JPS5857358A - Sulfonated cyclopentadiene derivative - Google Patents

Abstract

NEW MATERIAL:A compound of formulaI[R1, R2 and R3 are H or 1-6C alkyl; Ra and Rb are H or 1-3C alkyl; (n) is 1 or 2; M is H, alkali metal, alkaline earth metal, ammonium or amine]. USE:useful as a synthetic intermediate for dyes, cement admixtures, etc. The salts of the sulfonated cyclopentadiene derivatives as such are useful as surfactants. PROCESS:A compound of formula II is reacted with a sulfonating agent, e.g. acid sulfite or metabisulfite of an alkali metal, preferably in a solvent, e.g. propyl alcohol or water, at 70-150 deg.C to give the compound of formulaI. In this process, the pH of the reaction system is kept at 2-9, preferably 5-7, to suppress side reactions and reduce the formation of inorganic salts.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel sulfonated cyclopentadiene derivative containing a cyclopentadiene skeleton, a benzene nucleus and a sulfonic acid group in the molecule.

Sulfonic acids and many of their derivatives are strong acids comparable to mineral acids, and their salts are water-soluble and can impart unique properties to organic and inorganic materials, and are useful as synthetic intermediates for primary organic compounds. As such, it is extremely important.

However, most of the sulfonated compounds synthesized conventionally are aromatic, aliphatic, etc. sulfonated compounds, and there are almost no examples of sulfonated alicyclic compounds.

The present inventors have conducted intensive research into the synthesis and properties of sulfonated compounds using alicyclic compounds and their derivatives as starting materials, and as a result, have discovered that the compound shown in the following general formula +11 can be synthesized. The present invention was achieved by introducing that this is an extremely useful substance.

In accordance with the present invention, the general formula (11 (Formula R1s Rl and R1 are the same or different, hydrogen or an alkyl group having 1 to 6 carbon atoms, Ra and Rh are the same or different, hydrogen or an alkyl group having 1 to 3 carbon atoms, n is 1 or 2, M is hydrogen, an alkali metal, an alkaline earth metal, ammonium or an amine. Subulfonates are new substances.

Next, the present invention will be explained in detail.

In the compound of general formula (11), when M is hydrogen, alkali metal, ammonium or amine, l=1 and when M is an alkaline earth metal, n=2.

The alkali metals mentioned above include sodium, potassium, etc., and the amines include alkylamines such as methylamine, ethylamine, globilamine, dimethylamine, diethylamine, trimethylamine, triethylamine, butylamine, dibutylamine, and tributylamine, ethylenediamine, diethylenetriamine, triethylenetetramine, etc. Examples of alkaline earth metals include polyamines, morpholine, piperidine, etc., and examples of alkaline earth metals include calcium, magnesium, and zinc. These M can be interchanged with M of other species by tank-to-tube ion exchange techniques.

In addition, preferred R1 s R11 and R3 in the compound of general formula (J) are hydrogen, methyl A, group, 7''
Preferred as D hill group and butyl group CsR* and Rh is hydrogen.

Various manufacturing methods are conceivable for producing the compound of general formula +11 of the present invention, such as the method of sulfonating the compound of general formula (1) below and then converting it into a sulfonate salt if necessary. General formula (Two phrases that can produce a riff compound (R1, R3, R3, Ra and Rb are the same S as in general formula +11) Sulfonation method is Gilper) (E, E.

G11b@'rt)'s book ``Sulfonation and Related Anti-EJ (@5ulfon+ation and R
e1ated Reaeti'ontsu, Int@ri
elsnc@Publishers Inc, (19
1965), and the sulfonation method applied to unsaturated compounds, especially unsaturated aliphatic or uncelled aliphatic compounds, should be selected appropriately depending on the state of the reaction system. I can do it.

't+ Charles GA Twoton (Ohar1g+, J* Norton) et al.
Journal of Organic Chemistry (Th
・Journal of Organic Oh@m1
The compound of general formula +11 can also be obtained by the addition reaction of sulfites to unsaturated bonds, as shown in the study of 4158 (1968).

In this case, the sulfonating agent is usually an alkali metal acid sulfite, metasulfite, or sulfonate #I, either singly or in a mixture. Although the use of a catalyst is not necessarily required in the sulfonation reaction, the use of a catalyst such as an inorganic oxidizing agent usually has the effect of shortening the reaction time. As an inorganic oxidizing agent, for example, #41! ! salts,
Examples include nitrites and chlorates, but nitrates are particularly effective.

Furthermore, it is desirable to use an appropriate solvent to allow the reaction to proceed uniformly and smoothly.

Solvents that can be advantageously used include, for example, water, or methyl alcohol, ethyl alcohol, propyl alcohol, inpropyl alcohol, butyl alcohol, tertiary alcohol,
Examples include lower alcohols such as butyl alcohol, lower glycols, ketones, ethers, and esters.

Two or more of these solvents can be used in combination as appropriate. Among them, mixed solvents of lower alcohols and water,
Among these, a mixed solvent of propyl alcohol and water is particularly recommended as an excellent solvent.

The reaction temperature is usually 50-200°C, preferably 70-15°C.
It is carried out at 0°C, more preferably from 90 to 120°C, and can be carried out either under normal pressure or under pressure.

In order to suppress the progress of side reactions and reduce the production of inorganic salts, pIII in the reaction system is usually maintained at 2 to 9, preferably 5 to 7.

The compound of the above general formula (1) is, for example, a compound of the general formula (
11 compound and the following general formula +11+ compound (2)
713-Can be obtained by Delkraft reaction (Rs, Ras and R3 are the same as general formula m) (Ra
and Rb are the same as the general formula
-1m-1p-), ethylbenzene, n-solobylbenzene, Imo-7'ropylbenzene, methylethylbenzene (os --s p-), 1,2.4-)limethylbenzene, n-butylbenzene, *C-butylbenzene, t@rt-butylbenzene, 1so-propyltoluene (o-1m-1P-), amylbenzene, hexylbenzene, amyltoluene (0-.

Examples include mono-, di- or trialkyl-substituted benzenes such as m-1p-). The alkyl group in this case has 1 to 6 carbon atoms, and tetralin, which is a cultural compound in which two alkyl groups form a ring, can also be used.

Particularly preferable compounds of the general formula (厘) include benzene,
Examples include toluene, xylene, solobylbenzene, and butylbenzene.

In addition, the compound of the general formula (IVI) is a dimer consisting of one or two types of cyclopentadiene, and examples of the cyclopentadiene include cyclopentadiene, ethylcyclopentadiene, ethylcyclopentadiene, and propylcyclopentadiene. Examples include alkylcyclopentadiene such as pentadiene.The compound of general formula (IVI) is dicyclopentadiene from the viewpoint of availability and economy.

The next catalyst for synthesizing the compound of the general formula (厘) by the Friedel-Crafts reaction between the compound of the general formula (玽) and the compound of the general formula (IVIO) is an acidic compound such as sulfuric acid,
Examples include Lewis acids or organic protonic acids such as phosphoric acid, hydrogen fluoride, boron trifluoride and its complexes, aluminum chloride, aluminum bromide, tin tetrachloride, zinc chloride, and titanium trichloride, and the reaction can be carried out by known methods. (For example, JP-A No. 5
2-133968), for example, in the presence of the above catalyst, the compound of the general formula (button compound and the compound of the general formula flVl) is heated preferably at 0 to 100°C, particularly preferably at 20°C.
It can be obtained by reacting at ~70°C for about 1 to 5 hours.

The compound of the first general formula ill can also be synthesized by a 7 Liedl-Crafts reaction between a compound of the general formula (set) and a compound of the following general formula (■).

(Ra and Rb% (Same as general formula (1), X is a hydroxyl group or octane) Examples of adducts of the general formula
Examples include chloro-dihydro-dicyclopentadiene and promodihydrodicyclointadiene.

7 Riedel-Crafts reaction between a compound of general formula (set) and a compound of general formula (V) is a reaction between a compound of general formula (set) and a compound of general formula (I
It can be carried out using the same catalyst, the same reaction temperature, and the same reaction time as in the 7 Liedl-Crafts reaction with a compound of YI. The compound of the general formula M has a halodan atom that is active in the Friedel-Crafts reaction, and the compound of the general formula (1) has a higher selectivity than the Friedel-Crafts reaction using the compound of the general formula (Vl). can be obtained.

The compound of general formula +11 is generally a white to slightly yellow solid, but the compound of the general formula (ship compound,
It may vary depending on the type of compound of the general formula (ff+) and the compound of the general formula (Vl) and the combination thereof.

The sulfonated product of the cyclopentadiene derivative of the present invention is useful as a synthetic intermediate for dyes, admixtures for cement, etc., and can be obtained, for example, by condensing the sulfonated product of the cyclopentadiene derivative of the present invention with formalin. The compounds can be used as cement admixtures with a water-reducing effect. Primary Salts of sulfonated derivatives of cyclopentadiene of the present invention can be used in their own right as surfactants, such as emulsifiers, dispersants, wetting agents, detergents, leveling agents, and the like.

Next, the present invention will be specifically explained with reference to Examples.

[Example 1] (Friedel-Crafts reaction) Toluene 12709 and BP, - Phenol complex 12.
Of was added and the temperature was raised to 50°C. While stirring, dicyclopentadiene 417f with a purity of 9511) and toluene 3
After dropping 20 tons of mixed bath liquid over about 1 hour,
Continue the reaction at this temperature for 2 hours.

After the reaction was completed, the catalyst was decomposed in a sodium carbonate water bath and washed with water, and then the oil layer was distilled under reduced pressure. In the distillation, 114-b423 was obtained by distilling off the lowest boiling point substances including unreacted substances up to 150°C/3-Hf.

The infrared absorption spectrum of this fraction is 700 es- and 16
There is an absorption based on cyclopentene double bond at 20-1-, and 1000-1
And at 1605m-', absorption was observed due to the phenyl group. NMR spectra of octopus fractions (ODOts)
solution) has groups < s, s s pprn and 5.
The signal at 90 ppm disappeared and there was a signal at 5.4 ppm based on the cyclopendene double bond proton and a signal at 6.8 ppm based on the hyphenyl proton.90 Furthermore, the iodine value of this fraction was 113.・ From the above analysis results, it was confirmed that the structural formula of this fraction is the following (Al).

Hs (sulfonation reaction) Attach a stirrer and a thermometer and use a oriented volume 3. The compound obtained above (200 f,
Sulfite water wing) IJum 97.8? , potassium nitrate 8
．． Of, Inglovil Alcohol 1360- and distilled water 200-1 were added.

Furthermore, at room temperature, the internal pressure of the autoclave was 1.0 kg/e.
Air was supplied through a +JG tube, and then the balloon was sealed, and the reaction was carried out at 110° C. for 5 hours while mixing under strong stirring.

After cooling at room temperature, take out the reaction mixture and add 50 g of distilled water.
t. Add 1,500 ml of petroleum ether and mix the light. Then, the petroleum ether layer and precipitate were removed, and the remainder was concentrated.

At this time, it foamed violently, so it was evaporated to dryness while adding Inglobil alcohol to obtain 139 tons of pale yellow powder. This powder was extracted with petroleum ether for 1 hour using a Sox L-extractor, and after drying, it was dissolved in 300% of glacial acetic acid to remove the acetic acid insoluble matter consisting of NaH3O1, Na1SO1, etc. Separated. By concentrating the acetic acid soluble content, 129t of white-yellow solid was obtained. After this solid was purified by ethanol extraction, elemental analysis revealed that 0 = 53.41, H = 6.11i, 5 = 11.24 (calculated values: 0 = 52.01, H = 6.14, S = 9.8
). The acid value determined by the simple reverse foot method was 170.

When the infrared absorption spectrum of this product was measured using the KBr tablet method, the group absorption at the cyclopentene ring double bond observed in compound (4) disappeared;
Absorption based on sulfone groups was observed in 190 car-” and 1050 °-#, and it was confirmed that the cyclo-4-carbon double bond was sulfonated (ml factor).
.

As a result of the above analysis, it was confirmed that the product was a compound having the following structural formula fBl.

[Example 2] (Friedel-Crafts reaction) In the same manner as in Example 1, BF, phenol complex 122
Xylene 1060f was reacted with 954 purity dicyclopentadiene 350f in the presence of.

The fraction with a boiling point of 156-b to HP obtained by this method was 340f, and was confirmed to be a compound having the following *formula tel from its NMR spectrum, infrared absorption spectrum, and iodine value.

(Sulfonation reaction) A sulfonation reaction was carried out in the same manner as in Example 1 except that the compound +0120Of obtained above was used, and a pale yellow powder 124f was obtained by purification of the obtained reaction product.

This powder was purified by ethanol extraction and later subjected to elemental analysis. The results were 0 = 62.8, H = 6.6 tatami,
S = 9.7 (calculated value: C = 63, 34, H-6,
5, S = 9.4 tatami), and the acid value determined by back titration was 166.

In addition, as a result of measuring the infrared absorption spectrum of this product, the absorption based on the cyclopentene ring double bond disappeared, and in its place, absorption based on the 1187ctn-' and 104951-fC sulfone groups was observed (No. Figure 2).

Based on the above analysis results, it was confirmed that this product is a compound having the following structural formula (DJ).

IO [Example 3] (Friedel-Crafts reaction) In the same manner as in Example 1, benzene 1950F was reacted with 95-purity dicyclopentadiene 630F in the presence of BFs/7-ethanol complex 12f.

With this method, you can achieve a boiling point of 114-133℃/1wm HP
The fraction is 203F, and its NMR spectrum, infrared absorption spectrum, and iodine value confirm that it is a compound having the following structural formula (trout).

(Sulfonation reaction) A sulfonation reaction was carried out using the following compound (El 20 Of) in the same manner as in Example 1, and the resultant A7 was subjected to purification treatment of the reactant to obtain 122t of pale yellow powder. .

After this powder was purified by electrodialysis using an ion exchange membrane, single element analysis was performed and the results were 0 = 59.2 Excellent, H
=6.24.5=12.1 Shizuku, (calculated value: 0=61.3
H = 5.8, 5 = 10.2), and the phosphoric acid value determined by back titration was 168.

When we measured the infrared absorption spectrum of this substance, we found that the absorption based on cyclo-4-benzene and double bonds disappeared, and instead, the absorption based on sulfone groups on 1187sub-1 and 1049crR-0. Absorption was observed (Figure 3).

From the above analysis results, it was confirmed that this product is a compound having the following structural formula (Fl).

[Example 4] 300- with reflux condenser, stirrer and dropping funnel
9. 55 t of toluene and 22 f of zinc chloride were placed in a three-necked flask, and while stirring at 65°C, 271 chloro-dihydro-dicyclopentadiene was added dropwise over 1 hour. After the addition was completed, the reaction continued for another 5 hours.

After the reaction, the catalyst was decomposed with an aqueous sodium carbonate solution, washed with water, and the oil was distilled under reduced pressure.

Unreacted substances are distilled off as fraction 14 of 114~b1■Hta. I got it. This fraction is N M
From the infrared absorption spectrum, it was found that Ry was the same as the compound obtained in Example 1.

Thereafter, the sulfonation reaction δ was carried out in the same manner as in Example 1 to obtain the same compound fB1 as obtained in Example 1.

[Brief explanation of drawings]

1 to 3 show infrared absorption spectra of sulfonated cyclopentadiene derivatives of the present invention.

Claims (1)

[Claims] (1) General formula (summer) (In the formula, R1, R, and R3 are the same or different hydrogen or an alkyl group having 1 to 6 carbon atoms. A sulfonated product of a cyclopentadiene threaded conductor represented by an alkyl group, n is 1 or 2, and M is hydrogen, an alkali metal, an alkaline earth metal, ammonium or an amine.