CA1104145A - Process for the manufacture of butenolide derivatives - Google Patents
Process for the manufacture of butenolide derivativesInfo
- Publication number
- CA1104145A CA1104145A CA286,399A CA286399A CA1104145A CA 1104145 A CA1104145 A CA 1104145A CA 286399 A CA286399 A CA 286399A CA 1104145 A CA1104145 A CA 1104145A
- Authority
- CA
- Canada
- Prior art keywords
- formula
- compound
- single bond
- prepared
- methyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
- C07D307/58—One oxygen atom, e.g. butenolide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
- C07D307/60—Two oxygen atoms, e.g. succinic anhydride
Abstract
ABSTRACT OF THE DISCLOSURE An improved chemical process for the manufacture of a compound of the formula IV: IV by reacting an alkali metal salt of the formula V: V with 5-chloro-but-2-enolide or 5-chloro-3-methylbut-2-enolide.
Description
This inventicn relates to an improved chemical process and more particularly it rel.ates to an improved process for the manufacture of certain butenolide derivatives which are useful per se, or as the active ingredient in herbicidal compositions, for the control of the parasitic weeds Striga hermonthica, Striga asiatica (lutea), Orobanche crenata, Orobanche ramosa an~ Orobanche aegyptiaca.
_ It is known that compounds of the formula I or II:
r~
x CH - ol~ ~ ~X~CH-O~ ~
I II
wherein R is hydrog_n or an alkyl radical of one to five carbon atoms, X rep~esents a single bond or a -CH2- linkage and Y represents two hy~rogen atoms, an additional bond or an epoxy group, may be prepared by reacting an alkali metal salt of the formula IA or IIA:
~X ~ H-O '~1 ~ X ~ _H-O M
IA IIA
wherein X and Y have the meaning.stated above, and M~ is the ion of an alkali metal, with a methanesulphonate derivative of the formula III:
C~3.S02.0 ~ ~ O ~ 0 III
wherein R has the meaning state~d above.
The said process suffers from the disadvantage -that the methanesulphonate derivative used as a reactant tends to be rela-tively unstable and is prone to polymerize to a certain extent on keeping.
It has now been found, and herein lies the basis for the present invention, that if the said methanesulphonate derivative is replaced by the corresponding chloro derivative, the said dlsadvantage is reduced or obviated.
.lO According to the invention there is thus provided an improved process for the manufacture of a compound of the formula V: R
A lX~CH ~ ~-I
B
IV
wherein R is hydrogen or an alkyl radical of one to five carbon atoms, X represents a single bond or a -CH2- linkage and A and B each stands for a hydrogen atom or they may be joined, together with the two adjacent carbon atoms, to form the ring structure /
/ .
Y ~
wherein Y represents two hydrogen atoms, an additional bond or an epoxy group, which comprises reac-ting a compound of the formula V:
A ~ X \ ~ CH-B ~ o ~ O
wherein A, B and X have t.he meaning stated above and M~ is -the ion of an alkali metal, with a chloro derivative of the formula VI:
_~_ /
Cl ~ O / ~
VI
wherein R has the meaning stated above.
The reactant of the formula V may be a compound wherein the alkyl radical R is methyl, ethyl, n-propyl or isopropyl and of ~hese, methyl is preferred. The representation X is preferably a single bond and the representation Y i.s preferably an additional bond. As a suitable compound of the said formula there may be mentioned for example the sodium salt of 3-hydroxy-methylene-1,4-butyrolactone (:Eormula V wherein X is a sing].e bond, A and B are hydrogen and M is sodium); the sodium salt of 4-hydroxymethylene-1,5-val.erolactone (formula V wherein X is a -CH2- linkage, A and B are hydrogen and M is sodium); and the sodium salt of the y-lactone of 4-hydroxycyclopentenyl-5-(~-formylacetic acid) as represented by formula V wherein X is a single bond, Y is an additional bond and M is sodium.
As a suitable compound of the formula VI there may be mentioned for example 5-chloro-but-2-enolide and 5-chloro-3-methylbut-2-enolide.
The reaction may conveniently be carried out in the presence of an organic solvent or diluent, such as anhydrous glyme or tetrahydrofuran, and at ambient temperature of from about 15C to about 25C.
Particularly useful compounds which can be prepared according to the process of the present invention are the compounds ~4~
of formula IV where n R is methyl, A and B are hydrogen and X
is a single bond or a -CH2- linkage and the compound of the formula IV wherein P~ is methyl, X is a single bond and Y is an additional bond.
~ he invention is illustrated, bu-t not limited, by the following examples describing the preparation of compounds according to the process of the invention.
Example 1 -Preparation of the Chlorobutenolide (VI; R=CH3) A solution ol the lactol (16.0g) of the formula:
HO O
in glyme (50 ml), is added dropwise to a stirred mixture of thionyl chloride (30.0g) and anhydrous sodium carbonate (7.44g) over a period of 3 hours. The mixture is maintained at about 40 during this period and is heated to 80 for 1 hour. It is then cooled, filtered and the solvent removed in vacuo to give the chlorobutenolide (IV; R-CH3) which may be purified by distil]ation at 60/2 r~m~ Found: C,45.42; H,3.79; C5H5ClO2 requires C,45.28; H,3.77.
Preparation of_the Dilactone (IV; R=CH ; X=single bond; Y=
additional bond) 3 A mixture of the sodium salt of the ~-lac-tone of 4-hydroxy-cyclopentenyl-5~ ~ormylacetic acid) (V; M=Na; X=single bond;
Y-addit~onal bond) (0.87g) and the chlorobu-tenolide (0.67g) in anhydrous glyme (10 ml) is s-tirred at room temperature for 24 hours.
The mixture is then poured into ice-water (50 ml) and extracted with chloroform (3 x 50 ml). The combined extracts were washed with saturated salt solution, dried over sodium sulpha-te and evaporated to dryness to give a semi-crystalline residue (1.13y).
Recrystallization from methylene chloride-ether mixture gave the desired dilactone ~0.98g; 80%),m.p. 128-130C. and having the formula: CH3 ~ CH- O
Example 2 By replacing the sodium salt in Example 1 ~ith an equivalent amount of the sodium salt of 3~hydroxymethylene-1,4-butyrolactone and following a similar procedure as in Example 1, there is thus obtained the compound of the formula IV (R--CH3; A
and B = H; X=single bond), m.p. 92-94C. and having the formula:
CH- O
0~0 Example 3 _ _ By replacing the sodium salt in Example 1 with an equivalent amount of the sodium salt of 4-hydroxymethylene-1,5-valerolactone and following a similar procedure as in Example 1, there is thus obtained the compound of formula IV (R=CH3; A and B=H; X=-CH2-), m.p. 105-107C. and having the formula:
CH- O ~ oCH3 f~
~ o/bO
Example 4 By replacing the sodium salt in Example 1 with an equivalent amount of the sodium salt of the ~-lactone of 2-hydroxycyclopentane-formylacetic acid and following a similar procedure as in Example 1, there is thus obtained the compound of formula IV (R=CH3; X=single bond; Y-2H) having the formula:
CH
~r 3 c~-o ~o /bo ~o~ o Example 5 By replacing the sodium salt in Example 1 with an equivalent amount of the sodium salt of the ~-lactone of 2-hydroxy-4,5-epoxycyclopentane-formylacetic acid and following a similar procedure as in Example 1, there is thus obtained the compound of formula IV (R=CH3; X=single bond; Y=O) having the formula:
r-f ~ CH - o ~ ~
~0 0 Example 6 By replaci.ng the sodium salt in Example 1 with an equivalent amount of the sodium salt of the ~-lactone of 2-hydroxy-cyclopentane-formylacetic acid and the 3-methyl-chlorobutenolide by an equivalent amount of chlorobutenolide and following the similar procedure as in Example 1, there is thus obtained the compound of the formula IV (R=H; X=single bond; Y=2H) having the formula:
r-s r¦~CH - O J~ o,~
O O
Example 7 By replacing the sodium salt in Example 1 with an equivalent amount of the sodium salt of 3-hydroxymethylene-1,4-butyrolactone and the 3-methyl-chlorobutenolide by an equivalent amount of chlorobutenolide and following a similar procedure as in Example 1, there is thus obtained the compound of -the formula IV (R=H; A and B=H; X=single bond) having the formula:
~ CH -o
_ It is known that compounds of the formula I or II:
r~
x CH - ol~ ~ ~X~CH-O~ ~
I II
wherein R is hydrog_n or an alkyl radical of one to five carbon atoms, X rep~esents a single bond or a -CH2- linkage and Y represents two hy~rogen atoms, an additional bond or an epoxy group, may be prepared by reacting an alkali metal salt of the formula IA or IIA:
~X ~ H-O '~1 ~ X ~ _H-O M
IA IIA
wherein X and Y have the meaning.stated above, and M~ is the ion of an alkali metal, with a methanesulphonate derivative of the formula III:
C~3.S02.0 ~ ~ O ~ 0 III
wherein R has the meaning state~d above.
The said process suffers from the disadvantage -that the methanesulphonate derivative used as a reactant tends to be rela-tively unstable and is prone to polymerize to a certain extent on keeping.
It has now been found, and herein lies the basis for the present invention, that if the said methanesulphonate derivative is replaced by the corresponding chloro derivative, the said dlsadvantage is reduced or obviated.
.lO According to the invention there is thus provided an improved process for the manufacture of a compound of the formula V: R
A lX~CH ~ ~-I
B
IV
wherein R is hydrogen or an alkyl radical of one to five carbon atoms, X represents a single bond or a -CH2- linkage and A and B each stands for a hydrogen atom or they may be joined, together with the two adjacent carbon atoms, to form the ring structure /
/ .
Y ~
wherein Y represents two hydrogen atoms, an additional bond or an epoxy group, which comprises reac-ting a compound of the formula V:
A ~ X \ ~ CH-B ~ o ~ O
wherein A, B and X have t.he meaning stated above and M~ is -the ion of an alkali metal, with a chloro derivative of the formula VI:
_~_ /
Cl ~ O / ~
VI
wherein R has the meaning stated above.
The reactant of the formula V may be a compound wherein the alkyl radical R is methyl, ethyl, n-propyl or isopropyl and of ~hese, methyl is preferred. The representation X is preferably a single bond and the representation Y i.s preferably an additional bond. As a suitable compound of the said formula there may be mentioned for example the sodium salt of 3-hydroxy-methylene-1,4-butyrolactone (:Eormula V wherein X is a sing].e bond, A and B are hydrogen and M is sodium); the sodium salt of 4-hydroxymethylene-1,5-val.erolactone (formula V wherein X is a -CH2- linkage, A and B are hydrogen and M is sodium); and the sodium salt of the y-lactone of 4-hydroxycyclopentenyl-5-(~-formylacetic acid) as represented by formula V wherein X is a single bond, Y is an additional bond and M is sodium.
As a suitable compound of the formula VI there may be mentioned for example 5-chloro-but-2-enolide and 5-chloro-3-methylbut-2-enolide.
The reaction may conveniently be carried out in the presence of an organic solvent or diluent, such as anhydrous glyme or tetrahydrofuran, and at ambient temperature of from about 15C to about 25C.
Particularly useful compounds which can be prepared according to the process of the present invention are the compounds ~4~
of formula IV where n R is methyl, A and B are hydrogen and X
is a single bond or a -CH2- linkage and the compound of the formula IV wherein P~ is methyl, X is a single bond and Y is an additional bond.
~ he invention is illustrated, bu-t not limited, by the following examples describing the preparation of compounds according to the process of the invention.
Example 1 -Preparation of the Chlorobutenolide (VI; R=CH3) A solution ol the lactol (16.0g) of the formula:
HO O
in glyme (50 ml), is added dropwise to a stirred mixture of thionyl chloride (30.0g) and anhydrous sodium carbonate (7.44g) over a period of 3 hours. The mixture is maintained at about 40 during this period and is heated to 80 for 1 hour. It is then cooled, filtered and the solvent removed in vacuo to give the chlorobutenolide (IV; R-CH3) which may be purified by distil]ation at 60/2 r~m~ Found: C,45.42; H,3.79; C5H5ClO2 requires C,45.28; H,3.77.
Preparation of_the Dilactone (IV; R=CH ; X=single bond; Y=
additional bond) 3 A mixture of the sodium salt of the ~-lac-tone of 4-hydroxy-cyclopentenyl-5~ ~ormylacetic acid) (V; M=Na; X=single bond;
Y-addit~onal bond) (0.87g) and the chlorobu-tenolide (0.67g) in anhydrous glyme (10 ml) is s-tirred at room temperature for 24 hours.
The mixture is then poured into ice-water (50 ml) and extracted with chloroform (3 x 50 ml). The combined extracts were washed with saturated salt solution, dried over sodium sulpha-te and evaporated to dryness to give a semi-crystalline residue (1.13y).
Recrystallization from methylene chloride-ether mixture gave the desired dilactone ~0.98g; 80%),m.p. 128-130C. and having the formula: CH3 ~ CH- O
Example 2 By replacing the sodium salt in Example 1 ~ith an equivalent amount of the sodium salt of 3~hydroxymethylene-1,4-butyrolactone and following a similar procedure as in Example 1, there is thus obtained the compound of the formula IV (R--CH3; A
and B = H; X=single bond), m.p. 92-94C. and having the formula:
CH- O
0~0 Example 3 _ _ By replacing the sodium salt in Example 1 with an equivalent amount of the sodium salt of 4-hydroxymethylene-1,5-valerolactone and following a similar procedure as in Example 1, there is thus obtained the compound of formula IV (R=CH3; A and B=H; X=-CH2-), m.p. 105-107C. and having the formula:
CH- O ~ oCH3 f~
~ o/bO
Example 4 By replacing the sodium salt in Example 1 with an equivalent amount of the sodium salt of the ~-lactone of 2-hydroxycyclopentane-formylacetic acid and following a similar procedure as in Example 1, there is thus obtained the compound of formula IV (R=CH3; X=single bond; Y-2H) having the formula:
CH
~r 3 c~-o ~o /bo ~o~ o Example 5 By replacing the sodium salt in Example 1 with an equivalent amount of the sodium salt of the ~-lactone of 2-hydroxy-4,5-epoxycyclopentane-formylacetic acid and following a similar procedure as in Example 1, there is thus obtained the compound of formula IV (R=CH3; X=single bond; Y=O) having the formula:
r-f ~ CH - o ~ ~
~0 0 Example 6 By replaci.ng the sodium salt in Example 1 with an equivalent amount of the sodium salt of the ~-lactone of 2-hydroxy-cyclopentane-formylacetic acid and the 3-methyl-chlorobutenolide by an equivalent amount of chlorobutenolide and following the similar procedure as in Example 1, there is thus obtained the compound of the formula IV (R=H; X=single bond; Y=2H) having the formula:
r-s r¦~CH - O J~ o,~
O O
Example 7 By replacing the sodium salt in Example 1 with an equivalent amount of the sodium salt of 3-hydroxymethylene-1,4-butyrolactone and the 3-methyl-chlorobutenolide by an equivalent amount of chlorobutenolide and following a similar procedure as in Example 1, there is thus obtained the compound of -the formula IV (R=H; A and B=H; X=single bond) having the formula:
~ CH -o
Claims (21)
1. An improved process for the manufacture of a com-pound of the formula IV:
IV
wherein R is hydrogen or an alkyl radical of one to five carbon atoms, X represents a single bond or a -CH2- linkage and A and B each stands for a hydrogen atom or they may be joined, together with the two adjacent carbon atoms, to form the ring structure wherein Y represents two hydrogen atoms, an additional bond or an epoxy group, which comprises reacting a compound of the formula V:
V
wherein A, B and X have the meaning stated above and M? is the ion of an alkali metal, with a chloro derivative of the formula VI:
VI
wherein R has the meaning stated above.
IV
wherein R is hydrogen or an alkyl radical of one to five carbon atoms, X represents a single bond or a -CH2- linkage and A and B each stands for a hydrogen atom or they may be joined, together with the two adjacent carbon atoms, to form the ring structure wherein Y represents two hydrogen atoms, an additional bond or an epoxy group, which comprises reacting a compound of the formula V:
V
wherein A, B and X have the meaning stated above and M? is the ion of an alkali metal, with a chloro derivative of the formula VI:
VI
wherein R has the meaning stated above.
2. The process as claimed in claim 1 wherein the reac-tant of the formula VI is a compound wherein the alkyl radi-cal R is methyl, ethyl, n-propyl or isopropyl.
3. The process as claimed in claim 1 wherein the reac-tant of formula V is a compound wherein X is a single bond.
4. The process as claimed in claim 1, 2 or 3 wherein the reactant of the formula V is a compound wherein Y is an additional bond.
5. The process as claimed in claim 1 wherein R is methyl or ethyl, X is a single bond and A and B form the ring structure wherein Y is an additional bond.
6. The process as claimed in claim 1 wherein the re-actant of formula V is the sodium salt of 3-hydroxymethylene-1,4-butyrolactone; the sodium salt of 4-hydroxymethylene-1,5-valerolactone or the sodium salt of the .gamma.-lactone of 4-hydr-oxycyclopentenyl-5-(.alpha.-formylacetic acid).
7. The process as claimed in claim 6 wherein the re-actant of formula VI is 5-chloro-but-2-enolide or 5-chloro-3-methylbut-2-enolide.
8. The process as claimed in claim 1, 6 or 7 wherein the reaction is carried out in the presence of an organic solvent or diluent.
9. The process as claimed in claim 1, 6 or 7 wherein the reaction is carried out in the presence of anhydrous glyme or tetrahydrofuran.
10. The process as claimed in claim 1, 6 or 7 wherein the reaction is carried out at ambient temperature.
11. The process as claimed in claim 1, 6 or 7 wherein the reaction is carried out at a temperature from about 15°C.
to about 25°C.
to about 25°C.
12. The process as claimed in claim 1, 6 or 7 wherein the compound so obtained is a compound of the formula IV
wherein R is methyl, A and B are hydrogen and X is a single bond or a -CH2- linkage; or wherein R is methyl, A and B are joined, together with the two adjacent carbon atoms, to form the ring structure and X is a single bond.
wherein R is methyl, A and B are hydrogen and X is a single bond or a -CH2- linkage; or wherein R is methyl, A and B are joined, together with the two adjacent carbon atoms, to form the ring structure and X is a single bond.
13. The process as claimed in claim 1, 6 or 7 wherein A and B are joined, together with the two adjacent carbon atoms, to form the ring structure , X is a single bond and R is methyl.
14. The process as claimed in claim 1 wherein the sodium salt of the .gamma.-lactone of 4-hydroxycyclopentenyl-5-(.alpha.-formylacetic acid) is reacted with 5-chloro-3-methylbut-2-enolide in anhydrous glyme at ambient temperature and there is obtained the compound of formula IV wherein R is methyl; A and B are joined, together with the two adjacent carbon atoms, to form the ring structure and X
is a single bond.
is a single bond.
15. The process as claimed in claim 1, 6 or 7 wherein the compound thus prepared has the formula:
16. The process as claimed in claim 1, 6 or 7 wherein the compound thus prepared has the formula:
17. The process as claimed in claim 1, 6 or 7 wherein the compound thus prepared has the formula:
18. The process as claimed in claim 1, 6 or 7 wherein the compound thus prepared has the formula:
19. The process as claimed in claim 1, 6 or 7 wherein the compound thus prepared has the formula:
20. The process as claimed in claim 1, 6 or 7 wherein the compound thus prepared has the formula:
21. The process as claimed in claim 1, 6 or 7 wherein the compound thus prepared has the formula:
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB3776076 | 1976-09-13 | ||
| GB37760/76 | 1976-09-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1104145A true CA1104145A (en) | 1981-06-30 |
Family
ID=10398816
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA286,399A Expired CA1104145A (en) | 1976-09-13 | 1977-09-09 | Process for the manufacture of butenolide derivatives |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS5334769A (en) |
| BE (1) | BE858646A (en) |
| CA (1) | CA1104145A (en) |
| CH (1) | CH628631A5 (en) |
| DE (1) | DE2740801A1 (en) |
| DK (1) | DK406777A (en) |
| FR (1) | FR2364212A1 (en) |
| NL (1) | NL7709873A (en) |
| SE (1) | SE7710205L (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1470097A (en) * | 1974-04-18 | 1977-04-14 | Int Dev Res Centre | Alpha-butyrolactone derivatives as germination factors |
-
1977
- 1977-09-08 NL NL7709873A patent/NL7709873A/en not_active Application Discontinuation
- 1977-09-09 FR FR7727398A patent/FR2364212A1/en not_active Withdrawn
- 1977-09-09 DE DE19772740801 patent/DE2740801A1/en not_active Withdrawn
- 1977-09-09 CA CA286,399A patent/CA1104145A/en not_active Expired
- 1977-09-12 SE SE7710205A patent/SE7710205L/en unknown
- 1977-09-13 JP JP10955677A patent/JPS5334769A/en active Pending
- 1977-09-13 DK DK406777A patent/DK406777A/en not_active Application Discontinuation
- 1977-09-13 CH CH1115677A patent/CH628631A5/en not_active IP Right Cessation
- 1977-09-13 BE BE180863A patent/BE858646A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5334769A (en) | 1978-03-31 |
| NL7709873A (en) | 1978-03-15 |
| DE2740801A1 (en) | 1978-03-16 |
| BE858646A (en) | 1978-03-13 |
| CH628631A5 (en) | 1982-03-15 |
| FR2364212A1 (en) | 1978-04-07 |
| DK406777A (en) | 1978-03-14 |
| SE7710205L (en) | 1978-03-14 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry | ||
| MKEX | Expiry |
Effective date: 19980630 |