CA1155145A - Process of manufacturing sulfoxides - Google Patents
Process of manufacturing sulfoxidesInfo
- Publication number
- CA1155145A CA1155145A CA000196148A CA196148A CA1155145A CA 1155145 A CA1155145 A CA 1155145A CA 000196148 A CA000196148 A CA 000196148A CA 196148 A CA196148 A CA 196148A CA 1155145 A CA1155145 A CA 1155145A
- Authority
- CA
- Canada
- Prior art keywords
- carbon atoms
- alkyl
- phenyl
- benzyl
- alkoxy
- 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
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/20—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carbonic acid, or sulfur or nitrogen analogues thereof
- C07D295/21—Radicals derived from sulfur analogues of carbonic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/20—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carbonic acid, or sulfur or nitrogen analogues thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Hydrogenated Pyridines (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
IN THE UNITED STATES PATENT OFFICE
process of manufacturing sulfoxides Abstract of the Disclosure This invention relates to a process for manu-facturing sulfoxide compounds using thiocarbmate compounds as intermediates. More specifically, this invention relates to a process for manufacturing sulfoxide compounds by the reaction of a thio-carbamate and performic acid at reduced temperatures The performic acid is formed in situ by reacting hydrogen peroxide with formic acid. The end product is useful as herbicides,
process of manufacturing sulfoxides Abstract of the Disclosure This invention relates to a process for manu-facturing sulfoxide compounds using thiocarbmate compounds as intermediates. More specifically, this invention relates to a process for manufacturing sulfoxide compounds by the reaction of a thio-carbamate and performic acid at reduced temperatures The performic acid is formed in situ by reacting hydrogen peroxide with formic acid. The end product is useful as herbicides,
Description
llS514S
Detailed Description of the Invention In the practice of the present invention, sulfoxide com-pounds are manufactured having the following generic formula:
R-l-R-N ~ 1 R~
wherein R can be selected from lower alkyl having 1-6 carbon atoms, phenyl, benzyl, substituted phenyl, substituted benzyl wherein the S substituents can be selected from lower alkyl having 1-4 carbon atoms, thioalkyl, alkoxy, halogen, haloalkyl, nitro and cyano; Rl and R2 can be the same or different and can be selected from lower alkyl, cycloalkyl, the alkyl radicals having 1-10 carbon atoms, phenyl, benzyl, substituted phenyl and benzyl wherein said sub-stituents can be selected from lower alkyl having 1-4 carbon atoms, thioalkyl, alkoxy, halogen, haloalkyl, nitro and cyano;
Rl and ~ taken together can form an alkyl ring structure having
Detailed Description of the Invention In the practice of the present invention, sulfoxide com-pounds are manufactured having the following generic formula:
R-l-R-N ~ 1 R~
wherein R can be selected from lower alkyl having 1-6 carbon atoms, phenyl, benzyl, substituted phenyl, substituted benzyl wherein the S substituents can be selected from lower alkyl having 1-4 carbon atoms, thioalkyl, alkoxy, halogen, haloalkyl, nitro and cyano; Rl and R2 can be the same or different and can be selected from lower alkyl, cycloalkyl, the alkyl radicals having 1-10 carbon atoms, phenyl, benzyl, substituted phenyl and benzyl wherein said sub-stituents can be selected from lower alkyl having 1-4 carbon atoms, thioalkyl, alkoxy, halogen, haloalkyl, nitro and cyano;
Rl and ~ taken together can form an alkyl ring structure having
2-10 carbon atoms, the alkyl ring structure can be optionally sub-stituted with alkyl or haloalkyl having 1-4 carbon atoms or halo-gen, a heterocyclic ring that can optionally be substituted with lower alkyl radicals.
The compounds are manufactured by reacting a conventional thiocarbamate compound with performic acid. The thiocarbamate compound has the following formula:
R_S_R_N~
wherein R, Rl and R2 have been defined above.
It is preferred to form the performic acid in situ by reacting hydrogen peroxide with formic acid. Thus, the thio-carbamate is dissolved in sufficient fonmic acid so that after the - 2 - ~
`- llS5145 addition of the peroxide only one phase exists. Then, hydrogen peroxide is added slowly. Performic acid is formed and immediately reacts with the thiocarbamate to form the end pro-duct.
The reaction scheme is as follows:
(1) H22 + H-C-OH >H-C-O-OH + H20 + /~
(2) H-C-O-OH + R-S-~C-N ~ Rl~ R-~-C-N 1 + H-9C-oH
Since the reaction is exothermic, it is necessary to remove heat so that the temperature is maintained at between 0C.
and 60C., preferably between 15C. and 40C. In the event that the temperature exceeds 60C., undesirable by-products, such as the sulfone derivative, are formed. If desired, an ion exchange resin can be used as a catalyst.
In order to illustrate the merits of the present inven-tion, the following examples are provided:
Example 1 C2H5~ N~'n 3 7 ~n-C3H7 A mixture was formed in a reaction vessel containing 50 ml. of formic acid, 34 ml. of S-ethyl,N-di-n-propylthiocar-bamate and 2 gr. of treated amberlite ion exchange resin catalyst.
This solution was cooled to 15C. Then, 38-1/2 mls. of 17~rto hydrogen peroxide were added. The temperature was allowed to go to 55C. The reaction mass was stripped to yield 40 g. of pro-duct of 94% purity.
llS514S
Example 2 ~ ~ -C3H7 n-C3H7-S-C-N~
A solution was formed containing 203 g. (215 ml.) of S-n-propyl-N,N-di-n-propylthiocarbamate and 175 ml. of formic acid. The reaction mass was cooled to 15C. and then 105 ml. of a 35% solution of hydrogen peroxide was added over a period of 10 minutes. Then, the reaction mass was allowed to warm to 25C.
and held there for one hour. Thereafter, the reaction mass was cooled to 15C., then neutralized with sodium hydroxide. The reaction mass was transferred to a separation funnel, extracted with methylene chloride and stripped to provide 197 g. of pro-duct.
Example 3 C H Y ~ ~
A solution was formed containing 175 ml. of formic acid and 192 g. (technical grade) of S-ethyl hexahydro~lH-azepine-l-carbothioate. Thereafter, 100 ml. of a 35% solution of hydrogen peroxide was added over a period of ten minutes. The temperature r~se to 45C. and held there for the rest of the run (2 hours) and then was stripped under vacuum. The remaining solution was dis-solved in 100 ml. of methylene chloride and then neutralized with 33% sodium hydroxide. The methylene chloride was stripped to yield 188 g. of product assaying 937O.
` ` 115S14S
ExsmPle 4 8 jCN2-C(CH3)2H
~ Cn2-C(CH3)2H
A solution was formed containing 217 g. of g-ethyl-N,N-di~sobutylthiocarbamate in 175 ml. of formic acid. Thereafter, 103 ml. of a 35% solution of hydrogen peroxide was added. The temperature was allowed to raise to 45C. and held there for 3 hours. m e end product was worked up in the same manner as set forth in Example 3 except that the product was dissolved in benzene before neutralization instead of methylene chloride.
~-~ After seripping the product weighed 219 grams and assayed at 92.370.
~- Example 5 n-C3H7-~-8-N ~ 2)3 3 A solution was formed containing 125 ml. of formic acid ~`;10 and 101-1/2 g. of S-propyl-N-n-butyl-N-ethylthiocarbamate and was cooled to i5C. Thereafter, 80 ml. of 21% solution of hydrogen peroxide was added over a period of 30 minutes. The reaction product was worked up in a manner as set forth in Example 4 to yield 105 g. of product.
ExamPle 6 ~ CH2-~-C-N~i 3 7 A solution was fonmed containing 15 ml. of formic acid and 25.1 g. of S-benzyl-N,N-diisopropylthiocarbamate. This solu-tion was cooled to 20C. Thereafter, 10 ml. of 35% solution of , 1155~45 hydrogen peroxide were added over a period of 30 minutes. The reaction mass was worked up in a similar manner as set forth in Example 5 to yield 19.8 g. of product.
Other compounds can be prepared using the appropriate starting materials and following the above-defined procedure.
Exemplary compounds are listed below.
Example 7 ~R ~C N ~ n C3H7 ~n-C3H7 Ex~mple 8 cl~R C N,,n C3H7 ~n-C3H7 Example 9 Cil3~3~01 1l n-C3H7 Example 10 CH3-S ~ ~ ~ ~n C3H7 Example 11 CH3-0~ S C N~
n C3H7 l~S51~S
.
Example 12 CH2Cl~R ~3 n C3H7 Example 13 NrC~ ~n-C3N7 Example 14 ~: CN- ~ R C N ~ n C3H7 n~C3H7 Example 15 Cl- ~ CH2-S-C-N ~ 2 5 ~; Example 16 CH r CH -R-g-N ~ n C3H7 ~ ~ .
ExamPle 17 CH ~ H2-S-C-N ~ 2 5 Example 18 ~ CH2-R-RC-~
~155145 Example 19 CH2-~-C-N~
Example 20 C2H5-~-C-N~
Example 21 C2H5~ e-N~
CCl3 Example 22 C2H5-~-C-N ~
.
Example 23 CH
C H ~ 9 ~
Example_24 C H R ~ ~
-` 1155145 Example 25 C2HS~ -N ~ 2 5 - E~ample 26 C2H5-~-C-N
Example 27 C2H5-~-C-N~ 2~Cl Example 28 C2H5-~-C-N~ 2~CH3 Example 29 C2H5-~-C_N--02N5 Example 30 C2H5~ 3-N~C2H5 \ ~ 3 Cl _ g _ -l~SS145 Example 31 C2us ~! c-N~}
Example 32 C2H5 -~-R-N ~C2H5 \~CH2Cl
The compounds are manufactured by reacting a conventional thiocarbamate compound with performic acid. The thiocarbamate compound has the following formula:
R_S_R_N~
wherein R, Rl and R2 have been defined above.
It is preferred to form the performic acid in situ by reacting hydrogen peroxide with formic acid. Thus, the thio-carbamate is dissolved in sufficient fonmic acid so that after the - 2 - ~
`- llS5145 addition of the peroxide only one phase exists. Then, hydrogen peroxide is added slowly. Performic acid is formed and immediately reacts with the thiocarbamate to form the end pro-duct.
The reaction scheme is as follows:
(1) H22 + H-C-OH >H-C-O-OH + H20 + /~
(2) H-C-O-OH + R-S-~C-N ~ Rl~ R-~-C-N 1 + H-9C-oH
Since the reaction is exothermic, it is necessary to remove heat so that the temperature is maintained at between 0C.
and 60C., preferably between 15C. and 40C. In the event that the temperature exceeds 60C., undesirable by-products, such as the sulfone derivative, are formed. If desired, an ion exchange resin can be used as a catalyst.
In order to illustrate the merits of the present inven-tion, the following examples are provided:
Example 1 C2H5~ N~'n 3 7 ~n-C3H7 A mixture was formed in a reaction vessel containing 50 ml. of formic acid, 34 ml. of S-ethyl,N-di-n-propylthiocar-bamate and 2 gr. of treated amberlite ion exchange resin catalyst.
This solution was cooled to 15C. Then, 38-1/2 mls. of 17~rto hydrogen peroxide were added. The temperature was allowed to go to 55C. The reaction mass was stripped to yield 40 g. of pro-duct of 94% purity.
llS514S
Example 2 ~ ~ -C3H7 n-C3H7-S-C-N~
A solution was formed containing 203 g. (215 ml.) of S-n-propyl-N,N-di-n-propylthiocarbamate and 175 ml. of formic acid. The reaction mass was cooled to 15C. and then 105 ml. of a 35% solution of hydrogen peroxide was added over a period of 10 minutes. Then, the reaction mass was allowed to warm to 25C.
and held there for one hour. Thereafter, the reaction mass was cooled to 15C., then neutralized with sodium hydroxide. The reaction mass was transferred to a separation funnel, extracted with methylene chloride and stripped to provide 197 g. of pro-duct.
Example 3 C H Y ~ ~
A solution was formed containing 175 ml. of formic acid and 192 g. (technical grade) of S-ethyl hexahydro~lH-azepine-l-carbothioate. Thereafter, 100 ml. of a 35% solution of hydrogen peroxide was added over a period of ten minutes. The temperature r~se to 45C. and held there for the rest of the run (2 hours) and then was stripped under vacuum. The remaining solution was dis-solved in 100 ml. of methylene chloride and then neutralized with 33% sodium hydroxide. The methylene chloride was stripped to yield 188 g. of product assaying 937O.
` ` 115S14S
ExsmPle 4 8 jCN2-C(CH3)2H
~ Cn2-C(CH3)2H
A solution was formed containing 217 g. of g-ethyl-N,N-di~sobutylthiocarbamate in 175 ml. of formic acid. Thereafter, 103 ml. of a 35% solution of hydrogen peroxide was added. The temperature was allowed to raise to 45C. and held there for 3 hours. m e end product was worked up in the same manner as set forth in Example 3 except that the product was dissolved in benzene before neutralization instead of methylene chloride.
~-~ After seripping the product weighed 219 grams and assayed at 92.370.
~- Example 5 n-C3H7-~-8-N ~ 2)3 3 A solution was formed containing 125 ml. of formic acid ~`;10 and 101-1/2 g. of S-propyl-N-n-butyl-N-ethylthiocarbamate and was cooled to i5C. Thereafter, 80 ml. of 21% solution of hydrogen peroxide was added over a period of 30 minutes. The reaction product was worked up in a manner as set forth in Example 4 to yield 105 g. of product.
ExamPle 6 ~ CH2-~-C-N~i 3 7 A solution was fonmed containing 15 ml. of formic acid and 25.1 g. of S-benzyl-N,N-diisopropylthiocarbamate. This solu-tion was cooled to 20C. Thereafter, 10 ml. of 35% solution of , 1155~45 hydrogen peroxide were added over a period of 30 minutes. The reaction mass was worked up in a similar manner as set forth in Example 5 to yield 19.8 g. of product.
Other compounds can be prepared using the appropriate starting materials and following the above-defined procedure.
Exemplary compounds are listed below.
Example 7 ~R ~C N ~ n C3H7 ~n-C3H7 Ex~mple 8 cl~R C N,,n C3H7 ~n-C3H7 Example 9 Cil3~3~01 1l n-C3H7 Example 10 CH3-S ~ ~ ~ ~n C3H7 Example 11 CH3-0~ S C N~
n C3H7 l~S51~S
.
Example 12 CH2Cl~R ~3 n C3H7 Example 13 NrC~ ~n-C3N7 Example 14 ~: CN- ~ R C N ~ n C3H7 n~C3H7 Example 15 Cl- ~ CH2-S-C-N ~ 2 5 ~; Example 16 CH r CH -R-g-N ~ n C3H7 ~ ~ .
ExamPle 17 CH ~ H2-S-C-N ~ 2 5 Example 18 ~ CH2-R-RC-~
~155145 Example 19 CH2-~-C-N~
Example 20 C2H5-~-C-N~
Example 21 C2H5~ e-N~
CCl3 Example 22 C2H5-~-C-N ~
.
Example 23 CH
C H ~ 9 ~
Example_24 C H R ~ ~
-` 1155145 Example 25 C2HS~ -N ~ 2 5 - E~ample 26 C2H5-~-C-N
Example 27 C2H5-~-C-N~ 2~Cl Example 28 C2H5-~-C-N~ 2~CH3 Example 29 C2H5-~-C_N--02N5 Example 30 C2H5~ 3-N~C2H5 \ ~ 3 Cl _ g _ -l~SS145 Example 31 C2us ~! c-N~}
Example 32 C2H5 -~-R-N ~C2H5 \~CH2Cl
Claims (3)
1. A process for manufacturing a compound having the following generic formula:
wherein R can be selected from lower alkyl having 1-6 carbon atoms, phenyl, benzyl, substituted phenyl, substituted benzyl wherein the substituents can be selected from lower alkyl having 1-4 carbon atoms, thioalkyl having 1-4 carbon atoms, alkoxy having 1-4 carbon atoms, halogen, haloalkyl having 1-4 carbon atoms, nitro and cyano;.
Rl and R2 can be the same or different and can be selected from lower alkyl having 1-6 carbon atoms, cycloalkyl having 4-7 carbon atoms, phenyl, benzyl, substituted phenyl and benzyl wherein said substituents can be selected from lower-alkyl having 1-4 carbon atoms, thioalkyl having 1-4 carbon atoms, alkoxy having 1-4 carbon atoms, halogen, haloalkyl having 1-4 carbon atoms, nitro and cyano;
Rl and R2 taken together can form an alkyl ring structure having 4-7 carbon atoms, the alkyl ring structure can be optionally sub-stituted with alkyl having 1-4 carbon atoms or haloalkyl having 1-4 carbon atoms or halogen, with the proviso that when R is benzyl, Rl and R2 are not both-sec-C4Hg, comprising the steps of:
a) reacting a thiocarbamate compound having the following generic formula:
wherein R, Rl and R2 have been defined above, with;
(b) performic said:
(c) maintaining the temperature of the reaction between 0°C. and 60°C.
H
2. The process of Claim 1 wherein the performic acid is formed in situ and immediately reacts with the thiocarbamate defined in step (a).
3. The process of Claim 2 wherein formic acid is mixed with the thiocarbamate of step (a) and then reacted with hydrogen peroxide to form the performic acid.
4. The process of Claim 1 wherein the reaction is carried out in the presence of an ion exchange resin catalyst.
(5) Compounds of the class of carbamoyl sulphoxides having the general formula:
wherein R, R1, and R2 are selected from the following definitions:
1. R is selected from:
- phenyl which may be substituted with:
- alkyl containing 1 to 4 carbon atoms;
and - alkoxy containing 1 to 4 carbon atoms and wherein R1 and R2 can be the same or different and can be selected from:
- alkyl containing 1 to 4 carbon atoms; and - cycloalkyl containing 4 to 7 carbon atoms;
- phenyl which may be substituted with:
- alkyl containing 1 to 4 carbon atoms;
and - alkoxy containing 1 to 4 carbon atoms and wherein R1 and R2 can be the same or different and can be selected from:
- alkyl containing 1 to 4 carbon atoms; and - cycloalkyl containing 4 to 7 carbon atoms;
2. R is selected from:
- phenyl which may be substituted with:
- alkyl containing 1 to 4 carbon atoms;
- alkoxy containing 1 to 4 carbon atoms;
and - halogen and wherein R1 and R2, when taken together, re-present alkylene containing 4 to 7 carbon atoms; and
- phenyl which may be substituted with:
- alkyl containing 1 to 4 carbon atoms;
- alkoxy containing 1 to 4 carbon atoms;
and - halogen and wherein R1 and R2, when taken together, re-present alkylene containing 4 to 7 carbon atoms; and
3. R is alkoxybenzyl wherein the alkoxy group contains 1 to 4 carbon atoms and wherein R1 and R2 can be the same or different and can be selected from:
.
- alkyl containing 1 to 4 carbon atoms;
and - cycloalkyl containing 4 to 7 carbon atoms or wherein Rl and R2, when taken together, repre-sent alkylene containing 4 to 7 carbon atoms.
.
- alkyl containing 1 to 4 carbon atoms;
and - cycloalkyl containing 4 to 7 carbon atoms or wherein Rl and R2, when taken together, repre-sent alkylene containing 4 to 7 carbon atoms.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US34623573A | 1973-03-29 | 1973-03-29 | |
| US346,235 | 1973-03-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1155145A true CA1155145A (en) | 1983-10-11 |
Family
ID=23358524
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000196148A Expired CA1155145A (en) | 1973-03-29 | 1974-03-27 | Process of manufacturing sulfoxides |
Country Status (21)
| Country | Link |
|---|---|
| JP (1) | JPS49126621A (en) |
| AR (1) | AR214702A1 (en) |
| BE (1) | BE813085A (en) |
| BR (1) | BR7402289D0 (en) |
| CA (1) | CA1155145A (en) |
| CH (1) | CH593250A5 (en) |
| CS (1) | CS178166B2 (en) |
| DD (1) | DD111903A5 (en) |
| DE (1) | DE2413574A1 (en) |
| ES (1) | ES424720A1 (en) |
| FR (1) | FR2223363B1 (en) |
| GB (1) | GB1403875A (en) |
| HU (1) | HU169615B (en) |
| IL (1) | IL44513A (en) |
| IT (1) | IT1013084B (en) |
| NL (1) | NL7404241A (en) |
| PH (1) | PH10781A (en) |
| RO (1) | RO69723A (en) |
| SU (1) | SU576041A3 (en) |
| YU (1) | YU85374A (en) |
| ZA (1) | ZA741994B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AR219067A1 (en) * | 1976-03-29 | 1980-07-31 | Stauffer Chemical Co | NEW HERBICIDES COMPOUNDS DERIVED FROM S-METHYL SUBSTITUTED THIOCARBAMATE AND SULFOXIDES THEREOF |
| JPS58174356A (en) * | 1982-04-06 | 1983-10-13 | Nippon Tokushu Noyaku Seizo Kk | Industrial oxidation of thioethers or thiolcarboxylic acid derivative |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1164160A (en) * | 1966-12-30 | 1969-09-17 | Shell Int Research | N,N-Disubstituted Amino Acid Derivatives and their use as Herbicides |
-
1974
- 1974-03-08 PH PH15606A patent/PH10781A/en unknown
- 1974-03-13 AR AR252758A patent/AR214702A1/en active
- 1974-03-21 GB GB1256674A patent/GB1403875A/en not_active Expired
- 1974-03-21 DE DE2413574A patent/DE2413574A1/en not_active Withdrawn
- 1974-03-22 BR BR2289/74A patent/BR7402289D0/en unknown
- 1974-03-26 CH CH416774A patent/CH593250A5/xx not_active IP Right Cessation
- 1974-03-27 CA CA000196148A patent/CA1155145A/en not_active Expired
- 1974-03-27 JP JP49033583A patent/JPS49126621A/ja active Pending
- 1974-03-27 DD DD177486A patent/DD111903A5/xx unknown
- 1974-03-27 YU YU00853/74A patent/YU85374A/en unknown
- 1974-03-27 HU HUSA2617A patent/HU169615B/hu unknown
- 1974-03-28 FR FR7410947A patent/FR2223363B1/fr not_active Expired
- 1974-03-28 ZA ZA00741994A patent/ZA741994B/en unknown
- 1974-03-28 NL NL7404241A patent/NL7404241A/xx unknown
- 1974-03-28 SU SU7402008953A patent/SU576041A3/en active
- 1974-03-28 ES ES424720A patent/ES424720A1/en not_active Expired
- 1974-03-28 IL IL44513A patent/IL44513A/en unknown
- 1974-03-29 BE BE142672A patent/BE813085A/en unknown
- 1974-03-29 RO RO7478240A patent/RO69723A/en unknown
- 1974-03-29 CS CS2289A patent/CS178166B2/cs unknown
- 1974-03-29 IT IT49848/74A patent/IT1013084B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| JPS49126621A (en) | 1974-12-04 |
| PH10781A (en) | 1977-09-06 |
| BR7402289D0 (en) | 1974-11-19 |
| DD111903A5 (en) | 1975-03-12 |
| RO69723A (en) | 1981-06-30 |
| CH593250A5 (en) | 1977-11-30 |
| FR2223363B1 (en) | 1980-07-04 |
| DE2413574A1 (en) | 1974-10-17 |
| CS178166B2 (en) | 1977-08-31 |
| GB1403875A (en) | 1975-08-28 |
| ZA741994B (en) | 1975-03-26 |
| AU6722374A (en) | 1975-10-02 |
| ES424720A1 (en) | 1976-06-01 |
| AR214702A1 (en) | 1979-07-31 |
| IL44513A (en) | 1978-10-31 |
| YU85374A (en) | 1982-02-28 |
| IT1013084B (en) | 1977-03-30 |
| SU576041A3 (en) | 1977-10-05 |
| HU169615B (en) | 1976-12-28 |
| NL7404241A (en) | 1974-10-01 |
| FR2223363A1 (en) | 1974-10-25 |
| IL44513A0 (en) | 1974-06-30 |
| BE813085A (en) | 1974-09-30 |
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