JPH0254334B2 - - Google Patents

Description

[Detailed Description of the Invention] The present invention relates to the general formula (In the formula, both X ¹ and Y ¹ represent hydrogen or a methyl group, and either one may be SO ₃ H, and X ² and Y ² both represent hydrogen or together represents an ethylene group or a -SO ₂ - bridge, and Y represents an acetamido group substituted with chlorine, or a benzamide or unsubstituted phthalimide group optionally substituted with methyl, methoxy, ethoxy or chlorine). Regarding compounds. A group of compounds preferred in the present invention are of the formula (In the formula, Z represents chloroacetamide, dichloroacetamide, trichloroacetamide or benzamide, Z ¹ and Z ² both represent hydrogen, or either one represents SO ₃ H, and Z ³ and Z ⁴ both represent Both represent hydrogen or together represent ethylene or -SO ₂ - bridge). Also in connection with the present invention, the formula (wherein Z, ^Z2 , ^Z3 and ^Z4 have the same meanings as in formula (), X' has the same meaning as in formula (), Q is hydrogen, _C1 - _C4 alkyl , cyclohexyl,
C ₁ -C ₂ alkoxy, chlorine, bromine or SO ₃ H, provided that at most one of the groups Q and X ¹ represents SO ₃ H) may be mentioned as a reference. Compounds of formula () or () in which Z ³ and Z ⁴ represent hydrogen and Z represents chloroacetamide or benzamide are of particular industrial value. An advantageous method for preparing compounds of formula () is the general formula (wherein, X ¹ , X ² , Y ¹ and Y ² have the same meanings as in formula ()) is a compound of formula Y-CH ₂ -OH (), where Y is as in formula (). with the same meaning) and, if necessary, the product is then reacted with a sulfonating agent. Amidomethylation of () by () is Tscherniak-Einhorn (Tscherniak-Einhorn)
type reaction (Houben-Weyl XI/1 (1957);
795;Org.Reactions 14 (1, 65), 52 and
Synthesis 1970 , 49). A mixture of sulfuric acid and one or more lower fatty acids such as acetic acid or propionic acid serves as the reaction medium. The reaction is carried out at a temperature range of -10°C to +50°C, preferably 0 to 25°C. It must be said that it is truly surprising that under these reaction conditions the amidomethylated product of formula can be obtained in high yield and purity. This is because under standard conditions, ie concentrated sulfuric acid, this reaction does not proceed particularly selectively, leading to products which cannot be used industrially. It is also surprising that the more conventional methylol components such as methylolformamide or methylolacetamide do not react as smoothly as those of the formula. The starting compounds of formula () and () are known or can be obtained by known methods. Instead of the methylol compound of formula (), it is also advantageous to use a mixture of the corresponding amide Y--H with at least an equivalent amount of formaldehyde, preferably paraformaldehyde. Alternatively, it is also possible to use the corresponding nitriles, such as chloro-, dichloro-, trichloro- or trifluoro-acetonitrile or benzonitrile, instead of the primary amide Y-H. By the above method, 4,4'-bis-
It is also possible to obtain (phthalimidomethyl)-biphenyl in significantly high yields (93% of theory) and purity, which was previously available in Ukr.Khim.Zh.
26, 277 (1960), only 49 of the theory
%. Representative compounds of formula () containing sulfonic acid groups and/or -SO ₂ - bridges are generally sulfuric acid (free
SO ₃ containing 0-65%), chlorosulfonic acid, pyridine-N-sulfonic acid or by amidomethylation by reaction with a sulfonating agent such as SO ₃ . The reaction is carried out in the temperature range from -10<0>C to 130<0>C, generally preferably from 0 to 30<0>C, or preferably from 60 to 120<0>C in the case of compounds containing _-SO2- bridges. Amidomethyl compounds () which are not substituted at the 3-position and do not contain an SO ₃ H group and a -SO ₂ - bridge are generally
Reacts smoothly in 100% sulfuric acid to give the corresponding monosulfonic acid. On the contrary, surprisingly, the same compound gives the sulfone (X ² +Y ² =-SO ₂ -) in 20% oleum. The compounds of formula () are useful new intermediate products for making optical light volatiles, dyes and synthetic resins that are highly useful industrially. The first step in making optical light volatile agents or synthetic resins from novel intermediate products of formulas () to () is to hydrolyze this intermediate product to form the corresponding formula (In the formula, T represents hydrogen, -CH ₂ NH ₂ , SO ₃ H or group A, where A is C ₁ - C ₆ alkyl, trifluoromethyl, cyclohexyl, C ₁ - C ₄ alkoxy, chlorine, bromine or an aminomethyl compound representing fluorine, or an internal salt or acid salt of this aminomethyl compound, such as the hydrochloride, hydrobromide, hydrosulfate or hydroperchlorate.Hydrolysis is carried out under customary conditions. Below, a water-soluble mineral acid such as hydrochloric acid, hydrobromic acid, sulfuric acid or phosphoric acid, or an aqueous alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, preferably a water-soluble insoluble material such as ethylene glycol, is added. The phthalimidomethyl The compounds can be easily decomposed by hydrazine to the corresponding aminomethyl compounds of formula (). Compounds of formula () containing _-SO2 -bridges or sulfonic acid groups can also be decomposed by _-SO2 -bridges or It can be prepared starting from a compound that does not contain a sulfonic acid group and then using the sulfonating agent described above and applying the reaction conditions described above. Preferred representative compounds of formula () containing an _-SO2- bridge are ,formula (where n represents the number 0 or 1). Preferred representative compounds of the formula () that do not contain -SO ₂ - bridges but contain a sulfonic acid group are those of the formula (where X ¹ is hydrogen, methyl, chlorine or SO ₃ H
, Q ¹ is hydrogen, C ₁ - C ₄ alkyl, C ₁ - C ₂ alkoxy, chlorine, bromine, SO ₃ H or CH ₂ -NH ₃ A _o
, A _o represents an anion, Z ⁵ and Z ⁶ independently represent hydrogen or together represent ethylene, provided that at most one of the groups Q ¹ and X ¹ represents SO ₃ H ). Anion A _o means an equivalent of the usual acid anions such as chloride, sulfate, bisulfate, nitrate, phosphate, hydrogen phosphate, perchlorate, chlorozincate and acetate. But _Ao
is also SO ₃ group Q ¹ or X ¹ in the same molecule
It can also be represented by Although all of the compounds of formula () can be advantageously used in the synthesis of optical photovoltaic agents, certain types are used in other fields. Bifunctional compounds of formula (), which do not contain sulfo groups and where T stands for _-CH2 - _NH2 , are useful components for polyamides (U.S. Pat. No. 4,041,056);
It is also a useful component of anti-inflammatory and antipyretic agents (US Pat. No. 3,647,782). Contains no sulfo group,
Monopotent compounds of the formula (), in which T is _C1 - _C4 alkoxy, are direct precursors of compounds that reduce cholesterol and triglyceride levels (DE-OS 2500692). To obtain an optical photovoltaic agent, an aminomethyl compound of the formula can be used, for example, with nitrous acid or its C ₁ -C ₅
By reacting with an alkyl ester and a mineral acid by methods known per se (Houben-Weyl XI/2 (1958), 133-137), N ₂ is eliminated and the corresponding formula (In the formula, U represents hydrogen, -CH ₂ OH, SO ₃ H or a group A, where A and other groups have the same meanings as above.) A method known per se (Houben-Wey1,
/1 (1954) 177; Synthesis 1976, 88-89) under mild conditions to give the formula (In the formula, V is hydrogen, -CHO, SO ₃ H or group A
(wherein A and other groups have the same meanings as above) or the above compound is combined with hydrogen chloride or an inorganic acid chloride such as thionyl chloride, phosphorus trioxide or phosphorus pentachloride. A method known per se (Houben-Weyl /3
(1962) 830-837, 812-869, 899 and 905-911)
The corresponding reaction is given by the formula (wherein D represents hydrogen, -CH ₂ Cl, SO ₃ H or the group A, where A and the other groups have the same meanings as above, and sulfo is in each case in the form of an acid halide) the corresponding phosphorus-activated methyl compound (which may also be present) is then reacted with a reagent such as a trialkyl phosphite, an alkali metal dialkoxyphosphonate or triphenylphosphine. Generate a compound.
This compound of formula (XI) is, like the aldehyde of formula (
1794386, German Patent Publication No. 2201857, German Patent Publication No. 2209221, German Patent Publication No. 2262340, German Patent Publication No. 2262531,
Same No. 2262632, Same No. 2262633, Same No. 2241304,
Same No. 2453357, Same No. 2337845, Same No. 2700292,
No. 2841519, European Patent Publication No. 1991
and U.S. Pat. No. 3,907,904). Bischloromethyl compound of formula (XI) (D=
CH ₂ Cl) can also be converted to 4,4'-bis-(benzofuran)-2-yl- by 2 equivalents of salicylaldehyde.
Provides useful and important optical light volatiles of the biphenyl series (DE-A-2238734). The bischloromethyl compounds required as starting materials have hitherto been obtained on an industrial scale only by chloromethylation of biphenyl, with the formation of by-products which are harmful to health. Handling and removal of these by-products requires considerable equipment expense. The method according to the invention does not have such disadvantages. The preparation of aldehydes of formula () can also be prepared using formula ()
from the aminomethyl compounds of by other advantageous routes, such as Sommelet oxidation with hexamethylenetetramine in a weakly acidic medium (this method is described for example in J.Chem.Soc. 1953 , 1740-41); or oxidation with hydrogen peroxide in the presence of tungstate (this method is described in Chem.
Ber. 93 (1960) 133 and Houben-Weyl /4
(1957) 123-124, which leads to aldoximes), or the formula O=CR ¹ R ² (wherein R ¹ represents hydrogen or C ¹ -C ₈ alkyl, and R ² is C ₁ to _C8 alkyl, or ^R1 and
R ² together represent C ₄ - C ₈ alkylene) is condensed with a carbonyl compound of It can also be carried out by a method in which azomethine is separated under acidic conditions (this method is described in European Patent Publication No. 8323). Chloromethyl compounds of formula (XI) can also be prepared directly from the corresponding aminomethyl compounds of formula ()
It can also be advantageously prepared by reaction with nitrosyl chloride according to the method described in Houben-Weyl/3 (1962) 940. The chloromethyl compound of formula (XI) is obtained by converting a compound of formula () in which Y represents an optionally substituted benzamide into a compound represented by V.Braun reaction (Chem.
Ber. 87 (1904) 2678, 2812, 3210 and 3583;
Houben-Weyl /3 (1962) 92 and JACS 84
(1962) 769), it is particularly reasonably prepared in high yields by reaction with PCL ₅ or SOCl ₂ . This reaction is preferably carried out in an inert organic solvent such as chlorobenzene or o-dichlorobenzene at a temperature in the range from 60 DEG to 150 DEG C. with elimination of benzonitrile. Bromomethyl compounds analogous to the chloromethyl compounds of formula (XI) are represented by () as PBr ₃ , POBr ₃ or
React with PBr ₅ or Houben-Weyl /4
(1960) 455, or Houben-Weyl
4 (1960) 451 by reacting the benzamido-methyl compound () with PBr ₃ and bromine or PBr ₅ . In formula (), Y is chloro- or bromo-
By reacting a compound representing an acetamide group with an alkali metal cyanide, the formula (wherein X ¹ , X ² , Y ¹ and Y ² have the same meanings as in formula ()) can be provided. These novel dye precursors are capable of undergoing coupling and condensation, with 4,4'-biscyanoaceto-amidomethyl derivatives being preferred. The reaction between () and alkali metal cyanide is
polar water-miscible media such as methanol, ethanol, isopropanol, ethylene glycol or ethylene glycol monomethyl ether, preferably dipolar aprotic solvents such as dimethylformamide or dimethyl sulfoxide,
It is carried out at a temperature range of 10 to 80°C, preferably 30 to 60°C. It is worth noting that some of the secondary products described by formulas () and () have not been described in the literature to date. However, these are very suitable as gateway products for applications in the above-mentioned fields. In particular, examples thereof include sulfo groups and/or _-SO2 -bridges ( ^X2 + ^Y2 = _-SO2
-) is a compound of formula () or (). Thus, the provision of biphenyl compounds of formula () or related biphenyl compounds mentioned above and processes leading to these compounds according to the present invention opens up a rational path to these new important barrier products. Among these compounds, the formula (wherein M is -CH ₂ -NH ₂ (as a base or as an internal salt or acid addition salt), or -
CH=O, M ¹ and M ² independently represent hydrogen or together represent -SO ₂ -, m is 1 or 0 when M ¹ + M ² = -SO ₂ -. Compounds corresponding to (which can also be expressed as ) are of particular industrial importance. Characteristic examples of such secondary products of formula () are: As detailed above, these secondary products are obtained by acid hydrolysis (after reaction with a sulfonating agent) from the biphenyl compounds of formula () of the present invention to form the corresponding aminomethyl compounds and the required by oxidation with urotropin.
Easily obtained. Example 1 385 g of biphenyl was dissolved in 1.5 g of propionic acid at 30°C, and 0.9 g of concentrated sulfuric acid was dissolved in 10 to 10 g with strong cooling.
Add dropwise at 15°C. 514 g of chloroacetamide and 233 g of paraformaldehyde were added to the resulting suspension for 10 minutes.
Add at ~15°C. The reaction mixture is stirred at 15°C for 11 hours and left at 15-18°C without stirring for a further 20 hours. Then 3 kg of ice are added and the mixture is stirred for 1 hour at room temperature. The crystalline precipitate is passed through an acid-resistant filter, washed with 40 ml of water until neutral, and squeezed well. formula Approximately 1 kg of the compound is obtained as a wet press cake, which is advantageously further processed in raw form. If desired, the product was heated to 50°C under reduced pressure.
Can be dried with. Yield: colorless crystalline powder
820 g, sample recrystallized from glacial acetic acid has a melting point of 222 ~
224°C, m/e = 364 (M, dichloro). Examples 2-3 General formula The compound was prepared in the same manner. They are shown in the table below. [Table] Example 4 38.5g of biphenyl was mixed with 150ml of propionic acid at 35°C.
Dissolve in the water and add 90ml of concentrated sulfuric acid to the solution for 10~
Add dropwise at 15°C. 0.5 g of dichloroacetamide and 23.3 g of paraformaldehyde were added to the resulting suspension.
Add at 10-15℃. The reaction mixture is stirred at 15°C for 11 hours and left without stirring at 15-18°C for a further 20 hours. Then 300 g of ice are added and the mixture is stirred for 1 hour at room temperature. The crystalline precipitate is filtered through an acid-resistant filter, washed to neutrality with 0.5 of water and well pressed. After drying under reduced pressure at 50℃, the formula 97 g of the compound are obtained as a colorless crystalline powder. Melting point: 227-228℃ (recrystallized from glacial acetic acid; m/e
=432 (M, tetrachloro). Example 5 Using an equivalent amount of trichloroacetamide in place of dichloroacetamide in Example 4, the formula 114 g of the compound are obtained: m/e=500 (M, hexachloro). Similarly, if α-chloropropionamide or bromoacetamide is used instead of dichloroacetamide, 4,4′-(α-chloropropionyl-amidomethyl)-biphenyl, m/e=392
(M, dichloro) or 4,4'-(bromoacetamidomethyl)-biphenyl, m/e=454 (M)
is obtained. Example 6 308 g of biphenyl was dissolved in 1,750 ml of glacial acetic acid under heating, and 1,500 ml of concentrated sulfuric acid was dissolved under strong cooling.
Add dropwise at 20-25°C. Then 535g of benzamide
and 132 g of paraformaldehyde are added and the mixture is stirred at room temperature for 20 hours and poured out onto ice-water 10 g. After stirring the mixture for 2 hours, the crystalline precipitate is filtered off, washed to neutrality with water and dried under reduced pressure at 50°C. formula 840 g of the compound is obtained. Melting point: 247°C (recrystallized from glacial acetic acid); m/e = 420 (M ). Examples 7 to 15 Compounds of the following general formulas are prepared in a similar manner: [Table] Example 16 308 g of biphenyl is dissolved in 1,750 ml of glacial acetic acid with heating, and 1,300 ml of concentrated sulfuric acid is dissolved with strong cooling.
Add dropwise at 20-25°C. 789 g of N-methylol phthalimide are then added, the mixture is stirred at room temperature for 20 hours and 2.5 g of water are added dropwise at room temperature with strong cooling. After stirring the mixture for 1 hour, the crystalline precipitate is filtered off, washed to neutrality with water and dried under reduced pressure at 80°C. formula 878 g (93% of theory) of the compound are obtained. Melting point: 299°C (recrystallized from glacial acetic acid); m/e = 472 (M ). Example 17 (Reference Example) 38.5 g of biphenyl is dissolved in propionic acid 220 and the solution is cooled to 10°C. 30 ml of concentrated sulfuric acid are added dropwise at 10 DEG -15 DEG C. with strong cooling, and then 37.4 g of chloroacetamide and 12 g of paraformaldehyde are added to this solution. After stirring the reaction mixture at 15° C. for 20 hours, it is poured onto 1 portion of ice water, the crystalline precipitate is filtered off and washed to neutrality with water. The wet pressed cake is treated with toluene using a water separator to remove water.
Boil with 250 ml, thus forming a clear solution. After cooling the solution, filter the crystalline precipitate,
Wash with petroleum ether and dry under reduced pressure at 40°C. formula The compound is obtained. Melting point: 149-150℃; m/e=
259 (M, monochloro). By evaporating the solvent from the toluene mother liquor, 62% of the biphenyl used was recovered. Example 18 (Reference example) To 115 g of 4-methoxy-biphenyl in 2.5 g of propionic acid, 64.5 g of chloroacetamide and 29.5 g of paraformaldehyde were added, and the mixture was
Upon warming to 0.degree. C. a clear solution is formed. The solution is cooled to 20°C, 135 ml of concentrated sulfuric acid are added dropwise at 20-25°C with strong cooling, and the mixture is stirred for 5 hours at 20-25°C and then poured onto ice. The crystalline precipitate is filtered, washed to neutrality with water and dried under reduced pressure at 50°C. formula 164 g of the compound is obtained. Melting point: 132-133℃ (di-
sec.-recrystallized from butyl ether); m/e=289
(M, monochloro). Examples 19 to 27 (Reference column) Compounds shown below corresponding to the following general formula were produced in the same manner: [Table]
○＋

(M)
【table】
○＋

(M)
Example 28 (Reference example) 1/10 of the moist pressed cake of the compound () produced in Example 1 was added to 680 ml of dimethylformamide.
The suspension is stirred with 85 ml of 30% strength by volume sodium cyanide solution at 40-45 DEG C. for 4 hours, the mixture is poured onto ice water 4 and stirred. The crystalline precipitate is filtered, washed with water and dried under reduced pressure at 80°C. Yield: 78.5g of the following formula compound Melting point: 270-271℃ (from glacial acetic acid); m/e=346
(M). Example 29 60 g of the compound of formula (1) was placed in 600 g of 100% sulfuric acid,
It is introduced gradually at 5-20° C. with stirring and cooling, the mixture is stirred for 1 day at 20-25° C. and poured onto 1 kg of ice. After stirring the mixture for 1 hour, the crystalline precipitate is filtered off, washed with ice water and dried under reduced pressure at 60°C. formula 81.2 g of the compound is obtained. This can be purified by stirring with acetone. 1H-NMR ([ _D6 ]-DMSO/TMS); δ=4.12
(S; 4H, CH ₂ Cl), 4.30 (broad d, J = 6
Hz; 4H, - CH ₂ -NH-), 7.17 (d, J = 8Hz;
1H, H _a ), AA′BB′−signal (δ _A =7.50, δ _B =
7.17, J ₁ = 8Hz, J ₂ not resolved; 4H, H _a + H _d ),
7.50 (dd, J ₁ = 8Hz, J ₂ not resolved; 1H, H _b ),
7.85 (d, J=1.5Hz; 1H, H _C ) and 8.76 (t,
J=6Hz; 2H, NH ). Example 30 500 g of the compound of formula () prepared according to Example 1 and then extracted by stirring with glacial acetic acid and dried under reduced pressure at 80° C. are divided into small portions to give fuming sulfuric acid (20% free SO ₃ ). 2.6 Kg at 10-20° C., the mixture is stirred at room temperature for 18 hours and poured out onto ice. The crystalline precipitate is filtered, washed with water and optionally dried under vacuum at 60°C. formula 580 g of the compound is obtained. Melting point: 287℃ (decomposed) (from dimethylformamide) 1H-NMR ([D ₆ ]-DMSO/TMS): δ = 4.23
(s; 4H), 2CH ₂ Cl), 4.50 (d, J = 6Hz; 4H,
2CH ₂ NH), 7.71 (dd, J ₁ = 8Hz, J ₂ = 2Hz;
2H), 7.88 (d, J = 2Hz; 2H), 8.17 (d, J =
8Hz; 2H), and 8.92 (t, J = 6Hz; 2H, 2CH ₂
-NH- ). Example 31 Using the same weight part of compound (6) instead of compound (1),
Similarly, the expression 520 g of the compound is obtained. This compound is purified by boiling with ethylene glycol monomethyl ether. C ₂₈ H ₂₂ N ₂ SO ₄ (482.57) Calculated value C 69.69 Measured value C 69.5 H 4.60 H 4.8 N 5.81 N 5.8 S 6.64 S 6.8 Example 32 Sulfuric acid (100% concentration) was added to 50 g of the compound of formula (30) while stirring. ) in 250 g of fuming sulfuric acid (free
250 g of SO ₃ (65%) are added dropwise, the mixture is heated to 100° C. for 4 hours, poured onto 1.5 kg of ice and neutralized with concentrated sodium hydroxide solution. The crystalline precipitate is filtered through an acid-resistant filter, washed with 5% sodium chloride solution and dried under reduced pressure at 50°C. formula 48 g of the compound are obtained as a colorless, water-soluble crystalline powder. 1H-NMR ([ _D6 ]-DMSO/TMS): δ=4.20
(s; 4H, 2CH ₂ Cl), 4.45 (d, J=6Hz; 4H,
2-CH ₂ NH-), 7.66 (dd, J ₁ = 9Hz, J ₂ = 2
Hz; 1H, H _b ), 7.79 (d, J = 2H; 1H, H _a ),
AB-signal (δ _A = 8.19, δ _B = 7.79, J = 2Hz;
2H, H _d + H _e ), 8.92 (t, J=6Hz; 2H, −CH ₂
-NH-), and 9.26 (d, J = 9Hz; 1H, H _c ),
1H-NMR (D ₂ O/TMS): δ = 7.70 (dd, J ₁ = 8
Hz, J ₂ = 1.5Hz; 1H, H _b ), 7.84 (d, J = 1.5Hz;
1H, H _a ), AB-signal (δ _A = 8.23, δ _B = 7.97,
J = 1.5Hz; 2H, H _d + H _e ), and 8.87 (d, J = 8
Hz; 1H, _Hc ). Example 33 (Reference example) The entire amount of the wet press cake of compound (1) prepared according to Example 1 was introduced into a mixture of 1.6 ml of glacial acetic acid and 1.6 ml of concentrated hydrochloric acid, and the mixture was heated to 85° C. for 18 hours. do. After cooling to room temperature, the mixture is stirred at 20° C. for 20 hours. The crystalline precipitate is filtered through an acid-resistant filter and washed quickly with 2 portions of ethanol. Dry under reduced pressure at 80°C to obtain 506 g of a compound of the following formula. 1H-NMR (D ₂ O/TMS): δ = 4.30 (s; 4H),
4.82 (s; HDD, _-NH3 ) and AA'BB'-signal ( _δA = 7.85, _δB = 7.60, _J1 = 8.5Hz, _J2 not resolved; 8 aromatic H). m/e (base) = 212 (M ). Examples 34 to 35 (Reference Example) Compounds of formulas (2) to (5) are hydrolyzed in the same manner as above. [Table] Example 36 (Reference example) 100 g of the compound of formula (29) was mixed with 400 ml of concentrated hydrochloric acid and glacial acetic acid.
Heat to boiling point under reflux for 2 hours in a mixture with 400 ml. The solvent is evaporated under the vacuum of a water pump.
After cooling the residue to 20℃, add 500ml of acetone.
and stir for 2 hours. 72 g of a compound of the following formula are obtained as a colorless, crystalline powder that is easily soluble in water. 1H-NMR ([ _D6 ]-DMSO/TMS): δ=4.25
(S; 2H, CH ₂ ), 4.30 (s; 2H, CH ₂ ), 7.33
(d, J=8Hz; 1H, H _a ), 7.52 (s; 4H, 2H _d
+2H _e ), 7.68 (dd, J ₁ = 8Hz, J ₂ = 2Hz, 1H,
H _b ) and 8.16 (d, J=2Hz; 1H, H _c ). Example 37 (Reference example) 500 g of the compound of formula (30) was mixed with 2.5 g of concentrated hydrochloric acid and glacial acetic acid.
Warm to boiling point under reflux for 4 hours in a mixture with 2.5 and then cool the mixture. The crystalline precipitate is filtered, washed with ethanol and dried under vacuum at 50°C.
335 g of a compound of the following formula are obtained as a colorless crystalline powder which is readily soluble in water. 1H-NMR ([ _D6 ]-DMSO/TMS): δ=4.23
(s; 4H, 2CH ₂ ), 8.0 (dd, J ₁ = 8Hz; J ₂ = 2
Hz; 2H), 8.21 (d, J not resolved; 2H), 8.28
(d, J=8Hz; 2H), and 8.85(s; 6H, 2N
_H3 ). The compound of formula (32) is hydrolyzed in a similar manner to obtain the corresponding bisaminomethyl compound of the following formula. 1H-NMR ([ _D6 ]-DMSO/TMS): δ=4.16
(s; 2H, CH ₂ ), 4.25 (s; 2H, CH ₂ ), 7.92
(dd, J ₁ = 8Hz; J ₂ = 1.5Hz; 1H, H _b ), 8.12 (d,
J=1.5Hz; 1H, H _a ), AB− signal (δ _A =
8.37, δ _B = 8.16, J = 2Hz; 2H, H _d + H _e ), 8.68
(Broad S; 2NH ₃ ), and 9.35 (d, J = 8Hz;
1H, _Hc ). Example 38 (Reference Example) The entire amount of the compound of formula (18) obtained as a moist pressed cake in Example 18 was mixed with 825 ml of glacial acetic acid and concentrated hydrochloric acid.
Warm to 85 °C for 18 hours in a mixture with 275 ml. The solvent was then evaporated under reduced pressure and the residue was dissolved in acetone.
Rub with ml. Filter the crystalline precipitate, wash with acetone, and incubate at 50°C.
Dry under reduced pressure. formula 105 g of the compound is obtained. m/e (as base)=
213. Compounds (19), (20), (21), (22), (25), (
26)
and (27) are hydrolyzed in a similar manner to obtain the corresponding acid aminomethyl compound. Example 39 (Reference Example) Product of formula (33) made according to Example 33
142.5 g are introduced into 690 g of 100% strength sulfuric acid at 5 DEG to 15 DEG C., with hydrogen chloride escaping. The solution was stirred for 1 hour, then 690 g of oleum (20% free SO ₃ ) was added dropwise with cooling at 10-20°C,
The solution is left at room temperature for 3 days and drained onto 3 kg of ice. The crystalline precipitate is filtered through an acid-resistant filter, washed with ice water and dried under reduced pressure at 80°C. 116 g of a compound of the following formula are obtained. Melting point: 327℃ (decomposition) 1H-NMR spectrum ([D ₆ ]-DMSO): δ=
4.28 (s; 4H, CH ₂ ), 8.06 (dd, J ₁ = 1Hz; 2H),
8.23 (d, J = 1 Hz; 2H), 8.43 (d, J = 8.5 Hz;
2H) and 8.45 (broad s; 6H, _-NH3 ). Example 40 (Reference Example) A method similar to that described above is carried out to disulfonate the compound from Example 34. However, the mixture is allowed to stand for 20 hours (instead of 3 days) before being processed at room temperature.
A compound of the following formula is obtained as a colorless crystalline powder with a melting point of over 300°C (decomposition). Example 41 (Reference Example) 170 g of the compound of formula (33) is dissolved in 3.6 g of water at 85°C, and a total of 216 g of sodium nitrite is gradually added while stirring. 240 g of concentrated hydrochloric acid are then added dropwise below the surface of the solution, still at 85° C., over the course of 1 hour. After the mixture has cooled, the crystalline precipitate is filtered, washed with water, and using a water separator to remove the water, the butyl acetate 1
Boil with. The solution is strongly cooled after filtering out undissolved material. The crystalline precipitate is filtered, washed with petroleum ether and dried under vacuum at 50°C. Compound of formula
Obtain 100.5g. Melting point: 188°C; m/e = 214 (M) Example 42 (Reference example) 53.5 g of the compound of formula (41) was suspended in 200 ml of toluene, 75 g of thionyl chloride was added dropwise with stirring, and the mixture was Heat to 40°C for 2 hours. The solvent is then distilled off along with excess thionyl chloride. 63 g of a compound of the following formula is obtained as a residue. m/e=250 (M, dichloro) This compound is further processed without intermediate isolation as follows: A 4,4' as described in German Patent Application No. 1794386, column 18 -bis-(chloromethyl)-
Biphenyl (42) was converted to 4,4'-bis-(dimethoxy-phosphonomethyl)-biphenyl by reaction with trimethylphosphite, and this product was subjected to a condensation reaction with benzaldehyde-2-sulfonic acid to 4, 4'-bis-(2-sulfostyryl)-biphenyl. It is an optical light volatile agent that can be applied to cotton and polyamide from wash liquors. B According to the description in German Patent Publication No. 2238734, 4,4'-bis-(chloromethyl)-biphenyl (42) is reacted with salicylaldehyde to produce 4,4'-bis-(benzo[b]furan-2 -yl)-biphenyl and this product is further reacted with fuming sulfuric acid to give the corresponding mixture of tri- and tetrasulfonic acids. This mixture can also be used for optically brightening cotton and polyamides. Example 43 (Reference example) 150 g of the compound of formula (6) was mixed with 900 g of O-dichlorobenzene.
164.3 g of phosphorus pentachloride are added and the mixture is heated to 110-115° C. for 1.5 hours, during which time some of the POCl ₃ formed is distilled off. The remaining POCl ₃ , together with the solvent and the generated benzonitrile, is then distilled off under the reduced pressure of a water jet pump (bath temperature
(up to 130℃). 98g of the residue was dissolved in methylcyclohexane.
Recrystallize from 450ml. 78 g of the compound of formula (42) are obtained. A similar result can be obtained as follows. _PCl5
Use 115 ml of thionyl chloride instead of
Heat for 1.5 h at °C, distill off _excess SOCl,
The mixture is heated to 150° C. for a further 10 hours, the solvent and benzonitrile are distilled off under reduced pressure, and the residue is recrystallized as described above. When compounds of formulas (7) to (15) are used in place of compound (6), 4,4'-
(Bischloromethyl)-biphenyl (42) is obtained. Example 44 (Reference Example) To 50.2 g of the compound of formula (42) in 400 ml of dimethylformamide are added 70 ml of a 30% strength NaCN solution at 40°C, and the mixture is stirred at 40-45°C for 2 hours. After pouring the mixture onto ice water 2, the crystalline precipitate is filtered, washed with water and dried under reduced pressure at 50°C. Compound of formula
Get 38g. Melting point: 168°C; m/e=232 (M ). Example 45 (Reference example) 373 g of the compound of formula (33) (700 g as a moist pressed cake) and 730 g of urotropin were mixed with 1.3 g of glacial acetic acid.
and 1.3 of water and heated to boiling point under reflux for 2 hours, and the mixture is cooled. The crystalline precipitate is filtered, washed with water and dried under reduced pressure at 50°C. 252 g of a compound of the following formula are obtained as a colorless crystalline powder. Melting point: 139°C (from di-n-butyl ether);
m/e=210 (M). The mother liquor can advantageously be reused in subsequent batches, always requiring only half the amount of urotropin originally used. 4,4'-distyryl-
Useful optical light volatiles of the biphenyl series can be prepared from compound (45) according to German Patent Application No. 1794386 and German Patent Application No. 3001876, and useful dyes for paper can also be prepared. It can be manufactured according to German Patent Application No. 2901845. Examples 46-47 (Reference Example) Corresponding dialdehydes of the following formulas are produced from compounds (34) and (35) in the same manner as above. Example 48 (Reference example) 300 g of the compound of formula (37) and 250 g of urotropin
is heated to boiling temperature under reflux for 3 hours in a mixture of 1.5 Kg of glacial acetic acid and 70 ml of water, and the mixture is cooled. Filter the formed precipitate and wash with methanol,
Dry under reduced pressure at 50℃. 153 g of a compound of the following formula are obtained as a colorless crystalline powder. Melting point: 302°C; m/e = 272 (M) (from dimethylformamide) Example 49 (Reference example) Similarly, but without sulfuric acid treatment,
Compound (37a) is represented by the formula is converted to a dialdehyde, which is isolated after precipitation with isopropanol. Example 50 6.6 g of compound of formula (36) and 5.6 g of urotropin
was heated to boiling temperature under reflux in 90 ml of glacial acetic acid for 3 hours, cooled to 30°C, 6.2 g of p-nitrophenylhydrazine were added, the mixture was stirred at 30-40°C for 30 minutes, and then heated to 20°C. Cooling. The crystalline precipitate is filtered, washed with methanol and dried under vacuum at 40°C. The following formula 8.8 g of the compound are obtained as bis-p-nitrophenylhydrazone (orange crystalline powder, melting point: 300 DEG C.). Example 51 (Reference example) 200 g of the compound of formula () was added to fuming sulfuric acid (free
1 Kg of SO ₃ 20%) is introduced at room temperature with cooling stirring and the mixture is stirred at room temperature for 18 hours, thereby forming the compound of formula (30). This compound,
Without intermediate isolation, hydrolysis gives the compound of formula (37) (in this case _2HSO4 instead of 2Cl).
). This hydrolysis requires 430ml of water
was added dropwise with strong cooling and stirring, and the mixture was brought to 100°C.
A method was used in which the mixture was heated for 8 hours and then cooled. Filter the crystalline precipitate with 8% sodium chloride solution 600
ml and dry under reduced pressure at 60°C. 128 g of the compound of formula (37) are obtained as the 2HSO ₄ salt. Example 52 (Reference example) 200 g of the compound of formula (1) was added to fuming sulfuric acid (20% free SO ₃ ).
1 Kg at room temperature with cooling and stirring, and the mixture is stirred at room temperature for 18 hours, during which time a compound of formula (30) is formed. This compound can be sulfonated without intermediate isolation to form the formula (32).
(free sulfonic acid rather than the Na salt), and this product is then hydrolyzed to give compound (37a) (HSO ₄ salt) without intermediate isolation. This hydrolysis is performed using oleum (free SO ₃ 65
%) 1Kg was added dropwise, the mixture was heated to 80°C for 6 hours, and diluted with 1.6% water while cooling and stirring.
A method was used in which the mixture was heated to 100°C for 8 hours and then cooled. The crystalline precipitate is filtered off, washed with 8% sodium chloride solution and dried under reduced pressure at 60°C. 136 g of compound of formula (37a) are obtained as HSO ₄ salt.

Claims (1)

[Claims] 1. General formula (In the formula, both X ¹ and Y ¹ represent hydrogen or a methyl group, one of which may be SO ₃ H, and X ² and Y ² both represent hydrogen or together represents an ethylene group or an -SO ₂ - bridge, and Y represents an acetamido group substituted with chlorine, or a benzamide or unsubstituted phthalimide group optionally substituted with methyl, methoxy, ethoxy or chlorine). Compound. 2 General formula (In the formula, both X ¹ and Y ¹ represent hydrogen or a methyl group, one of which may be SO ₃ H, and X ² and Y ² both represent hydrogen or together. represents an ethylene group or an -SO ₂ - bridge, and Y represents an acetamido group substituted with chlorine, or a benzamide or unsubstituted phthalimide group optionally substituted with methyl, methoxy, ethoxy or chlorine). A method for producing a compound, wherein the general formula (In the formula, X ¹ , X ² , Y ¹ and Y ² have the _same meanings as above) A method characterized by subjecting the compound to a dehydration condensation reaction with 2 equivalents of the compound of 3. The method according to claim 2, characterized in that the amidomethylation is carried out in a mixture of sulfuric acid and lower fatty acids at a temperature range of -10°C to +50°C. 4 General formula (In the formula, both X ¹ and Y ¹ represent hydrogen or a methyl group, one of which may be SO ₃ H, and X ² and Y ² both represent hydrogen or together Represents an ethylene group or -SO ₂ - bridge, provided that SO ₃ H and -
at least one SO ₂ -bridge is present, Y represents an acetamido group substituted with chlorine, or a benzamide or unsubstituted phthalimide group optionally substituted with methyl, methoxy, ethoxy or chlorine). A method for producing a compound, wherein the general formula (In the formula, both X ¹ and Y ¹ represent hydrogen or a methyl group, and X ² and Y ² both represent hydrogen.) A compound of the general formula Y-CH ₂ -O-H (in the formula, Y has the same meaning as above) and the product is then subjected to a dehydration condensation reaction with a sulfonating agent selected from sulfuric acid, chlorosulfonic acid, pyridine-N-sulfonic acid and SO ³ A method characterized by causing a reaction. 5 General formula (In the formula, both X ¹ and Y ¹ represent hydrogen or a methyl group, one of which may be SO ₃ H, and X ² and Y ² both represent hydrogen or together represents an ethylene group or an -SO ₂ - bridge, and Y represents an acetamido group substituted with chlorine, or a benzamide or unsubstituted phthalimide group optionally substituted with methyl, methoxy, ethoxy or chlorine). A method for producing a compound, wherein the general formula (wherein X ¹ , X ² , Y ¹ and Y ² have the same meanings as above) is combined with at least a compound of the general formula A method characterized by subjecting the mixture to a dehydration condensation reaction with two equivalents of formaldehyde. 6 General formula (In the formula, both X ¹ and Y ¹ represent hydrogen or a methyl group, and either one may be SO ₃ H, and X ² and Y ² both represent hydrogen or together Represents an ethylene group or -SO ₂ - bridge, provided that SO ₃ H and -
at least one SO ₂ -bridge is present, Y represents an acetamido group substituted with chlorine, or a benzamide or unsubstituted phthalimide group optionally substituted with methyl, methoxy, ethoxy or chlorine). A method for producing a compound, wherein the general formula (In the formula, both X ¹ and Y ¹ represent hydrogen or a methyl group, and X ² and Y ² both represent hydrogen.) A compound of the general formula Y-H (wherein, Y has the same meaning as above) and at least an equivalent amount of formaldehyde, and the product is then subjected to a dehydration condensation reaction with a mixture of sulfuric acid, chlorosulfonic acid, pyridine-N-sulfonic acid and SO ₃ A method characterized by reacting with a sulfonating agent.