CA1303051C - Preparation of 4,4-disubstituted 5-methylene-1,3- dioxolan-2-ones - Google Patents
Preparation of 4,4-disubstituted 5-methylene-1,3- dioxolan-2-onesInfo
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- CA1303051C CA1303051C CA000490420A CA490420A CA1303051C CA 1303051 C CA1303051 C CA 1303051C CA 000490420 A CA000490420 A CA 000490420A CA 490420 A CA490420 A CA 490420A CA 1303051 C CA1303051 C CA 1303051C
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- radicals
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- dioxolan
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/72—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 spiro-condensed with carbocyclic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings 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
- C07D317/34—Oxygen atoms
- C07D317/40—Vinylene carbonate; Substituted vinylene carbonates
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE:
4,4-Disubstituted 5-methylene-1-3-dioxolan-2-ones I
(I)
4,4-Disubstituted 5-methylene-1-3-dioxolan-2-ones I
(I)
Description
13t~3C~
The present invention relates to an improved process for the preparation of 4,4-disubstituted 5-methylene-1,3-dioxolan-2-ones of the general formula (1):
R
R - C - C = CH2 (I) O O
C
o where Rl is a Cl-C40 organic radical and R2 is Cl-C4-alkyl, and R and R may furthermore be bonded to form a 5-m ~ ered or 6-membered ring, by reacting a prop-1-yn-3-ol of the general formula (II):
R - C - C - CH (II) OH
with carbon dioxide in the presence of a copper salt and a tertiary base as catalysts.
Apart from the improvement according to the invention, this process is disclosed in German Patent 1,098,953, but is unsatisfactory in that it either gives space-time yields which are too low or requires unecono-mically harsh reaction conditions.
It is an object of the present invention to overcome these disadvantages.
It has now been found that this object is achieved by an improvement of the process defined at the outset, wherein the process is carried out in the presence of an effective amount of a quaternary ammonium or phos-phonium salt of the general formulae IIIa and IIIb:
B
13~3~5~
The present invention relates to an improved process for the preparation of 4,4-disubstituted 5-methylene-1,3-dioxolan-2-ones of the general formula (1):
R
R - C - C = CH2 (I) O O
C
o where Rl is a Cl-C40 organic radical and R2 is Cl-C4-alkyl, and R and R may furthermore be bonded to form a 5-m ~ ered or 6-membered ring, by reacting a prop-1-yn-3-ol of the general formula (II):
R - C - C - CH (II) OH
with carbon dioxide in the presence of a copper salt and a tertiary base as catalysts.
Apart from the improvement according to the invention, this process is disclosed in German Patent 1,098,953, but is unsatisfactory in that it either gives space-time yields which are too low or requires unecono-mically harsh reaction conditions.
It is an object of the present invention to overcome these disadvantages.
It has now been found that this object is achieved by an improvement of the process defined at the outset, wherein the process is carried out in the presence of an effective amount of a quaternary ammonium or phos-phonium salt of the general formulae IIIa and IIIb:
B
13~3~5~
- 2 - 0. Z . 0050/37327 [ ~ ~ e and ~R R~
IIIa IIIb where the substituents R are identicaL or different hydro-carbon radicals, each of 1 to 20 carbon atoms, the total number of carbon atoms in the radicals R being no higher than 24 in each case, and X is halogen, preferably bromine.
Because the salts III generally are suitable, the choice of these salts depends mainly on their availability and their price. In particular, the ammonium salts IIIa are therefore used in practice, the commercially available 1û and read;ly prepared tetraethylammonium bromide be;ng a prime example. Other noteworthy compounds IIIa are those in which three of the radicals R are lower alkyl groups, such as methyl or ethyl, and the fourth is be`nzyl or a straight-chain C6-C18-alkyl radical.
Phosphonium salts IIIb which are most eas;ly obtainable are those which are derived from triphenyl-phosphine and whose fourth substituent has been introduced into the molecule by quaternization with a C1^C6-alkyl bromide.
In general, the hydrocarbon radicals in the com-pounds IIIa and IIIb may be branched or, preferably, stra;ght-chain C1-c2o-alkyl groups, aralkyl groups, such as benzyl, or cyclohexyl or aromatic groups such as phenyl or p-tolyl. Furthermore, alkyl rad;cals R may be 25 bonded to one another, for example with formation of a piperidine ring or of a corresponding phosphorus hereto-cycle.
Frequently, and part;cularly in the case of the bromides, it is not necessary to start from the salts III
themselves, but is suff;c;ent to employ their precursors, ie. the base and the quaternization reagent, from which the active quaternization products III form by themselves.
~3~3(~S~
~``` - 3 - O.Z. OOSO/37327 The onium salts III can in principle be used in any desired amount since observations to date have shown that they only influence the reaction rate, which in turn depends on the type of propynol II employed. For reaction times of about 0.5-5 hours, which are satisfactory indus-trially, about 1-5 millimoles of III are required per mole of II in the case of reactive propynols II, eg. 3-methyl-but-1-yn-3-ol, and 5-10 millimoles of III are prefer-ably used per mole of II in the case of less reactive propynols II.
A particular advantage of the novel process is that it can be carried out successfully at as low as atmospheric pressure, and as a rule a pressure higher than 20 bar is not necessary. On the other hand, the reaction can also readily be carried out under any superatmospheric pressure, for example where the propynol II used is very unreactive or particularly short reaction times are desired.
However, if the procedure is carried out under a pressure above 100 bar, a marked advantage would be obtained only in exceptional cases.
Furthermore, the reaction temperatures, which are preferably as hi~h as 200C in the process disclosed in German Patent 1,098,953, can be substantially reduced by the novel process, ie. to 50-100C. H;gher temperatures, eg. up to 200C, should as a rule therefore only be used in the case of propynols II which are not very reactive.
As in the case of the basic process of German Patent 1,098,953, co~per salts and tertiary bases serve as further catalysts.
Suitable copper salts are ;n principle all ionic compounds of monovalent and divalent copper, eg. the oxides, hydrox;des, sulfates, nitrates and phosphates, in parti-cular the halides and the salts of C2-C16-fatty acids, especially the acetates.
The copper salts can ;n pr;nc;ple be used in any amount but are preferably used ;n amounts of from 1 to 10 m;llimoles per mole of II in order to achieve ~3V3~
- 4 - O.Z. 0050/37327 satisfactory reaction rates.
Suitable tertiary bases are trialkylamines, such as triethylamine, and heterocyclic nitrogen bases, such as pyridine. Tertiary phosphines, such as tributylphos-phine and triphenylphosphine, are preferred. The amountof the base is not critical and is in general from 1 to 10 millimoles ~er mole of II.
The reaction is preferably carried out in the absence of a solvent, although an inert solvent, such as dioxane, toluene, acetone or glycol diethyl ether may be present in an amount of about 25-200X by weight, based on the propynol II employed. If the product I is a liquid under the reaction conditions, it is advantageously used as the solvent. To avoid hydrolysis of the products, it is advisable to carry out the procedure in the absence of water.
The novel process does not possess any special features in terms of process engineering, ie. it can be carried out batchwise or continuously in a conventional manner by bring;ng a mixture of II, the catalyst components and, if required, the solvent into contact with the carbon dioxide under the reaction conditions, while stirr;ng thoroughly.
Usually, II is converted virtually quantitatively, after which ~he reaction mixture is worked up in a con-ventional manner. Catalyst-containing residues obtained in this step can generally be used several times for further reaction batches.
Observations to date have shown that the success 3a of the novel process is independent of the type of pro-pynol II employed, provided, of course, that the radical R1 does not contain any substituents which are reactive under the reaction conqitions.
Examples of radicals R1 are - saturated and unsaturated, branched and straight-chain alipha.ic radicals of not more than 4û carbon atoms, - isocycLic and heterocyclic cycloaliphatic groups 13~?3~
- S - O.Z. 0050/37327 preferably possessing 5-7 ring members, - isocyclic or heterocyclic aromatic groups, - mixed radicals containing groups of the abovemen-tioned types, for example araliphatic radicals, such as benzyl and - radicals which are bonded to R2 to form 5-membered or 6-membered rings.
These groups may carry substituents such as halo-gen, nitro, free or substituted amino groups, hydroxyl, formyl or cyano, or contain ether, ketone or ester groups.
R2 is, as a rule, methyl, or may be bonded to R1 to give further radicals, eg. cyclohexylidene.
Examples of propynols II are 3-methyl-but-1-yn-3-ol, 3-methylpent-1-yn-3-ol, 3-ethylpent-1-yn-3-ol, 1-ethynyl-cyclohexan-1-ol and dehydrolinalool (3,7-dimethyloct-6-en-1-yn-3-ol).
The products I are useful intermediates for organic syntheses.
EXA~PLE 1 Preparation of 4,4-dimethyl-5-methylene-1,3-dioxolan-2-one 1260 9 (15 moles) of 3-methylbut-1-yn-3-ol were reacted, at 80c and under a C02 pressure of 20 bar, witn a copper salt, a tertiary base and tetraethylammonium bromide (TEAB), and for comparison also in the absence of TEAB.
The Table below gives details of the type and amount of catalyst components, the reaction time and the yields of the dioxolanone.
13~3C~5~
-- 6 - 0 . Z . 0050/37327 c o ~o ~ `C X o~ o~ o~ ~ r~
~ o o~ o~ o~ o~ o~ ~o Q~ O
~- ~ ~J ~ ~ ~ ~ ~o X
o ~J ~ ~o CO
~ ~ . ~
J C~ O . O C
m ` , ,~ ,~ O ,~ .
UJ ,~ o o . ~ o U~
I_ . ~ U~ ~ ~ ~
.
~ o ~ ~o o~ ~o oo ~
~ ~ ~o ~~ ~ ~ ~
., ~ o oo .
.,~ o ~ '~ ~ '~ ~~ ~ '~ ~ ~ '~ ~ '~
a~ ~ ~ o ~ o ~ u~ ~ o ~ ~ o ~ o~
Q Ln Z ~-- Q ~Q ~-- Q U~ Z M Z ~J
O
._ ~ a~ aJ ~ ~ ~ o aJ ~ ~ ~ ~ ~ ~ ~
~ ., a ~ a aJ ,_ a~
_ ., O O U-~ ~ ~ ~ ~ O U~
, E, ~ ., ~1 oo 00 oO oO , ~ ~ >~
. - . ~ ~ ~ . - . .
~ ~ ~ - o ~ o ~ o ~ o ~ o o -- o ~ o t- O _ . ~ _ _ _ _ ~1 ~ . ~ _ E
, a~ ~ ~ o ~ .~ ~ ~ ~ ~ ~ ~ ., ~ o ~ ~
~I_ C ~ ~ VU~ ~U~ ~ L ~ ~U~ O
~5 o ~
~ L . ~ t~
~ ~1 O
~ I ~ ~ ~ t, ~ ~ I ~ ~ a~ ~t 1~3~Sl - 7 - O.Z. 0050/37327 Preparation of 4-methyl-4-(4-methylpent-1-yl)-5-methylene-dioxolan-2-one This compound was prepared similarly to Example 1 from 924 9 (6 moles) of 3,7-dimethyloct-1-yn-3-ol, 5.53 9 (0~5 mol %, based on the octynol) of Cu(II) acetate, 7.93 9 (0.5 mol %, based on the octynol) of triphenylphosphine and 6.29 9 (0.5 mol X, based on the octynol) of TEAB, in a yield of 98X and a puri~y of 98Z, the reaction time being 8 hours.
Preparation of 4-methyl-4-(4-methylpent-3-en-1-yl)-5-methylenedioxolan-2-one This compound was prepared, in the manner stated in Example 2, from 912 9 (6 moles) of 3,7-dimethyloct-6-en-1-yn-3-ol (dehydrolinalool), the yield being 98X, the purity 98X, and the reaction time 9 hours.
Preparation of 4,4-pentamethylene-5-methylenedioxolan-2-one 1240 9 (10 moles) of ethynylcyclohexanol, 5 9 (0.28 mol X, based on the alkynol) of Cu(II) acetate, 10 9 (0.38 mol %, based on the alkynol) of tripnenylphosphine and 10 9 (0.48 mol X, based on the alkynol) of TEAB, were reacted in the course of 7.5 hours in the manner stated in Example 1 to give the abovementioned compound~ The yield and the purity were each 98X.
EXAMP~E 5 Preparation of 4-methyl-4-ethyl-5-methylenedioxolan-Z-one This compound was prepared, in the manner stated in Example 4, from 1,176 9 (12 moles) of 3-methylpent-1-yn-3-ol, the yield being 98%, the purity 99% and the reaction time 5 hours.
Preparation of 4,4-dimethyl-5-methylenedioxolan-2-one The dioxolanone was obtained by a method similar to that described in Example 1e, but using 20 9 (0.41 mol %, based on the butynol employed~ of tetrabutylammonium 13~
- 8 - O.Z. 0050/~7327 bromide instead of the TEAB, the yield and purity each being 99X and the reaction time 2.5 hours.
Preparation of 4,4-dimethyl-S-methylenedioxolan-2-one S The dioxolanone was obtained by a method similar to that described in Example 1e, but using 25 9 (0.45 mol X, based on the butynol) of ethyltriphenylphosphonium bromide instead of the TEAB, the yield and purity each being 99X and the reaction time 3 hours.
IIIa IIIb where the substituents R are identicaL or different hydro-carbon radicals, each of 1 to 20 carbon atoms, the total number of carbon atoms in the radicals R being no higher than 24 in each case, and X is halogen, preferably bromine.
Because the salts III generally are suitable, the choice of these salts depends mainly on their availability and their price. In particular, the ammonium salts IIIa are therefore used in practice, the commercially available 1û and read;ly prepared tetraethylammonium bromide be;ng a prime example. Other noteworthy compounds IIIa are those in which three of the radicals R are lower alkyl groups, such as methyl or ethyl, and the fourth is be`nzyl or a straight-chain C6-C18-alkyl radical.
Phosphonium salts IIIb which are most eas;ly obtainable are those which are derived from triphenyl-phosphine and whose fourth substituent has been introduced into the molecule by quaternization with a C1^C6-alkyl bromide.
In general, the hydrocarbon radicals in the com-pounds IIIa and IIIb may be branched or, preferably, stra;ght-chain C1-c2o-alkyl groups, aralkyl groups, such as benzyl, or cyclohexyl or aromatic groups such as phenyl or p-tolyl. Furthermore, alkyl rad;cals R may be 25 bonded to one another, for example with formation of a piperidine ring or of a corresponding phosphorus hereto-cycle.
Frequently, and part;cularly in the case of the bromides, it is not necessary to start from the salts III
themselves, but is suff;c;ent to employ their precursors, ie. the base and the quaternization reagent, from which the active quaternization products III form by themselves.
~3~3(~S~
~``` - 3 - O.Z. OOSO/37327 The onium salts III can in principle be used in any desired amount since observations to date have shown that they only influence the reaction rate, which in turn depends on the type of propynol II employed. For reaction times of about 0.5-5 hours, which are satisfactory indus-trially, about 1-5 millimoles of III are required per mole of II in the case of reactive propynols II, eg. 3-methyl-but-1-yn-3-ol, and 5-10 millimoles of III are prefer-ably used per mole of II in the case of less reactive propynols II.
A particular advantage of the novel process is that it can be carried out successfully at as low as atmospheric pressure, and as a rule a pressure higher than 20 bar is not necessary. On the other hand, the reaction can also readily be carried out under any superatmospheric pressure, for example where the propynol II used is very unreactive or particularly short reaction times are desired.
However, if the procedure is carried out under a pressure above 100 bar, a marked advantage would be obtained only in exceptional cases.
Furthermore, the reaction temperatures, which are preferably as hi~h as 200C in the process disclosed in German Patent 1,098,953, can be substantially reduced by the novel process, ie. to 50-100C. H;gher temperatures, eg. up to 200C, should as a rule therefore only be used in the case of propynols II which are not very reactive.
As in the case of the basic process of German Patent 1,098,953, co~per salts and tertiary bases serve as further catalysts.
Suitable copper salts are ;n principle all ionic compounds of monovalent and divalent copper, eg. the oxides, hydrox;des, sulfates, nitrates and phosphates, in parti-cular the halides and the salts of C2-C16-fatty acids, especially the acetates.
The copper salts can ;n pr;nc;ple be used in any amount but are preferably used ;n amounts of from 1 to 10 m;llimoles per mole of II in order to achieve ~3V3~
- 4 - O.Z. 0050/37327 satisfactory reaction rates.
Suitable tertiary bases are trialkylamines, such as triethylamine, and heterocyclic nitrogen bases, such as pyridine. Tertiary phosphines, such as tributylphos-phine and triphenylphosphine, are preferred. The amountof the base is not critical and is in general from 1 to 10 millimoles ~er mole of II.
The reaction is preferably carried out in the absence of a solvent, although an inert solvent, such as dioxane, toluene, acetone or glycol diethyl ether may be present in an amount of about 25-200X by weight, based on the propynol II employed. If the product I is a liquid under the reaction conditions, it is advantageously used as the solvent. To avoid hydrolysis of the products, it is advisable to carry out the procedure in the absence of water.
The novel process does not possess any special features in terms of process engineering, ie. it can be carried out batchwise or continuously in a conventional manner by bring;ng a mixture of II, the catalyst components and, if required, the solvent into contact with the carbon dioxide under the reaction conditions, while stirr;ng thoroughly.
Usually, II is converted virtually quantitatively, after which ~he reaction mixture is worked up in a con-ventional manner. Catalyst-containing residues obtained in this step can generally be used several times for further reaction batches.
Observations to date have shown that the success 3a of the novel process is independent of the type of pro-pynol II employed, provided, of course, that the radical R1 does not contain any substituents which are reactive under the reaction conqitions.
Examples of radicals R1 are - saturated and unsaturated, branched and straight-chain alipha.ic radicals of not more than 4û carbon atoms, - isocycLic and heterocyclic cycloaliphatic groups 13~?3~
- S - O.Z. 0050/37327 preferably possessing 5-7 ring members, - isocyclic or heterocyclic aromatic groups, - mixed radicals containing groups of the abovemen-tioned types, for example araliphatic radicals, such as benzyl and - radicals which are bonded to R2 to form 5-membered or 6-membered rings.
These groups may carry substituents such as halo-gen, nitro, free or substituted amino groups, hydroxyl, formyl or cyano, or contain ether, ketone or ester groups.
R2 is, as a rule, methyl, or may be bonded to R1 to give further radicals, eg. cyclohexylidene.
Examples of propynols II are 3-methyl-but-1-yn-3-ol, 3-methylpent-1-yn-3-ol, 3-ethylpent-1-yn-3-ol, 1-ethynyl-cyclohexan-1-ol and dehydrolinalool (3,7-dimethyloct-6-en-1-yn-3-ol).
The products I are useful intermediates for organic syntheses.
EXA~PLE 1 Preparation of 4,4-dimethyl-5-methylene-1,3-dioxolan-2-one 1260 9 (15 moles) of 3-methylbut-1-yn-3-ol were reacted, at 80c and under a C02 pressure of 20 bar, witn a copper salt, a tertiary base and tetraethylammonium bromide (TEAB), and for comparison also in the absence of TEAB.
The Table below gives details of the type and amount of catalyst components, the reaction time and the yields of the dioxolanone.
13~3C~5~
-- 6 - 0 . Z . 0050/37327 c o ~o ~ `C X o~ o~ o~ ~ r~
~ o o~ o~ o~ o~ o~ ~o Q~ O
~- ~ ~J ~ ~ ~ ~ ~o X
o ~J ~ ~o CO
~ ~ . ~
J C~ O . O C
m ` , ,~ ,~ O ,~ .
UJ ,~ o o . ~ o U~
I_ . ~ U~ ~ ~ ~
.
~ o ~ ~o o~ ~o oo ~
~ ~ ~o ~~ ~ ~ ~
., ~ o oo .
.,~ o ~ '~ ~ '~ ~~ ~ '~ ~ ~ '~ ~ '~
a~ ~ ~ o ~ o ~ u~ ~ o ~ ~ o ~ o~
Q Ln Z ~-- Q ~Q ~-- Q U~ Z M Z ~J
O
._ ~ a~ aJ ~ ~ ~ o aJ ~ ~ ~ ~ ~ ~ ~
~ ., a ~ a aJ ,_ a~
_ ., O O U-~ ~ ~ ~ ~ O U~
, E, ~ ., ~1 oo 00 oO oO , ~ ~ >~
. - . ~ ~ ~ . - . .
~ ~ ~ - o ~ o ~ o ~ o ~ o o -- o ~ o t- O _ . ~ _ _ _ _ ~1 ~ . ~ _ E
, a~ ~ ~ o ~ .~ ~ ~ ~ ~ ~ ~ ., ~ o ~ ~
~I_ C ~ ~ VU~ ~U~ ~ L ~ ~U~ O
~5 o ~
~ L . ~ t~
~ ~1 O
~ I ~ ~ ~ t, ~ ~ I ~ ~ a~ ~t 1~3~Sl - 7 - O.Z. 0050/37327 Preparation of 4-methyl-4-(4-methylpent-1-yl)-5-methylene-dioxolan-2-one This compound was prepared similarly to Example 1 from 924 9 (6 moles) of 3,7-dimethyloct-1-yn-3-ol, 5.53 9 (0~5 mol %, based on the octynol) of Cu(II) acetate, 7.93 9 (0.5 mol %, based on the octynol) of triphenylphosphine and 6.29 9 (0.5 mol X, based on the octynol) of TEAB, in a yield of 98X and a puri~y of 98Z, the reaction time being 8 hours.
Preparation of 4-methyl-4-(4-methylpent-3-en-1-yl)-5-methylenedioxolan-2-one This compound was prepared, in the manner stated in Example 2, from 912 9 (6 moles) of 3,7-dimethyloct-6-en-1-yn-3-ol (dehydrolinalool), the yield being 98X, the purity 98X, and the reaction time 9 hours.
Preparation of 4,4-pentamethylene-5-methylenedioxolan-2-one 1240 9 (10 moles) of ethynylcyclohexanol, 5 9 (0.28 mol X, based on the alkynol) of Cu(II) acetate, 10 9 (0.38 mol %, based on the alkynol) of tripnenylphosphine and 10 9 (0.48 mol X, based on the alkynol) of TEAB, were reacted in the course of 7.5 hours in the manner stated in Example 1 to give the abovementioned compound~ The yield and the purity were each 98X.
EXAMP~E 5 Preparation of 4-methyl-4-ethyl-5-methylenedioxolan-Z-one This compound was prepared, in the manner stated in Example 4, from 1,176 9 (12 moles) of 3-methylpent-1-yn-3-ol, the yield being 98%, the purity 99% and the reaction time 5 hours.
Preparation of 4,4-dimethyl-5-methylenedioxolan-2-one The dioxolanone was obtained by a method similar to that described in Example 1e, but using 20 9 (0.41 mol %, based on the butynol employed~ of tetrabutylammonium 13~
- 8 - O.Z. 0050/~7327 bromide instead of the TEAB, the yield and purity each being 99X and the reaction time 2.5 hours.
Preparation of 4,4-dimethyl-S-methylenedioxolan-2-one S The dioxolanone was obtained by a method similar to that described in Example 1e, but using 25 9 (0.45 mol X, based on the butynol) of ethyltriphenylphosphonium bromide instead of the TEAB, the yield and purity each being 99X and the reaction time 3 hours.
Claims (6)
1. A process for the preparation of a 4,4-disubstituted 5-methylene-1,3-dioxolan-2-one of the formula (I):
(I) where R1 is an organic radical having from 1 to 40 carbon atoms, and R2 is C1-C4-alkyl, and R1 and R2 may furthermore be bonded to form a 5-membered or 6-membered ring, by react-ing a prop-1-yn-3-ol of the formula (II):
(II) with carbon dioxide in the presence of a copper salt and a tertiary base as catalysts, which process is carried out in the presence of an effective amount of a quaternary ammonium or phosphonium salt of the general formulae IIIa and IIIb:
and IIIa IIIb where the substituents R are identical or different hydro-carbon radicals, each of 1 to 20 carbon atoms, the total number of carbon atoms in the radicals R being no higher than 24 in each case, and X is halogen
(I) where R1 is an organic radical having from 1 to 40 carbon atoms, and R2 is C1-C4-alkyl, and R1 and R2 may furthermore be bonded to form a 5-membered or 6-membered ring, by react-ing a prop-1-yn-3-ol of the formula (II):
(II) with carbon dioxide in the presence of a copper salt and a tertiary base as catalysts, which process is carried out in the presence of an effective amount of a quaternary ammonium or phosphonium salt of the general formulae IIIa and IIIb:
and IIIa IIIb where the substituents R are identical or different hydro-carbon radicals, each of 1 to 20 carbon atoms, the total number of carbon atoms in the radicals R being no higher than 24 in each case, and X is halogen
2. A process as claimed in claim 1, which is carried out under 1-20 bar.
3. A process as claimed in claim 1, wherein the quaternary ammonium salt used is tetraethylammonium bromide.
4. A process as claimed in claim 1, 2 or 3, wherein the copper salt used is copper (II) acetate.
5. A process as claimed in claim 1, 2 or 3, wherein the tertiary base used is triphenylphosphine.
6. A process as claimed in claim 1, 2 or 3, wherein use is made of a starting compound of formula (II) wherein R1 is a saturated or unsaturated, branched or unbranched alphatic radical having from 1 to 40 carbon atoms, an isocyclic or heterocyclic cycloalphatic group having 5-7 ring members, anisocyclic or heterocyclic aromatic group, or a mixed radical containing groups of the above mentioned type.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3433403.3 | 1984-09-12 | ||
| DE19843433403 DE3433403A1 (en) | 1984-09-12 | 1984-09-12 | METHOD FOR PRODUCING 4,4-DISUBSTITUTED 5-METHYLENE-1,3-DIOXOLAN-2-ONES |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1303051C true CA1303051C (en) | 1992-06-09 |
Family
ID=6245175
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000490420A Expired - Lifetime CA1303051C (en) | 1984-09-12 | 1985-09-11 | Preparation of 4,4-disubstituted 5-methylene-1,3- dioxolan-2-ones |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0175241B1 (en) |
| JP (1) | JPS6176479A (en) |
| CA (1) | CA1303051C (en) |
| DE (2) | DE3433403A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9062136B2 (en) | 2012-03-29 | 2015-06-23 | Basf Se | Polymerizable alkylidene-1,3-dioxolane-2-one and use thereof |
| US10000461B2 (en) | 2014-04-25 | 2018-06-19 | Swimc Llc | Polycyclocarbonate compounds and polymers formed therefrom |
| US10717897B2 (en) | 2014-04-25 | 2020-07-21 | The Sherwin-Williams Company | Polycyclocarbonate compounds and polymers and compositions formed therefrom |
| CN112135817A (en) * | 2018-05-18 | 2020-12-25 | 巴斯夫欧洲公司 | Monomer comprising at least one 4- (2-oxyethylene) -1, 3-dioxolan-2-one unit and use thereof |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1092191C (en) * | 1996-10-21 | 2002-10-09 | 霍夫曼-拉罗奇有限公司 | Manufacture of cyclocarbonates |
| WO2011157671A1 (en) | 2010-06-15 | 2011-12-22 | Basf Se | Use of cyclic carbonates in epoxy resin compositions |
| EP2758470A1 (en) | 2011-09-19 | 2014-07-30 | Basf Se | Curing of epoxy resin compositions comprising cyclic carbonates using mixtures of amino hardeners |
| US8586653B2 (en) | 2011-09-19 | 2013-11-19 | Basf Se | Curing of epoxy resin compositions comprising cyclic carbonates using mixtures of amino hardeners |
| EP2758447A1 (en) | 2011-09-21 | 2014-07-30 | Basf Se | Curing of epoxy resin compositions comprising cyclic carbonates using mixtures of amino hardeners and catalysts |
| US8877837B2 (en) | 2011-09-21 | 2014-11-04 | Basf Se | Curing of epoxy resin compositions comprising cyclic carbonates using mixtures of amino hardeners and catalysts |
| JP6150878B2 (en) | 2012-03-29 | 2017-06-21 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Polymerizable alkylidene-1,3-dioxolan-2-one and use thereof |
| EP2851379A1 (en) | 2013-09-23 | 2015-03-25 | BASF Coatings GmbH | Coating composition and coatings prepared therefrom which are curable at low temperatures as well as their use |
| EP2851403A1 (en) | 2013-09-23 | 2015-03-25 | BASF Coatings GmbH | Coating substance compounds and low temperature curable coatings made therefrom and their use |
| EP3052540B1 (en) | 2013-10-01 | 2017-11-15 | Basf Se | Multi-component epoxy resin composition |
| JP6443836B2 (en) * | 2014-08-06 | 2018-12-26 | 国立大学法人徳島大学 | Retardation film |
| FR3034770B1 (en) | 2015-04-10 | 2017-05-12 | Bostik Sa | HYDROCARBON POLYMERS COMPRISING TWO EXO-VINYLENE CYCLOCARBONATE TERMINAL GROUPS |
| FR3057269B1 (en) | 2016-10-07 | 2018-11-23 | Bostik Sa | NOVEL HYDROCARBON POLYMERS WITH EXO-VINYLENE CYCLOCARBONATE TERMINAL GROUPS |
| KR102605180B1 (en) * | 2017-08-14 | 2023-11-24 | 바스프 에스이 | How to make cyclic carbonate |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1098953B (en) * | 1959-09-29 | 1961-02-09 | Basf Ag | Process for the preparation of 5-methylene-4, 4-dialkyl-1, 3-dioxolan-2-ones |
| US4231937A (en) * | 1978-08-28 | 1980-11-04 | Atlantic Richfield Company | Preparation of alkylene carbonates from alkylene iodohydrins |
| DE3123165A1 (en) * | 1981-06-11 | 1983-01-05 | Basf Ag, 6700 Ludwigshafen | "METHOD FOR PRODUCING 2-ALKOXY- (1,3) -DIOXOLANES" |
-
1984
- 1984-09-12 DE DE19843433403 patent/DE3433403A1/en not_active Withdrawn
-
1985
- 1985-09-03 JP JP60193262A patent/JPS6176479A/en active Granted
- 1985-09-07 DE DE8585111315T patent/DE3564112D1/en not_active Expired
- 1985-09-07 EP EP85111315A patent/EP0175241B1/en not_active Expired
- 1985-09-11 CA CA000490420A patent/CA1303051C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9062136B2 (en) | 2012-03-29 | 2015-06-23 | Basf Se | Polymerizable alkylidene-1,3-dioxolane-2-one and use thereof |
| US10000461B2 (en) | 2014-04-25 | 2018-06-19 | Swimc Llc | Polycyclocarbonate compounds and polymers formed therefrom |
| US10717897B2 (en) | 2014-04-25 | 2020-07-21 | The Sherwin-Williams Company | Polycyclocarbonate compounds and polymers and compositions formed therefrom |
| US10759773B2 (en) | 2014-04-25 | 2020-09-01 | Swimc Llc | Polycyclocarbonate compounds and polymers formed therefrom |
| US12077676B2 (en) | 2014-04-25 | 2024-09-03 | Swimc Llc | Polycyclocarbonate compounds and polymers and compositions formed therefrom |
| CN112135817A (en) * | 2018-05-18 | 2020-12-25 | 巴斯夫欧洲公司 | Monomer comprising at least one 4- (2-oxyethylene) -1, 3-dioxolan-2-one unit and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3564112D1 (en) | 1988-09-08 |
| EP0175241A1 (en) | 1986-03-26 |
| EP0175241B1 (en) | 1988-08-03 |
| DE3433403A1 (en) | 1986-03-20 |
| JPH0566950B2 (en) | 1993-09-22 |
| JPS6176479A (en) | 1986-04-18 |
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