WO1984001577A1 - A process for preparing a cycloaddition compound - Google Patents
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- WO1984001577A1 WO1984001577A1 PCT/NL1983/000040 NL8300040W WO8401577A1 WO 1984001577 A1 WO1984001577 A1 WO 1984001577A1 NL 8300040 W NL8300040 W NL 8300040W WO 8401577 A1 WO8401577 A1 WO 8401577A1
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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
- C07D317/10—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
- C07D317/14—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 substituted hydrocarbon radicals attached to ring carbon atoms
- C07D317/18—Radicals substituted by singly bound oxygen or sulfur atoms
- C07D317/20—Free hydroxyl or mercaptan
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C33/05—Alcohols containing rings other than six-membered aromatic rings
- C07C33/14—Alcohols containing rings other than six-membered aromatic rings containing six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C401/00—Irradiation products of cholesterol or its derivatives; Vitamin D derivatives, 9,10-seco cyclopenta[a]phenanthrene or analogues obtained by chemical preparation without irradiation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
- C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D305/10—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having one or more double bonds between ring members or between ring members and non-ring members
- C07D305/12—Beta-lactones
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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
- C07D317/10—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
- C07D317/14—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 substituted hydrocarbon radicals attached to ring carbon atoms
- C07D317/16—Radicals substituted by halogen atoms or nitro radicals
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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
- C07D317/10—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
- C07D317/14—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 substituted hydrocarbon radicals attached to ring carbon atoms
- C07D317/18—Radicals substituted by singly bound oxygen or sulfur atoms
- C07D317/22—Radicals substituted by singly bound oxygen or sulfur atoms etherified
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/14—All rings being cycloaliphatic
- C07C2602/24—All rings being cycloaliphatic the ring system containing nine carbon atoms, e.g. perhydroindane
Definitions
- the invention relates to a process for preparing a cycloaddition compound.
- ketene is reacted for that purpose with a carbonyl group-containing compound having formula 1 of the sheet of formulae which contains a highly electron-attractant group in the ⁇ -position relative to the carbonyl group in the presence of a chiral tertiary amine as catalyst to form a cycloaddition compound having formula 2 of the sheet of formulae.
- Examples of compounds having formula 1 containing a carbonyl group and a highly electron-attractant group in the ⁇ -position relative to the carbonyl group are chloral and in particular 1,1,1,-tricholoropropanone-2.
- cholecalciferol compounds may be readily and stereo-selectively prepared, such as both 25 (S) . and 25(R)-1 ⁇ , 25, 26-trihydrojcycholecalciferol and both 25 (S) and 25(R)-dihydroxycholecalciferol which cholecalciferol compounds play their part in the human body, e.g. the 25 (S), 26-dihydroxycholecalciferol which is an important vitamin D 3 metabolite.
- Examples of the catalyst employed according to the process according to the invention are the chiral tertiary amines listed in Table A contained hereinafter.
- a comparison of the correlated values given in columns II, III and IV of Table A shows in what sense and degree the enantioselectivity is effected by the selection of the catalyst on the basis of the reaction of ketene with chloral as the compound having formula 1.
- the invention also relates to a cycloaddition compound having formula 2 of the sheet of formulae, in particular having formula 3 of the sheet of formulae, in which R represents H or CH 3 .
- a cycloaddition compound having formula 2 or formula 3 in the form of the R- or S-enantiomer thereof.
- Such cycloaddition compounds having formula 2 or formula 3 are novel and very advantageous as a starting material for the asymetric synthesis of chiral. compounds, e.g., of a hydroxyalkanedicarboxylic acid such as malic acid.
- these cycloaddition compounds are suitable as starting compounds for the preparation of novel acetonide compounds.
- the invention therefore also relates to a process for preparinganacetonide which is characterized in that a compound having formula 2 of the sheet of formulae is converted to an acetonide having formula 32 of the sheet of formulae, in a manner known per se, especially in that a compound having formula 3 , in which R is CH 3 , is converted to an acetonide having fofmula 33.
- X in formulae 32 and 33, respectively of the sheet of formulae represents OTs, OH, Cl, Br or J, OTs being tosylate. It is further preferred to prepare the R- or S-enantiomer of the acetonide compound having formulae 32 or 33 by starting from the corresponding enantiomer of the compound having formula 2 or formula 3.
- the compounds having formula 32, substituted in the 4-position, in particular the 4-substituted 2-methyl-1,2-butanediol-1,2-acetonides or the R- or S-enantiomer thereof also belong to the invention.
- the Grignard compounds of the 4-halogen-2-methyl-1,2-butanediol-1, 2-acetonides are important intermediates for a novel method of preparing 1 ⁇ , 25, 26-trihydroxycholecalciferols (formula 6) and 25, 26-dihydroxycholecalciferols (formula 5) .
- This preparation method with the use of the Grignard compounds of the acetonides having formula 33, has significant advantagesoyer the method employed thus far for synthesis of these cholecalciferols. (J.J. Partridge, M.R. Oskokovic et al. J. Am.Chem. Soc.,1981, 103, 1253; J.J. Partridge, M.R.
- the key compound for the preparation of a compound having formula 33 is the 4-methyl-4-(trichloromethyl)-2-oxetanone having formula 3, in which R is CH 3 .
- R is CH 3 .
- both the (S) and the (R) enantiomer resp. formulae 4a and 4b, sheet of formulae
- the two enantiomeric forms of compounds 8 through 11 (equation 14, sheet of formulae) as well as the compounds having formula 33 can be prepared, the Grignard compounds of which latter compounds can be used for the preparation of both 25 (S)- and 25(R)-1 ⁇ , 25-26-trihydroxycholecalciferol (formula 6) as well as for the preparation of both 25 (S)- and 25 (R)-25,26-dih ⁇ droxycholecalciferol (formula 9) .
- Example I a) Preparation of (S)- ⁇ -(trichloromethyl)- ⁇ -propiolactone (formula 16 of the sheet of formulae).
- Racemic lactone having formula 16 had mp 36-37°C. Example II.
- an enantiomer-pure compound having formula 4a could be prepared as follows. Under an atmosphere of dried nitrogen 389 mg (1.2 mmol) of quinidine was dissolved in 35 cm 3 of toluene, in a three-necked flask of 100 cm 3 , equipped with a thermometer and a ketene inlet. Then 10 g (63 mmol) of 1 , 1 , 1-thrichloropropanone-2 was added. The mixture was cooled to -25oC. Ketene was passed for 5 hours with stirring (about 10 mmol/h).
- the (R) -enantiomer of the 2-oxetanone could be isolated in 86% ee; starting from cinchonidine, the (R)-enantiomer could be isolated in 86% ee; and starting from cinchonine, the (S) -enantiomer could be isolated in 92% ee.
Abstract
A process for preparing a cycloaddition compound, which comprises reacting ketene with a carbonyl group-containing compound having formula (I), which contains a highly electron-attractant group in the alpha-position relative to the carbonyl group in the presence of a chiral tertiary amine as catalyst to form a cycloaddition compound having formula (II).
Description
A process for preparing a cycloaddition compound.
The invention relates to a process for preparing a cycloaddition compound.
According to the invention ketene is reacted for that purpose with a carbonyl group-containing compound having formula 1 of the sheet of formulae which contains a highly electron-attractant group in the α-position relative to the carbonyl group in the presence of a chiral tertiary amine as catalyst to form a cycloaddition compound having formula 2 of the sheet of formulae.
Surprisingly,ithas been found that in the reaction of ketene with the compound having formula 1 of the sheet of formulae the use of a chiral tertiary amine is highly enantioselective with respect to the reaction product formedeevalues as high as 90-95% and more being obtainable.
Examples of compounds having formula 1 containing a carbonyl group and a highly electron-attractant group in the α-position relative to the carbonyl group are chloral and in particular 1,1,1,-tricholoropropanone-2. By means of the reaction product formed by using this lastmentioned compound cholecalciferol compoundsmay be readily and stereo-selectively prepared, such as both 25 (S) . and 25(R)-1α, 25, 26-trihydrojcycholecalciferol and both 25 (S) and 25(R)-dihydroxycholecalciferol which cholecalciferol compounds play their part in the human body, e.g. the 25 (S), 26-dihydroxycholecalciferol which is an important vitamin D3 metabolite.
Examples of the catalyst employed according to the process according to the invention are the chiral tertiary amines listed in Table A contained hereinafter. A comparison of the correlated values given in columns II, III and IV of Table A shows in what sense and degree the enantioselectivity is effected by the selection of the catalyst on the basis of the reaction of ketene with chloral as the compound having formula 1.
Table A; Relationship between absolute configuration of the β-lactone formed and configuration of catalysta
Explanation of the table: a Standard conditions: 4 mol % katalyst in toluene at -50ºC. b Configuration of carbon atom adjacent to nitrogen atom (C8 for nos. 1-8; C2 for nos. 9 and 10). c Change in nomenclature because of change in substitution. d Reaction performed in CHCl3 because of solubility problems of catalyst e Chemical yields are lower in these cases (≈60%) because of intramolecular hydrogen bonding (epiquinine) and steric blocking of nitrogen by chlorine (epichlorocinchonidine) which causes reduced availability of nitrogen for catalysis.
The invention also relates to a cycloaddition compound having formula 2 of the sheet of formulae, in particular having formula 3 of the sheet of formulae, in which R represents H or CH3.Especially preferred are the cycloaddition compounds having formula 2 or formula 3 in the form of the R- or S-enantiomer thereof. Such cycloaddition compounds having formula 2 or formula 3 are novel and very advantageous as a starting material for the asymetric synthesis of chiral. compounds, e.g., of a hydroxyalkanedicarboxylic acid such as malic acid. Moreover, these cycloaddition compounds are suitable as starting compounds for the preparation of novel acetonide compounds.
The invention therefore also relates to a process for preparinganacetonide which is characterized in that a compound having formula 2 of the sheet of formulae is converted to an acetonide having formula 32 of the sheet of formulae, in a manner known per se, especially in that a compound having formula 3 , in which R is CH3, is converted to an acetonide having fofmula 33. Preferably, X in formulae 32 and 33, respectively of the sheet of formulae represents OTs, OH, Cl, Br or J, OTs being tosylate. It is further preferred to prepare the R- or S-enantiomer of the acetonide compound having formulae 32 or 33 by starting from the corresponding enantiomer of the compound having formula 2 or formula 3.
As for the preparation of a compound having formula 32, e.g., a compound having formula 33, in which X is Cl, Br or J, it is effective to start from a compound having formula 3, e.g., the R-enantiomer of the compound having formula 3, in which R is CH3, and subjecting the same to the following chemical operations (equation 14, sheet of formulae): a) Acid hydrolysis of the oxetanone having formula 23 to 3-hydroxy-3-(trichloromethyl)butanoic acid (formula 8); b) Basic hydrolysis of the compound having formula 8 to
2-methyl-2-hydroxy-succinic acid (formula 9) (isolation by treating with ion exchanger); c) Esterification of the compound having formula 9 to the diester (e.g., diethyl- or dimethylester) (formula 10); d) Reduction of the diester to 2-methyl-1,2,4-butanetriol having formula 11; e) Formation of the 1,2-acetonide of 2-methyl-1,2,4-butanetriol to the compound having formula 12;
f) Tosylation of this compound to 2-methyl-1,2,4-butane trial-1,2-acetonide-4-tosylate having formula 13; g) Substitution of the 4-tosyl group in the compound having formula 13 by a halogen (J, Br, Cl) gives a compound having formula 33 in which X is J, Br or Cl.
The compounds having formula 32, substituted in the 4-position, in particular the 4-substituted 2-methyl-1,2-butanediol-1,2-acetonides or the R- or S-enantiomer thereof also belong to the invention.
The Grignard compounds of the 4-halogen-2-methyl-1,2-butanediol-1, 2-acetonides are important intermediates for a novel method of preparing 1α, 25, 26-trihydroxycholecalciferols (formula 6) and 25, 26-dihydroxycholecalciferols (formula 5) . This preparation method, with the use of the Grignard compounds of the acetonides having formula 33, has significant advantagesoyer the method employed thus far for synthesis of these cholecalciferols. (J.J. Partridge, M.R. Oskokovic et al. J. Am.Chem. Soc.,1981, 103, 1253; J.J. Partridge, M.R. Uskokovic et al., Helv. Chem. Act. 64, 2138 (1981), disclosing an alkylation of the carbanion having formula 22 by the halogβi compound having formula 23 (sheet of formulae, equation 15). Moreover, the starting compound for the tosylate (formula 7) is accessible more readily than the starting compound for the carbanion having formula 22.
The key compound for the preparation of a compound having formula 33 is the 4-methyl-4-(trichloromethyl)-2-oxetanone having formula 3, in which R is CH3. Of this compound both the (S) and the (R) enantiomer (resp. formulae 4a and 4b, sheet of formulae) can be prepared in pure form by cycloaddition of 1,1,1-trichloropropanone-2 with ketene. Starting from either of the two enantiomer-pure oxetanones having formulae 4a and 4b, the two enantiomeric forms of compounds 8 through 11 (equation 14, sheet of formulae) as well as the compounds having formula 33 can be prepared, the Grignard compounds of which latter compounds can be used for the preparation of both 25 (S)- and 25(R)-1α, 25-26-trihydroxycholecalciferol (formula 6) as well as for the preparation of both 25 (S)- and 25 (R)-25,26-dihγdroxycholecalciferol (formula 9) .
The invention will be further elucidated by means of the examples given hereinbelow.
Example I a) Preparation of (S)-β-(trichloromethyl)-β-propiolactone (formula 16 of the sheet of formulae).
In a three-necked round-bottom flask (100 cm3 )equipped with a thermometer, a ketene inlet under the surface of the toluene, and a dropping funnel was dissolved 83 mg (0.25 mmol) of purified quinidine in 50 cm3 of toluene. The solution was cooled to -50°C. Then ketene was passed through the solution which was stirred by means of a magnetic stirrer, while 1.47 g (0.01 mol) of anhydrous chloral in 20 cm3 of toluene was added dropwise during 0.75-1 h. Excess of ketene was avoided in order to minimize formation of diketene. After the reaction was complete , the mixture was warmed to room temperature and transferred to a separatory funnel. The catalyst was removed by repeated (2x) washing with 4N HCl. The toluene layer was washed with saturated NaCl solution and dried over MgSO4. After removing MgSO4 by filtration, toluene was removed under reduced pressure. The residuewas purified by distillation: 120°C (0.5 mm Hg) , yield 1.67 g (89%); - 15.3°C (c1, cyclohexane)
corresponding to an ee of 98%; NMR 3.7(2 H, m) , 5.0 ppm (1H,t) . b) Preparation of optically pure (R)- and (S)-β-(trichloromethyl)-β-propiolactone (formula 16 of the sheet of formulae).
18g of the lactone having formula 16 (ee 95%) was dissolved in 41 cm3 of methylcyclohexane by warming. The solution was filtered and allowed to cool to rooin temperature. After filtration and washing with a little amount of methylcyclohexane, 15.5 g of (S)-lactone product could be recovered (85% yield), [α] - 15.6° (c1, cyclohexane),
mp 51-52°C. The specific rotation did not change after another crystallisation.
The same procedure starting with 19.7 g of lactone having formula 16 (72% ee) from 110 cm3 of methylcyclohexane yielded 12.8 g (R)-lactone (65% yield), [α] 15.4° (c1, cyclohexane), mp 51-52°C.
Again it turned out that the rotation did not change after another crystallisation. Racemic lactone having formula 16 had mp 36-37°C.
Example II.
By use of quinidine as catalyst in the reaction between ketene and 1,1,1-trichloropropanone-2 an enantiomer-pure compound having formula 4a could be prepared as follows. Under an atmosphere of dried nitrogen 389 mg (1.2 mmol) of quinidine was dissolved in 35 cm3 of toluene, in a three-necked flask of 100 cm3 , equipped with a thermometer and a ketene inlet. Then 10 g (63 mmol) of 1 , 1 , 1-thrichloropropanone-2 was added. The mixture was cooled to -25ºC. Ketene was passed for 5 hours with stirring (about 10 mmol/h). After 5 hours about 50% of 1,1, 1-trichloropropanone-2 was converted to the desired 2-oxetanone according to an NMR of the reaction mixture. The reaction was stopped byadding 25 cm3 of 4N HCl. In a separatory funnel the reaction mixture was then washed three times with 10 cm3 of 4 N HCl, further with 10 cm3 of saturated NaCL solution and dried over MgSO4. After filtration and evaporation of the solvent the residue was purified by bulb to bulb distillation (0.1 mmHg/120ºC). Chemical yield 5.6 g (45%); [α] + 6.0 (c=1.96% ethanol), corresponding to an ee of 95% S-enantiomer. By one recrystallisation frommethylcyclohexane the 2-oxetanone enantiomer could be obtained in pure form; [α] + 6.35 (c=1, 96% ethanol) (S-enantiomer) mp
39.5-40.5°C.
Starting from quinine, instead of quinidine, the (R) -enantiomer of the 2-oxetanone could be isolated in 86% ee; starting from cinchonidine, the (R)-enantiomer could be isolated in 86% ee; and starting from cinchonine, the (S) -enantiomer could be isolated in 92% ee.
Claims
1. A process for preparing a cycloaddition compound, characterized by reacting ketene with a carbonyl group-containing compound having formula 1 of the sheet of formulae which contains a highly electron- attractant group in the α-position relative to the carbonyl group, in the presence of a chiral tertiary amine as catalyst to form a cycloaddition compound having formula 2 of the sheet of formulae.
2. A process according to claim 1 , characterized by reacting ketene and 1,1, 1-trichloropropanone-2 in the presence of quinidine as the chiral catalyst.
3. A process according to claim 1 , characterized by reacting ketene with chloral in the presence of quinidine as the chiral catalyst.
4. A cycloaddition compound, characterized by formula 2 of the sheet of formulae.
5. A compound according to claim 4, characterized by formula 3 of the sheet of formulae, in which R is H or CH3.
6. A compound according to claim 4, characterized in that the compound is the R-or S-enantiomer having formula 2.
7. A compound according to claim 5, characterized in that the compound is the R- or S-enantiomer having formula 3.
8. A process for preparing an acetonide, characterized by converting a compound having formula 2 of the sheet of formulae to an acetonide having formula 32 of the sheet of formulae, in a manner known per se.
9. A process according to claim 8 , characterized by converting a compound having formula 3 , in which R is CH3, to an acetonide having having formula 33.
10. A process according to claims 8-9, characterized in that X is OTs, OH, Cl, Br or J and OTs is tosylate.
11. A process according to claims 8-10, characterized by preparing the R- or S-enantiomer of the acetonide compound having formula 32 or 33 by starting from the corresponding enantiomer of the compound having formula 2 or formula 3.
12. An acetonide compound, characterized, by formula 32 of the sheet of formulae.
13. A compound according to claim 12, characterized by formula 33, in which X is OTs,OH, Cl, Br of J and OTs is tosylate.
14. A compound according to claims 12-13, characterized in that the compound is the R- or S-enantiomer of the compound having formula 32 of formula 33.
15. A process for preparing a cholecalciferol compound, characterized by .performing on the tosylate of a compound having formula 7 substitution by a Grignard compound of a compound having formula 33 of the sheet of formulae, in which X is Cl, Br or J.
16. A process according to claim 15, characterized in that the 25 (R)- or 25 (S) -enantiomer of 25, 26-dihydroxycholecalciferol having formula 5 is prepared by starting from the corresponding enantiomer of the Grignard compound having formula 33.
17. A process according to claim 15,characterized in that the 25 (R) or 25 (S) -enantiomer of 1α, 25, 26-trihydroxycholecalciferol having formula 6 is prepared by starting from the corresponding enantiomer of the Grignard compound having formula 33.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP83503376A JPS60500133A (en) | 1982-10-21 | 1983-10-21 | Method for producing cycloaddition compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL8204070A NL8204070A (en) | 1982-10-21 | 1982-10-21 | METHOD FOR PREPARING A CYCLO ADDITION COMPOUND |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1984001577A1 true WO1984001577A1 (en) | 1984-04-26 |
Family
ID=19840446
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/NL1983/000040 WO1984001577A1 (en) | 1982-10-21 | 1983-10-21 | A process for preparing a cycloaddition compound |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0122279A1 (en) |
| JP (1) | JPS60500133A (en) |
| NL (1) | NL8204070A (en) |
| WO (1) | WO1984001577A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000061776A1 (en) * | 1999-04-14 | 2000-10-19 | Mercian Corporation | Vitamin d derivatives and process for producing the same |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2595973B1 (en) * | 2010-07-21 | 2017-07-12 | Lonza Ltd. | A process for the production of carnitine from beta-lactones |
| EP2409965A1 (en) * | 2010-07-21 | 2012-01-25 | Lonza Ltd. | A process for the production of carnitine by cycloaddition |
-
1982
- 1982-10-21 NL NL8204070A patent/NL8204070A/en not_active Application Discontinuation
-
1983
- 1983-10-21 JP JP83503376A patent/JPS60500133A/en active Pending
- 1983-10-21 EP EP83903420A patent/EP0122279A1/en not_active Withdrawn
- 1983-10-21 WO PCT/NL1983/000040 patent/WO1984001577A1/en not_active Application Discontinuation
Non-Patent Citations (4)
| Title |
|---|
| Chemische Berichte, Vol. 100, 1967 (Weinheim DE) D. BORRMANN et al.: "Optisch Aktive beta-Lactone", pages 1575-1579, see the complete article * |
| Journal of Organic Chemistry, Vol. 36, No. 12, 1971 (Columbus, Ohio, US) W.T. BRADY et al.: "Halogenated Ketenes. XXI", pages 1637-1640, see the complete article * |
| Journal of the American Chemical Society, Vol. 103, 1981 (Columbus, Ohio, US) J. PARTRIDGE et al.: "Synthesis and Structure Proof of a Vitamin D3 Metabolite, 25(S)26 Dihydroxycholecalciferol" pages 1253-1255, see the complete article cited in the application * |
| Journal of the American Chemical Society, Vol. 104, No. 1, January 1982 (Columbus, Ohio, US) H. WIJNBERG et al.: "Asymetric Synthesis of (S)- and (R)-Malic Acid from Ketene and Chloral", pages 166- 168, see the complete article * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000061776A1 (en) * | 1999-04-14 | 2000-10-19 | Mercian Corporation | Vitamin d derivatives and process for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0122279A1 (en) | 1984-10-24 |
| JPS60500133A (en) | 1985-01-31 |
| NL8204070A (en) | 1984-05-16 |
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