SU628811A3 - Diphenylamine derivative producing method - Google Patents
Diphenylamine derivative producing methodInfo
- Publication number
- SU628811A3 SU628811A3 SU762395606A SU2395606A SU628811A3 SU 628811 A3 SU628811 A3 SU 628811A3 SU 762395606 A SU762395606 A SU 762395606A SU 2395606 A SU2395606 A SU 2395606A SU 628811 A3 SU628811 A3 SU 628811A3
- Authority
- SU
- USSR - Soviet Union
- Prior art keywords
- producing method
- reaction
- diphenylamine
- diphenylamine derivative
- methyl
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D211/56—Nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/07—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by halogen atoms
- C07C205/11—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by halogen atoms having nitro groups bound to carbon atoms of six-membered aromatic rings
- C07C205/12—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by halogen atoms having nitro groups bound to carbon atoms of six-membered aromatic rings the six-membered aromatic ring or a condensed ring system containing that ring being substituted by halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
- C07C211/52—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
Description
1one
Изобретение относитс к способу получени новых производных дифениламина общей формулы 1This invention relates to a process for the preparation of new diphenylamine derivatives of the general formula 1
KOjKoj
где R метил, этил или пропил; и R независимо друг .от друга - водород, метил-или трифторметил; Я - водород или метил при условии, что не более,чем один из радикалов К , и К не вл етс водородом, oблa aющим биологической активностью.where R is methyl, ethyl or propyl; and R independently of each other is hydrogen, methyl or trifluoromethyl; I is hydrogen or methyl with the proviso that no more than one of the radicals K and K is not hydrogen, which has biological activity.
В литературе описан способ получени третичных аминов, заключающийс в реакции N -алкилировани вторичных аминов галоидными алкилами l Однако отсутствуют 1гакие-либо сведени о способе получени дифениламинов общей формулы I, обладающих биологической активностью. Целью изобретени вл етс расглирёние ассортимента соединений, обладающих антибиологичёской активностью, в частности , получение дифениламинов общей формулы I, .The literature describes a method for the preparation of tertiary amines, which consists in the reaction of N-alkylation of secondary amines with halide alkyls. However, there is no any information about the method of obtaining diphenylamines of general formula I, which have biological activity. The aim of the invention is the splitting of the range of compounds with antibiological activity, in particular, the preparation of diphenylamines of general formula I,.
Предлагаелмй способ заключаетс в том, что 2-галоид-3, 5-динитробензотрифториды общей формулы IIThe proposed method is that 2-halogen-3, 5-dinitrobenzotrifluorides of the general formula II
N02N02
OgNvXOgnvx
№3Number 3
где X - атгом галогена, подвергают взаимодействию с производным анилина общей формулы IIIwhere X is halogen atgom, is reacted with an aniline derivative of general formula III
Жг HIBurn HI
-кн-kn
г ;g;
1 -гэ 2 31-ge 2 3
где Я 1 г и Я имеют указанныеwhere I am 1 g and I have indicated
значени , в .инертном органическом растворителе в присутствии сильного основани при температуре от -20 до +25 С с последующим N -алкилированием полученного таким образом соединени диалкилсульфатом или гапоидным алкилом с числом углеродных атомов 1-3 в инертном органическом растворителе при температуре 20150с .value, in an inert organic solvent in the presence of a strong base at a temperature of from -20 to + 25 ° C, followed by N-alkylation of the compound thus obtained with dialkyl sulfate or hapoid alkyl of 1-3 carbon atoms in an inert organic solvent at a temperature of 20150s.
Как правило, дл успешного протекани этой реакции необходимо присутствие сильного основани , которое выполн ет роль.акцептора образующейс кислоты (галоидоводорода).As a rule, for the success of this reaction, the presence of a strong base, which plays the role of an acceptor of the resulting acid (hydrogen halide), is necessary.
Гидрид натри вл етс одним из наиболее предпочтительных оснований дл этой цели.Sodium hydride is one of the most preferred bases for this purpose.
При использовании диалкилсульфата наиболее предпочтительным растворителем дл проведени реакции вл етс ацетон. Дл этой цели пригодны также другие растворители, такие как тетрагидрофуран, диоксан и диэтиловы эфир, а также, некотороые алканы, такие как гексан и октан. При алкилировании алкилгалогенидами наиболее предпочтительным растворителем вл етс диметилформамид Другие указанные растворители также можно использовать дл этой цели. Наиболее предпочтительными основани ми дл использовани в реакци х К -алкилировани дифениламинов вл ютс те вещества основного характера, которые обладаю дегидратирующим эффектом, в частности , карбонат натри . Однако дл этой цели можно использовать и други неорганические основани , такие как карбонаты, бикарбонаты и гидроокиси щелочных металлов, а также гидриды щелочных металлов,When using dialkyl sulfate, acetone is the most preferred solvent for the reaction. Other solvents, such as tetrahydrofuran, dioxane and diethyl ether, as well as some alkanes, such as hexane and octane, are also suitable for this purpose. When alkylating with alkyl halides, dimethylformamide is the most preferred solvent. Other indicated solvents can also be used for this purpose. The most preferred bases for use in diphenylamine K-alkylation reactions are those basic substances that have a dehydrating effect, in particular sodium carbonate. However, other inorganic bases, such as carbonates, bicarbonates and alkali metal hydroxides, as well as alkali metal hydrides, can be used for this purpose.
Количество основани , используемого в том или случае, зависит от температуры реакции. Чем выше температура реакции на стадии алкилировани , тем больший избыток основани необходимо вводить в реакционную смесь. Когда реакцию алкилировани провод т при температурр, приблизительно соответствующей температурере окрух ающей среды, следует использовать небольшой избыток основани - примерно 2 мол основани на 1 моль дифениламина. Когда же реакцию провод т при очень высокой температуре (пор дка ) , то следует брать большой избыток основани - около 10 молей основани на 1 моль дифениламина .The amount of base used in either case depends on the reaction temperature. The higher the reaction temperature in the alkylation step, the greater the excess base must be introduced into the reaction mixture. When the alkylation reaction is carried out at a temperature approximately equal to the ambient temperature, a slight excess of base should be used — about 2 moles of base per 1 mole of diphenylamine. When the reaction is carried out at a very high temperature (on the order of), a large excess of base should be taken — about 10 moles of base per 1 mole of diphenylamine.
Пример 1. W -Метил-2,4-ди нитро-б-трифтормети1щифениламин.Example 1. W-Methyl-2,4-di-nitro-b-trifluoromethycchiphenylamine.
27 г 2-ХЛОР-355-Динитробензотри фторида прибавл ют к 20 г анилина и 75 мл этанола. После кратковремен . кого перемешивани при комнатной температуре в реакционную внос т затравку (небольшую порцию) желаемого промежуточного продукта. При этом наблюдаетс немедленное образование обильного осадка. Этот осадок отдел ют фильтрованием и получают 2,4-динитро-б-трифторметилдифениламин (28,5 г) .27 g of 2-HLOR-355-Dinitrobenzotri fluoride are added to 20 g of aniline and 75 ml of ethanol. After a short time. Whilst stirring at room temperature, the reaction is seeded with a seed (a small portion) of the desired intermediate product. There is an immediate formation of a heavy precipitate. This precipitate was separated by filtration to obtain 2,4-dinitro-b-trifluoromethyldiphenylamine (28.5 g).
Это промежуточное соединение подвергают Н -метилированию двум различными методами.This intermediate compound is subjected to H-methylation by two different methods.
Метод А. В 15 мл диметилформамида внос т навеску (3,3 г) дифениламина Method A. A suspension (3.3 g) of diphenylamine was added to 15 ml of dimethylformamide.
прибавл ют 1,3 I гидрида натри . Полученную смесь перемешивают при комнатной температуре и прибавл ют 1,5 мл йодистого метила. При этом наблюдаетс заметное выделение тепла Спуст 1,5ч прибавл ют еще 2 мл йодистого метила и реакционную смесь слегка подогревают. Спуст еще 2 ч реакционную смесь выливают в большое количество холодной воды и водный слой декантируют. Оставшеес масло обрабатьшают диэтиловьп- эфиром и полченный раствор перемешивают с безводным сульфатом магни и активированным углем. После фильтрации твердых веществ раствор упаривают досуха и получают в остатке 2,4 г темно-красного масл нистого вещества, которое при охлаждении закристаллизовываетс „ Это твердое вещество нагревают с петролейны;у1 эфиром, охлаждают и после фильтровани получают 2,4 г целевого N -метил-2,4-динитро-б-трифторметилдифениламина с т.пл. ,84- .1.3 I sodium hydride is added. The mixture was stirred at room temperature and 1.5 ml of methyl iodide was added. There was a noticeable heat release. After 1.5 hours, another 2 ml of methyl iodide was added and the reaction mixture was slightly warmed. After another 2 hours, the reaction mixture is poured into a large amount of cold water and the aqueous layer is decanted. The remaining oil is treated with diethyl ether and the resulting solution is mixed with anhydrous magnesium sulphate and activated carbon. After filtration of the solids, the solution is evaporated to dryness and a residue of 2.4 g of a dark red oily substance is obtained, which crystallizes upon cooling, This solid is heated from petroleum; 1 is ether, cooled, and after filtration, 2.4 g of the desired N-methyl are obtained -2,4-dinitro-b-trifluoromethyldiphenylamine with so pl. , 84-.
Найдено, %t С 49,24, Н 3,05, У 12,31.Found,% t C 49.24, H 3.05, Y 12.31.
Вычислено, %: С 49,28; Н 2,95, N 12,31,Calculated,%: C 49.28; H 2.95, N 12.31,
Метод Б. 11 г промежуточного дифениламина смешивают с 45 мл диоксана , 14 г карбоната натри и 6 мл диметилсульфата и реакционную смесь кип т т с обратным холодильником в течение 24 ч. После этого к реакционной смеси добавл ют еще 12 мл диметилсульфата и 10 г карбоната натри и смесь перемешивают при температуре кипени еще в течение 2 ч.Method B. 11 g of intermediate diphenylamine are mixed with 45 ml of dioxane, 14 g of sodium carbonate and 6 ml of dimethyl sulfate and the reaction mixture is heated under reflux for 24 hours. After this, another 12 ml of dimethyl sulfate and 10 g of carbonate are added to the reaction mixture. sodium and the mixture is stirred at boiling point for an additional 2 hours.
Затем ее выливают в воду и перемешивают в течение 4 ч. Далее водный слой декантируют, а остаток обрабатывают метиленхлоридом и полученный раствор фильтруют. Твердое вещество , полученное в результате упаривани этого раствора, идентифицируют как целевой N -метил-2,4-динитро-б-трифторметилдифениламин . Выход сырого продукта л 10 г.Then it is poured into water and stirred for 4 hours. Then the aqueous layer is decanted, and the residue is treated with methylene chloride and the resulting solution is filtered. The solid obtained by evaporation of this solution is identified as the desired N-methyl-2,4-dinitro-b-trifluoromethyldiphenylamine. The yield of crude product l 10 g
Пример 2. 2,4-Динитро-N -пропил-б-трифторметилдиФениламин .Example 2. 2,4-Dinitro-N-propyl-b-trifluoromethyldiPhenylamine.
Claims (1)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US70602376A | 1976-07-21 | 1976-07-21 |
Publications (1)
Publication Number | Publication Date |
---|---|
SU628811A3 true SU628811A3 (en) | 1978-10-15 |
Family
ID=24835897
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
SU762395606A SU628811A3 (en) | 1976-07-21 | 1976-09-13 | Diphenylamine derivative producing method |
Country Status (34)
Country | Link |
---|---|
JP (1) | JPS601298B2 (en) |
AR (1) | AR226409A1 (en) |
AT (1) | AT343624B (en) |
BE (1) | BE846205A (en) |
BG (1) | BG28845A3 (en) |
BR (1) | BR7607892A (en) |
CA (1) | CA1097372A (en) |
CH (1) | CH605615A5 (en) |
CS (1) | CS189032B2 (en) |
DD (1) | DD127399A5 (en) |
DE (1) | DE2640462C2 (en) |
DK (1) | DK431276A (en) |
EG (1) | EG12450A (en) |
ES (1) | ES451903A1 (en) |
FI (1) | FI762497A (en) |
FR (1) | FR2359116A1 (en) |
GB (1) | GB1548702A (en) |
GR (1) | GR61183B (en) |
HU (1) | HU174434B (en) |
IE (1) | IE43614B1 (en) |
IL (1) | IL50259A (en) |
IN (1) | IN141827B (en) |
IT (1) | IT1065258B (en) |
MX (1) | MX4392E (en) |
NL (1) | NL7610048A (en) |
NO (1) | NO143023C (en) |
PH (1) | PH12432A (en) |
PL (1) | PL102578B1 (en) |
PT (1) | PT65677B (en) |
RO (1) | RO70078A (en) |
SE (1) | SE435276B (en) |
SU (1) | SU628811A3 (en) |
YU (1) | YU214876A (en) |
ZA (1) | ZA764842B (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4316988A (en) * | 1976-07-21 | 1982-02-23 | Eli Lilly And Company | N-Alkyldiphenylamines |
US4215145A (en) | 1978-12-05 | 1980-07-29 | E. I. Du Pont De Nemours And Company | Miticidal, fungicidal, and ovicidal sulfenamides |
US4323580A (en) | 1980-01-24 | 1982-04-06 | E. I. Du Pont De Nemours And Company | Miticidal, fungicidal and ovicidal diphenylsulfenamides |
US4298613A (en) | 1980-05-05 | 1981-11-03 | E. I. Du Pont De Nemours And Company | Agricultural heterocyclic sulfenamides |
US4341772A (en) * | 1980-05-05 | 1982-07-27 | E. I. Du Pont De Nemours And Company | Agricultural phosphorus-containing sulfenamides |
US4407820A (en) | 1981-03-19 | 1983-10-04 | Eli Lilly And Company | Diphenylamine compounds |
MA19315A1 (en) * | 1981-03-19 | 1982-07-01 | Lilly Co Eli | IMPROVEMENTS RELATING TO N-ALKYLATED DIPHENYLAMINE DERIVATIVES. |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2212825A (en) * | 1937-12-31 | 1940-08-27 | Du Pont | Nitro-trifluoromethyl-aryl amines and process for making them |
-
1976
- 1976-07-25 PL PL1976192659A patent/PL102578B1/en not_active IP Right Cessation
- 1976-08-10 CA CA258,782A patent/CA1097372A/en not_active Expired
- 1976-08-10 IE IE1766/76A patent/IE43614B1/en not_active IP Right Cessation
- 1976-08-11 GR GR51456A patent/GR61183B/en unknown
- 1976-08-11 ZA ZA00764842A patent/ZA764842B/en unknown
- 1976-08-12 IL IL50259A patent/IL50259A/en unknown
- 1976-08-12 IN IN1466/CAL/76A patent/IN141827B/en unknown
- 1976-08-17 GB GB34127/76A patent/GB1548702A/en not_active Expired
- 1976-08-20 PH PH18815A patent/PH12432A/en unknown
- 1976-08-25 IT IT26532/76A patent/IT1065258B/en active
- 1976-08-30 SE SE7609586A patent/SE435276B/en unknown
- 1976-08-30 MX MX764867U patent/MX4392E/en unknown
- 1976-08-31 AR AR264525A patent/AR226409A1/en active
- 1976-08-31 FI FI762497A patent/FI762497A/fi not_active Application Discontinuation
- 1976-09-01 YU YU02148/76A patent/YU214876A/en unknown
- 1976-09-07 AT AT664176A patent/AT343624B/en not_active IP Right Cessation
- 1976-09-08 DE DE2640462A patent/DE2640462C2/en not_active Expired
- 1976-09-09 CH CH1148076A patent/CH605615A5/xx not_active IP Right Cessation
- 1976-09-10 HU HU76EI696A patent/HU174434B/en unknown
- 1976-09-10 DD DD194748A patent/DD127399A5/xx unknown
- 1976-09-10 NL NL7610048A patent/NL7610048A/en not_active Application Discontinuation
- 1976-09-13 SU SU762395606A patent/SU628811A3/en active
- 1976-09-15 BE BE1007626A patent/BE846205A/en not_active IP Right Cessation
- 1976-09-15 FR FR7627685A patent/FR2359116A1/en active Granted
- 1976-09-16 CS CS766025A patent/CS189032B2/en unknown
- 1976-09-17 RO RO7687564A patent/RO70078A/en unknown
- 1976-09-17 NO NO763192A patent/NO143023C/en unknown
- 1976-09-24 DK DK431276A patent/DK431276A/en not_active Application Discontinuation
- 1976-09-27 ES ES451903A patent/ES451903A1/en not_active Expired
- 1976-10-04 PT PT65677A patent/PT65677B/en unknown
- 1976-10-13 EG EG631/76A patent/EG12450A/en active
- 1976-10-28 BG BG7634548A patent/BG28845A3/en unknown
- 1976-11-18 JP JP51139413A patent/JPS601298B2/en not_active Expired
- 1976-11-25 BR BR7607892A patent/BR7607892A/en unknown
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