US1943148A - Process for preparing distjbstituted - Google Patents
Process for preparing distjbstituted Download PDFInfo
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- US1943148A US1943148A US1943148DA US1943148A US 1943148 A US1943148 A US 1943148A US 1943148D A US1943148D A US 1943148DA US 1943148 A US1943148 A US 1943148A
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- hydrazine
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- 238000004519 manufacturing process Methods 0.000 title description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 76
- 150000002148 esters Chemical class 0.000 description 56
- 238000000034 method Methods 0.000 description 56
- -1 oxime esters Chemical class 0.000 description 40
- 150000001408 amides Chemical class 0.000 description 34
- 150000001875 compounds Chemical class 0.000 description 34
- 239000000243 solution Substances 0.000 description 32
- LPXPTNMVRIOKMN-UHFFFAOYSA-M Sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 24
- HEDRZPFGACZZDS-UHFFFAOYSA-N chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 24
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 24
- 150000003536 tetrazoles Chemical class 0.000 description 24
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Substances C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 description 22
- 239000003795 chemical substances by application Substances 0.000 description 22
- 150000002923 oximes Chemical class 0.000 description 18
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000000203 mixture Substances 0.000 description 12
- 235000010288 sodium nitrite Nutrition 0.000 description 12
- 239000000126 substance Substances 0.000 description 10
- 101700060963 CBT1 Proteins 0.000 description 8
- VEZUQRBDRNJBJY-UHFFFAOYSA-N Cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 8
- 101710022515 MADS50 Proteins 0.000 description 8
- 102100008341 MKS1 Human genes 0.000 description 8
- 101700003333 MKS1 Proteins 0.000 description 8
- 101700086089 SOC1 Proteins 0.000 description 8
- YFHNDHXQDJQEEE-UHFFFAOYSA-N acetic acid;hydrazine Chemical compound NN.CC(O)=O YFHNDHXQDJQEEE-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000005755 formation reaction Methods 0.000 description 8
- 150000002429 hydrazines Chemical class 0.000 description 8
- IOVCWXUNBOPUCH-UHFFFAOYSA-N nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 230000001476 alcoholic Effects 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- CSKNSYBAZOQPLR-UHFFFAOYSA-N Benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 description 4
- JUINSXZKUKVTMD-UHFFFAOYSA-N Hydrazoic acid Chemical compound N=[N+]=[N-] JUINSXZKUKVTMD-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 150000001805 chlorine compounds Chemical class 0.000 description 4
- 230000000875 corresponding Effects 0.000 description 4
- 125000002587 enol group Chemical group 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000001131 transforming Effects 0.000 description 4
- HWHNFJYQDMSYAF-UHFFFAOYSA-N 1,5-dimethyltetrazole Chemical compound CC1=NN=NN1C HWHNFJYQDMSYAF-UHFFFAOYSA-N 0.000 description 2
- QYSASSWEUXOZEQ-UHFFFAOYSA-N 5-methyl-1-phenyltetrazole Chemical compound CC1=NN=NN1C1=CC=CC=C1 QYSASSWEUXOZEQ-UHFFFAOYSA-N 0.000 description 2
- FZERHIULMFGESH-UHFFFAOYSA-N Acetanilide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 2
- 229960000583 Acetic Acid Drugs 0.000 description 2
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 2
- 101710034608 PPCDC Proteins 0.000 description 2
- CWRVKFFCRWGWCS-UHFFFAOYSA-N Pentrazole Chemical compound C1CCCCC2=NN=NN21 CWRVKFFCRWGWCS-UHFFFAOYSA-N 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N Phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- UHZYTMXLRWXGPK-UHFFFAOYSA-N Phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 2
- 231100000614 Poison Toxicity 0.000 description 2
- 229910005948 SO2Cl Inorganic materials 0.000 description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N Sulfuryl chloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 2
- 229960001413 acetanilide Drugs 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 239000012045 crude solution Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005837 enolization reaction Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000001184 potassium carbonate Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N sulfonic acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- BBDNZMUIQBRBJH-UHFFFAOYSA-N sulfurochloridic acid;toluene Chemical class OS(Cl)(=O)=O.CC1=CC=CC=C1 BBDNZMUIQBRBJH-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
- C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D257/04—Five-membered rings
Definitions
- esters are obtained in either of two ways.
- the first method is to bring esters of oximes to a temperature at which intramolecular rearrangement to the enolic ester of the corresponding mono-substituted acid amide takes place. This rearrangement occurs in a manner which is known per se according to the following formula:
- the second method is to subject oximes to the action of acylating and enolizing agents, as for example PO15, P0013, S0012, CsH5.SO2Cl, CH3.C6H4.SO2C1, etc., by means of which the oxime esters, while being formed, undergo the said intramolecular rearrangement so that the resulting esters appear in the enolic form as esters of mono-substituted acid amides, or, as an alternative procedure, to esterify mono-substituted acid amides with the said acylating substances in the presence, or in the absence, of basic substances such as for instance pyridine, potassium carbonate or the like.
- the formation of the hydrazidines takes place according to the cquation:-
- the enol esters of the mono-substituted acid amides serving as starting materials need not be employed in a pure isolated form but can be used in the form in which they result in the reaction mixture, for example in the intramolecular rearrangement of oxime esters or in the esterii'lcation and enolization of mono-substituted acid amides.
- esters of the enolic form of the mono-substituted acid amides such as are obtained from oximes or its esters or monosubstituted acid amides, in which the radicles R1 and R2 are represented by radicals of the group consisting of, the phenyl radical and any saturated aliphatic radicals, and methylene radicals cyclically connected together by three additional methylene radicals to the pentamethylene ring, such as e-lfillClIlB lactam or its esters.
- the sulphonic acid esters for example the tolueneor benzene sulphonic acid ester, of the cyclohexanone oxime or their transformation products, have in many cases proved to be especially suitable.
- the process is carried out, for example, by treating the esters dissolved or suspended in a suitable organic solvent, for example benzene, with a solution of the hydrazine or hydrazine salt, for example the acetate, in a suitable solvent, for example alcohol, at ordinary temperature, then bringing the mixture to a temperature at which the intra-molecular rearrangement according to Formula 1 takes place, and then bringing and maintaining the mixture at the optimal reaction temperature for the formation of the hydrazidine until the formation of the hydrazidine has been entirely completed, for example by employing suitable cooling agents, the temperatures to be maintained from case to case depending on the kind of ester employed. Or in another way one may introduce the solution of the oxime ester in the solution or suspension of the hydrazine or hydrazine salt, maintained at the temperature the most convenient for the rearrangement and for the formation of the hydrazidine.
- a suitable organic solvent for example benzene
- the agent for introducing the nitroso group for example sodium nitrite and a mineral acid, is then added on cooling if desired and the tetrazole formed, separated in a suitable manner from the solution, for example by the addition of alkali until the solution reacts alkaline to phenolphthalein, evaporating and taking up the residue with chloroform.
- oximes may be acylated by substances such as for example PO15 undergoing at the same time the intra-molecular conversion.
- the reaction mixture may be treated with hydrazine or a hydrazine salt and nitrous acid in statu nascendi in the above described manner.
- acylating agents such as for example acid halogenides such as benzeneor toluene sulpho-chlorides
- alkaline reacting agents preferably pyridine
- inert solvents such as for example chloroform
- the hydrazine or hydrazine salt for example hydrazine acetate
- the present process offers inter alia the advantage over the known processes for preparing tetrazoles by m ans of free hydrazoic acid, of avoiding the use of hydrazoic acid, which is difiicult to handle and dangerous owing to its poisonous as well as to its explosive qualities.
- imido chlorides it ofiers the advantage of avoiding the substituted imido chlorides which particularly in the aliphatic and hydroaromatic series are with difliculty accessible and moreover unstable.
- acylating and enolizing agents in the specification and the claims are to be understood to include such substances which like inorganic acid halogenides for example P015, POCls, SOClz or organic acid halogenides, as for example benzeneor toluenesulfonyl chlorides or the like, which are adapted to esterify oximes or mono-substituted acid amides and to convert the esters formed by intra-molecular transformation into esters of the enolic form of monosubstituted acid amides.
- inorganic acid halogenides for example P015, POCls, SOClz or organic acid halogenides, as for example benzeneor toluenesulfonyl chlorides or the like, which are adapted to esterify oximes or mono-substituted acid amides and to convert the esters formed by intra-molecular transformation into esters of the enolic form of monosubstituted acid amide
- hydrazine in the specification and the claims is to be understood to include not only free hydrazine but also hydrazine in salt form for example in the form of acetate.
- nitrous acid salts particularly sodium nitrite, in the presence of or with addition of an acid.
- B" respectively represent a radical selected from the group consisting of the phenyl radical and any saturated aliphatic radicals, and methylene radicals cyclically connected together by three further methylene radicals to the pentamethylene ring, and then treating the hydrazidine thus formed with a compound containing and yielding the nitrous acid radical under the conditions of the process.
- R and R" respectively represent a radical selected from the group consisting of the phenyl radical and any saturated aliphatic radicals, and methylene radicals cyclically connected together by three further methylene radicals to the pentamethylene ring
- an acylating and enolizing agent of the group consisting of P015, POCls, SOClz, CsHsSOzCl and CH3.C6H4.SO2C1 to form an enolic ester of the type R-COAc wherein Ac is a monovalent radical selected from the group consisting of PC14, SOC1, POC12,
- R and R" respectively represent a radical selected from the group consisting of the phenyl radical and any saturated aliphatic radicals, and methylene radicals cyclically connected together by three further methylene radicals to the pentamethylene ring
- an acylating and enolizing agent of the group consisting of P015, POC13, S0012, CsH5.SO2C1 and CH3.C6H4.SO2C1 to form an enolic ester of the type wherein Ac is a monovalent radical selected from the group consisting of --PC14, -SOC1, -POC12, -SO2C6H5 and -SO2-C6H4-CH3, treating the enolic ester thus formed with a hydrazine to form a hydrazidine and treating the latter with a compound containing and yielding the nitrous acid radical under the conditions of the process.
- R and R respectively represent a radical selected from the group consisting of the phenyl radical and any saturated aliphatic radicals, and methylene radicals cyclically connected together by three further methylene radicals to the pentamethylene ring, whereby the first formed oxime ester undergoes an intramolecular rearrangement so that the ester of the enolic form of the corresponding acid amide is formed, treating the thus formed enolic ester with a hydrazine to form a hydrazidine and treating the latter with a compound containing and yielding the nitrous acid radical under the conditions of the process.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Description
Patented Jan. 9, 1934 UNITED STATES PATENT QFFM'ZE PROCESS FOR PREPARING DISUBSTITUTED TETRAZOLES Georg Scheuing and Bruno Walach, Nieder- Ingelheim-on-the-Rhine, Germany, assignors, by mesne assignments, to E. Bilhuber, Incorporated, Jersey City, N. J a corporation of New Jersey No Drawing. Application April 5, 1929, Serial No. 352,905, and in Germany April 18, 1928 11 Claims.
Such esters are obtained in either of two ways. The first method is to bring esters of oximes to a temperature at which intramolecular rearrangement to the enolic ester of the corresponding mono-substituted acid amide takes place. This rearrangement occurs in a manner which is known per se according to the following formula:
The second method is to subject oximes to the action of acylating and enolizing agents, as for example PO15, P0013, S0012, CsH5.SO2Cl, CH3.C6H4.SO2C1, etc., by means of which the oxime esters, while being formed, undergo the said intramolecular rearrangement so that the resulting esters appear in the enolic form as esters of mono-substituted acid amides, or, as an alternative procedure, to esterify mono-substituted acid amides with the said acylating substances in the presence, or in the absence, of basic substances such as for instance pyridine, potassium carbonate or the like. The formation of the hydrazidines takes place according to the cquation:-
Starting from the oximes:
Starting from the acid amides:
The hydrazidines thus obtained may be converted in a manner known per se into tetrazoles by means of a further treatment with compounds containing and yielding the nitrous acid radical under the conditions of the process according to the following equation:-
The enol esters of the mono-substituted acid amides serving as starting materials need not be employed in a pure isolated form but can be used in the form in which they result in the reaction mixture, for example in the intramolecular rearrangement of oxime esters or in the esterii'lcation and enolization of mono-substituted acid amides.
Since the free hydrazidines are unstable and difficult to handle as well as the enol esters of the monosubstituted acid amides it is in general advisable to avoid isolating them and to carry out the conversion in one step according to the Equations 2 to 4 by starting with oximes or oxime esters or from mono-substituted acid amides or their esters.
As starting materials for the di-substituted tetrazoles are employed the esters of the enolic form of the mono-substituted acid amides such as are obtained from oximes or its esters or monosubstituted acid amides, in which the radicles R1 and R2 are represented by radicals of the group consisting of, the phenyl radical and any saturated aliphatic radicals, and methylene radicals cyclically connected together by three additional methylene radicals to the pentamethylene ring, such as e-lfillClIlB lactam or its esters. Of the esters of the above-mentioned compounds, the sulphonic acid esters, for example the tolueneor benzene sulphonic acid ester, of the cyclohexanone oxime or their transformation products, have in many cases proved to be especially suitable.
When employing oxime esters the process is carried out, for example, by treating the esters dissolved or suspended in a suitable organic solvent, for example benzene, with a solution of the hydrazine or hydrazine salt, for example the acetate, in a suitable solvent, for example alcohol, at ordinary temperature, then bringing the mixture to a temperature at which the intra-molecular rearrangement according to Formula 1 takes place, and then bringing and maintaining the mixture at the optimal reaction temperature for the formation of the hydrazidine until the formation of the hydrazidine has been entirely completed, for example by employing suitable cooling agents, the temperatures to be maintained from case to case depending on the kind of ester employed. Or in another way one may introduce the solution of the oxime ester in the solution or suspension of the hydrazine or hydrazine salt, maintained at the temperature the most convenient for the rearrangement and for the formation of the hydrazidine.
The agent for introducing the nitroso group, for example sodium nitrite and a mineral acid, is then added on cooling if desired and the tetrazole formed, separated in a suitable manner from the solution, for example by the addition of alkali until the solution reacts alkaline to phenolphthalein, evaporating and taking up the residue with chloroform.
Or starting from oximes the latter may be acylated by substances such as for example PO15 undergoing at the same time the intra-molecular conversion. The reaction mixture may be treated with hydrazine or a hydrazine salt and nitrous acid in statu nascendi in the above described manner.
When employing mono-substituted acid amides these may be subjected to the action of acylating agents such as for example acid halogenides such as benzeneor toluene sulpho-chlorides, in the presence of the alkaline reacting agents, preferably pyridine, in the presence of inert solvents such as for example chloroform, the hydrazine or hydrazine salt, for example hydrazine acetate, being allowed to react on the reaction product so obtained.
The present process offers inter alia the advantage over the known processes for preparing tetrazoles by m ans of free hydrazoic acid, of avoiding the use of hydrazoic acid, which is difiicult to handle and dangerous owing to its poisonous as well as to its explosive qualities. Compared with the known processes starting with. imido chlorides it ofiers the advantage of avoiding the substituted imido chlorides which particularly in the aliphatic and hydroaromatic series are with difliculty accessible and moreover unstable.
The following examples serve to illustrate how the invention may be carried into effect:-
(1) 100 grms. of p-toluene sulphonic acid ester of cyclo-hexanone oxime are dissolved in 200 cc. of benzene in the cold. A concentrated alcoholic solution of hydrazine acetate (110% of theory) is then added and the mixture carefully warmed to 30-35 C. This temperature is maintained by suitable cooling until the temperature no more spontaneously rises. The resulting solution of hydrazidine is treated with a cold saturated aqueous solution of 28 grms. of sodium nitrite. After the reaction is complete the solution is acidulated with a mineral acid to congo, evaporated and the residue taken up with chloroform.
1.5 pentamethylene-1-2-3-4-tetrazole of melting point 59 C. and boiling point of 192 C. (under 10 mm. pressure) is obtained in a yield of of theory and more.
The reaction is believed to be as follows:
(2) 113 grms. of e-leucine lactam (1 mol) are esterified with 1'77 grms. of benzene sulphonic chloride at 0 C. in the presence of chloroform and 1.2 mols of pyridine and the resulting solution of the enol ester is introduced into an alcoholic solution of hydrazine acetate (1.2 mol). The mixture is treated with sodium nitrite solution as in Example 1 and the resulting 1.5 pentamethylene 1-2-3-4-tetrazole is isolated in a similar manner.
(3) 36 grms. of methyl-acetamide are dissolved in 200 cc. of chloroform with the addition of grms. of pyridine and treated whilst cooling with 104 grms. of phosphorus pentachloride. After the conversion has taken place the solution containing the enol ester is introduced with stirring into a concentrated alcoholic solution of hydrazine acetate and then the hydrazidine in the solution treated with a cold saturated aqueous solution of sodium nitrite. A yield of about 40% of theory of 1.5 dimethyltetrazole (melting point 70-'71 C.) is obtained. The isolation is effected in a manner similar to that described in Example 1 for pentamethylene tetrazole.
The reaction is believed to be as follows:
(4) 34 grms. of acetanilide are dissolved in a mixture of 44 grms. of pyridine and 300 cc. of chloroform. 44 grms. of benzene sulphonic chloride are introduced drop by drop under vigorous stirring at a temperature of 20-25 C. After standing for a short time the crude solution of the enol ester is introduced drop by drop at a temperature of 20-25 0., into a solution of 8.5 grms. of hydrazine in a mixture of 100 cc. of methyl alcohol in 16 cc. of glacial acetic acid. The reaction mixture is allowed to stand for some time and is then treated with aqueous sodium nitrite solution. The 1-phenyl-5-methyl-tetrazole (melting point 99-100 C.) obtained may be separated from the reaction mixture as in the previous examples. This reaction is believed to be as follows:
The words acylating and enolizing agents in the specification and the claims are to be understood to include such substances which like inorganic acid halogenides for example P015, POCls, SOClz or organic acid halogenides, as for example benzeneor toluenesulfonyl chlorides or the like, which are adapted to esterify oximes or mono-substituted acid amides and to convert the esters formed by intra-molecular transformation into esters of the enolic form of monosubstituted acid amides.
The word hydrazine in the specification and the claims is to be understood to include not only free hydrazine but also hydrazine in salt form for example in the form of acetate.
The phrase, the compounds containing and yielding the nitrous acid radical, in the specification and in the claims is to be understood to include any compounds yielding nitrous acid in statu nascendi under the conditions of the process,
as for example, nitrous acid salts, particularly sodium nitrite, in the presence of or with addition of an acid.
What we claim is:
1. The process of preparing tetrazoles which comprises treating with a hydrazine a compound having the structure wherein Ac is a monovalent radical selected from the group consisting of -PC14, SOC1, POC12,
B" respectively represent a radical selected from the group consisting of the phenyl radical and any saturated aliphatic radicals, and methylene radicals cyclically connected together by three further methylene radicals to the pentamethylene ring, and then treating the hydrazidine thus formed with a compound containing and yielding the nitrous acid radical under the conditions of the process.
2. The process of preparing tetrazoles which comprises treating with a hydrazine a compound having the structure COAc wherein Ac is a monovalent radical selected from the group consisting of -PCl4, SOC1, POCl2, -SO2C6H5 and SO2C6H4-CH3 and R and B" respectively represent a radical selected from the group consisting of the phenyl radical and any saturated aliphatic radicals, and methylene radicals, cyclically connected together by three further methylene radicals to the pentamethylene ring, and then treating the hydrazidine thus formed with an alkali metal salt of the nitrous acid.
3. The process of preparing tetrazoles which comprises treating with a hydrazine a compound having the structure wherein Ac is a monovalent radical selected from the group consisting of PC14, --SOC1, POC12, SO2-C6H5 and SO2-C6H4-CH3 and then treating the hydrazidine thus formed with a compound containing and yielding the nitrous acid radical under the conditions of the process.
4. The process of preparing tetrazoles which comprises treating a non-enolized acid amide of the type:
it-H (wherein R and R" respectively represent a radical selected from the group consisting of the phenyl radical and any saturated aliphatic radicals, and methylene radicals cyclically connected together by three further methylene radicals to the pentamethylene ring) with an acylating and enolizing agent of the group consisting of P015, POCls, SOClz, CsHsSOzCl and CH3.C6H4.SO2C1 to form an enolic ester of the type R-COAc wherein Ac is a monovalent radical selected from the group consisting of PC14, SOC1, POC12,
SO2C6H5 and SOzCsI-I4CH3, treating the enolic ester thus formed with a hydrazine to form a hydrazidine and treating the latter with a compound containing and yielding the nitrous acid radical under the conditions of the process.
5. The process of preparing tetrazoles which comprises treating in the presence of a basic substance a non-enolized acid amide of the type: R([3=O R"NH (wherein R and B" respectively represent a radical selected from the group consisting of the phenyl radical and any.saturated aliphatic radicals, and methylene radicals cyclically connected together by three further methylene radicals to the pentamethylene ring) with an acylating and enolizing agent of the group consisting of PC15, POC13, SOC12, C6H5.SO2C1 and CH3-C6H4.SO2C1 to form an enolic ester of the type wherein Ac is a monovalent radical selected from the group consisting of -PC14, SOC1, POC12, -SOzC6Hs and SO2C6H4CH3, treating the enolic ester thus formed with a hydrazine to form a hydrazidine and treating the latter with a compound containing and yielding the nitrous acid radical under the conditions of the process.
6. The process of preparing tetrazoles which comprises treating in the presence of pyridine a non-enolized acid amide of the type:
R"II\IH (wherein R and R" respectively represent a radical selected from the group consisting of the phenyl radical and any saturated aliphatic radicals, and methylene radicals cyclically connected together by three further methylene radicals to the pentamethylene ring) with an acylating and enolizing agent of the group consisting of P015, POC13, S0012, CsH5.SO2C1 and CH3.C6H4.SO2C1 to form an enolic ester of the type wherein Ac is a monovalent radical selected from the group consisting of --PC14, -SOC1, -POC12, -SO2C6H5 and -SO2-C6H4-CH3, treating the enolic ester thus formed with a hydrazine to form a hydrazidine and treating the latter with a compound containing and yielding the nitrous acid radical under the conditions of the process.
7. The process of preparing 1-5-pentamethylene-1-2-3-4-tetrazole which comprises treating the e-leucine lactam with an acylating and enolizing agent of the group consisting of P015, P0013, SOClz, CsH5.SO2C1 and CH3.C6H4.SO2C1, treating the resulting lactim ester with a hydrazine to form a hydrazidine and treating the latter with a compound containing and. yielding the nitrous acid radical under the conditions of the process.
8. The process of preparing tetrazoles, which comprises treating with a hydrazine, at a temperature at which an intramolecular rearrangement of the ester takes place, an ester of an oxime of the type R'C=NOAc wherein Ac is a monovalent radical selected from the group consisting of --PC14, -SOC1, -POCl2, -SO2--C6H5 and SO2CsH4-CH3 and R and B" respectively represent a radical selected from the group consisting of the phenyl radical and any saturated aliphatic radicals, and methylene radicals cyclically connected together by three further methylene radicals to the pentamethylene ring, and treating the thus formed hydrazidine with a compound containing and yielding the nitrous acid radical under the conditions of the process.
9. The process of preparing tetrazoles which comprises treating with an acylating agent of the group consisting of PC15, POCls, SOC12,
the type RC=NOH wherein R and R respectively represent a radical selected from the group consisting of the phenyl radical and any saturated aliphatic radicals, and methylene radicals cyclically connected together by three further methylene radicals to the pentamethylene ring, whereby the first formed oxime ester undergoes an intramolecular rearrangement so that the ester of the enolic form of the corresponding acid amide is formed, treating the thus formed enolic ester with a hydrazine to form a hydrazidine and treating the latter with a compound containing and yielding the nitrous acid radical under the conditions of the process.
10. The process of preparing 1-5-pentamethylene-1-2-3-4-tetrazole which comprises treating cyclohexanone-oxime with an acylating agent of the group consisting of PC15, P0013, SOC12, CsI-I5SO2C1 and CH3C6H4SO2C1, treating the resulting enolic ester of the e-leucine lactam with a hydrazine to form a hydrazidine and treating the latter with a compound containing and yielding the nitrous acid radical under the conditions of the process.
11. The process of preparing I-S-pentamethylene-l-2-3-4-tetrazole which comprises treating cyclohexanone-oxime with a sulfonyl chloride of the benzene series at a temperature at which intramolecular rearrangement to the first formed sulphonic acid ester of cyolohexanone oxime to the enolic ester of e-leucine lactam takes place, treating the thus formed enolic ester with a hydrazine to form a hydrazidine and treating the latter with a compound containing and yielding the nitrous acid radical under the conditions of the process.
GEORG SCHEUING. BRUNO WALACH.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US1943148A true US1943148A (en) | 1934-01-09 |
Family
ID=3426063
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US1943148D Expired - Lifetime US1943148A (en) | Process for preparing distjbstituted |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US1943148A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2507337A (en) * | 1946-06-12 | 1950-05-09 | Bilhuber Inc E | 1, 5-dialkyl tetrazoles and preparation thereof |
| US4632674A (en) * | 1985-12-27 | 1986-12-30 | Exxon Chemical Patents Inc. | Diesel fuel containing a tetrazole or triazole cetane improver |
-
0
- US US1943148D patent/US1943148A/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2507337A (en) * | 1946-06-12 | 1950-05-09 | Bilhuber Inc E | 1, 5-dialkyl tetrazoles and preparation thereof |
| US4632674A (en) * | 1985-12-27 | 1986-12-30 | Exxon Chemical Patents Inc. | Diesel fuel containing a tetrazole or triazole cetane improver |
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