JPS6213341B2 - - Google Patents
Info
- Publication number
- JPS6213341B2 JPS6213341B2 JP10456278A JP10456278A JPS6213341B2 JP S6213341 B2 JPS6213341 B2 JP S6213341B2 JP 10456278 A JP10456278 A JP 10456278A JP 10456278 A JP10456278 A JP 10456278A JP S6213341 B2 JPS6213341 B2 JP S6213341B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- acid
- present
- benzoic acid
- water
- 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
- 238000006243 chemical reaction Methods 0.000 claims description 34
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000005711 Benzoic acid Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 230000000802 nitrating effect Effects 0.000 claims 1
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N 4-methoxybenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 description 10
- 239000006227 byproduct Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- XFDUHJPVQKIXHO-UHFFFAOYSA-N 3-aminobenzoic acid Chemical compound NC1=CC=CC(C(O)=O)=C1 XFDUHJPVQKIXHO-UHFFFAOYSA-N 0.000 description 7
- 241000989747 Maba Species 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 4
- 238000006396 nitration reaction Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- ILUJQPXNXACGAN-UHFFFAOYSA-N O-methylsalicylic acid Chemical compound COC1=CC=CC=C1C(O)=O ILUJQPXNXACGAN-UHFFFAOYSA-N 0.000 description 3
- 235000010233 benzoic acid Nutrition 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical group CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 description 2
- SHSGDXCJYVZFTP-UHFFFAOYSA-N 4-ethoxybenzoic acid Chemical compound CCOC1=CC=C(C(O)=O)C=C1 SHSGDXCJYVZFTP-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- XDZMPRGFOOFSBL-UHFFFAOYSA-N 2-ethoxybenzoic acid Chemical compound CCOC1=CC=CC=C1C(O)=O XDZMPRGFOOFSBL-UHFFFAOYSA-N 0.000 description 1
- ASIBMPOSLZTHOI-UHFFFAOYSA-N 4-ethoxy-2-nitrobenzoic acid Chemical compound CCOC1=CC=C(C(O)=O)C([N+]([O-])=O)=C1 ASIBMPOSLZTHOI-UHFFFAOYSA-N 0.000 description 1
- ANXBDAFDZSXOPQ-UHFFFAOYSA-N 4-methoxy-3-nitrobenzoic acid Chemical compound COC1=CC=C(C(O)=O)C=C1[N+]([O-])=O ANXBDAFDZSXOPQ-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明はモノニトロ−低級アルコキシ−安息香
酸（以下、MABAと略称する。）の製造法に関す
るものである。
MABAは医薬、染料、顔料などの中間体とし
て広く利用されているが、その製造法としては、
低級アルコキシ−安息香酸を加熱下、硝酸中にて
ニトロ化する方法が一般的である。（例えば、ジ
ヤーナル、オブ、オルガニツク、ケミストリー、
第71巻第1221頁参照）しかしながら、この反応
は、従来知られている反応条件の下では、例え
ば、ジニトロ化合物、脱カルボキシル化物及びそ
の他副生物の生成が著しいため、高収率且つ高純
度でMABAを得ることが出来ず、更に、脱カル
ボキシル反応が起ると炭酸ガスが発生するため、
反応系内が発泡状態となり均一撹拌ができなくな
り良好な反応を行なうことができず、工業的には
不満足な点が多かつた。ジニトロ化物の副生のみ
を抑制するための方法としては、例えば原料に対
する硝酸の割合を低下させる方法が考えられる
が、この方法ではその他の副生物の生成抑制及び
反応系内の発泡抑制は困難である。
本発明者等は上記実情に鑑み、反応系内の発泡
を抑制し且つ副反応が極めて少なく、高収率且つ
高純度でMABAを製造することを目的として
種々検討した結果、反応系内の水分濃度及び温度
をある特定の範囲に保持することにより、この目
的が達成されることを知見し本発明を完成した。
すなわち、本発明の要旨は、低級アルコキシ−
安息香酸を硫酸中にて硝酸でニトロ化して
MABAを製造するに当り、反応系内の水分と硫
酸の和に対する水分の存在量を３〜20重量％と
し、しかも、反応温度を−20〜10℃に保持して反
応を行なうことを特徴とするMABAの製造法に
存する。
以下、本発明を詳細に説明する。
本発明で原料として使用する低級アルコキシ−
安息香酸としては、下記一般式〔〕
（式中、Ｒは低級アルキル基を示す）で表わさ
れる化合物であり、例えば、パラ−メトキシ−安
息香酸（アニス酸）、オルト−メトキシ−安息香
酸、パラ−エトキシ−安息香酸、オルト−エトキ
シ−安息香酸、パラ−プロポキシ−安息香酸、オ
ルト−ブトキシ−安息香酸などが挙げられ、本発
明は、パラ−メトキシ−安息香酸に適用すると特
に好ましい。
一方、ニトロ化のために使用する硝酸の使用量
は通常、原料をモノニトロ化するのに必要な理論
量の0.98〜1.20モル倍、好ましくは1.01〜1.05モ
ル倍である。硝酸量があまり多いとジニトロ体の
副生物生成が多くなり好ましくない。硝酸の濃度
は通常、20〜80重量％、好ましくは40〜70重量％
であり、あまり低濃度の場合には反応系内の水分
が多くなり反応速度が低下し、また、あまり高濃
度の場合には局部的に急激なニトロ化が起り、副
反応が進むので好ましくない。
本発明ではニトロ化反応を硝酸中にて行なう
が、使用する硫酸は少なくとも80重量％以上の高
濃度のものが使用される。すなわち、本発明では
反応系内の水分と硫酸との和に対する水分の存在
量を３〜20重量％、好ましくは３〜15重量％、更
に好ましくは３〜10重量％に保持することを必須
の要件とするものである。反応系内の水分量が上
記範囲より高いとニトロ化反応が本発明の温度範
囲では良好に進行しないので好ましくない。ま
た、硫酸の使用量は反応原料を分散させ十分に撹
拌できる程度の量であればよく、通常、反応原料
に対して３〜20重量倍である。
本発明における反応温度は−20〜10℃以下、好
ましくは−20〜５℃、更に好ましくは−５〜５℃
の範囲に保持することが必要である。反応温度が
10℃より高い場合には、副反応の進行が著しくな
り、また、反応系内が発泡状態となるので好まし
くない。逆に、低温では反応おそく、特に−20℃
より低い温度では反応速度が極めて遅くなり実用
的でない。反応時間は、上記反応温度で反応を行
う場合、通常１〜20時間である。
本発明は、例えば、反応原料を分散させた硫酸
中に撹拌下、硝酸を添加混合することにより容易
に行なうことができる。
以上、本発明によれば特定の水分濃度及び反応
温度を選ぶことにより副生物の生成が少なく高収
率でMABAを得ることができる。また、反応途
中で系内が発泡し撹拌不能となるようなこともな
いので好ましい。
次に、本発明を実施例により更に詳細に説明す
るが、本発明はその要旨を超えない限り以下の実
施例に限定されるものではない。
実施例 １
撹拌機及び冷却器を設置した200mlガラス製フ
ラスコに96％硫酸134.2ｇ及びＰ−メトキシ安息
香酸30.42ｇを仕込み、−７〜−５℃にスラリーの
温度を調節した。
これに撹拌下、65.5％硝酸20.20ｇ（モノニト
ロ化合物を得るための理論量の1.05モル倍）を２
時間かけて滴下混合したのち、液温を−７℃にて
７時間反応を行なつた。
反応終了後のスラリーに対し５℃の氷水300ml
を混合し撹拌処理して副生物を水に溶解させたの
ち、ケーキをろ過した。
このようにして得たケーキ（３−ニトロ−４−
メトキシ安息香酸）の収量、収率及び純度を測定
し第１表に示す結果を得た。
実施例２〜３及び比較例１〜２
実施例１の方法において、温度、反応原料、硫
酸濃度などの条件を第１表に示すように代えて同
様な反応を行なつた。（実施例３の生成物は３−
ニトロ−４−エトキシ安息香酸であり、それ以外
は実施例１と同様３−ニトロ−４−メトキシ安息
香酸である。）
The present invention relates to a method for producing mononitro-lower alkoxy-benzoic acid (hereinafter abbreviated as MABA). MABA is widely used as an intermediate for medicines, dyes, pigments, etc., but its production method is as follows.
A common method is to nitrate lower alkoxybenzoic acid in nitric acid under heating. (For example, journal, of, organ, chemistry,
(Refer to Vol. 71, p. 1221) However, under the conventionally known reaction conditions, this reaction is difficult to achieve in high yield and purity because, for example, dinitro compounds, decarboxylated products, and other by-products are produced significantly. MABA cannot be obtained, and carbon dioxide gas is generated when decarboxylation occurs, so
The inside of the reaction system became bubbling, making it impossible to stir uniformly, making it impossible to carry out a good reaction, and there were many unsatisfactory points from an industrial perspective. One possible method for suppressing only the dinitrate by-product is, for example, reducing the ratio of nitric acid to the raw materials, but this method is difficult to suppress the production of other by-products and foaming in the reaction system. be. In view of the above circumstances, the present inventors conducted various studies with the aim of suppressing foaming in the reaction system, producing extremely few side reactions, and producing MABA with high yield and high purity. The present invention was completed based on the finding that this objective can be achieved by maintaining the concentration and temperature within a certain range. That is, the gist of the present invention is that lower alkoxy
Benzoic acid is nitrated with nitric acid in sulfuric acid.
In producing MABA, the amount of water present in the reaction system is 3 to 20% by weight relative to the sum of water and sulfuric acid, and the reaction temperature is maintained at -20 to 10°C. The method of manufacturing MABA consists in the following. The present invention will be explained in detail below. Lower alkoxy used as raw material in the present invention
As benzoic acid, the following general formula [] (In the formula, R represents a lower alkyl group.) For example, para-methoxy-benzoic acid (anisic acid), ortho-methoxy-benzoic acid, para-ethoxy-benzoic acid, ortho-ethoxy-benzoic acid. Examples include benzoic acid, para-propoxy-benzoic acid, ortho-butoxy-benzoic acid, and the present invention is particularly preferably applied to para-methoxy-benzoic acid. On the other hand, the amount of nitric acid used for nitration is usually 0.98 to 1.20 times, preferably 1.01 to 1.05 times by mole, the theoretical amount required to mononitrate the raw material. If the amount of nitric acid is too large, a large amount of dinitro by-products will be produced, which is not preferable. The concentration of nitric acid is usually 20-80% by weight, preferably 40-70% by weight
Therefore, if the concentration is too low, water in the reaction system will increase and the reaction rate will be reduced, and if the concentration is too high, localized rapid nitration will occur and side reactions will proceed, which is undesirable. . In the present invention, the nitration reaction is carried out in nitric acid, and the sulfuric acid used has a high concentration of at least 80% by weight. That is, in the present invention, it is essential to maintain the amount of water present in the reaction system at 3 to 20% by weight, preferably 3 to 15% by weight, and more preferably 3 to 10% by weight. This is a requirement. If the amount of water in the reaction system is higher than the above range, the nitration reaction will not proceed well within the temperature range of the present invention, which is not preferred. Further, the amount of sulfuric acid used is sufficient as long as it can disperse and sufficiently stir the reaction raw materials, and is usually 3 to 20 times the weight of the reaction raw materials. The reaction temperature in the present invention is -20 to 10°C, preferably -20 to 5°C, more preferably -5 to 5°C.
It is necessary to maintain it within the range of . The reaction temperature is
If the temperature is higher than 10°C, the progress of side reactions will be significant and the inside of the reaction system will be in a foaming state, which is not preferable. On the other hand, the reaction is slow at low temperatures, especially at -20℃.
At lower temperatures, the reaction rate becomes extremely slow and is not practical. The reaction time is usually 1 to 20 hours when the reaction is carried out at the above reaction temperature. The present invention can be easily carried out, for example, by adding and mixing nitric acid into sulfuric acid in which reaction raw materials are dispersed, while stirring. As described above, according to the present invention, by selecting a specific water concentration and reaction temperature, MABA can be obtained in high yield with less generation of by-products. Further, it is preferable because the system does not foam during the reaction and become unable to stir. Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. Example 1 A 200 ml glass flask equipped with a stirrer and a cooler was charged with 134.2 g of 96% sulfuric acid and 30.42 g of P-methoxybenzoic acid, and the temperature of the slurry was adjusted to -7 to -5°C. To this was added 20.20 g of 65.5% nitric acid (1.05 mol times the theoretical amount to obtain a mononitro compound) under stirring.
After dropping and mixing over a period of time, the reaction was carried out at a liquid temperature of -7°C for 7 hours. Add 300ml of ice water at 5℃ to the slurry after the reaction is completed.
After mixing and stirring to dissolve the by-products in water, the cake was filtered. The cake thus obtained (3-nitro-4-
The yield, yield and purity of methoxybenzoic acid) were measured and the results shown in Table 1 were obtained. Examples 2 to 3 and Comparative Examples 1 to 2 Similar reactions were carried out in the method of Example 1 except that conditions such as temperature, reaction raw materials, and sulfuric acid concentration were changed as shown in Table 1. (The product of Example 3 is 3-
This is nitro-4-ethoxybenzoic acid, and 3-nitro-4-methoxybenzoic acid is the same as in Example 1 except for that. )
【表】
実施例 ４
撹拌機及び冷却器を設置したガラス製フラスコ
に98％硫酸271ｇ及びＰ−メトキシ安息香酸38.0
ｇ及び水41.5ｇを仕込み、これに撹拌下、70％硝
酸23.7ｇ（モノニトロ化物を得るための理論量の
1.51モル倍）を滴下混合したのち、液温を６℃に
て７時間反応を行なつた。
反応終了後のスラリーに対し５℃の氷水を混合
し撹拌処理して副生物を水に溶解させたのち、ケ
ーキをろ過した。
このようにして得たケーキの収量、収率及び純
度を測定し第２表に示す結果を得た。
実施例 ５
撹拌機及び冷却器を設置したガラス製フラスコ
に98％硫酸260ｇ及びＰ−メトキシ安息香酸30.42
ｇを仕込み、これに撹拌下、75％硝酸18ｇ（モノ
ニトロ化物を得るための理論量のモル倍）を滴下
混合したのち、液温を−16℃にて９時間反応を行
なつた。
反応終了後のスラリーに対し５℃の氷水を混合
し撹拌処理して副生物を水に溶解させたのち、ケ
ーキをろ過した。
このようにして得たケーキの収量、収率及び純
度を測定し第２表に示す結果を得た。[Table] Example 4 271 g of 98% sulfuric acid and 38.0 g of P-methoxybenzoic acid were placed in a glass flask equipped with a stirrer and a condenser.
23.7 g of 70% nitric acid (the theoretical amount to obtain a mononitrate) was added to this while stirring.
After dropping and mixing 1.51 mol times the solution, the reaction was carried out at a liquid temperature of 6° C. for 7 hours. After the reaction, the slurry was mixed with ice water at 5° C. and stirred to dissolve the by-products in water, and then the cake was filtered. The yield, yield and purity of the cake thus obtained were measured and the results shown in Table 2 were obtained. Example 5 260 g of 98% sulfuric acid and 30.42 g of P-methoxybenzoic acid were placed in a glass flask equipped with a stirrer and a condenser.
After stirring, 18 g of 75% nitric acid (mole times the theoretical amount to obtain a mononitrate) was added dropwise to the mixture, and the reaction was carried out at a temperature of -16° C. for 9 hours. After the reaction, the slurry was mixed with ice water at 5° C. and stirred to dissolve the by-products in water, and then the cake was filtered. The yield, yield and purity of the cake thus obtained were measured and the results shown in Table 2 were obtained.
Claims (1)
でニトロ化してモノニトロ−低級アルコキシ−安
息香酸を製造するに当り、反応系内の水分と硫酸
の和に対する水分の存在量を３〜20重量％とし、
しかも、反応温度を−20〜10℃に保持して反応を
行なうことを特徴とするモノニトロ−低級アルコ
キシ−安息香酸の製造法。1. When producing mononitro-lower alkoxy-benzoic acid by nitrating lower alkoxy-benzoic acid with nitric acid in sulfuric acid, the amount of water present in the reaction system should be 3 to 20% by weight based on the sum of water and sulfuric acid. ,
Moreover, the method for producing mononitro-lower alkoxy-benzoic acid is characterized in that the reaction temperature is maintained at -20 to 10°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10456278A JPS5531045A (en) | 1978-08-28 | 1978-08-28 | Preparation of mononitro-lower alkoxy-benzoic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10456278A JPS5531045A (en) | 1978-08-28 | 1978-08-28 | Preparation of mononitro-lower alkoxy-benzoic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5531045A JPS5531045A (en) | 1980-03-05 |
| JPS6213341B2 true JPS6213341B2 (en) | 1987-03-25 |
Family
ID=14383891
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10456278A Granted JPS5531045A (en) | 1978-08-28 | 1978-08-28 | Preparation of mononitro-lower alkoxy-benzoic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5531045A (en) |
-
1978
- 1978-08-28 JP JP10456278A patent/JPS5531045A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5531045A (en) | 1980-03-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3752841A (en) | Process for the preparation of carbamates of alkylthiolhydroxamates and intermediates | |
| EP0296221B1 (en) | Process for preparing 4,6-dinitroresorcinol | |
| JPS6213341B2 (en) | ||
| US4028410A (en) | Process of preparing 1,3-bis(2-chloroethyl)-1-nitrosourea | |
| US5520757A (en) | Low vulnerability propellants | |
| US5482581A (en) | Low vulnerability propellant plasticizers | |
| US2758132A (en) | Nitration of carbamate esters | |
| US3023241A (en) | Preparation of acyl hydrazine derivatives | |
| EP0110559A1 (en) | Process for the preparation of 4-chloro-2-nitrobenzonitrile | |
| US2950312A (en) | Process for producing n-trinitroethyl urethanes, amides, and ureas | |
| JPS6318573B2 (en) | ||
| US2225893A (en) | Production of secondary aliphatic nitrates | |
| IL31463A (en) | 1-formyl-3-nitro-azacycloalkan-2-ones and process for their production | |
| US3719717A (en) | Process for the production of aromatic dinitrohalogen compounds | |
| SU897108A3 (en) | Method of preparing 2,6-dinitroderivatives of n-alkyl or n,n-dialkylanilines | |
| US2749372A (en) | Trichlorodinitrobenzenes | |
| US3390183A (en) | Preparation of nitramines | |
| US3155716A (en) | Preparation of pure alpha-naphthalene sulfonic acid and alpha-naphthol | |
| US2759963A (en) | Substituted benzoates | |
| US4052419A (en) | Method of preparing 5-nitrofurfural diacetate | |
| US2444023A (en) | Preparation of dimethyl urea | |
| EP0005280B1 (en) | A process for the reduction of carboxylic acid halides to corresponding aldehydes | |
| KR810000230B1 (en) | Process for the preparation of nitro substitute amino benzoic acid amides | |
| US3015674A (en) | Process for the production of alkylacylamides | |
| JPH0419987B2 (en) |