JPS6327338B2 - - Google Patents
Info
- Publication number
- JPS6327338B2 JPS6327338B2 JP57155115A JP15511582A JPS6327338B2 JP S6327338 B2 JPS6327338 B2 JP S6327338B2 JP 57155115 A JP57155115 A JP 57155115A JP 15511582 A JP15511582 A JP 15511582A JP S6327338 B2 JPS6327338 B2 JP S6327338B2
- Authority
- JP
- Japan
- Prior art keywords
- chloride
- secondary amine
- added
- weight
- parts
- 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
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- 150000003335 secondary amines Chemical class 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 11
- 150000001412 amines Chemical class 0.000 claims description 6
- 239000012442 inert solvent Substances 0.000 claims description 6
- 125000005842 heteroatom Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- CKDWPUIZGOQOOM-UHFFFAOYSA-N Carbamyl chloride Chemical compound NC(Cl)=O CKDWPUIZGOQOOM-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 239000006227 byproduct Substances 0.000 description 10
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 10
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000370 acceptor Substances 0.000 description 9
- 150000003672 ureas Chemical class 0.000 description 9
- -1 secondary amine hydrochloride Chemical class 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- BWLUMTFWVZZZND-UHFFFAOYSA-N Dibenzylamine Chemical compound C=1C=CC=CC=1CNCC1=CC=CC=C1 BWLUMTFWVZZZND-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 125000005265 dialkylamine group Chemical group 0.000 description 2
- OFCCYDUUBNUJIB-UHFFFAOYSA-N n,n-diethylcarbamoyl chloride Chemical compound CCN(CC)C(Cl)=O OFCCYDUUBNUJIB-UHFFFAOYSA-N 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 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
- XNRHTMDHGDWBGP-UHFFFAOYSA-N carbamic acid;hydrochloride Chemical compound Cl.NC(O)=O XNRHTMDHGDWBGP-UHFFFAOYSA-N 0.000 description 1
- RJIAFTWIVJLVAW-UHFFFAOYSA-N carbamoyl chloride;piperidine Chemical compound NC(Cl)=O.C1CCNCC1 RJIAFTWIVJLVAW-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- XJZOWMZIBPJQLE-UHFFFAOYSA-N n,n-dibenzylcarbamoyl chloride Chemical compound C=1C=CC=CC=1CN(C(=O)Cl)CC1=CC=CC=C1 XJZOWMZIBPJQLE-UHFFFAOYSA-N 0.000 description 1
- PNLJKMRPJPRAST-UHFFFAOYSA-N n-morpholin-4-ylcarbamoyl chloride Chemical compound ClC(=O)NN1CCOCC1 PNLJKMRPJPRAST-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明はカルバミン酸クロライドの製造方法に
関し、更に詳しくはカルボニルクロライドと第２
級アミンとの反応によつて一般式
（ここで、R1、R2はそれぞれアルキル基または
アラルキル基であり、R1とR2は炭素−炭素結合
またはヘテロ原子を介して環構造を形成してもよ
い。）
で表わされるカルバミン酸クロライドを製造する
方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing carbamic acid chloride, and more specifically to a method for producing carbamic acid chloride and a second
By reaction with grade amine, the general formula (Here, R 1 and R 2 are each an alkyl group or an aralkyl group, and R 1 and R 2 may form a ring structure via a carbon-carbon bond or a hetero atom.) The present invention relates to a method for producing chloride.
第２級アミンから誘導されるカルバミン酸クロ
ライドは、これ迄に種々の合成方法が知られてお
り、その方法は大別して低温法と高温法に分ける
ことができる。例えば、低温でトルエンあるいは
ベンゼン溶媒中で第２級アミンとカルボニルクロ
ライドとを反応させる方法があるが、この方法で
は必ず第２級アミンの塩酸塩がカルバミン酸クロ
ライドと等モル生成し、さらに第２級アミン２分
子がカルボニル基で結合された尿素誘導体が少な
からぬ量生成する。そのため目的とするカルバミ
ン酸クロライドを単離することが困難であり、ま
た、その操作も複雑であつた。 Various methods for synthesizing carbamic acid chloride derived from secondary amines have been known, and these methods can be broadly divided into low-temperature methods and high-temperature methods. For example, there is a method of reacting a secondary amine with carbonyl chloride in a toluene or benzene solvent at a low temperature, but this method always produces equimolar amounts of the hydrochloride of the secondary amine and the carbamic acid chloride; A considerable amount of a urea derivative in which two molecules of a grade amine are bonded via a carbonyl group is produced. Therefore, it was difficult to isolate the desired carbamic acid chloride, and the operation was also complicated.
一方、高温下で行なう方法としては、目的とす
るカルバミン酸クロライドを溶媒として用い60〜
160℃で第２級アミンとカルボニルクロライドと
を反応させる方法があるが、この方法は副生する
塩化水素ガスを排除しつつ反応を進める必要があ
り、そのために反応制御が微妙で反応時間が長く
なり易く、カルボニルクロライドも過剰に必要と
なり、更にまた尿素誘導体も生成し易い。 On the other hand, as a method for carrying out at high temperature, the target carbamic acid chloride is used as a solvent and the
There is a method of reacting a secondary amine and carbonyl chloride at 160℃, but this method requires the reaction to proceed while eliminating by-product hydrogen chloride gas, which requires delicate reaction control and takes a long time. carbonyl chloride is required in excess, and urea derivatives are also likely to be produced.
従つて、これらの方法は工業的に有利な方法と
はいえなかつた。 Therefore, these methods cannot be said to be industrially advantageous.
本発明者らは、上記の如き欠点のない製造方法
について鋭意研究した結果、低温下不活性溶媒中
のカルボニルクロライドに第２級アミンと酸受容
体とを同時に添加すると、第２級アミン塩酸塩や
尿素誘導体等の副反応が起らず、目的とするカル
バミン酸クロライドが高収率（85〜95％）でしか
も高純度（98％以上）で得られることを見出し、
本発明に到つた。 As a result of intensive research into a production method that does not have the above drawbacks, the present inventors found that when a secondary amine and an acid acceptor are simultaneously added to carbonyl chloride in an inert solvent at low temperatures, secondary amine hydrochloride We discovered that the desired carbamic acid chloride could be obtained in high yield (85-95%) and with high purity (over 98%) without causing side reactions such as urea derivatives and urea derivatives.
We have arrived at the present invention.
すなわち、本発明は不活性溶媒中のカルボニル
クロライドに第２級アミンと酸受容体とを同時に
添加し、反応させることを特徴とする一般式
（ここで、R1、R2はそれぞれアルキル基または
アラルキル基であり、R1とR2は炭素−炭素結合
またはヘテロ原子を介して環構造を形成してもよ
い。）
で表わされるカルバミン酸クロライドの製造方法
である。 That is, the present invention provides a general formula characterized in that a secondary amine and an acid acceptor are simultaneously added to carbonyl chloride in an inert solvent and reacted. (Here, R 1 and R 2 are each an alkyl group or an aralkyl group, and R 1 and R 2 may form a ring structure via a carbon-carbon bond or a hetero atom.) This is a method for producing chloride.
本発明は、副生する塩化水素を効率よく排除す
るところに重要な意義がある。これ迄の製造方法
の欠点の大きな１つは副生する塩化水素の排除方
法であつた。第２級アミンとカルボニルクロライ
ドとからカルバミン酸クロライドを製造する際に
は必ず塩化水素が副生するが、塩化水素は第２級
アミンと塩酸塩を形成し易く、収率の低下を招
く。従つて、効率良く塩化水素を排除する必要が
あり、予め反応系に酸受容体例えばアルカリ金属
水酸化物等を共存させることもできる。しかし、
この場合には酸受容体は副生する塩化水素をその
塩として排除し、第２級アミン塩酸塩の生成を抑
制するが、同時に、生成したカルバミン酸クロラ
イドと第２級アミンとから脱塩化水素反応を促
し、尿素誘導体を副生させる。しかしながら、副
生する塩化水素に見合つた量の酸受容体を第２級
アミンと同時に添加すると驚くべきことには、第
２級アミンの塩酸塩の生成を抑えるばかりでな
く、尿素誘導体の反応も起らず、非常に効率良く
塩化水素を排除することができ、高収率、高純度
でカルバミン酸クロライドを得ることができる。 The present invention has important significance in that it efficiently eliminates by-product hydrogen chloride. One of the major drawbacks of the production methods up to now has been the method of eliminating by-product hydrogen chloride. Hydrogen chloride is always produced as a by-product when carbamic acid chloride is produced from a secondary amine and carbonyl chloride, but hydrogen chloride tends to form a hydrochloride with the secondary amine, resulting in a decrease in yield. Therefore, it is necessary to efficiently eliminate hydrogen chloride, and an acid acceptor such as an alkali metal hydroxide may be allowed to coexist in the reaction system in advance. but,
In this case, the acid acceptor eliminates the by-product hydrogen chloride as its salt and suppresses the formation of secondary amine hydrochloride, but at the same time dehydrochlorinates the generated carbamate chloride and secondary amine. Promotes the reaction and produces urea derivatives as a by-product. However, surprisingly, when an amount of acid acceptor commensurate with the by-product hydrogen chloride is added at the same time as a secondary amine, it not only suppresses the formation of secondary amine hydrochloride, but also inhibits the reaction of urea derivatives. Hydrogen chloride can be eliminated very efficiently, and carbamic acid chloride can be obtained in high yield and purity.
本発明で用いる酸受容体は、例えば水酸化ナト
リウム、水酸化カリウム等の如きアルカリ金属の
水酸化物あるいは水酸化バリウム、水酸化カルシ
ウム等の如きアルカリ土類金属の水酸化物であ
り、水溶液にして用いる。酸受容体の添加量は、
同時に添加する第２級アミンに対して１〜1.5倍
当量であるのが好ましく、副生する塩化水素を捕
捉し得る量のみを逐次添加する様調節するのが好
ましい。この量が１倍当量より少なくなると、第
２級アミンの塩酸塩が生成して好ましくなく、ま
た1.5倍当量を超える添加は尿素誘導体の副生を
促進し、収率の低下につながるので好ましくな
い。 The acid acceptor used in the present invention is, for example, an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, etc. or an alkaline earth metal hydroxide such as barium hydroxide, calcium hydroxide, etc., and is not dissolved in aqueous solution. used. The amount of acid acceptor added is
The amount is preferably 1 to 1.5 times equivalent to the secondary amine added at the same time, and it is preferable to adjust the amount to be added sequentially so that only the amount capable of capturing hydrogen chloride as a by-product is added. If this amount is less than 1-fold equivalent, it is undesirable because hydrochloride of the secondary amine is formed, and addition of more than 1.5-fold equivalent is undesirable because it promotes the by-production of urea derivatives and leads to a decrease in yield. .
本発明で用いる第２級アミンは、下記一般式
（ここで、R1、R2はそれぞれアルキル基または
アラルキル基であり、R1とR2は炭素−炭素結合
またはヘテロ原子を介して環構造を形成してもよ
い。）
で表わされる第２級アミンである。この第２級ア
ミンとしては、ジメチルアミン、ジエチルアミ
ン、ジ−ｎ−プロピルアミン等の如きジアルキル
アミン；ジベンジルアミンの如きジアラルキルア
ミン；ピロリジン、ピペリジン等の如き複素環を
形成したアミン；モルホリンの如き他のヘテロ原
子を含有した複素環アミン等が例示できる。 The secondary amine used in the present invention has the following general formula: (Here, R 1 and R 2 are each an alkyl group or an aralkyl group, and R 1 and R 2 may form a ring structure via a carbon-carbon bond or a hetero atom.) It is a grade amine. Examples of the secondary amines include dialkylamines such as dimethylamine, diethylamine, and di-n-propylamine; dialkylamines such as dibenzylamine; heterocyclic amines such as pyrrolidine and piperidine; and amines such as morpholine. Examples include heterocyclic amines containing other heteroatoms.
また、本発明で用いる不活性溶媒としては、ベ
ンゼン、トルエン、クロルベンゼン、塩化メチレ
ン、塩化エチレン等の如き不活性な溶媒を例示す
ることができる。 Furthermore, examples of the inert solvent used in the present invention include inert solvents such as benzene, toluene, chlorobenzene, methylene chloride, and ethylene chloride.
本発明においては、カルボニルクロライドを、
第２級アミンに対し等モル、場合によつては僅か
に過剰な量用いて予め−15〜＋５℃に冷却した上
記不活性溶媒に溶解し、これに撹拌冷却下で第２
級アミンと酸受容体とを同時に添加する。反応温
度は−15〜＋５℃になる様調節する。温度が＋５
℃より高くなると尿素誘導体が副生する反応が起
こり易くなると同時に、副反応が起こる事によつ
て酸受容体が消費されて不足することになり、第
２級アミンの塩酸塩の生成も起こり収率の低下に
つながる。また−15℃より低い場合反応的には不
都合はないが必要以上に冷却することになり製造
コスト的に不利となる。 In the present invention, carbonyl chloride is
It is dissolved in the above-mentioned inert solvent, which has been pre-cooled to -15 to +5°C, using an equimolar amount, or in some cases, a slightly excess amount, based on the secondary amine, and the secondary amine is added to the secondary amine under stirring and cooling.
amine and acid acceptor are added simultaneously. The reaction temperature is adjusted to -15 to +5°C. temperature is +5
When the temperature rises above ℃, reactions that produce urea derivatives as by-products tend to occur, and at the same time, acid acceptors are consumed and become insufficient due to the side reactions, and secondary amine hydrochloride is also formed, resulting in lower yields. leading to lower rates. Further, if the temperature is lower than -15°C, there is no disadvantage in terms of reaction, but the temperature is unnecessarily cooled, which is disadvantageous in terms of manufacturing cost.
反応終了と同時に水相と有機相とに分離し、有
機相から溶媒を除去すると収率が85〜95％で、純
度98％以上のカルバミン酸クロライドが得られ
る。必要に応じて蒸留することもできるが、粗製
品でも充分に使用できる。 Upon completion of the reaction, the reaction mixture is separated into an aqueous phase and an organic phase, and the solvent is removed from the organic phase to obtain carbamic acid chloride with a yield of 85 to 95% and a purity of 98% or higher. It can be distilled if necessary, but the crude product can also be used satisfactorily.
本発明によれば、第２級アミンの塩酸塩の生成
がなく、しかも尿素誘導体も副生せず、非常に効
率良く第２級アミンからカルバミン酸クロライド
を製造することが可能となる。化学工学上重要な
中間物質である第２級アミンから誘導されるカル
バミン酸クロライドを非常に容易かつ効率良く製
造することが出来る本発明は工業的意義大であ
る。 According to the present invention, there is no generation of hydrochloride of a secondary amine, and no urea derivative is produced as a by-product, making it possible to produce carbamic acid chloride from a secondary amine very efficiently. The present invention is of great industrial significance as it allows the production of carbamic acid chloride derived from secondary amines, which are important intermediates in chemical engineering, very easily and efficiently.
以下、実施例を掲げてさらに本発明を詳しく説
明する。 Hereinafter, the present invention will be further explained in detail with reference to Examples.
実施例 １
撹拌装置を取り付けた２丸底フラスコにベン
ゼン820重量部を入れ、−10〜−５℃に冷却してカ
ルボニルクロライド73重量部を入れた。撹拌しな
がらジエチルアミン51重量部及び10％水酸化ナト
リウム水溶液340重量部を同時に添加した。その
際ジエチルアミン及び水酸化ナトリウム水溶液は
それぞれ一定速度で60分かけて添加する様調節し
た。反応温度は−15〜＋５℃の範囲になる様冷却
を続けた。反応終了後、有機相よりベンゼンを留
去してジエチルカルバミン酸クロライド88重量部
（理論収量の93％）を得た。このものをガスクロ
マトグラフで分析（日立ガスクロマトグラフ073
形検出器FID、カラムクロモソルブw3％／シリ
コンガムSE−30（ガスクロ工業）3φ×２ｍ、100
〜200℃）したところ、ジエチルカルバミン酸ク
ロライド以外のピークは認められなかつた。Example 1 820 parts by weight of benzene was placed in a two-round bottom flask equipped with a stirrer, cooled to -10 to -5°C, and 73 parts by weight of carbonyl chloride was added. While stirring, 51 parts by weight of diethylamine and 340 parts by weight of a 10% aqueous sodium hydroxide solution were simultaneously added. At this time, diethylamine and the aqueous sodium hydroxide solution were each added at a constant rate over 60 minutes. Cooling was continued so that the reaction temperature was in the range of -15 to +5°C. After the reaction was completed, benzene was distilled off from the organic phase to obtain 88 parts by weight of diethylcarbamic acid chloride (93% of the theoretical yield). Analyze this using a gas chromatograph (Hitachi Gas Chromatograph 073
Shape detector FID, column chromosolve w3%/silicon gum SE-30 (Gas Kuro Kogyo) 3φ x 2m, 100
~200°C), no peaks other than diethylcarbamic acid chloride were observed.
実施例 ２
ジベンジルアミン130重量部を用いる以外は、
実施例１と同様に行なつた所、結晶性で沸点187
〜190℃／１mmHgを持つジベンジルカルバミン酸
クロライド149重量部（理論収量の87％）を得た。Example 2 Except using 130 parts by weight of dibenzylamine,
When carried out in the same manner as in Example 1, it was crystalline and had a boiling point of 187.
149 parts by weight (87% of theoretical yield) of dibenzylcarbamic acid chloride with ˜190° C./1 mmHg were obtained.
実施例 ３
撹拌装置を取り付けた２丸底フラスコに塩化
メチレン740重量部を仕込み、−10℃に冷却した後
カルボニルクロライド74重量部を加えた。−５℃
〜＋２℃を保ちながら撹拌下で60重量部のピペリ
ジンを1.2重量部／分で、また15％水酸化カリウ
ム水溶液342重量部を6.84重量部／分で同時に滴
下した。滴下終了後、反応液より有機相を分離
し、塩化メチレンを蒸発除去すると僅かに黄色に
着色した粗製ピペリジンカルバミン酸クロライド
95重量部（理論値の91％に相当）が得られた。こ
の生成物の純度は99％以上でほとんど不純物を含
んでいなかつた。またその沸点は108〜110℃／14
mmHgであつた。Example 3 740 parts by weight of methylene chloride was charged into a two round bottom flask equipped with a stirring device, and after cooling to -10°C, 74 parts by weight of carbonyl chloride was added. -5℃
60 parts by weight of piperidine were simultaneously added dropwise at a rate of 1.2 parts by weight/min and 342 parts by weight of a 15% aqueous potassium hydroxide solution were added dropwise at a rate of 6.84 parts by weight/min while maintaining the temperature at ~+2°C. After the dropwise addition, the organic phase was separated from the reaction solution and the methylene chloride was removed by evaporation, resulting in slightly yellow colored crude piperidine carbamic acid chloride.
95 parts by weight (corresponding to 91% of theory) were obtained. The purity of this product was over 99% and contained almost no impurities. Also, its boiling point is 108-110℃/14
It was mmHg.
実施例 ４
トルエン730重量部を撹拌装置を取り付けた２
丸底フラスコに入れ、−13℃に冷却した後カル
ボニルクロライド70重量部を加えた。−10℃〜０
℃を保持しつつ撹拌下で0.9重量部／分でモルホ
リンを、また6.2重量部／分で17％水酸化バリウ
ム水溶液を同時に滴下し、１時間で終了した。反
応液を分離し、有機相からトルエンを留去して粗
製モルホリンカルバミン酸クロライド82重量部
（理論値の88％）を得た。その純度は98.5％以上
であり、かつその沸点は110℃／10mmHgであつ
た。Example 4 730 parts by weight of toluene was added to 2 with a stirring device attached.
The mixture was placed in a round bottom flask, and after cooling to -13°C, 70 parts by weight of carbonyl chloride was added. -10℃〜0
While maintaining the temperature and stirring, morpholine was simultaneously added dropwise at a rate of 0.9 parts by weight/min, and a 17% aqueous barium hydroxide solution was simultaneously added dropwise at a rate of 6.2 parts by weight/min, and the reaction was completed in 1 hour. The reaction solution was separated and toluene was distilled off from the organic phase to obtain 82 parts by weight (88% of theory) of crude morpholinecarbamic acid chloride. Its purity was 98.5% or more, and its boiling point was 110°C/10mmHg.
Claims (1)
級アミンと酸受容体とを同時に添加し、反応させ
ることを特徴とする一般式 （ここで、R1、R2はそれぞれアルキル基または
アラルキル基であり、R1とR2は炭素−炭素結合
またはヘテロ原子を介して環構造を形成してもよ
い。） で表わされるカルバミン酸クロライドの製造方
法。 ２ 上記反応を−15℃〜＋５℃の範囲内にある温
度で行なうことを特徴とする特許請求の範囲第１
項記載の製造方法。 ３ 酸受容体の添加量が、同時に添加する第２級
アミンに対し１〜1.5倍当量であることを特徴と
する特許請求の範囲第１項記載の製造方法。 ４ 酸受容体がアルカリ金属水酸化物あるいはア
ルカリ土類金属水酸化物の水溶液であることを特
徴とする特許請求の範囲第２項または第３項記載
の製造方法。[Scope of Claims] 1. Carbonyl chloride in an inert solvent with a second
A general formula characterized by simultaneously adding and reacting a class amine and an acid acceptor. (Here, R 1 and R 2 are each an alkyl group or an aralkyl group, and R 1 and R 2 may form a ring structure via a carbon-carbon bond or a hetero atom.) Method for producing chloride. 2. Claim 1, characterized in that the above reaction is carried out at a temperature within the range of -15°C to +5°C.
Manufacturing method described in section. 3. The manufacturing method according to claim 1, wherein the amount of the acid acceptor added is 1 to 1.5 times equivalent to the secondary amine added at the same time. 4. The manufacturing method according to claim 2 or 3, wherein the acid acceptor is an aqueous solution of an alkali metal hydroxide or an alkaline earth metal hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57155115A JPS5944349A (en) | 1982-09-08 | 1982-09-08 | Preparation of carbamoyl chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57155115A JPS5944349A (en) | 1982-09-08 | 1982-09-08 | Preparation of carbamoyl chloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5944349A JPS5944349A (en) | 1984-03-12 |
| JPS6327338B2 true JPS6327338B2 (en) | 1988-06-02 |
Family
ID=15598909
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57155115A Granted JPS5944349A (en) | 1982-09-08 | 1982-09-08 | Preparation of carbamoyl chloride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5944349A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0345150U (en) * | 1988-11-30 | 1991-04-25 |
-
1982
- 1982-09-08 JP JP57155115A patent/JPS5944349A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0345150U (en) * | 1988-11-30 | 1991-04-25 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5944349A (en) | 1984-03-12 |
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