CA1076131A - Method for the transesterification of thiocarbamic acid esters - Google Patents
Method for the transesterification of thiocarbamic acid estersInfo
- Publication number
- CA1076131A CA1076131A CA250,553A CA250553A CA1076131A CA 1076131 A CA1076131 A CA 1076131A CA 250553 A CA250553 A CA 250553A CA 1076131 A CA1076131 A CA 1076131A
- Authority
- CA
- Canada
- Prior art keywords
- grams
- millimols
- transesterification
- trap
- solvent
- 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
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
- C07C273/1809—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas with formation of the N-C(O)-N moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/26—Polythioesters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A method is disclosed for the transeste-rification of thiocarbamic acid esters, the single-step method consisting in reacting the esters in question with compounds of the formula R'(X'H)n wherein X' is O, S, or NH; R' is C2 to C10 alkyl or phenyl radical and n is 1 to 5. The reaction takes place in the presence of a catalyst, the most suitable being a ter-tiary amine and the temperature range is from 50°C to the solvent boiling point, an organic solvent being used as the reaction medium. Diazobicyclooctane is a preferred catalyst.
A method is disclosed for the transeste-rification of thiocarbamic acid esters, the single-step method consisting in reacting the esters in question with compounds of the formula R'(X'H)n wherein X' is O, S, or NH; R' is C2 to C10 alkyl or phenyl radical and n is 1 to 5. The reaction takes place in the presence of a catalyst, the most suitable being a ter-tiary amine and the temperature range is from 50°C to the solvent boiling point, an organic solvent being used as the reaction medium. Diazobicyclooctane is a preferred catalyst.
Description
.!~, 1~7613~
.'. '' ~ .
This invention relates to a method or the transesterification of esters of -thiocarbamic acids, -having the formula :
X - A - NH - C -- S - R
11 .' . , .
.: - .
wherein R is methyl radical and A is phenyl radical, whereas X is hydrogen or one or more Cl to C10 alkyl or -NH-CO-SR groups.
, ,: :.
he existence cf these esters is known, ~ i .
and they are obtained, in the main, both by reacting ~ -h ~ an isocyanate with a mercaptan, and by reacting an amine with a chlorothiocarbonate, or also according :~; : : , " ..
to the reaction which forms the subject-matter of a copending patent application by the same~applicant.
It has now been found that it is possible to subject these compounds to appropriate transeste-rlficatlon reactions so as to obtain valuable products, whioh are very important for applications in the industrial field.
As a matter of fact, the subject matter of the present invention is the reaction between said es-ters and compounds of the formula R' (X'H)n wherein X' is O, S, or NH; R' is C2 to C10 alkyl or phenyl radical and n is l to 5. The reaction in question is preferably carried out in organic solvents at temperatures ranging ,~
from 50C to the boiling point temperature of the solvent.
It is also possible to employ a not too strong nitrogen stream in order to remove from the reaction environment the evolved mercaptan. The reaction can be carried out in the presence o a catalytic system which A
.
"
:, ' '"1. "".,,'~' ' '' ' , ',', "' "',' '; ' .. , ,, ' .,f ,: ' , ' ~ ' . . ., ' :
' " r' ',/'' ""' ' ' ' ~ ' ' ' ' " , ', ' ~ ' .' ' .'' ~' '' ' ' I . ' , . I .
~ can be composed by a ter-tiary amine, more particularly , ~
the diazobicyclooc~ane (DABCO).
In order to afford a better understanding of the present invention, a few explanatory examples of the invention are set forth, which are by no wise limiting of same.
EXAMPLE
A flask egoipped with a condenser is charged with 1.68 grams of S-methylthiocarbanylate (10 millimols), 0.88 grams of norbutylamine (12 millimols) and 10 mls.
of ben~ene. The mixture is heated until obtaining a vigorous refluxing of the solvent while concurrently : ~ .
maintaining a stream of an inert gas in the reactor.
The evolved gas is passed through a trap which is cooled to -78C. After one hour, 9.5 millimols of methyl mercaptan are recovered from the trap. From the reaction solution, by evaporation of the solvent; there are ` isolated 1.90 grams of N,N'-(norbutyl, phenyl) urea.
Yield : 99~-~; A flask equipped wi-th a condenser is charged with 1.68 grams of S-methylthiocarbanylate (10 millimols), 1.12 grams of aniline (12 millimols) and 10 mls. of xylene. The mixture is heated until maintaining a vigorous reflux of the solvent while concurrently maintaining a s-tream of an inert gas in the reactor.
The evolved gas is passed through a -trap cooled to -78C. After one hour there are recovered in the trap 9.4 millimols of methyl mercaptan. From the reaction solution there are isolated by filtration 2.0 grams of N, N'-biphenylurea. Yield 95~
~1 .
~ . ' , . :
- 10~6131 E~LE 3 ,:
flask equipped wi-th condenser is charged with 1.68 grams of S-methylthiocarbanylate (10 millimols), 0.89 grams of norbutanol (12 millimols), 0.10 grams of : ,: . -diazobicyclooctane and 10 mls. of toluene. The mixture is heated until obtaining a vigorous reflux of the sol-vent while concurrently maintaining a stream of inert ... ..
gas in the reactor. The evolved gas is passed through a trap which is cooled to -78C. After two hours there -are recovered in the trap 9.8 millimols of methyl mer- -~
captan. Erom the reaction solution, by evaporation of the solvent, and recrystallization of the residue from benzene-ether, there are isolated 1.85 grams of nor.butyl carbanylate. Yield 86%.
, -- ~ . .
.
A flask equipped with condenser is charged with 1.68 grams of S-methylthiocarbanylate (10 millimols), 1.13 grams :: :: : .: :
of phenol (12 millimols), 0.10 grams of diazobicyclooctane ~-and 10 mls. of xylene. The mixture is heated until obtai-ning a vigorous reflux of the solvent while concurrently :~ :: ~ , . . . .
maintaining a stream of inert gas in the reactor. The evolved gas is passed throuyh a trap which is cooled to ;- -i~i.. -. , -78C. After two hours there are recovered in the trap 9.9 millimols of methyl mercaptan. sy addiny petroleum ether to the reaction solution, 2.03 grams of phenyl-carbanylate are crystallized. Yield 95~.
E~MP$E 5 , ' ~".':' ' "' ':
- With exactly the same procedure as in Example 4, by reacting 1.68 grams of S-methylthiocarbanylate, 1.3 yrams of thiophenol an~ 0.10 yrams of diazobicyc~octane in 10 mls toluene, 1.85 grams of S-phenylthiocarbanylate have been obtained. Yield 80~
~ , ;
, . .
~: .: ' : - ' ' ~
, , ~ , . . . . . . . . .
: . . ' . ' ,' , . . "' ' ' ~
10~6~l31 A flask equipped with condenser is charged with 1.35 grams of toluene-2:4-dithiocarbamic acid S,S'-dimethylester (5 millimols), 1.4 grams of nor.heptanol (12 millimols), 0.10 grams of diazobicyclooctane and 20 mls. of xylene. The mixture is heated while concurrently maintaining a stream of an inert gas in the reactor. The evolved gas is passed through a trap which is cooled to -78C. After one hour 9.4 millimols of methylmercaptan are recovered in -the trap. The slightly cloudy solution is filtered and evapo-rated to one-fourth of its initial volume. By addition of petroleum ether and cooling to 0C, 1.4 grams of toluene-
.'. '' ~ .
This invention relates to a method or the transesterification of esters of -thiocarbamic acids, -having the formula :
X - A - NH - C -- S - R
11 .' . , .
.: - .
wherein R is methyl radical and A is phenyl radical, whereas X is hydrogen or one or more Cl to C10 alkyl or -NH-CO-SR groups.
, ,: :.
he existence cf these esters is known, ~ i .
and they are obtained, in the main, both by reacting ~ -h ~ an isocyanate with a mercaptan, and by reacting an amine with a chlorothiocarbonate, or also according :~; : : , " ..
to the reaction which forms the subject-matter of a copending patent application by the same~applicant.
It has now been found that it is possible to subject these compounds to appropriate transeste-rlficatlon reactions so as to obtain valuable products, whioh are very important for applications in the industrial field.
As a matter of fact, the subject matter of the present invention is the reaction between said es-ters and compounds of the formula R' (X'H)n wherein X' is O, S, or NH; R' is C2 to C10 alkyl or phenyl radical and n is l to 5. The reaction in question is preferably carried out in organic solvents at temperatures ranging ,~
from 50C to the boiling point temperature of the solvent.
It is also possible to employ a not too strong nitrogen stream in order to remove from the reaction environment the evolved mercaptan. The reaction can be carried out in the presence o a catalytic system which A
.
"
:, ' '"1. "".,,'~' ' '' ' , ',', "' "',' '; ' .. , ,, ' .,f ,: ' , ' ~ ' . . ., ' :
' " r' ',/'' ""' ' ' ' ~ ' ' ' ' " , ', ' ~ ' .' ' .'' ~' '' ' ' I . ' , . I .
~ can be composed by a ter-tiary amine, more particularly , ~
the diazobicyclooc~ane (DABCO).
In order to afford a better understanding of the present invention, a few explanatory examples of the invention are set forth, which are by no wise limiting of same.
EXAMPLE
A flask egoipped with a condenser is charged with 1.68 grams of S-methylthiocarbanylate (10 millimols), 0.88 grams of norbutylamine (12 millimols) and 10 mls.
of ben~ene. The mixture is heated until obtaining a vigorous refluxing of the solvent while concurrently : ~ .
maintaining a stream of an inert gas in the reactor.
The evolved gas is passed through a trap which is cooled to -78C. After one hour, 9.5 millimols of methyl mercaptan are recovered from the trap. From the reaction solution, by evaporation of the solvent; there are ` isolated 1.90 grams of N,N'-(norbutyl, phenyl) urea.
Yield : 99~-~; A flask equipped wi-th a condenser is charged with 1.68 grams of S-methylthiocarbanylate (10 millimols), 1.12 grams of aniline (12 millimols) and 10 mls. of xylene. The mixture is heated until maintaining a vigorous reflux of the solvent while concurrently maintaining a s-tream of an inert gas in the reactor.
The evolved gas is passed through a -trap cooled to -78C. After one hour there are recovered in the trap 9.4 millimols of methyl mercaptan. From the reaction solution there are isolated by filtration 2.0 grams of N, N'-biphenylurea. Yield 95~
~1 .
~ . ' , . :
- 10~6131 E~LE 3 ,:
flask equipped wi-th condenser is charged with 1.68 grams of S-methylthiocarbanylate (10 millimols), 0.89 grams of norbutanol (12 millimols), 0.10 grams of : ,: . -diazobicyclooctane and 10 mls. of toluene. The mixture is heated until obtaining a vigorous reflux of the sol-vent while concurrently maintaining a stream of inert ... ..
gas in the reactor. The evolved gas is passed through a trap which is cooled to -78C. After two hours there -are recovered in the trap 9.8 millimols of methyl mer- -~
captan. Erom the reaction solution, by evaporation of the solvent, and recrystallization of the residue from benzene-ether, there are isolated 1.85 grams of nor.butyl carbanylate. Yield 86%.
, -- ~ . .
.
A flask equipped with condenser is charged with 1.68 grams of S-methylthiocarbanylate (10 millimols), 1.13 grams :: :: : .: :
of phenol (12 millimols), 0.10 grams of diazobicyclooctane ~-and 10 mls. of xylene. The mixture is heated until obtai-ning a vigorous reflux of the solvent while concurrently :~ :: ~ , . . . .
maintaining a stream of inert gas in the reactor. The evolved gas is passed throuyh a trap which is cooled to ;- -i~i.. -. , -78C. After two hours there are recovered in the trap 9.9 millimols of methyl mercaptan. sy addiny petroleum ether to the reaction solution, 2.03 grams of phenyl-carbanylate are crystallized. Yield 95~.
E~MP$E 5 , ' ~".':' ' "' ':
- With exactly the same procedure as in Example 4, by reacting 1.68 grams of S-methylthiocarbanylate, 1.3 yrams of thiophenol an~ 0.10 yrams of diazobicyc~octane in 10 mls toluene, 1.85 grams of S-phenylthiocarbanylate have been obtained. Yield 80~
~ , ;
, . .
~: .: ' : - ' ' ~
, , ~ , . . . . . . . . .
: . . ' . ' ,' , . . "' ' ' ~
10~6~l31 A flask equipped with condenser is charged with 1.35 grams of toluene-2:4-dithiocarbamic acid S,S'-dimethylester (5 millimols), 1.4 grams of nor.heptanol (12 millimols), 0.10 grams of diazobicyclooctane and 20 mls. of xylene. The mixture is heated while concurrently maintaining a stream of an inert gas in the reactor. The evolved gas is passed through a trap which is cooled to -78C. After one hour 9.4 millimols of methylmercaptan are recovered in -the trap. The slightly cloudy solution is filtered and evapo-rated to one-fourth of its initial volume. By addition of petroleum ether and cooling to 0C, 1.4 grams of toluene-
2:44-dicarbamic acid-dieptylester crystallizes. Yield 70%.
~ ~ .
A flask equipped with condenser is charged with 1.35 grams of toluene-2:4-dithiocarhamic acid - S,S'~dimethylester (5 millimols), 0.94 grams of phenol (10 millimols), 0.10 grams of diazoblcyclooctane and 20 mls of xylene. Thé mix-ture is heated until maintaining a vigorous refluxing of the solvent, while concurrently~passing a stream of nitrogen through the reactor. The evolved gas is forwarded to a trap which is cooled to -78C. After 1.5 hours there are recovered in the trap 9.5 millimols of methyl mercaptan.
By cooling the reaction solution there are isolated 1.8 grams of toluene-2:4-dicarbamic acid-diphenyl ester.
Yield 99~.
All of the compounds as obtained in the preceding Examples have been identified by comparison with samples ~' as obtained from conventional synthesis. ~
~ .. .
' . . ~ ............. : . ' .: ; .........
,.: . .. ' ,, ,, . ',, . ' .,, , ~ . . . ,, : . ' ', J . . ' .
76~31 . ~ . ' .
A flask equipped with condenser is charged with , 1.35 grams of toluene-2:4-dithiocarbamic acid - S,S'-dimethyl ester (5 millimols~, 0.38 grams of propylene-1:2-glycol (5 millimols), 0.08 grams of diazobicyclooctane and 20 mls. of xylene. The mix~ure is heated until obtaining a vigorous reflux of the solvent while concur-rently maintaining a stream of an inert gas in -the reactor.
; The evolved gas is passed through a trap cooled to -78C.
After one hour, there are recovered in the trap 9.3 milli~
mols of methyl mercaptan. Once the solvent has been ~ ~ ;
removed by filtration, -there are recovered 1.5 grams of solid product. The I.R. spectrum in KBr exhibits the -following characteristic absorptions of urethan (3 microns;
5.8 microns). The polymer shows at the differential thermal analysis a vitreous transition (Tgj at 60C.
~' ~ ' ' '' ~'~ ' . , :~'. .:
.
''', .' :1 . ' . , ., ' , . . .
, ' ' ` , ' . ' ' , , .
," ,. , '' " ' ' ' , , ', ,' "' . ' ,',, '" . . '.'' " " , ,',' ';, ' '`,' ' ',',' ' ' " ' ` '" ' . ` ' '', . '', ' ' . ' ',', ' "'"' ,"' ",', " ' " ' ,'"'' ., ' ' , ' ,. ' '
~ ~ .
A flask equipped with condenser is charged with 1.35 grams of toluene-2:4-dithiocarhamic acid - S,S'~dimethylester (5 millimols), 0.94 grams of phenol (10 millimols), 0.10 grams of diazoblcyclooctane and 20 mls of xylene. Thé mix-ture is heated until maintaining a vigorous refluxing of the solvent, while concurrently~passing a stream of nitrogen through the reactor. The evolved gas is forwarded to a trap which is cooled to -78C. After 1.5 hours there are recovered in the trap 9.5 millimols of methyl mercaptan.
By cooling the reaction solution there are isolated 1.8 grams of toluene-2:4-dicarbamic acid-diphenyl ester.
Yield 99~.
All of the compounds as obtained in the preceding Examples have been identified by comparison with samples ~' as obtained from conventional synthesis. ~
~ .. .
' . . ~ ............. : . ' .: ; .........
,.: . .. ' ,, ,, . ',, . ' .,, , ~ . . . ,, : . ' ', J . . ' .
76~31 . ~ . ' .
A flask equipped with condenser is charged with , 1.35 grams of toluene-2:4-dithiocarbamic acid - S,S'-dimethyl ester (5 millimols~, 0.38 grams of propylene-1:2-glycol (5 millimols), 0.08 grams of diazobicyclooctane and 20 mls. of xylene. The mix~ure is heated until obtaining a vigorous reflux of the solvent while concur-rently maintaining a stream of an inert gas in -the reactor.
; The evolved gas is passed through a trap cooled to -78C.
After one hour, there are recovered in the trap 9.3 milli~
mols of methyl mercaptan. Once the solvent has been ~ ~ ;
removed by filtration, -there are recovered 1.5 grams of solid product. The I.R. spectrum in KBr exhibits the -following characteristic absorptions of urethan (3 microns;
5.8 microns). The polymer shows at the differential thermal analysis a vitreous transition (Tgj at 60C.
~' ~ ' ' '' ~'~ ' . , :~'. .:
.
''', .' :1 . ' . , ., ' , . . .
, ' ' ` , ' . ' ' , , .
," ,. , '' " ' ' ' , , ', ,' "' . ' ,',, '" . . '.'' " " , ,',' ';, ' '`,' ' ',',' ' ' " ' ` '" ' . ` ' '', . '', ' ' . ' ',', ' "'"' ,"' ",', " ' " ' ,'"'' ., ' ' , ' ,. ' '
Claims (6)
1. A method for the transesterification of esters of thiocarbamic acids having the formula wherein R is methyl radical and A is phenyl radical, whereas X is hydrogen or one or more C1 to C10 alkyl or -NH-CO-SR groups,comprising the step of reacting said esters with compounds of the formula R'(X'H)n wherein X' is O, S, or NH; R' is C2 to C10 alkyl or phenyl radical and n is 1 to 5.
2. A method according to claim 1, characterized in that the transesterification reaction takes place in the presence of a catalyst composed by a tertiary amine.
3. A method according to claim 2, characterized in that the tertiary amine is diazobicyclooctane.
4. A method according to claim 1, characterized in that the transesterification reaction is carried out in organic solvents.
5. A method according to claim 4, characterized in that the reaction temperature is maintained between 50°C
and the boiling point temperature of the solvent.
and the boiling point temperature of the solvent.
6. A method according to claim 1, characterized in that the transesterification reaction is carried out in the presence of a not too strong nitrogen stream.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT22616/75A IT1037577B (en) | 1975-04-23 | 1975-04-23 | PROCEDURE FOR THE TRANSESTERIFICATION OF ESTERS OF THIOCARBAMIC ACIDS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1076131A true CA1076131A (en) | 1980-04-22 |
Family
ID=11198467
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA250,553A Expired CA1076131A (en) | 1975-04-23 | 1976-04-20 | Method for the transesterification of thiocarbamic acid esters |
Country Status (22)
| Country | Link |
|---|---|
| JP (1) | JPS51128918A (en) |
| AT (1) | ATA294276A (en) |
| AU (1) | AU501786B2 (en) |
| BE (1) | BE841007A (en) |
| CA (1) | CA1076131A (en) |
| DE (1) | DE2617918C3 (en) |
| DK (1) | DK180076A (en) |
| ES (1) | ES447392A1 (en) |
| FR (1) | FR2308614A1 (en) |
| GB (1) | GB1507429A (en) |
| IE (1) | IE42800B1 (en) |
| IL (1) | IL49429A0 (en) |
| IN (1) | IN144588B (en) |
| IT (1) | IT1037577B (en) |
| LU (1) | LU74809A1 (en) |
| NL (1) | NL7604302A (en) |
| NO (1) | NO761374L (en) |
| PT (1) | PT65033B (en) |
| RO (1) | RO69169A (en) |
| SE (1) | SE431449B (en) |
| YU (1) | YU100776A (en) |
| ZA (1) | ZA762148B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR8106184A (en) * | 1980-01-25 | 1981-11-24 | Reanal Finomvegyszergyar | PROCESS FOR THE PREPARATION OF N-ARYL-N 'DERIVATIVES - (MONO-OR DISSUBSTITUTED) -UREA |
| US5621132A (en) * | 1992-10-19 | 1997-04-15 | Council Of Scientific And Industrial Research | Process for making alkyl N-alkyl or N-aryl-thiocarbamates |
-
1975
- 1975-04-23 IT IT22616/75A patent/IT1037577B/en active
-
1976
- 1976-04-09 ZA ZA762148A patent/ZA762148B/en unknown
- 1976-04-15 GB GB15729/76A patent/GB1507429A/en not_active Expired
- 1976-04-16 IL IL49429A patent/IL49429A0/en unknown
- 1976-04-20 YU YU01007/76A patent/YU100776A/en unknown
- 1976-04-20 AU AU13114/76A patent/AU501786B2/en not_active Expired
- 1976-04-20 CA CA250,553A patent/CA1076131A/en not_active Expired
- 1976-04-21 LU LU74809A patent/LU74809A1/xx unknown
- 1976-04-21 DK DK180076A patent/DK180076A/en not_active Application Discontinuation
- 1976-04-21 ES ES447392A patent/ES447392A1/en not_active Expired
- 1976-04-22 SE SE7604668A patent/SE431449B/en unknown
- 1976-04-22 RO RO7685763A patent/RO69169A/en unknown
- 1976-04-22 BE BE166371A patent/BE841007A/en not_active IP Right Cessation
- 1976-04-22 FR FR7611954A patent/FR2308614A1/en active Granted
- 1976-04-22 AT AT762942A patent/ATA294276A/en not_active IP Right Cessation
- 1976-04-22 NL NL7604302A patent/NL7604302A/en not_active Application Discontinuation
- 1976-04-22 PT PT65033A patent/PT65033B/en unknown
- 1976-04-22 NO NO761374A patent/NO761374L/no unknown
- 1976-04-23 DE DE2617918A patent/DE2617918C3/en not_active Expired
- 1976-04-23 IN IN704/CAL/76A patent/IN144588B/en unknown
- 1976-04-23 IE IE866/76A patent/IE42800B1/en unknown
- 1976-04-23 JP JP51045612A patent/JPS51128918A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| PT65033A (en) | 1976-05-01 |
| ZA762148B (en) | 1977-04-27 |
| PT65033B (en) | 1977-09-12 |
| DK180076A (en) | 1976-10-24 |
| ES447392A1 (en) | 1977-07-01 |
| IE42800L (en) | 1976-10-23 |
| FR2308614A1 (en) | 1976-11-19 |
| SE431449B (en) | 1984-02-06 |
| DE2617918A1 (en) | 1976-10-28 |
| SE7604668L (en) | 1976-10-24 |
| BE841007A (en) | 1976-10-22 |
| AU1311476A (en) | 1977-10-27 |
| IN144588B (en) | 1978-05-20 |
| FR2308614B1 (en) | 1980-04-11 |
| AU501786B2 (en) | 1979-06-28 |
| RO69169A (en) | 1981-04-30 |
| IE42800B1 (en) | 1980-10-22 |
| GB1507429A (en) | 1978-04-12 |
| NO761374L (en) | 1976-10-26 |
| JPS51128918A (en) | 1976-11-10 |
| NL7604302A (en) | 1976-10-26 |
| LU74809A1 (en) | 1977-01-12 |
| DE2617918B2 (en) | 1981-02-12 |
| DE2617918C3 (en) | 1981-12-24 |
| YU100776A (en) | 1982-10-31 |
| IT1037577B (en) | 1979-11-20 |
| IL49429A0 (en) | 1976-06-30 |
| ATA294276A (en) | 1978-06-15 |
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