JPS61151160A - Tertiary octylhydrazine, salt and derivative - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to t-octylhydrazine (tL5.3
-tetramethylbutylhydrazine), 1-octylhydrazine salts and t-octylhydrazine derivatives. More particularly, the present invention provides novel t-octylhydrazones, their hydrolysis to t-octylhydrazine salts, neutralization of said salts to the free base t-octylhydrazine, and the like. to derivatives such as acid salts, hydrazones, hydrazides, semicarbazides, carbazates or sulfonyl hydrazides.

Prior Art As far as the present inventors are aware, there is no example of t-octylhydrazine (i.e., 11m3-tetramethylbutylhydrazine) being successfully synthesized prior to the present invention.

Similarly, no salts or derivatives thereof have been reported in the literature.

One of the inventors, R.E., Maclea (Maclea7)
), filed on the same day, discloses for the first time the production of an asymmetric t-octyl-5ee-alkylazene. Asymmetric t-octyl t-alkyldiazenes are known, but cannot be isomerized to 1-octylhydrazone.

(J, W, Timberlake)
, M. Le Hodges and A.
W, Garner, Tetrahydrone Letters, p. 3843 (1975); J, W, Chimbarake, J, AIender, A, W, Garner, M, L, Hodges, C, Ozmera A/ (Ozm
eral), S, Shiraj (8zilag71),
Journal of Organic Chemistry, 46
, p. 2082 (1981)) It is known in the literature that sea-alkylazos can isomerize to hydrazones when heated. Corle
y) and Giblan are 5ee-
It has been reported that aralkylazo compounds are isomerized to hydrazone in chlorinated solvents. [R, Kohli and M,
Gibian, Journal of Organic Chemistry, 37, page 2910 SUMMARY OF THE INVENTION The present invention relates to a novel monosubstituted sterically hindered t-alkylhydrazine, t-octylhydrazine (I). This compound could not be synthesized conventionally due to the large t-octyl substituent.

Therefore, it had not been manufactured prior to the present invention.

[Here n is 1 or 2, and A is MCI when n=1, )(Br.

(R is H%CH,,C,H,,C,H,,iso-C
selected from B Hy and Cs Hs),
The present invention relates to a novel t-octyl and dorazine acid salt having or.

The present invention also relates to general formula (In) [wherein R1 and R2 are individually alkyl or substituted alkyl of 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, and alkyl of 3 to 12 carbon atoms, preferably 3 to 7 carbon atoms] cyclic, or R1 and R2 together may form an alkylene divalent group of 3 to 11 carbons, preferably 4 to 7 carbons, or R3 may be hydrogen and R yo is a carbon 6 to 14, preferably 6 to 10, phenyl or substituted phenyl.

The present invention also relates to general formulas (■) and (V)R.

Selected from Bi-8-R, Drunk Z)! -CORs OC-1-C-R, -C-1, R, is alkyl having 1 to 12 carbons, aryl or substituted aryl having 6 to 14 carbons, cycloalkyl having 3 to 8 carbons and aralkyl having 7 to 9 carbon atoms, R4 and R5 are each hydrogen, alkyl having 1 to 12 carbon atoms, aryl or substituted aryl having 6 to 14 carbon atoms, and aralkyl having 7 to 9 carbon atoms. and 7 with 3 to 8 carbons
selected from chloroalkyl, or R4 and R, together may form an alkylene divalent group having 4 to 7 carbon atoms, R6 is alkyl having 1 to 12 carbon atoms, and R6 is alkyl having 1 to 12 carbon atoms; cycloalkyl, alkylcycloalkylalkyl having 6 to 14 carbons, aryl having 6 to 14 carbons, 8 to 15 carbons
and wherein Ro optionally includes an ether linkage in the main chain and R7 is biphenylene.

DETAILED DESCRIPTION OF THE INVENTION T-octylhydrazine (I), a unique monosubstituted sterically hindered t-alkylhydrazine, is a very useful intermediate for preparing low temperature azo compounds. The t-octyl group has a significant effect in reducing the half-life of azoalkanes and asymmetric azonitrile.

The R.E. McCrae application, filed on the same day, is entitled "Azoalkane Mixtures Containing Unsymmetrical Azoalkanes and Processes for Their Preparation" and discloses the two-step preparation of mixtures of asymmetrical and symmetrical diazenes. The preparation involves first combining at least 2 af of a prim -furkyl-, cycloalkyl-, or aralkylamine and sulfuryl chloride in the presence of an anhydrous inert solvent until an N,N'-disubstituted sulfamide product mixture is formed. Make it react. The by-product amine hydrochloride is removed by an aqueous wash and the A/7 amide mixture is incubated with a basic bleach in a strongly basic medium to form a mixture of diazenes. In this method, low molecular weight Bee-alkyl-prims such as inpropylamine
- When the amine is used in mixed form with tert-octylamine, the low-boiling symmetrical diazene evaporates during the work-up;
After that, a mixture of monooctyldiazene and asymmetric diazene remains with the asymmetric diazene as the main component. This asymmetric 1-,octyl-5ea-alkyl (or prim-alkyl)diazene is also a novel compound.

Mixtures of diazenes can be prepared in chlorinated solvents such as chlorobenzene, dichlorobenzene or trichlorobenzene.
Heated at 150°C. Di-t-octyldiazene decomposes liberating nitrogen, diisobutylene and diisobutane. Surprisingly, the -octyl-5ee-alkyl (or prim -alkyl)diazene rearranges to t-octylhydrazone instead of decomposing. If the symmetry s
If any ee-(or prim-) azoalkane is present, it also rearranges to a hydrazone.

Therefore, to eliminate this problem, it is preferred to use a low molecular weight amine such as isopropylamine for the sulfamide reaction.

Asymmetric diazene is easily produced at about 80-90 degrees (1-
2 hours) transpose.

T-octylhydrazone can be extracted from a chlorobenzene solution with dilute sulfuric acid. T-octylhydrazone forms a sulfate salt that is water soluble. T-octylhydrazone can be partially extracted from a chlorobenzene solution with hydrochloric acid.

T-octylhydrazone forms a hydrochloride salt which is soluble in chlorobenzene solution and only partially passes into the aqueous phase. It is therefore advantageous to extract t-octylhydrazone from the chlorobenzene layer with dilute sulfuric acid. In the chlorobenzene layer, the decomposition product di-t-octyldiazene and unrearranged diazene remain. After separation, the chlorobenzene layer can be reloaded with fresh diazene mixture and the rearrangement repeated.

Upon neutralization of the sulfuric acid solution, t-octylhydrazone is obtained. Usually a small amount of hydrolysis occurs, contaminating the t-octylhydrazone with t-octylhydrazine and the corresponding ketone. If this mixture is brought to reflux, the free t-octylhydrazine reacts with the ketone to reform t-octylhydrazone.

If the sulfuric acid solution is heated, the ketone formed is removed by distillation, preferably under reduced pressure, and the t-octylhydrazine sulfate is fully hydrolyzed into an aqueous solution of t-octylhydrazine sulfate.

Pure salt can be obtained by evaporation of water.

Hydrolysis of t-octylhydrazone hydrochloride can be carried out in a similar manner, preferably under reduced pressure, to prevent dealkylation of t-octylhydrazine and the formation of hydrazine sulfate.

The t-octylhydrazine salt solution can be neutralized with an inorganic base such as sodium or potassium hydroxide, carbonate or bicarbonate to form free t-octylhydrazine. t-Octylhydrazine has poor water solubility and precipitates out of solution as an organic layer. It is absorbed in a hydrocarbon solvent such as pentane or hexane, dried and heated to evaporate the solvent.

Since t-octylhydrazine has a very unpleasant and pungent odor, it is advisable to preserve it as an acid salt. Also, care should be taken when handling free t-octylhydrazine since the free base is probably more toxic than the acid salt.

If the diazene mixture contains some symmetric di-5ea-alkyl (or prim-alkyl) diazene, and this is not removed before heating the diazene solution in the chlorinated solvent, the -octylhydrazone corresponds to 1lee-alkyl (or prim-alkyl) hydrazone and t-octylhydrazine will be contaminated by the corresponding prim- to Bee-alkylhydrazine. This is not a problem when using inpropylamine with t-octylamine in the sulfamide reaction.

t-octylhuman didine is 2-t-octyl azo-2
- Useful as an intermediate for low temperature azo compounds such as cyanopropane, as an antioxidant, antiozonant and as a pharmaceutical intermediate.

The acid salt of t-octylhydrazine (It) is easily prepared by reaction of t-octylhydrazine and an equimolar amount of the desired acid. This can be done in an aqueous solution, most often resulting in an aqueous solution of the salt. An acid can also be added to the hydrocarbon solution of -octylhydrazine. Then,
Stripping off the hydrocarbon, preferably pentane or hexane, leaves behind the salt. The hydrochloride or sulfate salt may also be prepared by reacting t-octylhydrazone with an equimolar amount of acid and stripping the ketone formed as described above.

In addition to being a convenient form for preserving oxygen-sensitive t-octylhydrazine, such salts
amena) (U.S. Patent No. 4.595)
．． 148) is an efficient blowing agent for polyester resins.

t-Octylhydrazone (■) is usually PAMed by reaction of t-octylhydrazine (I) with a ketone or aldehyde. This reaction is usually performed using t-octylhydrazine sulfur i! This is accomplished with most aliphatic ketones and aldehydes by neutralizing an aqueous solution of the 12 salt (or hydrochloride), adding an equimolar amount of the ketone or aldehyde, and refluxing the aqueous mixture for about 1 hour.

The extent of the reaction can be followed by gas chromatography. In the case of less reactive ketones such as acetophenol, it is desirable to carry out the reaction in an inert solvent such as toluene and drive the reaction by azeotropic removal of the water that forms. The reaction can be catalyzed by adding small amounts of p-)luenesulfonic acid.

t-octylhydrazone (III) (R is not H, R
2 is not Cm Hs) is useful in the synthesis of low temperature azo compounds. Hydrocyanic acid can be added across the double bond and the resulting hydrazonitrile can be oxidized to the corresponding azonitrile.

t-Octylhydrazide (V) and (V) can be prepared by reacting t-octylhydrazine with an acid chloride or dichloride in the presence of an acid acceptor. These compounds are useful as blowing agents. The compounds can be oxidized to the corresponding azo compounds, which are useful as blowing agents and as initiators for the polymerization of vinyl monomers.

T-octyl substituted carbazates can be prepared by reacting t-octylhydrazine with chloroformate or bischloroformate in the presence of an acid acceptor. Such compounds are also useful as blowing agents. It is used as a blowing agent and as an initiator for vinyl monomer polymerization.
It can be oxidized to useful corresponding azo esters.

Substituted t-octyl semicarbazide is a combination of t-octylhydrazine and alkali metal cyanate, incyanate,
It can be produced by reacting with diisocyanates or substituted ureas.

This compound is also useful as a blowing agent. This can be oxidized to the corresponding azoamide, which is useful as a blowing agent and initiator for vinyl monomer polymerization.

Substituted t-octylsulfonyl hydrazides and bissulfonyl hydrazides can be prepared by reacting t-octylhydrazine with sulfonyl chloride or disulfonyl chloride in the presence of an acid acceptor. These compounds are also useful as blowing agents and blowing agents for unsaturated polyester resins.

Example ■ 95% t-octylamine (40.89 (0)
, 5 mol), cyclohexylamine 735.99 (0-5
25 moN) and hexay3o.

- was inserted. The flask was equipped with a magnetic stirrer, a thermometer, and a Dean-Stark trap connected to a reflux condenser. Place the flask in an oil bath preheated to 80°C,
The hexane solution was refluxed using a Dean-Stark trap and water was removed from the reaction mixture by azeotroping with hexane for 15 hours.

The water produced in the trap was separated and the hexane layer was returned to the reaction flask. Replace the electromagnetic stirrer with a mechanical stirrer,
The flask was also equipped with a 25-dropping funnel, an air condenser, and a thermometer. A solution of the dried amine in hexane was cooled to 0°C and diluted with 97% sulfur chloride/l/7L2 (1977 (0
, 15% k) was added dropwise from the addition funnel over a period of 20-50 minutes while maintaining the temperature below 15°C. After the dropwise addition was complete, the reaction was warmed to 30°C and incubated for 1/2 hour at 25°C.
Stir at ~30°C. The reaction was diluted with water to dissolve the hydrochloride salt and transferred to a separatory funnel. The aqueous layer was separated and the hexane layer was washed with 10 g of H't 804100- to remove any residual amine. The pickling solution was separated and added to the aqueous layer for neutralization and amine recovery.

The hexane layer was returned to the 1/3-hole flask, and a phase transfer catalyst, Adogen 464 (trade name of methyltrialkyl (C.~C1.) ammonium chloride, commercially available from Aldrich Chemical Company) n,
sg and a solution of 40.51 (0.5 mol) of sodium hydroxide in 50 g of 14.2% bleach was added. The flask was equipped with a magnetic stirrer, a thermometer, and a distillation head connected to a condenser and receiver. The flask was submerged in a preheated oil bath (~80°C) and stirred vigorously with a magnetic stirrer. When the reaction mixture was heated to 62°C,
The hexane began to distill and formation began to occur. Oxidation was essentially complete by the time distillation ceased. The reaction mixture was stirred for an additional hour at 85°C and then cooled to room temperature. The reaction mixture was diluted with 100ml/hexane and transferred to a separatory funnel. The aqueous precipitate was separated and the hexane solution of diazene was washed successively with water, 15% sodium bisulfite solution, 10% HtSO, and 100% saturated solution of hydrogen carbonate. The hexane solution was dried over anhydrous sodium sulfate, filtered, and heated under reduced pressure on a rotary evaporator to strip the solvent. The residue was 29.1 p and consisted of about 20 g of di-t-octyldiazene, about 12% dicyclohexyldiazene and about 65 g of the desired cyclohexyl-t-octyldiazene.

Subsequent experiments were performed with slight changes in the molar ratio of cyclohexylamine to t-octylamine. The results are summarized in Table IVc below.

EXAMPLE 1 Preparation of isopropyl-t-octyldiazene Several experiments with isopropyl-t-octyldiazene were carried out following the procedure described in Example 1, except that inpropylamine was used in place of Schiff-tetrahexylamine. The crude product is mainly di-t-octyldiazene and inpropyl-t
- It was a mixture with octyldiazene. This product did not contain any diisopropyldiazene.

The reaction was carried out in a 2/3-necked flask with 3 moles of inpropylamine/lz, 12 moles of i-octylamine, 6 moles of sulfuryl chloride, hexane Book, Adgen 46'4
A larger scale test was carried out using a solution of 300 g of 50% sodium hydroxide in 1200 g of 19 and 12 inch pulp. The product after finishing was 66931, consisting of about 65 units of isopropyl-octyldiazene and about 25 units of di-t-octyldiazene.

Example ■ Cyclohextenone-t-octylhydrazone and t-
Production of octylhydrazine hydrochloride Di-t-octyldiazene (32.5%), dicyclohexyldiazene (9%
) and cyclohexyl t-octyldiazene (53%
) was diluted with 133 g of o-dichlorobenzene and placed in a 250-3 neck round bottom flask. This flask was equipped with a magnetic stirring bar and a reflux condenser and purged with nitrogen. The solution was heated at 120-125°C for 5.5 hours. Gas chromatography analysis showed that approximately 75 units of cyclohexyl-t-octyldiazene had been rearranged to cyclohexanone-t-octylhydrazone. The reaction mixture was cooled to room temperature and the dichlorobenzene solution was extracted with 50-50% HCl. The acid extract was set aside and the dichlorobenzene solution was recharged with an additional 15I diazene mixture and heated at 120-150°C for 2 hours. Gas chromatograph 2 filter analysis showed that the cyclohexyl-t-octyldiazene was rearranged to approximately 70 thihydrazones. Cool the solution to room temperature and add 50
- Extracted with 5% HCI. This acid extract was added to the first extract and the dichlorobenzene solution was added to another diazene mixture 14.4. Reloaded with p. About 70'% of dichlorobenzene was rearranged to cyclohexanone-t-octylhydrazone. Add this dichlorobenzene solution to 1
Heated at 20-125°C for 2 hours and cooled to room temperature. Gas chromatography analysis showed that the cyclohexyl-t-octyldiazene had rearranged to about 70 cyclohexanone-t-octylhydrazone. The dichlorobenzene solution was extracted with another 51HC1so- and the acid oils were combined. These acid extracts were washed twice with pentane to remove any residual dichlorobenzene.

This acid was then neutralized with 10% N&OH60+d,
Extracted twice with pentane 50+d. The pentane extracts were combined and analyzed by gas chromatography.

The pentane solution contained t-octylhydrazine (~75%
) and cyclohexanone-t-octylhydrazone (~2
0chi) was included.

Since the hydrolysis of hydrazone is not complete, the pentane solution is diluted with 10 HC1 (s Qd) until pH α5 is obtained.
Processed with. The aqueous solution was separated and incubated overnight. Pure t-octylhydrazine hydrochloride was obtained by stripping the solution to dryness and recrystallizing the residue from ethanol. The hydrochloride salt that could be recrystallized was a white crystalline solid that melted at 141-143° C. while vaporizing.

When the dichlorobenzene solution was neutralized with sodium bicarbonate solution, a considerable amount of cyclohexanone-1-octylhydrazone was obtained. This is cyclohexanone-t
-Octylhydrazone hydrochloride is fairly soluble in dichlorobenzene, indicating that it is not very efficiently extracted from dichlorobenzene by water. Residual cycloxanone-t-octylhydrazone was efficiently extracted from dichlorobenzene with dilute sulfuric acid.

Example ■ Production of acetone-t-octylhydrazone and t-octylhydrazine sulfate Di-t-octyldiazene (27%) and isopropyl t
The mixture sybsg with -octyldiazene (55%) was diluted with 67 g of chlorobenzene and placed in a 250-Mikka round bottom flask. The flask was equipped with a magnetic stir bar and reflux condenser and purged with a constant flow of nitrogen. Solution at 154℃
The mixture was gently refluxed for 3 hours, and then cooled to below 20°C. Gas chromatography analysis showed that the isopropyl t-octyldiazene rearranged to about 88 thiacetone t-octylhydrazones. This reaction mixture was mixed with 75 ml of water.
- diluted with 70 H! 8042 G Ii was added dropwise. The mixture was stirred vigorously for 5 minutes and transferred to a separatory funnel. Separate the aqueous layer and add the chlorobenzene layer to another 2 mL of water.
Washed with 5 wIt. This aqueous wash was added to the acid layer. A small sample of the chlorobenzene layer was neutralized and found to be free of any acetone t-octylhydrazone. This indicates that all of the compound is extracted into the acid layer. The acid layer was washed with 50ml hexane to remove any residual chlorobenzene. Neutralization of a small sample of the acid layer revealed that 60% of the acetone t-octylhydrazone had been hydrolyzed to t-octylhydrazine.

The aqueous acid solution weighed 141 g. This was then vacuum stripped on a rotary evaporator at 30-40°C. This final aqueous solution weighed 62.8 g with t present as the sulfate salt.
- 24.9 g of octylhydrazine (iodine reduction titration). Neutralization of a small sample of this acid solution revealed the presence of a small amount (~5%) of unhydrolyzed acetone t-octylhydrazone in the t-octylhydrazine.

Example V Preparation of t-octylhydrazine Di-t-octyldiazene (280 and isopropyl t-
Mixture 2z21 with octyldiazene (52%) in Example W
The mixture was diluted with chlorobenzene 659 as shown above and refluxed at 134°C for 3 hours. The reaction mixture was cooled to 20°C and added with 1 part of water.
00- and 70% H=804141 was added dropwise. The aqueous layer was treated as in Example 2 and then on a rotary evaporator.
Vacuum stripping was performed at 0-40°C for 1 hour. This t-
The octylhydrazine sulfate solution made a small sample of 55.2 g basic and extracted with hexane. A vPC scan of this extract showed that the hydrolysis was complete.

The aqueous solution was diluted with 100% of water and 50q6 of NaOH2
It was made strongly basic by adding 4 g.

The mixture was cooled to 20° C. and extracted with 100 d of pentane. The pentane extract was dried over anhydrous sodium sulfate, filtered, and heated to strip off the pentane. The residue was 1 to, liter of yellow liquid. Gas chromatography analysis indicates that the product is approximately 85% t-
It was shown to be octylhydrazine. When attempting to distill this product under reduced pressure, vaporization at around 50°C and slow decomposition occurred.

Example ■ Preparation of methyl ethyl ketone-t-octylhydrazone 24.2 g (11,1
In a solution of water (4a, 8fI) with 0 mol) of
Added 0I. The flask was equipped with a magnetic stirrer, thermometer, and reflux condenser and heated in an oil bath. The reaction mixture was gently refluxed for 1 hour, cooled to 60° C., and transferred to a separatory funnel. The aqueous layer is drained from the organic layer, then the organic layer is diluted with 50-hexane, dried over anhydrous NJSO4, filtered, and on a rotary evaporator! The solvent was stripped off by heating under reduced pressure at IO°C. Crude product is 17.5p
According to gas chromatography analysis, it was determined to be approximately 90%. The corrected yield of methyl ethyl ketone-t-octylhydrazone was about 80%. No methyl ethyl ketone ketazine was present. This indicates that the t-octylhydrazine sulfate was not contaminated at all by hydrazine sulfate.

Example ■ Production of sulfate of t-octylhydrazine Ether 20d
and 5 g of methyl ethyl ketone-t-octylhydrazone were added to a solution of oxalic acid dibasic acid salt 5y in ethanol 15-. This mixture was stirred at room temperature for 1 hour. After 10 minutes a white precipitate began to form. After stirring, the white solid was separated, washed with 5-ethanol, moderately dried on a filter, and air-dried on a weighed watch glass.

The product weighed 2.2 g and had a melting point of 128-130°C.

By concentrating solution F and filtering again, the second tOg
yield was obtained.

The F mass was slurried in water, neutralized with caustic, and extracted with hexane. Nap this hexane extract
804, filtered, and heated under reduced pressure on a rotary evaporator to strip off the hexane. 10g of residue
It was identified as t-octylhydrazine based on the amount and residence time on gas chromatography.

Example ■ Preparation of 1-t-octyl-2-ethoxycarbonylhydrazine 5.84 g of t-octylhydrazine (as sulfate) (
To 62 g of a solution containing α026 mol) was added enough 1:(&li') 504 NaOH to raise the pH to 9. Then 5 g of sodium carbonate was added and the mixture was cooled to 10°C.

t-Octylhydrazine precipitated out of solution. Added 25-ounces of hexane. The mixture was stirred and a solution of 2.89 (0,026 mol) of ethyl chlorochlorate in hexane (5-) was added dropwise over a period of 1 hour, while the temperature was maintained at 10-15°C.
I kept it. The addition was monitored by gas chromatography. When approximately 80 units of chloroformate were added, all of the t-octylhydrazine appeared to be consumed. Therefore, the addition of the ester was discontinued to prevent diacylation. The reaction mixture was transferred to a separatory funnel and the aqueous layer was separated. This hexane solution is diluted with hydrogen carbonate) I
) IJ
The hexane was stripped off by heating under reduced pressure on a rotary evaporator. The residue is 57g.
It was a pale yellow liquid.

The infrared spectrum of the residue showed a strong broad NH peak at 3315 cIrL and a very strong broad carbonyl peak at 1710 crrL.

This product was oxidized to the corresponding azo ester using Bleach 30,9)C. The product weighed 58 g and was 93% pure by gas chromatography analysis.

The infrared spectrum of the oxide is in the NH region 3200-330
0α-”)Ic, and the carbonyl peak is very sharp, at 1770 cm
shifted to. The azo ester was an orange liquid that evaporated slowly from 150°C to 186°C and rapidly at temperatures above 180°C. This was useful as a blowing agent for vinyl resins.

Example (1) Preparation of 1-t-octyl semicarbazide A solution containing 5.29 (0,056 moles) of t-octylhydrazine as a sulfate was weighed out into a 125-mm Erlenmeyer flask-ff.

Add a magnetic stirring bar and mix the solution with 50 I of sodium hydroxide! (104 mol) was partially neutralized. A solution of 5.249 (1065 mol) of potassium cyanate in water (20 s/) was added slowly over 15 minutes while maintaining the temperature at 20°C to 25°C. After the aqueous solution was added, the reaction mixture was stirred for 1 hour and the solids that formed were filtered out. The door block was washed with pentane and air-dried. The dried F mass was A7p-11 and had a melting point of 176-178°C.

A second crop of product was obtained by charging aqueous Part F with 2 g of potassium cyanate and stirring the mixture for 1 hour. The solids formed were separated and air-dried.

This second crop weighed 2.2 g and had a melting point of 175-177°C. Infrared of the product-! The spectrum shows NH bands at 5200 cm, 3250 cm and 3450 cm, j Qc
Strong carbonyl band at m-” and 1580 cML
It had an amide (II) band.

1-t-Octyl semicarbazide was oxidized to t-octylazoformamide in a yield of 22% with neutral permanganate. This t-octylazoformamide is 6
It was a yellow crystalline solid with a melting point of 3-64°C. It began to vaporize at 110-120°C and vaporized rapidly at temperatures above 130°C.

Example I weighed it and put it in. This solution was diluted with 50 g of water and then 28.8 g of 10 g of sodium hydroxide.
(α072 mol) and 116 g (0,1 mol) of sodium carbonate
mol) was added. The flask was equipped with a magnetic stir bar, thermometer, and addition funnel and placed in a cold water bath. On the other hand, p-chloride
Toluene sulfo = #7.6 ji to toluene 50-
into a dropping funnel. This toluene solution is added to the rapidly stirred aqueous solution while the temperature is increased to 15-2.
It was kept at 0°C. Addition of the toluene solution took 15 minutes, after which the reaction mixture was stirred for an additional hour. A white solid formed during the addition. After stirring, the reaction mixture was filtered, and the de-mass was stirred in hexane, refiltered, and air-dried. The amount of white powder was 13g. The product is 1
When melted at 08-110°C, it rapidly vaporized and decomposed.

Example and 25
Placed in a 0-3-hole flask. This solution was diluted with 50% water and then 6.2g of 50% sodium hydroxide (α0
After adding 78 mol) and raising the pH to 9, carbonic acid was added).
4.24 g (cL04 mol) of IJum was added. This flask was equipped with a magnetic stirring bar, a thermometer, and m-chlorobenzoyl chloride 4.9. Equipped with an addition funnel containing li+ ((3 moles of LO). The above reaction mixture was diluted with 25-hexane and then m-chlorobenzoyl chloride was added dropwise over a period of 10 minutes with rapid stirring, during which time the temperature was increased from 18 to 2
It was maintained at 5°C. After the addition was complete, the reaction mixture was stirred for an additional 30 minutes and the white solid that formed was discarded. The block was slurried in a mixture of 100% hexane and 100% warm water and filtered again. The F mass was dried to an appropriate degree on a filter, and then air-dried to a constant weight. The product is 135
There was up to 73 g of white powder with a melting point of ~157°C. The infrared spectrum of the product has a strong NH band at 3200 cIIL and a strong and sharp carbonyl band at 1620 crrL.

Example■ Tetraphthaloylbis(2-1-octylhydrazide)
Weigh out 3 g of t-octylhydrazine, 20 y of water, and 2.1 g of sodium carbonate, and prepare 125 ml of t-octylhydrazine.
into a Meyer flask. The flask was equipped with a magnetic stir bar and thermometer, and then ether 25- was added. This mixture was stirred rapidly and terephthaloyl chloride t8y
of ether (25-) solution was added dropwise while the temperature was increased to 25
It was maintained at ~30°C. A white solid formed immediately upon addition of the ether solution. The reaction mixture was further stirred for 5 hours and treated with F. The F mass was rinsed with fresh ether, reslurried in hot water, and filtered again. The door block was dried to an appropriate degree on a filter, and then air-dried on a weighed watch glass until it reached a constant temperature. The dry product has an amount of L5,9 and 24
It was melted and decomposed at 2-245°C. The infrared spectrum is 324
N) I band at 0 and 5280 cm and 1630
It had a sharp carbonyl band at cIrL.

Example 1. Preparation of 15-di-t-octyl-1,2,12,15-tetraazo-3,11-dioxo-4,7,10-trioxotridecane 4 g of 85% t-octylhydrazine, water 20y and 2-65g of sodium carbonate were weighed into a 135-Erlenmeyer flask. The flask was equipped with a magnetic stir bar and thermometer, and then 25-hexane was added.

The mixture was stirred rapidly and 2.65 g of diethylene glycol bischloroformate was added dropwise, while the reaction temperature was maintained at 20-30°C by a cold water bath. After the addition was complete, the reaction mixture was stirred for an additional hour at room temperature. Gas chromatography analysis showed that all of the t-octylhydrazine had reacted. The mixture was transferred to a separatory funnel and the aqueous layer was separated. The hexane layer was washed with 25 hours of saturated sodium bicarbonate solution, dried over anhydrous sodium sulfate, filtered, and heated under reduced pressure on a rotary evaporator to strip the hexane. The residue was a pale yellow liquid weighing 5.5 g. The infrared spectrum of the product shows a strong broad NH band at 3300 α and 1700 ctti-”
It had a strong broad carbonyl band at .

Pleate 5 methylene chloride solution of bishydrazoester.
The hydrazoester was oxidized to the corresponding bisazoester by stirring with 0.09 for about 4 hours. A solution of the azo ester in methylene chloride was washed with saturated sodium bicarbonate solution and water, dried over anhydrous sodium sulfate, filtered, and heated under reduced pressure on a rotary evaporator to strip off the methylene chloride. The residue was 4.7g-1i of a dark yellow-orange liquid. The infrared spectrum of the azo ester showed no NH band, and the carbonyl band was sharp, at 1760 crrL. The azoester vaporized mildly at 140-150°C, moderately at 150-165°C and rapidly at temperatures above 160°C.

Example W Unsaturated polyester resin foamed by W t-octylhydrazine derivative is Laminac (Laminac).
) 4123 (0-phthalic acid based resin containing about 30% styrene monomer, commercially available from Nis Nis Chemicals). This resin was added with s phr of styrene monomer and 1 phr of Dow Corning 1
The resin was modified by adding 93 surfactant.

The resin and all other ingredients except the peroxide catalyst were weighed into a 9 ounce wax paper cup and blended using a high shear electric mixer. The peroxide catalyst was then added and blended. At this time, set the electric clock and gel time (
The time required for foaming to reach its peak was investigated. After mixing at high shear for approximately 10 seconds, the mixture was placed in multiple 30 fl portions of 3 ounce paper cups and allowed to foam. Gel time and foam density were measured from each sample. The density was measured by the water displacement method. The results are summarized in the table below.

Lamicchiku 4125 resin, which hardens but foams a lot, is 70
i/ft''.

Number of copies of table ■ 0.86
t45 t345%FeC1g, phr
[lL4 α4 Q, 46% Co neodecanoate, p
hr Q, 05 α10.35 thinaphthenic acid cu%phr -0,4-ruversol・
Delta X-9! 'phr! 1.0 5050 gel time, min 2.0 2.
OI O density, lb/ft” 35
41 41*(Lupersol Delta)
Commercial formulation of hydrogen peroxide and methyl ethyl ketone peroxide in dimethyl phthalate - Pennwalt's Lucidor division.

Procedural amendment January 23, 1985 Michibu Uga, Commissioner of the Patent Office Indication of the case Patent application filed in 1985 No. 7941.6 Name of the invention Tertiary octylhydrodine, its salts and medeductors amended person

Claims (1)

[Claims] 1. t-octylhydrazine having the structure ▲ Numerical formula, chemical formula, table, etc. ▼. 2.Structure ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [Here, n is 1 or 2, and A is HCl, HBr, H_2SO_4, H_3PO_4, ▲ Mathematical formulas, chemical formulas, tables, etc. There are ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R is H, CH_3, C_2H_5, C_3H_7,
iso-C_3H_7 and C_6H_5), or when n=2, A is selected from H_2SO_4, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and ▲There are mathematical formulas, chemical formulas, tables, etc.▼ t-octylhydrazine. 3. The salt according to claim 2, wherein n is 1 and A is HCl. 4. The salt according to claim 2, wherein n is 1 and A is H_2SO_4. 5. Structure ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [Here, R_1 and R_2 are individually selected from alkyl or substituted alkyl having 1 to 12 carbon atoms and alicyclic formula having 3 to 12 carbon atoms, or R_1 and R_2 may together form an alkylene divalent group of 3 to 11 carbons, or R_1 is hydrogen and R_2 is selected from phenyl or substituted phenyl of 6 to 14 carbons. Octylhydrazine. 6. The compound according to claim 5, wherein R_1 and R_2 are CH_3. 7. The compound according to claim 5, wherein R_1 is CH_3 and R_2 is C_2H_5. 8. The compound according to claim 5, wherein R_1 and R_2 together form an alkylene divalent group of 5 carbons. 9. Structure ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [Here, Y is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲Mathematical formulas, chemical formulas, tables, etc.▼
R_3 is alkyl having 1 to 12 carbons, aryl or substituted aryl having 6 to 14 carbons, and R_3 is selected from
~8 cycloalkyl and 7 to 9 carbon aralkyl, R_4 and R_5 are each hydrogen,
selected from alkyl of 1 to 12 carbons, aryl or substituted aryl of 6 to 14 carbons, aralkyl of 7 to 9 carbons, and cycloalkyl of 3 to 8 carbons, or R
A compound in which _4 and R_5 can be taken together to form an alkylene divalent group having 4 to 7 carbon atoms. 10.Y is ▲There are mathematical formulas, chemical formulas, tables, etc.▼,
A compound according to claim 9. 11. The compound according to claim 9, wherein Y is m-chlorobenzoyl. 12.Y is ▲There are mathematical formulas, chemical formulas, tables, etc.▼,
A compound according to claim 9. 13. The compound according to claim 9, wherein Y is p-toluenesulfonyl. 14. Structure ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [Here, Z is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, R_4 is H, alkyl with 1 to 12 carbons, 6 carbons
~14 aryl or substituted aryl, 7-9 carbons
aralkyl of 1 to 12 carbons and cycloalkyl of 3 to 8 carbons, R_6 is alkyl of 1 to 12 carbons, cycloalkyl of 3 to 10 carbons, alkyl of 5 to 10 carbonscycloalkylalkyl, 6 to 14 carbons aryl of 7 to 14 carbons, alkylaralkyl of 7 to 14 carbons, and carbon 7
~14 aralkylaryl divalent groups, R
_7 is biphenylene] Compound. 15. The compound according to claim 14, wherein Z is selected from o-, m- or p-phthaloyl divalent groups.