SU386921A1 - METHOD OF OBTAINING PROPARGIL CYCLOPROPLNLAMINES - Google Patents
METHOD OF OBTAINING PROPARGIL CYCLOPROPLNLAMINESInfo
- Publication number
- SU386921A1 SU386921A1 SU1621369A SU1621369A SU386921A1 SU 386921 A1 SU386921 A1 SU 386921A1 SU 1621369 A SU1621369 A SU 1621369A SU 1621369 A SU1621369 A SU 1621369A SU 386921 A1 SU386921 A1 SU 386921A1
- Authority
- SU
- USSR - Soviet Union
- Prior art keywords
- cyclopropylamine
- obtaining
- cycloproplnlamines
- propargil
- halide
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 5
- ZYHMJXZULPZUED-UHFFFAOYSA-N propargite Chemical compound C1=CC(C(C)(C)C)=CC=C1OC1C(OS(=O)OCC#C)CCCC1 ZYHMJXZULPZUED-UHFFFAOYSA-N 0.000 title 1
- HTJDQJBWANPRPF-UHFFFAOYSA-N Cyclopropylamine Chemical compound NC1CC1 HTJDQJBWANPRPF-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims 1
- QNJFRCLMHDVMQQ-UHFFFAOYSA-N n-prop-2-ynylcyclopropanamine Chemical class C#CCNC1CC1 QNJFRCLMHDVMQQ-UHFFFAOYSA-N 0.000 claims 1
- 150000003335 secondary amines Chemical class 0.000 claims 1
- 150000003512 tertiary amines Chemical class 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 3
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical group C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- -1 cyclopropane amines Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Предлагаетс способ получени не описанных IB литературе аминов ци1кло:проп.а1нового р да. Эти .соединени содержат одновременно заместители ацетиленового и алищиклического р дов и могут быть использованы дл синтеза сложных физиологически активных веществ . П:ре.длагаемый способ основан на известной реакции ал:килиров1ани первичных амннов галоидными алкилами, однако использованне новых исходных продуктов приводит к получению не известных ранее аминов циклопропанового р да, содержащих у атома азота проп;аршльные заместители. Способ (Получени про аргилциклонролиламинов за-ключаетс в алкилироваиии циклопроПиламива галоидным пропаргилом, цреимущес1Ввнно бромистым пропа.ргилом, с последующнм выделением целевого продукта известным способом. В зависимости от условий проведени реакции мож1но НОлучать преимущественно либо вторнчные, либо третичные амины. Прол,аргилциклопропиламин он-нтезируют при мол рном отношении циклопропиламина к галоидному лро1паргилу 5:1, а дипропаргилциклопропиламиН-три мол рном отношении циклопропиламина к галоидному нроналгилу 1 : 1-1 : 2. Выдел ющийс галоидводород в обоих случа х св зывают 40%-ным раствором едкого натра. Пример 1. 12,0 г (0,1 моль} бромистого проларгила прикапывают при неремешивании к смеси 28,5 г (0,5 моль) циклопроииламина и 50 мл 40%-ного раствора натра, охлажденной до 5-10°С. З.атем температуру повышают до 40°С и неремещивают смесь 3- 4 час. После охлаждени реакционной колбы до 10-15°С отдел ют верхний слой амина. Оставшийс амин из водно-щелочного сло экстрагируют бензолом. Экстракт смешивают с ocHOiBiHbiM (Количеством амина и высушивают над .поташом. Затем при атмосферном давлении отгон ют ци клопропиламин и растворитель , а остаток перегон ют в вакууме. Получают 7,2 г продукта (74% от теоретического , счита на бромистый пронарпил), т. .кип. 80°С/40 мм рт. ст.; 135°С/760 мм рт. ст.; «.,1,4621; ,9014; MR найдено 29,25; вычислено 29,87. Степень чистоты, по данным газо-жидкостной х/роматографии, 96,8%. В ИК-спектре соединени присутствуют полосы, ел-: 770, 1560, 3325 (вторичный амн«), 1272, 2115, 3300 (ацетиленова группа), 811, 1033, 1170, ЗОЮ, 3085 (циклопропановое кольцо).A method is proposed for the preparation of undescribed IB literature of amines of cyclo: prop. A1 of a new series. These compounds simultaneously contain substituents of the acetylene and alisclic series and can be used to synthesize complex physiologically active substances. P: The proposed method is based on the known reaction of al: cylation of primary amnes with halide alkyls, but the use of new initial products results in previously unknown cyclopropane amines containing a prop atom at the nitrogen atom; The ones (Obtaining pro argyl cyclonrolylamines include the alkylating of cyclopropylamine by halogen propargyl, which is required1) Bpyl propylganol, with subsequent isolation of the desired product in a known manner. with a molar ratio of cyclopropylamine to halide lro-pargil 5: 1, and dipropargylcyclopropylamino-three molar ratio of cyclopropylamine to halide nronalg 1: 1-1: 2. Hydrogen halide released in both cases is bound with 40% sodium hydroxide solution. Example 1. 12.0 g (0.1 mol) of prolar bromide are added dropwise, without stirring, to a mixture of 28.5 g (0.5 mol) cyclopropylamine and 50 ml of a 40% sodium chloride solution cooled to 5-10 ° C. Then the temperature is raised to 40 ° C and the mixture is not placed for 3 to 4 hours. After cooling the reaction flask to 10-15 The upper amine layer is separated and the remaining amine is extracted from the alkaline water layer with benzene. The extract is mixed with ocHOiBiHbiM (Amount of amine and dried over potash. Then cyclopropylamine and solvent are distilled off at atmospheric pressure and the residue is distilled in vacuum. 7.2 g of product are obtained (74% of theoretical, calculated from methyl pronarpyl), t .Kip. 80 ° C / 40 mm Hg; 135 ° C / 760 mm Hg; "., 1.4621;, 9014; MR found 29.25; calculated 29.87. Degree of purity, according to gas-liquid x / romatography, 96.8%. In the IR spectrum of the compound there are bands, el-: 770, 1560, 3325 (secondary amn "), 1272, 2115, 3300 (acetylene group), 811, 1033, 1170, ZOYU, 3085 (cyclopropane ring).
Найдено, %: С 76,36; 76,61; Н 9,03; 9,16; N 14,42; 14,20.Found,%: C 76.36; 76.61; H 9.03; 9.16; N 14.42; 14.20.
CeHgNCeHgN
Вычислено, %: С 76,40; Н 9,04; N 14,56.Calculated,%: C, 76.40; H 9.04; N 14.56.
Качестве1вно налич ие вторичной аминогруппы лодтверждено реакцией диазотирова«и с получением нитрозопроизводиого, а кооцевой ацетиленовой группы - реакцией с аммиачным раствором полухлористой меди.The quality of the presence of the secondary amino group is confirmed by the reaction of diazotirs and with the formation of the nitro-producing, and that of the acetylenic group by the reaction with an ammonia solution of copper chloride.
Пример 2. Дипропаргилциклопропиламин получают аналогичио «з 12 г (0,2 моль циклопрооиламина и 48 г (0,4 моль) броми-стото прошаргила в присутствии 50 мл 40%-ного раствора едкого натра. Выход 23,0 г (89%, счита «а ци-клопропиламии); т. кип. 85°С/20 мм рт. ст.; 179°С/760 мм рт. ст.; п2о 1Д715; d| 0,9182; MR «айдено 41,35, вычислено 41,88.Example 2. Dipropargilcyclopropylamine get analogue "C 12 g (0.2 mol of cyclopropyl amine and 48 g (0.4 mol) bromo-stoto proshargila in the presence of 50 ml of 40% aqueous solution of sodium hydroxide. Yield 23.0 g (89%, counting “a tsiklopropilamiya”; kip. 85 ° С / 20 mm Hg; 179 ° С / 760 mm Hg; п2о 1Д715; d | 0.9182; MR “found 41.35, calculated 41.88.
Степень чистоты (по данным газо-жид)костной хроматографии) полученного продукта 97,6%.The degree of purity (according to gas-liquid) bone chromatography) of the obtained product is 97.6%.
В ИК-icneiKTpe соединени найдены полосы, еж-: 1270, 2115, 3300 (колебани ацетиленовой группы); 811, 1033, 1170, ЗОЮ, 3085 (циклопропановое кольцо).Bands were found in the IR-icneKTpe compound, hedgehog-: 1270, 2115, 3300 (vibrations of the acetylene group); 811, 1033, 1170, ZOYU, 3085 (cyclopropane ring).
Найдено, %: С 81,07; 81,11; Н 8,20; 8,40; N 10,54.Found,%: C 81.07; 81.11; H 8.20; 8.40; N 10.54.
CgHiiNCgHiiN
Вычислено, %: С 81,26; Н 8,34; N 10,40.Calculated,%: C 81.26; H 8.34; N 10.40.
Предмет изобретени Subject invention
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SU1621369A SU386921A1 (en) | 1971-02-15 | 1971-02-15 | METHOD OF OBTAINING PROPARGIL CYCLOPROPLNLAMINES |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SU1621369A SU386921A1 (en) | 1971-02-15 | 1971-02-15 | METHOD OF OBTAINING PROPARGIL CYCLOPROPLNLAMINES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| SU386921A1 true SU386921A1 (en) | 1973-06-21 |
Family
ID=20465857
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| SU1621369A SU386921A1 (en) | 1971-02-15 | 1971-02-15 | METHOD OF OBTAINING PROPARGIL CYCLOPROPLNLAMINES |
Country Status (1)
| Country | Link |
|---|---|
| SU (1) | SU386921A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109264886A (en) * | 2018-09-17 | 2019-01-25 | 大丰跃龙化学有限公司 | A kind of wastewater treatment method in cyclopropylamine production process |
-
1971
- 1971-02-15 SU SU1621369A patent/SU386921A1/en active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109264886A (en) * | 2018-09-17 | 2019-01-25 | 大丰跃龙化学有限公司 | A kind of wastewater treatment method in cyclopropylamine production process |
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