Isothiocyanate

In organic chemistry, isothiocyanate is a functional group as found in compounds with the formula R–N=C=S. Isothiocyanates are the more common isomers of thiocyanates, which have the formula R–S–C≡N.

## Contents

* 1 Occurrence
* 2 Structure
* 3 Synthesis
* 4 Reactions
* 5 Flavor research
* 6 Uses
* 7 Coordination chemistry
* 8 See also
* 9 References

## Occurrence

Many isothiocyanates from plants are produced by enzymatic conversion of metabolites called glucosinolates. A prominent natural isothiocyanate is allyl isothiocyanate, also known as mustard oils.

Cruciferous vegetables, such as bok choy, broccoli, cabbage, cauliflower, kale, and others, are rich sources of glucosinolate precursors of isothiocyanates.[1]

## Structure

The N=C and C=S distances are 117 and 158 pm.[2] By contrast, in methyl thiocyanate, N≡C and C–S distances are 116 and 176 pm.

Typical bond angles for C–N=C in aryl isothiocyanates are near 165°. Again, the thiocyanate isomers are quite different with C–S–C angle near 100°.[3] In both isomers the SCN angle approaches 180°.

## Synthesis

Allyl thiocyanate isomerizes to the isothiocyanate:[4]

2=CHCH
2SCN → CH
2=CHCH
2NCS

Isothiocyanates can be prepared by treating organic dithiocarbamate salts with lead nitrate or tosyl chloride.[5][6]

Synthesis of phenyl isothiocyanate

Isothiocyanates may also be accessed by the fragmentation reactions of 1,4,2-oxathiazoles.[7] This methodology has been applied to a polymer-supported synthesis of isothiocyanates.[8]

## Reactions

Isothiocyanates are weak electrophiles, susceptible to hydrolysis. In general, nucleophiles attack at carbon:

The reaction of acetophenone enolate with phenyl isothiocyanate. In this one-pot synthesis[9] the ultimate reaction product is a Thiazolidine. This reaction is stereoselective with the formation of the Z-isomer only.

Electrochemical reduction gives thioformamides.[10]: 340

## Flavor research

Isothiocyanates occur widely in nature and are of interest in food science and medical research.[1] Vegetable foods with characteristic flavors due to isothiocyanates include bok choy, broccoli, cabbage, cauliflower, kale, wasabi, horseradish, mustard, radish, Brussels sprouts, watercress, papaya seeds, nasturtiums, and capers.[1] These species generate isothiocyanates in different proportions, and so have different, but recognizably related, flavors. They are all members of the order Brassicales, which is characterized by the production of glucosinolates, and of the enzyme myrosinase, which acts on glucosinolates to release isothiocyanates.[1]

* Sinigrin is the precursor to allyl isothiocyanate
* Glucotropaeolin is the precursor to benzyl isothiocyanate
* Gluconasturtiin is the precursor to phenethyl isothiocyanate
* Glucoraphanin is the precursor to sulforaphane

## Uses

Phenyl isothiocyanate, is used for amino acid sequencing in the Edman degradation.

## Coordination chemistry

Isothiocyanate and its linkage isomer thiocyanate are ligands in coordination chemistry. Thiocyanate is a more common ligand.

## See also

* Methyl isothiocyanate

## References

1. ↑ 1.0 1.1 1.2 1.3 "Isothiocyanates". Micronutrient Information Center, Linus Pauling Institute, Oregon State University. 1 April 2017. https://lpi.oregonstate.edu/mic/dietary-factors/phytochemicals/isothiocyanates.
2. ↑ Majewska, Paulina; Rospenk, Maria; Czarnik-Matusewicz, Bogusława; Kochel, Andrzej; Sobczyk, Lucjan; Dąbrowski, Roman (2008). "Structure and polarized IR spectra of 4-isothiocyanatophenyl 4-heptylbenzoate (7TPB)". Chemical Physics 354 (1–3): 186–195. doi:10.1016/j.chemphys.2008.10.024. Bibcode: 2008CP....354..186M.
3. ↑ Erian, Ayman W.; Sherif, Sherif M. (1999). "The chemistry of thiocyanic esters". Tetrahedron 55 (26): 7957–8024. doi:10.1016/S0040-4020(99)00386-5.
4. ↑ Emergon, David W. (1971). "The Preparation and Isomerization of Allyl Thiocyanate. An Organic Chemistry Experiment". Journal of Chemical Education 48 (1): 81. doi:10.1021/ed048p81. Bibcode: 1971JChEd..48...81E.
5. ↑ Dains FB; Brewster RQ; Olander CP (1926). "Phenyl Isothiocyanate". Organic Syntheses 6: 72. doi:10.15227/orgsyn.006.0072.
6. ↑ Wong, R; Dolman, SJ (2007). "Isothiocyanates from tosyl chloride mediated decomposition of in situ generated dithiocarbamic acid salts". The Journal of Organic Chemistry 72 (10): 3969–3971. doi:10.1021/jo070246n. PMID 17444687.
7. ↑ O'Reilly, RJ; Radom, L (2009). "Ab initio investigation of the fragmentation of 5,5-diamino-substituted 1,4,2-oxathiazoles". Organic Letters 11 (6): 1325–1328. doi:10.1021/ol900109b. PMID 19245242.
8. ↑ Burkett, BA; Kane-Barber, JM; O'Reilly, RJ; Shi, L (2007). "Polymer-supported thiobenzophenone : a self-indicating traceless 'catch and release' linker for the synthesis of isothiocyanates". Tetrahedron Letters 48 (31): 5355–5358. doi:10.1016/j.tetlet.2007.06.025.
9. ↑ Ortega-Alfaro, M. C.; López-Cortés, J. G.; Sánchez, H. R.; Toscano, R. A.; Carrillo, G. P.; Álvarez-Toledano, C. (2005). "Improved approaches in the synthesis of new 2-(1, 3-thiazolidin-2Z-ylidene)acetophenones". Arkivoc 2005 (6): 356–365. doi:10.3998/ark.5550190.0006.631.
10. ↑ Hammerich, Ole; Parke, Vernon D. (1977). "The electrochemistry of cyanates and related compounds". in Patai, Saul. The Chemistry of Cyanates and Their Thio Derivatives. Part 1. Chichester: Wiley. ISBN 0-471-99477-4.

* v
* t
* e

Salts and covalent derivatives of the cyanide ion

1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | 13 | 14 | 15 | 16 | 17 | 18

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HCN |  |  |  | He
LiCN | Be(CN)2 | B  | C  | NH4CN, N3CN | OCN−,
-NCO | FCN | Ne
NaCN | Mg(CN)2 | Al(CN)3 | Si(CN)4,
Me3SiCN | P(CN)3 | SCN−,
-NCS,
(SCN)2,
S(CN)2 | ClCN | Ar
KCN | Ca(CN)2 | Sc(CN)3 | Ti(CN)4 | V  | Cr(CN)64−
Cr(CN)63− | Mn(CN)2 | Fe(CN)3,
Fe(CN)64−,
Fe(CN)63− | Co(CN)2,
Co(CN)3 | Ni(CN)2
Ni(CN)42− | CuCN,
Cu(CN)2 | Zn(CN)2 | Ga(CN)3 | Ge  | As(CN)3 | SeCN−
(SeCN)2
Se(CN)2 | BrCN | Kr
RbCN | Sr(CN)2 | Y(CN)3 | Zr(CN)4 | Nb  | Mo(CN)84− | Tc  | Ru(CN)63− | Rh(CN)63− | Pd(CN)2 | AgCN | Cd(CN)2 | In(CN)3 | Sn  | Sb(CN)3 | Te  | ICN | Xe
CsCN | Ba(CN)2 |  | Hf  | Ta  | W(CN)84− | Re  | Os(CN)63− | Ir(CN)63− | Pt(CN)42-,
Pt(CN)64-
| AuCN,
Au(CN)2− | Hg2(CN)2,
Hg(CN)2 | TlCN | Pb(CN)2 | Bi(CN)3 | Po  | At  | Rn
Fr  | Ra  |  | Rf  | Db  | Sg  | Bh  | Hs  | Mt  | Ds  | Rg  | Cn  | Nh  | Fl  | Mc  | Lv  | Ts  | Og
| ↓  |  |
La  | Ce(CN)3,
Ce(CN)4 | Pr  | Nd  | Pm  | Sm  | Eu  | Gd(CN)3 | Tb  | Dy  | Ho  | Er  | Tm  | Yb  | Lu
Ac  | Th  | Pa  | UO2(CN)2 | Np  | Pu  | Am  | Cm  | Bk  | Cf  | Es  | Fm  | Md  | No  | Lr

* v
* t
* e

Nitrogen species

* Hydrides:
* NH3
* NH4+
* NH2− MNH2
* N3−
* NH2OH
* N2H4
* N3–
* Organic:
* -NH2
* -CHR=NHR
* -CONHR2
* HCN
* CN−
* C2N2
* H2NCN
* CH2N2
* Oxides:
* N2O
* NO
* NO2
* N2O3
* N2O4
* N2O5
* H2N2O2
* H4N2O4
* HNO2
* HNO3
* HONO3
* HN2O2−
* N2O22−
* NO2−
* ONOO−
* NO3−
* NO43−
* O2NOO−
* NO+
* NO2+
* Halides:
* NF3
* NCl3
* NBr3
* NI3
* FN3
* ClN3
* BrN3
* NH2Cl
* NHCl2

Chemical formulas

* v
* t
* e

Functional groups

| Only carbon,
hydrogen,
and oxygen|

| Hydrocarbons|

* Allene
* Alkene (Allyl group

|

Other|

* Acetoxy
* Acetyl
* Acryloyl
* Acyl
* Aldehyde
* Alkoxy (Methoxy)
* Benzoyl
* Carbonyl
* Carboxyl
* Carboxylic anhydride
* Dioxirane
* Epoxide
* Ester
* Ether
* Ethylenedioxy
* Hydroxy
* Ketone
* Methylenedioxy
* Peroxide (Organic)
* Ynone

Only one
element
apart from
C, H, O|

| Nitrogen|

* Amine
* Azo compound
* Cyanate
* Hydrazone
* Imide
* Imine
* Isocyanate
* Isonitrile
* Nitrene
* Nitrile
* Nitro compound
* Nitroso compound
* Organic amide
* Oxime

|

Phosphorus|

* Phosphonate
* Phosphonous

Sulfur|

* Disulfide
* Sulfone
* Sulfonic acid
* Sulfoxide
* Thial
* Thioester
* Thioether
* Thioketone
* Thiol

Selenium|

* Selenol
* Selenonic acid
* Seleninic acid
* Selenenic acid
* Selone

Tellurium|

* Tellurol
* Telluroketone

Other|

* Isothiocyanate
* Phosphoramide
* Sulfenyl chloride
* Sulfonamide
* Thiocyanate

See also chemical classification, chemical nomenclature ([[Chemistry:IUPAC nomenclature of inorganic, IUPAC nomenclature of organic chemistry|organic]])

* v
* t
* e

Cruciferous biochemistry

Types of compounds|

* Phenylthiocarbamide (PTC/PTU)
* Thiocyanates
* Nitriles
* Indoles
* Gibberellin

Glucosinolates|

* Glucobrassicin
* Glucocapparin
* Glucoraphanin
* Gluconasturtiin
* Glucotropaeolin
* Progoitrin
* Sinigrin
* Sinalbin

Isothiocyanates (ITC, mustard oils)|

* Sulforaphane (SFN)
* Raphanin
* Allyl isothiocyanate (AITC)
* Methyl isothiocyanate (MITC)
* Benzyl isothiocyanate (BITC)
* Fluorescein isothiocyanate (FITC)
* Phenyl isothiocyanate (PITC)
* Phenethyl isothiocyanate (PEITC)
* 6-MITC

Bioactive metabolites|

* Goitrin
* Indole-3-carbinol

* Brassicaceae (Cruciferous vegetables): Brassica
* Raphanus
* Cruciferous Biochemistry
* genera (list)

* v
* t
* e

TRP channel modulators

TRPA|

| Activators|

* 4-Hydroxynonenal
* 4-Oxo-2-nonenal
* 4,5-EET
* 12S-HpETE
* 15-Deoxy-Δ12,14-prostaglandin J2
* α-Sanshool (ginger, Sichuan and melegueta peppers)
* Acrolein
* Allicin (garlic)
* Allyl isothiocyanate (mustard, radish, horseradish, wasabi)
* AM404
* Bradykinin
* Cannabichromene (cannabis)
* Cannabidiol (cannabis)
* Cannabigerol (cannabis)
* Cinnamaldehyde (cinnamon)
* CR gas (dibenzoxazepine; DBO)
* CS gas (2-chlorobenzal malononitrile)
* Curcumin (turmeric)
* Dehydroligustilide (celery)
* Diallyl disulfide
* Dicentrine (Lindera spp.)
* Farnesyl thiosalicylic acid
* Formalin
* Gingerols (ginger)
* Hepoxilin A3
* Hepoxilin B3
* Hydrogen peroxide
* Icilin
* Isothiocyanate
* Ligustilide (celery, Angelica acutiloba)
* Linalool (Sichuan pepper, thyme)
* Methylglyoxal
* Methyl salicylate (wintergreen)
* N-Methylmaleimide
* Nicotine (tobacco)
* Oleocanthal (olive oil)
* Paclitaxel (Pacific yew)
* Paracetamol (acetaminophen)
* PF-4840154
* Phenacyl chloride
* Polygodial (Dorrigo pepper)
* Shogaols (ginger, Sichuan and melegueta peppers)
* Tear gases
* Tetrahydrocannabinol (cannabis)
* Thiopropanal S-oxide (onion)
* Umbellulone (Umbellularia californica)
* WIN 55,212-2

|

Blockers|

* Dehydroligustilide (celery)
* Nicotine (tobacco)
* Ruthenium red

TRPC|

| Activators|

* Adhyperforin (St John's wort)
* Diacyl glycerol
* GSK1702934A
* Hyperforin (St John's wort)
* Substance P

|

Blockers|

* DCDPC
* DHEA-S
* Flufenamic acid
* GSK417651A
* GSK2293017A
* Meclofenamic acid
* N-(p-Amylcinnamoyl)anthranilic acid
* Niflumic acid
* Pregnenolone sulfate
* Progesterone
* Pyr3
* Tolfenamic acid

TRPM|

| Activators|

* ADP-ribose
* BCTC
* Calcium (intracellular)
* Cold
* Coolact P
* Cooling Agent 10
* CPS-369
* Eucalyptol (eucalyptus)
* Frescolat MGA
* Frescolat ML
* Geraniol
* Hydroxycitronellal
* Icilin
* Linalool
* Menthol (mint)
* PMD 38
* Pregnenolone sulfate
* Rutamarin (Ruta graveolens)
* Steviol glycosides (e.g., stevioside) (Stevia rebaudiana)
* Sweet tastants (e.g., glucose, fructose, sucrose; indirectly)
* Thio-BCTC
* WS-3
* WS-12
* WS-23

|

Blockers|

* Capsazepine
* Clotrimazole
* DCDPC
* Elismetrep
* Flufenamic acid
* Meclofenamic acid
* Mefenamic acid
* N-(p-Amylcinnamoyl)anthranilic acid
* Nicotine (tobacco)
* Niflumic acid
* Ruthenium red
* Rutamarin (Ruta graveolens)
* Tolfenamic acid
* TPPO

TRPML|

| Activators|

* MK6-83
* PI(3,5)P2
* SF-22

|

TRPP|

| Activators|

* Triptolide (Tripterygium wilfordii)

|

Blockers|

* Ruthenium red

TRPV|

| Activators|

* 2-APB
* 5',6'-EET
* 9-HODE
* 9-oxoODE
* 12S-HETE
* 12S-HpETE
* 13-HODE
* 13-oxoODE
* 20-HETE
* α-Sanshool (ginger, Sichuan and melegueta peppers)
* Allicin (garlic)
* AM404
* Anandamide
* Bisandrographolide (Andrographis paniculata)
* Camphor (camphor laurel, rosemary, camphorweed, African blue basil, camphor basil)<!--TRPV1 and TRPV3-->
* Cannabidiol (cannabis)
* Cannabidivarin (cannabis)
* Capsaicin (chili pepper)
* Carvacrol (oregano, thyme, pepperwort, wild bergamot, others)
* DHEA
* Diacyl glycerol
* Dihydrocapsaicin (chili pepper)
* Estradiol
* Eugenol (basil, clove)
* Evodiamine (Euodia ruticarpa)
* Gingerols (ginger)
* GSK1016790A
* Heat
* Hepoxilin A3
* Hepoxilin B3
* Homocapsaicin (chili pepper)
* Homodihydrocapsaicin (chili pepper)
* Incensole (incense)
* Lysophosphatidic acid
* Low pH (acidic conditions)
* Menthol (mint)
* N-Arachidonoyl dopamine
* N-Oleoyldopamine
* N-Oleoylethanolamide
* Nonivamide (PAVA) (PAVA spray)
* Nordihydrocapsaicin (chili pepper)
* Paclitaxel (Pacific yew)
* Paracetamol (acetaminophen)
* Phorbol esters (e.g., 4α-PDD)
* Piperine (black pepper, long pepper)
* Polygodial (Dorrigo pepper)
* Probenecid
* Protons
* RhTx
* Rutamarin (Ruta graveolens)
* Resiniferatoxin (RTX) (Euphorbia resinifera/pooissonii)
* Shogaols (ginger, Sichuan and melegueta peppers)
* Tetrahydrocannabivarin (cannabis)
* Thymol (thyme, oregano)
* Tinyatoxin (Euphorbia resinifera/pooissonii)
* Tramadol
* Vanillin (vanilla)
* Zucapsaicin

|

Blockers|

* α-Spinasterol (Vernonia tweediana)
* AMG-517
* Asivatrep
* BCTC
* Cannabigerol (cannabis)
* Cannabigerolic acid (cannabis)
* Cannabigerovarin (cannabis)
* Cannabinol (cannabis)
* Capsazepine
* DCDPC
* DHEA
* DHEA-S
* Flufenamic acid
* GRC-6211
* HC-067047
* Lanthanum
* Mavatrep
* Meclofenamic acid
* N-(p-Amylcinnamoyl)anthranilic acid
* NGD-8243
* Niflumic acid
* Pregnenolone sulfate
* RN-1734
* RN-9893
* Ruthenium red
* SB-705498
* Tivanisiran
* Tolfenamic acid

See also: Receptor/signaling modulators • Ion channel modulators

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*[TRP]: Transient receptor potential
*[TRPA]: Transient receptor potential ankyrin channel
*[TRPC]: Transient receptor potential canonical channel
*[TRPM]: Transient receptor potential melastatin channel
*[TRPML]: Transient receptor potential mucolipin channel
*[TRPP]: Transient receptor potential polycystin channel
*[TRPV]: Transient receptor potential vanilloid channel