
さらに塩基としてはアルカリ金属およびアルカ
リ土類金属の水酸化物または炭酸化物、たとえば
水酸化ナトリウム、水酸化カリウム、水酸化カル
シウム、炭酸ナトリウム、炭酸カリウム、炭酸カ
ルシユウム等を通常使用する。
また、本発明において溶媒の使用は撹拌および
反応をスムーズに進行させる上から好ましく、た
とえばＮ，Ｎ―ジメチルホルムアミド、Ｎ，Ｎ―
ジメチルアセトアミド、テトラメチル尿素、ヘキ
サメチルスルホンアミド、ジメチルスルホキシ
ド、Ｎ―メチルピロリドン、Ｎ，Ｎ―ジエチルア
セトアミド、ヘキサメチルリン酸トリアミド、ス
ルホラン、テトラメチレンスルホラン等の溶剤の
使用が好ましい。また、これらの溶剤と非極性溶
剤を混合して使用してもよい。非極性溶剤として
は、ベンゼン、トルエン、クロロベンゼン、２―
クロロトルエン、３―クロロトルエン、４―クロ
ロトルエン、Ｏ―キシレン、ｍ―キシレン、ｐ―
キシレン、エチルベンゼン、クメン、ジイソプロ
ピルエーテル等が好ましい。
本発明の方法により製造されるビス（アミノベ
ンゾエート）類の代表化合物を例示するが、以上
の記述を含め本発明はこれらにより何ら限定され
るものではない。The present invention was made based on the recognition that bis(aminobenzoates) represented by the formula can be produced in one step and in high yield, and that the drawbacks of the conventional methods can be solved. That is, the present invention relates to the general formula X-R 1 -A-R 1 -Y [ wherein ,
represents a lower alkane group, A is a sulfur atom, a lower alkylimino group, a phenylene group, a phenylene dioxy group, or -O-(CH 2 CH 2 O) o - (n is 0
Indicates an integer between ~2. ) is shown. ] Dihalides (hereinafter referred to as dihalides)
A general formula characterized by reacting with aminobenzoic acids and a base (In the formula, R 1 and A have the same meanings as above.) Bis(aminobenzoates) [hereinafter, bis(aminobenzoates) have the same meaning. ]
The present invention provides a method for manufacturing. In the dihalide represented by the general formula X-R 1 -A-R 1 -Y used in the present invention, A is a sulfur atom, a lower alkylimino group, a phenylene group, a phenylenedioxy group, or -O-
(CH 2 CH 2 O) o - (n is an integer of 0 to 2), for example, bis(2
-Chloroethyl) ether. Bis(2-bromoethyl)ether, 1,8-dichloro-3,6-dioxaoctane, 1,11-dichloro-3,6,9
-trioxaundecane, bis(2-chloroethyl) sulfide, N,N-bis(2-chloroethyl)N-methylamine, 1,4-bis chloromethyl benzene, 1,3-bis chloromethyl
Benzene, 1,2-bis chloromethyl benzene, 1,4-bis(2-chloroethoxy)benzene, 1,3-bis(2-chloroethoxy)benzene, 1,2-bis(2-chloroethoxy)benzene, etc. can be given. In addition, as aminobenzoic acid, for example, 2-
Examples include aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, and the like. Furthermore, as bases, hydroxides or carbonates of alkali metals and alkaline earth metals, such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, etc., are usually used. In addition, in the present invention, it is preferable to use a solvent from the viewpoint of smooth stirring and reaction. For example, N,N-dimethylformamide, N,N-
It is preferred to use solvents such as dimethylacetamide, tetramethylurea, hexamethylsulfonamide, dimethylsulfoxide, N-methylpyrrolidone, N,N-diethylacetamide, hexamethylphosphoric triamide, sulfolane, tetramethylenesulfolane and the like. Further, these solvents and non-polar solvents may be used in combination. Non-polar solvents include benzene, toluene, chlorobenzene, 2-
Chlorotoluene, 3-chlorotoluene, 4-chlorotoluene, O-xylene, m-xylene, p-
Xylene, ethylbenzene, cumene, diisopropyl ether and the like are preferred. Representative compounds of bis(aminobenzoates) produced by the method of the present invention are illustrated, but the present invention, including the above description, is not limited thereto.
【表】【table】
【表】
本発明においてジハロゲン化物とアミノ安息香
酸および塩基の使用量は化学量論量あればよい。
また溶媒を使用する場合は、その使用量は特に限
定されないが、もちろん反応混合物が十分に撹拌
状態が維持できる量があればよい。
このような量関係で、ジハロゲン化物と、アミ
ノ安息香酸および塩基を60〜180℃、好ましくは、
100〜120℃で反応させる。反応時間は0.5〜６時
間、好ましくは１〜３時間で、反応を行うことが
できる。また反応は、常圧、減圧および加圧いづ
れの方法で行つて何らさしつかえない。さらに、
不活性ガスの雰囲気下に反応を行つても何ら支障
ない。
このように本発明は、ジハロゲン化物とアミノ
安息香酸および塩基を反応させるようにしたの
で、ビス（アミノベンゾエート）類が一工程で、
しかも高収率で得られるなど、従来の方法に比較
して格段の効果を発揮しえたものであつて、ビス
（アミノベンゾエート）類の工業的製法として効
果の高い方法である。
さらに実施例により具体的に説明する。
実施例 １
温度計、コンデンサー、撹拌機を備えた１４
径フラスコに、４―アミノ安息香酸をメタノール
に溶解し、当量の水酸化ナトリウム水溶液を加え
た後に、減圧下、メタノール、水を除去する。得
られた４―アミノ安息香酸のナトリウム塩100ｇ
（0.628モル）、ビス（２―クロロエチル）エーテ
ル44.9ｇ（0.314モル）およびDMF430mlを仕込ん
だ、撹拌下、昇温し、液温を120℃まであげた。
120℃で３時間反応し反応を終了した。反応液を
１のナスフラスコに移し、減圧下DMFを除去
した。ナスフラスコに残つた粘稠油分を撹拌下１
の水中に投入した。析出した結晶を吸引ろ過し
乾燥した。これにより融点109〜113℃、淡黄色の
結晶として、ジエチレングリコールビス（４―ア
ミノベンゾエート）を得た。収率90.1％、純度
97.3％であつた。同定はNMR、1Rで行い、純度
は高速液体クロマトグラフイーで分析した。
実施例 ２〜10
アミノ安息香酸類、ジハロゲン化物および塩基
の種類を変え以下実施例１と同様の方法で行つ
た。結果を次表に示す。[Table] In the present invention, the dihalide, aminobenzoic acid, and base may be used in stoichiometric amounts.
When a solvent is used, the amount used is not particularly limited, as long as it is sufficient to maintain the reaction mixture in a sufficiently stirred state. In such an amount relationship, the dihalide, aminobenzoic acid and base are heated at 60 to 180°C, preferably,
React at 100-120℃. The reaction time can be 0.5 to 6 hours, preferably 1 to 3 hours. Further, the reaction may be carried out under normal pressure, reduced pressure or increased pressure. moreover,
There is no problem even if the reaction is carried out in an inert gas atmosphere. In this way, in the present invention, the dihalide, aminobenzoic acid, and base are reacted, so that bis(aminobenzoate) can be prepared in one step.
In addition, it is a highly effective method for producing bis(aminobenzoates) on an industrial scale, and is much more effective than conventional methods, as it can be obtained in high yield. This will be further explained in more detail with reference to Examples. Example 1 14 equipped with thermometer, condenser and stirrer
After dissolving 4-aminobenzoic acid in methanol and adding an equivalent amount of aqueous sodium hydroxide to a diameter flask, methanol and water are removed under reduced pressure. 100g of the obtained sodium salt of 4-aminobenzoic acid
(0.628 mol), 44.9 g (0.314 mol) of bis(2-chloroethyl) ether, and 430 ml of DMF were charged, and the temperature was raised to 120° C. while stirring.
The reaction was completed at 120°C for 3 hours. The reaction solution was transferred to No. 1 eggplant flask, and DMF was removed under reduced pressure. Stir the viscous oil remaining in the eggplant flask.
was put into the water. The precipitated crystals were suction filtered and dried. This gave diethylene glycol bis(4-aminobenzoate) as pale yellow crystals with a melting point of 109-113°C. Yield 90.1%, purity
It was 97.3%. Identification was performed by NMR and 1R, and purity was analyzed by high performance liquid chromatography. Examples 2 to 10 The same procedure as in Example 1 was repeated except that the types of aminobenzoic acids, dihalides, and bases were changed. The results are shown in the table below.
Claims (1)
級アルカン基を示し、Ａはイオウ原子、低級アル
キルイミノ基、フエニレン基、フエニレンジオキ
シ基または―Ｏ―（CH2CH2O）o―（ｎは０〜２
の整数を示す）を示す。〕で表わされるジハロゲ
ン化物とアミノ安息香酸類および塩基を反応せし
めることを特徴とする、一般式 （式中、R1とＡは上記と同様の意味を示す。）で
表わされるビス（アミノベンゾエート）類の製造
法。[Claims] 1 General formula: X-R 1 -A-R 1 -Y [wherein, group, phenylene group, phenylenedioxy group or -O-(CH 2 CH 2 O) o - (n is 0 to 2
). A general formula characterized by reacting a dihalide represented by ] with an aminobenzoic acid and a base (In the formula, R 1 and A have the same meanings as above.) A method for producing bis(aminobenzoate).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15786880A JPS5781445A (en) | 1980-11-10 | 1980-11-10 | Preparation of bis(aminobenzoate) compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15786880A JPS5781445A (en) | 1980-11-10 | 1980-11-10 | Preparation of bis(aminobenzoate) compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5781445A JPS5781445A (en) | 1982-05-21 |
| JPS6332063B2 true JPS6332063B2 (en) | 1988-06-28 |
Family
ID=15659152
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15786880A Granted JPS5781445A (en) | 1980-11-10 | 1980-11-10 | Preparation of bis(aminobenzoate) compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5781445A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5719307A (en) * | 1994-04-13 | 1998-02-17 | Air Products And Chemicals, Inc. | Diamine chain extenders and method of use |
-
1980
- 1980-11-10 JP JP15786880A patent/JPS5781445A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5781445A (en) | 1982-05-21 |
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