JPS6412263B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a tertiary amine having a long-chain alkyl group, and more specifically, the present invention relates to a method for producing a tertiary amine having a long-chain alkyl group. The present invention relates to a method for producing a tertiary amine having one or two alkyl groups. Higher amines and their derivatives having long-chain alkyl groups are useful substances that have a variety of uses depending on their structure, such as emulsifiers, rust preventives, and intermediates for fiber softening agents, and currently most of them are are commercially produced from natural fatty acids such as coconut oil, palm oil, and tallow. On the other hand, it is also known to synthesize tertiary amines from long-chain olefins, carbon monoxide, hydrogen, and primary or secondary amines.
No. 9527 discloses a one-step method for the synthesis of tertiary amines from olefins, carbon monoxide, hydrogen, and secondary amines using a catalyst containing a complex compound of tri(hydrocarbyl)phosphine and cobalt carbonyl. However, this method produces a large amount of alcohol as a by-product and is not necessarily effective as a method for producing the desired tertiary amine. Helvetica Chimica Acta.54 (1971) 1440
-1445 and US Pat. No. 3,947,458 disclose a method for producing amines from olefins, carbon monoxide, water, and nitrogen-containing compounds by using a catalyst consisting of iron pentacarbonyl and a rhodium compound. Although this method has a fairly good amine yield, it does not use a cheap mixture of hydrogen and carbon monoxide as a raw material gas, but requires pure carbon monoxide, and requires recovery of expensive rhodium compounds. is necessary. In JP-A-49-88812, the electron-donating atom is oxygen,
A process is disclosed for producing a tertiary amine by reacting an olefin, carbon monoxide, hydrogen, and a secondary amine in the presence of a group metal complex with a ligand that is nitrogen or sulfur. Although this method also has an extremely good yield of the target amine, the recovery and reuse of expensive group metals such as rhodium and ruthenium, which are used in considerable amounts, poses a problem for industrial use. is not mentioned at all. That is, in the method of synthesizing higher amines having long-chain alkyl groups using long-chain olefins, the reaction selectivity is low when cobalt, etc., which is relatively inexpensive among group metal compounds, is used. Yield is low. On the other hand, when an expensive metal compound such as rhodium is used, a high yield can be obtained, but it is not necessarily industrially advantageous because the catalyst cost is high. Therefore, the one-step synthesis method of higher amines having long-chain alkyl groups from olefins is difficult to achieve when expensive catalysts such as rhodium are used to obtain high yields. is necessary. In the past, various proposals have been made regarding the recovery of rhodium catalysts used in hydroformylation reactions, etc., such as (1) a method of separating the product and catalyst by evaporation or distillation (for example, JP-A-52-125103) ( 2) A method of separating the generated aldehyde by extracting it with a polar solvent such as water (e.g., JP-A No. 51-29412) (3) A method of separating the rhodium complex by adsorption (e.g., JP-A-50-62936) ( 4) A method of separation using a membrane made of silicone rubber, cellulose, etc. (for example, Japanese Patent Publication No. 7365/1983) is known. However, method (1) above is applicable when the product is a lower aldehyde with a low boiling point and the catalyst is a rhodium complex modified with triphenylphosphine etc., which has relatively high thermal stability. However, there are various problems in applying it to the production process of high boiling point higher amines, which is the object of the present invention. Furthermore, the method (2) above cannot be applied to higher amines with low water solubility. The adsorption method (3) is applied to the industrial production of higher aldehydes, but it is not an effective method when the product is a nitrogen-containing compound such as an amine that may have a negative effect on the adsorbent. sea bream. Furthermore, membrane separation in (4) requires a large difference in molecular size between the product and the catalyst complex, and is not an effective method for higher amine products with relatively large molecules. As a result of intensive research into industrially advantageous methods for producing higher amines, the present inventors have found that by carrying out the reaction using specific alcohols as a solvent, after the reaction is completed, the reaction solution is It is necessary to separate into a phase mainly composed of amine and a phase mainly composed of the solvent used, and in addition, the complex catalyst such as rhodium used substantially exists in the solvent phase and still maintains sufficient catalytic activity. It has been found that the phase-separated solvent phase can be used again for the reaction. That is, the present invention involves reacting a long-chain olefin having 8 to 30 carbon atoms, carbon monoxide, hydrogen, and a primary or secondary amine in the presence of a catalyst whose main component is a compound containing rhodium or ruthenium. , a method for producing tertiary amines having a long-chain alkyl group, in which the solvent has 1 to 3 carbon atoms.
Consisting of monohydric alcohols, dihydric alcohols having 2 to 6 carbon atoms, trihydric alcohols having 3 to 6 carbon atoms, and intermolecular dehydration condensates of dihydric or trihydric alcohols having 2 to 3 carbon atoms. reacting with an alcohol selected from the group or a mixture thereof with water,
This is a method for producing tertiary amines, which comprises phase-separating a reaction product into an amine layer containing the produced tertiary amine and a solvent layer containing a catalyst. The catalyst used in the present invention is a rhodium or ruthenium compound in the form of a halide, nitrate, halocarbonyl or carbonyl complex. Specifically, rhodium chloride, rhodium nitrate, rhodium bromide, rhodium iodide, chlorodicarbonyl rhodium dimer, rhodium carbonyl, ruthenium chloride, ruthenium nitrate, ruthenium bromide, ruthenium iodide, dichlorotricarbonyl ruthenium dimer. and ruthenium carbonyl. The amount of these catalysts used is in the range of 1 mole of catalyst per 100 to 20,000 moles of raw material olefin, and the amount of catalyst is increased from this range (i.e., 1 mole or more of catalyst per 100 moles of raw material olefin).
This is not harmful, but it makes it economically unattractive. Also, reduce the amount of catalyst from the above range (i.e. 1 mole or less of catalyst per 20,000 moles of raw material olefin).
This results in a decrease in reaction rate and a sharp deterioration in reaction selectivity, making it difficult to carry out the present invention effectively. Particularly preferred is a range of 1 mole of the catalyst per 500 to 10,000 moles of raw material olefin. The long-chain olefin used as a raw material in the present invention is an olefinic unsaturated compound having a hydrocarbon structure, and in particular, the hydrocarbon structure is linear and the number of carbon atoms is 8.
~30 is suitable. Such linear olefins can be produced, for example, by ethylene oligomers having terminal double bonds obtained by low polymerization of ethylene, by catalytic dehydrogenation of linear hydrocarbons obtained from kerosene and gas oil fractions, or by α-containing olefins such as ethylene oligomers. -Long-chain olefins having internal double bonds obtained by isomerization or disproportionation of olefins, etc. can be mentioned. The primary amine or secondary amine used as a raw material is selected depending on the desired higher amine and is not particularly limited. For example, if the desired product is a long-chain alkyldimethyl- or diethyl-amine, which is an intermediate for textile softeners, dimethyl or diethylamine is selected as the secondary amine, and the desired product is a long-chain dialkylmethyl- or diethylamine. Alternatively, in the case of ethylamine, methylamine or ethylamine is selected as the primary amine. The molar ratio of raw material olefin and raw material amines is
The case where a long-chain monoalkyl type tertiary amine is synthesized using a secondary amine is different from the case where a long-chain dialkyl type tertiary amine is synthesized using a primary amine. In the former case, the molar ratio of olefin:secondary amine is preferably 1:1 to 1:3, and in the latter case, the molar ratio of olefin:primary amine is preferably about 2:1. When using a primary amine, if the amount of the primary amine is large, long-chain monoalkyl type secondary amines are likely to be produced as by-products, and if the amount is small, aldehydes as intermediates may be produced, or heavy substances may be produced. is likely to be produced as a by-product, and the yield of tertiary amine decreases. In the present invention, specific alcohols are used as solvents. These alcohols tend to undergo phase separation from the amines in the reaction product, and reduce the elution of the rhodium compound or ruthenium compound of the catalyst into the amine phase. The phase separation between the tertiary amine product and the alcohol used as a solvent is slightly affected by the carbon chain length of the long-chain alkyl group of the tertiary amine. That is, as the carbon chain length of the long-chain alkyl group becomes shorter, the compatibility with alcohols increases, so in this case, it is preferable to select alcohols with high polarity as solvents. . If the polarity of the solvent is insufficient, a long standing time is required to phase separate the reaction products;
Furthermore, the amount of catalyst eluted into the produced amine increases.
In this case, it can be improved by changing the solvent to a more polar solvent or adding a polar medium such as water to the reaction system. When the carbon chain length of the long-chain alkyl group in the produced amine is large,
Alternatively, even if the carbon chain length is the same, if it is a long-chain dialkyl type, phase separation from the solvent alcohol is generally good. Regarding the alcohols used as a solvent in the present invention, monohydric alcohols with 1 to 3 carbon atoms include methanol, ethanol, n-propanol, and isopropanol, and dihydric alcohols with 2 to 6 carbon atoms include ethylene glycol and propylene. These include glycol, butanediol, pentanediol, hexanediol, neopentyl glycol, and the like. Glycerin, trimethylolpropane, etc. are used as the trihydric alcohol having 3 to 6 carbon atoms. In addition, diethylene glycol, an intermolecular dehydration condensate of dihydric alcohol having 2 to 3 carbon atoms,
Polyethylene glycol, polypropylene glycol, or block or random polymers of ethylene glycol and propylene glycol with an average molecular weight of 2000 or less, such as triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol, are used, and diglycerin can also be used. . In addition, N,N-dimethylformamide, N,N-dimethylacetamide, sulfolane, dimethylsulfone, and the like can be used as solvents that have polarity like the above-mentioned alcohols and cause good phase separation from the produced amine. The amount of solvent used is not particularly limited, but using a larger amount of solvent than necessary will reduce the yield per reactor capacity, and the amount of amine produced will be relatively small, making phase separation difficult. Due to the catalyst concentration, it becomes necessary to increase the amount of catalyst used. on the other hand,
Similarly, if the amount of solvent used is extremely small, it will be difficult to phase separate the solvent, which is relatively small compared to the amount of amine produced, and the elution of the catalyst into the amine phase will increase, reducing the effect of reusing the catalyst. There is a risk that it will decrease. Therefore, the amount of solvent used is usually 20 to 70 parts by weight per 100 parts by weight of the total amount of olefin and primary or secondary amine charged as raw materials,
It is particularly preferable to use 30 to 50 parts by weight in order to effectively carry out the present invention. The reaction conditions for the tertiary amine synthesis of the present invention are temperatures of about 70-240°C and pressures of about 30-300 atmospheres, particularly temperatures of 100-200°C and pressures of 60-200 atmospheres.
Atmospheric pressure is preferred. The reaction pressure is substantially determined by the partial pressures of carbon monoxide and hydrogen used in the reaction, but in some cases, gases inert to the reaction such as nitrogen, helium, and methane may also be present at the same time. can not use. The hydrogen:carbon monoxide molar ratio can also be varied over a wide range, but in most cases a ratio of 1.5 to 2.0 moles of carbon monoxide per mole of hydrogen will improve olefin conversion and tertiary amine conversion. Good results are obtained in both yields. The reaction is carried out under stirring, but by standing still after the reaction is complete, the phase separates into an upper layer rich in the produced amine and a lower layer mainly composed of the solvent. Most of the catalyst used in the reaction is contained in the separated solvent phase, and the reaction can be carried out by adding the raw material olefin and raw material amine to this solvent phase again, and the catalyst has sufficient activity. keeping. In the method of the present invention, the catalyst is recovered by phase separation, so there is no need to apply heat to the catalyst as in conventional distillative separation, and as a result, the catalyst is not denatured or deteriorated by heat. Moreover, since it is recovered together with the phase-separated solvent, it has the excellent advantage that it can be used again in the reaction as it is. This advantage is particularly important in the synthesis reaction of tertiary amines having long-chain alkyl groups from olefins, carbon monoxide, hydrogen and amines, which is the subject of the present invention. The rhodium complex, which does not contain carbon dioxide, is highly active as a catalyst, and this catalyst has a relatively low stability against heat, and the reaction product, a higher amine, has a relatively high boiling point, so it has an extremely excellent effect. be. Another advantage of the present invention is that since there are almost no heavy substances produced as by-products in the reaction in the solvent containing the phase-separated catalyst, the solvent containing the catalyst can be recycled into the reaction system. There should be no accumulation of heavy substances. In methods where products are separated by distillation, the by-product heavy substances remain together with the catalyst, and as the catalyst is recycled, the by-product heavy substances are also returned to the reaction system, causing heavy substances to be added to the reaction system. It causes accumulation and adversely affects the reaction system. In order to suppress this accumulation below a certain limit, it is necessary to remove a portion of the circulating catalyst from the reaction system, and along with this, a portion of the effective catalyst is also removed.
In the method of the present invention, such treatment is not required, the catalyst utilization efficiency is extremely high, and no trouble occurs due to the circulation of heavy substances. Another advantage of the present invention is the high stability of the catalyst in the reaction system. That is, when the reaction of the present invention is carried out using benzene, toluene, etc. as a solvent, a part of the complex catalyst is decomposed and insoluble substances are produced, but in the solvent system used in the present invention, insoluble substances are generated after the reaction. In addition, the reaction can be carried out at lower reaction pressures and at higher temperatures at the same reaction pressure than when using a solvent system that does not cause phase separation, such as benzene or toluene. However, no insoluble substances are observed after the reaction. Therefore, the range of reaction conditions that can be selected is expanded, making it possible to carry out the reaction under more advantageous conditions. EXAMPLES The present invention will be specifically explained below using Examples, but the present invention is not limited to the following Examples unless the gist of the invention is exceeded. Example 1 40 ml of methanol containing 0.014 g of RhCl _{3.3H 2} O,
30g of 1-dodecene and 20g of diethylamine
The mixture was charged into a 200 ml autoclave, and the reaction was carried out at 140° C. for about 3 hours under a pressure of 120 Kg/cm ² of a mixed gas with a hydrogen:carbon monoxide molar ratio of 1.8:1.0. After the reaction was completed, the contents phase-separated into an upper layer rich in the produced amine and a lower layer mainly composed of a yellowish solvent. Analysis of the compositions of the upper and lower layers revealed that the olefin conversion rate was 99% and the yield of tridecyldiethylamine, the desired product, was 85%. 7ppm rhodium in the produced amine phase and in the solvent phase.
It was found that 160 ppm of rhodium was contained, with most of the rhodium being contained in the solvent phase. Adding 30 g of 1-dodecene and 20 g of diethylamine again to 40 g of this solvent phase and carrying out the same reaction, the olefin conversion rate was 98%, the yield of the produced amine was 81%, and the catalyst in the solvent phase was active and selective. Both genders were good. Example 2 Except that an ethanol aqueous solution with an ethanol/water weight ratio of 4/1 was used instead of methanol.
All reactions were carried out as described in Example 1. After the reaction was completed, it was separated into the produced amine phase and the solvent phase as in Example 1, and as a result of compositional analysis of each phase, the olefin conversion rate was 99% and the yield of the desired product tridecyldiethylamine was 87%. It was hot. The rhodium concentrations in the produced amine phase and solvent phase are respectively
4ppm and 130ppm, most of the rhodium was contained in the solvent phase. When 25 g of 1-dodecene and 18 g of diethylamine were added to 30 g of this solvent phase and the reaction was carried out in the same manner, the olefin conversion rate was 97% and the yield of the amine produced was
80%, and both activity and selectivity were maintained. Example 3 40 ml of ethanol containing 0.015 g of RhCl ₃ 3H ₂ O,
35 g of 1-hexadecene and 18 g of diethylamine
was charged into a 200 ml autoclave, and the reaction was carried out under the conditions described in Example 1. After the reaction was completed, the contents phase-separated into a produced amine phase and a yellow solvent phase.
The same amount of 1-hexadecene and diethylamine as used in the first reaction was added to this solvent phase again, the reaction was carried out, the phases were separated, and the reaction was repeated by replenishing the raw materials and carrying out the reaction. . The olefin conversion rate and heptadecyl diethylamine yield at that time were as follows.

[Table] Example 4 A C ₁₂ -internal olefin obtained by dehydrogenating n-dodecane as a raw material and adsorbing and separating it was used as a raw material olefin. Ethanol 30 containing 0.012g RhCl _{3.3H 2} O
ml, 30 g of the above C ₁₂ -n-olefin and 15 g of dimethylamine in a hydrogen:carbon monoxide molar ratio.
The reaction was carried out at 150° C. for about 3 hours under a pressure of 100 Kg/cm ² of a mixed gas of 1.7:1.0. After the reaction, the phase separated as in Examples 1 to 3, and the analysis results of the upper and lower layers showed that the olefin conversion rate was 98%.
The yield of the produced amine was 85%, which is similar to that of 1-olefin. In addition, the rhodium concentration in each phase was 10 ppm in the amine phase and 10 ppm in the solvent phase.
It was found that most of the rhodium was present in the solvent phase. Example 5 30 ml of methanol containing 0.010 g of RhCl ₃ 3H ₂ O,
35 g of 1-octene and 7.7 g of monoethylamine
was charged into a 200ml autoclave, and a gas with a hydrogen:carbon monoxide molar ratio of 1.8:1.0 was added under a pressure of 100Kg/ ^cm2 .
The reaction was carried out at 140°C for about 3 hours. It was separated into an upper layer rich in produced amines and a lower layer mainly composed of solvent, and the composition was analyzed, and the results showed that the olefin conversion rate was 99% and the yield of dinonylethylamine was 81%. The concentrations of rhodium contained in the upper and lower phases were 10 ppm and 110 ppm, respectively, and most of it was dissolved in the solvent phase. Example 6 40 ml of ethylene glycol containing 0.017 g of RhCl ₃ .3H ₂ O, 30 g of 1-tetradecane and 15 g of dimethylamine were charged into a 200 ml autoclave, and a reaction was carried out under the conditions described in Example 1. After the reaction was complete, the contents phase-separated into an almost transparent product amine phase and a green solvent phase. The solvent phase contained almost no pentadecyldimethylamine product, and the rhodium concentration in the amine phase was 3 ppm, indicating that the amine product and the catalyst could be separated very well. As a result of analysis, the conversion rate of olefin was 99%, and the yield of pentadecyldimethylamine, the desired product, was 86%. Example 7 The reaction was carried out as described in Example 6 except that triethylene glycol was used as the solvent. After the reaction, the contents phase-separate into an almost colorless product amine phase and a pale green solvent phase, and the rhodium concentration in the product amine phase is 4 ppm, and the solvent phase contains almost no product. Some pentadecyldimethylamine was not included and the separation of product and catalyst was very good. As a result of the analysis, the olefin conversion rate was 99%, and the yield of the desired product, pentadecyldimethylamine, was
It was 83%. Example 8 A reaction was carried out in accordance with the method described in Example 6, except that 34 g of 1-hexadecene and 20 g of diethylamine were used as raw materials, and polyethylene glycol with an average molecular weight of 600 was used as a solvent. After the reaction, the contents phase-separate into a colorless and transparent produced amine phase and a pale green solvent phase, and almost no rhodium is detected in the produced amine phase, and no produced amine is found in the solvent phase. , indicating that the separation of catalyst and product was almost complete. As a result of analysis, the conversion rate of olefin was 98%, and the yield of heptadecyldiethylamine, the desired product, was 86%. Add 40 g of this solvent phase to the amount of 1-
The olefin conversion rate and amine yield when hexadecene and diethylamine were added and the reaction was repeated are shown below.

[Table] Example 9 The reaction was carried out as described in Example 6 except that propylene glycol was used as the solvent. The phase separation between the produced amine and the solvent was good, and the rhodium concentration in the produced amine phase was 5 ppm, indicating that most of the catalyst was present in the solvent phase. As a result of analysis, the olefin conversion rate was 99%, and the yield of the desired product, pentadecyldimethylamine, was 86%. Example 10 1,4-butanediol as a solvent, 36 g of 1-octadecene and 20 g of dimethylamine as raw materials
All reactions were carried out according to the method described in Example 6, except that g was used. The contents after the reaction are a formed amine phase mainly composed of the product nonadecyldimethylamine and 1,4-
The phase separated into a solvent phase mainly containing butanediol. As a result of analyzing the composition, the olefin conversion rate was 98.
%, the yield of nonadecyldimethylamine was 82%. Example 11 40 ml of glycerin containing 0.020 g of RhCl ₃ 3H ₂ O,
25 g of 1-decene and 30 g of diethylamine in 200 g
ml into autoclave, hydrogen: carbon monoxide
The reaction was carried out at a temperature of 140° C. for about 2 hours under a pressure of 130 Kg/cm ² of a 1.7:1.0 mixed gas. After the reaction, the contents rapidly separated into an almost colorless amine phase and a solvent phase mainly composed of glycerin. Almost no product undecyldiethylamine was observed in the solvent phase, and almost no rhodium concentration was detected in the produced amine phase, indicating that the separation of the produced amine and catalyst rhodium was almost complete. Ta. As a result of the analysis, the olefin conversion rate was 99%, and the yield of the desired product, undecyldiethylamine, was 89%.
It was %. Example 12 The reaction was carried out in the same manner as in Example 11, except that diglycerin, which is a dehydrated condensate of glycerin, was used as the solvent. Phase separation after the reaction was rapid, and almost no produced amine was observed in the solvent phase. Analysis results showed that the olefin conversion was 98% and the yield of the desired product, undecyldiethylamine, was 86%.
It was %. When 20 g of 1-decene and 25 g of diethylamine were added to 35 g of this solvent phase and the reaction was carried out again, the olefin conversion was 96% and the yield of the desired amine was 79%. Example 13 40 ml of methanol containing 0.050 g of RhCl _{3.3H 2} O,
35 g of 1-hexadecene and 20 g of dimethylamine
was charged into a 200 ml autoclave, and reaction was carried out at 160° C. for about 5 hours under a pressure of 150 kg/cm ² of a mixed gas with a hydrogen:carbon monoxide molar ratio of 1.8:1.0. After the reaction, the contents separated into a phase rich in the produced amine and unreacted olefin and a solvent phase mainly consisting of methanol. As a result of analyzing the composition of each phase,
The olefin conversion rate was 38%, and the yield relative to the amine was
It was 33%. Example 14 40 ml of ethylene glycol containing 0.120 g of RuCl ₃ .3H ₂ O, 30 g of 1-tetradecene and 25 g of diethylamine were charged into a 200 ml autoclave and the reaction was carried out under the conditions described in Example 13. After the reaction, the contents were separated into a phase rich in produced amines and unreacted olefins and a solvent phase mainly containing ethylene glycol, and the solvent phase contained extremely small amounts of unreacted olefins and produced amines. 20 g of 1-tetradecene and 15 g of diethylamine were added to 30 g of this solvent phase, and the reaction was carried out again under the same conditions. When the contents were taken out, they were separated into two phases as in the first time. As a result of compositional analysis of the produced amine phase, the olefin conversion rate and yield relative to the produced amine in the above two reactions are as shown below, and when a ruthenium-containing compound is used as a catalyst, it is the same as in the case of a rhodium-containing compound. This shows that it is basically possible to apply the method of the present invention to.

[Table] Comparative example 1 n-butanol 40 containing RhCl ₃・3H ₂ O 0.015g
ml, 1-octadecene 34g and diethylamine
25 g was charged into a 200 ml autoclave, and the reaction was carried out at 150° C. for about 2 hours under a pressure of 110 kg/cm ² of a mixed gas with a hydrogen:carbon monoxide molar ratio of 1.6:1.0. Although the conversion rate of 1-octadecene was 98% and the yield of nonadecyldiethylamine, the desired product, was 83%, good results were obtained, but no phase separation of the contents was observed.

Claims (1)

[Claims] 1. A long-chain olefin having 8 to 30 carbon atoms, carbon monoxide, hydrogen, and a primary or secondary amine in the presence of a catalyst containing a rhodium- or ruthenium-containing compound as a main component. In the method for producing tertiary amines having a long-chain alkyl group by reaction, the solvent may be monohydric alcohols having 1 to 3 carbon atoms, dihydric alcohols having 2 to 6 carbon atoms, or tertiary amines having 3 to 6 carbon atoms. A reaction product is produced by reacting with an alcohol selected from the group consisting of trihydric alcohols, intermolecular dehydration condensates of dihydric or trihydric alcohols having 2 to 3 carbon atoms, or a mixture thereof with water. A method for producing tertiary amines, which comprises phase-separating an amine layer containing a tertiary amine and a solvent layer containing a catalyst. 2. The method of claim 1, wherein the solvent layer containing the catalyst is recycled to the reaction zone. 3 An intermolecular dehydration condensate of a dihydric or trihydric alcohol having 2 to 3 carbon atoms is polyethylene glycol, polypropylene glycol, a block or random polymer of ethylene glycol and propylene glycol, or diglycerin with an average molecular weight of 2000 or less. The method according to claim 1 or 2, wherein: