JPH0318608B2 - - Google Patents
Info
- Publication number
- JPH0318608B2 JPH0318608B2 JP11456382A JP11456382A JPH0318608B2 JP H0318608 B2 JPH0318608 B2 JP H0318608B2 JP 11456382 A JP11456382 A JP 11456382A JP 11456382 A JP11456382 A JP 11456382A JP H0318608 B2 JPH0318608 B2 JP H0318608B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- higher alkyl
- product
- water
- alkenylamine
- 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 20
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 9
- 150000001805 chlorine compounds Chemical class 0.000 claims description 6
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000006482 condensation reaction Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 6
- 239000007859 condensation product Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000012433 hydrogen halide Substances 0.000 description 4
- 229910000039 hydrogen halide Inorganic materials 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 3
- -1 benzoyl halide Chemical class 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- RKIDDEGICSMIJA-UHFFFAOYSA-N 4-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=C(Cl)C=C1 RKIDDEGICSMIJA-UHFFFAOYSA-N 0.000 description 1
- NQUVCRCCRXRJCK-UHFFFAOYSA-N 4-methylbenzoyl chloride Chemical compound CC1=CC=C(C(Cl)=O)C=C1 NQUVCRCCRXRJCK-UHFFFAOYSA-N 0.000 description 1
- JPVUWCPKMYXOKW-UHFFFAOYSA-N 4-phenylbenzoyl chloride Chemical compound C1=CC(C(=O)Cl)=CC=C1C1=CC=CC=C1 JPVUWCPKMYXOKW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- MXMOTZIXVICDSD-UHFFFAOYSA-N anisoyl chloride Chemical compound COC1=CC=C(C(Cl)=O)C=C1 MXMOTZIXVICDSD-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Chemical group 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005935 hexyloxycarbonyl group Chemical group 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- CVXXHXPNTZBZEL-UHFFFAOYSA-N methyl 4-carbonochloridoylbenzoate Chemical compound COC(=O)C1=CC=C(C(Cl)=O)C=C1 CVXXHXPNTZBZEL-UHFFFAOYSA-N 0.000 description 1
- HWEOYOXBRATLKT-UHFFFAOYSA-N n-octadecylbenzamide Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)C1=CC=CC=C1 HWEOYOXBRATLKT-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000004742 propyloxycarbonyl group Chemical group 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は、一般式
（式中、R1は高級アルキル又はアルケニル基
であり、R2は低級アルキル基、低級アルコキシ
基、低級アルコキシカルボニル基、ハロゲン原子
又は前記した置換基により置換されていてもよい
アリール基であり、ｎは０〜５の整数である）
で表わされるＮ−高級アルキル又はアルケニルカ
ルバモイルベンゼン及びその核置換体の製造方法
に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the general formula (In the formula, R 1 is a higher alkyl or alkenyl group, R 2 is a lower alkyl group, a lower alkoxy group, a lower alkoxycarbonyl group, a halogen atom, or an aryl group optionally substituted with the above-mentioned substituent, n is an integer of 0 to 5) The present invention relates to a method for producing N-higher alkyl or alkenylcarbamoylbenzene represented by the formula (n is an integer of 0 to 5) and a nuclear substituted product thereof.
従来、前記したような構造のＮ−高級アルキル
又はアルケニルカルバモイルベンゼン及びその核
置換体を製造するには、Ｎ−高級アルキル又はア
ルケニルアミンをトルエン等の有機溶媒に溶解
し、ハロゲン化ベンゾイル又はその核置換体を滴
下し、加熱することにより、脱ハロゲン化水素縮
合反応を生起させることにより行われてきた。し
かしながら、この方法では、縮合生成物に着色が
見られ、再結晶を繰返しても脱色しにくいという
問題がある上、縮合生成物は強い酸性を示すこと
から、中和工程を必要とする。さらに、反応中ハ
ロゲン化水素が放出されるので、その処理装置も
必要になる。一方、この反応系中にハロゲン化水
素中和用の塩基性物質を存在させる方法も知られ
ているが、この場合、反応終了後、塩基性物質の
ハロゲン化水素中和塩を溶解するために縮合生成
物を水洗すると、縮合生成物のゲル化や収率低下
等が生じて実用的ではない。例えば、反応溶媒と
して芳香族炭化水素を用いると、水洗に際して縮
合生成物にゲル化が生じ、目的物の分離回収に著
しい困難が伴なう。 Conventionally, in order to produce N-higher alkyl or alkenylcarbamoylbenzene having the above structure and its nuclear substituted product, N-higher alkyl or alkenylamine is dissolved in an organic solvent such as toluene, and a benzoyl halide or its nucleus is dissolved. This has been carried out by dropping a substituent and heating to cause a dehydrohalogenation condensation reaction. However, this method has the problem that the condensation product is colored and is difficult to decolor even after repeated recrystallization, and the condensation product is strongly acidic, so a neutralization step is required. Furthermore, since hydrogen halide is released during the reaction, a treatment device for the hydrogen halide is also required. On the other hand, a method is also known in which a basic substance for neutralizing hydrogen halide is present in this reaction system. Washing the condensation product with water causes gelation of the condensation product, decrease in yield, etc., and is not practical. For example, when an aromatic hydrocarbon is used as a reaction solvent, gelation occurs in the condensation product upon washing with water, making separation and recovery of the target product extremely difficult.
本発明者は、従来法における前記欠点を克服す
べく鋭意研究を重ねた結果、本発明を完成するに
到つた。 The present inventor has completed the present invention as a result of intensive research to overcome the above-mentioned drawbacks of conventional methods.
即ち、本発明によれば、一般式
R1−NH2
（式中、R1は高級アルキル又はアルケニル基
である）
で表わされるＮ−高級アルキル又はアルケニルア
ミンと、一般式
（式中、Ｘはハロゲン原子、R2は低級アルキ
ル基、低級アルコキシ基、低級アルコキシカルボ
ニル基、ハロゲン原子又は前記のような置換基に
より核置換されていてもよいアリール基であり、
ｎは０〜５の整数である）
で表わされるハロゲン化ベンゾイル又はその核置
換体とを脱ハロゲン化水素縮合する方法におい
て、前記Ｎ−高級アルキル又はアルケニルアミン
をあらかじめ塩素化合物系溶媒中に溶解した溶液
に対し、塩基性物質の存在下、前記ハロゲン化ベ
ンゾイル又はその核置換体を液状又は固体状で
徐々に加えて縮合反応を行い、反応終了後、水又
は温水を加えて生成した中和塩を溶解除去するこ
とを特徴とする、一般式
（式中、R1，R2及びｎは前記と同じ意味を有
する）
で表わされるＮ−高級アルキル又はアルケニルカ
ルバモイルベンゼン及びその核置換体の製造方法
が提供される。 That is, according to the present invention, an N-higher alkyl or alkenylamine represented by the general formula R 1 -NH 2 (wherein R 1 is a higher alkyl or alkenyl group); (In the formula ,
n is an integer of 0 to 5), in which the N-higher alkyl or alkenylamine is dissolved in advance in a chlorine compound solvent. A neutralized salt produced by gradually adding the halogenated benzoyl or its nuclear substituted product in liquid or solid form to a solution in the presence of a basic substance to perform a condensation reaction, and after the reaction is completed, water or warm water is added. A general formula characterized by dissolving and removing (wherein R 1 , R 2 and n have the same meanings as above) A method for producing N-higher alkyl or alkenylcarbamoylbenzene and its nuclear substituted product is provided.
本発明で用いるＮ−高級アルキル又はアルケニ
ルアミンは次の一般式で表わされる。 The N-higher alkyl or alkenylamine used in the present invention is represented by the following general formula.
R1−NH2 （）
式中、R1は高級アルキル又はアルケニル基で
あり、その炭素数は一般には10〜30、好ましくは
８〜22である。 R 1 -NH 2 () In the formula, R 1 is a higher alkyl or alkenyl group, and generally has 10 to 30 carbon atoms, preferably 8 to 22 carbon atoms.
本発明で用いるハロゲン化ベンゾイル又はその
核置換体は次の一般式で表わされる。 The halogenated benzoyl or its nuclear substituted product used in the present invention is represented by the following general formula.
式中、Ｘは塩素、臭素などのハロゲン原子であ
り、R2は低級アルキル基、例えば、メチル、エ
チル、プロピル、ヘキシルなどの炭素数１〜６の
アルキル基、低級アルコキシ基、例えばメトキ
シ、エトキシ、プロポキシ、ヘキシロキシなどの
炭素数１〜６のアルコキシ基、低級アルコキシカ
ルボニル基、例えば、メトキシカルボニル、エト
キシカルボニル、プロポキシカルボニル、ヘキシ
ロキシカルボニルなどの炭素数１〜６のアルコキ
シ基を有するアルコキシカルボニル基、塩素、臭
素などのハロゲン原子又は前記の置換基で置換さ
れていてもよいアリール基、例えばフエニル、ト
リルなどを表わす。ｎは０〜５の整数であり、ｎ
が２〜５の場合、２〜５個の置換基R2は同一又
は異つたものであることができる。 In the formula , , an alkoxy group having 1 to 6 carbon atoms such as propoxy, hexyloxy, lower alkoxycarbonyl group, for example, an alkoxycarbonyl group having an alkoxy group having 1 to 6 carbon atoms such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, hexyloxycarbonyl, It represents a halogen atom such as chlorine or bromine, or an aryl group optionally substituted with the above-mentioned substituents, such as phenyl and tolyl. n is an integer from 0 to 5, and n
is 2 to 5, 2 to 5 substituents R 2 can be the same or different.
本発明においては、溶媒として、塩素化合物系
の溶媒を用いる。このような溶媒としては、例え
ば、テトラクロロエチレン、クロロホルム、１，
２−ジクロロエタン、トリクロロエチレン等があ
る。この溶媒の使用量は、目的生成物の溶解度と
の関連で規定するのがよく、一般には、反応温度
において、目的生成物を完全に溶解する理論量以
上、通常その理論量の１〜２倍量用いられる。ハ
ロゲン化ベンゾイルの使用割合は、Ｎ−高級アル
キル又はアルケニルアミン１モルに対し、１〜
1.5モル、好ましくは１〜1.1モルの割合である。
またハロゲン化ベンゾイルの滴下割合は、Ｎ−高
級アルキル又はアルケニルアミン１モルに対し、
毎秒0.00001〜0.003モル、好ましくは0.00008〜
0.0004モルの割合である。また、本発明の反応は
塩基性物質の存在下で行われるが、その量は、反
応系をPH７〜10、好ましくはPH7.5〜９を保持す
るような量であり、通常、この塩基性物質は水溶
液の形で滴下される。この塩基性物質の具体例と
しては、例えば、水酸化ナトリウムや、水酸化カ
リウムなどのアルカリ金属の水酸化物などを適用
することもできる。反応系に滴下する場合の塩基
性物質の水溶液中濃度は、通常５〜60重量％、好
ましくは10〜40重量％である。反応温度は、一般
には30〜90℃、好ましくは40〜70℃である。 In the present invention, a chlorine compound-based solvent is used as the solvent. Examples of such solvents include tetrachloroethylene, chloroform, 1,
Examples include 2-dichloroethane and trichloroethylene. The amount of this solvent to be used is preferably determined in relation to the solubility of the target product, and is generally at least the theoretical amount that completely dissolves the target product at the reaction temperature, usually 1 to 2 times the theoretical amount. amount used. The usage ratio of halogenated benzoyl is 1 to 1 mole of N-higher alkyl or alkenylamine.
The proportion is 1.5 mol, preferably 1 to 1.1 mol.
Furthermore, the dropping ratio of benzoyl halide is as follows: per mole of N-higher alkyl or alkenylamine.
0.00001~0.003 mol per second, preferably 0.00008~
The proportion is 0.0004 mol. Further, the reaction of the present invention is carried out in the presence of a basic substance, and the amount thereof is such that the reaction system maintains a pH of 7 to 10, preferably 7.5 to 9. The substance is dropped in the form of an aqueous solution. As specific examples of this basic substance, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide can be used. The concentration of the basic substance in the aqueous solution when added dropwise to the reaction system is usually 5 to 60% by weight, preferably 10 to 40% by weight. The reaction temperature is generally 30-90°C, preferably 40-70°C.
本発明においては、反応が実質的に終了後、反
応系の温度を、反応温度よりも３〜20℃、好まし
くは５〜10℃程度上げ、５〜40分間、好ましくは
10〜30分間この温度に保つて反応を完結させる。
その後、得られた反応生成物に対し、水又は温水
を、反応生成物に対し10〜50％（容量）、好まし
くは10〜30％程度添加混合し、塩基性物質とハロ
ゲン化水素との中和塩を水中に溶出させる。この
操作を１〜３回行うことより高純度の生成物が得
られる。この場合、操作温度は40〜70℃の範囲の
温度に保つ。次に、反応生成物は温度25〜15℃程
度に撹拌冷却し、目的物を晶析させる。このよう
にして目的物の結晶（10〜45重量％）と溶媒（35
〜85重量％）と水（10〜55重量％）とのスラリー
状混合物が得られるが、この混合物は、水を含む
ためにその結晶が反応槽壁に付着しにくく、反応
槽からの抜出しを円滑に行うことができる。この
スラリー状混合物は、ロ過や遠心分離等の固液分
離手段により固液分離し、得られた固形物を乾燥
し、製品とする。 In the present invention, after the reaction is substantially completed, the temperature of the reaction system is raised by 3 to 20°C, preferably 5 to 10°C above the reaction temperature, and the temperature is increased for 5 to 40 minutes, preferably.
Keep at this temperature for 10-30 minutes to complete the reaction.
Thereafter, 10 to 50% (volume), preferably 10 to 30%, of water or warm water is added and mixed to the obtained reaction product, and the mixture is mixed with the basic substance and hydrogen halide. Dissolve Japanese salt into water. By performing this operation 1 to 3 times, a highly pure product can be obtained. In this case, the operating temperature is kept at a temperature in the range of 40-70 °C. Next, the reaction product is stirred and cooled to a temperature of about 25 to 15°C to crystallize the target product. In this way, the target crystals (10-45% by weight) and the solvent (35% by weight) are combined.
A slurry-like mixture of water (~85% by weight) and water (10~55% by weight) is obtained, but since this mixture contains water, its crystals are difficult to adhere to the walls of the reaction vessel, making it difficult to extract them from the reaction vessel. It can be done smoothly. This slurry mixture is subjected to solid-liquid separation using a solid-liquid separation means such as filtration or centrifugation, and the obtained solid is dried to form a product.
本発明の方法によれば、塩基性物質の共在下、
溶媒として塩素化合物系のものを用いたことによ
り、従来法に見られたような製品の着色等の問題
はない上、反応生成物を水洗する場合に、ゲル化
を生じるようなこともなく、目的物を高収率でか
つ容易に得ることができる。 According to the method of the present invention, in the coexistence of a basic substance,
By using a chlorine compound-based solvent as a solvent, there are no problems such as coloring of the product as seen in conventional methods, and there is no gelation when washing the reaction product with water. The target product can be easily obtained in high yield.
次に本発明を実施例によりさらに詳細に説明す
る
実施例
Ｎ−オクタデシルアミン134.75ｇを温度計、撹
拌装置、塩化ベンゾイル滴下装置、25％苛性ソー
ダ水溶液滴下装置及び開放弁の備えた容器にテト
ラクロルエチレン375c.c.と共に入れ、ウオーター
バスで55℃に加熱溶解した。完全に溶解させ、ウ
オーターバス温度設定を53℃にして次いで撹拌を
開始し、同時に25％苛性ソーダ水溶液90ｇを滴下
開始する。25％苛性ソーダ水溶液を５〜６滴滴下
してから塩化ベンゾイル72.67％ｇを滴下開始す
る。滴下速度は25％苛性ソーダ水溶液が毎分0.5
ｇ程度塩化ベンゾイル毎分0.4ｇ程度の速度で滴
下する。滴下直後反応槽内に塩酸ガスが見られる
が、反応槽内にこもる程度である。約３時間で滴
下終了、反応温度は54〜62℃であつた。反応終了
後、60〜65℃で15分加熱し反応を完結させた後、
50℃の温水150c.c.を加えて塩化ナトリウムを溶解
した。溶解後室温で撹拌しながら冷却晶析を行な
つた。水道水で17℃迄冷却して吸引ロ過して室温
放置で乾燥させ、融点87〜88℃の白色リン片結晶
181.24ｇを得た。収率は97％であつた。 Next, the present invention will be explained in more detail with reference to examples.Example: 134.75 g of N-octadecylamine was placed in a container equipped with a thermometer, a stirring device, a benzoyl chloride dropping device, a 25% caustic soda aqueous solution dropping device, and a release valve. 375 c.c. and heated to 55°C in a water bath to dissolve. After completely dissolving the mixture, set the water bath temperature to 53°C, then start stirring, and at the same time start dropping 90 g of a 25% aqueous solution of caustic soda. After dropping 5 to 6 drops of 25% aqueous sodium hydroxide solution, 72.67% g of benzoyl chloride is started. The dropping rate is 0.5 per minute for 25% caustic soda aqueous solution.
About 100 g of benzoyl chloride is added dropwise at a rate of about 0.4 g per minute. Hydrochloric acid gas can be seen in the reaction tank immediately after dropping, but it is only to the extent that it stays inside the reaction tank. The dropwise addition was completed in about 3 hours, and the reaction temperature was 54-62°C. After the reaction is completed, heat at 60-65℃ for 15 minutes to complete the reaction.
150 c.c. of 50°C warm water was added to dissolve the sodium chloride. After dissolution, cooling crystallization was performed while stirring at room temperature. Cool to 17℃ with tap water, filter with suction, and dry at room temperature to obtain white flake crystals with a melting point of 87-88℃.
181.24g was obtained. The yield was 97%.
また前記Ｎ−オクタデシルアミンに代えてＮ−
ラウリルアミンを用いて同様の実験を行なうこと
により、融点68〜69℃の白色リン片状結晶とし
て、収率93％でＮ−ラウリルカルバモイルベンゼ
ンの核置換体を得た。同様にして前記塩化ベンゾ
イルに代えて４−メトキシカルボニル−塩化ベン
ゾイルを用いることにより、融点117〜118℃白色
リン片状の結晶として、収率96％でその塩化ベン
ゾイルの核置換体に対応するＮ−オクタデシルカ
ルバモイルベンゼンの核置換体を得ることができ
た。同様に前記塩化ベンゾイルに代えて、４−メ
チル−塩化ベンゾイル、４−メトキシ−塩化ベン
ゾイル、４−クロル塩化ベンゾイル及び４−フエ
ニル−塩化ベンゾイルを用いても同様の実験を行
なうことにより、それらの塩化ベンゾイルの核置
換体に対応するＮ−オクタデシルカルバモイルベ
ンゼンの核置換体を得ることが出来た。 Also, in place of the N-octadecylamine, N-
By conducting a similar experiment using laurylamine, a nuclear substituted product of N-laurylcarbamoylbenzene was obtained as white flaky crystals with a melting point of 68 to 69°C in a yield of 93%. Similarly, by using 4-methoxycarbonyl-benzoyl chloride in place of the benzoyl chloride described above, the N corresponding to the nuclear substituted product of benzoyl chloride was obtained as white flaky crystals with a melting point of 117 to 118°C in a yield of 96%. - Nuclear substituted product of octadecylcarbamoylbenzene could be obtained. Similarly, by performing similar experiments using 4-methyl-benzoyl chloride, 4-methoxy-benzoyl chloride, 4-chlorobenzoyl chloride, and 4-phenyl-benzoyl chloride in place of the benzoyl chloride, A nuclear substituted product of N-octadecylcarbamoylbenzene corresponding to a nuclear substituted product of benzoyl could be obtained.
なお、比較のために、前記塩素化合物系溶媒の
代りに、トルエン、エタノールを用いた以外は同
様にして実験を行つたところ、トルエンを用いた
場合、中和塩溶解用温水を加えたところゲル化し
た。また、エタノールを用いた場合、縮合生成物
に着色が見られ、再結晶を２回繰返したが脱色で
きなかつた。又、収率も塩素化合物系溶媒を使用
した場合に比べ、収率が５〜10％ダウンした。 For comparison, an experiment was conducted in the same manner except that toluene and ethanol were used instead of the chlorine compound solvent. It became. Furthermore, when ethanol was used, the condensation product was colored, and although recrystallization was repeated twice, the color could not be removed. Furthermore, the yield was 5 to 10% lower than when a chlorine compound solvent was used.
Claims (1)
である） で表わされるＮ−高級アルキル又はアルケニルア
ミンと、一般式 （式中、Ｘはハロゲン原子、R2は低級アルキ
ル基、低級アルコキシ基、低級アルコキシカルボ
ニル基、ハロゲン原子又は前記のような置換基に
より核置換されていてもよいアリール基であり、
ｎは０〜５の整数である） で表わされるハロゲン化ベンゾイル又はその核置
換体とを脱ハロゲン化水素縮合する方法におい
て、前記Ｎ−高級アルキル又はアルケニルアミン
をあらかじめ塩素化合物系溶媒中に溶解した溶液
に対し、塩基性物質の存在下、前記ハロゲン化ベ
ンゾイル又はその核置換体を液状又は固体状で
徐々に加えて縮合反応を行い、反応終了後、水又
は温水を加えて生成した中和塩を溶解除去するこ
とを特徴とする、一般式 （式中、R1，R2及びｎは前記と同じ意味を有
する） で表わされるＮ−高級アルキル又はアルケニルカ
ルバモイルベンゼン及びその核置換体の製造方
法。[Scope of Claims] 1 N-higher alkyl or alkenylamine represented by the general formula R 1 -NH 2 (wherein R 1 is a higher alkyl or alkenyl group); (In the formula ,
n is an integer of 0 to 5), in which the N-higher alkyl or alkenylamine is dissolved in advance in a chlorine compound solvent. A neutralized salt produced by gradually adding the halogenated benzoyl or its nuclear substituted product in liquid or solid form to a solution in the presence of a basic substance to perform a condensation reaction, and after the reaction is completed, water or warm water is added. A general formula characterized by dissolving and removing (In the formula, R 1 , R 2 and n have the same meanings as above.) A method for producing N-higher alkyl or alkenylcarbamoylbenzene and a nuclear substituted product thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11456382A JPS595151A (en) | 1982-07-01 | 1982-07-01 | Preparation of n-substituted carbamoylbenzene and its nucleus-substituted derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11456382A JPS595151A (en) | 1982-07-01 | 1982-07-01 | Preparation of n-substituted carbamoylbenzene and its nucleus-substituted derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS595151A JPS595151A (en) | 1984-01-12 |
| JPH0318608B2 true JPH0318608B2 (en) | 1991-03-13 |
Family
ID=14640940
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11456382A Granted JPS595151A (en) | 1982-07-01 | 1982-07-01 | Preparation of n-substituted carbamoylbenzene and its nucleus-substituted derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS595151A (en) |
-
1982
- 1982-07-01 JP JP11456382A patent/JPS595151A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS595151A (en) | 1984-01-12 |
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