EP0449917A1 - Sels antideflagrants de 1-dimethylamino-3-dimethylimino-2-arylpropene-1, procede de fabrication et applications - Google Patents
Sels antideflagrants de 1-dimethylamino-3-dimethylimino-2-arylpropene-1, procede de fabrication et applicationsInfo
- Publication number
- EP0449917A1 EP0449917A1 EP90900851A EP90900851A EP0449917A1 EP 0449917 A1 EP0449917 A1 EP 0449917A1 EP 90900851 A EP90900851 A EP 90900851A EP 90900851 A EP90900851 A EP 90900851A EP 0449917 A1 EP0449917 A1 EP 0449917A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- salts
- formula
- trimethine
- water
- soluble
- 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.)
- Withdrawn
Links
- 150000003839 salts Chemical class 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 12
- 150000007513 acids Chemical class 0.000 claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 230000022244 formylation Effects 0.000 claims abstract description 6
- 238000006170 formylation reaction Methods 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 5
- 239000000543 intermediate Substances 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- 239000012736 aqueous medium Substances 0.000 claims abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 4
- 239000011541 reaction mixture Substances 0.000 claims abstract description 4
- 238000005874 Vilsmeier-Haack formylation reaction Methods 0.000 claims abstract description 3
- 230000007062 hydrolysis Effects 0.000 claims abstract description 3
- 150000003222 pyridines Chemical class 0.000 claims abstract description 3
- 150000003230 pyrimidines Chemical class 0.000 claims abstract description 3
- -1 Biphenylyl Chemical group 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 claims description 6
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims description 4
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 4
- NJQFCQXFOHVYQJ-PMACEKPBSA-N BF 4 Chemical compound C1([C@@H]2CC(=O)C=3C(O)=C(C)C4=C(C=3O2)[C@H](C(C)C)C2=C(O4)C(C)=C(C(C2=O)(C)C)OC)=CC=CC=C1 NJQFCQXFOHVYQJ-PMACEKPBSA-N 0.000 claims description 2
- 229910018286 SbF 6 Inorganic materials 0.000 claims description 2
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- XTEGVFVZDVNBPF-UHFFFAOYSA-L naphthalene-1,5-disulfonate(2-) Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1S([O-])(=O)=O XTEGVFVZDVNBPF-UHFFFAOYSA-L 0.000 claims description 2
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000003373 pyrazinyl group Chemical group 0.000 claims description 2
- 125000002098 pyridazinyl group Chemical group 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 2
- 125000005329 tetralinyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 125000000129 anionic group Chemical group 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 150000002391 heterocyclic compounds Chemical class 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 4
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- YWPOLRBWRRKLMW-UHFFFAOYSA-M sodium;naphthalene-2-sulfonate Chemical compound [Na+].C1=CC=CC2=CC(S(=O)(=O)[O-])=CC=C21 YWPOLRBWRRKLMW-UHFFFAOYSA-M 0.000 description 3
- XQXPVVBIMDBYFF-UHFFFAOYSA-N 4-hydroxyphenylacetic acid Chemical compound OC(=O)CC1=CC=C(O)C=C1 XQXPVVBIMDBYFF-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000003542 behavioural effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001610 cryolite Inorganic materials 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- IOXPXHVBWFDRGS-UHFFFAOYSA-N hept-6-enal Chemical compound C=CCCCCC=O IOXPXHVBWFDRGS-UHFFFAOYSA-N 0.000 description 1
- APPXAPLOULWUGO-UHFFFAOYSA-H hexasodium hexafluoride Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+] APPXAPLOULWUGO-UHFFFAOYSA-H 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- MGGNIEDZABVSCC-UHFFFAOYSA-J tetrasodium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Na+].[Na+].[Na+].[Na+] MGGNIEDZABVSCC-UHFFFAOYSA-J 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
- C07C251/30—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having nitrogen atoms of imino groups quaternised
Definitions
- 1-Dimethylamino-3-dimethylimino-2-arylpropene-1-perchlorates are known to be important intermediates for the synthesis of heterocycles, e.g. Pyrimidines (see Zaschke, Z. Chem. 17 (1977) pp. 63 and 293; Arnold, Collect. Czech.
- the present invention was therefore based on the object of making trimethine salts available which can be handled in an explosion-proof manner, in the required purity
- trimethine salts in an aqueous medium with no acids with an oxidizing effect which can form trimethine salts which are sparingly or slightly soluble in water and which are inert towards the trimethine cation, or with
- the invention therefore relates to explosion-proof and poorly to sparingly water-soluble trimethine salts
- R aryl or heteroaryl, which are optionally mono- or polysubstituted by halogen, (C 1 -C 12 ) -alkyl, (C 1 -C 12 ) -alkoxy or hydroxy, aryl preferably for phenyl, naphthyl, biphenylyl, anthracenyl or Tetralinyl, and heteroaryl is preferably pyridinyl, pyrimidinyl, pyrazinyl or pyridazinyl, halogen is preferably F, Cl or Br, in particular F or Cl, and the radicals are (C 1 -C 12 ) -alkyl or
- (C 1 -C 12 ) alkoxy are optionally mono- or polysubstituted by halogen, in particular F or Cl;
- X an anion equivalent of a non-oxidizing and inert to the trimethine cation
- trimethine salts preferably from the group p-toluenesulfonate, naphthalene-2-sulfonate,
- the invention further relates to a method for
- trimethine salts of the formula I which are sparingly soluble in water, are separated off in preferably fine-crystalline form.
- Preferred acids of the formula III or their water-soluble salts are p-toluenesulfonic acid, p-toluenesulfonate sodium, boron tetrafluoride sodium, antimony hexafluoride sodium,
- Naphthalene-2-sulfonic acid Naphthalene-2-sulfonic acid, naphthalene-2-sulfonate sodium, naphthalene-1-sulfonate sodium,
- Naphthalene-1,5-disodium disulfonate or mixtures of these salts or acids, especially with the acids or salts on which they are based. are particularly preferred
- trimethine salts of the formula I prepared according to the invention are preferably obtained in fine crystalline form and
- the solution obtained is cooled to -10 ° C. and 30 g (0.2 mol) is added to it in portions while stirring.
- Example 1 is repeated with the modification that the clear aqueous solution obtained, instead of 38 g (0.22 mol) of sodium hexafluorophosphate, dissolved in 60 ml of water, is dissolved with 53 g (0.23 mol) of naphthalene-2-sulfonate sodium in 1.2 l of water. A light yellow immediately falls
- Example 2 is repeated with the modification that instead of naphthalene-2-sulfonate sodium the same amount
- Naphthalene-1-sulfonate sodium is added.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pyridine Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
Fabrication de sels de triméthine antidéflagrants et peu solubles dans l'eau, de formule (I) avec: R = aryle ou hétéroaryle, le cas échéant substitués une fois ou plusieurs fois, X = équivalent anionique d'un résidu acide non oxydant et inerte par rapport à l'action du triméthine, pouvant former des sels de triméthine peu solubles dans l'eau, par formylation de composés de formule (II): R-CH2-COOH, où R a la même signification que dans la formule (I), dans les conditions de la réaction de Vilsmeier-Haack et avec une hydrolyse ultérieure du produit de formylation dans un milieu aqueux, avec formation de sels primaires de triméthine solubles dans l'eau et réaction de ces sels primaires de triméthine solubles dans l'eau dans le mélange de réaction aqueux avec des acides de formule (III): (H)nX, où X a la même notation que dans la formule (I) et n représente un nombre de 1 à 3, ou avec les sels, solubles dans l'eau, de ces acides, au moins en quantités stoechiométriques, et séparation des sels de triméthine de formule (I) peu solubles dans l'eau qui en résultent. Les sels de triméthine de formule (I) ont des applications comme produits intermédiaires pour la synthèse de composés hétérocycliques, principalement de pyrimidines et de pyridines.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3842062 | 1988-12-14 | ||
| DE3842062A DE3842062A1 (de) | 1988-12-14 | 1988-12-14 | Explosionssichere 1-dimethylamino-3-dimethylimino-2-arylpropen-1-salze, verfahren zu ihrer herstellung und ihre verwendung |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0449917A1 true EP0449917A1 (fr) | 1991-10-09 |
Family
ID=6369135
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP90900851A Withdrawn EP0449917A1 (fr) | 1988-12-14 | 1989-12-09 | Sels antideflagrants de 1-dimethylamino-3-dimethylimino-2-arylpropene-1, procede de fabrication et applications |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0449917A1 (fr) |
| JP (1) | JPH04502158A (fr) |
| KR (1) | KR910700227A (fr) |
| CA (1) | CA2005330A1 (fr) |
| DE (1) | DE3842062A1 (fr) |
| NO (1) | NO912279L (fr) |
| WO (1) | WO1990006913A1 (fr) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1178658C (zh) * | 1998-04-24 | 2004-12-08 | 麦克公司 | 合成环加氧酶-2抑制剂的方法 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3288784A (en) * | 1966-04-11 | 1966-11-29 | Monsanto Co | Method of preparing substituted chlorominium salts |
| US3993656A (en) * | 1974-11-19 | 1976-11-23 | Merck & Co., Inc. | 1,8-Naphthyridine compounds |
| US4310670A (en) * | 1980-02-26 | 1982-01-12 | Sterling Drug Inc. | Low-temperature, aqueous conversion of 4-picoline derivative to 5-cyano-[3,4'-bipyridin]-6(1H)-one |
| DE3173083D1 (en) * | 1980-03-22 | 1986-01-16 | Fbc Ltd | Pesticidal heterocyclic compounds, processes for preparing them, compositions containing them, and their use |
| US4489011A (en) * | 1983-05-16 | 1984-12-18 | Merrell Dow Pharmaceuticals Inc. | Hypoglycemic N-(2-substituted-3-dialkylamino-2-propenylidene)-N-alkylalkanaminium camsylate salts |
-
1988
- 1988-12-14 DE DE3842062A patent/DE3842062A1/de not_active Withdrawn
-
1989
- 1989-12-09 EP EP90900851A patent/EP0449917A1/fr not_active Withdrawn
- 1989-12-09 JP JP90501459A patent/JPH04502158A/ja active Pending
- 1989-12-09 WO PCT/EP1989/001510 patent/WO1990006913A1/fr not_active Ceased
- 1989-12-09 KR KR1019900701770A patent/KR910700227A/ko not_active Withdrawn
- 1989-12-13 CA CA002005330A patent/CA2005330A1/fr not_active Abandoned
-
1991
- 1991-06-13 NO NO91912279A patent/NO912279L/no unknown
Non-Patent Citations (1)
| Title |
|---|
| See references of WO9006913A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3842062A1 (de) | 1990-06-28 |
| NO912279D0 (no) | 1991-06-13 |
| KR910700227A (ko) | 1991-03-14 |
| NO912279L (no) | 1991-06-13 |
| WO1990006913A1 (fr) | 1990-06-28 |
| CA2005330A1 (fr) | 1990-06-14 |
| JPH04502158A (ja) | 1992-04-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| 17P | Request for examination filed |
Effective date: 19910529 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE ES FR GB IT LI NL SE |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN |
|
| 18W | Application withdrawn |
Withdrawal date: 19930609 |