US2237542A - Quinoline compounds - Google Patents
Quinoline compounds Download PDFInfo
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- US2237542A US2237542A US161278A US16127837A US2237542A US 2237542 A US2237542 A US 2237542A US 161278 A US161278 A US 161278A US 16127837 A US16127837 A US 16127837A US 2237542 A US2237542 A US 2237542A
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- Prior art keywords
- base
- ethylquinoline
- dimethyl
- bases
- acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/12—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D215/14—Radicals substituted by oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom 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
- C07D215/48—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
Definitions
- This invention relates to a composition of matter and the method of producing the same. More specifically the invention relates to the production of 2,3-dimethyl-8-ethylquinoline and the method of producing this alkylated quinoline.
- the extract thus obtained comprising the nitrogen bases and various hydrocarbons had a boiling point range of 430-520 F. and a pressure of 64-85 mm. of mercury; a specific gravity at 60 F. of 0.995; an A. P. I. gravity at 60 F. of 10.7; a Savbolt Universal viscosity of 60 seconds at 100 F.; a sulphur content of 0.36% by weight; a nitrogen content of 4.62% by weight; and an alkalinity, calculated as NaOH of 18.5% by weight.
- This mixture of bases was charged to a 10 gallon iron still and fractionally distilled under reduced pressure to obtain cuts of 500 cc. volume. These cuts were recombined and redistilled. from a 5 liter Pyrex glass still to cuts of cc. each. After five distillations the cuts boiling from 283- 287 C. were combined to form 5700 cc. of distillate which served as the material from which the new base was isolated.
- Picrate-Thls salt which is dlfllcultly soluble in the common solvents, crystallizes from glacial acetic acid in slender yellow needles melting at 220 C.
- Hydrochloride On dissolving the base in a slight excess of concentrated hydrochloric acid, the hydrochloride separates and can be recrystallized from alcohol or water in long slender .needies melting at 212-2l4 C. with decomposition.
- Acid sulphate This salt, prepared by adding a slight excess of concentrated sulphuric acid to an acetone solution of the base, crystallizes from alcohol in fine needles melting at 239-240 C. undecomposed.
- Mercuric chloride salt 2-Mercuric chloride (one mole) added to the base (one mole) in dilute hydrochloric acid solution precipitates the double salt. It crystallizes from water in large needles and from alcohol in microscopic needles melting at 212-214 C. undecornposed.
- 2,3-dimethyl quinoiine-$-carhoscylic acidM-A mixture of 6 grams of chromic anhydride and 78 cc. of 1:5 sulphuric acid is refluxed for 60 hours with about 10 grams or" the base.
- the solution after neutralization with ammonium hydroxide to where precipitation of chromic hydroxide begins, is extrac ed with chloroform in a yield oi about 19%.
- the reaction prodnot is decolorized in acueous solution with filtchar. followed by recrystallization from alcohol and water in long needles melting at 202 C.
- a mixed melting point with a known sample of 2,3- dimethyl quinoline-s-carboxylic acid showed no de ression.
- Picrate.-This salt precipitates on the addition of an alcoholic solution of picric acid to the dimethylol base in ether and can b recrystallized from water or alcohol in long slender needles melting at 165.5 0.
- a process for the recovery of 2,3-dimethyl-8- ethylquinoline from asphalt base petroleum which comprises distilling the petroleum to obtain a distillate comprising kerosene, extraction of the said distillate with a mineral acid to obtain a mixture of nitrogen bases, separation or this mixture into aromatic and non-aromatic portions, and fractionally distilling the aromatic portion to obtain outs boiling within 2 of 284 C. at atmospheric pressure and which consists substantially of 2,3-
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
Patented Apr. 8, 1941 QUINOLINE COMPOUNDS James R. Bailey assignors to Union Los Angcles, Calii'.,
and Carrol L. Key,
Oil Company of California, a corporation of California Austin, Tex.,
No Drawing. Application August 27, 1937, Serial No. 161,278
6 Claims.
This invention relates to a composition of matter and the method of producing the same. More specifically the invention relates to the production of 2,3-dimethyl-8-ethylquinoline and the method of producing this alkylated quinoline.
We have discovered a method whereby 2,3- dimethyl-B-ethylquinoline may be directly synthesized. Furthermore, we have discovered that 2,3-dimethyl-8-ethylquinoline is present in certain fractions of certain petroleum oils, shale oils, and oils obtained by Dyrolitic decomposition of protein matter such as cotton seed meal and may be recovered therefrom by my process. Furthermore we have discovered a method whereby 3-methyl-8-ethylquinoline may be synthesized.
We have discovered that 2..3-dimethyl-8-ethylquinoline is a constituent of certain petroleum oil. More specifically, we have discovered that nitrogen base mixtures recovered from the kerosene cut of California asphalt base crude contain an appreciable quantity of 2,3-dimethyl-8-ethylquinoline. The specific petroleum fraction which we use to recover this nitrogen. base is, as explained above, a crude kerosene distillate obtained from California asphalt base crude oil by fractional distillation. We prefer to first concentrate the nitrogen bases by extraction of such a distillate with a selective solvent. In a particular instance kerosene distillate was extracted with sulphur dioxide, as in the well known Edeleanu refining process. and an extract was obtained which comprises the bulk of the nitrogen bases present in the kerosene distillate, as well as the usual extract constituents such as aromatic and naphthenic hydrocarbons. The extract thus obtained comprising the nitrogen bases and various hydrocarbons had a boiling point range of 430-520 F. and a pressure of 64-85 mm. of mercury; a specific gravity at 60 F. of 0.995; an A. P. I. gravity at 60 F. of 10.7; a Savbolt Universal viscosity of 60 seconds at 100 F.; a sulphur content of 0.36% by weight; a nitrogen content of 4.62% by weight; and an alkalinity, calculated as NaOH of 18.5% by weight.
The above extract was then treated in the following manner for the recovery of the nitrogen bases contained therein.
To a barrel of the extract was added 19 gallons of 20% sulphuric acid and the mixture was agitated with air for six hours. The mixture was then allowed to stand for several hours to effect stratification. The hydrocarbon oil layer was removed and discarded and the aqueous acid layer was then treated with caustic alkali to ef-' feet liberation of the nitrogen bases, as on oily phase insoluble in the water.
After removal of the water this mixture of bases was then treated in the following manner for the recovery of its content of the 2,3-dimethyl-8-ethylquinoline:
This mixture of bases was charged to a 10 gallon iron still and fractionally distilled under reduced pressure to obtain cuts of 500 cc. volume. These cuts were recombined and redistilled. from a 5 liter Pyrex glass still to cuts of cc. each. After five distillations the cuts boiling from 283- 287 C. were combined to form 5700 cc. of distillate which served as the material from which the new base was isolated.
These combined cuts were brought into solution in strong hydrochloric acid which has been diluted with an equal volume of water and this aqueous solution was then extracted with a volume of chloroform equal to the original volume of the bases. By this method non-aromatic base hydrochlorides are substantially all extracted by the chloroform, while the aromatic base hydrochlorides remain in the aqueous phase. From the extracted aqueous solution 1500 cc. of arcmatic bases were recovered with a boiling point of 284 C. and a refractive index, n 25/D of 1.5812. These aromatic bases were then fractionally distilled in a Pyrex still and a cut was made of the condensate boiling between 282 C. and 287 C. This cut was then subjected to an amplified distillation in which the bases were dissolved in' 12 volumes of hydrocarbon oil of a boiling range of 260-290 C. prior to the distillation. The cuts taken from 282-285" C. during this amplified distillation were found to contain almost pure 2,3-dimethyl-8-ethylquinoline, in admixture with hydrocarbons from the diluent oil. This base was then separated from these cuts by extraction with aqueous sulphurous acid and treatment of the aqueous extract with caustic alkali. Final purification was effected by crystallization of the pic-rate and liberation of the base from the picrate with caustic alkali.
In another instance we omitted the step of amplified distillation, i. e. we carried out the final distillation in the absence of any added hydrocarbon oil, and from the cuts boiling in the neighborhood of 284 C. we obtained substantially the same yield of 2,3-dimethyl-8-ethylqulnoline.
The base recovered in the above manner and which has the structure 2,3-dimethyl-8-ethylquinoline was identified as follows:
Analysis calculated for C1aH15N: C, 84.32; H, 8.10; N, 7.57. Found:. C, 83.94; H, 7.89; N, 7.54.
Calculated molecular weight. for CraHmN:
2 Molecular weight: substance, 15.50 mg.; camphor 155.55 mg.; freezing point depression, 21 18 Found: molecular weight 189.
Physical characteristics: boiling point 284.6" C.; n 20/D 1.5940, D.20/4 1.017.
Picrate-Thls salt, which is dlfllcultly soluble in the common solvents, crystallizes from glacial acetic acid in slender yellow needles melting at 220 C.
Knalysis calculated for CieH1aO1N4: C, 55.07; H, 4.35; N, 13.53. Found: C, 55.19; H, 4.34; N, 13.46.
Nitrate.-This salt crystallizes from alcohol or water in fine needles melting at 166 C. and decomposing just above this temperature.
Analysis calculated for CnHreOaNa: C, 62.90; H, 6.45; N, 11.29. Found: C, 63.19; H, 6.39; N, 11.30.
Hydrochloride.-On dissolving the base in a slight excess of concentrated hydrochloric acid, the hydrochloride separates and can be recrystallized from alcohol or water in long slender .needies melting at 212-2l4 C. with decomposition.
Analysis calculated for C13H15N.HC12 C, 70.40; H, 7.22; N, 6.32; Cl, 16.02. Found: C, 70.43; H, 7.24; N, 6.33; Cl, 16.06.
Acid sulphate.-This salt, prepared by adding a slight excess of concentrated sulphuric acid to an acetone solution of the base, crystallizes from alcohol in fine needles melting at 239-240 C. undecomposed.
Analysis calculated for CiaHi5N.H2SO42 Found: N, 4.98.
Mercuric chloride salt.-Mercuric chloride (one mole) added to the base (one mole) in dilute hydrochloric acid solution precipitates the double salt. It crystallizes from water in large needles and from alcohol in microscopic needles melting at 212-214 C. undecornposed.
Analysis calculated for CmHmNCHLHgCh: N, 2.84; Found: N, 2.88.
C'hromata-On addition of potassium chromate to the hydrochloride in weal: acid solution, the chromate separates in a gelatinous form which on standing becomes crystalline. It crystallizes from 50% glacial acetic acid in microscopic rhombic prisms which decompose around 100 C.
Analysis calculated for C13H1sN.HzCIO4Z N, 4.62; Found: N, 4.61.
2,3-dimethyl quinoiine-$-carhoscylic acidM-A mixture of 6 grams of chromic anhydride and 78 cc. of 1:5 sulphuric acid is refluxed for 60 hours with about 10 grams or" the base. The solution, after neutralization with ammonium hydroxide to where precipitation of chromic hydroxide begins, is extrac ed with chloroform in a yield oi about 19%. For purification, the reaction prodnot is decolorized in acueous solution with filtchar. followed by recrystallization from alcohol and water in long needles melting at 202 C. A mixed melting point with a known sample of 2,3- dimethyl quinoline-s-carboxylic acid showed no de ression.
Analysis calculated for Cmi-l'nOaN: C, 71.64: H, 5.47: N. 6.97. Found: C, 71.64; H, 5.46; N, 6.87.
2.3-dimethyl auinoZz'ne.-'I'he above acid was decarboxylated by distillation with soda-lime and the resulting base was dissolved in ether and precioitated with an alcoholic solution of plcric acid. The picrate recrystallizes from glacial acetic acid in microscopic hexagonal prisms melting at 231 C. This product, mixed with a known sample of 2,3-dimethyl quinoline plcrate' showed no depression in melting point.
3 methyl 8-ethyl-Z-dimethylolmethulquinoline.-In conformity with the procedure or Keenigs and Stockhausen (W. Koenlgs and F. Stockhausen, Ber. 84, 4331 (1901) 5 g. of dimethylethylqulnoline and 25 ml. of formalin in a sealed tube are heated on a steam cone for 45 hours. The reaction mixture, processed in the usual way, yields the dimethylol compound which, after recrystallization from chloroform and ethyl acetate, melts at 94-95 0.
Analysis calculated for CitHnOzNZ C, 73.47; H, 7.75; N, 5.71. Found: C, 73.31; H, 7.69; N, 5.91.
Picrate.-This salt precipitates on the addition of an alcoholic solution of picric acid to the dimethylol base in ether and can b recrystallized from water or alcohol in long slender needles melting at 165.5 0.
Analysis calculated for Carl-1:20am: C, 53.16; H, 4.64; N, 11.81. Found: C, 53.47; H, 4.80; N, 11.88.
3 methyl 8 ethylquinoline.The dimethylol compound (5 g.) in 250 ml. of 1:1 nitric acid is boiled for 6 hours. On evaporation of the solution, a practically quantitative yield of 3-methyl- B-ethylquinoline 2-carboxylic acid melting at 84- C. results. Since a well known procedure is involved here for conversion of a methyl at position 2 to carboxyl in quinoline homologs, this product was not analyzed. After decarboxylation at a temperatur of 180 C., the resulting base is purified through recrystallization of its picrate (A) from benzene and glacial acetic acid. The assigned structure, B-methyl-S-ethylquinoline, was confirmed by synthesis. (Cf. Carl Beyer, J. prakt. Chem. 33, 419 (1886) von Miller and Klnkelin, Ber. 20, 1916 (1887).)
Synthesis of 3-methyl-8-eihylquinoline.--Dry hydrogen chloride is introduced at a moderate rate into a mixture of propionic aldehyde (5 g.) and methylal (6 g.) for 5 minutes. On the addition of o-ethylaniline (1.8 g.) in concentrated hydrochloric acid (5 g), a reaction begins and is completed by boiling the solution for 3 hours. An equal volume of water is added, the filtered solution is treated with a slight excess of sodium nitrite, and after concentration to a small volume,
the bases are liberated with sodium hydroxide and extracted with ether. Final purification of the methylethylquinoline, aiter fractional distillation at diminished pressure, is effected through the picrate. (B) The identity of salts A and B was confirmed by a mixed melting point determination. The new base which was obtained in a yield of 8% has a refractive index 71. 25/13, of 1.5946.
Picrate A.-Ana.lysis calculated for GlBIIIGOINl lI C, 54.00; H, 4.00; N, 14.00. Found: C, 53.84; H, 4.07; N, 14.02.
Piorate B.--Found: C, 54.01; H, 4.00; N, 14.03.
Synthesis of 2,3-dz'methyl-B-ethylquinoline.- Final confirmation of the structure of the original kerosene base was effected through its synthesis (Ci'. Doebner and von Miller, Ber. 16, 2464 (1883)), which can be carried out as follows: a mixture of tiglic aldehyde (1 mole) and o -ethylaniline (4 moles) is heated open to the air for 4 hours on a water bath and then steam distilled. The solution, after liberation of the bases with sodium hydroxide, is again steam distilled and the distillate, acidified with hydrochloric acid, is treated at room temperature with sodium nitrite. Following the removal of the supernatant oil by other extraction, the solution is boiled, fil-= tered, made alkaline with sodium hydroxide, steam distilled and again extracted with ether. The base, regained from the solvent, gave a picrate which, admixed with the kerosene base picrate, produced no depression of the melting point (220 (3.).
Analysis calculated for Ci9H1aO7N42 C, 55.07; H, 4.27; N, 13.53. Found: C, 55.19; H, 4.34; N, 13.46.
It is to be understood that the disclosures here made are to be considered as illustrativeand not as limiting except as required by the state of the prior art.
We claim:
1. 2,3-dimethyl-S-ethylquinoline.
2. 2,3-dimethyl-8-ethylquinoline with a boiling point oi. 284.6 C.
3. A process for the recovery of 2,3-dimethyl-8- ethylquinoline from asphalt base petroleum which comprises distilling the petroleum to obtain a distillate comprising kerosene, extraction of the said distillate with a mineral acid to obtain a mixture of nitrogen bases, separation or this mixture into aromatic and non-aromatic portions, and fractionally distilling the aromatic portion to obtain outs boiling within 2 of 284 C. at atmospheric pressure and which consists substantially of 2,3-
dimethyL-8-ethylquinoline 4. A process as in claim 3, plus a further purification step of fractional crystallization of a salt of the crude 2,3-dimethyl 8-ethylquinoline.
5. A process as in claim 3, in which the aromatic bases are separated from the non-aromatic bases by extraction of an aqueous HCl solution of the mixed bases with chloroform.
6. A process as in claim 3, in which at least a part of fractional distillation of the aromatic bases is made in the presence 01' a diluent hydrocarbon oil with a distillation range comprehending the distillation range of the aromatic bases.
JAMES R. BAILEY. CARROLL. KEY. v
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US161278A US2237542A (en) | 1937-08-27 | 1937-08-27 | Quinoline compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US161278A US2237542A (en) | 1937-08-27 | 1937-08-27 | Quinoline compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2237542A true US2237542A (en) | 1941-04-08 |
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ID=22580555
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US161278A Expired - Lifetime US2237542A (en) | 1937-08-27 | 1937-08-27 | Quinoline compounds |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2237542A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2999794A (en) * | 1958-09-24 | 1961-09-12 | Union Carbide Corp | Recovery of quinoline |
-
1937
- 1937-08-27 US US161278A patent/US2237542A/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2999794A (en) * | 1958-09-24 | 1961-09-12 | Union Carbide Corp | Recovery of quinoline |
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