US2670376A - N-alpha-naphthyl n, n' n,'-trialkylethylene diamines - Google Patents

N-alpha-naphthyl n, n' n,'-trialkylethylene diamines Download PDF

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US2670376A
US2670376A US251634A US25163451A US2670376A US 2670376 A US2670376 A US 2670376A US 251634 A US251634 A US 251634A US 25163451 A US25163451 A US 25163451A US 2670376 A US2670376 A US 2670376A
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naphthyl
alpha
diamines
trialkylethylene
compounds
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US251634A
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John V Scudi
Godfrey F Grail
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Nepera Chemical Co Inc
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Nepera Chemical Co Inc
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/04—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • C10M133/12—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C217/04—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C217/06—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted
    • C07C217/08—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one etherified hydroxy group and one amino group bound to the carbon skeleton, which is not further substituted the oxygen atom of the etherified hydroxy group being further bound to an acyclic carbon atom

Definitions

  • R is a longkchain alkyl radical containi'rig 6'to li'ca'rbon atoms
  • R "anci"R are short chainalkyl radicals containingl to 3 carbon" atoms.
  • R and R1 maybe, but are not necessaril'yal-ike;
  • the compounds of our invention have a very.
  • Minimal fungistatic concentrations (ma/73) compound is separated and purifiedg' as described in'the specific example below.
  • firstthe alkylnaphthylamines by react- 127.5 grams (0.5 mole) of a-naphthyl-octylamine, the above prepared intermediate, was dissolved in 250 mls. of xylene and 23.5 grams (0.6 mole) of sodium amide was added. It was slowly heated up to 90 C. and was kept at that temperature for thirty-six hours. The mixture was allowed to cool to room temperature and 58.75 grams (0.5 mole) of fl-dimethylaminoethyl chloride was added. The reaction mixture was then heated to 105110 C. and kept at that temperature for forty-eight hours under continous stirring.
  • the reaction mixture was then allowed to cool to room temperature and acidified to a pH of 1.0 with a 1:1 HCl solution.
  • the aqueous layer was separated from the xylene layer, cooled and the pH adjusted to 10.6 with sodium hydroxide solution (40%).
  • the aqueous alkaline mixture was extracted three times with ether.
  • the combined ether extractions were dried with KOH pellets. After separating from the KOH pellets, the ether was distilled off on the steam bath. The residue was fractionated in vacuum and the fraction between 102-169 C. at 3 mm. was collected.
  • the product, N-a-naphthyLN-octyLN,N- dimethylethylenediamine forms a viscous, oily liquid. It was obtained in about 52.3% yield. In a nitrogen determination (Micro-Dumas) there .was found: N:8.39% (theory:8.60%).
  • the compounds of our invention present highly valuable and unexpected fungistatic properties especially against pathogenic fungi, although their usefulness is not limited to that particular group.
  • R. is an alkyl radical containing 6 to 14 carbon atoms
  • R and R are alkyl radicals containing one to three carbon atoms, and their water soluble hydrochlorides.
  • the method which comprises reacting a.- naphthylamine with a long chain alkylbromide to produce an alkylnaphthylamine containing a long chain alkyl radical, preparing the sodium salt of the last named compound, and reacting the said sodium salt with p dialkylaminoethylene chloride.
  • the method which comprises reacting a.- naphthylamin with a long chain alkylbromide having 6 to 14 carbon atoms to produce an alkylnaphthylamine containing a long chain alkyl radical, preparing the sodium salt of the last named compound, and reacting the said sodium salt with B dialkylaminoethylene chloride in which the alkyl radical contains 1 to 3 carbon atoms.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)

Description

Patented Feb. 23, 1954 UN IIED oFF'rcE;
N-ALPHA-NAPHTHYL N,-l l.N', -TRIALKYL- ETHYLENE DIAMINES- John'V. S cudi and Godfrey E'Grail; Bronx, N. Y'., assignors "to Nepera Chemical: 06. Ina, Nepera Park; Yonkers, N Y., a corporation-of N err-York No Drawing. Applicationoctober 16; 1951, Serial-N0. 251.634
in w-hich R is a longkchain alkyl radical containi'rig 6'to li'ca'rbon atoms, R "anci"R are short chainalkyl radicals containingl to 3 carbon" atoms. R and R1 maybe, but are not necessaril'yal-ike;
The compounds of our invention have a very.
2 ing-a-naphthylamine with along chain alkylbromide in which the alkyl' radical contains 6 t 142 carbon atoms and purify the product by distilla'e tion. Then we prepare the sodium salt of the:- intermediate alkylnaphthylamine by reacting 1 it with sodiumamide. The sodi'umsalt is then reacted with' fi-dialkylaminoethyl chloride inwhich the alkyl radical contains 1 t0"'3 cai bonato'ins' i'n" anonpolar solvent, after which the desir'ed-new remarkable antifungal activity. In vit'ro, they. 7
show fungistatic activityagainst many fungi'even in-a di1ution of 1:400,000; activity-is apparently a function of the .alkylsubstituents in R. In compoundswhere-R is a short chain alkyl radical -likemethyl, ethyl even butyl, the antifungal activity is only slight. Where this radical is hexyl' or ahigher-alkyl group -the -activity surprisingly increases, as can be -seen irom the following table:
Minimal fungistatic concentrations (ma/73) compound is separated and purifiedg' as described in'the specific example below.
The products so obtainedar'e -high boiling,- vis cou's'; oily liquids, soluble in the usual org ni'c solvents. They are insolublein' water; butrorm' a" water soluble addition salt with hydrochloric and other acids.
The following is an illustrative'e'xam'ple 'of our preferred. procedure of carrying out our inverttion, which is given for illustration and notfor' limitation.
Preparation of one of the-intermediates:
300*grams (2.11 moles) of"a'-naphthylamiiie were dissolved in 500'm1s. of ethanol *and' to this 340 grams (1.76 moles) ofoctyl bromide were added; The solution was refluxed for 48 hours after which the ethanol was removed by distillation. The semisolid residue was placed'in 100 mls'wof water which was made alkaline with sodium hydroxide solution l (40%) to pl-I-- 10.0 and In the compounds of this tablelfR and B im both methyl and Ris Fungus Tested .q a.
' iii'th'yl ethyl" lifityl' hexyl 'octyl nonyi decyl Tkichophytcn-menta 4 4 64' o.25 0xfis= 0i'25 0.25'" Trichophytonrubrum; Y 4 s- 4- 0. 25 o;2 5 0szs 0. 5. Spor0t1ichumSchenckn 2 8 16 0,25 ((3.25 Q.25 2 Epidermaphyton flocclisu 2 4 0.5 ().-25 0.25 0. 25 l Microsparum cams"..- 8 8 8 l). 5 1.0 0. 5 4 Microsfibiiti'nadouini-.- 4 8 4 0.25 (L5, 0. 25 2 Candida aZbicans- 1 64 32- 64 2.0 2.0 1.0 8
These in vitro tests against pathogenic fungi thenwaseiitractedthreetimes' with chloroform? indicate the utility of our compounds against The chloroform extracts were combined and fungus infections of the skin. Such infections dried with anhydrous sodium sulfate, filtered and are ringworm of the scalp, barbers itch, athletes the chloroform distilled oif at 60-65 C. The foot and others. We have employed the hydroresidue was distilled in vacuum and the fraction chlorides of our compounds in hydrophilic ointdistilling at ZOO-209 C. at 4 mm. (a-naphthylment with gratifying results. The ointment was octylamine) was collected. The yield obtained made up from 0.5 to 2% in strength. Lotions may be prepared by dissolving our compounds in suitable vehicles.
To prepare the compounds of our invention we was 72.6%. In a nitrogen determination (Micro- Dumas) there was found N=5.10% (theory: 5.47%).
Preparation of one of the products:
prepare firstthe alkylnaphthylamines, by react- 127.5 grams (0.5 mole) of a-naphthyl-octylamine, the above prepared intermediate, was dissolved in 250 mls. of xylene and 23.5 grams (0.6 mole) of sodium amide was added. It was slowly heated up to 90 C. and was kept at that temperature for thirty-six hours. The mixture was allowed to cool to room temperature and 58.75 grams (0.5 mole) of fl-dimethylaminoethyl chloride was added. The reaction mixture was then heated to 105110 C. and kept at that temperature for forty-eight hours under continous stirring. The reaction mixture was then allowed to cool to room temperature and acidified to a pH of 1.0 with a 1:1 HCl solution. The aqueous layer was separated from the xylene layer, cooled and the pH adjusted to 10.6 with sodium hydroxide solution (40%). The aqueous alkaline mixture was extracted three times with ether. The combined ether extractions were dried with KOH pellets. After separating from the KOH pellets, the ether was distilled off on the steam bath. The residue was fractionated in vacuum and the fraction between 102-169 C. at 3 mm. was collected. The product, N-a-naphthyLN-octyLN,N- dimethylethylenediamine forms a viscous, oily liquid. It was obtained in about 52.3% yield. In a nitrogen determination (Micro-Dumas) there .was found: N:8.39% (theory:8.60%).
Preparation of the water soluble hydrochloride of above compound:
3.26 grams (0.01 mole) of N-a-naphthyLN-noctyl,-N',N-dimethylethylenediarnine was dissolved in 50 mls. of dry ether. To this solution was added 0.36 grams (0.01 mole) of HCl dissolved in ether. The solutions were intimately mixed and cooled over night. The precipitate was then collected, washed with dry ether and recrystallized from a mixture of isopropanol and ether. The melting point of the hydrochloride is 102-104 C. In a nitrogen determination (Micro-Dumas) there was found N:'7.60% (theory:7.55%
Following the above procedure, a number of our compounds were prepared, differing in the length of the alkyl radical in the R substitution. They have the following characteristics:
The hydrochloride of the last compound (R=C1oHz1) melts at 93-4 C. In the nitrogen determination was found N:'7.39% (theory:
As can be seen from our specifications the compounds of our invention present highly valuable and unexpected fungistatic properties especially against pathogenic fungi, although their usefulness is not limited to that particular group.
We do not limit ourselves to the specific limitations mentioned, as these are given solely for the purpose of clearly describing our invention as set forth herein.
What we claim is:
1. Compounds of the group consisting of alphanaphthyl, tri-alkylethylenediamines of the general formula:
where R. is an alkyl radical containing 6 to 14 carbon atoms, R and R are alkyl radicals containing one to three carbon atoms, and their water soluble hydrochlorides.
2. N alpha naphthyl N hexyl N',N'- dimethyl-ethylenediamine.
3. N alpha naphthyl N heptyl N',N',- dimethylethylenediamine.
4. N alpha naphthyl N octyl N,N'- dimethylethylenediamine.
5. N alpha naphthyl N nonyl dimethylethylenediamine.
6. N alpha naphthyl N decyl N',N'- dimethylethylenediamine.
'7. The method which comprises reacting a.- naphthylamine with a long chain alkylbromide to produce an alkylnaphthylamine containing a long chain alkyl radical, preparing the sodium salt of the last named compound, and reacting the said sodium salt with p dialkylaminoethylene chloride.
8. The method which comprises reacting a.- naphthylamin with a long chain alkylbromide having 6 to 14 carbon atoms to produce an alkylnaphthylamine containing a long chain alkyl radical, preparing the sodium salt of the last named compound, and reacting the said sodium salt with B dialkylaminoethylene chloride in which the alkyl radical contains 1 to 3 carbon atoms.
JOHN V. SCUDI. GODFREY F. GRAIL.
References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 1,757,394 Schulemann et al. May 6, 1930 2,121,619 Williams et a1 June 21, 1938 2,430,722 Ladd Nov. 11, 1947 2,451,149 Boehm Oct. 12, 1948 2,457,048 Kyrides et al. Dec. 21, 1948 2,494,355 Paul et al. Jan. 10, 1950 2,536,750 Kamlet Jan. 2, 1951 2,627,491 Szabo et al Feb. 3, 1953 FOREIGN PATENTS Number Country Date 67,972 Denmark Nov. 22, 1948

Claims (1)

1. COMPOUNDS OF THE GROUP CONSISTING OF ALPHANAPHTHYL, TRI-ALKYLETHYLENEDIAMINES OF THE GENERAL FORMULA:
US251634A 1951-10-16 1951-10-16 N-alpha-naphthyl n, n' n,'-trialkylethylene diamines Expired - Lifetime US2670376A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3153093A (en) * 1961-11-22 1964-10-13 Abbott Lab Amino derivatives of nu-cyclopropylbenzylamines
US3923813A (en) * 1969-12-19 1975-12-02 Christiaens Sa A Derivatives of 2-aminoindanes
US4209302A (en) * 1979-05-10 1980-06-24 Morton-Norwich Products, Inc. Marker for petroleum fuels
US20060142387A1 (en) * 2003-06-10 2006-06-29 Rodolfo Cadilla Chemical compounds

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1757394A (en) * 1926-07-08 1930-05-06 Winthrop Chem Co Inc Aminoalkylamino derivative of aromatic aminohydroxy or polyamino compounds
US2121619A (en) * 1937-09-18 1938-06-21 Du Pont Preservation of rubber
US2151149A (en) * 1935-05-31 1939-03-21 Rca Corp Television apparatus
US2430722A (en) * 1946-04-25 1947-11-11 Us Rubber Co Derivatives of chlorinated quinones as fungicides
US2457048A (en) * 1946-10-04 1948-12-21 Monsato Chemical Company Process of making tertiary amines
US2494355A (en) * 1944-11-01 1950-01-10 Us Rubber Co Salts of aromatic dithiocarboxylic acids as fungicides
US2536750A (en) * 1947-05-19 1951-01-02 Pittsburgh Coke & Chemical Co Organic mercury compounds and germicidal compositions thereof
US2627491A (en) * 1950-07-15 1953-02-03 Wyeth Corp Penicillin salts of substituted alkylene diamines

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1757394A (en) * 1926-07-08 1930-05-06 Winthrop Chem Co Inc Aminoalkylamino derivative of aromatic aminohydroxy or polyamino compounds
US2151149A (en) * 1935-05-31 1939-03-21 Rca Corp Television apparatus
US2121619A (en) * 1937-09-18 1938-06-21 Du Pont Preservation of rubber
US2494355A (en) * 1944-11-01 1950-01-10 Us Rubber Co Salts of aromatic dithiocarboxylic acids as fungicides
US2430722A (en) * 1946-04-25 1947-11-11 Us Rubber Co Derivatives of chlorinated quinones as fungicides
US2457048A (en) * 1946-10-04 1948-12-21 Monsato Chemical Company Process of making tertiary amines
US2536750A (en) * 1947-05-19 1951-01-02 Pittsburgh Coke & Chemical Co Organic mercury compounds and germicidal compositions thereof
US2627491A (en) * 1950-07-15 1953-02-03 Wyeth Corp Penicillin salts of substituted alkylene diamines

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3153093A (en) * 1961-11-22 1964-10-13 Abbott Lab Amino derivatives of nu-cyclopropylbenzylamines
US3923813A (en) * 1969-12-19 1975-12-02 Christiaens Sa A Derivatives of 2-aminoindanes
US4209302A (en) * 1979-05-10 1980-06-24 Morton-Norwich Products, Inc. Marker for petroleum fuels
US20060142387A1 (en) * 2003-06-10 2006-06-29 Rodolfo Cadilla Chemical compounds

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