US3925374A

US3925374A - Aminodicyano alkene compounds

Info

Publication number: US3925374A
Application number: US460044A
Authority: US
Inventors: Van C Vives
Original assignee: Phillips Petroleum Co
Current assignee: Phillips Petroleum Co
Priority date: 1974-04-11
Filing date: 1974-04-11
Publication date: 1975-12-09
Anticipated expiration: 1992-12-09

Abstract

WHEREIN EACH Rii is an alkyl radical and Riii is selected from the group consisting of alkylene and oxydialkylene radicals. Also described are (1) a process for preparing the novel compounds of this invention which comprises reacting a secondary amine and a dicyano-substituted conjugated diene, and (2) a process for preparing the trans isomer of the novel compounds of this invention which comprises reacting a secondary amine and a dicyano-substituted conjugated diene in the presence of an aliphatic monocarboxylic acid. The compounds of this invention are useful as bactericides.

HAVING FROM 8 TO 26 CARBON ATOMS PER MOLECULE, WHEREIN EACH R is individually selected from the group consisting of hydrogen, alkyl and cycloalkyl; each Ri is individually selected from the group consisting of R and aryl and Q is selected from the group consisting of

Described herein are novel aminodicyano alkenes of the formula

Description

United States Patent [191 Vives AMINODICYANO ALKENE COMPOUNDS [75] Inventor: Van C. Vives, Bartlesville, Okla.

[73] Assignee: Phillips Petroleum Company,

Bartlesville, Okla.

22} Filed: Apr. 11, 1974 [211 Appl. No: 460,044

[52] 13.8. CI 260/247; 260/239 B; 260/293.51; 260/293.75; 260/326.62; 260/465 E; 260/4655 R; 260/465.8 R; 424/244; 424/248; 424/267; 424/274; 424/304 [51] Int. Cl. ..C07C 121/45; CO7D 211/34; CO7D 295/14 [58] Field Of Search 260/247, 465 E, 465.5 R, 260/293.51, 293.75, 239 B, 326.62

{56] References Cited UNITED STATES PATENTS 2,444,882 7/1948 Tawney 260/465.8 R 2,527,510 10/1950 Allen et al. 260/4655 R 3,138,631 6/1964 Frazza et a1 260/465 E Primary ExaminerAnton H. Sutto Assistant ExaminerMichael Shippen [57] ABSTRACT Described herein are novel aminodicyano alkenes of the formula Dec. 9, 1975 having from 8 to 26 carbon atoms per molecule, wherein each R is individually selected from the group consisting of hydrogen, alkyl and cycloalkyl; each R is individually selected from the group consisting of R and aryl and Q is selected from the group consisting of 20 Claims, N0 Drawings AMINODICYANO ALKENE COMPOUNDS This invention relates to aminodicyano alkene compounds.

Heretofore, aminodicyano alkene compounds of the formula having from 8 to 26 carbon atoms per molecule, wherein R is hydrogen, alkyl or cycloalkyl, R is R or aryl, and Q is R" rr R iN CNR containing from 8 to 26 carbon atoms per molecule, wherein each R is individually selected from the group consisting of hydrogen, alk yl having from l to 4 carbon atoms and cycloalkyl having from 3 to 6 carbon atoms; each R is individually selected from the group consisting of R and aryl having from 6 to l carbon atoms; and Q is selected from the group consisting of wherein each R is individually selected from the group consisting of alkyl having from 1 to 10 carbon atoms and R is selected from the group consisting of alkylene and oxydialkylene having from 4 to 6 carbon atoms.

In one embodiment of this invention there is provide a process for the preparation of novel aminodicyano compounds of the formula Jill. l l

as hereinbefore described, which comprises reacting a secondaryarnine having the formula in H 0 wherein Q is as described above, with a dicyano-substituted conjugated diene according to the following general reaction equation wherein R and R are as described above.

In another embodiment of this invention there is provided a process for the preparation of the trans isomer of the novel aminodicyano alkene compounds of this invention, which comprises conducting the above reaction for the preparation of (l) in the presence of an aliphatic monocarboxylic acid having from I to 4 carbon atoms per molecule.

Representative compounds described by formula (I) include: l-piperidino-2,3-dicyano-2-butene, l-pyrrolidino-2,3-dicyano-2-butene, l-dimethylamino-2,3- dicyano-2-butene, l-di-n-octylamino-2 ,3 -dicyano-2- butene, l-morpholin o-2,3-dicyano-2-butene, 2- piperidino-3,4-dicyano-3-hexene, 2-morpholino-3,4- dicyano-3-pentene, 5-dimethylamino-6,7-dicyano-6- dodecene, l-p-tolyll -pyrrolidino-2,3-dicyano-2- butene, l -pheny1- l -di-n-butylamino-2,3-dicyano-2- butene, l-cyclopro pyll-piperidin o-2,3-dicyano-2- butene, l-cyclohexyll -morpholino-2,3'dicyano-2- butene, l -alpha-naphth yll -pyrro1idino-2,3-dicyano-2- butene, 2-dimethylamino-3,4-dicyano-3-octene, S-din-butylamino-6,7-dicyano-o-dodecene, 2,l l-dimethyl- 5-diethylamino-6,7-dicy ano--dodecene, l-di-ndecylamino-2,3-dicyano-2-butene and the like.

Representative compounds described by formula (II) include: dimethylamine, diethylamine, dibutylamine, di-n-octylamine, didecylamine, pyrrolidine, piperidine, morpholine and the like.

Representative compounds described by formula (ill) include: l,3-butadiene-2,3-dicarbonitrile; 2,4-hexadiene-3,4-dicarbonitrile; 2,4-pentadiene-3,4-dicarbonitrile', 5,7-dodecadiene6,7-dicarbonitrile; l-ptolyl-1,3-butadiene-2,3-dicarbonitrile; l-phenyl-l ,3- butadiene-2,3dicarbonitrile; 5,8-di-n-butyl-5,7- dodecadiene-6,7-dicarbonitrile; 2,7-dimethyl-3,6- diphenyl-3,S-octadiene-4,5-dicarbonitrile; l-cyclopropyl-l ,3-butadiene-2,3-dicarbonitrile; l-cyclohexyll ,3- butadiene-Z ,3-dicarbonitrile', l'alpha-naphthyl-l ,3- butadiene-2,3dicarbonitrile; 2,4-octadiene-3,4-dicarbonitrile, and the like.

in a presently preferred embodiment, the dicyanosubstituted cnnjugated diene of formula (Ill) is l,3- butadiene-2,3-dicarbonitrile, which, on amination with a suitable secondary amine, gives the l-amino-2-butene derivative.

l,3-Butadiene-2,3dicarbonitriles can be obtained by the known thermal isomerization of a cyclobutene-l ,2- dicarbonitrile, which is prepared from a cyclobutanel ,2-dicarbonitrile.

Representative monocarboxylic acids which can be used in the process of this invention include formic acid, acetic acid, propionic acid, butyric acid and isobutyric acid. In a presently preferred embodiment the acid is acetic acid.

The process of this invention is preferably conducted in the presence of an inert diluent. Suitable diluents include polar and non-polar diluents which are inert to the reactants under reaction conditions, including but not limited to acyclic and cyclic aliphatic ethers. aliphatic nitriles. aromatic hydrocarbons. halogenated aromatic and aliphatic hydrocarbons and the like. Representative diluents include benzene. toluene. tetrahydrofuran, diethyl ether, chlorobenzene. chloroform, methylene chloride. carbon tetrachloride. acetonitrile and the like. Ethereal diluents can be used without spe cial purification; however. it may be advantageous to remove any peroxidic residues from such diluents prior to contacting such diluent with the dicarbonitrile feedstock. Such peroxidic residues can initiate polymeriza tion of such feedstock. The peroxidic residues can be removed by distilling the ether from a slurry with lithium aluminum hydride.

The molar ratio of secondary amine to diene can be in the range of 5:1 to 1:5, preferably 3:1 to 1:3. Very large excesses of either reactant should be avoided to minimize side products which can complicate isolation and recovery of the product.

In the process for the preparation of the trans isomer of the aminodicyano alkene compounds of this inven tion, the molar ratio of monocarboxylic acid to secondary amine can range from 0.1:] to :1, preferably from 0.511 to 2:1.

The reaction is carried out at a temperature in the range of 50 to 150 C.. preferably from 0 to about 100 C.

The reaction is normally conducted under atmospheric pressure. although a pressure in the range of 0 to 100 psig can be used.

Reaction time will vary. inter alia. according to the reactants, reaction temperature. relative reactant concentrations and the like. In general. reaction time will be between 0.1 and 24 hours.

The reaction can be conducted in any suitable apparatus. An inert reaction atmosphere can be used if desired. The reaction can be conducted batchwise or as a continuous process.

The novel aminodicyano alkene compounds of this invention can be separated from the reaction mixture by methods known in the art, such as by precipitation, extraction, fractional crystallization, fractional distillation and the like.

The compounds of this invention are useful as bactericides. Application of the compounds of this invention for the purpose disclosed can be made from solutions in suitable solvent carriers or in combination with supplementary agents, adjuvants, other control agents and the like. They are employed in a bactericidal amount, generally from about 0.01 to about 90 weight percent of the tea] composition.

The following examples illustrate the invention:

EXAMPLE I A mixture of 0.4659 g (0.0045 mol) of 1,3-butadiene-2,3-dicarbonitrile and 50 ml of tetrahydrofuran was charged to a 100 ml 3-neck round-bottom flask equipped with magnetic stirrer and fitted with a cold finger condenser, thermometer and rubber septum. The condenser was cooled with dry ice. The system was maintained under a nitrogen atmosphere. 130 ml (0.0054 mol) of gaseous dimethylamine were injected below the surface of the stirred solution. The reaction mixture was stirred at room temperature for about 3.5 hours.

The reaction mixture was concentrated on a rotary evaporator. giving 0.64 g of a dark brown liquid resi due. Vacuum sublimation of the liquid residue at about 55-65 C. and 2 mm pressure gave 0.3423 g of a hygroscopic white low melting solid. Recrystallization of the solid from dichloromethane/hexane gave two crops of white crystals having a combined weight of0. 1267 g. The first crop of crystals had a melting point of 34.535.5 C. The two crops of crystals were combined for elemental analysis:

Calculated for C H N C. 64.4; H, 7.43; N, 28.17. Found: C, 64.4; H, 7.4; N. 28.3.

Mass and nuclear magnetic resonance spectral data indicated that the product was l-dimethylamino-2.3- dicyano-Z-butene.

EXAMPLE ll To a stirred mixture of 2.19 g (0.02 mol) 1,3-butadiene-2,3-dicarbonitrile in ml tetrahydrofuran was added 1.74 g (0.02 mol) of morpholine at room temperature. After 1.5 hours the mixture had taken on a dark blue color.

After standing overnight the dark blue reaction mixture was treated with charcoal and filtered. The filtrate was concentrated on a rotary evaporator giving 3.6 g of a brown residue. This residue was extracted several times with hexane and the hexane extracts were combined and treated with charcoal. After filtration to remove the charcoal, the hexane solution was cooled to 20 C. to give 1.88 g of fine white crystals having a melting point of 7983 C. which gave the following elemental analysis:

Calculated for C l-l N O:% C, 62.87; H, 6.76; N. 22.00. Found: C. 63.22: H.674: N. 22.40.

Mass and nuclear magnetic resonance spectral data indicated that the product was l-morpholino-2,3- dicyano-Z-butene.

EX AMPLE III A mixture of 1.47 g (0.0l4 mol) l,3-butadiene-2,3- dicarbonitrile and 50 ml benzene was charged to a 3- neck round-bottom flask fitted with water-cooled condenser. thermometer and a dropping funnel containing 1.24 g (0.015 mol) piperidine in about 15 ml benzene. The solution in the reaction vessel was stirred and heated to reflux as the piperidinebenzene solution was added dropwise over a period of 9 minutes. The reaction mixture was heated an additional 32 minutes after all the piperidine had been added.

The reaction mixture was cooled to room temperature, filtered, and the filtrate was treated with charcoal before most of the benzene solvent was evaporated under a stream of nitrogen to give a black viscous oil. Through the use of silica gel column chromatography two major components were recovered to give 1.89 g of cisand transisomers of lpiperidino-2,3-dicyano-2- butene. The trans-isomer (m.p. 6869 C.) eluted first from the silica gel chromatography column and was purified by rcrystallization from a mixture of ether and hexane. The transisomer was eluted from the column with a 30/70 volume mixture of ether/hexane. The cisisomer (mp 48-49 C.) was eluted from the column with ether and was purified by recrystallization from a mixture of ether and hexane. The structural assignment of cisand transwas made on the basis of nuclear magnetic resonance spectral data.

EXAMPLE IV A sample of lpiperidino-Z.3-dicyano-2butene was tested for use as a bactericide. The sample, containing a mixture of cisand trans-isomers, was incorporated into an agar nutrient medium to produce a concentration of 32 ppm. The resulting plates were innoculated with each of Escherichia coli, Haemophilus gallinarum and Staphylococcus aureus bacteria and incubated for 48 hours. Growth inhibition was rated by visual comparison with growth on untreated agar. No growth of the organisms was apparent.

This example illustrates the effectiveness of lpipcridino-2,3-dicyano-2-butene as a bactericide.

EXAMPLE V A mixture of 3.15 g (0.037 mol) of piperidine, 2.5 ml (0.043 mol) of glacial acetic acid and 75 ml of benzene was charged to a 3-neck round-bottom flask fitted with water-cooled condenser, thermometer, dropping funnel and magnetic stirrer. The solution in the reaction vessel was stirred and heated to refiux. A solution of 1.86 g (0.018 mol) of 1,3-butadiene-2,3-dicarbonitrile in about 50 ml of benzene was added dropwise to the stirred reaction mixture over a period of about 17 minutes. When addition was complete, the reaction mixture was stirred at reflux for an additional 33 minutes.

The reaction mixture was cooled to room temperature and the benzene was removed under vacuum leaving a dark brown residue. This residue was extracted with hexane. The hexane extract was concentrated, then cooled to 20 C. to give 2.92 g of off-white crystals. An additional 0.23 g of such crystals was obtained from the mother liquor. The crystals were combined, then recrystallized from hexane to give 2.13 g of translpiperidino-Z,3-dicyano-2-butene, having a melting point of 6768.2 C. The trans-structure was assigned on the basis of melting point and nuclear magnetic resonance spectral data.

this example illustrates the stereospecific reaction of a secondary amine and a dicyano-substituted conjugated diene.

EXAMPLE VI A mixture'of 1.47 g 0.014 mol) of 1,3-butadiene- 2,3-dicarbonitrile and 50 ml of benzene was charged to a 3-neck round-bottom flask equipped with a watercooled condenser, thermometer, dropping funnel and magnetic stirrer. The solution was heated to reflux, with stirring. A solution of 3.4 g (0.014 mol) of di-noctylamine in benzene was added, dropwise over a period of 30 minutes. to the reaction vessel.

The reaction mixture was cooled to room temperature, then concentrated on a rotary evaporator, giving a greenish-black residue. This residue was extracted with hexane. The hexane extract was treated with charcoal, filtered, and concentrated to give 4.57 g of a greenish-black oil. Through the use of silica gel column chromatography, two compounds were separated from the oil. Component I was a bright yellow oil which weighed 0.36 g. Component 1] weighed 0.32 g. Infrared and nuclear magnetic resonance spectral data indicated that components I and 11 were the cisand transisomers of ldi-n-octylamino-2,3-dicyano-2-butene.

EXAMPLE VII A 1.4 g (0.02 mol) sample of freshly distilled pyrrolidine was added at room temperature to a stirred solution of 1.97 g (0.019 mol) l,3-butadiene-2,3-dicarbonitrile in 75 m1 tetrahydrofuran. At the end of 1.5 hours, the mixture was concentrated under reduced pressure to give 3.36 g of a dark greenish-brown oil.

This oil was extracted with hexane and the hexane extract was treated with charcoal. After filtration to remove charcoal, the hexane extract was concentrated to give 2.21 g of yellow oil. This yellow oil was resolved to give a major component and a minor component. Infrared spectral data indicated that the components were the cisand transisomers of l-pyrrolidino-2,3- dicyano-Z-butene.

Reasonable variations and modifications of this invention will be apparent to those skilled in the art in view of this disclosure. Such variations and modifications are within the scope and spirit of the disclosure.

1 claim:

1. An aminodicyano alkene of the formula o-ijd=d it having from 8 to 26 carbon atoms per molecule, wherein each R is individually selected from the group consisting of hydrogen, alkyl having from 1 to 4 carbon atoms and cycloalkyl having from 3 to 6 carbon atoms, each R is individually selected from the group consisting of R and aryl having from 6 to 10 carbon atoms, and Q is selected from the group consisting of and Cl wherein each R is individually selected from the group consisting of alkyl radicals having from 1 to 10 carbon atoms and R is selected from the group consisting of alkylene and oxydialkylene radicals having from 4 to 6 carbon atoms.

2. The compound of claim 1 wherein each R is H, each R is H and Q is dimethylamino.

3. The compound of claim 1 wherein each R is H, each R is H and Q is morpholino.

4. The compound of claim 1 wherein each R is H, each R is H and Q is piperidino.

5. The compound of claim 1 wherein each R is H, each R is H and Q is di-n-octylamino.

6. The compound of claim 1 wherein each R is H, each R is H and Q is pyrrolidino.

7. A process for the preparation of an aminodicyano alkene compound of the formula having from 8 to 26 carbon atoms per molecule, wherein each R is individually selected from the group consisting of hydrogen, alkyl having from 1 to 4 carbon atoms and cycloalkyl having from 3 to 6 carbon atoms; each R is individually selected from the group consisting of R and aryl having from 6 to 10 carbon atoms; and Q is selected from the group consisting of wherein each R is individually selected from the group consisting of alkyl having from l to 10 carbon atoms and R" is selected from the group consisting of alkylene and oxydialkylene radicals having from 4 to 6 carbon atoms, which comprises reacting a secondary amine having the formula l-l Q, wherein Q is as defined above with a dicyano-substituted conjugated diene having the formula wherein R and R are as defined above, wherein said reaction is conducted at a temperature in the range of -50 to 150C and wherein the molar ratio of said amine to said diene is in the range of :1 to I15.

8. The process of claim 7 wherein said reaction is conducted at a temperature in the range of 0 to about 100C.

9. The process of claim 7 wherein the molar ratio of said amine to said diene is in the range of 3:1 to 1:3.

10. The process of claim 7 wherein said conjugated diene is 1,3-butadiene-2,3-dicarbonitrile.

11. The process of claim 10 wherein said amine is dimethylamine.

12. The process of claim 10 wherein said amine is morpholine.

13. The process of claim 10 wherein said amine is piperidine.

14. The process of claim 10 wherein said amine is din-octylamine.

15. The process of claim 10 wherein said amine is pyrrolidine.

16. A process for the preparation of the trans-isomer of an aminodicyano alkene compound of the formula R" -N and n"' wherein each R is individually selected from the group consisting of alkyl having from i to 10 carbon atoms and R is selected from the group consisting of alkylene and oxydialkylene radicals having from 4 to 6 carbon atoms which comprises reacting a secondary amine having the formula iN iN g wherein R and R are as defined above, in the presence of an aliphatic monocarboxylic acid having from 1 to 4 carbon atoms per molecule, wherein said reaction is conducted at a temperature in the range of 50 to l50C and wherein the molar ratio of said amine to said diene is in the range of 5:1 to 1:5 and the molar ratio of said acid to said amine is in the range of 0.111 to 10:1.

17. The process of claim 16 wherein said reaction is conducted at a temperature in the range of 0 to about C.

18. The process of claim 16 wherein the molar ratio of said amine to said diene is in the range of 3:1 to l :3.

19. The process of claim 16 wherein said conjugated diene is l,3-butadiene-2,3-dicarbonitrile, said amine is piperidine and said acid is acetic acid.

20. The process of claim 16 wherein the molar ratio of said acid to said amine is in the range of0.5:l to 2:1.

Claims

1. AN AMINODICYANO ALKENE OF THE FORMULA

2. The compound of claim 1 wherein each R is H, each Ri is H and Q is dimethylamino.

3. The compound of claim 1 wherein each R is H, each Ri is H and Q is morpholino.

4. The compound of claim 1 wherein each R is H, each Ri is H and Q is piperidino.

5. The compound of claim 1 wherein each R is H, each Ri is H and Q is di-n-octylamino.

6. The compound of claim 1 wherein each R is H, each Ri is H and Q is pyrrolidino.

7. A process for the preparation of an aminodicyano alkene compound of the formula

8. The process of claim 7 wherein said reaction is conducted at a temperature in the range of 0* to about 100*C.

11. The process of claim 10 wherein said amine is dimethylamine.

12. The process of claim 10 wherein said amine is morpholine.

13. The process of claim 10 wherein said amine is piperidine.

14. The process of claim 10 wherein said amine is di-n-octylamine.

15. The process of claim 10 wherein said amine is pyrrolidine.

16. A process for the preparation of the trans-isomer of an aminodicyano alkene compound of the formula

17. The process of claim 16 wherein said reaction is conducted at a temperature in the range of 0* to about 100*C.

18. The process of claim 16 wherein the molar ratio of said amine to said diene is in the range of 3:1 to 1:3.

19. The process of claim 16 wherein said conjugated diene is 1, 3-butadiene-2,3-dicarbonitrile, said amine is piperidine and said acid is acetic acid.

20. The process of claim 16 wherein the molar ratio of said acid to said amine is in the range of 0.5:1 to 2:1.