USRE29195E - 7-(3-Chloro-2-propenyl)-1,3,5,7-tetraazabicyclo(3.3.1)nonane and its preparation - Google Patents
7-(3-Chloro-2-propenyl)-1,3,5,7-tetraazabicyclo(3.3.1)nonane and its preparation Download PDFInfo
- Publication number
- USRE29195E USRE29195E US05/638,790 US63879075A USRE29195E US RE29195 E USRE29195 E US RE29195E US 63879075 A US63879075 A US 63879075A US RE29195 E USRE29195 E US RE29195E
- Authority
- US
- United States
- Prior art keywords
- cis
- iaddend
- iadd
- propenyl
- chloro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- XKDWJPWYSVZSAU-UHFFFAOYSA-N 3-(3-chloroprop-2-enyl)-1,3,5,7-tetrazabicyclo[3.3.1]nonane Chemical compound C1NCN2CN(CC=CCl)CN1C2 XKDWJPWYSVZSAU-UHFFFAOYSA-N 0.000 title 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 2
- 239000012429 reaction media Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical compound NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002585 base Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000000845 anti-microbial effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 241000588915 Klebsiella aerogenes Species 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910004809 Na2 SO4 Inorganic materials 0.000 description 1
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 238000002814 agar dilution Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- MGJURKDLIJVDEO-UHFFFAOYSA-N formaldehyde;hydrate Chemical compound O.O=C MGJURKDLIJVDEO-UHFFFAOYSA-N 0.000 description 1
- 230000009036 growth inhibition Effects 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229960004011 methenamine Drugs 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains three hetero rings
- C07D487/18—Bridged systems
Definitions
- This invention concerns the novel compounds .[.7-.]. .Iadd.3-.Iaddend.cis- and .[.7-.]. .Iadd.3-cis-trans-.Iaddend.(3-chloro-2-propenyl)-1,3,5,7-tetraazabicyclo(3.3.1)nonane.[.-3-methanol hereinafter referred to as "Carbinolamine” or "Carbinolamines”.].. The .[. Carbinolamines.].
- the .[.Carbinolamines.]. .Iadd.N-(chloropropenyl)-tetraazabicyclononanes .Iaddend.of this invention have antimicrobial activity.
- both the cis- and the cis-trans- .[.Carbinolamines.]. .Iadd.III .Iaddend. when tested for antimicrobial activity using conventional agar dilution tests give complete growth inhibition against Staphylococcus aureus and Aerobacter aerogenes at a concentration of 50 p.p.m. and against Pseudomonas aeruginosa at 75 p.p.m. What is claimed is:
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
.[.7-.]..Iadd.3.Iaddend.-Cis- or .[.7.]..Iadd.3.Iaddend.-cis-trans-(3-Chloro-2-propenyl)-1,3,5,7-tetraazabicyclo(3.3.1)nonane.[.-3-methanol.]. is prepared by reacting cis-, or cis-trans-.[.7.]..Iadd.1.Iaddend.-(3-chloro-2-propenyl)-3,5,7-triaza-1-azoniatricyclo(3.3.1.13,7)decane chloride with excess aqueous strong base at room temperature to give the corresponding .[.carbinolamine, 7-.]..Iadd.3.Iaddend.-(3-chloro-2-propenyl)-1,3,5,7-tetraazabicyclo(3.3.1)nonane.[.-3-methanol.]..
Description
The art describes the conversion of N-methyl hexamethylene tetramine salts to form in low yields the N-methyl hexamethylene tetramine hydroxide; U.S. Pat. No. 1,336,709, Apr. 13, 1920 and Foss et al., J. Chem. Soc., 1950, 624. Neither reference shows any utility for the resulting hydroxide. In the first reference, a solution of barium hydroxide is used to react with the N-methyl hexamethylenetetramine salt, while in the second reference, moist silver oxide is used.
This invention concerns the novel compounds .[.7-.]. .Iadd.3-.Iaddend.cis- and .[.7-.]. .Iadd.3-cis-trans-.Iaddend.(3-chloro-2-propenyl)-1,3,5,7-tetraazabicyclo(3.3.1)nonane.[.-3-methanol hereinafter referred to as "Carbinolamine" or "Carbinolamines".].. The .[. Carbinolamines.]. .Iadd.title compounds .Iaddend.are prepared by reacting cis-1-(3-chloro-2-propenyl)-3,5,7-triaza-1-azoniatricyclo(3.3.1.13,7)decane chloride, commercially available as DowicilR 200 or cis-trans-1-(3-chloro-2-propenyl)-3,5,7-triaza-1-azoniatricyclo(3.3.1.1.sup.3,7)-decane chloride, commercially available as DowicilR 100, with excess aqueous strong base, e.g., an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or other strong water-soluble base at substantially room temperature, i.e., at or slightly below 25° C., according to the following equation ##STR1## .Iadd.In the reaction, the intermediate carbinolamine, II, is in equilibrium in the aqueous media with product, III, and hydrated formaldehyde. The equilibrium, as observed with C13 nuclear magnetic resonance spectroscopy, apparently lies predominantly toward product III. In isolating III by extraction into organic solvent, the reaction to the tetraazabicyclononane, III is essentially complete, leaving the dissociated formaldehyde in the aqueous phase. .Iaddend.In the reaction, up to about 5 moles of base per mole of starting cis- or cis-trans- compound (I) are used, and preferably from about 2 to about 5 moles of base per mole of starting cis- or cis-trans- compound. The .[.Carbinolamine.]. product is extracted from the reaction medium with a water-immiscible organic solvent, such as methylene chloride or benzene, to give in high yield the .[.Carbinolamines.]. .Iadd.N-(chloropropenyl)tetraazabicyclononanes .Iaddend.as high boiling viscous oils, slightly immiscible with water but highly soluble in organic solvents such as aromatic solvents, chlorinated hydrocarbons, ethers, alcohols and ketones. The structures of .[.the Carbinolamines.]. .Iadd.III .Iaddend.are confirmed by proton and C13 nuclear magnetic resonance spectra, and by mass spectrometry.
The following examples and teachings additionally describe specific embodiments and the best mode contemplated by the inventor of carrying out the invention.
50.0 Grams of cis-1-(3-chloro-2-propenyl)-3,5,7-triaza-1-azoniatricyclo(3.3.1.13,7)decane chloride (0.2 mole) was added gradually to a solution of 16.0 grams NaOH (0.4 mole) in 10 ml. of H2 O and the reaction mixture stirred about 15 minutes at room temperature. The oily aqueous reaction mixture was extracted twice with 200 ml. portions of CH2 Cl2 and the phases allowed to separate. The CH2 Cl2 phases were drawn off in a separatory funnel and dried with molecular sieves. The CH2 Cl2 was removed in vacuo, 40°/20 mm. mercury, to give 36.0 grams of product.Iadd., .Iaddend..[.cis-Carbinolamine..]. .Iadd.cis-III..Iaddend.
100 Grams (0.4 mole) of cis-1-(3-chloro-2-propenyl)-3,5,7-triaza-1-azoniatricyclo(3.3.1.13,7)decane chloride was added slowly to a solution of 80 grams (2.0 mole) NaOH dissolved in 500 ml. H2 O and the reaction mixture stirred 15 minutes at room temperature. Product cis-.[.Carbinolamine.]. was extracted with benzene, dried over Na2 SO4 and the benzene evaporated to give 72 grams (.[.78%.]. .Iadd.89% .Iaddend.yield) .[.at.]. .Iadd.as .Iaddend.a viscous oil, .[.cis-Carbinolamine..]. .Iadd.cis-III..Iaddend.
The procedures of Example 1 and 2 when repeated with DowicilR 100 give .[.cis-trans- Carbinolamine product..]. .Iadd.cis-trans-III. .Iaddend.
The .[.Carbinolamines.]. .Iadd.N-(chloropropenyl)-tetraazabicyclononanes .Iaddend.of this invention have antimicrobial activity. In representative operations, both the cis- and the cis-trans- .[.Carbinolamines.]. .Iadd.III .Iaddend.when tested for antimicrobial activity using conventional agar dilution tests give complete growth inhibition against Staphylococcus aureus and Aerobacter aerogenes at a concentration of 50 p.p.m. and against Pseudomonas aeruginosa at 75 p.p.m. What is claimed is:
Claims (4)
1. A member of the group consisting of .[.7-.]. .Iadd.3-.Iaddend.cis-(3-chloro-2-propenyl)-1,3,5,7-tetraazabicyclo(3.3.1)-nonane.[.-3-methanol.]. and .[.7-.]. .Iadd.3-.Iaddend.cis-trans-(3-chloro-2-propenyl)-1,3,5,7-tetraazabicyclo(3.3.1)nonane.[.-3-methanol.]..
2. .[.7-.]. .Iadd.3-.Iaddend.Cis-(3-chloro-2-propenyl)-1,3,5,7-tetraazabicyclo(3.3.1)nonane.[.-3-methanol.]..
3. .[.7-.]. .Iadd.3-.Iaddend.Cis-trans-(3-chloro-2-propenyl)-1,3,5,7-tetraazabicyclo(3.3.1)nonane.[.-3-methanol.]..
4. A method for making a .Iadd.3-.Iaddend.cis- or a mixture of .Iadd.3-.Iaddend.cis- and trans- .[.7-.]. -(3-chloro-2-propenyl)-1,3,5,7-tetraazabicyclo(3.3.1)nonane .[.-3-methanol.]. which comprises reacting at room temperature cis- or cis-trans- 1-(3-chloro-2-propenyl)-3,5,7-triaza-1-azoniatricyclo(3.3.1.13,7)-decane chloride with excess aqueous strong base and recovering the respective product .[.7-.]. .Iadd.3-.Iaddend.(3-chloro-2-propenyl)-1,3,5,7-tetraazabicyclo(3.3.1)nonane.[.-3-methanol.]. from the reaction medium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/638,790 USRE29195E (en) | 1973-10-23 | 1975-12-08 | 7-(3-Chloro-2-propenyl)-1,3,5,7-tetraazabicyclo(3.3.1)nonane and its preparation |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US408889A US3862939A (en) | 1973-10-23 | 1973-10-23 | 3-(3-chloro-2 -propenyl)-1,3,5,7-tetraazabicyclo(3.3.1) nonane-3-methanol and its preparation |
| US05/638,790 USRE29195E (en) | 1973-10-23 | 1975-12-08 | 7-(3-Chloro-2-propenyl)-1,3,5,7-tetraazabicyclo(3.3.1)nonane and its preparation |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US408889A Reissue US3862939A (en) | 1973-10-23 | 1973-10-23 | 3-(3-chloro-2 -propenyl)-1,3,5,7-tetraazabicyclo(3.3.1) nonane-3-methanol and its preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USRE29195E true USRE29195E (en) | 1977-04-26 |
Family
ID=27020416
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/638,790 Expired - Lifetime USRE29195E (en) | 1973-10-23 | 1975-12-08 | 7-(3-Chloro-2-propenyl)-1,3,5,7-tetraazabicyclo(3.3.1)nonane and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | USRE29195E (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050085645A1 (en) * | 2003-10-17 | 2005-04-21 | Honeywell Corporation | O-(3-chloropropenyl) hydroxylamine free base |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3228829A (en) * | 1963-11-04 | 1966-01-11 | Dow Chemical Co | Preservation of aqueous dispersions |
-
1975
- 1975-12-08 US US05/638,790 patent/USRE29195E/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3228829A (en) * | 1963-11-04 | 1966-01-11 | Dow Chemical Co | Preservation of aqueous dispersions |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050085645A1 (en) * | 2003-10-17 | 2005-04-21 | Honeywell Corporation | O-(3-chloropropenyl) hydroxylamine free base |
| US7214825B2 (en) | 2003-10-17 | 2007-05-08 | Honeywell International Inc. | O-(3-chloropropenyl) hydroxylamine free base |
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