CN106699603A - Synthetic method of isotope-labelled carbamate - Google Patents

Synthetic method of isotope-labelled carbamate Download PDF

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Publication number
CN106699603A
CN106699603A CN201611015272.4A CN201611015272A CN106699603A CN 106699603 A CN106699603 A CN 106699603A CN 201611015272 A CN201611015272 A CN 201611015272A CN 106699603 A CN106699603 A CN 106699603A
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carbamate
synthetic method
methyl
isotope
compound
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CN106699603B (en
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邱俊
王帅
方华仁
李虎林
姜永悦
蔡扬
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Shanghai Research Institute of Chemical Industry SRICI
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C269/04—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from amines with formation of carbamate groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/05—Isotopically modified compounds, e.g. labelled

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a synthetic method of isotope-labelled carbamate. The synthetic method comprises the following steps: by utilizing stable isotope 13C-labelled carbon monoxide (99.3%atom13C) as a raw material, reacting with an amino compound or a stable isotope-labelled amino compound (99%atom 15N) and a hydroxyl compound in presence of a catalyst, controlling reaction temperature to be 150-250 DEG C, and stirring and reacting for 8-30 hours; then cooling to room temperature, carrying out concentration and evaporation to dry reaction liquid, then adding water and activated carbon, controlling reaction temperature to be 20-100 DEG C, stirring for 0.1-3 hours, and separating filtrate after filtration, thus obtaining 13C-labelled carbamate or 13C and 15N-labelled carbamate. According to the synthetic method provided by the invention, the synthetic route is short, the operation is simple, the purity of the prepared stable isotope-labelled carbamate reaches 98.5% or above, isotope abundance reaches 99%atom13C and 99%atom 15N or above, and requirements applied to carbamate pesticide residue monitoring on food, soil and the like can be met.

Description

A kind of synthetic method of the carbamate of isotope marks
Technical field
The invention belongs to stable isotope labelled compound synthesis technical field, more particularly, to a kind of isotope marks The synthetic method of carbamate.
Background technology
Nineteen thirty-seven Votai Benfold and its colleague obtain ammonia first in the I.K. Fa Ermo laboratories of Leverkusen, Germany Carbamate, carbamate chemicals for agriculture is the synthetic pesticide grown up after organophosphorus ester, typically without special odor, The stabilization under sour environment, meets alkaline environment and decomposes.The poisoning symptom of carbamate chemicals for agriculture is the Cholinergic stream of characteristic Tear, salivation, myosis are fainted from fear and dead.Additionally, carbamate chemicals for agriculture also has mutagenesis, teratogenesis and carcinogenesis, Researcher can cause carbamate chemicals for agriculture " sevin " is with oral, injection or is coated on mouse and Hamster skin Canceration, and also have teratogenesis to cavy, dog, pig, chicken and duck.Show the carbamates agriculture such as sevin by study mechanism After medicine enters human body, the N- nitroso chemical combination that can be generated with the NO3-N and NO2-N in food under the acid condition of stomach Thing, shows stronger Mutagenicity.Therefore, carbamates was classified as 2A classes by international cancer research institution in 2007 Carcinogenic substance.Some fermented foods in the research in Japan and Hong Kong shows daily life, such as soy sauce, pickles, salty sauce, bread, Roll, steamed bun, biscuit, bean curd adds wine, has carbamates agriculture higher in the conventional food of the Asia such as pure mellow wine and plum wine Liquid medicine is put down.
Being will be known for stable isotope dilution mass spectrometry IDMS (Isotope Dilution Mass Spectrometry) The enriched stable isotopic of quality and abundance mixes in adding sample as internal standard compound, by measuring respective quality number ionic ratios And compare with typical ratio, so as to determine material content in the sample.Liquid chromatogram and high resolution mass spec combined instrument With it is accurate, efficient, sensitive the features such as, be widely used in the residue detection of trace agricultural chemicals.Using cold labeling ammonia Carbamate, can provide standard reagent for the trace residue of carbamate in more accurately quantitative determination food.
The content of the invention
The purpose of the present invention is exactly short, the behaviour that provides a kind of synthetic route for the defect for overcoming above-mentioned prior art to exist Make easy, stable isotope atom utilization is high, be adapted to the isotope marks of the special synthetic technology of cold labeling The synthetic method of carbamate, can apply to the Monitoring Pesticide Residues such as food, soil.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of synthetic method of the carbamate of isotope marks, using following steps：
(1) stable isotope is utilized13C flag carbon monoxide is raw material, under conditions of catalyst, with amino chemical combination Thing, hydroxy compounds, or cold labeling amino-compound, hydroxy compounds reaction, controlling reaction temperature be 150~ 250 DEG C, 8~30h of stirring reaction；
(2) product that step (1) is obtained is cooled to room temperature, reaction solution carries out concentration and is evaporated, and adds water and activated carbon, Controlling reaction temperature is 20~100 DEG C, stirs 0.1~3h, and the filtrate after separating and filtering obtains13C flag carbamate or13C、15N marks carbamate.
In step (1)：
Described catalyst is selenium powder, sulphur powder, iodine, 1- butyl -3- methyl -2- selenos imidazoles, 1- isopropyl -3- first One or more in base -2- selenos imidazoles, magnesia, zinc oxide, palladium bichloride or palladium.
Described amino-compound is one or more in ammonia, methylamine, ethamine, isopropylamine, dimethylamine or diethylamine.
Described hydroxy compounds is methyl alcohol, ethanol, ortho-methyl phenol, 1- naphthols, 2 methyl thioacetaldehyde oxime, 3- (first sulphur Base) -2- diacetylmonoximes, 3- mesyl -2- diacetylmonoximes, 2- methyl -2- mesyls propionaldoxime or 2- methyl -2- (methyl mercapto) third One or more in aldoxime.
The amino-compound of described cold labeling is15N- ammonias,15N- methylamines,15N- ethamine or15TMSDMA N dimethylamine In one or more.
Described13C flag carbon monoxide is with the mol ratio of amino-compound or cold labeling amino-compound 1:2~1:6,13C flag carbon monoxide is 1 with catalyst molar ratio:0.2~1:2,13C flag carbon monoxide and hydroxy compounds Mol ratio be 1:5~1:20.
In step (2), concentrating filter liquor carries out separated after being evaporated, or using organic solvent extraction, concentration filtrate Carry out filtrate separation.
Described organic solvent is in dichloromethane, ethyl acetate, petroleum ether, ether, hexamethylene, n-hexane or chloroform One or more.
13The synthesis route of C flag carbamate, it is as follows：
13C、15N marks the synthesis route of carbamate, as follows：
Compared with the existing correlation technique such as amino carbonic ester of " two-step method " synthesis nonisotopic labels, the present invention have with Lower advantage：
(1) present invention is developed with the mark of simplest carbon 13 carbon monoxide, amino-compound and hydroxy compounds first It is initiation material, is synthesized by novel, easy " one kettle way ", obtains the carbamate of cold labeling, it is to avoid With complex structure, it is difficult to " two-step method " synthetic route that the isotope marks carbamide compounds that obtain are participated in.
(2) present invention develops the technological parameter of " one kettle way " synthesizing stable isotope marks carbamate, explores To efficient, cheap and easily-available catalyst, and key reaction temperature and time parameter so that the reaction smoothly obtains target product Thing, operating technology is simple and safe, the potentiality for possessing large-scale production.
(3) present invention is with the mark carbon monoxide of the carbon 13 (99.3%atom of high abundance13C) and nitrogen 15 mark amino-compound (99%atom15N it is) raw material, obtains high abundance, high-purity13C or13C、15N mark urethane product (be higher than 99%atom13C and 99%atom15N, purity are higher than 98.5%), and stable isotope atom utilization is high, and abundance dilution is smaller, The requirement for the monitoring of the carbamate chemicals residuals such as food, soil can fully be met.
(4) present invention has good economy and use value, has good hair in food, environment measuring field Exhibition prospect.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.
Embodiment 1
In 2.5L stainless steel autoclaves, selenium powder 19.75g (0.25mol), methyl alcohol 150mL are added, added13C- Carbon monoxide 11.2L (0.5mol) and ammonia 21.25g (1.25mol), control oil bath temperature stabilizes to 160 DEG C, stirring reaction 16h, after the completion of reaction, is overnight cooled to room temperature, and collection reaction solution carries out concentration and is evaporated, and adds water and activated carbon, and control is anti- Temperature is answered for 50 DEG C, 0.25h is stirred, filtering, filtrate concentration is evaporated, and then carries out separated, collects 175~177 DEG C of cuts, Obtain 29.4g13C- urethanes, reaction yield 77.3%, chemical purity reaches 99.0%, and isotope abundance reaches 99.1atom%13C, using infrared spectrum and nmr analysis, its chemical constitution is correct.
Embodiment 2
In 2.5L stainless steel autoclaves, sulphur powder 8.0g (0.25mol), methyl alcohol 150mL are added, added13C- mono- Carbonoxide 11.2L (0.5mol) and ammonia 25.5g (1.5mol), control oil bath temperature stabilizes to 180 DEG C, stirring reaction 18h, instead After the completion of answering, room temperature is overnight cooled to, collection reaction solution carries out concentration and is evaporated, and adds water and activated carbon, controlling reaction temperature It is 60 DEG C, stirs 0.5h, filtering, filtrate concentration is evaporated, and then carries out separated, collects 175~177 DEG C of cuts, obtains 30.5g 13C- methyl carbamates, reaction yield 79.2%, chemical purity reaches 99.1%, and isotope abundance reaches 99.2atom%13C, using infrared spectrum and nmr analysis, its chemical constitution is correct.
Embodiment 3
In 2.5L stainless steel autoclaves, sulphur powder 16.0g (0.5mol), methyl alcohol 150mL are added, added13C- mono- Carbonoxide 11.2L (0.5mol) and methylamine 61g (2mol), control oil bath temperature stabilizes to 200 DEG C, and stirring reaction 20h has reacted Cheng Hou, is overnight cooled to room temperature, and collection reaction solution carries out concentration and is evaporated, and adds water and activated carbon, and controlling reaction temperature is 60 DEG C, 0.75h is stirred, filtering, filtrate profit is extracted with ethyl acetate three times, after extract is dried, is evaporated and obtains 28.4g13C-N- first Ylcarbamic acid methyl ester, reaction yield 63.1%, chemical purity reaches 98.5%, and isotope abundance reaches 99.0atom%13C, Using infrared spectrum and nmr analysis, its chemical constitution is correct.
Embodiment 4
In 2.5L stainless steel autoclaves, sulphur powder 16.0g (0.5mol), methyl alcohol 150mL are added, added13C- mono- Carbonoxide 11.2L (0.5mol) and dimethylamine 92g (2mol), control oil bath temperature stabilizes to 220 DEG C, stirring reaction 24h, reaction After the completion of, room temperature is overnight cooled to, collection reaction solution carries out concentration and is evaporated, and adds water and activated carbon, and controlling reaction temperature is 60 DEG C, 1h is stirred, filtering, filtrate is extracted three times using dichloromethane, after extract is dried, is evaporated and is obtained 18.4g13C-N,N- Dimethyl carbamic acid methyl esters, reaction yield 35.4%, chemical purity reaches 98.7%, and isotope abundance reaches 99.0atom %13C, using infrared spectrum and nmr analysis, its chemical constitution is correct.
Embodiment 5
In 2.5L stainless steel autoclaves, add sulphur powder 19.75g (0.5mol), zinc oxide 3.6g (0.05mol), Ethanol 150mL, adds13C- carbon monoxide 11.2L (0.5mol) and ammonia 21.25g (1.5mol), control oil bath temperature stabilization It it is 240 DEG C, stirring reaction 24h after the completion of reaction, is overnight cooled to room temperature, and collection reaction solution carries out concentration and is evaporated, and adds water And activated carbon, controlling reaction temperature is 60 DEG C, stirs 1h, and filtering, filtrate concentration is evaporated, and then carries out separated, collects 182 ~184 DEG C of cuts, obtain 18.7g13C- urethanes, reaction yield 41.9%, chemical purity reaches 99.1%, isotope Abundance reaches 99.1atom%13C, using infrared spectrum and nmr analysis, its chemical constitution is correct.
Embodiment 6
In 2.5L stainless steel autoclaves, selenium powder 19.75g (0.25mol), methyl alcohol 150mL are added, added13C- Carbon monoxide 11.2L (0.5mol) and15N- ammonias 36.0g (2mol), control oil bath temperature stabilizes to 200 DEG C, stirring reaction 24h, after the completion of reaction, is overnight cooled to room temperature, and collection reaction solution carries out concentration and is evaporated, and adds water and activated carbon, and control is anti- Temperature is answered for 60 DEG C, 0.5h is stirred, filtering, filtrate concentration is evaporated, and then carries out separated, collects 175~177 DEG C of cuts, Obtain 33.1g 1-13C,15N- methyl carbamates, reaction yield 87.2%, chemical purity reaches 99.1%, isotope abundance Reach 99.2atom%13C and 99.3atom%15N, using infrared spectrum and nmr analysis, its chemical constitution is correct.
Embodiment 7
It is a kind of13The synthetic method of the carbamate of C flag, using following steps：
(1) stable isotope is utilized13C flag carbon monoxide is raw material, under conditions of the catalysis of catalyst sulphur powder, with first Amine, the reaction of 2 methyl thioacetaldehyde oxime,13C flag carbon monoxide is 1 with the mol ratio of methylamine:2, it is 1 with catalyst molar ratio: 0.2, it is 1 with the mol ratio of 2 methyl thioacetaldehyde oxime:5, controlling reaction temperature is 150 DEG C, stirring reaction 30h；
(2) product that step (1) is obtained is cooled to room temperature, reaction solution carries out concentration and is evaporated, and adds water and activated carbon, Controlling reaction temperature is 20 DEG C, stirs 3h, and the filtrate after separating and filtering obtains13C flag carbamate.
Embodiment 8
It is a kind of13C、15The synthetic method of the carbamate of N marks, using following steps：
(1) stable isotope is utilized13C flag carbon monoxide is raw material, under conditions of catalyst chlorination palladium chtalyst, with15TMSDMA N dimethylamine, the reaction of 3- mesyl -2- diacetylmonoximes,13C flag carbon monoxide with15The mol ratio of TMSDMA N dimethylamine is 1:6, with Catalyst molar ratio is 1:2, it is 1 with the mol ratio of 3- mesyl -2- diacetylmonoximes:20, controlling reaction temperature is 250 DEG C, is stirred Mix reaction 8h；
(2) product that step (1) is obtained is cooled to room temperature, reaction solution is using the extraction of petroleum ether organic solvent, concentration filter Liquid carries out filtrate separation, adds water and activated carbon, and controlling reaction temperature is 100 DEG C, stirs 0.1h, the filter after separating and filtering Liquid, obtains13C、15N marks carbamate.

Claims (9)

1. a kind of synthetic method of the carbamate of isotope marks, it is characterised in that the method uses following steps：
(1) stable isotope is utilized13C flag carbon monoxide be raw material, under conditions of catalyst, with amino-compound, Hydroxy compounds, or the reaction of cold labeling amino-compound, hydroxy compounds, controlling reaction temperature is 150~250 DEG C, 8~30h of stirring reaction；
(2) product that step (1) is obtained is cooled to room temperature, reaction solution carries out concentration and is evaporated, and adds water and activated carbon, is controlled Reaction temperature is 20~100 DEG C, stirs 0.1~3h, and the filtrate after separating and filtering obtains13C flag carbamate or13C、15N Mark carbamate.
2. a kind of synthetic method of the carbamate of isotope marks according to claim 1, it is characterised in that step (1) catalyst described in is selenium powder, sulphur powder, iodine, 1- butyl -3- methyl -2- selenos imidazoles, 1- isopropyl -3- methyl - One or more in 2- selenos imidazoles, magnesia, zinc oxide, palladium bichloride or palladium.
3. a kind of synthetic method of the carbamate of isotope marks according to claim 1, it is characterised in that step (1) amino-compound described in is one or more in ammonia, methylamine, ethamine, isopropylamine, dimethylamine or diethylamine.
4. a kind of synthetic method of the carbamate of isotope marks according to claim 1, it is characterised in that step (1) hydroxy compounds described in is methyl alcohol, ethanol, ortho-methyl phenol, 1- naphthols, 2 methyl thioacetaldehyde oxime, 3- (methyl mercapto)- 2- diacetylmonoximes, 3- mesyl -2- diacetylmonoximes, 2- methyl -2- mesyls propionaldoxime or 2- methyl -2- (methyl mercapto) propionaldoxime In one or more.
5. a kind of synthetic method of the carbamate of isotope marks according to claim 1, it is characterised in that step (1) amino-compound of the cold labeling described in is15N- ammonias,15N- methylamines,15N- ethamine or15In TMSDMA N dimethylamine One or more.
6. a kind of synthetic method of the carbamate of isotope marks according to claim 1, it is characterised in that step (1) described in13C flag carbon monoxide is 1 with the mol ratio of amino-compound or cold labeling amino-compound:2 ~1:6,13C flag carbon monoxide is 1 with catalyst molar ratio:0.2~1:2,13C flag carbon monoxide and hydroxy compounds Mol ratio is 1:5~1:20.
7. a kind of synthetic method of the carbamate of isotope marks according to claim 1, it is characterised in that step (2) separated is carried out after concentrating filter liquor is evaporated in.
8. a kind of synthetic method of the carbamate of isotope marks according to claim 1, it is characterised in that step (2) filtrate separation is carried out in using organic solvent extraction, concentration filtrate.
9. the synthetic method of the carbamate of a kind of isotope marks according to claim 8, it is characterised in that described Organic solvent be one or more in dichloromethane, ethyl acetate, petroleum ether, ether, hexamethylene, n-hexane or chloroform.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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US5502241A (en) * 1990-02-06 1996-03-26 Council Of Scientific & Industrial Research Process for the preparation of alkyl carbamates
CN101747234A (en) * 2008-12-08 2010-06-23 河南师范大学 Method for synthesizing phenyl carbamate

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
US5502241A (en) * 1990-02-06 1996-03-26 Council Of Scientific & Industrial Research Process for the preparation of alkyl carbamates
EP0442173A1 (en) * 1990-02-13 1991-08-21 Council of Scientific and Industrial Research Process for the preparation of alkyl methylcarbamates
CN101747234A (en) * 2008-12-08 2010-06-23 河南师范大学 Method for synthesizing phenyl carbamate

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Title
AGNIESZKA KROGUL等: ""One pot synthesis of ureas and carbamates via oxidative carbonylation of aniline-type substrates by CO/O2 mixture catalyzed by Pd-complexes"", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》 *
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