CH478735A - Process for the preparation of acetals and ketals of propanediols-1-3 substituted in position 2 - Google Patents
Process for the preparation of acetals and ketals of propanediols-1-3 substituted in position 2Info
- Publication number
- CH478735A CH478735A CH1063067A CH1063067A CH478735A CH 478735 A CH478735 A CH 478735A CH 1063067 A CH1063067 A CH 1063067A CH 1063067 A CH1063067 A CH 1063067A CH 478735 A CH478735 A CH 478735A
- Authority
- CH
- Switzerland
- Prior art keywords
- formula
- preparation
- substituted
- methylene
- acetals
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 9
- 238000002360 preparation method Methods 0.000 title claims description 7
- 150000001241 acetals Chemical class 0.000 title 1
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 2
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- -1 diene compound Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 206010037833 rales Diseases 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/69—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to carbon-to-carbon double or triple bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
- C07D303/24—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
- C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
- C07D319/08—1,3-Dioxanes; Hydrogenated 1,3-dioxanes condensed with carbocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/04—Esters of boric acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Procédé de préparation d'acétals et cétals des propanediols-1-3 substitués en position 2 La présente invention concerne un procédé de pré paration des dérivés d'un méthylène-2-propanediol-1-3, éventuellement substitué, répondant à la formule géné rale ci-après
EMI0001.0003
dans laquelle R1 et Rz représentent un atome d'hydro gène ou un reste aliphatique saturé, ou aliphatique non saturé, alicyclique, aromatique, arylaliphatique ou hété- rocyclique, et R3 et R4 représentent un atome d'hydro gène ou un reste aliphatique saturé ou aliphatique non saturé,
alicyclique, aromatique, arylaliphatique ou hété- rocyclique, ces restes pouvant être substitués par des atomes d'halogène ou par d'autres groupes fonctionnels, ou R3 et R4 ensemble représentent un groupe saturé ou non saturé de formule -(CR3R1)n dans laquelle n a une valeur comprise entre 2 et 11.
Le procédé selon l'invention est caractérisé en ce qu'on fait réagir un méthylène -2-propanediol-1-3 de formule
EMI0001.0018
avec un aldéhyde ou une cétone de formule
EMI0001.0020
Le méthylène-2-propanediol-1-3 de départ peut être préparé par un procédé qui consiste, dans un premier stade, à engager un aldéhyde a,(3 éthylénique de la forme
EMI0001.0024
dans une réaction de Diels-Alder avec un composé diéni- que,
à soumettre dans un deuxième stade l'aldéhyde cyclique obtenu au premier stade à l'action du formal- déhyde en milieu alcalin pour préparer le dérivé gem- diméthylolé correspondant par une réaction d'aldolisa- tion suivie d'une réaction de Cannizaro, enfin, dans un troisième stade, à pyrolyser le dérivé obtenu au deuxième stade pour aboutir au diol éthylénique recherché, avec régénération et recyclage du composé diénique mis en jeu dans le premier stade.
Dans la formule I, les substituants des restes R3 autres que des halogènes peuvent être des groupes fonctionnels tels que hydroxy, éther, ester, carboxy, époxy, amine, amide, nitro, nitrile, etc.
Les dérivés suivant la formule I .sont des métadioxan- nes. A titre d'exemples, on peut citer les méthylènes-5- métadioxannes de formule
EMI0001.0042
dans laquelle R6 et R.t peuvent avoir la signification ci-après
EMI0002.0000
EMI0002.0001
Les composés préparés par le procédé selon l'inven tion constituent des produits industriels nouveaux d'un grand intérêt. C'est ainsi qu'ils peuvent être <RTI
ID="0002.0006"> utilisés par exemple comme solvants, plastifiants, monomères, inter- médiaires de synthèse, matières premières pour la prépa ration de résines synthétiques, etc. L'exemple ci-après illustre l'invention.
<I>Exemple</I> Cet exemple concerne à .préparation du méthylène-5- vinyl-2-métadioxanne de formule
EMI0002.0018
On a placé dans un ballon à distiller de 1 litre,: 88 g de méthylène-2-propanediol-1-3 (1 mole), 129 g d'acro léine (2,3 moles), 400 cm3 de chlorure de méthylène, 0,1 g d'acide p-toluènesulfonique, utilisé comme catalyseur, et chauffé à reflux pendant 5 heures. Puis, on a chassé l'eau de réaction sous la forme d'un azéotrope avec le chlorure de méthylène, et distillé l'excès de solvant et d'acroléine.
Le catalyseur- a été neutralisé par addition. de bièarbonate de sodium et le produit de réaction a été .rectifié sous pression réduite.
Le tableau suivant résume la préparation, par un pro cessus analogue, de divers métadioxannes.
Process for the preparation of acetals and ketals of propanediols-1-3 substituted in position 2 The present invention relates to a process for the preparation of derivatives of a methylene-2-propanediol-1-3, optionally substituted, corresponding to the general formula rale below
EMI0001.0003
in which R1 and Rz represent a hydrogen atom or a saturated aliphatic, or unsaturated aliphatic, alicyclic, aromatic, arylaliphatic or heterocyclic residue, and R3 and R4 represent a hydrogen atom or a saturated aliphatic residue or unsaturated aliphatic,
alicyclic, aromatic, arylaliphatic or heterocyclic, these residues possibly being substituted by halogen atoms or by other functional groups, or R3 and R4 together represent a saturated or unsaturated group of formula - (CR3R1) n in which n has a value between 2 and 11.
The process according to the invention is characterized in that a methylene -2-propanediol-1-3 of formula
EMI0001.0018
with an aldehyde or a ketone of the formula
EMI0001.0020
The starting methylene-2-propanediol-1-3 can be prepared by a process which consists, in a first stage, in initiating an α, (3-ethylene aldehyde of the form
EMI0001.0024
in a Diels-Alder reaction with a diene compound,
in a second stage subjecting the cyclic aldehyde obtained in the first stage to the action of formaldehyde in an alkaline medium to prepare the corresponding gem-dimethylol derivative by an aldolization reaction followed by a Cannizaro reaction, finally , in a third stage, in pyrolyzing the derivative obtained in the second stage to result in the desired ethylenic diol, with regeneration and recycling of the diene compound involved in the first stage.
In formula I, the substituents of R3 radicals other than halogens can be functional groups such as hydroxy, ether, ester, carboxy, epoxy, amine, amide, nitro, nitrile, etc.
The derivatives according to formula I are metadioxanes. By way of examples, mention may be made of methylene-5-metadioxanes of formula
EMI0001.0042
in which R6 and R.t can have the following meaning
EMI0002.0000
EMI0002.0001
The compounds prepared by the process according to the invention constitute new industrial products of great interest. This is how they can be <RTI
ID = "0002.0006"> used for example as solvents, plasticizers, monomers, synthetic intermediates, raw materials for the preparation of synthetic resins, etc. The example below illustrates the invention.
<I> Example </I> This example relates to the preparation of methylene-5-vinyl-2-metadioxane of formula
EMI0002.0018
Was placed in a 1 liter distillation flask: 88 g of methylene-2-propanediol-1-3 (1 mole), 129 g of acrolein (2.3 moles), 400 cm3 of methylene chloride, 0.1 g of p-toluenesulfonic acid, used as a catalyst, and heated under reflux for 5 hours. Then, the water of reaction was removed as an azeotrope with methylene chloride, and the excess solvent and acrolein were distilled off.
The catalyst was neutralized by addition. of sodium bièarbonate and the reaction product was rectified under reduced pressure.
The following table summarizes the preparation, by a similar process, of various metadioxanes.
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR952986A FR1387099A (en) | 1963-11-07 | 1963-11-07 | Functional derivatives of 2-methylene propanediol-1-3 and methods of preparation |
| CH1437264A CH441284A (en) | 1963-11-07 | 1964-11-06 | Process for the preparation of optionally substituted methylene-2-propanediol-1,3 ethers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH478735A true CH478735A (en) | 1969-09-30 |
Family
ID=25714354
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH1063067A CH478735A (en) | 1963-11-07 | 1964-11-06 | Process for the preparation of acetals and ketals of propanediols-1-3 substituted in position 2 |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH478735A (en) |
-
1964
- 1964-11-06 CH CH1063067A patent/CH478735A/en not_active IP Right Cessation
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PL | Patent ceased | ||
| PL | Patent ceased |