JPS60155185A - Tetraaryl boron-ammonium complex - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (R1 is H, halogen or lower alkyl; R2 is halogen, lower alkyl or lower alkenyl; R3 is heterocyclic amine). EXAMPLE:Tetra(4-chlorophenyl)boron-pyridinium complex. USE:An antiseptic and antimold agent for non-medical use. It is chemically stable, exhibits sufficient effect in acidic and alkaline ranges, and is resistant to precipitation and discoloration even in the presence of metallic salts. PREPARATION:The objective compound can be prepared by (1) reacting the aryl magnesium halide of formula II with the diethyl ether complex of boron trifluoride, (2) reacting the product with a sodium source, and (3) reacting the resultant tetraaryl boron sodium [e.g. tetra(4-chlorophenyl)boron Na] with the heterocyclic amine hydrogen halide of formula IV (e.g. pyridine hydrochloride).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to tetraaryldron-ammonium complexes as novel compounds and their use as preservatives and fungicides.

More specifically, the first invention is based on the general formula +1+ (wherein,
R1 represents a hydrogen atom, a halogen atom, or a lower alkyl group, R2 represents a )-rogen atom, a lower alkyl group, or a lower alkenyl group, and "3 represents a heterocyclic amine."
A tetraaryldron-ammonium complex represented by n is provided.

Further, the second aspect of the present invention is a preservative and fungicide, characterized in that the entire active ingredient is a tetraarylumilon-ammonium complex represented by the general formula (1). This is what we provide.

Conventionally, as an aryl zero/compound, general formula (II) (
In the formula, X represents a potassium atom, an ammonium group, or a quaternized organic nitrogen group, and the organic nitrogen group may further form a nitrogen atom-containing heterocycle. Boron compounds (Tokukosho! Boots No. 3 Fufu publication number) and triphenylboron compounds represented by the general formula (in the formula, Y is a hydrogen atom, a halogen atom, or a lower alkyl group) (
US Pat. However, it is not known that these are effective as industrial preservatives and fungicides.1. Not yet.

The present inventors have conducted extensive research into the use of phenylboron compounds as preservatives and fungicides. As a result, a novel tetraarylporone represented by the general formula (1)
Does ammonium lead r4- have excellent antibacterial properties against molds such as Aspergillus, Penicillium, Rhizopus and Fusarium, bacteria such as Nogtilus and Pseudomonas, and fungi? To have? Headline: Is it useful as a non-medical bactericidal and fungicide, especially as an industrial preservative and fungicide? These findings led to the creation of the compound of the present invention.

The tetraaryl zero ammonium complex of the present invention is
[It is chemically stable, exhibits sufficient bactericidal and antifungal effects in acidic and alkaline areas, does not cause precipitation or coloring even when various metal salts are present, and is suitable for plastics. It is advantageous in practical terms as a sterilizing, disinfecting, preservative, and fungicidal agent because it can also be blended with other substances.

In the compound of the present invention of general formula fl), when 1 and 2 are atoms, it is preferably bromine, chlorine or fluorine, and 1 and R2 are lower alkyl groups having carbon number/~t. When R2 is a linear methyl group, ethyl group, propyl group, inpropyl group, butyl group, or isodityl group, and when R2 is a lower alknyl group having -2 to B carbon atoms, it is an allyl group or a methylallyl group. is preferable. It, which represents a heterocyclic amine, can be S (', 1'd), and is preferably pyridine, imidazole, or methylimidazole. (几3
・I() is in the form of a 9th class 1-hinobutylene or ammonium group, and is preferably in the form of pyridinium, imidazolium or methylimidazolium.

Preferred examples of the tetraphenylzeron-ammonium complex of the present invention are shown in Table 1. i, r The "ifi number" shown in Table 1 is also referred to in the Examples and Test Examples in this IJJ Hosho.

General formula (11) Kinye aArFS@-monoha, general formula (■)
tetraarylzolo/·sodium and the hydrogen halide salt of the heterocyclic amine of general formula (V)? It can be produced according to the following reaction formula.

(IV) (V) (1) (wherein, X represents a halogen atom, R,, R2, 几3
has the same meaning as Ar1) The method for producing the compound of the present invention will be explained in detail below.

First, but-2aryl i? of the general formula (R') used as a raw material in the production of the compound of the present invention? Synthesis for o:/a Natolic is performed as follows7'L.

First, in general formula (IV), 几! halogenated arylmagnesium at a cumolar ratio or a slight excess of which R and are expressed by the same basic mean (however, 1+X has the same meaning as above), or the formula, (◇-L+'''c艮wa几1. In a diethyl ether or tetrahydrofuran bath solution containing aryl lithium in a 9 molar ratio or diperfII amount, a diethyl ether complex of trifluoroboron in a 7 molar ratio is added as is or in a solvent such as toluene. The ill solution diluted with R is added dropwise under stirring and cooling, and then reacted under reflux conditions for 7 hours.Then, while cooling the reaction solution and stirring, add excess common salt, charcoal 62 soda,
Add a water bath solution such as sodium hydroxide dropwise. After the completion of the reaction, the upper organic layer is collected and the bath medium is distilled off to obtain white crystals, which are then washed with a non-polar solvent such as toluene and dried to obtain the desired general formula. The tetraaryl sodium salt represented by (IV) is obtained as white crystals. What if Sei MJ? If hair is required,
This white crystal may be recrystallized using a lower alkanol solvent such as ethanol or isozorobyl alcohol.

Furthermore, in the general formula (IV), suke and 几2 are different groups r
To synthesize the asymmetric tetraarylporone compound shown below, first use the same method as described in Section 6iJ to prepare a halogenated arylmagnesium or aryllithium compound. After reacting with boron trisulfide, the reaction solution gives the Ronke 1>13 force...
Or arylmagnesium halide or ←1, the initial force of the reaction between aryllithium and trifluoroboron, etc.
The 1-1 substituent (11,,) on the aryl group of triarylboron after forming triaryl by dividing the molar ratio of the reactants kE&m by 3:/ is 14; J: I:,j %p group (几2) 〒Aryl group (=(ΣriH, 8 people, an asymmetric tetraarylboron is synthesized t], ru.

Sodium tetraarylborone of the general formula (IV) obtained in this way, hydrogen halide salt of a heterocyclic amine of the general formula (■), lower alkanols such as methanol, ethanol, and isopropyl alcohol, and ketones such as acetone , dissolved in an inert polar medium such as water,
/ At a temperature of 0-40 ℃? The reaction is completed by simply mixing and stirring for 0 minutes to λ time. Is the reaction solvent the same as above? They may be used alone or in combination. In addition, if the reaction product is precipitated in a solvent as a crystal, it can be separated separately, but usually it is not a solvent. After distilling off and concentrating, the crystals are separated by kF, washed with water to remove inorganic salts, and dried to form a highly pure complex. obtain. The general formula thus obtained (
The tetraaryl 73-ammonium complex of 1) can be further purified by recrystallization with a medium such as methanol, ethanol, chloroform, or dimethylformamide, if necessary.

Next, we will explain the method for producing sodium tetraarylpolone, which is a raw material for the compound of the present invention, as a reference example. This will be explained in detail.

Reference example/ Ato(<7-chloro-phenyl) boron.
A solution of 11 cu chlorophenylmagnesium chloride (hecomoles) in tetrahydrofuran (ZOOme) 'x,
3.3. & f(
A toluene solution of 0,2j mol) was cooled in a water bath, and 10 to .3
Pour the reaction mixture at 0°C under reflux condition f1.
7 JII was heated.

After the reaction was completed, 200 ml of saturated sodium carbonate solution (kg) was added dropwise to the cooling iron of the reaction e. When the Takeiso layer is dispersed and the Wi medium is distilled off, white crystals are formed.
It's L. Toluyev, 300m1'? After adding 1°C, the crystals were peeled off and separated by σ, washed twice with 700 ml of toluene, and dried. (Yield %) was obtained.

Next, how to produce inventive behavior? LOL I'll explain it in detail as I'm busy with examples.

Real IM ff'J/Synthesis of ato2(4t-chlorophenyl)zerone-biricinium complex (f-compound JK;j),! ; In a 00 ml flask, add tetra(q-chloro1-1-phenyl)phoron')'ym;zy;
of (o, o, 5 mol) r methanol, dissolved in 200- and added, and 7Lf7C pyridine hydrochloride, dissolved in 60 ml methanol,! ;,3 F (0,0,!3-
Mol)? It was added dropwise while stirring. Trowel that has finished flowing down, 7
Reaction, continuing stirring for an hour? Completed it. Then the solvent in the reaction solution? The mixture was distilled off, and the precipitated crystals were dissolved by adding 00 ml of water to separate the crystals. and,
When this crystalline ligature is further washed with water and dried, the melting point becomes /3゛7~
/, 2a, 9? of the title as white crystals at 7°C.
(Yield: 9 pieces, 65 inches).

The original 8 analysis values are as follows.

Measured value Calculation 1 direct Olke, 7% 2 Da, 7% He, /y; y, /q and real ti:l I; !;)
Synthesis of pyridine hydrochloride instead of pyridine hydrochloride? Example 47 (conduct 7 reaction operations, l', iH point/j7
~// of the title compound as white crystals at 1 °C, 2 to OV
(1g% in yield)? Obtained.

The elemental analysis value is υ(noto2I-;-D'c).

i+111 constant 11 reduced value attt, t96 4 pieces, 9C 1-(+,, 2% q, 7% % IJili 51J,? But7(lI-fluorophenyl)boron-2-methylimidazolium (1)
Synthesis of body (ratio @ substance) j, ・g) 10 Add tetra(lI-
(fluorophenyl)
(0.07 mol) in ethanol leg 0-) After finishing 9 sips, I added ethanol to Jl, 2o-&t-1B, no-methylimidazole hydrochloride/,,! f (0,0
(1 mol) was added dropwise while stirring. After the dripping is finished/
Stirring was continued for an hour to complete the reaction. After that, all the solvent in the reaction solution was distilled off, and tOml of water was added to the precipitated crystals. In addition, I loosened it and lost the crystal. And this crystal? After further washing with water 7 times and drying, the melting point becomes 20. S~, 32 (yield'?o1.2) of the title compound as white crystals at 207°C.
'X) r i4I ta.

The elemental analysis values are as follows.

61 fixed value Needle gamma value 0 70,! ;% 70.9% 11. 5. oXl/, q93 Actual 911 Synthesis of gudetodi(gufluorophenyl)borono-methylimidazolium complex (compound 15 g) Impropyl alcohol 'x <t L for the reaction solvent,
Example,,? fC operation early? The melting point is 2 c)
j ~, 4 of the Yasui compound Qyy as white crystals at 207 °C
'Jp (yield λ-9'/+6) was obtained.

Elemental analysis 1m is as follows.

Foot measurement value Elbow'JL value 0 7.7. g% Ta3. ri9σ Hda, 79C-tei, 7% 'Ablf5'IJ-! i Tet, Nia (Hiro-methylphenyl) yfron-pyridinium complex (compound i;
Synthesis of i),! ; 00 tn No. 1 II; Put tetra (
Goomethylphenyl) holon sodium/'? ,Y
r (0,0,3 mol) ligated tetrahydrofy 7.2
o 01. , / to rU R'l (/to, to this, pyridine'I OW (0,0,!; mol) and to this /l/ fii: (7) tM b・l water k 7J11
Add 1 drop of water while stirring. Hereinafter, the same process as sushi rule/ will be carried out to give a white color with a melting point of /83~/J'J-℃. jj' f (9/
, 39) k4ri yv.

The elemental analysis values are as follows.

i11'l 511 area B1 stitch value a it, zaXl? 7.0% H7, 5+6 7. ．． 596 Actual Synthesis of phenyl-(4-alinoliphenylboron-λ-methylimidazolium (1) (f-hypolymerate ap) using 7-ton as a medium) When 9IJ 3 and recycled nitriphenyl-(4-allyl)phenylboron sodium and no-methylimidazole hydrochloride were reacted, white crystals with a melting point of 13~2.3J°C were obtained in Table 4. :3 (-2c of arsenic compound, of (yield q, 3.
796>? Obtained.

The elemental analysis value is 9 as shown below.

Measurement Asahi Calculated value 0F evening, '9F; g Q, J
Compound B1 of the tetraarylboron-ammonium complex of qrJ of the general formula (1) was also found up to 4.

When carrying out this study, 82! of the compounds of the present invention as described above! How can the tetraarylboron-ammonium complex of the present invention be used to efficiently express the antiseptic and antifungal effect? Emulsions, flowable agents (sols),
VCHJ agents such as hydrating powders and liquid agents may be used in the same way as general antiseptic and fungicides, and are not limited to any special usage. Further, the tetraarylboron-ammonium complex of the present invention can be used by appropriately selecting its concentration depending on the object of antiseptic and fungal protection.

(11) of the present invention can be mixed or used in combination with other known mulberry preservatives and fungicides. For example, the chemical names include zinc diethylthiol carbamate, tetramethylthiurano, disulfide, tetrachloroinphthalonitrile 1.2-('%-thiazoryl)kinzimitazole, methylpenzimitazole carpame-1.
, p'lachlorphenol, cudetrahexylphenol, no?chloromekoxy17nol, bis(nopyridylthio-/-opysil?), /, +-chlorphenyl-3-iotofuronoξgylpolmar, etc. To be suspended or limited to these examples: I,
do not have. The preservative and fungicidal agent of the present invention can also be used in combination with or in combination with an insecticidal compound for the purpose of preservative and insecticidal (or insect repellent) trays.

υζ is specifically illustrated by Examples of formulations of industrial IH antiseptic molds of the compounds of the present invention.

Fruit & 34 Example 7 (Irrigation agent) 1 compound Aδ/OErVs, lauryl sulfate 761 to 1/-73 parts? Evenly spread the active ingredients? , an irrigation agent containing 20%? obtain.

Misuichi 1flJza (70 apples) Compound A, 20 parts of the compound, 2 parts of lauryl sulfate, 2 parts of xanthan gum and hydroxyglopyllose/H1 - Mix uniformly and add the active ingredient y (,2
A flowable agent containing 0% is obtained.

Fruit mountain side 9 (emulsion) Compound//compound/part, dimethyl nulphoxod 77
Miyako, 50 parts of tetrahydrofuran and norbol goo
k (trade name of emulsifier manufactured by Tohohigakko Awa Co., Ltd.), 2 parts? By uniformly rtying emulsion 2 containing 5 effective molecules/%.

Next, a method for using the tetraarylporone-ammonium complex of the present invention as a preservative and fungicide will be described with reference to test examples.

Test fl/ Antibacterial test against various fungi The test was carried out by the agar smear method (Ga V method). That is, among the t'+'j of each forest known as t'l degrading bacteria for industrial materials, potato decoction culture J1 (1 (pHj, za)) and &l!l Ci □For 1, add sterile water to each test bacterium cultured in broth astonishment medium (pH 7,0) in advance on bamboo slant medium. Then, the cells were cultured for 9 hours at a temperature of +/-2°C on the 11'H medium of T1. k tiL'lbe, zosai1.yosi r3
The minimum amount of citrus agent in the medium that inhibits the growth of J.
'! +! 4: (minimum growth β11 stop 1lW8 degrees 1・p
I asked for the river. The result is the second R's, ・υ.

Table 2 Inhibition Productivity (ppm) 3 people 7g9/l // >50 >, 5 to l >,! ;0>, fO30>30
307, s >, so > so >, so so >
6-0/3! ;0 >JO! 0 /, 5 /, S > J
O/Jj, SO/, 5. 30 30>60 /j/
3 >! ;0 /,,S ('-/,,S 30'')
, 50 >Jo, 5. 30/J/J, S 30
．． 50/, 3 J, 5/,! 6 7.5 /j
"J SO/, 3 /j' 7.5 AO/6, S s
o /, s s /s >, so /s/J , 50
/J , S /J”: $0 /,!;/,,5 j
J /, j A' /j jO,, S J /,, S
,5/,,! ;,5'0/,,SO,,S-,3
/, J /, J' j 3'0 /, 'meo >, so
,so so >so meO>500,,S j j
/,,S J"'>30 7.S>,so>so
>, 3o >so Σ0 >, 50 >60, S-0>
60 >30 >30 >, 50 >, SO'>, 30
0,. 3- j /,, S /,, 5 j,! ;0
/, J”';so >so, <-o i,s Σo
>so >, s.

,5 >,50 ,SO/,5/,! ; ”'),,
50 /J＞, so ＞, so so so 〉so
'>sO>60/, S>30 7.5. 5.S.O.
>JOA-07,A;,5'/,evening/,j,3
;、!;OJl:・(Experiment Example) Emulsion Paint Antifungal Effect Test The irrigation agent prepared in accordance with Example 7 was added so that the active ingredient was enough for the emulsion additive, and wood chips and 01 paper were added. The mold resistance test was carried out in accordance with JIS Z, Z'?//-7 paint test.For wood chips,
After culturing, 3rd hole removal, 7th hole removal, 8th plating, and natural preservation (,
27℃, 6th +11ij U), 0 after sunset
), '7'El"R1℃nitsui"C1':1. ,
3 days after applying?・、7th (sword after 2nd and /Q-8) Binoshiro raw grade, below 21′・quasi-yoshi-toned IELrC
6.The results are as shown in ESS Table 3 and Table 9.

Sword ＼ generation old mantle construction 3: Sample i rC + J trial] Inoculated part of the piece
The development of r4 threads is not recorded first.

, 2: The surface of the white growing part of the 6゛1 yarn, which is observed at 811 minutes after the sample or test piece is inoculated, does not exceed 8/r of the total area.

/: a observed in the inoculated part of the sample or test piece
[The growing part of the thread AJ (is over 3/3 of the entire surface Kt1.

Comparative drug A in the 8th thorn and table is recognized as an active ingredient and contains 2% of cuthiazolylpenzimidazole and t% of /2.2-benzisothiazolin-3-one, and comparative drug B contains (tributyltin) oxide 1
It is a commercially available fungicide containing 0 CX2, and these comparative agents i''j:j: are also referred to in the following examples.

3rd garment (wood piece & C exchange J1-ru force and force generation situation) 6J
(Experiment f(1,? Preservative effect on
96
Since each was added to a and mixed uniformly, the synthetic 4MJ
The mixture was placed in a fat cup and covered with an aluminum boiler and stored in a thermostatic chamber (yo℃).

1.4 hills were kept, sample 1 was prepared on 7 days and after 77 days.
Incubate streaks on a bouillon agar medium (at 37°C).
), and based on the following criteria, p - 〇 occurrence situation r tone 3'E
Shita.

The results are shown in the glr, s, and s tables.

Investigation iat 艷+: Thin rl 6 to 3 ii -: a'll+ paste in which no bacteria were generated In addition, comparative drugs (jt, as active ingredients) ξ dichloromethoxy 1 phenol + 20'X and 2 -Promo 2-Nitropronozone-/, 3-. ) is a commercially available antifoam agent containing 20% grape.

Fl; s disaster (occurrence status of 11J bacteria in OMOJill) Test method for wood fungicide effect test is based on the wood fungicide described in the Japan Wood Preservation Association Standard No. 2 (/979 edition) It was conducted according to the efficacy test method of . That is, an emulsion prepared according to the example was diluted with pheasant so as to contain the active ingredient, and a piece of wood [thickness: J, j cm x, 2. jcm
X O, J cm's ka"es ngemotte, (
! ↓The one that was immersed in bell yam broth (called Uesakashita FD medium enriched with 20% potato starch and 2% crucose) for 3 minutes to absorb the Eiwa broth and dried at 1,0°C, and such -ePD+ What are the two types of foods that do not absorb nutrients without soaking in the culture medium? use] to absorb the system j'+'lk. This wood piece was air-dried for 2 days and used as a test piece.

This test specimen r was placed in a petri dish at t1. , JIS Z, 2Y
Aspergillus niger (Aspergillus niger) cultured on potato decoction agar medium as specified in //, ATCC9J e, 2, Penl
cillum funiculosum (Penicillium funiculosum) hq゛cc qniri61izop
us 5tolonlfcr (Rezogis 8 strokes 7 fu) G to UFO! i 'I, At+reobas
idium pulana (Aureopan, Noumusozorran, <)II='0/;3!; 3. Gl
iocladium virens (brioff 2jiuA・hii/7s) A'l'CCf l'l
6, l (D m mixture), soy fluid (a mixture of single spore suspensions and q species) was added to the test specimen VC/
Apply ml by ml using a brush. Betori Toku Nifu 7jv
Temperature ≦2°C, acidity 70~g.

Cultivate at %. 17″] The test was cultured 30 seeds, 71 eggs, /g
Tests 1.27 days and 2g days after Li (・To no Sword・
The current situation is very busy at 31! Yorim 14 intervened.

The results are shown in Table 7 and INg disaster.

Investigation criteria , 3=〃Tamehino)b raw material is not hardened at all in the test specimen.

, 2: Mold growth was observed only on the sides of the test specimen.

/: Mold growth is observed on less than 3/3 of the upward surface 6 of the test specimen.

0: Mold growth is observed on 7/3 or more of the area of the upper surface of the test piece.

In addition, the comparative drug DiJ, active ingredients include Ko-thiazolylbenzimidazole, 2%, 2-<nzothiazole/-3-onc%, and short methyl paratolylsulfone/96k @commercially available fungicide published. It is a drug.

Table 2 (FD medium in wiping sample? Symptoms of mold growth on lifting platform that should not be included) Procedural amendment (spontaneous) April 24, 1985, Commissioner of the Japan Patent Office], Indication of the case, 1988 Patent application No. 9516 2, Title of the invention: Tetraarylporon-ammonium complex 3, Relationship to the amended person's case Address of the applicant for the amendment: 4-2, Nihonbashi Honseki-cho, Chuo-ku, Tokyo (66
45) Name Yamoto 1) Shigeru (, Okina) 5, content of persimmon 6 sodode of the detailed description of the invention of the Ministry of Specifications subject to amendment (1) 1 Allyl group or methyl allyl in the detailed description of the invention of the Ministry of Specifications subject to amendment (1) Specifications Aoi page 5 lines 7-8 1 Allyl group or methyl allyl Delete ``group'' and insert 1゛hinyl group.

(2) 1-195 in the 3rd line from F in the 6th negative 1st evening
~17tjJ is corrected as 1-195~197.

(3) Mll 4% 12 negative 14 lines r1249y
and insert 124.91FJ.

(4) The number 0 on page 14, lines 19-21 is corrected as follows.

1 side fixed value total value C705% 709% H5.0chi 4.9% (5) 140yJ′i1″14.o of the 15th negative ma line
Correct it as f'J.

Claims (1)

[Claims] / General formula (in the formula, R1 is a hydrogen atom), a rogen atom, or a lower alkyl Mk, "e" is a rogen atom, a lower alkyl group, or a lower alkenyl group, "e" is a rogen atom, a lower alkyl group, or a lower alkenyl group, Tetraaryl-ammonium complex represented by the general formula (in the formula (in the formula, R1 is a hydrogen atom)) represents a rogen atom or a lower argyl group; 1. A preservative and fungicide characterized by containing as an active ingredient a tetraaryldirone-ammonium complex represented by a lower alkyl group or a lower alkenyl group, where 3 is a heterocyclic amine.