US 2861065 A
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United States Patent ARYLGUANIDINE ARENEDIAZOSULFONATES Clilford E. Herrick, Jr., Chenango Forks, N. Y., assignor to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application December 31, 1956 Serial No.'631,424
6 Claims. (Cl. 260-141) The present invention relates to arylguanidine arenediazosulfonates which are photosensitive, solvent-soluble compounds having particular utility in the manufacture of light-sensitive diazotype materials and lithographic plates.
It has become increasingly apparent in recent years i that high molecular weight, photosensitive compounds which are soluble in organic solvents, such as alcohols, esters, ketones, methyl Cellosolve, dimethylformamide, chloroform and the like, have important applications in the diazotype and lithographic fields. Representative of such compounds on which considerable work has already been done are the diazooxides, diazoimides, 3- diazoindoles, 3-diazoindiazoles and nitrones. Each of these fills an important segment of the involved fields, 'but considerable research is under way to find new compounds serving to bridge the hiatus in said fields which cannot be served adequately by the presently known compounds.
It has now been discovered that arylguanidine arene diazosulfonates, which are salts of high molecular weight, are photosensitive, solventsoluble substances having such characteristics. These compounds, because of their attributes, are particularly suitable for use in lithography, i. e., in the manufacture of paper and metal lithographic plates.
Arylguanidine arenediazosulfonates, their preparation and their use in diazotypy and lithography constitute the purposes and objects of the present invention.
The new general class of photosensitive, solvent-soluble substances contemplated herein is typified by the following general formula:
tylaminophenyl, benzoylaminophenyl, phenylacetylaminophenyl and the like; and phenoxyphenyl; phenylthiophenyl; diphenyleneoxide; naphthyl', diphenylenesulfide; benzylphenyl, phenethylphenyl and such aromatic radiice cals starting with said phenoxyphenyl as bear the same substituents as those listed for the phenyl radicals; R being hydrogen or aryl such as phenyl; alkylphenyl such as methylphenyl, dimethylphenyl and the like; naphthyl such as 1- or 2-naphthyl and the like, at least two R's being aryl and at least one R being hydrogen.
The new salts are made by preparing in a known manner the required alkali metal arenediazosulfonate and reacting the same in an aqueous medium with the selected arylguanidine acetate with gentle heating if desired. The arylguanidine arenediazosulfonates separate from the aqueous solution, sometimes as solids, sometimes as oils which later crystallize. The photosensitive solids which have a color ranging from yellow to orange, red or brown are insoluble in water but soluble in such solvents as isopropyl alcohol, acetone and chloroform. They may be, accordingly, coated on a suitable base from such solvents to prepare diazqtype and lithographic materials. 4
Examples of the arenediazosulfonates which are suitable for the preparation of the photosensitive compounds are the alkali metal salts such as sodium p-ethoxybenzenediazosulfonate; sodium 3-chloro-4,G-dimethoxybenzenediazosulfonate; sodium p-acetamidobenzenediazosulfonate; sodium N-benzyl-N-ethyl-p-aminobenzenediazosulfonate; sodium 2,5-diethoxy-4-methylbenzenediazosulfonate, sodium 2,5-dimethoxybenzenediazosulfonate; sodium 4-bromoor chloro-2,S-diethoxybenzenediazosulfonate; sodium 5 chloro-Z,4-diethoxybenzenediazosulfonate; sodium Z-chlor044,S-dimethoxybenzenediazosulfonate; sodium 4-diethylamino-G-ethoxybenzenediazosulfonate; sodium 4-diethylamino-2,6-diethoxybenzenediazosulfonate; sodium 4-dimethylamino-6-methoxybenzenediazosulfonate; sodium N ethyl-N-propylt-arninofi-ethoxybenzenediazosulfonate; sodium N-ethyl-N-B-hydroxyethyl 4 an1ino-6-ethoxybenzenediazosulfonate; sodium-4-ethyl-amino-3-methylbenzenediazosulfonate; sodium 4-diethylaminobenzenediazosulfonate; sodium N-ethyl-N-benzyl-4-aminobenzenediazosulfonate; sodium N- ethyl-N-p-hydroxyethyl 4 aminobenzenediazosulfonate; sodium 4-dimethylaminobenzenediazosulfonate; sodium 4-benzylamino-2-methoxy-5-methylbenzenediazosulfonate; sodium 4 benzoylamino-2-methoxy-5-methylbenzenediazosulfonate; sodium 4-benzoylamino-2-chloro-5-methoxybenzenediazosulfonate; sodium 4-(4'-methoxyphenyl amino)benzenediazosulfonate; sodium 4-phenylthioacetylamino-2,5-diethoxybenzenediazosulfonate; sodium 4-cyclohexylaminobenzenediazosulfonate; sodium 2,4,5-triethoxybenzenediazosulfonate; sodium 4-acetylamino-2,5- dibutoxybenzenediazosulfonate; sodium 4-phenylacetylamino-2,5-diethoxybenzenediazosulfonate; sodium 4-ethylmercapto 2,5 diethoxybenzenediazosulfonate; sodium 4 ethylmercapto-2,5-diethoxybenzenediazosulfonate; sodium 4-morpholinobenzenediazosulfonate; sodium 4-19- naphthylaminobenzenediazosulfonate; disodium 3,3'-dimethoxy-4,4-biphenyltetrazodisulfonate; disodium 4,4- biphenyltetrazodisulfonate; sodium 4-tolyl-2,5-diethoxybenzenediazosulfonate; sodium 4' acetylamino 2,5-diethoxy-4-biphenyldiazosulfonate; sodium 4'-2,5-triethoxy- 4-biphenyldiazosulfonate; sodium 4'-ethoxy-2,5-dibutoxy- 4-biphenyldiazosulfonate; sodium l-naphthalenediazosulfonate; sodium 2-naphthalenediazosulfonate; the tetrazodisulfonate from 4,4'-diaminodiphenyleneoxide; the tetrazodisulfonate from 4,4'-diaminodiphenylenesulfide; the sodium diazosulfonate from 4'-amino-m-terphenyl; disodium 3,3'-methylenebis (4 ethoxybenzenediazosulfonate); disodium 3,3'-ethylenebis (4-ethoxybenzenediazosulfonate); the sodium tetrazodisulfonate from p,p'- ethylenediaminoaniline and the like.
The arylguanidines which are reacted with any of the aforesaid diazosulfonates to produce the photosensitive 4 compounds hereof are those of the following general acid. A red oil appeared. This oil was washed with formula: water and left for two days. Some yellow crystals were observed on the third day. On the fourth day crystallization occurred. The crystals were washed with water, filtered, and dried in vacuo. The crystals melted at 162,- 164 C. The yield was 72%.
The probable structure is: 01 cm 01110 N,s0,H.HN=c(NH- wherein R is hydrogen or an aromatic radical of the CH benzene or naphthalene series such as phenyl, alkyl- 1 phenyl, i. e., tolyl, xylyl or the like; acylaminophenyl Example such as lauroylaminophenyl and the like; alkylsulfamoyl- 1,3-di-o-tolylguanidine 3,3'-dimethoxy 4,4 biphenylphenyl such as dodecylsulfamoylphenyl and the like; tetrazodisulfonate was prepared in the same manner as naphthyl such as l-naphthyl, Z-naphthyl and the like, in Example I. The reddish yellow crystals melted at it being understood that at least two R's are such arO- 153-155 C. with decomposition and probably possessed matic radicals and at least one R is hydrogen. the following structure:
0H, OCH; OCH; OH:
Illustrative of such arylguanidines are: 1,3-di-o-tolylguanidine Example IV 1,3-dixylylguanidine 1,2,34ripheny1guanidine 1,3-di-o-tolylguanidine 4,4-biphenyltetrazodisulfonate 1,1,2,3-tetraphenylguanidine was prepared from sodium biphenyltetrazodisulfonate in P Y -9' y the same manner as in Example I. The sodium biphenyl- 1(P'laury1ammphenyl)'3'phenylguamdme. tetrazodisulfonate was made by tetrazotizing benzidine l-(p-dodecylsulfoamoylphenyl)-3-phenylguan1dme d h 1,3 di 1 naphthylguanidine an treating t e solution w1th solutions of sodium bicar- 1,3-di-2-naphthylguanidine bonate and sodium sulfite. 1,3-diphenyl-2(1-naphthyl)guanidine, and the like. The structure of the product is probably:
CH: CH; (ONH)=C=NH.HO;SN N;S0;H.HN=C(NH)| The invention is further illustrated by the following Example V examples, but it is to be understood that the invention A Solution f 5 grams f sodium p-atamidben- 15 not restricted thereozenediazosulfonate in mls. of warm water was treated Example I with a warm solution of 33.5 grams of 1,3-di-o-tolylguanidine in 100 mls. of acetic acid, 50% by volume. An oil separated which solidified to orange crystals when in vacuo. The product weighed 28.0 grams, an 84% tion was added a solution of 175 gms. of 1,3-di-o-tolylguanidine in 700 mls. of water and 620 mls. of acetic gii gg fi gzg ggg fiiifigg at 176480 and acid.
175 gms. of sodium p-ethoxybenzenediazosulfonate A heavy yellow precipitate formed upon slow addition 50 with stirring at 35- 10 C. The slurry was cooled to 18- 20 C. and filtered. The cake was then slurried twice CHCONH N'SO'H'HN=C( NH with water, refiltered and dried in vacuo over sodium Example VI hydroxide. The yield was 90 percent. The crystals methylenebisu nitrophenol) (Chamway and i s: t fifig h of the roduct' Goepp, I Chem. Soc. 1933, 699) was converted by means P p of ethyl sulfate and alkali into 2,2'-methylenebis(4-nitrophenetol), which was reduced catalytically over palladium on carbon to 3,3'-methylenebis(p-phenetidine). The by- O SO M NHO drochloride of this base was diazotized and converted to sodium 3,3'-methylenebis(4-ethoxybenzenediazosul- Exam H fonate) in the usual way. I
p A filtered solution of 18.5 grams of sodium 3,3-methyl- Thirty grams of sodium 3-chloro-4,6-dimethoxybcnenebis(4-ethoxybenzenediazosulfonate) in about 500 mls. zenediazosulfonate was dissolved in one liter of water of water was treated with 38 grams of 1,3-di-o-tolylplus 20 mls. of glacial acetic acid. A little methanol was 5 guanidine in mls. of water and 100 mls. of acetic added. The material did not entirely dissolve and was acid. The product separated as a yellowish-brown mass, filtered. To the filtrate was added a solution of 24 grams weight 12 grams, decomposition point C. after of 1,3-di-o-tolyl guanidine in mls. of 50% acetic softening at 80 C. The structure is probably:
OCsHl O accrues Example VI! A filtered solution of 36.0 grams of N-benzyl-N-ethylp-aminobenzenediazonium chloride zinc chloride double salt was treated with a solution of 25.2 grams of sodium sulfite in 100 mls. of water. The yellowish-orange crystals of sodium N-benzyl-N-ethyl-p-aminobenzenediazosulfonate were collected, dissolved in 100 mls. of water and 5 mls. of acetic acid, treated with a warm solution of 35.8 grams of 1,3-di-o-tolylguanidine in about 100 mls.
of acetic acid, 50% by volume. The yellow crystalline product, after being filtered, washed and dried in vacuo, weighed 18.3 grams, a 33% yield, melted at l75-8 C. and was very sensitive to light. The probable formula is:
R N 3 ArNgBOsH.BN=O
wherein Ar is selected from the class consisting of aromatic radicals of the benzene and naphthalene series and heterocyclic radicals of the diphenyleneoxide and diphenylenesulfide series, R is selected from the class consisting of hydrogen and an aromatic radical of the benzene and naphthalene series, at least two R's being such an aromatic radical and at least one R being hydrogen.
2. A photosensitive compound soluble in organic solvents having the following formula:
om otmoOmaom-ot-zm-c 3. A photosensitive compound soluble in organic solvents having the following formula:
on em omoQ-aasmmmam-un-O cm 4. A photosensitive compound soluble in organic'solvents having the following formula:
OCH: 0cm cm 5. The process of producing photosensitive compounds soluble in organic solvents and having the following structural formula:
wherein Ar is selected from the class consisting of aromatic radicals of the benzene and naphthalene series and heterocyclic radicals of the diphenyleneoxide and diphenylenesulfide series and R is selected from the class consisting of hydrogen and an aromatic radical of the benzene and naphthalene series, at least two Rs being such an aromatic radical and at least one R being hydrogen, which comprises reacting an alkali metal arenediazosulfonate in an aqueous medium with the acetate of an arylguanidine of the following furrnula:
in which R is selected from the class consisting of hydrogen and an aromatic radical of the benzene and naphthalene series, at least two Rs being such an aromatic radical and at least one R being hydrogen.
6. The process as defined in claim 5, wherein the arenediazosulfonate is sodium p-ethoxybenzenediazosulfonate and the arylguanidine acetate is the acetate of 1,3-di-otolylguanidine.