CN100486956C - Process for the preparation of alkanediamines from 1, 8-terpene diols - Google Patents

Process for the preparation of alkanediamines from 1, 8-terpene diols Download PDF

Info

Publication number
CN100486956C
CN100486956C CNB2006100963086A CN200610096308A CN100486956C CN 100486956 C CN100486956 C CN 100486956C CN B2006100963086 A CNB2006100963086 A CN B2006100963086A CN 200610096308 A CN200610096308 A CN 200610096308A CN 100486956 C CN100486956 C CN 100486956C
Authority
CN
China
Prior art keywords
alkane
mixture
terpinum
diazido
diamines
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CNB2006100963086A
Other languages
Chinese (zh)
Other versions
CN101085740A (en
Inventor
赵振东
冯志勇
毕良武
王婧
李冬梅
古研
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hunan Sonbon Forestry Science & Technology Co ltd
Original Assignee
Institute of Chemical Industry of Forest Products of CAF
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institute of Chemical Industry of Forest Products of CAF filed Critical Institute of Chemical Industry of Forest Products of CAF
Priority to CNB2006100963086A priority Critical patent/CN100486956C/en
Publication of CN101085740A publication Critical patent/CN101085740A/en
Application granted granted Critical
Publication of CN100486956C publication Critical patent/CN100486956C/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a method for preparing alkyl-diamine with 1, 8- terpin. It comprises following steps: preparing sulphuric acid solution with mass concentration being 10- 75% at closed condition, adding NaN3 at 10- 15 Deg. C, stirring thoroughly to disslove it in said sulphuric acid solution, then adding 1, 8- terpin, controlling temperature to be between 15-100 Deg. C, stewing, separating and drying after reaction finished and getting diazanyl. The molar ratio between NaN3 and 1, 8- terpin is (2.0- 3.0): 1, the invention employs 5%Pd-C or Lindlar as catalyst to reduce diazanyl and gets alkyl-diamine mixture, distilling, rectifying and getting final product alkyl-diamine. The invention employs NaN3 as raw material, which reduces raw material toxicity, it employs sulfuric acid solution as reaction medium and catalyst, which can be reused when the concentration is moderated, the cost is saved and pollution to enviroment is decreased.

Description

Process for the preparation of alkanediamines from 1, 8-terpene diols
Technical field
The present invention relates to a kind of by 1,8-terpinum preparation
Figure C200610096308D00032
The method of alkane diamines.
Background technology
The alkane diamines (4-amino-α, α are a kind of derivatives of monoterpenes compound firpene 4-trimethyl-cyclohexanemethanamine), are synthetics, and molecular structure is:
Figure C200610096308D00034
Figure C200610096308D00035
The alkane diamines has in very big temperature range all to be liquid and to keep low viscosity, heat-resisting, at high temperature also can be not oxidized, good solvability is arranged in hydrocarbon petroleum solvent, high basicity is arranged and can control its reactive behavior and stereoselective characteristic.
Figure C200610096308D00036
The alkane diamines is the important cycloaliphatic epoxy resin solidifying agent of having determined, it can also be used as the raw material of the bacterial inhibitor in the perfumed soap and polymeric amide, urethane, silicon alcohol condensation catalyst and some novel alkylation parts in addition
Figure C200610096308D00037
Diamines is handled vibrin can also improve the colouring power that vibrin is accepted matching stain.
Existing up to now synthetic
Figure C200610096308D00038
The method of alkane diamines has:
(1) Rohm﹠amp; Having synthesized of success for the first time such as the Newman M.Bortnick of Haas company (US2632022 (1953))
Figure C200610096308D00039
The alkane diamines.They are raw material with kautschin, terpinum or firpene etc., and the aqueous phase reaction in that sodium cyanide, sulfuric acid exist generates 1 earlier, 8-dimethyl formamide-p-
Figure C200610096308D000310
Alkane, hydrolysis obtains purpose product 1,8-then
Figure C200610096308D000311
The alkane diamines.This method has realized suitability for industrialized production, and makes Rohm﹠amp; Haas company becomes unique supplier of this product of the whole world.
(2) A.PANCRAZI etc. (Bull Soc Chim Fr, (and 1-2, Pt.2), 1977:162-164) with N 3H/BF 3-Et 2O is a catalyst system, is solvent with benzene, with α-Pai Xi, beta-pinene, terpinum or kautschin and HN 3Reaction generates 1,8-diazido-p-
Figure C200610096308D000312
Alkane is used NaBH then 4Reduction obtains purpose product 1,8-diamino-p-
Figure C200610096308D000313
Alkane.The weak point of this method maximum is the HN that needs preparation special 3Solution, danger are very big, this method N 3H/BF 3-Et 2O is a catalyst system, and system is very responsive to moisture, and used solvent all be organic solvent, and damage ratio more seriously is difficult to the realization industrialization, and Practical significance is little.
The method of synthetic triazo-compound related to the present invention:
(Synth Commun 1997:1465-1467) proposes at 25 ℃ of following NaN Jeffrey C.Bottaro etc. 3In 50% (wt) sulphuric acid soln, leave standstill 30h with the trimethyl carbinol and obtain tertiary butyl trinitride, the characteristics of this method are that economy, environmental protection, product are easy to separate and the purity height of product, but the shortcoming of this method maximum is that the Schmidt rearrangement reaction can take place, and generates acid amides, reduces productive rate.
Triazo-compound reductive method related to the present invention:
(1) A.T.Moore etc. (Organ Synth V, 1973:586-589) proposing with 5%Pd/C is catalyzer, methyl alcohol is solvent, realizes the reduction to trinitride at normal temperatures and pressures:
Figure C200610096308D00041
R＝(CH 3) 3COOCC
(2) (Synth 1975:590-591) proposes with Lindlar catalyzer (5%Pd/CaCO for E.J.Corey etc. 3), the reduction triazo-compound is an amine in ethanolic soln:
Figure C200610096308D00042
Summary of the invention
The purpose of this invention is to provide a kind of easy to operate, can reduce danger in the reaction process, save cost, reduce to pollute and can improve productive rate by 1, the preparation of 8-terpinum
Figure C200610096308D0004164147QIETU
The method of alkane diamines.
The present invention adopts following technical scheme:
The first step: under closed environment, the preparation mass concentration is 10%～75% sulphuric acid soln, 10 ℃～add NaN below 15 ℃ 3, fully stir it is dissolved in the aqueous sulfuric acid fully, add 1 then, the 8-terpinum, temperature is controlled under 15 ℃～100 ℃, leaves standstill and reacts, and separates after question response is finished, drying obtains diazido
Figure C200610096308D00043
Alkylating mixture, above-mentioned NaN 3With 1, the mol ratio of the add-on of 8-terpinum is (2.0～3.0): 1;
Second step: with 5%Pd/C or Lindlar is catalyzer, reduction 1,8-diazido
Figure C200610096308D00044
The mixture of alkane obtains
Figure C200610096308D0004164147QIETU
The mixture of alkane diamines, distillation, rectifying obtain the purpose product
Figure C200610096308D00046
Alkane two amine products.
In aforesaid operations, adding 1, behind the 8-terpinum, temperature preferably is controlled under 20 ℃～70 ℃, leaves standstill.
With existing synthetic
Figure C200610096308D00047
The method of alkane diamines is compared, and the present invention has following beneficial effect: use NaN in (1) the first step reaction of the present invention 3Be one of raw material, with respect to Rohm﹠amp; The method of the use severe toxicity chemical sodium cyanide that (US2632022 (1953)) such as the Newman M.Bortnick of Haas company propose has significantly reduced the toxicity of raw material, has also just reduced the danger in the reaction process; (2) be that reaction medium and catalyzer and aqueous sulfuric acid can be reused after adjusting concentration with the aqueous sulfuric acid in the first step of the present invention reaction, provide cost savings and reduced pollution; (3) the first step reaction of the present invention is a reaction vessel with airtight reactor, has avoided hydrazoic acid effusion (HN under the normal pressure in reaction process 3Boiling point be 37 ℃), in order to avoid cause unnecessary pollution and loss; (4) reactive system of the first step of the present invention is the inhomogeneous reaction system, leaves standstill to obtain diazido
Figure C200610096308D00048
Alkane, and diazido
Figure C200610096308D00049
Alkane is insoluble to aqueous sulfuric acid very easily in separation, and operation is simple; (5) the present invention The productive rate of alkane diamines is 63.1%, is higher than existing synthetic The productive rate 61.9% of alkane diamines method.
Description of drawings
Fig. 1 separates the diazido that obtains through column chromatography
Figure C200610096308D00051
The IR figure of the pure product of alkane, among the figure, 2100.18cm -1The strong peak at place is the characteristic group of azido-; 3000cm -1More than at 3337.86cm -1The place only has weak peak may be the N-H stretching vibration peak of primary amine groups, but does not contain substantially in the description standard thing at least-the OH group, and promptly unreacted Terpine hydrate and monohydroxy-alcohol by product are separated to be removed; At 3040cm -1～3010cm -1Near no peak, do not contain the by product that has pair keys in the interpret sample, the single azido-by product that promptly dewaters by product and slough a part water also is removed.Result by top IR spectrum elucidation can infer that in conjunction with the structure and the character of raw material Terpine hydrate molecule sample can only be the diazido compound again.
Fig. 2 is a synthetic
Figure C200610096308D0004164147QIETU
The GC figure of the thick product of diamines, one of the 1# position group of peak is a kautschin class material among the figure, and one group of peak of 2# position is the pine tar alcohols material, and the 3# peak is
Figure C200610096308D00052
The alkene monoamine, 5# peak and 7# peak are 1,8-
Figure C200610096308D00053
Alkane diamines, 4# peak and 6# peak are isomery
Figure C200610096308D00054
The alkane diamines.
Fig. 3 is a synthetic of the present invention
Figure C200610096308D00055
The IR figure of two amine products.
Embodiment
Preparation of the present invention The method of alkane diamines is: can prepare sulphuric acid soln in the airtight fully container at one, its mass concentration scope is 10%～75%, mass concentration can select 10%, 15%, 20%, 45%, 66% or 75%, 10 ℃～add amount of substance below 15 ℃ and be 2.0～3.0 times to 1, the NaN of 8-terpinum 3, in the present embodiment, optional 2.0,2.2,2.7 or 3.0 times to 1, the NaN of 8-terpinum 3Fully stirring makes it be dissolved in the aqueous sulfuric acid fully, add 1 then, 8-terpinum, temperature are controlled under 15 ℃～100 ℃, preferred 20 ℃～70 ℃, actual temp can be controlled under 15 ℃, 20 ℃, 42 ℃, 70 ℃, 80 ℃, 92 ℃ or 100 ℃, stir or put only, reaction can be finished in 0.5h～50h, and separation, drying obtain diazido then The mixture of alkane; Then with 5%Pd/C catalyzer or Lindlar catalyst reduction diazido
Figure C200610096308D00058
The mixture of alkane obtains
Figure C200610096308D00059
The mixture of alkane diamines, distillation, rectifying obtain the purpose product
Figure C200610096308D000510
The alkane diamines.With TLC (developping agent: normal hexane: ethyl acetate=85: 15), column chromatography (eluent: normal hexane: ethyl acetate=90: 10), high performance liquid chromatography (methyl alcohol: water=95: 5) in conjunction with the external standard method diazido
Figure C200610096308D000511
Diazido in the mixture of alkane
Figure C200610096308D0004164147QIETU
The content of alkane, and through tentatively definite its structure of IR (accompanying drawing 1).With the TLC tracking reaction process, developping agent is a normal hexane in the reductive process: ethyl acetate=85: 15, reaction finish the back with in the gas Chromatographic Determination mixture
Figure C200610096308D000512
The content of alkane diamines (accompanying drawing 2) determines that with IR (accompanying drawing 3) and gas chromatography mass spectrometry (subordinate list 1) structure of the product that the thick product of rectifying obtains, result prove that product mainly is made up of following three kinds of diamine compounds, and the diamine contents that GC analyzes is 96%.
GC analyzes among the present invention instrument and condition: on divide 1102GC gas chromatograph.SE-54 quartz capillary gas chromatographic column (Φ 0.25mm * 30m), 130～220 ℃ of temperature programmings, heat-up rate: 5 ℃/min, 260 ℃ of sampler temperature, 230 ℃ of fid detector temperature, carrier gas is a high-purity N 2.
(1) synthetic diazido
Figure C200610096308D0004164147QIETU
The embodiment of alkane is as follows:
Embodiment one
One can be airtight fully the 250mL container in add 74.3g water, stir and the condition of ice-water bath under drip the sulphuric acid soln that vitriol oil 90.8g is mixed with 55% (wt), adding NaN below 15 ℃ 311.8g, stir 5min it is dissolved fully, add 15.7g 1 then, the 8-terpinum is heated to 45 ℃ of constant temperature and leaves standstill 6h, and separation, drying obtain diazido
Figure C200610096308D00062
The mixture 11.6g of alkane, diazido in the mixture by analysis
Figure C200610096308D00063
The content of alkane is 58.59% (wt).
Embodiment two
One can be airtight fully the 250mL container in add 90.8g water, stir and the condition of ice-water bath under drip the sulphuric acid soln that vitriol oil 74.3g is mixed with 45% (wt), adding NaN below 15 ℃ 311.8g, stir 5min it is dissolved fully, add 15.7g 1 then, the 8-terpinum is heated to 50 ℃ of constant temperature and leaves standstill 8h, and separation, drying obtain diazido
Figure C200610096308D00064
The mixture 13.2g of alkane, diazido in the mixture by analysis
Figure C200610096308D0004164147QIETU
The content of alkane is 89.24% (wt).
Embodiment three
One can be airtight fully the 250mL container in add 90.8g water, stir and the condition of ice-water bath under drip the sulphuric acid soln that vitriol oil 74.3g is mixed with 45% (wt), adding NaN below 15 ℃ 311.8g, stir 5min it is dissolved fully, add 15.7g 1 then, the 8-terpinum is heated to 35 ℃ of constant temperature and leaves standstill 40h, and separation, drying obtain diazido
Figure C200610096308D00066
The mixture 12.4g of alkane, diazido in the mixture by analysis
Figure C200610096308D00067
The content of alkane is 50.3% (wt).
Embodiment four
One can be airtight fully the 250mL container in add 123.8g water, stir and the condition of ice-water bath under drip the sulphuric acid soln that vitriol oil 41.3g is mixed with 25% (wt), adding NaN below 15 ℃ 311.8g, stir 5min it is dissolved fully, add 15.7g 1 then, the 8-terpinum is heated to 25 ℃ of constant temperature and leaves standstill 40h, and separation, drying obtain diazido
Figure C200610096308D00068
The mixture 5.6g of alkane, diazido in the mixture by analysis The content of alkane is 20.3% (wt).
(2) reduction 1, the 8-diazido
Figure C200610096308D000610
The embodiment of alkane:
Embodiment one
It with content 47.6% diazido
Figure C200610096308D000611
Alkylating mixture 3.5g adds in the 100mL four-necked bottle, adds the dehydrated alcohol of 30mL, then logical N under whipped state 2Approximately 5min then adds 0.33g 5%Pd-C catalyzer, keeps reaction system at 60 ℃, and TLC demonstration reaction is finished substantially during reaction 10h, then cools off, filters, removes ethanol and obtain
Figure C200610096308D00071
The mixture of alkane diamines, rectifying obtains
Figure C200610096308D00072
The alkane diamines through the gas chromatography mass spectrometry analysis, is defined as
Figure C200610096308D00073
The alkane diamines.
Embodiment two
It with content 47.6% diazido
Figure C200610096308D0004164147QIETU
Alkylating mixture 4.3g adds in the 100mL four-necked bottle, adds the dehydrated alcohol of 55mL, then logical N under whipped state 2Approximately 5min then adds 0.8g 5%Pd-C catalyzer, keeps reaction system at 30 ℃, and TLC demonstration reaction is finished substantially during reaction 13h, then cools off, filters, removes ethanol and obtain
Figure C200610096308D00074
The mixture of alkane diamines, rectifying obtains
Figure C200610096308D0004164147QIETU
The alkane diamines through the gas chromatography mass spectrometry analysis, is defined as
Figure C200610096308D00075
The alkane diamines.
Embodiment three
It with content 47.6% diazido
Figure C200610096308D00076
Alkylating mixture 2.87g adds in the 100mL four-necked bottle, adds the 37mL dehydrated alcohol, then logical N under whipped state 2Approximately 5min then adds 0.27g 5%Lindlar catalyzer, keeps reaction system at 50 ℃, and TLC demonstration reaction is finished during reaction 3h, then cools off, filters, removes ethanol and obtain The mixture of alkane diamines, rectifying obtains The alkane diamines through the gas chromatography mass spectrometry analysis, is defined as
Figure C200610096308D00079
The alkane diamines.
Embodiment four
It with content 47.6% diazido
Figure C200610096308D000710
Alkylating mixture 3.05g adds in the 50mL four-necked bottle, adds the 13mL dehydrated alcohol, then logical N under whipped state 2Approximately 5min then adds 0.15g 5%Lindlar catalyzer, keeps reaction system at 50 ℃, and TLC demonstration reaction is finished substantially during reaction 9h, then cools off, filters, removes ethanol and obtain
Figure C200610096308D000711
The mixture of alkane diamines, rectifying obtains
Figure C200610096308D000712
The alkane diamines through the gas chromatography mass spectrometry analysis, is defined as
Figure C200610096308D000713
The alkane diamines.
Embodiment five
It with content 47.6% diazido
Figure C200610096308D000714
Alkylating mixture 8.56g adds in the 250mL four-necked bottle, adds the 110mL dehydrated alcohol, then logical N under whipped state 2Approximately 5min then adds 0.41g 5%Lindlar catalyzer, keeps reaction system at 25 ℃, and TLC demonstration reaction is finished substantially during reaction 7h, then cools off, filters, removes ethanol and obtain
Figure C200610096308D000715
The mixture of alkane diamines, rectifying obtains
Figure C200610096308D000716
The alkane diamines through the gas chromatography mass spectrometry analysis, is defined as
Figure C200610096308D000717
The alkane diamines.
Subordinate list 1 is reduction 1, the 8-diazido
Figure C200610096308D000718
The MS analytical results of the product component that embodiment one to embodiment five rectifying of alkane embodiment obtains.
Subordinate list 1
Figure C200610096308D000719
Synthetic
Figure C200610096308D00081
The experimental example of alkane diamines:
One can be airtight fully the 250mL container in add 90.8g water, stir and the condition of ice-water bath under drip the sulphuric acid soln that vitriol oil 74.3g is mixed with 45% (wt), adding NaN below 15 ℃ 311.8g, stir 5min it is dissolved fully, add 15.7g 1 then, the 8-terpinum is heated to 50 ℃ of constant temperature and leaves standstill 8h, and separation, drying obtain diazido The mixture 13.2g of alkane, diazido in the mixture by analysis
Figure C200610096308D00083
The content of alkane is 89.24% (wt).Previous step synthetic mixture 5.0g is added in the four-necked bottle of 250mL, add the dehydrated alcohol of 120mL, then logical N under whipped state 2Approximately 5min then adds 0.45g Lindlar catalyzer, keeps reaction system at 30 ℃, and TLC shows that reaction finishes substantially during reaction 6h, then cooling, filters, removes ethanol with Rotary Evaporators and obtain
Figure C200610096308D00084
The thick product of alkane diamines, then rectifying
Figure C200610096308D00085
The thick product of alkane diamines, the cut of collecting 130 ℃/2.4kPa (vacuum meter is not proofreaied and correct), are defined as through IR and contrast of standard spectrogram and gas chromatography mass spectrometry analysis as product
Figure C200610096308D00086
The alkane diamines.

Claims (2)

1, a kind of by 1, the preparation of 8-terpinum
Figure C200610096308C0002140833QIETU
The method of alkane diamines is characterized in that:
The first step: under closed environment, the preparation mass concentration is 10%～75% sulphuric acid soln, adds NaN at 10 ℃～15 ℃ 3, fully stirring is dissolved in the aqueous sulfuric acid it fully, adds 1 then, the 8-terpinum, and temperature is controlled at 15 ℃～100 ℃, leaves standstill, and separation, drying obtained diazido after question response was finished
Figure C200610096308C0002140833QIETU
The mixture of alkane, above-mentioned NaN 3With 1, the mol ratio of the add-on of 8-terpinum is 2.0～3.0:1;
Second step: with 5%Pd-C or Lindlar is catalyzer, the reduction diazido
Figure C200610096308C0002140833QIETU
The mixture of alkane obtains
Figure C200610096308C0002140833QIETU
The mixture of alkane diamines, distillation, rectifying obtain the purpose product
Figure C200610096308C0002140833QIETU
The alkane diamines.
2, according to claim 1 by 1, the preparation of 8-terpinum
Figure C200610096308C0002140833QIETU
The method of alkane diamines is characterized in that adding 1, and behind the 8-terpinum, temperature is controlled at 20 ℃～70 ℃, leaves standstill.
CNB2006100963086A 2006-09-19 2006-09-19 Process for the preparation of alkanediamines from 1, 8-terpene diols Active CN100486956C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB2006100963086A CN100486956C (en) 2006-09-19 2006-09-19 Process for the preparation of alkanediamines from 1, 8-terpene diols

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2006100963086A CN100486956C (en) 2006-09-19 2006-09-19 Process for the preparation of alkanediamines from 1, 8-terpene diols

Publications (2)

Publication Number Publication Date
CN101085740A CN101085740A (en) 2007-12-12
CN100486956C true CN100486956C (en) 2009-05-13

Family

ID=38936937

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2006100963086A Active CN100486956C (en) 2006-09-19 2006-09-19 Process for the preparation of alkanediamines from 1, 8-terpene diols

Country Status (1)

Country Link
CN (1) CN100486956C (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10674723B2 (en) 2016-10-26 2020-06-09 Institute of Chemical Industry of Forest Products, CAF 1,8-bis(Schiff base)-p-menthane derivatives as well as preparation method and applications thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102040525B (en) * 2010-11-25 2013-10-02 重庆紫光化工股份有限公司 Preparation method of menthane diamine

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB681688A (en) * 1950-07-07 1952-10-29 Rohm & Haas Improvements in or relating to the preparation of 1,8-diamino-p-menthane
US2632022A (en) * 1950-07-07 1953-03-17 Rohm & Haas Method of preparing 1, 8-diamino-p-menthane
US2955138A (en) * 1958-05-28 1960-10-04 Rohm & Haas Process for the preparation of menthane diamine

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB681688A (en) * 1950-07-07 1952-10-29 Rohm & Haas Improvements in or relating to the preparation of 1,8-diamino-p-menthane
US2632022A (en) * 1950-07-07 1953-03-17 Rohm & Haas Method of preparing 1, 8-diamino-p-menthane
US2955138A (en) * 1958-05-28 1960-10-04 Rohm & Haas Process for the preparation of menthane diamine

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10674723B2 (en) 2016-10-26 2020-06-09 Institute of Chemical Industry of Forest Products, CAF 1,8-bis(Schiff base)-p-menthane derivatives as well as preparation method and applications thereof

Also Published As

Publication number Publication date
CN101085740A (en) 2007-12-12

Similar Documents

Publication Publication Date Title
Stork et al. Alkylation and Michael additions of glycine ethyl ester. Use in. alpha.-amino acid synthesis and as acyl carbanion equivalent
Corey et al. New stereospecific synthesis of trisubstituted olefins. Stereospecific synthesis of farnesol
CN111039769B (en) Method for synthesizing methyl heptenone from methyl butynol
CN100486956C (en) Process for the preparation of alkanediamines from 1, 8-terpene diols
CN101628860A (en) Method for preparing methylal
CN106083604B (en) A method of by unsaturated turpentine oil monoterpene preparation 1,8- to Meng's alkane diamines
KR100893965B1 (en) Process for preparing succinonitrile
Zuech et al. Isomerization and cyclization of octatrienes
CN111099986A (en) Hydrogenation process
US9994596B2 (en) Process for preparing a composition containing 2-ethylhexyl silicate
Jiricny et al. The conversion of aldehydes and ketones via their 2, 4, 6-tri-isopropylbenzenesulphonyl hydrazones into nitrites containing one additional carbon atom
US5478953A (en) Process for the preparation of cis-syn-cis-4,4' (5')-[di-t-butyldicyclohexano]-18-crown-6
Yi et al. Deoxygenative hydroboration of primary, secondary, and tertiary amides: Catalyst‐free synthesis of various substituted amines
WO2022141699A1 (en) Method for preparing 9-fluorenyl formaldehyde
CN101792393A (en) Method for synthesizing N-arylalkylamine compound
CN102442923B (en) Synthesis method of dimethylformamide
US4210604A (en) Process for preparing secondary amines from mixtures of aliphatic alcohols and nitriles
CN111302947A (en) Synthetic method of 3, 5-dimethylaniline
Mandelt et al. Mono-and Bicyclic Cyclopentenes by Rearrangement of 1-Methylcyclobutylmethanols: Synthesis of (±)-Cuparene and Formal Syntheses of (±)-Laurene and (±)-Herbertene
CN114773206B (en) Synthesis method of o-tert-butylaniline
CN110511147B (en) Method for reducing nitroolefin
RU2739242C1 (en) Method of producing high-density and high-energy rocket and aviation fuel component based on methyl-substituted 2,2'-bis (norbornanyl) (versions)
RU2739190C1 (en) Method of producing high-density and high-energy rocket and aviation fuel based on 2-vinyl norbornane (versions)
US3971830A (en) Process for the semihydrogenation of citral to citronellal
US3936490A (en) Process for conducting organonitrile addition reactions

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
EE01 Entry into force of recordation of patent licensing contract

Assignee: Zhuzhou sonbon Forest Chemical Co.,Ltd.

Assignor: INSTITUTE OF CHEMICAL INDUSTRY OF FOREST PRODUCTS, CAF

Contract record no.: 2012430000072

Denomination of invention: By 1, the 8-terpinum prepares the method for alkane diamines

Granted publication date: 20090513

License type: Exclusive License

Open date: 20071212

Record date: 20120510

EE01 Entry into force of recordation of patent licensing contract

Application publication date: 20071212

Assignee: Zhuzhou sonbon Forest Chemical Co.,Ltd.

Assignor: INSTITUTE OF CHEMICAL INDUSTRY OF FOREST PRODUCTS, CAF

Contract record no.: 2012430000072

Denomination of invention: Method for preparing 4-amino-alpha, alpha,4-trimethyl-cyclohexanemethanamine from 1,8- terpinum

Granted publication date: 20090513

License type: Exclusive License

Record date: 20120510

LICC Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model
C41 Transfer of patent application or patent right or utility model
TR01 Transfer of patent right

Effective date of registration: 20160928

Address after: Office building 412007 Hunan city of Zhuzhou province Yunlong demonstration zone Hongqi Road in Chemical Factory

Patentee after: HUNAN SONBON FORESTRY SCIENCE & TECHNOLOGY CO.,LTD.

Address before: Five suojin village of Nanjing city in Jiangsu province 210042 No. 16

Patentee before: INSTITUTE OF CHEMICAL INDUSTRY OF FOREST PRODUCTS, CAF

PP01 Preservation of patent right
PP01 Preservation of patent right

Effective date of registration: 20230418

Granted publication date: 20090513