CA1230601A - Imidyl-mercaptans and -sulfenylhalogenides - Google Patents

Abstract

Novel imidyl-mercaptans and -sulfenylhalogenides Abstract Compounds of the formula Ia or Ib ( Ia) or ( Ib) in which R and R' independently of each other are C1-4-alkyl or together are unsubstituted or methyl-substituted trimethylene or tetramethylene, R1 and R2 independently of each other are hydrogen, halogen, C1-4-alkyl or methoxy, A is -CH2-, -CH2CH2- or -OCH2- where the oxygen is bonded to the aromatic ring and E is hydrogen or A is -O-and E is -CH3, n is 1 or 2, Z, if n = 1, is a halogen atom and, if n = 2, hydrogen or a halogen atom and Y is -CaH2a- where a = 1-12, C3-8-cycloalkylene, C6-10-arylene, C7-8-aralkylene or -alkylarylene or

Description

I

Case 3-13896/+/ZFO/B

Novel imidyl-mercaptane and -sulfenylhalogenides This application is a divisional application from application No. ~26,756, filed April 26~h, 1983.
The invention relates to novel starting materials developed for preparing photocrosslinkable polymers having thioetherimidyl side groups.
German O-ffenlegungsschrift 2,626,769 and European Patent Application published under No. 3552 disclose photo-crosslinkable polymers having imidyl side groups, in part-cuter dimethylmaleinimidyl and certain tricyclic imidyl groups.
The invention relates to novel compounds of the formula It and/or It KIWI\ OR /C\ I l I (Y)n--lN~ if and/or US no lo !' (It) (It) I
in which R and R' independently o-f each other are I 4-alkyd or together are unsubstituted or methyl-substituted trim ethylene or tetramethylene, R1 and R2 independently of each other are hydrogen, halogen, C1 alkali or methoxy, A is -SHEA-, -CH2CH2- or OUCH- where oxygen is bonded to the aromatic. ring and E is hydrogen or A is -O- and E
is -SHEA-, n is 1 or 2, Z, if n = 1, is a halogen atom and, it n 2, hydrogen or a halogen atom and Y is -Kiwi- where a = 1-12, in particular 2-8, C3_8-cycloalkylene, C6_10-Arlene, C7 ~-aralkylene or -alkylarylene or I

where X is a direct bond, -O-, -S- or -SHEA and said Y

., I,;, .....

foe substituents can also be substituted by alkyd or alkoxy groups having each I C atoms, by vitro groups or halogen atoms The compounds of the formula It and It are especially suitable for the preparation of polymers.
Such polymers can be prepared by known methods of synthesizing macromolecules having photoactive side groups.
In principle the following ways are possible:
1) incorporating imidyl groups derived from formulae It and It in existing polymer chains; and

2) building the polymer chain by polymerization, polyp addition or polycondensation from monomers which contain-groups derived from formula It and/or IBM
Polymers of the invention - as is clear from the general def;n;t;on - can also be copolymers made up of structural elements having groups derived from formula It and/or It and other structural elements, the various structural elements being present in the copolymer in a random or at least partly block-like arrangement The polymers of the invention are preferably prepared by the incorporating method, for example by a) the addition of a compound of the formula It or It in which R, R', R1, R2, A, E, Y and n are as defined above and Z, if n = 1, is halogen atom, such as fluorine, r ii bromide or, in particular, chlorine and, if n = 2, us hydrogen or a halogen atom such as fluorine, bromide or, in particular, chlorine, onto a polymer having C=C double bonds, in such a way that the ratio of compound of the formula It or It to the number of C=C double bonds present in the starting polymer is 1:20 to 1:1, in particular 1:10 to 1:1, especially 1:5 to 1:1, or b) reacting a compound of the formula It or It where n = 2 and Z = hydrogen by condensation or ring-open;ng add-lion reactions with polymers having suitable functional I

groups, such as COO, Cowl, android or -SHEA- groups, on such a way that the ratio of compound of the formula It or It to the polymer is 1:20 to 1:1, in particular 1:10 to 1:1, especially 1:5 to 101, based on the number of the polymer's recurring structural elements.
It us preferred to use compounds of the formula It or It in which Z is chlorine if n = 1, and especially compounds of the formula It or It on which n is 2 and Z
us hydrogen or chlorine.
A substituted Y group us substituted by, for ox-ample, alkyd or alkoxy subst;tuents having 1-4 C atoms, on particular 1 or 2 C atoms, each, Nero groups and espy-Shelley halogen atoms, such as broM;ne, fluorine or, on particular, chlorine. A -Kiwi- Y us a striation or branched radical Shea us preferably unsubst;tuted or substituted by halogen atoms, especially chlorine.
The examples of such a radical are ethylene, -CH(Cl~CH2-~ 1,3- and propylene, 2,2~d;methylpropyl~
one, 1-chloro-1,3-propylene, tetramethylene, hexamethylene, octamethylene, decathlon and dodecamethylene. A cycle-alkaline group Y us on particular a 1,3-cyclopentylene or a 1~3- or especially a 1,4-cyclohexylene group.
A substituted Arlene group Y preferably has only one subst;tuent per rung, on particular an alkyd or alkoxy group having 1-4~ especially 1 or 2, C atoms each or a Nero group. Examples of Arlene groups Y are the 1,2-, 1,3- and 1,4-phenylene group, the 1,3~toluylene group, the 5-~ethoxy-1,3-phenylene group, the 3-n;tro-1~4-phenylene group and the 1,7- and 2,7-naphthylene group. Unsubst;-tuned Arlene groups, especially the 1,4- and 1~3-phenylene groups are preferred.

An aralkylene group Y us especially a -OH
I_ O
group, and or CH2CH2~ group, and an run alkylarylene group is especially a -SHEA or _ O
CH2c~2-sroup~
.=.
A bicyclic radical Y

I

is preferably unsubstituted and bonded on the pus-ton.
Alkyd groups R, R', R1 and R2 can also be striation or branched and are, for example, methyl ethyl, n-propyl, isopropyl, n-butyl or scan bottle. A halo-gun atom R1 or Rz us especially a chlorine, brom;ne or fluorine atom. Alkyd groups R1 and R2 are Advent-juicily striation and each has 1 or 2 C atoms. How-ever, R1 and R2 are preferably hydrogen.
Preferred polymers have side groups derived from formula It in which A is -SHEA-, E, R1 and R2 are hydrogen, n is 2 and Y is unsubstituted or halogen on particular chlorine substituted C2_8-alkylene or 1,3 or phenol one, and are especially those on which no A, En R1 and R2 are as preferred above and Y us ethylene, -CHtCl3CH2-, or 1,3- or 1,4-phenylene. However, particularly preferred .. . . . . . . . . . . .
polymers have side groupings derived from formula It on which R and R' are methyl, n us 1 or, on particular, 2, and Y us unsubst;tuted or halogen-, on particular chlorine , subset-tuned C2_~-alkylene or 1,3- or 1,4-phenylene. Very highly preferred polymers have side groupings of the formula It on Shea R and R' are methyl, n us 2, and Y is ethylene, -CHtCl)CH2-, or 1,3- or 1r4-phenylene.
Examples of starting polymers which can be reacted with compounds of the -formula It or Ida are polyacrylic acid polymethacrylic acid and derivatives thereof, co-polymers of these acids and other ethylen;cally unsaturated monomers Milwaukee android polymers and copolymers, I

polymers with reactive chloroalkylene groups polymers with free glyc;dyl groups, such as copolymers based on glycidyl acrylate or methacrylate, at least partially us-saturated polyamides, polyesters and polyurethane, elicit-mews, such as polybutadiene, polyisoprene, polychloroprene and copolymers of the corresponding dines with other ethylen;cally unsaturated comonomers, for example those of the above mentioned type.
Compounds of the formula It or It can be incur-prorated on existing polymers on a manner known per so. The addition of compounds of the formula It or It in which Z
us halogen onto polymers having C=C double bonds is ad van-tageously carried out at temperatures between -20C and +50C, preferably 0 to 30C, in suitable inert organic solvents with the exclusion of moisture. The add ton of compounds of the formula It or It where n = 2 and Z = H
onto polymers having C=C double bonds us also advantageously carried out at temperatures between I and 150C, prefer-ably 70 to ~0C, on an inert organic solvent in an inert gas atmosphere, such as nitrogen. This reaction proceeds via free radicals and us therefore carried out on the pro-since of free-rad;cal in;t;atorsr Examples of solvents suitable for these addition reactions are aromatic or elf-phatic hydrocarbons, such as Bunsen, Tulane, chloroben-zone, dichlorobenzene, chloroform or carbon tetrachloride, and cyclic or al;phat;c am;desr such as N-methyl-2-pyrrol;-done, N-ethyl-2-pyrrol;done, methyl- ~caprolactam, NUN-d;methylformamide, ~',N-dimethylacetamide or N,N-d;ethyl-acetam;de~ The free-rad;cal initiators used can be come pounds known per son d;benzoyl peroxide and assess-butyronitr;le being preferred.
The incorporation of compounds of the formula It or It where n 2 and on polymers having suitable functional groups by means of condensation or ring-open;n~
add ton reactions us also preferably carried out on an inert organic solvent or solvent mixture, in the case of condensation reactions preferably at temperatures of -20C
to Nikko. Ring-open;n9 addition reactions are Advent-juicily carried out at elevated temperatures, generally at temperatures between ~0 and 120C or at the reflex temperature Examples of solvents suitable for these react lions are aliphatic or cyclic kittens, such as acetone, methyl ethyl kitten, cyclohexanone or cyclopentanone, cyclic ethers, such as tetrahydrofuran or Dixon, cyclic or aliphat;c asides, such as N-methyl-2-pyrrolidone, N-methyl--caprolactam, No dimethylformamide, No dim ethyl-acetam;de or N,r!-diethylacetamide, and dialkyl sulfoxides, such as methyl sulfox;de or deathly sulfox;de.
After the reaction the polymers modified with imidyl groups of the type defined can be precipitated in suitable precipitating agents such as deathly ether, d;-n-propyl ether, methanol, ethanol, ;sopropanol, n-pentane, Nixon, Bunsen or Tulane.
Polymers can also be obtained by the addition of compounds of the formula It or It where Z = H or halogen (n = 2) onto acetylene and copolymerising the monomers thus obtained, if desired in the presence of other ethylemically unsaturated monomers, such as acrylic acid or methacrylic acid or their esters, vinyl acetate or malefic android.
Compounds of the formula It or It where Z H can also be added onto, for example, unsaturated dicarbonyl halides and the resulting compounds reacted with suitable co-conden-station components, such as dominoes or dills.
The starting materials of the formula It and It can be prepared by methods known per so, for example by reacting an android of the formula Ida or Jib (n = 2) I ,!\ kiwi if Jo or if Jo I C0 R --*_ j C0/

(Ida) R2 (Jib) with a compound of the formula III
Ho ASH (III) and treating the resulting Marquette compounds, of desired with elemental halogen, especially Bra or Clue. Compounds of the formula Ida or Jib where n = 1 can be obtained by treating a compound of the formula XIxa or XIxb CO
I KIWI

R' C0 Jo /.
(Ivy) (Ivy) with an S-halogen-introducing agent, such as sulfur dip chloride, sulfur dibromide or sulfur tetrafluoride, if desired on the presence of an acid acceptor, such as pyre-dyne or triethylam;ne, whole R, R', R1~ R2~ A, E and Y
are as defined under the formulae It and IBM
he above reactions are preferably carried out in the presence of an inert organic solvent. Examples of such solvents suitable for the reaction of androids of the for-mule Ida and Jib with aminoth;ols of the formula III
are aromatic hydrocarbons, such as Bunsen or Tulane.
The reaction of Marquette compounds with elemental halogen as well as the reaction of the compounds of the formulae Ivy and Ivy with the S-haloqen-introduc;ng agent is advantageously carried out on a halogenated aliphat;c or aromatic hydrocarbon, such as carbon tetrachlor;de, carbon tetrabrom;de, d;chloromethane, chloroform or d;chlorobenz-one.
Example 1: eye 9 (0.~88 molt of dimethylmale;c android and 80 g (1.037 mows) of 2-mercaptoethylamine are dispersed on 1,15û ml of Tulane. The water formed is separated off at reflection Tulane. After cooling down, the clear soul-ton is extracted three tomes with 300 g of plater each time the aqueous phase is separated off, and the Tulane -~Z3~

solution is dried over Coequal and distilled. rJ-(2-l1er-captoethyl~-dimethylmaleinimide passes over at 94C/1 Pa.
Yield: 120 9 (65.~% of theory).
Elemental analysis:
calculated C 51.87 H 5.99 7.56 S 17.31X
found C 51.83 H 5.94 N 7.51 S 16.92%.
NOR spectrum dtppm): 2.5( \ / ) , SHEA
C~3 3 2.7 (-CHIHUAHUAS-) and 1.4 (S-H).
A 1,000 ml sulfonating flask which is equipped with a Clue inlet tube, a stirrer, a Coequals tube and a dropping funnel is charged with 400 ml of Cal and Saturn axed at 20C with Clue. The solution is cooled down to 0-5C, and a solution of 2~.5 g of ~1-(2-mercaptoethyl)-dimethylmalein;mide in 250 ml of CCl4 is added drops in the course of 3û minutes while the Clue stream continues.
Claus is passed in at 5C for 30 minutes and then at 20C
for a further 2 hours. The solvent is drawn off until constant weight. This gives 46 of the sulfenyl chloride of N-(2~mercaptoethyl)-dimethylmalein;mide, of the formula H3C\ kiwi Of CH2-~-SC
H \C0 rim spectrum ~tppm~: 2.0 ,4.15 (-N-CH2) and

3 SHEA
5.6 (OH, -Shekels).
Example 2- 94.6 9 (0.75 molt of dimethylmaleic android and 93.9 9 (0.75 molt of 4-aminothiophenol are dispersed in 750 ml of Tulane the dispersion is heated to the reflex temperature and the dispersed starting materials become dissolved in the Tulane. 9 ml of water are spear-axed off in the course of 130 hours of refluxing. The Tulane us then drawn off, and the ~-(4-mercaptophenyldi-methyl~-maleinimide distill over at 155-160C/13 Pa.

I

g Yield: 91.0 9 (52.0~ of theory); melting point: 124-SKYE) Elemental analysts:
calculated C 61.~0 H 4.72 N 6.01 S 13.73%
found ~1.75 H 4.81 N 5~5 S 13.65~.
A 1,000 ml sulfonating flask which is equipped with a C'2 inlet tube, a stirrer, a Coequals tube, a reflex condenser and a dropping funnel is charged with 500 ml of CCl4. Clue is passed in at 0-5C for 15 minutes. Chile the Clue stream continues, a solution of 28~0 9 of Roy-mercaptophenyl)-dimethylmaleinimide in 300 ml of CCl4 is added drops in the course of 90 minutes. Clue is then passed in for a further hour. Complete removal of the sol-vent gives 28.0 9 (87.1X of theory) of the sulfenyl color-ire of ~1-(4-mercaptophenyl)-dimethylmaleinimide which can be used without further purification.
Elemental analysts:
calculated C 53.83 H 3.70 N 5.23 Of 13.24 S 11.~7~
found C 53.70 H 3.~3 N 5.46 Of 13.76 S 11.47X.
Example 3: 11.3 g Tao molt of 3,4~dihydronaphthalene-1,2-d;carboxyl;c android prepared on accordance with Org. Syntheses, Cot. Vol. 2, 1~4 (1943)] and 4.36 9 of 2-mercaptoethylamine (0.0565 molt are dispersed in so ml of Tulane. The dispersion is heated to the reflex tempera-lure. About 1 ml of water is separated off in the course of 40 hours of refluxing. The Tulane is distilled off in vacua, the precipitated product is dissolved in 1~0 ml of Shekel and the solution us extracted four times with 150 ml of I HAL each time. The Shekel phase is then washed twice with no ml of water each time, dried over calcium chloride and evaporated. Thus gives 14.2 9 tax of theory) of ~-(2-mercaptoethyl~-3,4-d;hydronaphthalene-1,2-d;carbox;mide. All steps are carried out under yellow lighting.
Elemental analysis:
calculated C 64.86 H 5.02 N 5.41 S 1Z.36X
found C 64.70 H 4.90 N 5.31 S 12.22X.

Jut 14 Tao molt of N-(2-mercaptoethyL~-3~4-di-hydronaphthalene-1,2-dicarboximide are added drops at 0-5C in the course of 70 minutes together with a Clue stream to KIWI no of CCl4 which has been saturated with chlorine. After the addition has ended, chlorine is passed in for a further hour. The solvent is then removed and the resulting compound of the formula kiwi l; >1~C~2C-rl ( Of ) -S-C 1 \

is dried at Sue 1700 Pa. All steps are carried out under yellow lighting. Yield :20.0 9 NOR Spectrum Pam 4.15 (~rll-CI~2), 5.6 t1H,-CH~Cl)-S-).
The above sulfenyl chloride is used without fur-then purification as a starting material in the reaction with unsaturated polymers (cf. Example 21~.
Example 4- 10.5 9 (0.084 molt of dimethylmaleinimide are dissolved in 45 ml of Shekel, and the solution is cooled Dylan to -10C~ 11.2 9 Tao molt of freshly distilled Scholl are then added. 7.3 9 (0.092 molt of pardon are added drops at 0-10C to the resulting orange solution, and the reaction mixture is stirred at 25C for 4 hours. The precipitated product is filtered off, and the filtrate is concentrated to dryness and dried.
This gives 14.1 9 (87.7% of theory) of the sulfenyl color-ode of dimethylmaleinimide.
Elemental analysis:
calculated H 3.16 N 7.31 Of 18.50 S 16.73X
found H 3.75 N 7.90 Of 16.90 S 15.90%
Examples 5-8: A 10û ml sulfonating flask which is equipped with a nitrogen inlet and outlet, a stirrer, a thwarter, a reflex condenser and a dropping funnel is charged with 5X solutions in dry chloroform of the unsaturated polyamide I

shown in Table 1, below. A 20X5 chloroform solution o-F the sulfenyl chloride of Example 1 is then added drops with thorough stirring at 20C in the course of 30 minutes, during which the temperature rises to 25-30C. The solution is kept under nitrogen for 16 hours and is then concentrated to one third of its original volume. The resulting polymer is precipitated in 1 lithe of deathly ether and us dried at 40C on a high vacuum.

:

. ................. Jo It Ryan '>- ox _, wool o E . Jo E
_ . I, * I
Al L C I J
O n ox o o Jo _ . . _ O Ox J O
ox o to Jo us ED I 00 r`J
_ 0 I
Cut I
En o * + E Jo O o o Us I
I E I ox o lo O O O O O Jo C O oil Jo I, Us at - owe _ to rod 17 E
, . Jo I , z _ Use examples 13 -Example I: 1 g of each of the polymers given in Table II, below, and 50 my of the compound of the formula 5Q~ ./ 3 C H COO/ I-/ US/ \-~

are dissolved on 5.4 ml of each of the solvents likewise given in Table II. The solutions are applied with a 50 em doctor blade onto a copper conductor board and dried at 100C for 3 minutes.
The coatings are exposed through a Stouffer 21 step sensitivity guide with a S000 W high-pressure mercury lamp a distance of 70 cm away from the vacuum table, and then developed.

Table II
_ _ _ _ _ _ _ Jo Polymer Exposure time Developed Last step reproduced of (seconds/ Time on the sensitivity Example WOW) In (seas.) - guide _ .
., 5-8 20 Shekel 60 5-7 l S-8 - CHIC 13 60 6-8 .

.. ,

Claims (4)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A compounds of the formula Ia or Ib or ( Ia) ( Ib) in which R and R' independently of each other are C1-4-alkyl or together are unsubstituted or methyl-substituted trimmethylene or tetramethylene, R1 and R2 independently of each other are hydrogen, halogen, C1-4-alkyl or methoxy, A is -CH2-, -CH2CH2- or -OCH2-where the oxygen is bonded to the aromatic ring and E is hydrogen or A is -O- and E is -CH3, n is 1 or 2, Z, if n = 1, is a halogen atom and, if n = 2, hydrogen or a halogen atom and Y is -CaH2a-where a = 1-12, C3-8-cycloalkylene, C6-10-arylene, C7-8-aralkylene or -alkylarylene or where X = a direct bond, -O-, -S- or -CH? , where said substi-tuents Y can also be substituted by alkyl or alkoxy groups having each 1-4 C atoms, by nitro groups or halogen atoms.

2. N-(2-mercaptoethyl)-dimethylmaleinimide.

3. The compound

4. The compound